Computer program for calculation of complex chemical equilibrium compositions and applications. Part 1: Analysis

NASA Technical Reports Server (NTRS)

Gordon, Sanford; Mcbride, Bonnie J.

1994-01-01

This report presents the latest in a number of versions of chemical equilibrium and applications programs developed at the NASA Lewis Research Center over more than 40 years. These programs have changed over the years to include additional features and improved calculation techniques and to take advantage of constantly improving computer capabilities. The minimization-of-free-energy approach to chemical equilibrium calculations has been used in all versions of the program since 1967. The two principal purposes of this report are presented in two parts. The first purpose, which is accomplished here in part 1, is to present in detail a number of topics of general interest in complex equilibrium calculations. These topics include mathematical analyses and techniques for obtaining chemical equilibrium; formulas for obtaining thermodynamic and transport mixture properties and thermodynamic derivatives; criteria for inclusion of condensed phases; calculations at a triple point; inclusion of ionized species; and various applications, such as constant-pressure or constant-volume combustion, rocket performance based on either a finite- or infinite-chamber-area model, shock wave calculations, and Chapman-Jouguet detonations. The second purpose of this report, to facilitate the use of the computer code, is accomplished in part 2, entitled 'Users Manual and Program Description'. Various aspects of the computer code are discussed, and a number of examples are given to illustrate its versatility.

Numerical simulation of hypersonic inlet flows with equilibrium or finite rate chemistry

NASA Technical Reports Server (NTRS)

Yu, Sheng-Tao; Hsieh, Kwang-Chung; Shuen, Jian-Shun; Mcbride, Bonnie J.

1988-01-01

An efficient numerical program incorporated with comprehensive high temperature gas property models has been developed to simulate hypersonic inlet flows. The computer program employs an implicit lower-upper time marching scheme to solve the two-dimensional Navier-Stokes equations with variable thermodynamic and transport properties. Both finite-rate and local-equilibrium approaches are adopted in the chemical reaction model for dissociation and ionization of the inlet air. In the finite rate approach, eleven species equations coupled with fluid dynamic equations are solved simultaneously. In the local-equilibrium approach, instead of solving species equations, an efficient chemical equilibrium package has been developed and incorporated into the flow code to obtain chemical compositions directly. Gas properties for the reaction products species are calculated by methods of statistical mechanics and fit to a polynomial form for C(p). In the present study, since the chemical reaction time is comparable to the flow residence time, the local-equilibrium model underpredicts the temperature in the shock layer. Significant differences of predicted chemical compositions in shock layer between finite rate and local-equilibrium approaches have been observed.

An implicit flux-split algorithm to calculate hypersonic flowfields in chemical equilibrium

NASA Technical Reports Server (NTRS)

Palmer, Grant

1987-01-01

An implicit, finite-difference, shock-capturing algorithm that calculates inviscid, hypersonic flows in chemical equilibrium is presented. The flux vectors and flux Jacobians are differenced using a first-order, flux-split technique. The equilibrium composition of the gas is determined by minimizing the Gibbs free energy at every node point. The code is validated by comparing results over an axisymmetric hemisphere against previously published results. The algorithm is also applied to more practical configurations. The accuracy, stability, and versatility of the algorithm have been promising.

Extension of CE/SE method to non-equilibrium dissociating flows

NASA Astrophysics Data System (ADS)

Wen, C. Y.; Saldivar Massimi, H.; Shen, H.

2018-03-01

In this study, the hypersonic non-equilibrium flows over rounded nose geometries are numerically investigated by a robust conservation element and solution element (CE/SE) code, which is based on hybrid meshes consisting of triangular and quadrilateral elements. The dissociating and recombination chemical reactions as well as the vibrational energy relaxation are taken into account. The stiff source terms are solved by an implicit trapezoidal method of integration. Comparison with laboratory and numerical cases are provided to demonstrate the accuracy and reliability of the present CE/SE code in simulating hypersonic non-equilibrium flows.

A numerical code for the simulation of non-equilibrium chemically reacting flows on hybrid CPU-GPU clusters

NASA Astrophysics Data System (ADS)

Kudryavtsev, Alexey N.; Kashkovsky, Alexander V.; Borisov, Semyon P.; Shershnev, Anton A.

2017-10-01

In the present work a computer code RCFS for numerical simulation of chemically reacting compressible flows on hybrid CPU/GPU supercomputers is developed. It solves 3D unsteady Euler equations for multispecies chemically reacting flows in general curvilinear coordinates using shock-capturing TVD schemes. Time advancement is carried out using the explicit Runge-Kutta TVD schemes. Program implementation uses CUDA application programming interface to perform GPU computations. Data between GPUs is distributed via domain decomposition technique. The developed code is verified on the number of test cases including supersonic flow over a cylinder.

Thermodynamic properties of gaseous fluorocarbons and isentropic equilibrium expansions of two binary mixtures of fluorocarbons and argon

NASA Technical Reports Server (NTRS)

Talcott, N. A., Jr.

1977-01-01

Equations and computer code are given for the thermodynamic properties of gaseous fluorocarbons in chemical equilibrium. In addition, isentropic equilibrium expansions of two binary mixtures of fluorocarbons and argon are included. The computer code calculates the equilibrium thermodynamic properties and, in some cases, the transport properties for the following fluorocarbons: CCl2F, CCl2F2, CBrF3, CF4, CHCl2F, CHF3, CCL2F-CCl2F, CCLF2-CClF2, CF3-CF3, and C4F8. Equilibrium thermodynamic properties are tabulated for six of the fluorocarbons(CCl3F, CCL2F2, CBrF3, CF4, CF3-CF3, and C4F8) and pressure-enthalpy diagrams are presented for CBrF3.

APOLLO: A computer program for the calculation of chemical equilibrium and reaction kinetics of chemical systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, H.D.

1991-11-01

Several of the technologies being evaluated for the treatment of waste material involve chemical reactions. Our example is the in situ vitrification (ISV) process where electrical energy is used to melt soil and waste into a ``glass like`` material that immobilizes and encapsulates any residual waste. During the ISV process, various chemical reactions may occur that produce significant amounts of products which must be contained and treated. The APOLLO program was developed to assist in predicting the composition of the gases that are formed. Although the development of this program was directed toward ISV applications, it should be applicable tomore » other technologies where chemical reactions are of interest. This document presents the mathematical methodology of the APOLLO computer code. APOLLO is a computer code that calculates the products of both equilibrium and kinetic chemical reactions. The current version, written in FORTRAN, is readily adaptable to existing transport programs designed for the analysis of chemically reacting flow systems. Separate subroutines EQREACT and KIREACT for equilibrium ad kinetic chemistry respectively have been developed. A full detailed description of the numerical techniques used, which include both Lagrange multiplies and a third-order integrating scheme is presented. Sample test problems are presented and the results are in excellent agreement with those reported in the literature.« less

APOLLO: A computer program for the calculation of chemical equilibrium and reaction kinetics of chemical systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, H.D.

1991-11-01

Several of the technologies being evaluated for the treatment of waste material involve chemical reactions. Our example is the in situ vitrification (ISV) process where electrical energy is used to melt soil and waste into a glass like'' material that immobilizes and encapsulates any residual waste. During the ISV process, various chemical reactions may occur that produce significant amounts of products which must be contained and treated. The APOLLO program was developed to assist in predicting the composition of the gases that are formed. Although the development of this program was directed toward ISV applications, it should be applicable tomore » other technologies where chemical reactions are of interest. This document presents the mathematical methodology of the APOLLO computer code. APOLLO is a computer code that calculates the products of both equilibrium and kinetic chemical reactions. The current version, written in FORTRAN, is readily adaptable to existing transport programs designed for the analysis of chemically reacting flow systems. Separate subroutines EQREACT and KIREACT for equilibrium ad kinetic chemistry respectively have been developed. A full detailed description of the numerical techniques used, which include both Lagrange multiplies and a third-order integrating scheme is presented. Sample test problems are presented and the results are in excellent agreement with those reported in the literature.« less

Computer code for single-point thermodynamic analysis of hydrogen/oxygen expander-cycle rocket engines

NASA Technical Reports Server (NTRS)

Glassman, Arthur J.; Jones, Scott M.

1991-01-01

This analysis and this computer code apply to full, split, and dual expander cycles. Heat regeneration from the turbine exhaust to the pump exhaust is allowed. The combustion process is modeled as one of chemical equilibrium in an infinite-area or a finite-area combustor. Gas composition in the nozzle may be either equilibrium or frozen during expansion. This report, which serves as a users guide for the computer code, describes the system, the analysis methodology, and the program input and output. Sample calculations are included to show effects of key variables such as nozzle area ratio and oxidizer-to-fuel mass ratio.

Combustion chamber analysis code

NASA Technical Reports Server (NTRS)

Przekwas, A. J.; Lai, Y. G.; Krishnan, A.; Avva, R. K.; Giridharan, M. G.

1993-01-01

A three-dimensional, time dependent, Favre averaged, finite volume Navier-Stokes code has been developed to model compressible and incompressible flows (with and without chemical reactions) in liquid rocket engines. The code has a non-staggered formulation with generalized body-fitted-coordinates (BFC) capability. Higher order differencing methodologies such as MUSCL and Osher-Chakravarthy schemes are available. Turbulent flows can be modeled using any of the five turbulent models present in the code. A two-phase, two-liquid, Lagrangian spray model has been incorporated into the code. Chemical equilibrium and finite rate reaction models are available to model chemically reacting flows. The discrete ordinate method is used to model effects of thermal radiation. The code has been validated extensively against benchmark experimental data and has been applied to model flows in several propulsion system components of the SSME and the STME.

Development of a 3-D upwind PNS code for chemically reacting hypersonic flowfields

NASA Technical Reports Server (NTRS)

Tannehill, J. C.; Wadawadigi, G.

1992-01-01

Two new parabolized Navier-Stokes (PNS) codes were developed to compute the three-dimensional, viscous, chemically reacting flow of air around hypersonic vehicles such as the National Aero-Space Plane (NASP). The first code (TONIC) solves the gas dynamic and species conservation equations in a fully coupled manner using an implicit, approximately-factored, central-difference algorithm. This code was upgraded to include shock fitting and the capability of computing the flow around complex body shapes. The revised TONIC code was validated by computing the chemically-reacting (M(sub infinity) = 25.3) flow around a 10 deg half-angle cone at various angles of attack and the Ames All-Body model at 0 deg angle of attack. The results of these calculations were in good agreement with the results from the UPS code. One of the major drawbacks of the TONIC code is that the central-differencing of fluxes across interior flowfield discontinuities tends to introduce errors into the solution in the form of local flow property oscillations. The second code (UPS), originally developed for a perfect gas, has been extended to permit either perfect gas, equilibrium air, or nonequilibrium air computations. The code solves the PNS equations using a finite-volume, upwind TVD method based on Roe's approximate Riemann solver that was modified to account for real gas effects. The dissipation term associated with this algorithm is sufficiently adaptive to flow conditions that, even when attempting to capture very strong shock waves, no additional smoothing is required. For nonequilibrium calculations, the code solves the fluid dynamic and species continuity equations in a loosely-coupled manner. This code was used to calculate the hypersonic, laminar flow of chemically reacting air over cones at various angles of attack. In addition, the flow around the McDonnel Douglas generic option blended-wing-body was computed and comparisons were made between the perfect gas, equilibrium air, and the nonequilibrium air results.

Liquid rocket combustor computer code development

NASA Technical Reports Server (NTRS)

Liang, P. Y.

1985-01-01

The Advanced Rocket Injector/Combustor Code (ARICC) that has been developed to model the complete chemical/fluid/thermal processes occurring inside rocket combustion chambers are highlighted. The code, derived from the CONCHAS-SPRAY code originally developed at Los Alamos National Laboratory incorporates powerful features such as the ability to model complex injector combustion chamber geometries, Lagrangian tracking of droplets, full chemical equilibrium and kinetic reactions for multiple species, a fractional volume of fluid (VOF) description of liquid jet injection in addition to the gaseous phase fluid dynamics, and turbulent mass, energy, and momentum transport. Atomization and droplet dynamic models from earlier generation codes are transplated into the present code. Currently, ARICC is specialized for liquid oxygen/hydrogen propellants, although other fuel/oxidizer pairs can be easily substituted.

LSENS, a general chemical kinetics and sensitivity analysis code for gas-phase reactions: User's guide

NASA Technical Reports Server (NTRS)

Radhakrishnan, Krishnan; Bittker, David A.

1993-01-01

A general chemical kinetics and sensitivity analysis code for complex, homogeneous, gas-phase reactions is described. The main features of the code, LSENS, are its flexibility, efficiency and convenience in treating many different chemical reaction models. The models include static system, steady, one-dimensional, inviscid flow, shock initiated reaction, and a perfectly stirred reactor. In addition, equilibrium computations can be performed for several assigned states. An implicit numerical integration method, which works efficiently for the extremes of very fast and very slow reaction, is used for solving the 'stiff' differential equation systems that arise in chemical kinetics. For static reactions, sensitivity coefficients of all dependent variables and their temporal derivatives with respect to the initial values of dependent variables and/or the rate coefficient parameters can be computed. This paper presents descriptions of the code and its usage, and includes several illustrative example problems.

A computer program for two-dimensional and axisymmetric nonreacting perfect gas and equilibrium chemically reacting laminar, transitional and-or turbulent boundary layer flows

NASA Technical Reports Server (NTRS)

Miner, E. W.; Anderson, E. C.; Lewis, C. H.

1971-01-01

A computer program is described in detail for laminar, transitional, and/or turbulent boundary-layer flows of non-reacting (perfect gas) and reacting gas mixtures in chemical equilibrium. An implicit finite difference scheme was developed for both two dimensional and axisymmetric flows over bodies, and in rocket nozzles and hypervelocity wind tunnel nozzles. The program, program subroutines, variables, and input and output data are described. Also included is the output from a sample calculation of fully developed turbulent, perfect gas flow over a flat plate. Input data coding forms and a FORTRAN source listing of the program are included. A method is discussed for obtaining thermodynamic and transport property data which are required to perform boundary-layer calculations for reacting gases in chemical equilibrium.

Solute transport with equilibrium aqueous complexation and either sorption or ion exchange: Simulation methodology and applications

USGS Publications Warehouse

Lewis, F.M.; Voss, C.I.; Rubin, J.

1987-01-01

Methodologies that account for specific types of chemical reactions in the simulation of solute transport can be developed so they are compatible with solution algorithms employed in existing transport codes. This enables the simulation of reactive transport in complex multidimensional flow regimes, and provides a means for existing codes to account for some of the fundamental chemical processes that occur among transported solutes. Two equilibrium-controlled reaction systems demonstrate a methodology for accommodating chemical interaction into models of solute transport. One system involves the sorption of a given chemical species, as well as two aqueous complexations in which the sorbing species is a participant. The other reaction set involves binary ion exchange coupled with aqueous complexation involving one of the exchanging species. The methodology accommodates these reaction systems through the addition of nonlinear terms to the transport equations for the sorbing species. Example simulation results show (1) the effect equilibrium chemical parameters have on the spatial distributions of concentration for complexing solutes; (2) that an interrelationship exists between mechanical dispersion and the various reaction processes; (3) that dispersive parameters of the porous media cannot be determined from reactive concentration distributions unless the reaction is accounted for or the influence of the reaction is negligible; (4) how the concentration of a chemical species may be significantly affected by its participation in an aqueous complex with a second species which also sorbs; and (5) that these coupled chemical processes influencing reactive transport can be demonstrated in two-dimensional flow regimes. ?? 1987.

Upwind MacCormack Euler solver with non-equilibrium chemistry

NASA Technical Reports Server (NTRS)

Sherer, Scott E.; Scott, James N.

1993-01-01

A computer code, designated UMPIRE, is currently under development to solve the Euler equations in two dimensions with non-equilibrium chemistry. UMPIRE employs an explicit MacCormack algorithm with dissipation introduced via Roe's flux-difference split upwind method. The code also has the capability to employ a point-implicit methodology for flows where stiffness is introduced through the chemical source term. A technique consisting of diagonal sweeps across the computational domain from each corner is presented, which is used to reduce storage and execution requirements. Results depicting one dimensional shock tube flow for both calorically perfect gas and thermally perfect, dissociating nitrogen are presented to verify current capabilities of the program. Also, computational results from a chemical reactor vessel with no fluid dynamic effects are presented to check the chemistry capability and to verify the point implicit strategy.

A Simple and Accurate Network for Hydrogen and Carbon Chemistry in the Interstellar Medium

NASA Astrophysics Data System (ADS)

Gong, Munan; Ostriker, Eve C.; Wolfire, Mark G.

2017-07-01

Chemistry plays an important role in the interstellar medium (ISM), regulating the heating and cooling of the gas and determining abundances of molecular species that trace gas properties in observations. Although solving the time-dependent equations is necessary for accurate abundances and temperature in the dynamic ISM, a full chemical network is too computationally expensive to incorporate into numerical simulations. In this paper, we propose a new simplified chemical network for hydrogen and carbon chemistry in the atomic and molecular ISM. We compare results from our chemical network in detail with results from a full photodissociation region (PDR) code, and also with the Nelson & Langer (NL99) network previously adopted in the simulation literature. We show that our chemical network gives similar results to the PDR code in the equilibrium abundances of all species over a wide range of densities, temperature, and metallicities, whereas the NL99 network shows significant disagreement. Applying our network to 1D models, we find that the CO-dominated regime delimits the coldest gas and that the corresponding temperature tracks the cosmic-ray ionization rate in molecular clouds. We provide a simple fit for the locus of CO-dominated regions as a function of gas density and column. We also compare with observations of diffuse and translucent clouds. We find that the CO, {{CH}}x, and {{OH}}x abundances are consistent with equilibrium predictions for densities n=100{--}1000 {{cm}}-3, but the predicted equilibrium C abundance is higher than that seen in observations, signaling the potential importance of non-equilibrium/dynamical effects.

Equilibrium chemistry down to 100 K. Impact of silicates and phyllosilicates on the carbon to oxygen ratio

NASA Astrophysics Data System (ADS)

Woitke, P.; Helling, Ch.; Hunter, G. H.; Millard, J. D.; Turner, G. E.; Worters, M.; Blecic, J.; Stock, J. W.

2018-06-01

We have introduced a fast and versatile computer code, GGCHEM, to determine the chemical composition of gases in thermo-chemical equilibrium down to 100 K, with or without equilibrium condensation. We have reviewed the data for molecular equilibrium constants, kp(T), from several sources and discussed which functional fits are most suitable for low temperatures. We benchmarked our results against another chemical equilibrium code. We collected Gibbs free energies, ΔGf⊖, for about 200 solid and liquid species from the NIST-JANAF database and the geophysical database SUPCRTBL. We discussed the condensation sequence of the elements with solar abundances in phase equilibrium down to 100 K. Once the major magnesium silicates Mg2SiO4[s] and MgSiO3[s] have formed, the dust to gas mass ratio jumps to a value of about 0.0045 which is significantly lower than the often assumed value of 0.01. Silicate condensation is found to increase the carbon to oxygen ratio (C/O) in the gas from its solar value of 0.55 up to 0.71, and, by the additional intake of water and hydroxyl into the solid matrix, the formation of phyllosilicates at temperatures below 400 K increases the gaseous C/O further to about 0.83. Metallic tungsten (W) is the first condensate found to become thermodynamically stable around 1600-2200 K (depending on pressure), several hundreds of Kelvin before subsequent materials such as zirconium dioxide (ZrO2) or corundum (Al2O3) can condense. We briefly discuss whether tungsten, despite its low abundance of 2 × 10-7 times the silicon abundance, could provide the first seed particles for astrophysical dust formation. GGCHEM code is publicly available at http://https://github.com/pw31/GGchemTable D.1 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/614/A1

A generalized chemistry version of SPARK

NASA Technical Reports Server (NTRS)

Carpenter, Mark H.

1988-01-01

An extension of the reacting H2-air computer code SPARK is presented, which enables the code to be used on any reacting flow problem. Routines are developed calculating in a general fashion, the reaction rates, and chemical Jacobians of any reacting system. In addition, an equilibrium routine is added so that the code will have frozen, finite rate, and equilibrium capabilities. The reaction rate for the species is determined from the law of mass action using Arrhenius expressions for the rate constants. The Jacobian routines are determined by numerically or analytically differentiating the law of mass action for each species. The equilibrium routine is based on a Gibbs free energy minimization routine. The routines are written in FORTRAN 77, with special consideration given to vectorization. Run times for the generalized routines are generally 20 percent slower than reaction specific routines. The numerical efficiency of the generalized analytical Jacobian, however, is nearly 300 percent better than the reaction specific numerical Jacobian used in SPARK.

BLAKE - A Thermodynamics Code Based on TIGER: Users’ Guide to the Revised Program

DTIC Science & Technology

1998-07-01

thermodynamics program derived from an older version of TIGER.-*-2 Although it is applicable to a wide range of chemical equilibrium calculations...BLAKE is specifically intended for computing the properties of gun propellants at chamber conditions. Its principal difference from other chemical ...for Use with Electrothermal- Chemical (ETC) Systems," ARL-TR-488 (July 1994). The rationale for excluding charged species is presented here. 2

Improvements on non-equilibrium and transport Green function techniques: The next-generation TRANSIESTA

NASA Astrophysics Data System (ADS)

Papior, Nick; Lorente, Nicolás; Frederiksen, Thomas; García, Alberto; Brandbyge, Mads

2017-03-01

We present novel methods implemented within the non-equilibrium Green function code (NEGF) TRANSIESTA based on density functional theory (DFT). Our flexible, next-generation DFT-NEGF code handles devices with one or multiple electrodes (Ne ≥ 1) with individual chemical potentials and electronic temperatures. We describe its novel methods for electrostatic gating, contour optimizations, and assertion of charge conservation, as well as the newly implemented algorithms for optimized and scalable matrix inversion, performance-critical pivoting, and hybrid parallelization. Additionally, a generic NEGF "post-processing" code (TBTRANS/PHTRANS) for electron and phonon transport is presented with several novelties such as Hamiltonian interpolations, Ne ≥ 1 electrode capability, bond-currents, generalized interface for user-defined tight-binding transport, transmission projection using eigenstates of a projected Hamiltonian, and fast inversion algorithms for large-scale simulations easily exceeding 106 atoms on workstation computers. The new features of both codes are demonstrated and bench-marked for relevant test systems.

Chemically Reacting One-Dimensional Gas-Particle Flows

NASA Technical Reports Server (NTRS)

Tevepaugh, J. A.; Penny, M. M.

1975-01-01

The governing equations for the one-dimensional flow of a gas-particle system are discussed. Gas-particle effects are coupled via the system momentum and energy equations with the gas assumed to be chemically frozen or in chemical equilibrium. A computer code for calculating the one-dimensional flow of a gas-particle system is discussed and a user's input guide presented. The computer code provides for the expansion of the gas-particle system from a specified starting velocity and nozzle inlet geometry. Though general in nature, the final output of the code is a startline for initiating the solution of a supersonic gas-particle system in rocket nozzles. The startline includes gasdynamic data defining gaseous startline points from the nozzle centerline to the nozzle wall and particle properties at points along the gaseous startline.

Recent advances in modeling Hugoniots with Cheetah

NASA Astrophysics Data System (ADS)

Glaesemann, Kurt

2005-07-01

The detonation of an energetic material is the result of a complex interaction between kinetic chemical reactions and thermodynamic chemical equilibrium. Unfortunately, little is known concerning the detailed chemical kinetics of reacting energetic materials. Cheetah uses rate laws to treat species with the slowest chemical reactions, while assuming other chemical species are in equilibrium. Cheetah supports a wide range of elements and condensed detonation products and can also be applied to gas phase reactions. Improvements have been made to Cheetah's equilibrium solver, that allow it to find a wider range of thermodynamic states. Many of the difficulties experienced by users in earlier versions of Cheetah have been fixed. New capabilities have also been added. The ultimate result is a code that can be applied to a wide range of shock problems involving both energetic and non-energetic materials. New experimental validations of Cheetah's equation of state methodology have been performed, including both reacted and unreacted Hugoniots. This work was performed under the auspices of the U.S. Department of Energy by the University of California Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48.

CET93 and CETPC: An interim updated version of the NASA Lewis computer program for calculating complex chemical equilibria with applications

NASA Technical Reports Server (NTRS)

Mcbride, Bonnie J.; Reno, Martin A.; Gordon, Sanford

1994-01-01

The NASA Lewis chemical equilibrium program with applications continues to be improved and updated. The latest version is CET93. This code, with smaller arrays, has been compiled for use on an IBM or IBM-compatible personal computer and is called CETPC. This report is intended to be primarily a users manual for CET93 and CETPC. It does not repeat the more complete documentation of earlier reports on the equilibrium program. Most of the discussion covers input and output files, two new options (ONLY and comments), example problems, and implementation of CETPC.

Simplified Two-Time Step Method for Calculating Combustion and Emission Rates of Jet-A and Methane Fuel With and Without Water Injection

NASA Technical Reports Server (NTRS)

Molnar, Melissa; Marek, C. John

2005-01-01

A simplified kinetic scheme for Jet-A, and methane fuels with water injection was developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) or even simple FORTRAN codes. The two time step method is either an initial time averaged value (step one) or an instantaneous value (step two). The switch is based on the water concentration in moles/cc of 1x10(exp -20). The results presented here results in a correlation that gives the chemical kinetic time as two separate functions. This two time step method is used as opposed to a one step time averaged method previously developed to determine the chemical kinetic time with increased accuracy. The first time averaged step is used at the initial times for smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, initial water to fuel mass ratio, temperature, and pressure. The second instantaneous step, to be used with higher water concentrations, gives the chemical kinetic time as a function of instantaneous fuel and water mole concentration, pressure and temperature (T4). The simple correlations would then be compared to the turbulent mixing times to determine the limiting rates of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates are used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide and NOx are obtained for Jet-A fuel and methane with and without water injection to water mass loadings of 2/1 water to fuel. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentrations of carbon monoxide and nitrogen oxide as functions of overall equivalence ratio, water to fuel mass ratio, pressure and temperature (T3). The temperature of the gas entering the turbine (T4) was also correlated as a function of the initial combustor temperature (T3), equivalence ratio, water to fuel mass ratio, and pressure.

Validation of the Chemistry Module for the Euler Solver in Unified Flow Solver

DTIC Science & Technology

2012-03-01

traveling through the atmosphere there are three types of flow regimes that exist; the first is the continuum regime, second is the rarified regime and...The second method has been used in a program called Unified Flow Solver (UFS). UFS is currently being developed under collaborative efforts the Air...thermal non-equilibrium case and finally to a thermo-chemical non- equilibrium case. The data from the simulations will be compared to a second code

Li-SF(6) Combustion in Stored Chemical Energy Propulsion Systems

DTIC Science & Technology

1990-07-01

S 3. STRUCTURE OF SF6 3ETS IN MOLTEN LI ........... ................. 8 3.1 Mathematical Model ...ill - ABSTRACT Appropriate thermodynamic models and thermo-chemical data for multicompo- nents and immiscible phases have been Incorporated into a code...by a simplified integral model which was improved9 by the use of the local homogeneous flow approximation, equilibrium combustion model and Kc-C-g

An improved flux-split algorithm applied to hypersonic flows in chemical equilibrium

NASA Technical Reports Server (NTRS)

Palmer, Grant

1988-01-01

An explicit, finite-difference, shock-capturing numerical algorithm is presented and applied to hypersonic flows assumed to be in thermochemical equilibrium. Real-gas chemistry is either loosely coupled to the gasdynamics by way of a Gibbs free energy minimization package or fully coupled using species mass conservation equations with finite-rate chemical reactions. A scheme is developed that maintains stability in the explicit, finite-rate formulation while allowing relatively high time steps. The codes use flux vector splitting to difference the inviscid fluxes and employ real-gas corrections to viscosity and thermal conductivity. Numerical results are compared against existing ballistic range and flight data. Flows about complex geometries are also computed.

SP_Ace: Stellar Parameters And Chemical abundances Estimator

NASA Astrophysics Data System (ADS)

Boeche, C.; Grebel, E. K.

2018-05-01

SP_Ace (Stellar Parameters And Chemical abundances Estimator) estimates the stellar parameters Teff, log g, [M/H], and elemental abundances. It employs 1D stellar atmosphere models in Local Thermodynamic Equilibrium (LTE). The code is highly automated and suitable for analyzing the spectra of large spectroscopic surveys with low or medium spectral resolution (R = 2000-20 000). A web service for calculating these values with the software is also available.

The effect of non-equilibrium metal cooling on the interstellar medium

NASA Astrophysics Data System (ADS)

Capelo, Pedro R.; Bovino, Stefano; Lupi, Alessandro; Schleicher, Dominik R. G.; Grassi, Tommaso

2018-04-01

By using a novel interface between the modern smoothed particle hydrodynamics code GASOLINE2 and the chemistry package KROME, we follow the hydrodynamical and chemical evolution of an isolated galaxy. In order to assess the relevance of different physical parameters and prescriptions, we constructed a suite of 10 simulations, in which we vary the chemical network (primordial and metal species), how metal cooling is modelled (non-equilibrium versus equilibrium; optically thin versus thick approximation), the initial gas metallicity (from 10 to 100 per cent solar), and how molecular hydrogen forms on dust. This is the first work in which metal injection from supernovae, turbulent metal diffusion, and a metal network with non-equilibrium metal cooling are self-consistently included in a galaxy simulation. We find that properly modelling the chemical evolution of several metal species and the corresponding non-equilibrium metal cooling has important effects on the thermodynamics of the gas, the chemical abundances, and the appearance of the galaxy: the gas is typically warmer, has a larger molecular-gas mass fraction, and has a smoother disc. We also conclude that, at relatively high metallicity, the choice of molecular-hydrogen formation rates on dust is not crucial. Moreover, we confirm that a higher initial metallicity produces a colder gas and a larger fraction of molecular gas, with the low-metallicity simulation best matching the observed molecular Kennicutt-Schmidt relation. Finally, our simulations agree quite well with observations that link star formation rate to metal emission lines.

Effects of Nonequilibrium Chemistry and Darcy-Forchheimer Pyrolysis Flow for Charring Ablator

NASA Technical Reports Server (NTRS)

Chen, Yih-Kanq; Milos, Frank S.

2013-01-01

The fully implicit ablation and thermal response code simulates pyrolysis and ablation of thermal protection materials and systems. The governing equations, which include energy conservation, a three-component decomposition model, and a surface energy balance, are solved with a moving grid.This work describes new modeling capabilities that are added to a special version of code. These capabilities include a time-dependent pyrolysis gas flow momentum equation with Darcy-Forchheimer terms and pyrolysis gas species conservation equations with finite rate homogeneous chemical reactions. The total energy conservation equation is also enhanced for consistency with these new additions. Two groups of parametric studies of the phenolic impregnated carbon ablator are performed. In the first group, an Orion flight environment for a proposed lunar-return trajectory is considered. In the second group, various test conditions for arcjet models are examined. The central focus of these parametric studies is to understand the effect of pyrolysis gas momentum transfer on material in-depth thermal responses with finite-rate, equilibrium, or frozen homogeneous gas chemistry. Results indicate that the presence of chemical nonequilibrium pyrolysis gas flow does not significantly alter the in-depth thermal response performance predicted using the chemical equilibrium gas model.

LSENS: A General Chemical Kinetics and Sensitivity Analysis Code for homogeneous gas-phase reactions. Part 1: Theory and numerical solution procedures

NASA Technical Reports Server (NTRS)

Radhakrishnan, Krishnan

1994-01-01

LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 1 of a series of three reference publications that describe LENS, provide a detailed guide to its usage, and present many example problems. Part 1 derives the governing equations and describes the numerical solution procedures for the types of problems that can be solved. The accuracy and efficiency of LSENS are examined by means of various test problems, and comparisons with other methods and codes are presented. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions.

Supersonic Flow of Chemically Reacting Gas-Particle Mixtures. Volume 2: RAMP - A Computer Code for Analysis of Chemically Reacting Gas-Particle Flows

NASA Technical Reports Server (NTRS)

Penny, M. M.; Smith, S. D.; Anderson, P. G.; Sulyma, P. R.; Pearson, M. L.

1976-01-01

A computer program written in conjunction with the numerical solution of the flow of chemically reacting gas-particle mixtures was documented. The solution to the set of governing equations was obtained by utilizing the method of characteristics. The equations cast in characteristic form were shown to be formally the same for ideal, frozen, chemical equilibrium and chemical non-equilibrium reacting gas mixtures. The characteristic directions for the gas-particle system are found to be the conventional gas Mach lines, the gas streamlines and the particle streamlines. The basic mesh construction for the flow solution is along streamlines and normals to the streamlines for axisymmetric or two-dimensional flow. The analysis gives detailed information of the supersonic flow and provides for a continuous solution of the nozzle and exhaust plume flow fields. Boundary conditions for the flow solution are either the nozzle wall or the exhaust plume boundary.

Data Parallel Line Relaxation (DPLR) Code User Manual: Acadia - Version 4.01.1

NASA Technical Reports Server (NTRS)

Wright, Michael J.; White, Todd; Mangini, Nancy

2009-01-01

Data-Parallel Line Relaxation (DPLR) code is a computational fluid dynamic (CFD) solver that was developed at NASA Ames Research Center to help mission support teams generate high-value predictive solutions for hypersonic flow field problems. The DPLR Code Package is an MPI-based, parallel, full three-dimensional Navier-Stokes CFD solver with generalized models for finite-rate reaction kinetics, thermal and chemical non-equilibrium, accurate high-temperature transport coefficients, and ionized flow physics incorporated into the code. DPLR also includes a large selection of generalized realistic surface boundary conditions and links to enable loose coupling with external thermal protection system (TPS) material response and shock layer radiation codes.

New Reduced Two-Time Step Method for Calculating Combustion and Emission Rates of Jet-A and Methane Fuel With and Without Water Injection

NASA Technical Reports Server (NTRS)

Molnar, Melissa; Marek, C. John

2004-01-01

A simplified kinetic scheme for Jet-A, and methane fuels with water injection was developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) or even simple FORTRAN codes that are being developed at Glenn. The two time step method is either an initial time averaged value (step one) or an instantaneous value (step two). The switch is based on the water concentration in moles/cc of 1x10(exp -20). The results presented here results in a correlation that gives the chemical kinetic time as two separate functions. This two step method is used as opposed to a one step time averaged method previously developed to determine the chemical kinetic time with increased accuracy. The first time averaged step is used at the initial times for smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, initial water to fuel mass ratio, temperature, and pressure. The second instantaneous step, to be used with higher water concentrations, gives the chemical kinetic time as a function of instantaneous fuel and water mole concentration, pressure and temperature (T4). The simple correlations would then be compared to the turbulent mixing times to determine the limiting properties of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates were then used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide and NOx were obtained for Jet-A fuel and methane with and without water injection to water mass loadings of 2/1 water to fuel. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentrations of carbon monoxide and nitrogen oxide as functions of overall equivalence ratio, water to fuel mass ratio, pressure and temperature (T3). The temperature of the gas entering the turbine (T4) was also correlated as a function of the initial combustor temperature (T3), equivalence ratio, water to fuel mass ratio, and pressure.

SOPHAEROS code development and its application to falcon tests

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lajtha, G.; Missirlian, M.; Kissane, M.

1996-12-31

One of the key issues in source-term evaluation in nuclear reactor severe accidents is determination of the transport behavior of fission products released from the degrading core. The SOPHAEROS computer code is being developed to predict fission product transport in a mechanistic way in light water reactor circuits. These applications of the SOPHAEROS code to the Falcon experiments, among others not presented here, indicate that the numerical scheme of the code is robust, and no convergence problems are encountered. The calculation is also very fast being three times longer on a Sun SPARC 5 workstation than real time and typicallymore » {approx} 10 times faster than an identical calculation with the VICTORIA code. The study demonstrates that the SOPHAEROS 1.3 code is a suitable tool for prediction of the vapor chemistry and fission product transport with a reasonable level of accuracy. Furthermore, the fexibility of the code material data bank allows improvement of understanding of fission product transport and deposition in the circuit. Performing sensitivity studies with different chemical species or with different properties (saturation pressure, chemical equilibrium constants) is very straightforward.« less

Program Helps To Determine Chemical-Reaction Mechanisms

NASA Technical Reports Server (NTRS)

Bittker, D. A.; Radhakrishnan, K.

1995-01-01

General Chemical Kinetics and Sensitivity Analysis (LSENS) computer code developed for use in solving complex, homogeneous, gas-phase, chemical-kinetics problems. Provides for efficient and accurate chemical-kinetics computations and provides for sensitivity analysis for variety of problems, including problems involving honisothermal conditions. Incorporates mathematical models for static system, steady one-dimensional inviscid flow, reaction behind incident shock wave (with boundary-layer correction), and perfectly stirred reactor. Computations of equilibrium properties performed for following assigned states: enthalpy and pressure, temperature and pressure, internal energy and volume, and temperature and volume. Written in FORTRAN 77 with exception of NAMELIST extensions used for input.

Computer Program for Calculation of Complex Chemical Equilibrium Compositions and Applications II. Users Manual and Program Description. 2; Users Manual and Program Description

NASA Technical Reports Server (NTRS)

McBride, Bonnie J.; Gordon, Sanford

1996-01-01

This users manual is the second part of a two-part report describing the NASA Lewis CEA (Chemical Equilibrium with Applications) program. The program obtains chemical equilibrium compositions of complex mixtures with applications to several types of problems. The topics presented in this manual are: (1) details for preparing input data sets; (2) a description of output tables for various types of problems; (3) the overall modular organization of the program with information on how to make modifications; (4) a description of the function of each subroutine; (5) error messages and their significance; and (6) a number of examples that illustrate various types of problems handled by CEA and that cover many of the options available in both input and output. Seven appendixes give information on the thermodynamic and thermal transport data used in CEA; some information on common variables used in or generated by the equilibrium module; and output tables for 14 example problems. The CEA program was written in ANSI standard FORTRAN 77. CEA should work on any system with sufficient storage. There are about 6300 lines in the source code, which uses about 225 kilobytes of memory. The compiled program takes about 975 kilobytes.

Diffusion and Equilibrium Swelling of Macromolecular Networks by Their Linear Homologs.

DTIC Science & Technology

1982-10-01

C/ . 29 OYN 6/81 DISTRIBUTION LIST No. Copies No. Copies Dr. L.V. Schmtdt 1 Dr. F. Roberto 1 Assistant Secretary of the Navy Code AFRPL MKPA (RE, and...Scientific Advisor Directorate of Aerospace Sciences Commandant of the Marine Corps Bolling Air Force Base Code RD-1 Washington, D.C. 20332 Washington...Directorate of Chemical Sciences Arlington VA 22217 Bolling Air Force Base t VWashington, D.C. 20332 Mr. David Siegel Office of Naval Research Dr. John S

Numerical simulation of advective-dispersive multisolute transport with sorption, ion exchange and equilibrium chemistry

USGS Publications Warehouse

Lewis, F.M.; Voss, C.I.; Rubin, Jacob

1986-01-01

A model was developed that can simulate the effect of certain chemical and sorption reactions simultaneously among solutes involved in advective-dispersive transport through porous media. The model is based on a methodology that utilizes physical-chemical relationships in the development of the basic solute mass-balance equations; however, the form of these equations allows their solution to be obtained by methods that do not depend on the chemical processes. The chemical environment is governed by the condition of local chemical equilibrium, and may be defined either by the linear sorption of a single species and two soluble complexation reactions which also involve that species, or binary ion exchange and one complexation reaction involving a common ion. Partial differential equations that describe solute mass balance entirely in the liquid phase are developed for each tenad (a chemical entity whose total mass is independent of the reaction process) in terms of their total dissolved concentration. These equations are solved numerically in two dimensions through the modification of an existing groundwater flow/transport computer code. (Author 's abstract)

LSENS, a general chemical kinetics and sensitivity analysis code for homogeneous gas-phase reactions. 2: Code description and usage

NASA Technical Reports Server (NTRS)

Radhakrishnan, Krishnan; Bittker, David A.

1994-01-01

LSENS, the Lewis General Chemical Kinetics Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 2 of a series of three reference publications that describe LSENS, provide a detailed guide to its usage, and present many example problems. Part 2 describes the code, how to modify it, and its usage, including preparation of the problem data file required to execute LSENS. Code usage is illustrated by several example problems, which further explain preparation of the problem data file and show how to obtain desired accuracy in the computed results. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions. Part 1 (NASA RP-1328) derives the governing equations describes the numerical solution procedures for the types of problems that can be solved by lSENS. Part 3 (NASA RP-1330) explains the kinetics and kinetics-plus-sensitivity-analysis problems supplied with LSENS and presents sample results.

Data Needs and Modeling of the Upper Atmosphere

NASA Astrophysics Data System (ADS)

Brunger, M. J.; Campbell, L.

2007-04-01

We present results from our enhanced statistical equilibrium and time-step codes for atmospheric modeling. In particular we use these results to illustrate the role of electron-driven processes in atmospheric phenomena and the sensitivity of the model results to data inputs such as integral cross sections, dissociative recombination rates and chemical reaction rates.

Implementation of equilibrium aqueous speciation and solubility (EQ3 type) calculations into Cantera for electrolyte solutions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moffat, Harry K.; Jove-Colon, Carlos F.

2009-06-01

In this report, we summarize our work on developing a production level capability for modeling brine thermodynamic properties using the open-source code Cantera. This implementation into Cantera allows for the application of chemical thermodynamics to describe the interactions between a solid and an electrolyte solution at chemical equilibrium. The formulations to evaluate the thermodynamic properties of electrolytes are based on Pitzer's model to calculate molality-based activity coefficients using a real equation-of-state (EoS) for water. In addition, the thermodynamic properties of solutes at elevated temperature and pressures are computed using the revised Helgeson-Kirkham-Flowers (HKF) EoS for ionic and neutral aqueous species.more » The thermodynamic data parameters for the Pitzer formulation and HKF EoS are from the thermodynamic database compilation developed for the Yucca Mountain Project (YMP) used with the computer code EQ3/6. We describe the adopted equations and their implementation within Cantera and also provide several validated examples relevant to the calculations of extensive properties of electrolyte solutions.« less

LSENS: A General Chemical Kinetics and Sensitivity Analysis Code for homogeneous gas-phase reactions. Part 3: Illustrative test problems

NASA Technical Reports Server (NTRS)

Bittker, David A.; Radhakrishnan, Krishnan

1994-01-01

LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 3 of a series of three reference publications that describe LSENS, provide a detailed guide to its usage, and present many example problems. Part 3 explains the kinetics and kinetics-plus-sensitivity analysis problems supplied with LSENS and presents sample results. These problems illustrate the various capabilities of, and reaction models that can be solved by, the code and may provide a convenient starting point for the user to construct the problem data file required to execute LSENS. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions.

Self-assembly and transformation of hybrid nano-objects and nanostructures under equilibrium and non-equilibrium conditions

NASA Astrophysics Data System (ADS)

Mann, Stephen

2009-10-01

Understanding how chemically derived processes control the construction and organization of matter across extended and multiple length scales is of growing interest in many areas of materials research. Here we review present equilibrium and non-equilibrium self-assembly approaches to the synthetic construction of discrete hybrid (inorganic-organic) nano-objects and higher-level nanostructured networks. We examine a range of synthetic modalities under equilibrium conditions that give rise to integrative self-assembly (supramolecular wrapping, nanoscale incarceration and nanostructure templating) or higher-order self-assembly (programmed/directed aggregation). We contrast these strategies with processes of transformative self-assembly that use self-organizing media, reaction-diffusion systems and coupled mesophases to produce higher-level hybrid structures under non-equilibrium conditions. Key elements of the constructional codes associated with these processes are identified with regard to existing theoretical knowledge, and presented as a heuristic guideline for the rational design of hybrid nano-objects and nanomaterials.

Liquid Engine Design: Effect of Chamber Dimensions on Specific Impulse

NASA Technical Reports Server (NTRS)

Hoggard, Lindsay; Leahy, Joe

2009-01-01

Which assumption of combustion chemistry - frozen or equilibrium - should be used in the prediction of liquid rocket engine performance calculations? Can a correlation be developed for this? A literature search using the LaSSe tool, an online repository of old rocket data and reports, was completed. Test results of NTO/Aerozine-50 and Lox/LH2 subscale and full-scale injector and combustion chamber test results were found and studied for this task. NASA code, Chemical Equilibrium with Applications (CEA) was used to predict engine performance using both chemistry assumptions, defined here. Frozen- composition remains frozen during expansion through the nozzle. Equilibrium- instantaneous chemical equilibrium during nozzle expansion. Chamber parameters were varied to understand what dimensions drive chamber C* and Isp. Contraction Ratio is the ratio of the nozzle throat area to the area of the chamber. L is the length of the chamber. Characteristic chamber length, L*, is the length that the chamber would be if it were a straight tube and had no converging nozzle. Goal: Develop a qualitative and quantitative correlation for performance parameters - Specific Impulse (Isp) and Characteristic Velocity (C*) - as a function of one or more chamber dimensions - Contraction Ratio (CR), Chamber Length (L ) and/or Characteristic Chamber Length (L*). Determine if chamber dimensions can be correlated to frozen or equilibrium chemistry.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simunovic, Srdjan; Piro, Markus H.A.

Thermochimica is a software library that determines a unique combination of phases and their compositions at thermochemical equilibrium. Thermochimica can be used for stand-alone calculations or it can be directly coupled to other codes. This release of the software does not have a graphical user interface (GUI) and it can be executed from the command line or from an Application Programming Interface (API). Also, it is not intended for thermodynamic model development or for constructing phase diagrams. The main purpose of the software is to be directly coupled with a multi-physics code to provide material properties and boundary conditions formore » various physical phenomena. Significant research efforts have been dedicated to enhance computational performance through advanced algorithm development, such as improved estimation techniques and non-linear solvers. Various useful parameters can be provided as output from Thermochimica, such as: determination of which phases are stable at equilibrium, the mass of solution species and phases at equilibrium, mole fractions of solution phase constituents, thermochemical activities (which are related to partial pressures for gaseous species), chemical potentials of solution species and phases, and integral Gibbs energy (referenced relative to standard state). The overall goal is to provide an open source computational tool to enhance the predictive capability of multi-physics codes without significantly impeding computational performance.« less

An interactive computer code for calculation of gas-phase chemical equilibrium (EQLBRM)

NASA Technical Reports Server (NTRS)

Pratt, B. S.; Pratt, D. T.

1984-01-01

A user friendly, menu driven, interactive computer program known as EQLBRM which calculates the adiabatic equilibrium temperature and product composition resulting from the combustion of hydrocarbon fuels with air, at specified constant pressure and enthalpy is discussed. The program is developed primarily as an instructional tool to be run on small computers to allow the user to economically and efficiency explore the effects of varying fuel type, air/fuel ratio, inlet air and/or fuel temperature, and operating pressure on the performance of continuous combustion devices such as gas turbine combustors, Stirling engine burners, and power generation furnaces.

Simplified Two-Time Step Method for Calculating Combustion Rates and Nitrogen Oxide Emissions for Hydrogen/Air and Hydorgen/Oxygen

NASA Technical Reports Server (NTRS)

Molnar, Melissa; Marek, C. John

2005-01-01

A simplified single rate expression for hydrogen combustion and nitrogen oxide production was developed. Detailed kinetics are predicted for the chemical kinetic times using the complete chemical mechanism over the entire operating space. These times are then correlated to the reactor conditions using an exponential fit. Simple first order reaction expressions are then used to find the conversion in the reactor. The method uses a two-time step kinetic scheme. The first time averaged step is used at the initial times with smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, temperature, and pressure. The second instantaneous step is used at higher water concentrations (> 1 x 10(exp -20) moles/cc) in the mixture which gives the chemical kinetic time as a function of the instantaneous fuel and water mole concentrations, pressure and temperature (T4). The simple correlations are then compared to the turbulent mixing times to determine the limiting properties of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates are used to calculate the necessary chemical kinetic times. This time is regressed over the complete initial conditions using the Excel regression routine. Chemical kinetic time equations for H2 and NOx are obtained for H2/air fuel and for the H2/O2. A similar correlation is also developed using data from NASA s Chemical Equilibrium Applications (CEA) code to determine the equilibrium temperature (T4) as a function of overall fuel/air ratio, pressure and initial temperature (T3). High values of the regression coefficient R2 are obtained.

Summary of Simplified Two Time Step Method for Calculating Combustion Rates and Nitrogen Oxide Emissions for Hydrogen/Air and Hydrogen/Oxygen

NASA Technical Reports Server (NTRS)

Marek, C. John; Molnar, Melissa

2005-01-01

A simplified single rate expression for hydrogen combustion and nitrogen oxide production was developed. Detailed kinetics are predicted for the chemical kinetic times using the complete chemical mechanism over the entire operating space. These times are then correlated to the reactor conditions using an exponential fit. Simple first order reaction expressions are then used to find the conversion in the reactor. The method uses a two time step kinetic scheme. The first time averaged step is used at the initial times with smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, temperature, and pressure. The second instantaneous step is used at higher water concentrations (greater than l x 10(exp -20)) moles per cc) in the mixture which gives the chemical kinetic time as a function of the instantaneous fuel and water mole concentrations, pressure and temperature (T(sub 4)). The simple correlations are then compared to the turbulent mixing times to determine the limiting properties of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates are used to calculate the necessary chemical kinetic times. This time is regressed over the complete initial conditions using the Excel regression routine. Chemical kinetic time equations for H2 and NOx are obtained for H2/Air fuel and for H2/O2. A similar correlation is also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium temperature (T(sub 4)) as a function of overall fuel/air ratio, pressure and initial temperature (T(sub 3)). High values of the regression coefficient R squared are obtained.

LSENS, A General Chemical Kinetics and Sensitivity Analysis Code for Homogeneous Gas-Phase Reactions. Part 2; Code Description and Usage

NASA Technical Reports Server (NTRS)

Radhakrishnan, Krishnan; Bittker, David A.

1994-01-01

LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part II of a series of three reference publications that describe LSENS, provide a detailed guide to its usage, and present many example problems. Part II describes the code, how to modify it, and its usage, including preparation of the problem data file required to execute LSENS. Code usage is illustrated by several example problems, which further explain preparation of the problem data file and show how to obtain desired accuracy in the computed results. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions. Part I (NASA RP-1328) derives the governing equations and describes the numerical solution procedures for the types of problems that can be solved by LSENS. Part III (NASA RP-1330) explains the kinetics and kinetics-plus-sensitivity-analysis problems supplied with LSENS and presents sample results.

The effects of finite rate chemical processes on high enthalpy nozzle performance - A comparison between SPARK and SEAGULL

NASA Technical Reports Server (NTRS)

Carpenter, M. H.

1988-01-01

The generalized chemistry version of the computer code SPARK is extended to include two higher-order numerical schemes, yielding fourth-order spatial accuracy for the inviscid terms. The new and old formulations are used to study the influences of finite rate chemical processes on nozzle performance. A determination is made of the computationally optimum reaction scheme for use in high-enthalpy nozzles. Finite rate calculations are compared with the frozen and equilibrium limits to assess the validity of each formulation. In addition, the finite rate SPARK results are compared with the constant ratio of specific heats (gamma) SEAGULL code, to determine its accuracy in variable gamma flow situations. Finally, the higher-order SPARK code is used to calculate nozzle flows having species stratification. Flame quenching occurs at low nozzle pressures, while for high pressures, significant burning continues in the nozzle.

Adding kinetics and hydrodynamics to the CHEETAH thermochemical code

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fried, L.E., Howard, W.M., Souers, P.C.

1997-01-15

In FY96 we released CHEETAH 1.40, which made extensive improvements on the stability and user friendliness of the code. CHEETAH now has over 175 users in government, academia, and industry. Efforts have also been focused on adding new advanced features to CHEETAH 2.0, which is scheduled for release in FY97. We have added a new chemical kinetics capability to CHEETAH. In the past, CHEETAH assumed complete thermodynamic equilibrium and independence of time. The addition of a chemical kinetic framework will allow for modeling of time-dependent phenomena, such as partial combustion and detonation in composite explosives with large reaction zones. Wemore » have implemented a Wood-Kirkwood detonation framework in CHEETAH, which allows for the treatment of nonideal detonations and explosive failure. A second major effort in the project this year has been linking CHEETAH to hydrodynamic codes to yield an improved HE product equation of state. We have linked CHEETAH to 1- and 2-D hydrodynamic codes, and have compared the code to experimental data. 15 refs., 13 figs., 1 tab.« less

Thermodynamic Analysis of the Combustion of Metallic Materials

NASA Technical Reports Server (NTRS)

Wilson, D. Bruce; Stoltzfus, Joel M.

2000-01-01

Two types of computer codes are available to assist in the thermodynamic analysis of metallic materials combustion. One type of code calculates phase equilibrium data and is represented by CALPHAD. The other type of code calculates chemical reaction by the Gordon-McBride code. The first has seen significant application for alloy-phase diagrams, but only recently has it been considered for oxidation systems. The Gordon-McBride code has been applied to the combustion of metallic materials. Both codes are limited by their treatment of non-ideal solutions and the fact they are limited to treating volatile and gaseous species as ideal. This paper examines the significance of these limitations for combustion of metallic materials. In addition, the applicability of linear-free energy relationships for solid-phase oxidation and their possible extension to liquid-phase systems is examined.

Critical evaluation of Jet-A spray combustion using propane chemical kinetics in gas turbine combustion simulated by KIVA-2

NASA Technical Reports Server (NTRS)

Nguyen, H. L.; Ying, S.-J.

1990-01-01

Jet-A spray combustion has been evaluated in gas turbine combustion with the use of propane chemical kinetics as the first approximation for the chemical reactions. Here, the numerical solutions are obtained by using the KIVA-2 computer code. The KIVA-2 code is the most developed of the available multidimensional combustion computer programs for application of the in-cylinder combustion dynamics of internal combustion engines. The released version of KIVA-2 assumes that 12 chemical species are present; the code uses an Arrhenius kinetic-controlled combustion model governed by a four-step global chemical reaction and six equilibrium reactions. Researchers efforts involve the addition of Jet-A thermophysical properties and the implementation of detailed reaction mechanisms for propane oxidation. Three different detailed reaction mechanism models are considered. The first model consists of 131 reactions and 45 species. This is considered as the full mechanism which is developed through the study of chemical kinetics of propane combustion in an enclosed chamber. The full mechanism is evaluated by comparing calculated ignition delay times with available shock tube data. However, these detailed reactions occupy too much computer memory and CPU time for the computation. Therefore, it only serves as a benchmark case by which to evaluate other simplified models. Two possible simplified models were tested in the existing computer code KIVA-2 for the same conditions as used with the full mechanism. One model is obtained through a sensitivity analysis using LSENS, the general kinetics and sensitivity analysis program code of D. A. Bittker and K. Radhakrishnan. This model consists of 45 chemical reactions and 27 species. The other model is based on the work published by C. K. Westbrook and F. L. Dryer.

Retrieval of exoplanet emission spectra with HyDRA

NASA Astrophysics Data System (ADS)

Gandhi, Siddharth; Madhusudhan, Nikku

2018-02-01

Thermal emission spectra of exoplanets provide constraints on the chemical compositions, pressure-temperature (P-T) profiles, and energy transport in exoplanetary atmospheres. Accurate inferences of these properties rely on the robustness of the atmospheric retrieval methods employed. While extant retrieval codes have provided significant constraints on molecular abundances and temperature profiles in several exoplanetary atmospheres, the constraints on their deviations from thermal and chemical equilibria have yet to be fully explored. Our present work is a step in this direction. We report HyDRA, a disequilibrium retrieval framework for thermal emission spectra of exoplanetary atmospheres. The retrieval code uses the standard architecture of a parametric atmospheric model coupled with Bayesian statistical inference using the Nested Sampling algorithm. For a given dataset, the retrieved compositions and P-T profiles are used in tandem with the GENESIS self-consistent atmospheric model to constrain layer-by-layer deviations from chemical and radiative-convective equilibrium in the observable atmosphere. We demonstrate HyDRA on the Hot Jupiter WASP-43b with a high-precision emission spectrum. We retrieve an H2O mixing ratio of log(H2O) = -3.54^{+0.82}_{-0.52}, consistent with previous studies. We detect H2O and a combined CO/CO2 at 8-sigma significance. We find the dayside P-T profile to be consistent with radiative-convective equilibrium within the 1-sigma limits and with low day-night redistribution, consistent with previous studies. The derived compositions are also consistent with thermochemical equilibrium for the corresponding distribution of P-T profiles. In the era of high precision and high resolution emission spectroscopy, HyDRA provides a path to retrieve disequilibrium phenomena in exoplanetary atmospheres.

Geochemical evolution of groundwater in the Culebra dolomite near the Waste Isolation Pilot Plant, southeastern New Mexico, USA

USGS Publications Warehouse

Siegel, M.D.; Anderholm, S.

1994-01-01

The Culebra Dolomite Member of the Rustler Formation, a thin (10 m) fractured dolomite aquifer, lies approximately 450 m above the repository horizon of the Waste Isolation Pilot Plant (WIPP) in southeastern New Mexico, USA. Salinities of water in the Culebra range roughly from 10,000 to 200,000 mg/L within the WIPP site. A proposed model for the post-Pleistocene hydrochemical evolution of the Culebra tentatively identifies the major sources and sinks for many of the groundwater solutes. Reaction-path simulations with the PHRQPITZ code suggest that the Culebra dolomite is a partial chemical equilibrium system whose composition is controlled by an irreversible process (dissolution of evaporites) and equilibrium with gypsum and calcite. Net geochemical reactions along postulated modern flow paths, calculated with the NETPATH code, include dissolution of halite, carbonate and evaporite salts, and ion exchange. R-mode principal component analysis revealed correlations among the concentrations of Si, Mg, pH, Li, and B that are consistent with several clay-water reactions. The results of the geochemical calculations and mineralogical data are consistent with the following hydrochemical model: 1. (1) solutes are added to the Culebra by dissolution of evaporite minerals 2. (2) the solubilities of gypsum and calcite increase as the salinity increases; these minerals dissolve as chemical equilibrium is maintained between them and the groundwater 3. (3) equilibrium is not maintained between the waters and dolomite; sufficient Mg is added to the waters by dissolution of accessory carnallite or polyhalite such that the degree of dolomite supersaturation increases with ionic strength 4. (4) clays within the fractures and rock matrix exert some control on the distribution of Li, B, Mg, and Si via sorption, ion exchange, and dissolution. ?? 1994.

A method for the direct numerical simulation of hypersonic boundary-layer instability with finite-rate chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marxen, Olaf, E-mail: olaf.marxen@vki.ac.be; Aeronautics and Aerospace Department, von Karman Institute for Fluid Dynamics, Chaussée de Waterloo, 72, 1640 Rhode-St-Genèse; Magin, Thierry E.

2013-12-15

A new numerical method is presented here that allows to consider chemically reacting gases during the direct numerical simulation of a hypersonic fluid flow. The method comprises the direct coupling of a solver for the fluid mechanical model and a library providing the physio-chemical model. The numerical method for the fluid mechanical model integrates the compressible Navier–Stokes equations using an explicit time advancement scheme and high-order finite differences. This Navier–Stokes code can be applied to the investigation of laminar-turbulent transition and boundary-layer instability. The numerical method for the physio-chemical model provides thermodynamic and transport properties for different gases as wellmore » as chemical production rates, while here we exclusively consider a five species air mixture. The new method is verified for a number of test cases at Mach 10, including the one-dimensional high-temperature flow downstream of a normal shock, a hypersonic chemical reacting boundary layer in local thermodynamic equilibrium and a hypersonic reacting boundary layer with finite-rate chemistry. We are able to confirm that the diffusion flux plays an important role for a high-temperature boundary layer in local thermodynamic equilibrium. Moreover, we demonstrate that the flow for a case previously considered as a benchmark for the investigation of non-equilibrium chemistry can be regarded as frozen. Finally, the new method is applied to investigate the effect of finite-rate chemistry on boundary layer instability by considering the downstream evolution of a small-amplitude wave and comparing results with those obtained for a frozen gas as well as a gas in local thermodynamic equilibrium.« less

DESPOTIC - a new software library to Derive the Energetics and SPectra of Optically Thick Interstellar Clouds

NASA Astrophysics Data System (ADS)

Krumholz, Mark R.

2014-01-01

I describe DESPOTIC, a code to Derive the Energetics and SPectra of Optically Thick Interstellar Clouds. DESPOTIC represents such clouds using a one-zone model, and can calculate line luminosities, line cooling rates, and in restricted cases line profiles using an escape probability formalism. It also includes approximate treatments of the dominant heating, cooling and chemical processes for the cold interstellar medium, including cosmic ray and X-ray heating, grain photoelectric heating, heating of the dust by infrared and ultraviolet radiation, thermal cooling of the dust, collisional energy exchange between dust and gas, and a simple network for carbon chemistry. Based on these heating, cooling and chemical rates, DESPOTIC can calculate clouds' equilibrium gas and dust temperatures, equilibrium carbon chemical state and time-dependent thermal and chemical evolution. The software is intended to allow rapid and interactive calculation of clouds' characteristic temperatures, identification of their dominant heating and cooling mechanisms and prediction of their observable spectra across a wide range of interstellar environments. DESPOTIC is implemented as a PYTHON package, and is released under the GNU General Public License.

Equation of state of detonation products based on statistical mechanical theory

NASA Astrophysics Data System (ADS)

Zhao, Yanhong; Liu, Haifeng; Zhang, Gongmu; Song, Haifeng

2015-06-01

The equation of state (EOS) of gaseous detonation products is calculated using Ross's modification of hard-sphere variation theory and the improved one-fluid van der Waals mixture model. The condensed phase of carbon is a mixture of graphite, diamond, graphite-like liquid and diamond-like liquid. For a mixed system of detonation products, the free energy minimization principle is used to calculate the equilibrium compositions of detonation products by solving chemical equilibrium equations. Meanwhile, a chemical equilibrium code is developed base on the theory proposed in this article, and then it is used in the three typical calculations as follow: (i) Calculation for detonation parameters of explosive, the calculated values of detonation velocity, the detonation pressure and the detonation temperature are in good agreement with experimental ones. (ii) Calculation for isentropic unloading line of RDX explosive, whose starting points is the CJ point. Comparison with the results of JWL EOS it is found that the calculated value of gamma is monotonically decreasing using the presented theory in this paper, while double peaks phenomenon appears using JWL EOS.

Equation of state of detonation products based on statistical mechanical theory

NASA Astrophysics Data System (ADS)

Zhao, Yanhong; Liu, Haifeng; Zhang, Gongmu; Song, Haifeng; Iapcm Team

2013-06-01

The equation of state (EOS) of gaseous detonation products is calculated using Ross's modification of hard-sphere variation theory and the improved one-fluid van der Waals mixture model. The condensed phase of carbon is a mixture of graphite, diamond, graphite-like liquid and diamond-like liquid. For a mixed system of detonation products, the free energy minimization principle is used to calculate the equilibrium compositions of detonation products by solving chemical equilibrium equations. Meanwhile, a chemical equilibrium code is developed base on the theory proposed in this article, and then it is used in the three typical calculations as follow: (i) Calculation for detonation parameters of explosive, the calculated values of detonation velocity, the detonation pressure and the detonation temperature are in good agreement with experimental ones. (ii) Calculation for isentropic unloading line of RDX explosive, whose starting points is the CJ point. Comparison with the results of JWL EOS it is found that the calculated value of gamma is monotonically decreasing using the presented theory in this paper, while double peaks phenomenon appears using JWL EOS.

Tearing Mode Stability of Evolving Toroidal Equilibria

NASA Astrophysics Data System (ADS)

Pletzer, A.; McCune, D.; Manickam, J.; Jardin, S. C.

2000-10-01

There are a number of toroidal equilibrium (such as JSOLVER, ESC, EFIT, and VMEC) and transport codes (such as TRANSP, BALDUR, and TSC) in our community that utilize differing equilibrium representations. There are also many heating and current drive (LSC and TORRAY), and stability (PEST1-3, GATO, NOVA, MARS, DCON, M3D) codes that require this equilibrium information. In an effort to provide seamless compatibility between the codes that produce and need these equilibria, we have developed two Fortran 90 modules, MEQ and XPLASMA, that serve as common interfaces between these two classes of codes. XPLASMA provides a common equilibrium representation for the heating and current drive applications while MEQ provides common equilibrium and associated metric information needed by MHD stability codes. We illustrate the utility of this approach by presenting results of PEST-3 tearing stability calculations of an NSTX discharge performed on profiles provided by the TRANSP code. Using the MEQ module, the TRANSP equilibrium data are stored in a Fortran 90 derived type and passed to PEST3 as a subroutine argument. All calculations are performed on the fly, as the profiles evolve.

Nonequilibrium air radiation (Nequair) program: User's manual

NASA Technical Reports Server (NTRS)

Park, C.

1985-01-01

A supplement to the data relating to the calculation of nonequilibrium radiation in flight regimes of aeroassisted orbital transfer vehicles contains the listings of the computer code NEQAIR (Nonequilibrium Air Radiation), its primary input data, and explanation of the user-supplied input variables. The user-supplied input variables are the thermodynamic variables of air at a given point, i.e., number densities of various chemical species, translational temperatures of heavy particles and electrons, and vibrational temperature. These thermodynamic variables do not necessarily have to be in thermodynamic equilibrium. The code calculates emission and absorption characteristics of air under these given conditions.

A chemical model for the interstellar medium in galaxies

NASA Astrophysics Data System (ADS)

Bovino, S.; Grassi, T.; Capelo, Pedro R.; Schleicher, D. R. G.; Banerjee, R.

2016-05-01

Aims: We present and test chemical models for three-dimensional hydrodynamical simulations of galaxies. We explore the effect of changing key parameters such as metallicity, radiation, and non-equilibrium versus equilibrium metal cooling approximations on the transition between the gas phases in the interstellar medium. Methods: The microphysics was modelled by employing the public chemistry package KROME, and the chemical networks were tested to work in a wide range of densities and temperatures. We describe a simple H/He network following the formation of H2 and a more sophisticated network that includes metals. Photochemistry, thermal processes, and different prescriptions for the H2 catalysis on dust are presented and tested within a one-zone framework. The resulting network is made publicly available on the KROME webpage. Results: We find that employing an accurate treatment of the dust-related processes induces a faster HI-H2 transition. In addition, we show when the equilibrium assumption for metal cooling holds and how a non-equilibrium approach affects the thermal evolution of the gas and the HII-HI transition. Conclusions: These models can be employed in any hydrodynamical code via an interface to KROME and can be applied to different problems including isolated galaxies, cosmological simulations of galaxy formation and evolution, supernova explosions in molecular clouds, and the modelling of star-forming regions. The metal network can be used for a comparison with observational data of CII 158 μm emission both for high-redshift and for local galaxies.

A sorption model for alkalis in cement-based materials - Correlations with solubility and electrokinetic properties

NASA Astrophysics Data System (ADS)

Henocq, Pierre

2017-06-01

In cement-based materials, radionuclide uptake is mainly controlled by calcium silicate hydrates (C-S-H). This work presents an approach for defining a unique set of parameters of a surface complexation model describing the sorption behavior of alkali ions on the C-S-H surface. Alkali sorption processes are modeled using the CD-MUSIC function integrated in the Phreeqc V.3.0.6 geochemical code. Parameterization of the model was performed based on (1) retention, (2) zeta potential, and (3) solubility experimental data from the literature. This paper shows an application of this model to sodium ions. It was shown that retention, i.e. surface interactions, and solubility are closely related, and a consistent sorption model for radionuclides in cement-based materials requires a coupled surface interaction/chemical equilibrium model. In case of C-S-H with low calcium-to-silicon ratios, sorption of sodium ions on the C-S-H surface strongly influences the chemical equilibrium of the C-S-H + NaCl system by significantly increasing the aqueous calcium concentration. The close relationship between sorption and chemical equilibrium was successfully illustrated by modeling the effect of the solid-to-liquid ratio on the calcium content in solution in the case of C-S-H + NaCl systems.

Computation of Thermodynamic Equilibria Pertinent to Nuclear Materials in Multi-Physics Codes

NASA Astrophysics Data System (ADS)

Piro, Markus Hans Alexander

Nuclear energy plays a vital role in supporting electrical needs and fulfilling commitments to reduce greenhouse gas emissions. Research is a continuing necessity to improve the predictive capabilities of fuel behaviour in order to reduce costs and to meet increasingly stringent safety requirements by the regulator. Moreover, a renewed interest in nuclear energy has given rise to a "nuclear renaissance" and the necessity to design the next generation of reactors. In support of this goal, significant research efforts have been dedicated to the advancement of numerical modelling and computational tools in simulating various physical and chemical phenomena associated with nuclear fuel behaviour. This undertaking in effect is collecting the experience and observations of a past generation of nuclear engineers and scientists in a meaningful way for future design purposes. There is an increasing desire to integrate thermodynamic computations directly into multi-physics nuclear fuel performance and safety codes. A new equilibrium thermodynamic solver is being developed with this matter as a primary objective. This solver is intended to provide thermodynamic material properties and boundary conditions for continuum transport calculations. There are several concerns with the use of existing commercial thermodynamic codes: computational performance; limited capabilities in handling large multi-component systems of interest to the nuclear industry; convenient incorporation into other codes with quality assurance considerations; and, licensing entanglements associated with code distribution. The development of this software in this research is aimed at addressing all of these concerns. The approach taken in this work exploits fundamental principles of equilibrium thermodynamics to simplify the numerical optimization equations. In brief, the chemical potentials of all species and phases in the system are constrained by estimates of the chemical potentials of the system components at each iterative step, and the objective is to minimize the residuals of the mass balance equations. Several numerical advantages are achieved through this simplification. In particular, computational expense is reduced and the rate of convergence is enhanced. Furthermore, the software has demonstrated the ability to solve systems involving as many as 118 component elements. An early version of the code has already been integrated into the Advanced Multi-Physics (AMP) code under development by the Oak Ridge National Laboratory, Los Alamos National Laboratory, Idaho National Laboratory and Argonne National Laboratory. Keywords: Engineering, Nuclear -- 0552, Engineering, Material Science -- 0794, Chemistry, Mathematics -- 0405, Computer Science -- 0984

Tokamak plasma high field side response to an n = 3 magnetic perturbation: a comparison of 3D equilibrium solutions from seven different codes

NASA Astrophysics Data System (ADS)

Reiman, A.; Ferraro, N. M.; Turnbull, A.; Park, J. K.; Cerfon, A.; Evans, T. E.; Lanctot, M. J.; Lazarus, E. A.; Liu, Y.; McFadden, G.; Monticello, D.; Suzuki, Y.

2015-06-01

In comparing equilibrium solutions for a DIII-D shot that is amenable to analysis by both stellarator and tokamak three-dimensional (3D) equilibrium codes, a significant disagreement has been seen between solutions of the VMEC stellarator equilibrium code and solutions of tokamak perturbative 3D equilibrium codes. The source of that disagreement has been investigated, and that investigation has led to new insights into the domain of validity of the different equilibrium calculations, and to a finding that the manner in which localized screening currents at low order rational surfaces are handled can affect global properties of the equilibrium solution. The perturbative treatment has been found to break down at surprisingly small perturbation amplitudes due to overlap of the calculated perturbed flux surfaces, and that treatment is not valid in the pedestal region of the DIII-D shot studied. The perturbative treatment is valid, however, further into the interior of the plasma, and flux surface overlap does not account for the disagreement investigated here. Calculated equilibrium solutions for simple model cases and comparison of the 3D equilibrium solutions with those of other codes indicate that the disagreement arises from a difference in handling of localized currents at low order rational surfaces, with such currents being absent in VMEC and present in the perturbative codes. The significant differences in the global equilibrium solutions associated with the presence or absence of very localized screening currents at rational surfaces suggests that it may be possible to extract information about localized currents from appropriate measurements of global equilibrium plasma properties. That would require improved diagnostic capability on the high field side of the tokamak plasma, a region difficult to access with diagnostics.

EQ3NR, a computer program for geochemical aqueous speciation-solubility calculations: Theoretical manual, user`s guide, and related documentation (Version 7.0); Part 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolery, T.J.

1992-09-14

EQ3NR is an aqueous solution speciation-solubility modeling code. It is part of the EQ3/6 software package for geochemical modeling. It computes the thermodynamic state of an aqueous solution by determining the distribution of chemical species, including simple ions, ion pairs, and complexes, using standard state thermodynamic data and various equations which describe the thermodynamic activity coefficients of these species. The input to the code describes the aqueous solution in terms of analytical data, including total (analytical) concentrations of dissolved components and such other parameters as the pH, pHCl, Eh, pe, and oxygen fugacity. The input may also include a desiredmore » electrical balancing adjustment and various constraints which impose equilibrium with special pure minerals, solid solution end-member components (of specified mole fractions), and gases (of specified fugacities). The code evaluates the degree of disequilibrium in terms of the saturation index (SI = 1og Q/K) and the thermodynamic affinity (A = {minus}2.303 RT log Q/K) for various reactions, such as mineral dissolution or oxidation-reduction in the aqueous solution itself. Individual values of Eh, pe, oxygen fugacity, and Ah (redox affinity) are computed for aqueous redox couples. Equilibrium fugacities are computed for gas species. The code is highly flexible in dealing with various parameters as either model inputs or outputs. The user can specify modification or substitution of equilibrium constants at run time by using options on the input file.« less

The Navy/NASA Engine Program (NNEP89): A user's manual

NASA Technical Reports Server (NTRS)

Plencner, Robert M.; Snyder, Christopher A.

1991-01-01

An engine simulation computer code called NNEP89 was written to perform 1-D steady state thermodynamic analysis of turbine engine cycles. By using a very flexible method of input, a set of standard components are connected at execution time to simulate almost any turbine engine configuration that the user could imagine. The code was used to simulate a wide range of engine cycles from turboshafts and turboprops to air turborockets and supersonic cruise variable cycle engines. Off design performance is calculated through the use of component performance maps. A chemical equilibrium model is incorporated to adequately predict chemical dissociation as well as model virtually any fuel. NNEP89 is written in standard FORTRAN77 with clear structured programming and extensive internal documentation. The standard FORTRAN77 programming allows it to be installed onto most mainframe computers and workstations without modification. The NNEP89 code was derived from the Navy/NASA Engine program (NNEP). NNEP89 provides many improvements and enhancements to the original NNEP code and incorporates features which make it easier to use for the novice user. This is a comprehensive user's guide for the NNEP89 code.

Coupling of PIES 3-D Equilibrium Code and NIFS Bootstrap Code with Applications to the Computation of Stellarator Equilibria

NASA Astrophysics Data System (ADS)

Monticello, D. A.; Reiman, A. H.; Watanabe, K. Y.; Nakajima, N.; Okamoto, M.

1997-11-01

The existence of bootstrap currents in both tokamaks and stellarators was confirmed, experimentally, more than ten years ago. Such currents can have significant effects on the equilibrium and stability of these MHD devices. In addition, stellarators, with the notable exception of W7-X, are predicted to have such large bootstrap currents that reliable equilibrium calculations require the self-consistent evaluation of bootstrap currents. Modeling of discharges which contain islands requires an algorithm that does not assume good surfaces. Only one of the two 3-D equilibrium codes that exist, PIES( Reiman, A. H., Greenside, H. S., Compt. Phys. Commun. 43), (1986)., can easily be modified to handle bootstrap current. Here we report on the coupling of the PIES 3-D equilibrium code and NIFS bootstrap code(Watanabe, K., et al., Nuclear Fusion 35) (1995), 335.

The NATA code; theory and analysis. Volume 2: User's manual

NASA Technical Reports Server (NTRS)

Bade, W. L.; Yos, J. M.

1975-01-01

The NATA code is a computer program for calculating quasi-one-dimensional gas flow in axisymmetric nozzles and rectangular channels, primarily to describe conditions in electric archeated wind tunnels. The program provides solutions based on frozen chemistry, chemical equilibrium, and nonequilibrium flow with finite reaction rates. The shear and heat flux on the nozzle wall are calculated and boundary layer displacement effects on the inviscid flow are taken into account. The program contains compiled-in thermochemical, chemical kinetic and transport cross section data for high-temperature air, CO2-N2-Ar mixtures, helium, and argon. It calculates stagnation conditions on axisymmetric or two-dimensional models and conditions on the flat surface of a blunt wedge. Included in the report are: definitions of the inputs and outputs; precoded data on gas models, reactions, thermodynamic and transport properties of species, and nozzle geometries; explanations of diagnostic outputs and code abort conditions; test problems; and a user's manual for an auxiliary program (NOZFIT) used to set up analytical curvefits to nozzle profiles.

Simulating Chemistry in Star Forming Environments

NASA Astrophysics Data System (ADS)

Gong, Munan

Chemistry plays an important role in the interstellar medium (ISM), regulating the heating and cooling of the gas and determining abundances of molecular species that trace gas properties in observations. One of the most abundant and important molecules in the ISM is CO. CO is a main coolant for the molecular ISM, and the CO(J = 1 - 0) line emission is a widely used observational tracer for molecular clouds. In Chapter 2, we propose a new simplified chemical network for hydrogen and carbon chemistry in the atomic and molecular ISM. We compare results from our chemical network in detail with results from a full photodissociation region (PDR) code, and also with the Nelson & Langer (NL99) network previously adopted in the simulation literature. We show that our chemical network gives similar results to the PDR code in the equilibrium abundances of all species over a wide range of densities, temperature, and metallicities, whereas the NL99 network shows significant disagreement. We also compare with observations of diffuse and translucent clouds. We find that the CO, CHx and OHx abundances are consistent with equilibrium predictions for densities n = 100 - 1000 cm-3, but the predicted equilibrium CI abundance is higher than observations, signaling the potential importance of non-equilibrium/dynamical effects. In Chapter 3, we apply our new chemistry network to a study of the XCO conversion factor, which is used to convert the CO luminosity to the total H2 mass. We use numerical simulations to investigate how XCO depends on numerical resolution, non-equilibrium chemistry, physical environment, and observational beam size. Our study employs 3D magnetohydrodynamics (MHD) simulations of galactic disks with solar neighborhood conditions, where star formation and the three-phase interstellar medium (ISM) is self-consistently generated by the interaction between gravity and stellar feedback. Synthetic CO maps are obtained by post-processing the MHD simulations with chemistry and radiation transfer. We find that CO is only an approximate tracer of H2. Nevertheless, 〈 XCO〉 = 0.7 - 1.0 x 1020 cm-2K-1km-1 s consistent with observations, insensitive to the evolutionary ISM state or the far-ultraviolet (FUV) radiation field strength. Our numerical simulations successfully reproduce the observed variations of X CO on parsec scales, as well as the dependence of X CO on extinction and the CO excitation temperature.

Benchmarking of Improved DPAC Transient Deflagration Analysis Code

DOE PAGES

Laurinat, James E.; Hensel, Steve J.

2017-09-27

The deflagration pressure analysis code (DPAC) has been upgraded for use in modeling hydrogen deflagration transients. The upgraded code is benchmarked using data from vented hydrogen deflagration tests conducted at the HYDRO-SC Test Facility at the University of Pisa. DPAC originally was written to calculate peak pressures for deflagrations in radioactive waste storage tanks and process facilities at the Savannah River Site. Upgrades include the addition of a laminar flame speed correlation for hydrogen deflagrations and a mechanistic model for turbulent flame propagation, incorporation of inertial effects during venting, and inclusion of the effect of water vapor condensation on vesselmore » walls. In addition, DPAC has been coupled with chemical equilibrium with applications (CEA), a NASA combustion chemistry code. The deflagration tests are modeled as end-to-end deflagrations. As a result, the improved DPAC code successfully predicts both the peak pressures during the deflagration tests and the times at which the pressure peaks.« less

Benchmarking of Improved DPAC Transient Deflagration Analysis Code

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laurinat, James E.; Hensel, Steve J.

The deflagration pressure analysis code (DPAC) has been upgraded for use in modeling hydrogen deflagration transients. The upgraded code is benchmarked using data from vented hydrogen deflagration tests conducted at the HYDRO-SC Test Facility at the University of Pisa. DPAC originally was written to calculate peak pressures for deflagrations in radioactive waste storage tanks and process facilities at the Savannah River Site. Upgrades include the addition of a laminar flame speed correlation for hydrogen deflagrations and a mechanistic model for turbulent flame propagation, incorporation of inertial effects during venting, and inclusion of the effect of water vapor condensation on vesselmore » walls. In addition, DPAC has been coupled with chemical equilibrium with applications (CEA), a NASA combustion chemistry code. The deflagration tests are modeled as end-to-end deflagrations. As a result, the improved DPAC code successfully predicts both the peak pressures during the deflagration tests and the times at which the pressure peaks.« less

Observations and Thermochemical Calculations for Hot-Jupiter Atmospheres

NASA Astrophysics Data System (ADS)

Blecic, Jasmina; Harrington, Joseph; Bowman, M. Oliver; Cubillos, Patricio; Stemm, Madison

2015-01-01

I present Spitzer eclipse observations for WASP-14b and WASP-43b, an open source tool for thermochemical equilibrium calculations, and components of an open source tool for atmospheric parameter retrieval from spectroscopic data. WASP-14b is a planet that receives high irradiation from its host star, yet, although theory does not predict it, the planet hosts a thermal inversion. The WASP-43b eclipses have signal-to-noise ratios of ~25, one of the largest among exoplanets. To assess these planets' atmospheric composition and thermal structure, we developed an open-source Bayesian Atmospheric Radiative Transfer (BART) code. My dissertation tasks included developing a Thermochemical Equilibrium Abundances (TEA) code, implementing the eclipse geometry calculation in BART's radiative transfer module, and generating parameterized pressure and temperature profiles so the radiative-transfer module can be driven by the statistical module.To initialize the radiative-transfer calculation in BART, TEA calculates the equilibrium abundances of gaseous molecular species at a given temperature and pressure. It uses the Gibbs-free-energy minimization method with an iterative Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature-pressure pairs. The code is tested against the original method developed by White at al. (1958), the analytic method developed by Burrows and Sharp (1999), and the Newton-Raphson method implemented in the open-source Chemical Equilibrium with Applications (CEA) code. TEA, written in Python, is modular, documented, and available to the community via the open-source development site GitHub.com.Support for this work was provided by NASA Headquarters under the NASA Earth and Space Science Fellowship Program, grant NNX12AL83H, by NASA through an award issued by JPL/Caltech, and through the Science Mission Directorate's Planetary Atmospheres Program, grant NNX12AI69G.

Light element opacities of astrophysical interest from ATOMIC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Colgan, J.; Kilcrease, D. P.; Magee, N. H. Jr.

We present new calculations of local-thermodynamic-equilibrium (LTE) light element opacities from the Los Alamos ATOMIC code for systems of astrophysical interest. ATOMIC is a multi-purpose code that can generate LTE or non-LTE quantities of interest at various levels of approximation. Our calculations, which include fine-structure detail, represent a systematic improvement over previous Los Alamos opacity calculations using the LEDCOP legacy code. The ATOMIC code uses ab-initio atomic structure data computed from the CATS code, which is based on Cowan's atomic structure codes, and photoionization cross section data computed from the Los Alamos ionization code GIPPER. ATOMIC also incorporates a newmore » equation-of-state (EOS) model based on the chemical picture. ATOMIC incorporates some physics packages from LEDCOP and also includes additional physical processes, such as improved free-free cross sections and additional scattering mechanisms. Our new calculations are made for elements of astrophysical interest and for a wide range of temperatures and densities.« less

HELIOS: An Open-source, GPU-accelerated Radiative Transfer Code for Self-consistent Exoplanetary Atmospheres

NASA Astrophysics Data System (ADS)

Malik, Matej; Grosheintz, Luc; Mendonça, João M.; Grimm, Simon L.; Lavie, Baptiste; Kitzmann, Daniel; Tsai, Shang-Min; Burrows, Adam; Kreidberg, Laura; Bedell, Megan; Bean, Jacob L.; Stevenson, Kevin B.; Heng, Kevin

2017-02-01

We present the open-source radiative transfer code named HELIOS, which is constructed for studying exoplanetary atmospheres. In its initial version, the model atmospheres of HELIOS are one-dimensional and plane-parallel, and the equation of radiative transfer is solved in the two-stream approximation with nonisotropic scattering. A small set of the main infrared absorbers is employed, computed with the opacity calculator HELIOS-K and combined using a correlated-k approximation. The molecular abundances originate from validated analytical formulae for equilibrium chemistry. We compare HELIOS with the work of Miller-Ricci & Fortney using a model of GJ 1214b, and perform several tests, where we find: model atmospheres with single-temperature layers struggle to converge to radiative equilibrium; k-distribution tables constructed with ≳ 0.01 cm-1 resolution in the opacity function (≲ {10}3 points per wavenumber bin) may result in errors ≳ 1%-10% in the synthetic spectra; and a diffusivity factor of 2 approximates well the exact radiative transfer solution in the limit of pure absorption. We construct “null-hypothesis” models (chemical equilibrium, radiative equilibrium, and solar elemental abundances) for six hot Jupiters. We find that the dayside emission spectra of HD 189733b and WASP-43b are consistent with the null hypothesis, while the latter consistently underpredicts the observed fluxes of WASP-8b, WASP-12b, WASP-14b, and WASP-33b. We demonstrate that our results are somewhat insensitive to the choice of stellar models (blackbody, Kurucz, or PHOENIX) and metallicity, but are strongly affected by higher carbon-to-oxygen ratios. The code is publicly available as part of the Exoclimes Simulation Platform (exoclime.net).

CHEETAH: A fast thermochemical code for detonation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fried, L.E.

1993-11-01

For more than 20 years, TIGER has been the benchmark thermochemical code in the energetic materials community. TIGER has been widely used because it gives good detonation parameters in a very short period of time. Despite its success, TIGER is beginning to show its age. The program`s chemical equilibrium solver frequently crashes, especially when dealing with many chemical species. It often fails to find the C-J point. Finally, there are many inconveniences for the user stemming from the programs roots in pre-modern FORTRAN. These inconveniences often lead to mistakes in preparing input files and thus erroneous results. We are producingmore » a modern version of TIGER, which combines the best features of the old program with new capabilities, better computational algorithms, and improved packaging. The new code, which will evolve out of TIGER in the next few years, will be called ``CHEETAH.`` Many of the capabilities that will be put into CHEETAH are inspired by the thermochemical code CHEQ. The new capabilities of CHEETAH are: calculate trace levels of chemical compounds for environmental analysis; kinetics capability: CHEETAH will predict chemical compositions as a function of time given individual chemical reaction rates. Initial application: carbon condensation; CHEETAH will incorporate partial reactions; CHEETAH will be based on computer-optimized JCZ3 and BKW parameters. These parameters will be fit to over 20 years of data collected at LLNL. We will run CHEETAH thousands of times to determine the best possible parameter sets; CHEETAH will fit C-J data to JWL`s,and also predict full-wall and half-wall cylinder velocities.« less

Modern CFD applications for the design of a reacting shear layer facility

NASA Technical Reports Server (NTRS)

Yu, S. T.; Chang, C. T.; Marek, C. J.

1991-01-01

The RPLUS2D code, capable of calculating high speed reacting flows, was adopted to design a compressible shear layer facility. In order to create reacting shear layers at high convective Mach numbers, hot air streams at supersonic speeds, rendered by converging-diverging nozzles, must be provided. A finite rate chemistry model is used to simulate the nozzle flows. Results are compared with one-dimensional solutions at chemical equilibrium. Additionally, a two equation turbulence model with compressibility effects was successfully incorporated with the RPLUS code. The model was applied to simulate a supersonic shear layer. Preliminary results show favorable comparisons with the experimental data.

FY06 L2C2 HE program report Zaug et al.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zaug, J M; Crowhurst, J C; Howard, W M

2008-08-01

The purpose of this project is to advance the improvement of LLNL thermochemical computational models that form the underlying basis or input for laboratory hydrodynamic simulations. Our general work approach utilizes, by design, tight experimental-theoretical research interactions that allow us to not empirically, but rather more scientifically improve LLNL computational results. The ultimate goal here is to confidently predict through computer models, the performance and safety parameters of currently maintained, modified, and newly designed stockpile systems. To attain our goal we make relevant experimental measurements on candidate detonation products constrained under static high-pressure and temperature conditions. The reduced information frommore » these measurements is then used to construct analytical forms that describe the potential surface (repulsive energy as a function of interatomic separation distance) of single and mixed fluid or detonation product species. These potential surface shapes are also constructed using input from well-trusted shock wave physics and assorted thermodynamic data available in the open literature. Our potential surfaces permit one to determine the equations of state (P,V,T), the equilibrium chemistry, phase, and chemical interactions of detonation products under a very wide range of extreme pressure temperature conditions. Using our foundation of experimentally refined potential surfaces we are in a position to calculate, with confidence, the energetic output and chemical speciation occurring from a specific combustion and/or detonation reaction. The thermochemical model we developed and use for calculating the equilibrium chemistry, kinetics, and energy from ultrafast processes is named 'Cheetah'. Computational results from our Cheetah code are coupled to laboratory ALE3D hydrodynamic simulation codes where the complete response behavior of an existing or proposed system is ultimately predicted. The Cheetah thermochemical code is also used by well over 500 U.S. government DoD and DOE community users who calculate the chemical properties of detonated high explosives, propellants, and pyrotechnics. To satisfy the growing needs of LLNL and the general user community we continue to improve the robustness of our Cheetah code. The P-T range of current speed of sound experiments will soon be extended by a factor of four and our recently developed technological advancements permit us to, for the first time, study any chemical specie or fluid mixture. New experiments will focus on determining the miscibility or coexistence curves of detonation product mixtures. Our newly constructed ultrafast laser diagnostics will permit us to determine what chemical species exist under conditions approaching Chapman-Jouguet (CJ) detonation states. Furthermore we will measure the time evolution of candidate species and use our chemical kinetics data to develop new and validate existing rate laws employed in future versions of our Cheetah thermochemical code.« less

Edge equilibrium code for tokamaks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Xujing; Zakharov, Leonid E.; Drozdov, Vladimir V.

2014-01-15

The edge equilibrium code (EEC) described in this paper is developed for simulations of the near edge plasma using the finite element method. It solves the Grad-Shafranov equation in toroidal coordinate and uses adaptive grids aligned with magnetic field lines. Hermite finite elements are chosen for the numerical scheme. A fast Newton scheme which is the same as implemented in the equilibrium and stability code (ESC) is applied here to adjust the grids.

Numerical simulation of electromagnetic wave attenuation in a nonequilibrium chemically reacting hypervelocity flow

NASA Astrophysics Data System (ADS)

Nusca, Michael Joseph, Jr.

The effects of various gasdynamic phenomena on the attenuation of an electromagnetic wave propagating through the nonequilibrium chemically reacting air flow field generated by an aerodynamic body travelling at high velocity is investigated. The nonequilibrium flow field is assumed to consist of seven species including nitric oxide ions and free electrons. The ionization of oxygen and nitrogen atoms is ignored. The aerodynamic body considered is a blunt wedge. The nonequilibrium chemically reacting flow field around this body is numerically simulated using a computer code based on computational fluid dynamics. The computer code solves the Navier-Stokes equations including mass diffusion and heat transfer, using a time-marching, explicit Runge-Kutta scheme. A nonequilibrium air kinetics model consisting of seven species and twenty-eight reactions as well as an equilibrium air model consisting of the same seven species are used. The body surface boundaries are considered as adiabatic or isothermal walls, as well as fully-catalytic and non-catalytic surfaces. Both laminar and turbulent flows are considered; wall generated flow turbulence is simulated using an algebraic mixing length model. An electromagnetic wave is considered as originating from an antenna within the body and is effected by the free electrons in the chemically reacting flow. Analysis of the electromagnetics is performed separately from the fluid dynamic analysis using a series solution of Maxwell's equations valid for the propagation of a long-wavelength plane electromagnetic wave through a thin (i.e., in comparison to wavelength) inhomogeneous plasma layer. The plasma layer is the chemically reacting shock layer around the body. The Navier-Stokes equations are uncoupled from Maxwell's equations. The results of this computational study demonstrate for the first time and in a systematic fashion, the importance of several parameters including equilibrium chemistry, nonequilibrium chemical kinetics, the reaction mechanism, flow viscosity, mass diffusion, and wall boundary conditions on modeling wave attenuation resulting from the interaction of an electromagnetic wave with an aerodynamic plasma. Comparison is made with experimental data.

Edge Equilibrium Code (EEC) For Tokamaks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Xujling

2014-02-24

The edge equilibrium code (EEC) described in this paper is developed for simulations of the near edge plasma using the finite element method. It solves the Grad-Shafranov equation in toroidal coordinate and uses adaptive grids aligned with magnetic field lines. Hermite finite elements are chosen for the numerical scheme. A fast Newton scheme which is the same as implemented in the equilibrium and stability code (ESC) is applied here to adjust the grids

Material point method of modelling and simulation of reacting flow of oxygen

NASA Astrophysics Data System (ADS)

Mason, Matthew; Chen, Kuan; Hu, Patrick G.

2014-07-01

Aerospace vehicles are continually being designed to sustain flight at higher speeds and higher altitudes than previously attainable. At hypersonic speeds, gases within a flow begin to chemically react and the fluid's physical properties are modified. It is desirable to model these effects within the Material Point Method (MPM). The MPM is a combined Eulerian-Lagrangian particle-based solver that calculates the physical properties of individual particles and uses a background grid for information storage and exchange. This study introduces chemically reacting flow modelling within the MPM numerical algorithm and illustrates a simple application using the AeroElastic Material Point Method (AEMPM) code. The governing equations of reacting flows are introduced and their direct application within an MPM code is discussed. A flow of 100% oxygen is illustrated and the results are compared with independently developed computational non-equilibrium algorithms. Observed trends agree well with results from an independently developed source.

Investigating High School Students' Understanding of Chemical Equilibrium Concepts

ERIC Educational Resources Information Center

Karpudewan, Mageswary; Treagust, David F.; Mocerino, Mauro; Won, Mihye; Chandrasegaran, A. L.

2015-01-01

This study investigated the year 12 students' (N = 56) understanding of chemical equilibrium concepts after instruction using two conceptual tests, the "Chemical Equilibrium Conceptual Test 1" ("CECT-1") consisting of nine two-tier multiple-choice items and the "Chemical Equilibrium Conceptual Test 2"…

Inclusion of pressure and flow in a new 3D MHD equilibrium code

NASA Astrophysics Data System (ADS)

Raburn, Daniel; Fukuyama, Atsushi

2012-10-01

Flow and nonsymmetric effects can play a large role in plasma equilibria and energy confinement. A concept for such a 3D equilibrium code was developed and presented in 2011. The code is called the Kyoto ITerative Equilibrium Solver (KITES) [1], and the concept is based largely on the PIES code [2]. More recently, the work-in-progress KITES code was used to calculate force-free equilibria. Here, progress and results on the inclusion of pressure and flow in the code are presented. [4pt] [1] Daniel Raburn and Atsushi Fukuyama, Plasma and Fusion Research: Regular Articles, 7:240381 (2012).[0pt] [2] H. S. Greenside, A. H. Reiman, and A. Salas, J. Comput. Phys, 81(1):102-136 (1989).

Exploring Chemical Equilibrium with Poker Chips: A General Chemistry Laboratory Exercise

ERIC Educational Resources Information Center

Bindel, Thomas H.

2012-01-01

A hands-on laboratory exercise at the general chemistry level introduces students to chemical equilibrium through a simulation that uses poker chips and rate equations. More specifically, the exercise allows students to explore reaction tables, dynamic chemical equilibrium, equilibrium constant expressions, and the equilibrium constant based on…

Students' and Teachers' Misapplication of Le Chatelier's Principle: Implications for the Teaching of Chemical Equilibrium.

ERIC Educational Resources Information Center

Quilez-Pardo, Juan; Solaz-Portoles, Joan Josep

1995-01-01

Study of strategies and procedures of 170 students and 40 teachers when solving chemical equilibrium problems found misconceptions emerging through: misapplication of Le Chatelier's Principle, use of rote-learning recall, incorrect control of variables, limited use of chemical equilibrium law, lack of mastery of chemical equilibrium principles,…

A Review of Equation of State Models, Chemical Equilibrium Calculations and CERV Code Requirements for SHS Detonation Modelling

DTIC Science & Technology

2009-10-01

parameters for a large number of species. These authors provide many sample calculations with the JCZS database incorporated in CHEETAH 2.0, including...FORM (highest classification of Title, Abstract, Keywords) DOCUMENT CONTROL DATA (Security classification of title, body of abstract and...CLASSIFICATION OF FORM 13. ABSTRACT (a brief and factual summary of the document. It may also appear elsewhere in the body of the document itself

From Chemical Forces to Chemical Rates: A Historical/Philosophical Foundation for the Teaching of Chemical Equilibrium

ERIC Educational Resources Information Center

Quilez, Juan

2009-01-01

With this paper, our main aim is to contribute to the realisation of the chemical reactivity concept, tracing the historical evolution of the concept of chemical affinity that eventually supported the concept of chemical equilibrium. We will concentrate on searching for the theoretical grounds of three key chemical equilibrium ideas: "incomplete…

A general intermolecular force field based on tight-binding quantum chemical calculations

NASA Astrophysics Data System (ADS)

Grimme, Stefan; Bannwarth, Christoph; Caldeweyher, Eike; Pisarek, Jana; Hansen, Andreas

2017-10-01

A black-box type procedure is presented for the generation of a molecule-specific, intermolecular potential energy function. The method uses quantum chemical (QC) information from our recently published extended tight-binding semi-empirical scheme (GFN-xTB) and can treat non-covalently bound complexes and aggregates with almost arbitrary chemical structure. The necessary QC information consists of the equilibrium structure, Mulliken atomic charges, charge centers of localized molecular orbitals, and also of frontier orbitals and orbital energies. The molecular pair potential includes model density dependent Pauli repulsion, penetration, as well as point charge electrostatics, the newly developed D4 dispersion energy model, Drude oscillators for polarization, and a charge-transfer term. Only one element-specific and about 20 global empirical parameters are needed to cover systems with nuclear charges up to radon (Z = 86). The method is tested for standard small molecule interaction energy benchmark sets where it provides accurate intermolecular energies and equilibrium distances. Examples for structures with a few hundred atoms including charged systems demonstrate the versatility of the approach. The method is implemented in a stand-alone computer code which enables rigid-body, global minimum energy searches for molecular aggregation or alignment.

A Thermal Management Systems Model for the NASA GTX RBCC Concept

NASA Technical Reports Server (NTRS)

Traci, Richard M.; Farr, John L., Jr.; Laganelli, Tony; Walker, James (Technical Monitor)

2002-01-01

The Vehicle Integrated Thermal Management Analysis Code (VITMAC) was further developed to aid the analysis, design, and optimization of propellant and thermal management concepts for advanced propulsion systems. The computational tool is based on engineering level principles and models. A graphical user interface (GUI) provides a simple and straightforward method to assess and evaluate multiple concepts before undertaking more rigorous analysis of candidate systems. The tool incorporates the Chemical Equilibrium and Applications (CEA) program and the RJPA code to permit heat transfer analysis of both rocket and air breathing propulsion systems. Key parts of the code have been validated with experimental data. The tool was specifically tailored to analyze rocket-based combined-cycle (RBCC) propulsion systems being considered for space transportation applications. This report describes the computational tool and its development and verification for NASA GTX RBCC propulsion system applications.

The Conceptual Change Approach to Teaching Chemical Equilibrium

ERIC Educational Resources Information Center

Canpolat, Nurtac; Pinarbasi, Tacettin; Bayrakceken, Samih; Geban, Omer

2006-01-01

This study investigates the effect of a conceptual change approach over traditional instruction on students' understanding of chemical equilibrium concepts (e.g. dynamic nature of equilibrium, definition of equilibrium constant, heterogeneous equilibrium, qualitative interpreting of equilibrium constant, changing the reaction conditions). This…

Chemical Principles Revisited: Chemical Equilibrium.

ERIC Educational Resources Information Center

Mickey, Charles D.

1980-01-01

Describes: (1) Law of Mass Action; (2) equilibrium constant and ideal behavior; (3) general form of the equilibrium constant; (4) forward and reverse reactions; (5) factors influencing equilibrium; (6) Le Chatelier's principle; (7) effects of temperature, changing concentration, and pressure on equilibrium; and (8) catalysts and equilibrium. (JN)

Updated Chemical Kinetics and Sensitivity Analysis Code

NASA Technical Reports Server (NTRS)

Radhakrishnan, Krishnan

2005-01-01

An updated version of the General Chemical Kinetics and Sensitivity Analysis (LSENS) computer code has become available. A prior version of LSENS was described in "Program Helps to Determine Chemical-Reaction Mechanisms" (LEW-15758), NASA Tech Briefs, Vol. 19, No. 5 (May 1995), page 66. To recapitulate: LSENS solves complex, homogeneous, gas-phase, chemical-kinetics problems (e.g., combustion of fuels) that are represented by sets of many coupled, nonlinear, first-order ordinary differential equations. LSENS has been designed for flexibility, convenience, and computational efficiency. The present version of LSENS incorporates mathematical models for (1) a static system; (2) steady, one-dimensional inviscid flow; (3) reaction behind an incident shock wave, including boundary layer correction; (4) a perfectly stirred reactor; and (5) a perfectly stirred reactor followed by a plug-flow reactor. In addition, LSENS can compute equilibrium properties for the following assigned states: enthalpy and pressure, temperature and pressure, internal energy and volume, and temperature and volume. For static and one-dimensional-flow problems, including those behind an incident shock wave and following a perfectly stirred reactor calculation, LSENS can compute sensitivity coefficients of dependent variables and their derivatives, with respect to the initial values of dependent variables and/or the rate-coefficient parameters of the chemical reactions.

Equilibrium Reconstruction on the Large Helical Device

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samuel A. Lazerson, D. Gates, D. Monticello, H. Neilson, N. Pomphrey, A. Reiman S. Sakakibara, and Y. Suzuki

Equilibrium reconstruction is commonly applied to axisymmetric toroidal devices. Recent advances in computational power and equilibrium codes have allowed for reconstructions of three-dimensional fields in stellarators and heliotrons. We present the first reconstructions of finite beta discharges in the Large Helical Device (LHD). The plasma boundary and magnetic axis are constrained by the pressure profile from Thomson scattering. This results in a calculation of plasma beta without a-priori assumptions of the equipartition of energy between species. Saddle loop arrays place additional constraints on the equilibrium. These reconstruction utilize STELLOPT, which calls VMEC. The VMEC equilibrium code assumes good nested fluxmore » surfaces. Reconstructed magnetic fields are fed into the PIES code which relaxes this constraint allowing for the examination of the effect of islands and stochastic regions on the magnetic measurements.« less

Minimizing the Free Energy: A Computer Method for Teaching Chemical Equilibrium Concepts.

ERIC Educational Resources Information Center

Heald, Emerson F.

1978-01-01

Presents a computer method for teaching chemical equilibrium concepts using material balance conditions and the minimization of the free energy. Method for the calculation of chemical equilibrium, the computer program used to solve equilibrium problems and applications of the method are also included. (HM)

Utilizing CFD for Prediction of HD1.3 Pressure Loads in a Cell with Venting

DTIC Science & Technology

2010-07-01

room. The gas load is a result of the heat released during the explosion and afterburning of explosives that was not consumed by the initial...Structural Systems Design Guide HNDED-CS-93-72 specifies that all HD 1.3 in a room will be summed and converted to an equivalent TNT mass (based on...the H2 and CO are shown in Table 5. The Pre- Afterburning quantities are based on the chemical equilibrium calculations performed in the AFCESI code

An Implicit Finite Difference Solution to the Viscous Radiating Shock Layer with Strong Blowing. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Garrett, L. B.

1971-01-01

An implicit finite difference scheme is developed for the fully coupled solution of the viscous radiating stagnation line equations, including strong blowing. Solutions are presented for both air injection and carbon phenolic ablation products injection into air at conditions near the peak radiative heating point in an earth entry trajectory from interplanetary return missions. A detailed radiative transport code that accounts for the important radiative exchange processes for gaseous mixtures in local thermodynamic and chemical equilibrium is utilized.

Design and Testing of a Liquid Nitrous Oxide and Ethanol Fueled Rocket Engine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Youngblood, Stewart

A small-scale, bi-propellant, liquid fueled rocket engine and supporting test infrastructure were designed and constructed at the Energetic Materials Research and Testing Center (EMRTC). This facility was used to evaluate liquid nitrous oxide and ethanol as potential rocket propellants. Thrust and pressure measurements along with high-speed digital imaging of the rocket exhaust plume were made. This experimental data was used for validation of a computational model developed of the rocket engine tested. The developed computational model was utilized to analyze rocket engine performance across a range of operating pressures, fuel-oxidizer mixture ratios, and outlet nozzle configurations. A comparative study ofmore » the modeling of a liquid rocket engine was performed using NASA CEA and Cantera, an opensource equilibrium code capable of being interfaced with MATLAB. One goal of this modeling was to demonstrate the ability of Cantera to accurately model the basic chemical equilibrium, thermodynamics, and transport properties for varied fuel and oxidizer operating conditions. Once validated for basic equilibrium, an expanded MATLAB code, referencing Cantera, was advanced beyond CEAs capabilities to predict rocket engine performance as a function of supplied propellant flow rate and rocket engine nozzle dimensions. Cantera was found to comparable favorably to CEA for making equilibrium calculations, supporting its use as an alternative to CEA. The developed rocket engine performs as predicted, demonstrating the developedMATLAB rocket engine model was successful in predicting real world rocket engine performance. Finally, nitrous oxide and ethanol were shown to perform well as rocket propellants, with specific impulses experimentally recorded in the range of 250 to 260 seconds.« less

Equilibrium Spline Interface (ESI) for magnetic confinement codes

NASA Astrophysics Data System (ADS)

Li, Xujing; Zakharov, Leonid E.

2017-12-01

A compact and comprehensive interface between magneto-hydrodynamic (MHD) equilibrium codes and gyro-kinetic, particle orbit, MHD stability, and transport codes is presented. Its irreducible set of equilibrium data consists of three (in the 2-D case with occasionally one extra in the 3-D case) functions of coordinates and four 1-D radial profiles together with their first and mixed derivatives. The C reconstruction routines, accessible also from FORTRAN, allow the calculation of basis functions and their first derivatives at any position inside the plasma and in its vicinity. After this all vector fields and geometric coefficients, required for the above mentioned types of codes, can be calculated using only algebraic operations with no further interpolation or differentiation.

The Adverse Effects of Le Châtelier's Principle on Teacher Understanding of Chemical Equilibrium

NASA Astrophysics Data System (ADS)

Cheung, Derek

2009-04-01

Although the scientific inadequacy of Le Châtelier's principle has long been documented in the literature, the principle is still treated as a central concept of chemical equilibrium by textbook writers and teachers in many countries. In the past, researchers' interest has focused on student misconceptions about chemical equilibrium and has neglected teacher misconceptions. This study aimed to determine how Le Châtelier's principle adversely affects teachers' ability to solve chemical equilibrium problems. This area of research is critically important because teachers cannot help their students understand what they themselves do not understand. In this study, a misconception test was developed and administered to a sample of 33 secondary chemistry teachers in Hong Kong. The test consisted of three open-ended chemical equilibrium questions. Analysis of teacher responses revealed that most of the 33 teachers failed the test as they relied on Le Châtelier's principle rather than the equilibrium law to tackle the three chemical equilibrium problems. Teachers' misconceptions about chemical equilibrium were categorized. Implications of these findings for chemistry teacher education and selection of curriculum content for school chemistry are discussed.

Implementation of Premixed Equilibrium Chemistry Capability in OVERFLOW

NASA Technical Reports Server (NTRS)

Olsen, M. E.; Liu, Y.; Vinokur, M.; Olsen, T.

2003-01-01

An implementation of premixed equilibrium chemistry has been completed for the OVERFLOW code, a chimera capable, complex geometry flow code widely used to predict transonic flowfields. The implementation builds on the computational efficiency and geometric generality of the solver.

Implementation of Premixed Equilibrium Chemistry Capability in OVERFLOW

NASA Technical Reports Server (NTRS)

Olsen, Mike E.; Liu, Yen; Vinokur, M.; Olsen, Tom

2004-01-01

An implementation of premixed equilibrium chemistry has been completed for the OVERFLOW code, a chimera capable, complex geometry flow code widely used to predict transonic flowfields. The implementation builds on the computational efficiency and geometric generality of the solver.

Chemical equilibrium. [maximizing entropy of gas system to derive relations between thermodynamic variables

NASA Technical Reports Server (NTRS)

1976-01-01

The entropy of a gas system with the number of particles subject to external control is maximized to derive relations between the thermodynamic variables that obtain at equilibrium. These relations are described in terms of the chemical potential, defined as equivalent partial derivatives of entropy, energy, enthalpy, free energy, or free enthalpy. At equilibrium, the change in total chemical potential must vanish. This fact is used to derive the equilibrium constants for chemical reactions in terms of the partition functions of the species involved in the reaction. Thus the equilibrium constants can be determined accurately, just as other thermodynamic properties, from a knowledge of the energy levels and degeneracies for the gas species involved. These equilibrium constants permit one to calculate the equilibrium concentrations or partial pressures of chemically reacting species that occur in gas mixtures at any given condition of pressure and temperature or volume and temperature.

Equations of state for explosive detonation products: The PANDA model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kerley, G.I.

1994-05-01

This paper discusses a thermochemical model for calculating equations of state (EOS) for the detonation products of explosives. This model, which was first presented at the Eighth Detonation Symposium, is available in the PANDA code and is referred to here as ``the Panda model``. The basic features of the PANDA model are as follows. (1) Statistical-mechanical theories are used to construct EOS tables for each of the chemical species that are to be allowed in the detonation products. (2) The ideal mixing model is used to compute the thermodynamic functions for a mixture of these species, and the composition ofmore » the system is determined from assumption of chemical equilibrium. (3) For hydrocode calculations, the detonation product EOS are used in tabular form, together with a reactive burn model that allows description of shock-induced initiation and growth or failure as well as ideal detonation wave propagation. This model has been implemented in the three-dimensional Eulerian code, CTH.« less

Finite element code development for modeling detonation of HMX composites

NASA Astrophysics Data System (ADS)

Duran, Adam V.; Sundararaghavan, Veera

2017-01-01

In this work, we present a hydrodynamics code for modeling shock and detonation waves in HMX. A stable efficient solution strategy based on a Taylor-Galerkin finite element (FE) discretization was developed to solve the reactive Euler equations. In our code, well calibrated equations of state for the solid unreacted material and gaseous reaction products have been implemented, along with a chemical reaction scheme and a mixing rule to define the properties of partially reacted states. A linear Gruneisen equation of state was employed for the unreacted HMX calibrated from experiments. The JWL form was used to model the EOS of gaseous reaction products. It is assumed that the unreacted explosive and reaction products are in both pressure and temperature equilibrium. The overall specific volume and internal energy was computed using the rule of mixtures. Arrhenius kinetics scheme was integrated to model the chemical reactions. A locally controlled dissipation was introduced that induces a non-oscillatory stabilized scheme for the shock front. The FE model was validated using analytical solutions for SOD shock and ZND strong detonation models. Benchmark problems are presented for geometries in which a single HMX crystal is subjected to a shock condition.

Dynamic Processes of Conceptual Change: Analysis of Constructing Mental Models of Chemical Equilibrium.

ERIC Educational Resources Information Center

Chiu, Mei-Hung; Chou, Chin-Cheng; Liu, Chia-Ju

2002-01-01

Investigates students' mental models of chemical equilibrium using dynamic science assessments. Reports that students at various levels have misconceptions about chemical equilibrium. Involves 10th grade students (n=30) in the study doing a series of hands-on chemical experiments. Focuses on the process of constructing mental models, dynamic…

Modeling Hemispheric Detonation Experiments in 2-Dimensions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Howard, W M; Fried, L E; Vitello, P A

2006-06-22

Experiments have been performed with LX-17 (92.5% TATB and 7.5% Kel-F 800 binder) to study scaling of detonation waves using a dimensional scaling in a hemispherical divergent geometry. We model these experiments using an arbitrary Lagrange-Eulerian (ALE3D) hydrodynamics code, with reactive flow models based on the thermo-chemical code, Cheetah. The thermo-chemical code Cheetah provides a pressure-dependent kinetic rate law, along with an equation of state based on exponential-6 fluid potentials for individual detonation product species, calibrated to high pressures ({approx} few Mbars) and high temperatures (20000K). The parameters for these potentials are fit to a wide variety of experimental data,more » including shock, compression and sound speed data. For the un-reacted high explosive equation of state we use a modified Murnaghan form. We model the detonator (including the flyer plate) and initiation system in detail. The detonator is composed of LX-16, for which we use a program burn model. Steinberg-Guinan models5 are used for the metal components of the detonator. The booster and high explosive are LX-10 and LX-17, respectively. For both the LX-10 and LX-17, we use a pressure dependent rate law, coupled with a chemical equilibrium equation of state based on Cheetah. For LX-17, the kinetic model includes carbon clustering on the nanometer size scale.« less

Modelling of the reactive transport for rock salt-brine in geological repository systems based on improved thermodynamic database (Invited)

NASA Astrophysics Data System (ADS)

Müller, W.; Alkan, H.; Xie, M.; Moog, H.; Sonnenthal, E. L.

2009-12-01

The release and migration of toxic contaminants from the disposed wastes is one of the main issues in long-term safety assessment of geological repositories. In the engineered and geological barriers around the nuclear waste emplacements chemical interactions between the components of the system may affect the isolation properties considerably. As the chemical issues change the transport properties in the near and far field of a nuclear repository, modelling of the transport should also take the chemistry into account. The reactive transport modelling consists of two main components: a code that combines the possible chemical reactions with thermo-hydrogeological processes interactively and a thermodynamic databank supporting the required parameters for the calculation of the chemical reactions. In the last decade many thermo-hydrogeological codes were upgraded to include the modelling of the chemical processes. TOUGHREACT is one of these codes. This is an extension of the well known simulator TOUGH2 for modelling geoprocesses. The code is developed by LBNL (Lawrence Berkeley National Laboratory, Univ. of California) for the simulation of the multi-phase transport of gas and liquid in porous media including heat transfer. After the release of its first version in 1998, this code has been applied and improved many times in conjunction with considerations for nuclear waste emplacement. A recent version has been extended to calculate ion activities in concentrated salt solutions applying the Pitzer model. In TOUGHREACT, the incorporated equation of state module ECO2N is applied as the EOS module for non-isothermal multiphase flow in a fluid system of H2O-NaCl-CO2. The partitioning of H2O and CO2 between liquid and gas phases is modelled as a function of temperature, pressure, and salinity. This module is applicable for waste repositories being expected to generate or having originally CO2 in the fluid system. The enhanced TOUGHREACT uses an EQ3/6-formatted database for both Pitzer ion-interaction parameters and thermodynamic equilibrium constants. The reliability of the parameters is as important as the accuracy of the modelling tool. For this purpose the project THEREDA (www.thereda.de)was set up. The project aims at a comprehensive and internally consistent thermodynamic reference database for geochemical modelling of near and far-field processes occurring in repositories for radioactive wastes in various host rock formations. In the framework of the project all data necessary to perform thermodynamic equilibrium calculations for elevated temperature in the system of oceanic salts are under revision, and it is expected that related data will be available for download by 2010-03. In this paper the geochemical issues that can play an essential role for the transport of radioactive contaminants within and around waste repositories are discussed. Some generic calculations are given to illustrate the geochemical interactions and their probable effects on the transport properties around HLW emplacements and on CO2 generating and/or containing repository systems.

Addition of equilibrium air to an upwind Navier-Stokes code and other first steps toward a more generalized flow solver

NASA Technical Reports Server (NTRS)

Rosen, Bruce S.

1991-01-01

An upwind three-dimensional volume Navier-Stokes code is modified to facilitate modeling of complex geometries and flow fields represented by proposed National Aerospace Plane concepts. Code enhancements include an equilibrium air model, a generalized equilibrium gas model and several schemes to simplify treatment of complex geometric configurations. The code is also restructured for inclusion of an arbitrary number of independent and dependent variables. This latter capability is intended for eventual use to incorporate nonequilibrium/chemistry gas models, more sophisticated turbulence and transition models, or other physical phenomena which will require inclusion of additional variables and/or governing equations. Comparisons of computed results with experimental data and results obtained using other methods are presented for code validation purposes. Good correlation is obtained for all of the test cases considered, indicating the success of the current effort.

A multidimensional framework of conceptual change for developing chemical equilibrium learning

NASA Astrophysics Data System (ADS)

Chanyoo, Wassana; Suwannoi, Paisan; Treagust, David F.

2018-01-01

The purposes of this research is to investigate the existing chemical equilibrium lessons in Thailand based on the multidimensional framework of conceptual change, to determine how the existing lessons could enhance students' conceptual change. This research was conducted based on qualitative perspective. Document, observations and interviews were used to collect data. To comprehend all students conceptions, diagnostic tests were applied comprised of The Chemical Equilibrium Diagnostic Test (the CEDT) and The Chemical Equilibrium Test for Reveal Conceptual Change (the CETforRCC). In addition, to study students' motivations, the Motivated Strategies for Learning Questionnaire (the MSLQ) and students' task engagement were applied. Following each perspective of conceptual change - ontological, epistemological, and social/affective - the result showed that the existing chemical equilibrium unit did not enhance students' conceptual change, and some issues were found. The problems obstructed students conceptual change should be remedy under the multidimensional framework of conceptual change. Finally, some suggestions were provided to enhance students' conceptual change in chemical equilibrium effectively

Pulse-density modulation control of chemical oscillation far from equilibrium in a droplet open-reactor system

PubMed Central

Sugiura, Haruka; Ito, Manami; Okuaki, Tomoya; Mori, Yoshihito; Kitahata, Hiroyuki; Takinoue, Masahiro

2016-01-01

The design, construction and control of artificial self-organized systems modelled on dynamical behaviours of living systems are important issues in biologically inspired engineering. Such systems are usually based on complex reaction dynamics far from equilibrium; therefore, the control of non-equilibrium conditions is required. Here we report a droplet open-reactor system, based on droplet fusion and fission, that achieves dynamical control over chemical fluxes into/out of the reactor for chemical reactions far from equilibrium. We mathematically reveal that the control mechanism is formulated as pulse-density modulation control of the fusion–fission timing. We produce the droplet open-reactor system using microfluidic technologies and then perform external control and autonomous feedback control over autocatalytic chemical oscillation reactions far from equilibrium. We believe that this system will be valuable for the dynamical control over self-organized phenomena far from equilibrium in chemical and biomedical studies. PMID:26786848

Pulse-density modulation control of chemical oscillation far from equilibrium in a droplet open-reactor system.

PubMed

Sugiura, Haruka; Ito, Manami; Okuaki, Tomoya; Mori, Yoshihito; Kitahata, Hiroyuki; Takinoue, Masahiro

2016-01-20

The design, construction and control of artificial self-organized systems modelled on dynamical behaviours of living systems are important issues in biologically inspired engineering. Such systems are usually based on complex reaction dynamics far from equilibrium; therefore, the control of non-equilibrium conditions is required. Here we report a droplet open-reactor system, based on droplet fusion and fission, that achieves dynamical control over chemical fluxes into/out of the reactor for chemical reactions far from equilibrium. We mathematically reveal that the control mechanism is formulated as pulse-density modulation control of the fusion-fission timing. We produce the droplet open-reactor system using microfluidic technologies and then perform external control and autonomous feedback control over autocatalytic chemical oscillation reactions far from equilibrium. We believe that this system will be valuable for the dynamical control over self-organized phenomena far from equilibrium in chemical and biomedical studies.

Transport and equilibrium in field-reversed mirrors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boyd, J.K.

Two plasma models relevant to compact torus research have been developed to study transport and equilibrium in field reversed mirrors. In the first model for small Larmor radius and large collision frequency, the plasma is described as an adiabatic hydromagnetic fluid. In the second model for large Larmor radius and small collision frequency, a kinetic theory description has been developed. Various aspects of the two models have been studied in five computer codes ADB, AV, NEO, OHK, RES. The ADB code computes two dimensional equilibrium and one dimensional transport in a flux coordinate. The AV code calculates orbit average integralsmore » in a harmonic oscillator potential. The NEO code follows particle trajectories in a Hill's vortex magnetic field to study stochasticity, invariants of the motion, and orbit average formulas. The OHK code displays analytic psi(r), B/sub Z/(r), phi(r), E/sub r/(r) formulas developed for the kinetic theory description. The RES code calculates resonance curves to consider overlap regions relevant to stochastic orbit behavior.« less

Computing Equilibrium Chemical Compositions

NASA Technical Reports Server (NTRS)

Mcbride, Bonnie J.; Gordon, Sanford

1995-01-01

Chemical Equilibrium With Transport Properties, 1993 (CET93) computer program provides data on chemical-equilibrium compositions. Aids calculation of thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93/PC is version of CET93 specifically designed to run within 640K memory limit of MS-DOS operating system. CET93/PC written in FORTRAN.

The Lewis Chemical Equilibrium Program with parametric study capability

NASA Technical Reports Server (NTRS)

Sevigny, R.

1981-01-01

The program was developed to determine chemical equilibrium in complex systems. Using a free energy minimization technique, the program permits calculations such as: chemical equilibrium for assigned thermodynamic states; theoretical rocket performance for both equilibrium and frozen compositions during expansion; incident and reflected shock properties; and Chapman-Jouget detonation properties. It is shown that the same program can handle solid coal in an entrained flow coal gasification problem.

Implementing an Equilibrium Law Teaching Sequence for Secondary School Students to Learn Chemical Equilibrium

ERIC Educational Resources Information Center

Ghirardi, Marco; Marchetti, Fabio; Pettinari, Claudio; Regis, Alberto; Roletto, Ezio

2015-01-01

A didactic sequence is proposed for the teaching of chemical equilibrium law. In this approach, we have avoided the kinetic derivation and the thermodynamic justification of the equilibrium constant. The equilibrium constant expression is established empirically by a trial-and-error approach. Additionally, students learn to use the criterion of…

Computing Properties Of Chemical Mixtures At Equilibrium

NASA Technical Reports Server (NTRS)

Mcbride, B. J.; Gordon, S.

1995-01-01

Scientists and engineers need data on chemical equilibrium compositions to calculate theoretical thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93 is general program that calculates chemical equilibrium compositions and properties of mixtures for any chemical system for which thermodynamic data are available. Includes thermodynamic data for more than 1,300 gaseous and condensed species and thermal-transport data for 151 gases. Written in FORTRAN 77.

Identification and Analysis of Student Conceptions Used To Solve Chemical Equilibrium Problems.

ERIC Educational Resources Information Center

Voska, Kirk W.; Heikkinen, Henry W.

2000-01-01

Identifies and quantifies the chemistry conceptions used by students when solving chemical equilibrium problems requiring application of LeChatelier's Principle, and explores the feasibility of designing a paper and pencil test to accomplish these purposes. Eleven prevalent incorrect student conceptions about chemical equilibrium were identified…

Computational methods for reactive transport modeling: A Gibbs energy minimization approach for multiphase equilibrium calculations

NASA Astrophysics Data System (ADS)

Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg

2016-02-01

We present a numerical method for multiphase chemical equilibrium calculations based on a Gibbs energy minimization approach. The method can accurately and efficiently determine the stable phase assemblage at equilibrium independently of the type of phases and species that constitute the chemical system. We have successfully applied our chemical equilibrium algorithm in reactive transport simulations to demonstrate its effective use in computationally intensive applications. We used FEniCS to solve the governing partial differential equations of mass transport in porous media using finite element methods in unstructured meshes. Our equilibrium calculations were benchmarked with GEMS3K, the numerical kernel of the geochemical package GEMS. This allowed us to compare our results with a well-established Gibbs energy minimization algorithm, as well as their performance on every mesh node, at every time step of the transport simulation. The benchmark shows that our novel chemical equilibrium algorithm is accurate, robust, and efficient for reactive transport applications, and it is an improvement over the Gibbs energy minimization algorithm used in GEMS3K. The proposed chemical equilibrium method has been implemented in Reaktoro, a unified framework for modeling chemically reactive systems, which is now used as an alternative numerical kernel of GEMS.

Misconceptions of Students and Teachers in Chemical Equilibrium.

ERIC Educational Resources Information Center

Banerjee, Anil C.

1991-01-01

Written test was developed and administered to diagnose misconceptions in different areas of chemical equilibrium among 162 undergraduate chemistry students and 69 teachers of chemistry. Responses reveal widespread misconceptions among students and teachers in areas related to the prediction of equilibrium conditions, rate and equilibrium,…

On the Concept "Chemical Equilibrium": The Associative Framework.

ERIC Educational Resources Information Center

Gussarsky, Esther; Gorodetsky, Malka

1990-01-01

Word associations were used to map high school students' concepts of "chemical equilibrium" and "equilibrium." It was found that the preconception of the two concepts was differentiated on noncritical dimensions. (Author/CW)

Using Analogies to Prevent Misconceptions about Chemical Equilibrium

ERIC Educational Resources Information Center

Sahin Pekmez, Esin

2010-01-01

The main purpose of this study was to find the effectiveness of using analogies to prevent misconceptions about chemical equilibrium. Nineteen analogies, which were based on dynamic aspects of chemical equilibrium and application of Le Chatelier's principle, were developed. The participations of this study consisted of 11th grade students (n: 151)…

Teachers' Misconceptions about the Effects of Addition of More Reactants or Products on Chemical Equilibrium

ERIC Educational Resources Information Center

Cheung, Derek; Ma, Hong-jia; Yang, Jie

2009-01-01

The importance of research on misconceptions about chemical equilibrium is well recognized by educators, but in the past, researchers' interest has centered on student misconceptions and has neglected teacher misconceptions. Focusing on the effects of adding more reactants or products on chemical equilibrium, this article discusses the various…

The Adverse Effects of Le Chatelier's Principle on Teacher Understanding of Chemical Equilibrium

ERIC Educational Resources Information Center

Cheung, Derek

2009-01-01

Although the scientific inadequacy of Le Chatelier's principle has long been documented in the literature, the principle is still treated as a central concept of chemical equilibrium by textbook writers and teachers in many countries. In the past, researchers' interest has focused on student misconceptions about chemical equilibrium and has…

A Colorful Demonstration to Visualize and Inquire into Essential Elements of Chemical Equilibrium

ERIC Educational Resources Information Center

Eilks, Ingo; Gulacar, Ozcan

2016-01-01

One of the topics that chemistry teachers have a great challenge introducing is chemical equilibrium. When being introduced to chemical equilibrium, many students have difficulties in understanding that some reactions do not go to completion, as this contrasts most of their supposed prior experiences in chemistry lessons. Students may also…

Geometrical Description of Chemical Equilibrium and Le Cha^telier's Principle: Two-Component Systems

ERIC Educational Resources Information Center

Novak, Igor

2018-01-01

Chemical equilibrium is one of the most important concepts in chemistry. The changes in properties of the chemical system at equilibrium induced by variations in pressure, volume, temperature, and concentration are always included in classroom teaching and discussions. This work introduces a novel, geometrical approach to understanding the…

Conceptual Integration of Chemical Equilibrium by Prospective Physical Sciences Teachers

ERIC Educational Resources Information Center

Ganaras, Kostas; Dumon, Alain; Larcher, Claudine

2008-01-01

This article describes an empirical study concerning the mastering of the chemical equilibrium concept by prospective physical sciences teachers. The main objective was to check whether the concept of chemical equilibrium had become an integrating and unifying concept for them, that is to say an operational and functional knowledge to explain and…

Effectiveness of Instruction Based on the Constructivist Approach on Understanding Chemical Equilibrium Concepts

ERIC Educational Resources Information Center

Akkus, Huseyin; Kadayifci, Hakki; Atasoy, Basri; Geban, Omer

2003-01-01

The purpose of this study was to identify misconceptions concerning chemical equilibrium concepts and to investigate the effectiveness of instruction based on the constructivist approach over traditional instruction on 10th grade students' understanding of chemical equilibrium concepts. The subjects of this study consisted of 71 10th grade…

Applications of Radiative Heating for Space Exploration

NASA Technical Reports Server (NTRS)

Brandis, Aaron

2017-01-01

Vehicles entering planetary atmospheres at high speeds (6 - 12 kms) experience intense heating by flows with temperatures of the order 10 000K. The flow around the vehicle experiences significant dissociation and ionization and is characterized by thermal and chemical non-equilibrium near the shock front, relaxing toward equilibrium. Emission from the plasma is intense enough to impart a significant heat flux on the entering spacecraft, making it necessary to predict the magnitude of radiative heating. Shock tubes represent a unique method capable of characterizing these processes in a flight-similar environment. The Electric Arc Shock tube (EAST) facility is one of the only facilities in its class, able to produce hypersonic flows at speeds up to Mach 50. This talk will review the characterization of radiation measured in EAST with simulations by the codes DPLR and NEQAIR, and in particular, focus on the impact these analyses have on recent missions to explore the solar system.

Students' and teachers' misapplication of le chatelier's principle: Implications for the teaching of chemical equilibrium

NASA Astrophysics Data System (ADS)

Quílez-Pardo, Juan; Solaz-Portolés, Joan Josep

The aim of this article was to study the reasons, strategies, and procedures that both students and teachers use to solve some chemical equilibrium questions and problems. Inappropriate conceptions on teaching and a lack of knowledge regarding the limited usefulness of Le Chatelier's principle, with its vague and ambiguous formulation and textbook presentation, may be some of the sources of misconceptions about the prediction of the effect of changing conditions on chemical equilibrium. To diagnose misconceptions and their possible sources, a written test was developed and administered to 170 1st-year university chemistry students. A chemical equilibrium problem, relating to the students' test, was solved by 40 chemistry teachers. First, we ascertained that teacher's conceptions might influence the problem-solving strategies of the learner. Based on this first aspect, our discussion also concerns students' and teachers' misconceptions related to the Le Chatelier's principle. Misconceptions emerged through: (a) misapplication and misunderstanding of Le Chatelier's principle; (b) use of rote-learning recall and algorithmic procedures; (c) incorrect control of the variables involved; (d) limited use of the chemical equilibrium law; (e) a lack of mastery of chemical equilibrium principles and difficulty in transferring such principles to new situations. To avoid chemical equilibrium misconceptions, a specific pattern of conceptual and methodological change may be considered.Received: 16 November 1993; Revised: 21 September 1994;

Phase Equilibrium, Chemical Equilibrium, and a Test of the Third Law: Experiments for Physical Chemistry.

ERIC Educational Resources Information Center

Dannhauser, Walter

1980-01-01

Described is an experiment designed to provide an experimental basis for a unifying point of view (utilizing theoretical framework and chemistry laboratory experiments) for physical chemistry students. Three experiments are described: phase equilibrium, chemical equilibrium, and a test of the third law of thermodynamics. (Author/DS)

Promoting Pre-Service Elementary Students' Understanding of Chemical Equilibrium through Discussions in Small Groups

ERIC Educational Resources Information Center

Bilgin, Ibrahim

2006-01-01

The purpose of this study was to investigate the effectiveness of small group discussion on students' conceptual understanding of chemical equilibrium. Students' understanding of chemical equilibrium concepts was measured using the Misconception Identification Test. The test consisted of 30 items and administered as pre-posttests to a total of 81…

Response to Contradiction: Conflict Resolution Strategies Used by Students in Solving Problems of Chemical Equilibrium.

ERIC Educational Resources Information Center

Niaz, Mansoor

2001-01-01

Illustrates how a novel problem of chemical equilibrium based on a closely related sequence of items can facilitate students' conceptual understanding. Students were presented with a chemical reaction in equilibrium to which a reactant was added as an external effect. Three studies were conducted to assess alternative conceptions. (Author/SAH)

Study and modeling of finite rate chemistry effects in turbulent non-premixed flames

NASA Technical Reports Server (NTRS)

Vervisch, Luc

1993-01-01

The development of numerical models that reflect some of the most important features of turbulent reacting flows requires information about the behavior of key quantities in well defined combustion regimes. In turbulent flames, the coupling between turbulent and chemical processes is so strong that it is extremely difficult to isolate the role played by one individual physical phenomenon. Direct numerical simulation (hereafter DNS) allows us to study in detail the turbulence-chemistry interaction in some restricted but completely defined situations. Globally, non-premixed flames are controlled by two limiting regimes: the fast chemistry case, where the turbulent flame can be pictured as a random distribution of local chemical equilibrium problems; and the slow chemistry case, where the chemistry integrates in time the turbulent fluctuations. The Damkoehler number, ratio of a mechanical time scale to chemical time scale, is used to distinguish between these regimes. Today most of the industrial computer codes are able to perform predictions in the hypothesis of local equilibrium chemistry using a presumed shape for the probability density function (pdt) of the conserved scalar. However, the finite rate chemistry situation is of great interest because industrial burners usually generate regimes in which, at some points, the flame is undergoing local extinction or at least non-equilibrium situations. Moreover, this variety of situations strongly influences the production of pollutants. To quantify finite rate chemistry effect, the interaction between a non-premixed flame and a free decaying turbulence is studied using DNS. The attention is focused on the dynamic of extinction, and an attempt is made to quantify the effect of the reaction on the small scale mixing process. The unequal diffusivity effect is also addressed. Finally, a simple turbulent combustion model based on the DNS observations and tractable in real flow configurations is proposed.

Ozone chemical equilibrium in the extended mesopause under the nighttime conditions

NASA Astrophysics Data System (ADS)

Belikovich, M. V.; Kulikov, M. Yu.; Grygalashvyly, M.; Sonnemann, G. R.; Ermakova, T. S.; Nechaev, A. A.; Feigin, A. M.

2018-01-01

For retrieval of atomic oxygen and atomic hydrogen via ozone observations in the extended mesopause region (∼70-100 km) under nighttime conditions, an assumption on photochemical equilibrium of ozone is often used in research. In this work, an assumption on chemical equilibrium of ozone near mesopause region during nighttime is proofed. We examine 3D chemistry-transport model (CTM) annual calculations and determine the ratio between the correct (modeled) distributions of the O3 density and its equilibrium values depending on the altitude, latitude, and season. The results show that the retrieval of atomic oxygen and atomic hydrogen distributions using an assumption on ozone chemical equilibrium may lead to large errors below ∼81-87 km. We give simple and clear semi-empirical criterion for practical utilization of the lower boundary of the area with ozone's chemical equilibrium near mesopause.

Influence of arc current and pressure on non-chemical equilibrium air arc behavior

NASA Astrophysics Data System (ADS)

Yi, WU; Yufei, CUI; Jiawei, DUAN; Hao, SUN; Chunlin, WANG; Chunping, NIU

2018-01-01

The influence of arc current and pressure on the non-chemical equilibrium (non-CE) air arc behavior of a nozzle structure was investigated based on the self-consistent non-chemical equilibrium model. The arc behavior during both the arc burning and arc decay phases were discussed at different currents and different pressures. We also devised the concept of a non-equilibrium parameter for a better understanding of non-CE effects. During the arc burning phase, the increasing current leads to a decrease of the non-equilibrium parameter of the particles in the arc core, while the increasing pressure leads to an increase of the non-equilibrium parameter of the particles in the arc core. During the arc decay phase, the non-CE effect will decrease by increasing the arc burning current and the nozzle pressure. Three factors together—convection, diffusion and chemical reactions—influence non-CE behavior.

Wave propagation in a quasi-chemical equilibrium plasma

NASA Technical Reports Server (NTRS)

Fang, T.-M.; Baum, H. R.

1975-01-01

Wave propagation in a quasi-chemical equilibrium plasma is studied. The plasma is infinite and without external fields. The chemical reactions are assumed to result from the ionization and recombination processes. When the gas is near equilibrium, the dominant role describing the evolution of a reacting plasma is played by the global conservation equations. These equations are first derived and then used to study the small amplitude wave motion for a near-equilibrium situation. Nontrivial damping effects have been obtained by including the conduction current terms.

Numerical simulation of weakly ionized hypersonic flow over reentry capsules

NASA Astrophysics Data System (ADS)

Scalabrin, Leonardo C.

The mathematical and numerical formulation employed in the development of a new multi-dimensional Computational Fluid Dynamics (CFD) code for the simulation of weakly ionized hypersonic flows in thermo-chemical non-equilibrium over reentry configurations is presented. The flow is modeled using the Navier-Stokes equations modified to include finite-rate chemistry and relaxation rates to compute the energy transfer between different energy modes. The set of equations is solved numerically by discretizing the flowfield using unstructured grids made of any mixture of quadrilaterals and triangles in two-dimensions or hexahedra, tetrahedra, prisms and pyramids in three-dimensions. The partial differential equations are integrated on such grids using the finite volume approach. The fluxes across grid faces are calculated using a modified form of the Steger-Warming Flux Vector Splitting scheme that has low numerical dissipation inside boundary layers. The higher order extension of inviscid fluxes in structured grids is generalized in this work to be used in unstructured grids. Steady state solutions are obtained by integrating the solution over time implicitly. The resulting sparse linear system is solved by using a point implicit or by a line implicit method in which a tridiagonal matrix is assembled by using lines of cells that are formed starting at the wall. An algorithm that assembles these lines using completely general unstructured grids is developed. The code is parallelized to allow simulation of computationally demanding problems. The numerical code is successfully employed in the simulation of several hypersonic entry flows over space capsules as part of its validation process. Important quantities for the aerothermodynamics design of capsules such as aerodynamic coefficients and heat transfer rates are compared to available experimental and flight test data and other numerical results yielding very good agreement. A sensitivity analysis of predicted radiative heating of a space capsule to several thermo-chemical non-equilibrium models is also performed.

PIES free boundary stellarator equilibria with improved initial conditions

NASA Astrophysics Data System (ADS)

Drevlak, M.; Monticello, D.; Reiman, A.

2005-07-01

The MFBE procedure developed by Strumberger (1997 Nucl. Fusion 37 19) is used to provide an improved starting point for free boundary equilibrium computations in the case of W7-X (Nührenberg and Zille 1986 Phys. Lett. A 114 129) using the Princeton iterative equilibrium solver (PIES) code (Reiman and Greenside 1986 Comput. Phys. Commun. 43 157). Transferring the consistent field found by the variational moments equilibrium code (VMEC) (Hirshmann and Whitson 1983 Phys. Fluids 26 3553) to an extended coordinate system using the VMORPH code, a safe margin between plasma boundary and PIES domain is established. The new EXTENDER_P code implements a generalization of the virtual casing principle, which allows field extension both for VMEC and PIES equilibria. This facilitates analysis of the 5/5 islands of the W7-X standard case without including them in the original PIES computation.

Fate of polychlorinated biphenyls in a contaminated lake ecosystem: combining equilibrium passive sampling of sediment and water with total concentration measurements of biota.

PubMed

Mäenpää, Kimmo; Leppänen, Matti T; Figueiredo, Kaisa; Mayer, Philipp; Gilbert, Dorothea; Jahnke, Annika; Gil-Allué, Carmen; Akkanen, Jarkko; Nybom, Inna; Herve, Sirpa

2015-11-01

Equilibrium sampling devices can be applied to study and monitor the exposure and fate of hydrophobic organic chemicals on a thermodynamic basis. They can be used to determine freely dissolved concentrations and chemical activity ratios and to predict equilibrium partitioning concentrations of hydrophobic organic chemicals in biota lipids. The authors' aim was to assess the equilibrium status of polychlorinated biphenyls (PCBs) in a contaminated lake ecosystem and along its discharge course using equilibrium sampling devices for measurements in sediment and water and by also analyzing biota. The authors used equilibrium sampling devices (silicone rubber and polyethylene [PE]) to determine freely dissolved concentrations and chemical activities of PCBs in the water column and sediment porewater and calculated for both phases the corresponding equilibrium concentrations and chemical activities in model lipids. Overall, the studied ecosystem appeared to be in disequilibrium for the studied phases: sediment, water, and biota. Chemical activities of PCBs were higher in sediment than in water, which implies that the sediment functioned as a partitioning source of PCBs and that net diffusion occurred from the sediment to the water column. Measured lipid-normalized PCB concentrations in biota were generally below equilibrium lipid concentrations relative to the sediment (CLip ⇌Sed ) or water (CLip ⇌W ), indicating that PCB levels in the organisms were below the maximum partitioning levels. The present study shows the application versatility of equilibrium sampling devices in the field and facilitates a thermodynamic understanding of exposure and fate of PCBs in a contaminated lake and its discharge course. © 2015 SETAC.

User's manual for the FLORA equilibrium and stability code

DOE Office of Scientific and Technical Information (OSTI.GOV)

Freis, R.P.; Cohen, B.I.

1985-04-01

This document provides a user's guide to the content and use of the two-dimensional axisymmetric equilibrium and stability code FLORA. FLORA addresses the low-frequency MHD stability of long-thin axisymmetric tandem mirror systems with finite pressure and finite-larmor-radius effects. FLORA solves an initial-value problem for interchange, rotational, and ballooning stability.

Non-equilibrium Quasi-Chemical Nucleation Model

NASA Astrophysics Data System (ADS)

Gorbachev, Yuriy E.

2018-04-01

Quasi-chemical model, which is widely used for nucleation description, is revised on the basis of recent results in studying of non-equilibrium effects in reacting gas mixtures (Kolesnichenko and Gorbachev in Appl Math Model 34:3778-3790, 2010; Shock Waves 23:635-648, 2013; Shock Waves 27:333-374, 2017). Non-equilibrium effects in chemical reactions are caused by the chemical reactions themselves and therefore these contributions should be taken into account in the corresponding expressions for reaction rates. Corrections to quasi-equilibrium reaction rates are of two types: (a) spatially homogeneous (caused by physical-chemical processes) and (b) spatially inhomogeneous (caused by gas expansion/compression processes and proportional to the velocity divergency). Both of these processes play an important role during the nucleation and are included into the proposed model. The method developed for solving the generalized Boltzmann equation for chemically reactive gases is applied for solving the set of equations of the revised quasi-chemical model. It is shown that non-equilibrium processes lead to essential deviation of the quasi-stationary distribution and therefore the nucleation rate from its traditional form.

User's guide for the computer code COLTS for calculating the coupled laminar and turbulent flow over a Jovian entry probe

NASA Technical Reports Server (NTRS)

Kumar, A.; Graeves, R. A.

1980-01-01

A user's guide for a computer code 'COLTS' (Coupled Laminar and Turbulent Solutions) is provided which calculates the laminar and turbulent hypersonic flows with radiation and coupled ablation injection past a Jovian entry probe. Time-dependent viscous-shock-layer equations are used to describe the flow field. These equations are solved by an explicit, two-step, time-asymptotic finite-difference method. Eddy viscosity in the turbulent flow is approximated by a two-layer model. In all, 19 chemical species are used to describe the injection of carbon-phenolic ablator in the hydrogen-helium gas mixture. The equilibrium composition of the mixture is determined by a free-energy minimization technique. A detailed frequency dependence of the absorption coefficient for various species is considered to obtain the radiative flux. The code is written for a CDC-CYBER-203 computer and is capable of providing solutions for ablated probe shapes also.

Radiation in Space and Its Control of Equilibrium Temperatures in the Solar System

NASA Technical Reports Server (NTRS)

Juhasz, Albert J.

2004-01-01

The problem of determining equilibrium temperatures for reradiating surfaces in space vacuum was analyzed and the resulting mathematical relationships were incorporated in a code to determine space sink temperatures in the solar system. A brief treatment of planetary atmospheres is also included. Temperature values obtained with the code are in good agreement with available spacecraft telemetry and meteorological measurements for Venus and Earth. The code has been used in the design of space power system radiators for future interplanetary missions.

The Painting-Sponging Analogy for Chemical Equilibrium

NASA Astrophysics Data System (ADS)

Gamitz, Adoni

1997-05-01

An analogy for chemical equilibrium is presented, in which high school or younger students can follow the advance towards equilibrium and its final dynamic nature. The relative opposition between forward and backward processes in a real chemical reaction is exemplified by the distance of a road line that is painted by one person and erased by another, both with different skills and working speeds. The graphical results of the progress of the line distance is entirely similar to the increasing of products concentration in a chemical reaction starting from the reactants. In the analogy, the final equilibrium position is independent of the starting point, as well as in a real chemical process. A simple basic program is included for interactive learning purposes.

Estimates of nonequilibrium radiation for Venus entry. [generated by chemical reactions in shock layers

NASA Technical Reports Server (NTRS)

Grose, W. L.; Nealy, J. E.

1975-01-01

The present investigation is an analysis of the radiation from the chemical nonequilibrium region in the shock layer about a vehicle during Venus entry. The radiation and the flow were assumed to be uncoupled. An inviscid, nonequilibrium flowfield was calculated and an effective electronic temperature was determined for the predominant radiating species. Species concentrations and electronic temperature were then input into a radiation transport code to calculate heating rates. The present results confirm earlier investigations which indicate that the radiation should be calculated using electronic temperatures for the radiating species. These temperatures are not related in a simple way to the local translational temperature. For the described mission, the nonequilibrium radiative heating rate is approximately twice the corresponding equilibrium value at peak heating.

Chemistry resolved kinetic flow modeling of TATB based explosives

NASA Astrophysics Data System (ADS)

Vitello, Peter; Fried, Laurence E.; William, Howard; Levesque, George; Souers, P. Clark

2012-03-01

Detonation waves in insensitive, TATB-based explosives are believed to have multiple time scale regimes. The initial burn rate of such explosives has a sub-microsecond time scale. However, significant late-time slow release in energy is believed to occur due to diffusion limited growth of carbon. In the intermediate time scale concentrations of product species likely change from being in equilibrium to being kinetic rate controlled. We use the thermo-chemical code CHEETAH linked to an ALE hydrodynamics code to model detonations. We term our model chemistry resolved kinetic flow, since CHEETAH tracks the time dependent concentrations of individual species in the detonation wave and calculates EOS values based on the concentrations. We present here two variants of our new rate model and comparison with hot, ambient, and cold experimental data for PBX 9502.

An Initial Non-Equilibrium Porous-Media Model for CFD Simulation of Stirling Regenerators

NASA Technical Reports Server (NTRS)

Tew, Roy; Simon, Terry; Gedeon, David; Ibrahim, Mounir; Rong, Wei

2006-01-01

The objective of this paper is to define empirical parameters (or closwre models) for an initial thermai non-equilibrium porous-media model for use in Computational Fluid Dynamics (CFD) codes for simulation of Stirling regenerators. The two CFD codes currently being used at Glenn Research Center (GRC) for Stirling engine modeling are Fluent and CFD-ACE. The porous-media models available in each of these codes are equilibrium models, which assmne that the solid matrix and the fluid are in thermal equilibrium at each spatial location within the porous medium. This is believed to be a poor assumption for the oscillating-flow environment within Stirling regenerators; Stirling 1-D regenerator models, used in Stirling design, we non-equilibrium regenerator models and suggest regenerator matrix and gas average temperatures can differ by several degrees at a given axial location end time during the cycle. A NASA regenerator research grant has been providing experimental and computational results to support definition of various empirical coefficients needed in defining a noa-equilibrium, macroscopic, porous-media model (i.e., to define "closure" relations). The grant effort is being led by Cleveland State University, with subcontractor assistance from the University of Minnesota, Gedeon Associates, and Sunpower, Inc. Friction-factor and heat-transfer correlations based on data taken with the NASAlSunpower oscillating-flow test rig also provide experimentally based correlations that are useful in defining parameters for the porous-media model; these correlations are documented in Gedeon Associates' Sage Stirling-Code Manuals. These sources of experimentally based information were used to define the following terms and parameters needed in the non-equilibrium porous-media model: hydrodynamic dispersion, permeability, inertial coefficient, fluid effective thermal conductivity (including themal dispersion and estimate of tortuosity effects}, and fluid-solid heat transfer coefficient. Solid effective thermal conductivity (including the effect of tortuosity) was also estimated. Determination of the porous-media model parameters was based on planned use in a CFD model of Infinia's Stirling Technology Demonstration Convertor (TDC), which uses a random-fiber regenerator matrix. The non-equilibrium porous-media model presented is considered to be an initial, or "draft," model for possible incorporation in commercial CFD codes, with the expectation that the empirical parameters will likely need to be updated once resulting Stirling CFD model regenerator and engine results have been analyzed. The emphasis of the paper is on use of available data to define empirical parameters (and closure models) needed in a thermal non-equilibrium porous-media model for Stirling regenerator simulation. Such a model has not yet been implemented by the authors or their associates. However, it is anticipated that a thermal non-equilibrium model such as that presented here, when iacorporated in the CFD codes, will improve our ability to accurately model Stirling regenerators with CFD relative to current thermal-equilibrium porous-media models.

An Initial Non-Equilibrium Porous-Media Model for CFD Simulation of Stirling Regenerators

NASA Technical Reports Server (NTRS)

Tew, Roy C.; Simon, Terry; Gedeon, David; Ibrahim, Mounir; Rong, Wei

2006-01-01

The objective of this paper is to define empirical parameters for an initial thermal non-equilibrium porous-media model for use in Computational Fluid Dynamics (CFD) codes for simulation of Stirling regenerators. The two codes currently used at Glenn Research Center for Stirling modeling are Fluent and CFD-ACE. The codes porous-media models are equilibrium models, which assume solid matrix and fluid are in thermal equilibrium. This is believed to be a poor assumption for Stirling regenerators; Stirling 1-D regenerator models, used in Stirling design, use non-equilibrium regenerator models and suggest regenerator matrix and gas average temperatures can differ by several degrees at a given axial location and time during the cycle. Experimentally based information was used to define: hydrodynamic dispersion, permeability, inertial coefficient, fluid effective thermal conductivity, and fluid-solid heat transfer coefficient. Solid effective thermal conductivity was also estimated. Determination of model parameters was based on planned use in a CFD model of Infinia's Stirling Technology Demonstration Converter (TDC), which uses a random-fiber regenerator matrix. Emphasis is on use of available data to define empirical parameters needed in a thermal non-equilibrium porous media model for Stirling regenerator simulation. Such a model has not yet been implemented by the authors or their associates.

A two-phase restricted equilibrium model for combustion of metalized solid propellants

NASA Technical Reports Server (NTRS)

Sabnis, J. S.; Dejong, F. J.; Gibeling, H. J.

1992-01-01

An Eulerian-Lagrangian two-phase approach was adopted to model the multi-phase reacting internal flow in a solid rocket with a metalized propellant. An Eulerian description was used to analyze the motion of the continuous phase which includes the gas as well as the small (micron-sized) particulates, while a Lagrangian description is used for the analysis of the discrete phase which consists of the larger particulates in the motor chamber. The particulates consist of Al and Al2O3 such that the particulate composition is 100 percent Al at injection from the propellant surface with Al2O3 fraction increasing due to combustion along the particle trajectory. An empirical model is used to compute the combustion rate for agglomerates while the continuous phase chemistry is treated using chemical equilibrium. The computer code was used to simulate the reacting flow in a solid rocket motor with an AP/HTPB/Al propellant. The computed results show the existence of an extended combustion zone in the chamber rather than a thin reaction region. The presence of the extended combustion zone results in the chamber flow field and chemical being far from isothermal (as would be predicted by a surface combustion assumption). The temperature in the chamber increases from about 2600 K at the propellant surface to about 3350 K in the core. Similarly the chemical composition and the density of the propellant gas also show spatially non-uniform distribution in the chamber. The analysis developed under the present effort provides a more sophisticated tool for solid rocket internal flow predictions than is presently available, and can be useful in studying apparent anomalies and improving the simple correlations currently in use. The code can be used in the analysis of combustion efficiency, thermal load in the internal insulation, plume radiation, etc.

A rapid method for the computation of equilibrium chemical composition of air to 15000 K

NASA Technical Reports Server (NTRS)

Prabhu, Ramadas K.; Erickson, Wayne D.

1988-01-01

A rapid computational method has been developed to determine the chemical composition of equilibrium air to 15000 K. Eleven chemically reacting species, i.e., O2, N2, O, NO, N, NO+, e-, N+, O+, Ar, and Ar+ are included. The method involves combining algebraically seven nonlinear equilibrium equations and four linear elemental mass balance and charge neutrality equations. Computational speeds for determining the equilibrium chemical composition are significantly faster than the often used free energy minimization procedure. Data are also included from which the thermodynamic properties of air can be computed. A listing of the computer program together with a set of sample results are included.

Chemical equilibria of thermal waters for the application of geothermometers from the Guanzhong basin, China

NASA Astrophysics Data System (ADS)

Xilai, Zheng; Armannsson, Halldor; Yongle, Li; Hanxue, Qiu

2002-03-01

In this study, representative samples from thermal wells and springs were chemically analyzed and geothermometers were used to calculate the deep temperatures of geothermal reservoirs on the basis of water-mineral equilibrium. In some cases, however, the chemical components are not in equilibrium with the minerals in the reservoir. Therefore, log( Q/ K) diagrams are used to study the chemical equilibrium for the minerals that are likely to participate. The Na-K-Mg triangular diagram is also applied to evaluate the equilibrium of water with reservoir rocks. Standard curves at the reference temperatures are prepared to reveal which type of silica geothermometer is appropriate for the specified condition. This study shows that water samples from geothermal wells W9 and W12 are in equilibrium with the selective minerals, and chalcedony may control the fluid-silica equilibrium. It is estimated that there is an exploitable low-temperature reservoir with possible temperatures of 80-90°C in the Guanzhong basin.

Numerical optimization of perturbative coils for tokamaks

NASA Astrophysics Data System (ADS)

Lazerson, Samuel; Park, Jong-Kyu; Logan, Nikolas; Boozer, Allen; NSTX-U Research Team

2014-10-01

Numerical optimization of coils which apply three dimensional (3D) perturbative fields to tokamaks is presented. The application of perturbative 3D magnetic fields in tokamaks is now commonplace for control of error fields, resistive wall modes, resonant field drive, and neoclassical toroidal viscosity (NTV) torques. The design of such systems has focused on control of toroidal mode number, with coil shapes based on simple window-pane designs. In this work, a numerical optimization suite based on the STELLOPT 3D equilibrium optimization code is presented. The new code, IPECOPT, replaces the VMEC equilibrium code with the IPEC perturbed equilibrium code, and targets NTV torque by coupling to the PENT code. Fixed boundary optimizations of the 3D fields for the NSTX-U experiment are underway. Initial results suggest NTV torques can be driven by normal field spectrums which are not pitch-resonant with the magnetic field lines. Work has focused on driving core torque with n = 1 and edge torques with n = 3 fields. Optimizations of the coil currents for the planned NSTX-U NCC coils highlight the code's free boundary capability. This manuscript has been authored by Princeton University under Contract Number DE-AC02-09CH11466 with the U.S. Department of Energy.

Investigation of island formation due to RMPs in DIII-D plasmas with the SIESTA resistive MHD equilibrium code

NASA Astrophysics Data System (ADS)

Hirshman, S. P.; Shafer, M. W.; Seal, S. K.; Canik, J. M.

2016-04-01

> The SIESTA magnetohydrodynamic (MHD) equilibrium code has been used to compute a sequence of ideally stable equilibria resulting from numerical variation of the helical resonant magnetic perturbation (RMP) applied to an axisymmetric DIII-D plasma equilibrium. Increasing the perturbation strength at the dominant , resonant surface leads to lower MHD energies and increases in the equilibrium island widths at the (and sidebands) surfaces, in agreement with theoretical expectations. Island overlap at large perturbation strengths leads to stochastic magnetic fields which correlate well with the experimentally inferred field structure. The magnitude and spatial phase (around the dominant rational surfaces) of the resonant (shielding) component of the parallel current are shown to change qualitatively with the magnetic island topology.

Prediction of U-Mo dispersion nuclear fuels with Al-Si alloy using artificial neural network

DOE Office of Scientific and Technical Information (OSTI.GOV)

Susmikanti, Mike, E-mail: mike@batan.go.id; Sulistyo, Jos, E-mail: soj@batan.go.id

2014-09-30

Dispersion nuclear fuels, consisting of U-Mo particles dispersed in an Al-Si matrix, are being developed as fuel for research reactors. The equilibrium relationship for a mixture component can be expressed in the phase diagram. It is important to analyze whether a mixture component is in equilibrium phase or another phase. The purpose of this research it is needed to built the model of the phase diagram, so the mixture component is in the stable or melting condition. Artificial neural network (ANN) is a modeling tool for processes involving multivariable non-linear relationships. The objective of the present work is to developmore » code based on artificial neural network models of system equilibrium relationship of U-Mo in Al-Si matrix. This model can be used for prediction of type of resulting mixture, and whether the point is on the equilibrium phase or in another phase region. The equilibrium model data for prediction and modeling generated from experimentally data. The artificial neural network with resilient backpropagation method was chosen to predict the dispersion of nuclear fuels U-Mo in Al-Si matrix. This developed code was built with some function in MATLAB. For simulations using ANN, the Levenberg-Marquardt method was also used for optimization. The artificial neural network is able to predict the equilibrium phase or in the phase region. The develop code based on artificial neural network models was built, for analyze equilibrium relationship of U-Mo in Al-Si matrix.« less

HELIOS–RETRIEVAL: An Open-source, Nested Sampling Atmospheric Retrieval Code; Application to the HR 8799 Exoplanets and Inferred Constraints for Planet Formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lavie, Baptiste; Mendonça, João M.; Malik, Matej

We present an open-source retrieval code named HELIOS–RETRIEVAL, designed to obtain chemical abundances and temperature–pressure profiles by inverting the measured spectra of exoplanetary atmospheres. In our forward model, we use an exact solution of the radiative transfer equation, in the pure absorption limit, which allows us to analytically integrate over all of the outgoing rays. Two chemistry models are considered: unconstrained chemistry and equilibrium chemistry (enforced via analytical formulae). The nested sampling algorithm allows us to formally implement Occam’s Razor based on a comparison of the Bayesian evidence between models. We perform a retrieval analysis on the measured spectra ofmore » the four HR 8799 directly imaged exoplanets. Chemical equilibrium is disfavored for HR 8799b and c. We find supersolar C/H and O/H values for the outer HR 8799b and c exoplanets, while the inner HR 8799d and e exoplanets have a range of C/H and O/H values. The C/O values range from being superstellar for HR 8799b to being consistent with stellar for HR 8799c and being substellar for HR 8799d and e. If these retrieved properties are representative of the bulk compositions of the exoplanets, then they are inconsistent with formation via gravitational instability (without late-time accretion) and consistent with a core accretion scenario in which late-time accretion of ices occurred differently for the inner and outer exoplanets. For HR 8799e, we find that spectroscopy in the K band is crucial for constraining C/O and C/H. HELIOS–RETRIEVAL is publicly available as part of the Exoclimes Simulation Platform (http://www.exoclime.org).« less

Emergence of life from multicomponent mixtures of chemicals: the case for experiments with cycling physicochemical gradients.

PubMed

Spitzer, Jan

2013-04-01

The emergence of life from planetary multicomponent mixtures of chemicals is arguably the most complicated and least understood natural phenomenon. The fact that living cells are non-equilibrium systems suggests that life can emerge only from non-equilibrium chemical systems. From an astrobiological standpoint, non-equilibrium chemical systems arise naturally when solar irradiation strikes rotating surfaces of habitable planets: the resulting cycling physicochemical gradients persistently drive planetary chemistries toward "embryonic" living systems and an eventual emergence of life. To better understand the factors that lead to the emergence of life, I argue for cycling non-equilibrium experiments with multicomponent chemical systems designed to represent the evolving chemistry of Hadean Earth ("prebiotic soups"). Specifically, I suggest experimentation with chemical engineering simulators of Hadean Earth to observe and analyze (i) the appearances and phase separations of surface active and polymeric materials as precursors of the first "cell envelopes" (membranes) and (ii) the accumulations, commingling, and co-reactivity of chemicals from atmospheric, oceanic, and terrestrial locations.

Diffusion approximations to the chemical master equation only have a consistent stochastic thermodynamics at chemical equilibrium

NASA Astrophysics Data System (ADS)

Horowitz, Jordan M.

2015-07-01

The stochastic thermodynamics of a dilute, well-stirred mixture of chemically reacting species is built on the stochastic trajectories of reaction events obtained from the chemical master equation. However, when the molecular populations are large, the discrete chemical master equation can be approximated with a continuous diffusion process, like the chemical Langevin equation or low noise approximation. In this paper, we investigate to what extent these diffusion approximations inherit the stochastic thermodynamics of the chemical master equation. We find that a stochastic-thermodynamic description is only valid at a detailed-balanced, equilibrium steady state. Away from equilibrium, where there is no consistent stochastic thermodynamics, we show that one can still use the diffusive solutions to approximate the underlying thermodynamics of the chemical master equation.

Diffusion approximations to the chemical master equation only have a consistent stochastic thermodynamics at chemical equilibrium.

PubMed

Horowitz, Jordan M

2015-07-28

The stochastic thermodynamics of a dilute, well-stirred mixture of chemically reacting species is built on the stochastic trajectories of reaction events obtained from the chemical master equation. However, when the molecular populations are large, the discrete chemical master equation can be approximated with a continuous diffusion process, like the chemical Langevin equation or low noise approximation. In this paper, we investigate to what extent these diffusion approximations inherit the stochastic thermodynamics of the chemical master equation. We find that a stochastic-thermodynamic description is only valid at a detailed-balanced, equilibrium steady state. Away from equilibrium, where there is no consistent stochastic thermodynamics, we show that one can still use the diffusive solutions to approximate the underlying thermodynamics of the chemical master equation.

NASA Glenn Coefficients for Calculating Thermodynamic Properties of Individual Species

NASA Technical Reports Server (NTRS)

McBride, Bonnie J.; Zehe, Michael J.; Gordon, Sanford

2002-01-01

This report documents the library of thermodynamic data used with the NASA Glenn computer program CEA (Chemical Equilibrium with Applications). This library, containing data for over 2000 solid, liquid, and gaseous chemical species for temperatures ranging from 200 to 20,000 K, is available for use with other computer codes as well. The data are expressed as least-squares coefficients to a seven-term functional form for C((sup o)(sub p)) (T) / R with integration constants for H (sup o) (T) / RT and S(sup o) (T) / R. The NASA Glenn computer program PAC (Properties and Coefficients) was used to calculate thermodynamic functions and to generate the least-squares coefficients. PAC input was taken from a variety of sources. A complete listing of the database is given along with a summary of thermodynamic properties at 0 and 298.15 K.

Chemistry Resolved Kinetic Flow Modeling of TATB Based Explosives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vitello, P A; Fried, L E; Howard, W M

2011-07-21

Detonation waves in insensitive, TATB based explosives are believed to have multi-time scale regimes. The initial burn rate of such explosives has a sub-microsecond time scale. However, significant late-time slow release in energy is believed to occur due to diffusion limited growth of carbon. In the intermediate time scale concentrations of product species likely change from being in equilibrium to being kinetic rate controlled. They use the thermo-chemical code CHEETAH linked to an ALE hydrodynamics code to model detonations. They term their model chemistry resolved kinetic flow as CHEETAH tracks the time dependent concentrations of individual species in the detonationmore » wave and calculates EOS values based on the concentrations. A HE-validation suite of model simulations compared to experiments at ambient, hot, and cold temperatures has been developed. They present here a new rate model and comparison with experimental data.« less

Computational analysis of Variable Thrust Engine (VTE) performance

NASA Technical Reports Server (NTRS)

Giridharan, M. G.; Krishnan, A.; Przekwas, A. J.

1993-01-01

The Variable Thrust Engine (VTE) of the Orbital Maneuvering Vehicle (OMV) uses a hypergolic propellant combination of Monomethyl Hydrazine (MMH) and Nitrogen Tetroxide (NTO) as fuel and oxidizer, respectively. The performance of the VTE depends on a number of complex interacting phenomena such as atomization, spray dynamics, vaporization, turbulent mixing, convective/radiative heat transfer, and hypergolic combustion. This study involved the development of a comprehensive numerical methodology to facilitate detailed analysis of the VTE. An existing Computational Fluid Dynamics (CFD) code was extensively modified to include the following models: a two-liquid, two-phase Eulerian-Lagrangian spray model; a chemical equilibrium model; and a discrete ordinate radiation heat transfer model. The modified code was used to conduct a series of simulations to assess the effects of various physical phenomena and boundary conditions on the VTE performance. The details of the models and the results of the simulations are presented.

SIERRA/Aero Theory Manual Version 4.46.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sierra Thermal/Fluid Team

2017-09-01

SIERRA/Aero is a two and three dimensional, node-centered, edge-based finite volume code that approximates the compressible Navier-Stokes equations on unstructured meshes. It is applicable to inviscid and high Reynolds number laminar and turbulent flows. Currently, two classes of turbulence models are provided: Reynolds Averaged Navier-Stokes (RANS) and hybrid methods such as Detached Eddy Simulation (DES). Large Eddy Simulation (LES) models are currently under development. The gas may be modeled either as ideal, or as a non-equilibrium, chemically reacting mixture of ideal gases. This document describes the mathematical models contained in the code, as well as certain implementation details. First, themore » governing equations are presented, followed by a description of the spatial discretization. Next, the time discretization is described, and finally the boundary conditions. Throughout the document, SIERRA/ Aero is referred to simply as Aero for brevity.« less

SIERRA/Aero Theory Manual Version 4.44

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sierra Thermal /Fluid Team

2017-04-01

SIERRA/Aero is a two and three dimensional, node-centered, edge-based finite volume code that approximates the compressible Navier-Stokes equations on unstructured meshes. It is applicable to inviscid and high Reynolds number laminar and turbulent flows. Currently, two classes of turbulence models are provided: Reynolds Averaged Navier-Stokes (RANS) and hybrid methods such as Detached Eddy Simulation (DES). Large Eddy Simulation (LES) models are currently under development. The gas may be modeled either as ideal, or as a non-equilibrium, chemically reacting mixture of ideal gases. This document describes the mathematical models contained in the code, as well as certain implementation details. First, themore » governing equations are presented, followed by a description of the spatial discretization. Next, the time discretization is described, and finally the boundary conditions. Throughout the document, SIERRA/ Aero is referred to simply as Aero for brevity.« less

Thermal Analysis on Plume Heating of the Main Engine on the Crew Exploration Vehicle Service Module

NASA Technical Reports Server (NTRS)

Wang, Xiao-Yen J.; Yuko, James R.

2007-01-01

The crew exploration vehicle (CEV) service module (SM) main engine plume heating is analyzed using multiple numerical tools. The chemical equilibrium compositions and applications (CEA) code is used to compute the flow field inside the engine nozzle. The plume expansion into ambient atmosphere is simulated using an axisymmetric space-time conservation element and solution element (CE/SE) Euler code, a computational fluid dynamics (CFD) software. The thermal analysis including both convection and radiation heat transfers from the hot gas inside the engine nozzle and gas radiation from the plume is performed using Thermal Desktop. Three SM configurations, Lockheed Martin (LM) designed 604, 605, and 606 configurations, are considered. Design of multilayer insulation (MLI) for the stowed solar arrays, which is subject to plume heating from the main engine, among the passive thermal control system (PTCS), are proposed and validated.

Evidence-Based Approaches to Improving Chemical Equilibrium Instruction

ERIC Educational Resources Information Center

Davenport, Jodi L.; Leinhardt, Gaea; Greeno, James; Koedinger, Kenneth; Klahr, David; Karabinos, Michael; Yaron, David J.

2014-01-01

Two suggestions for instruction in chemical equilibrium are presented, along with the evidence that supports these suggestions. The first is to use diagrams to connect chemical reactions to the effects of reactions on concentrations. The second is the use of the majority and minority species (M&M) strategy to analyze chemical equilibrium…

Finite element code development for modeling detonation of HMX composites

NASA Astrophysics Data System (ADS)

Duran, Adam; Sundararaghavan, Veera

2015-06-01

In this talk, we present a hydrodynamics code for modeling shock and detonation waves in HMX. A stable efficient solution strategy based on a Taylor-Galerkin finite element (FE) discretization was developed to solve the reactive Euler equations. In our code, well calibrated equations of state for the solid unreacted material and gaseous reaction products have been implemented, along with a chemical reaction scheme and a mixing rule to define the properties of partially reacted states. A linear Gruneisen equation of state was employed for the unreacted HMX calibrated from experiments. The JWL form was used to model the EOS of gaseous reaction products. It is assumed that the unreacted explosive and reaction products are in both pressure and temperature equilibrium. The overall specific volume and internal energy was computed using the rule of mixtures. Arrhenius kinetics scheme was integrated to model the chemical reactions. A locally controlled dissipation was introduced that induces a non-oscillatory stabilized scheme for the shock front. The FE model was validated using analytical solutions for sod shock and ZND strong detonation models and then used to perform 2D and 3D shock simulations. We will present benchmark problems for geometries in which a single HMX crystal is subjected to a shock condition. Our current progress towards developing microstructural models of HMX/binder composite will also be discussed.

Equilibrium sampling to determine the thermodynamic potential for bioaccumulation of persistent organic pollutants from sediment.

PubMed

Jahnke, Annika; MacLeod, Matthew; Wickström, Håkan; Mayer, Philipp

2014-10-07

Equilibrium partitioning (EqP) theory is currently the most widely used approach for linking sediment pollution by persistent hydrophobic organic chemicals to bioaccumulation. Most applications of the EqP approach assume (I) a generic relationship between organic carbon-normalized chemical concentrations in sediments and lipid-normalized concentrations in biota and (II) that bioaccumulation does not induce levels exceeding those expected from equilibrium partitioning. Here, we demonstrate that assumption I can be obviated by equilibrating a silicone sampler with chemicals in sediment, measuring chemical concentrations in the silicone, and applying lipid/silicone partition ratios to yield concentrations in lipid at thermodynamic equilibrium with the sediment (CLip⇌Sed). Furthermore, we evaluated the validity of assumption II by comparing CLip⇌Sed of selected persistent, bioaccumulative and toxic pollutants (polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB)) to lipid-normalized concentrations for a range of biota from a Swedish background lake. PCBs in duck mussels, roach, eel, pikeperch, perch and pike were mostly below the equilibrium partitioning level relative to the sediment, i.e., lipid-normalized concentrations were ≤CLip⇌Sed, whereas HCB was near equilibrium between biota and sediment. Equilibrium sampling allows straightforward, sensitive and precise measurement of CLip⇌Sed. We propose CLip⇌Sed as a metric of the thermodynamic potential for bioaccumulation of persistent organic chemicals from sediment useful to prioritize management actions to remediate contaminated sites.

Understanding Chemical Reaction Kinetics and Equilibrium with Interlocking Building Blocks

ERIC Educational Resources Information Center

Cloonan, Carrie A.; Nichol, Carolyn A.; Hutchinson, John S.

2011-01-01

Chemical reaction kinetics and equilibrium are essential core concepts of chemistry but are challenging topics for many students, both at the high school and undergraduate university level. Visualization at the molecular level is valuable to aid understanding of reaction kinetics and equilibrium. This activity provides a discovery-based method to…

Using a Spreadsheet Scroll Bar to Solve Equilibrium Concentrations

ERIC Educational Resources Information Center

Raviolo, Andres

2012-01-01

A simple, conceptual method is described for using the spreadsheet scroll bar to find the composition of a system at chemical equilibrium. Simulation of any kind of chemical equilibrium can be carried out using this method, and the effects of different disturbances can be predicted. This simulation, which can be used in general chemistry…

Model-based analysis of coupled equilibrium-kinetic processes: indirect kinetic studies of thermodynamic parameters using the dynamic data.

PubMed

Emami, Fereshteh; Maeder, Marcel; Abdollahi, Hamid

2015-05-07

Thermodynamic studies of equilibrium chemical reactions linked with kinetic procedures are mostly impossible by traditional approaches. In this work, the new concept of generalized kinetic study of thermodynamic parameters is introduced for dynamic data. The examples of equilibria intertwined with kinetic chemical mechanisms include molecular charge transfer complex formation reactions, pH-dependent degradation of chemical compounds and tautomerization kinetics in micellar solutions. Model-based global analysis with the possibility of calculating and embedding the equilibrium and kinetic parameters into the fitting algorithm has allowed the complete analysis of the complex reaction mechanisms. After the fitting process, the optimal equilibrium and kinetic parameters together with an estimate of their standard deviations have been obtained. This work opens up a promising new avenue for obtaining equilibrium constants through the kinetic data analysis for the kinetic reactions that involve equilibrium processes.

Parallelization of Lower-Upper Symmetric Gauss-Seidel Method for Chemically Reacting Flow

NASA Technical Reports Server (NTRS)

Yoon, Seokkwan; Jost, Gabriele; Chang, Sherry

2005-01-01

Development of technologies for exploration of the solar system has revived an interest in computational simulation of chemically reacting flows since planetary probe vehicles exhibit non-equilibrium phenomena during the atmospheric entry of a planet or a moon as well as the reentry to the Earth. Stability in combustion is essential for new propulsion systems. Numerical solution of real-gas flows often increases computational work by an order-of-magnitude compared to perfect gas flow partly because of the increased complexity of equations to solve. Recently, as part of Project Columbia, NASA has integrated a cluster of interconnected SGI Altix systems to provide a ten-fold increase in current supercomputing capacity that includes an SGI Origin system. Both the new and existing machines are based on cache coherent non-uniform memory access architecture. Lower-Upper Symmetric Gauss-Seidel (LU-SGS) relaxation method has been implemented into both perfect and real gas flow codes including Real-Gas Aerodynamic Simulator (RGAS). However, the vectorized RGAS code runs inefficiently on cache-based shared-memory machines such as SGI system. Parallelization of a Gauss-Seidel method is nontrivial due to its sequential nature. The LU-SGS method has been vectorized on an oblique plane in INS3D-LU code that has been one of the base codes for NAS Parallel benchmarks. The oblique plane has been called a hyperplane by computer scientists. It is straightforward to parallelize a Gauss-Seidel method by partitioning the hyperplanes once they are formed. Another way of parallelization is to schedule processors like a pipeline using software. Both hyperplane and pipeline methods have been implemented using openMP directives. The present paper reports the performance of the parallelized RGAS code on SGI Origin and Altix systems.

Nonambipolar Transport and Torque in Perturbed Equilibria

NASA Astrophysics Data System (ADS)

Logan, N. C.; Park, J.-K.; Wang, Z. R.; Berkery, J. W.; Kim, K.; Menard, J. E.

2013-10-01

A new Perturbed Equilibrium Nonambipolar Transport (PENT) code has been developed to calculate the neoclassical toroidal torque from radial current composed of both passing and trapped particles in perturbed equilibria. This presentation outlines the physics approach used in the development of the PENT code, with emphasis on the effects of retaining general aspect-ratio geometric effects. First, nonambipolar transport coefficients and corresponding neoclassical toroidal viscous (NTV) torque in perturbed equilibria are re-derived from the first order gyro-drift-kinetic equation in the ``combined-NTV'' PENT formalism. The equivalence of NTV torque and change in potential energy due to kinetic effects [J-K. Park, Phys. Plas., 2011] is then used to showcase computational challenges shared between PENT and stability codes MISK and MARS-K. Extensive comparisons to a reduced model, which makes numerous large aspect ratio approximations, are used throughout to emphasize geometry dependent physics such as pitch angle resonances. These applications make extensive use of the PENT code's native interfacing with the Ideal Perturbed Equilibrium Code (IPEC), and the combination of these codes is a key step towards an iterative solver for self-consistent perturbed equilibrium torque. Supported by US DOE contract #DE-AC02-09CH11466 and the DOE Office of Science Graduate Fellowship administered by the Oak Ridge Institute for Science & Education under contract #DE-AC05-06OR23100.

First-Principles Monte Carlo Simulations of Reaction Equilibria in Compressed Vapors

PubMed Central

2016-01-01

Predictive modeling of reaction equilibria presents one of the grand challenges in the field of molecular simulation. Difficulties in the study of such systems arise from the need (i) to accurately model both strong, short-ranged interactions leading to the formation of chemical bonds and weak interactions arising from the environment, and (ii) to sample the range of time scales involving frequent molecular collisions, slow diffusion, and infrequent reactive events. Here we present a novel reactive first-principles Monte Carlo (RxFPMC) approach that allows for investigation of reaction equilibria without the need to prespecify a set of chemical reactions and their ideal-gas equilibrium constants. We apply RxFPMC to investigate a nitrogen/oxygen mixture at T = 3000 K and p = 30 GPa, i.e., conditions that are present in atmospheric lightning strikes and explosions. The RxFPMC simulations show that the solvation environment leads to a significantly enhanced NO concentration that reaches a maximum when oxygen is present in slight excess. In addition, the RxFPMC simulations indicate the formation of NO2 and N2O in mole fractions approaching 1%, whereas N3 and O3 are not observed. The equilibrium distributions obtained from the RxFPMC simulations agree well with those from a thermochemical computer code parametrized to experimental data. PMID:27413785

Coefficients for calculating thermodynamic and transport properties of individual species

NASA Technical Reports Server (NTRS)

Mcbride, Bonnie J.; Gordon, Sanford; Reno, Martin A.

1993-01-01

Libraries of thermodynamic data and transport properties are given for individual species in the form of least-squares coefficients. Values of C(sup 0)(sub p)(T), H(sup 0)(T), and S(sup 0)(T) are available for 1130 solid, liquid, and gaseous species. Viscosity and thermal conductivity data are given for 155 gases. The original C(sup 0)(sub p)(T) values were fit to a fourth-order polynomial with integration constants for H(sup 0)(T) and S(sup 0)(T). For each species the integration constant for H(sup 0)(T) includes the heat of formation. Transport properties have a different functional form. The temperature range for most of the data is 300 to 5000 K, although some of the newer thermodynamic data have a range of 200 to 6000 K. Because the species are mainly possible products of reaction, the data are useful for chemical equilibrium and kinetics computer codes. Much of the data has been distributed for several years with the NASA Lewis equilibrium program CET89. The thermodynamic properties of the reference elements were updated along with about 175 species that involve the elements carbon, hydrogen, oxygen, and nitrogen. These sets of data will be distributed with the NASA Lewis personal computer program for calculating chemical equilibria, CETPC.

Development of the PARVMEC Code for Rapid Analysis of 3D MHD Equilibrium

NASA Astrophysics Data System (ADS)

Seal, Sudip; Hirshman, Steven; Cianciosa, Mark; Wingen, Andreas; Unterberg, Ezekiel; Wilcox, Robert; ORNL Collaboration

2015-11-01

The VMEC three-dimensional (3D) MHD equilibrium has been used extensively for designing stellarator experiments and analyzing experimental data in such strongly 3D systems. Recent applications of VMEC include 2D systems such as tokamaks (in particular, the D3D experiment), where application of very small (delB/B ~ 10-3) 3D resonant magnetic field perturbations render the underlying assumption of axisymmetry invalid. In order to facilitate the rapid analysis of such equilibria (for example, for reconstruction purposes), we have undertaken the task of parallelizing the VMEC code (PARVMEC) to produce a scalable and temporally rapidly convergent equilibrium code for use on parallel distributed memory platforms. The parallelization task naturally splits into three distinct parts 1) radial surfaces in the fixed-boundary part of the calculation; 2) two 2D angular meshes needed to compute the Green's function integrals over the plasma boundary for the free-boundary part of the code; and 3) block tridiagonal matrix needed to compute the full (3D) pre-conditioner near the final equilibrium state. Preliminary results show that scalability is achieved for tasks 1 and 3, with task 2 still nearing completion. The impact of this work on the rapid reconstruction of D3D plasmas using PARVMEC in the V3FIT code will be discussed. Work supported by U.S. DOE under Contract DE-AC05-00OR22725 with UT-Battelle, LLC.

Regenerative combustion device

DOEpatents

West, Phillip B.

2004-03-16

A regenerative combustion device having a combustion zone, and chemicals contained within the combustion zone, such as water, having a first equilibrium state, and a second combustible state. Means for transforming the chemicals from the first equilibrium state to the second combustible state, such as electrodes, are disposed within the chemicals. An igniter, such as a spark plug or similar device, is disposed within the combustion zone for igniting combustion of the chemicals in the second combustible state. The combustion products are contained within the combustion zone, and the chemicals are selected such that the combustion products naturally chemically revert into the chemicals in the first equilibrium state following combustion. The combustion device may thus be repeatedly reused, requiring only a brief wait after each ignition to allow the regeneration of combustible gasses within the head space.

The present state and future directions of PDF methods

NASA Technical Reports Server (NTRS)

Pope, S. B.

1992-01-01

The objectives of the workshop are presented in viewgraph format, as is this entire article. The objectives are to discuss the present status and the future direction of various levels of engineering turbulence modeling related to Computational Fluid Dynamics (CFD) computations for propulsion; to assure that combustion is an essential part of propulsion; and to discuss Probability Density Function (PDF) methods for turbulent combustion. Essential to the integration of turbulent combustion models is the development of turbulent model, chemical kinetics, and numerical method. Some turbulent combustion models typically used in industry are the k-epsilon turbulent model, the equilibrium/mixing limited combustion, and the finite volume codes.

Hybrid Rocket Performance Prediction with Coupling Method of CFD and Thermal Conduction Calculation

NASA Astrophysics Data System (ADS)

Funami, Yuki; Shimada, Toru

The final purpose of this study is to develop a design tool for hybrid rocket engines. This tool is a computer code which will be used in order to investigate rocket performance characteristics and unsteady phenomena lasting through the burning time, such as fuel regression or combustion oscillation. When phenomena inside a combustion chamber, namely boundary layer combustion, are described, it is difficult to use rigorous models for this target. It is because calculation cost may be too expensive. Therefore simple models are required for this calculation. In this study, quasi-one-dimensional compressible Euler equations for flowfields inside a chamber and the equation for thermal conduction inside a solid fuel are numerically solved. The energy balance equation at the solid fuel surface is solved to estimate fuel regression rate. Heat feedback model is Karabeyoglu's model dependent on total mass flux. Combustion model is global single step reaction model for 4 chemical species or chemical equilibrium model for 9 chemical species. As a first step, steady-state solutions are reported.

Kinetic Modeling of Slow Energy Release in Non-Ideal Carbon Rich Explosives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vitello, P; Fried, L; Glaesemann, K

2006-06-20

We present here the first self-consistent kinetic based model for long time-scale energy release in detonation waves in the non-ideal explosive LX-17. Non-ideal, insensitive carbon rich explosives, such as those based on TATB, are believed to have significant late-time slow release in energy. One proposed source of this energy is diffusion-limited growth of carbon clusters. In this paper we consider the late-time energy release problem in detonation waves using the thermochemical code CHEETAH linked to a multidimensional ALE hydrodynamics model. The linked CHEETAH-ALE model dimensional treats slowly reacting chemical species using kinetic rate laws, with chemical equilibrium assumed for speciesmore » coupled via fast time-scale reactions. In the model presented here we include separate rate equations for the transformation of the un-reacted explosive to product gases and for the growth of a small particulate form of condensed graphite to a large particulate form. The small particulate graphite is assumed to be in chemical equilibrium with the gaseous species allowing for coupling between the instantaneous thermodynamic state and the production of graphite clusters. For the explosive burn rate a pressure dependent rate law was used. Low pressure freezing of the gas species mass fractions was also included to account for regions where the kinetic coupling rates become longer than the hydrodynamic time-scales. The model rate parameters were calibrated using cylinder and rate-stick experimental data. Excellent long time agreement and size effect results were achieved.« less

Diffusion approximations to the chemical master equation only have a consistent stochastic thermodynamics at chemical equilibrium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Horowitz, Jordan M., E-mail: jordan.horowitz@umb.edu

The stochastic thermodynamics of a dilute, well-stirred mixture of chemically reacting species is built on the stochastic trajectories of reaction events obtained from the chemical master equation. However, when the molecular populations are large, the discrete chemical master equation can be approximated with a continuous diffusion process, like the chemical Langevin equation or low noise approximation. In this paper, we investigate to what extent these diffusion approximations inherit the stochastic thermodynamics of the chemical master equation. We find that a stochastic-thermodynamic description is only valid at a detailed-balanced, equilibrium steady state. Away from equilibrium, where there is no consistent stochasticmore » thermodynamics, we show that one can still use the diffusive solutions to approximate the underlying thermodynamics of the chemical master equation.« less

Teaching Chemical Equilibrium with the Jigsaw Technique

NASA Astrophysics Data System (ADS)

Doymus, Kemal

2008-03-01

This study investigates the effect of cooperative learning (jigsaw) versus individual learning methods on students’ understanding of chemical equilibrium in a first-year general chemistry course. This study was carried out in two different classes in the department of primary science education during the 2005-2006 academic year. One of the classes was randomly assigned as the non-jigsaw group (control) and other as the jigsaw group (cooperative). Students participating in the jigsaw group were divided into four “home groups” since the topic chemical equilibrium is divided into four subtopics (Modules A, B, C and D). Each of these home groups contained four students. The groups were as follows: (1) Home Group A (HGA), representin g the equilibrium state and quantitative aspects of equilibrium (Module A), (2) Home Group B (HGB), representing the equilibrium constant and relationships involving equilibrium constants (Module B), (3) Home Group C (HGC), representing Altering Equilibrium Conditions: Le Chatelier’s principle (Module C), and (4) Home Group D (HGD), representing calculations with equilibrium constants (Module D). The home groups then broke apart, like pieces of a jigsaw puzzle, and the students moved into jigsaw groups consisting of members from the other home groups who were assigned the same portion of the material. The jigsaw groups were then in charge of teaching their specific subtopic to the rest of the students in their learning group. The main data collection tool was a Chemical Equilibrium Achievement Test (CEAT), which was applied to both the jigsaw and non-jigsaw groups The results indicated that the jigsaw group was more successful than the non-jigsaw group (individual learning method).

Evaluation of a hybrid kinetics/mixing-controlled combustion model for turbulent premixed and diffusion combustion using KIVA-II

NASA Technical Reports Server (NTRS)

Nguyen, H. Lee; Wey, Ming-Jyh

1990-01-01

Two-dimensional calculations were made of spark ignited premixed-charge combustion and direct injection stratified-charge combustion in gasoline fueled piston engines. Results are obtained using kinetic-controlled combustion submodel governed by a four-step global chemical reaction or a hybrid laminar kinetics/mixing-controlled combustion submodel that accounts for laminar kinetics and turbulent mixing effects. The numerical solutions are obtained by using KIVA-2 computer code which uses a kinetic-controlled combustion submodel governed by a four-step global chemical reaction (i.e., it assumes that the mixing time is smaller than the chemistry). A hybrid laminar/mixing-controlled combustion submodel was implemented into KIVA-2. In this model, chemical species approach their thermodynamics equilibrium with a rate that is a combination of the turbulent-mixing time and the chemical-kinetics time. The combination is formed in such a way that the longer of the two times has more influence on the conversion rate and the energy release. An additional element of the model is that the laminar-flame kinetics strongly influence the early flame development following ignition.

Evaluation of a hybrid kinetics/mixing-controlled combustion model for turbulent premixed and diffusion combustion using KIVA-2

NASA Technical Reports Server (NTRS)

Nguyen, H. Lee; Wey, Ming-Jyh

1990-01-01

Two dimensional calculations were made of spark ignited premixed-charge combustion and direct injection stratified-charge combustion in gasoline fueled piston engines. Results are obtained using kinetic-controlled combustion submodel governed by a four-step global chemical reaction or a hybrid laminar kinetics/mixing-controlled combustion submodel that accounts for laminar kinetics and turbulent mixing effects. The numerical solutions are obtained by using KIVA-2 computer code which uses a kinetic-controlled combustion submodel governed by a four-step global chemical reaction (i.e., it assumes that the mixing time is smaller than the chemistry). A hybrid laminar/mixing-controlled combustion submodel was implemented into KIVA-2. In this model, chemical species approach their thermodynamics equilibrium with a rate that is a combination of the turbulent-mixing time and the chemical-kinetics time. The combination is formed in such a way that the longer of the two times has more influence on the conversion rate and the energy release. An additional element of the model is that the laminar-flame kinetics strongly influence the early flame development following ignition.

Effect of a Perturbation on the Chemical Equilibrium: Comparison with Le Chatelier's Principle

ERIC Educational Resources Information Center

Torres, Emilio Martinez

2007-01-01

This article develops a general thermodynamic treatment to predict the direction of shift in a chemical equilibrium when it is subjected to a stress. This treatment gives an inequality that relates the change in the perturbed variable and the change that the equilibrium shift produces in the conjugated variable. To illustrate the generality of…

Teaching Chemical Equilibrium and Thermodynamics in Undergraduate General Chemistry Classes.

ERIC Educational Resources Information Center

Banerjee, Anil C.

1995-01-01

Discusses some of the conceptual difficulties encountered by undergraduate students in learning certain aspects of chemical equilibrium and thermodynamics. Discusses teaching strategies for dealing with these difficulties. (JRH)

The role of non-equilibrium fluxes in the relaxation processes of the linear chemical master equation

NASA Astrophysics Data System (ADS)

de Oliveira, Luciana Renata; Bazzani, Armando; Giampieri, Enrico; Castellani, Gastone C.

2014-08-01

We propose a non-equilibrium thermodynamical description in terms of the Chemical Master Equation (CME) to characterize the dynamics of a chemical cycle chain reaction among m different species. These systems can be closed or open for energy and molecules exchange with the environment, which determines how they relax to the stationary state. Closed systems reach an equilibrium state (characterized by the detailed balance condition (D.B.)), while open systems will reach a non-equilibrium steady state (NESS). The principal difference between D.B. and NESS is due to the presence of chemical fluxes. In the D.B. condition the fluxes are absent while for the NESS case, the chemical fluxes are necessary for the state maintaining. All the biological systems are characterized by their "far from equilibrium behavior," hence the NESS is a good candidate for a realistic description of the dynamical and thermodynamical properties of living organisms. In this work we consider a CME written in terms of a discrete Kolmogorov forward equation, which lead us to write explicitly the non-equilibrium chemical fluxes. For systems in NESS, we show that there is a non-conservative "external vector field" whose is linearly proportional to the chemical fluxes. We also demonstrate that the modulation of these external fields does not change their stationary distributions, which ensure us to study the same system and outline the differences in the system's behavior when it switches from the D.B. regime to NESS. We were interested to see how the non-equilibrium fluxes influence the relaxation process during the reaching of the stationary distribution. By performing analytical and numerical analysis, our central result is that the presence of the non-equilibrium chemical fluxes reduces the characteristic relaxation time with respect to the D.B. condition. Within a biochemical and biological perspective, this result can be related to the "plasticity property" of biological systems and to their capabilities to switch from one state to another as is observed during synaptic plasticity, cell fate determination, and differentiation.

The role of non-equilibrium fluxes in the relaxation processes of the linear chemical master equation.

PubMed

de Oliveira, Luciana Renata; Bazzani, Armando; Giampieri, Enrico; Castellani, Gastone C

2014-08-14

We propose a non-equilibrium thermodynamical description in terms of the Chemical Master Equation (CME) to characterize the dynamics of a chemical cycle chain reaction among m different species. These systems can be closed or open for energy and molecules exchange with the environment, which determines how they relax to the stationary state. Closed systems reach an equilibrium state (characterized by the detailed balance condition (D.B.)), while open systems will reach a non-equilibrium steady state (NESS). The principal difference between D.B. and NESS is due to the presence of chemical fluxes. In the D.B. condition the fluxes are absent while for the NESS case, the chemical fluxes are necessary for the state maintaining. All the biological systems are characterized by their "far from equilibrium behavior," hence the NESS is a good candidate for a realistic description of the dynamical and thermodynamical properties of living organisms. In this work we consider a CME written in terms of a discrete Kolmogorov forward equation, which lead us to write explicitly the non-equilibrium chemical fluxes. For systems in NESS, we show that there is a non-conservative "external vector field" whose is linearly proportional to the chemical fluxes. We also demonstrate that the modulation of these external fields does not change their stationary distributions, which ensure us to study the same system and outline the differences in the system's behavior when it switches from the D.B. regime to NESS. We were interested to see how the non-equilibrium fluxes influence the relaxation process during the reaching of the stationary distribution. By performing analytical and numerical analysis, our central result is that the presence of the non-equilibrium chemical fluxes reduces the characteristic relaxation time with respect to the D.B. condition. Within a biochemical and biological perspective, this result can be related to the "plasticity property" of biological systems and to their capabilities to switch from one state to another as is observed during synaptic plasticity, cell fate determination, and differentiation.

SOLAR OPACITY CALCULATIONS USING THE SUPER-TRANSITION-ARRAY METHOD

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krief, M.; Feigel, A.; Gazit, D., E-mail: menahem.krief@mail.huji.ac.il

A new opacity model has been developed based on the Super-Transition-Array (STA) method for the calculation of monochromatic opacities of plasmas in local thermodynamic equilibrium. The atomic code, named STAR (STA-Revised), is described and used to calculate spectral opacities for a solar model implementing the recent AGSS09 composition. Calculations are carried out throughout the solar radiative zone. The relative contributions of different chemical elements and atomic processes to the total Rosseland mean opacity are analyzed in detail. Monochromatic opacities and charge-state distributions are compared with the widely used Opacity Project (OP) code, for several elements near the radiation–convection interface. STARmore » Rosseland opacities for the solar mixture show a very good agreement with OP and the OPAL opacity code throughout the radiation zone. Finally, an explicit STA calculation was performed of the full AGSS09 photospheric mixture, including all heavy metals. It was shown that, due to their extremely low abundance, and despite being very good photon absorbers, the heavy elements do not affect the Rosseland opacity.« less

TReacLab: An object-oriented implementation of non-intrusive splitting methods to couple independent transport and geochemical software

NASA Astrophysics Data System (ADS)

Jara, Daniel; de Dreuzy, Jean-Raynald; Cochepin, Benoit

2017-12-01

Reactive transport modeling contributes to understand geophysical and geochemical processes in subsurface environments. Operator splitting methods have been proposed as non-intrusive coupling techniques that optimize the use of existing chemistry and transport codes. In this spirit, we propose a coupler relying on external geochemical and transport codes with appropriate operator segmentation that enables possible developments of additional splitting methods. We provide an object-oriented implementation in TReacLab developed in the MATLAB environment in a free open source frame with an accessible repository. TReacLab contains classical coupling methods, template interfaces and calling functions for two classical transport and reactive software (PHREEQC and COMSOL). It is tested on four classical benchmarks with homogeneous and heterogeneous reactions at equilibrium or kinetically-controlled. We show that full decoupling to the implementation level has a cost in terms of accuracy compared to more integrated and optimized codes. Use of non-intrusive implementations like TReacLab are still justified for coupling independent transport and chemical software at a minimal development effort but should be systematically and carefully assessed.

Computational models for the analysis of three-dimensional internal and exhaust plume flowfields

NASA Technical Reports Server (NTRS)

Dash, S. M.; Delguidice, P. D.

1977-01-01

This paper describes computational procedures developed for the analysis of three-dimensional supersonic ducted flows and multinozzle exhaust plume flowfields. The models/codes embodying these procedures cater to a broad spectrum of geometric situations via the use of multiple reference plane grid networks in several coordinate systems. Shock capturing techniques are employed to trace the propagation and interaction of multiple shock surfaces while the plume interface, separating the exhaust and external flows, and the plume external shock are discretely analyzed. The computational grid within the reference planes follows the trace of streamlines to facilitate the incorporation of finite-rate chemistry and viscous computational capabilities. Exhaust gas properties consist of combustion products in chemical equilibrium. The computational accuracy of the models/codes is assessed via comparisons with exact solutions, results of other codes and experimental data. Results are presented for the flows in two-dimensional convergent and divergent ducts, expansive and compressive corner flows, flow in a rectangular nozzle and the plume flowfields for exhausts issuing out of single and multiple rectangular nozzles.

FastChem: A computer program for efficient complex chemical equilibrium calculations in the neutral/ionized gas phase with applications to stellar and planetary atmospheres

NASA Astrophysics Data System (ADS)

Stock, Joachim W.; Kitzmann, Daniel; Patzer, A. Beate C.; Sedlmayr, Erwin

2018-06-01

For the calculation of complex neutral/ionized gas phase chemical equilibria, we present a semi-analytical versatile and efficient computer program, called FastChem. The applied method is based on the solution of a system of coupled nonlinear (and linear) algebraic equations, namely the law of mass action and the element conservation equations including charge balance, in many variables. Specifically, the system of equations is decomposed into a set of coupled nonlinear equations in one variable each, which are solved analytically whenever feasible to reduce computation time. Notably, the electron density is determined by using the method of Nelder and Mead at low temperatures. The program is written in object-oriented C++ which makes it easy to couple the code with other programs, although a stand-alone version is provided. FastChem can be used in parallel or sequentially and is available under the GNU General Public License version 3 at https://github.com/exoclime/FastChem together with several sample applications. The code has been successfully validated against previous studies and its convergence behavior has been tested even for extreme physical parameter ranges down to 100 K and up to 1000 bar. FastChem converges stable and robust in even most demanding chemical situations, which posed sometimes extreme challenges for previous algorithms.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ivanov, A. A., E-mail: aai@a5.kiam.ru; Martynov, A. A., E-mail: martynov@a5.kiam.ru; Medvedev, S. Yu., E-mail: medvedev@a5.kiam.ru

In the MHD tokamak plasma theory, the plasma pressure is usually assumed to be isotropic. However, plasma heating by neutral beam injection and RF heating can lead to a strong anisotropy of plasma parameters and rotation of the plasma. The development of MHD equilibrium theory taking into account the plasma inertia and anisotropic pressure began a long time ago, but until now it has not been consistently applied in computational codes for engineering calculations of the plasma equilibrium and evolution in tokamak. This paper contains a detailed derivation of the axisymmetric plasma equilibrium equation in the most general form (withmore » arbitrary rotation and anisotropic pressure) and description of the specialized version of the SPIDER code. The original method of calculation of the equilibrium with an anisotropic pressure and a prescribed rotational transform profile is proposed. Examples of calculations and discussion of the results are also presented.« less

Investigation of island formation due to RMPs in DIII-D plasmas with the SIESTA resistive MHD equilibrium code

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hirshman, S. P.; Shafer, M. W.; Seal, S. K.

The SIESTA magnetohydrodynamic (MHD) equilibrium code has been used to compute a sequence of ideally stable equilibria resulting from numerical variation of the helical resonant magnetic perturbation (RMP) applied to an axisymmetric DIII-D plasma equilibrium. Increasing the perturbation strength at the dominant m=2, n=-1 , resonant surface leads to lower MHD energies and increases in the equilibrium island widths at the m=2 (and sidebands) surfaces, in agreement with theoretical expectations. Island overlap at large perturbation strengths leads to stochastic magnetic fields which correlate well with the experimentally inferred field structure. The magnitude and spatial phase (around the dominant rational surfaces)more » of the resonant (shielding) component of the parallel current are shown to change qualitatively with the magnetic island topology.« less

Investigation of island formation due to RMPs in DIII-D plasmas with the SIESTA resistive MHD equilibrium code

DOE PAGES

Hirshman, S. P.; Shafer, M. W.; Seal, S. K.; ...

2016-03-03

The SIESTA magnetohydrodynamic (MHD) equilibrium code has been used to compute a sequence of ideally stable equilibria resulting from numerical variation of the helical resonant magnetic perturbation (RMP) applied to an axisymmetric DIII-D plasma equilibrium. Increasing the perturbation strength at the dominant m=2, n=-1 , resonant surface leads to lower MHD energies and increases in the equilibrium island widths at the m=2 (and sidebands) surfaces, in agreement with theoretical expectations. Island overlap at large perturbation strengths leads to stochastic magnetic fields which correlate well with the experimentally inferred field structure. The magnitude and spatial phase (around the dominant rational surfaces)more » of the resonant (shielding) component of the parallel current are shown to change qualitatively with the magnetic island topology.« less

Thermal Conductivity of Gas Mixtures in Chemical Equilibrium

NASA Technical Reports Server (NTRS)

Brokaw, Richard S.

1960-01-01

The expression for the thermal conductivity of gas mixtures in chemical equilibrium is presented in a simpler and less restrictive form. This new form is shown to be equivalent to the previous equations.

tRNA Shifts the G-quadruplex-Hairpin Conformational Equilibrium in RNA towards the Hairpin Conformer.

PubMed

Rode, Ambadas B; Endoh, Tamaki; Sugimoto, Naoki

2016-11-07

Non-coding RNAs play important roles in cellular homeostasis and are involved in many human diseases including cancer. Intermolecular RNA-RNA interactions are the basis for the diverse functions of many non-coding RNAs. Herein, we show how the presence of tRNA influences the equilibrium between hairpin and G-quadruplex conformations in the 5' untranslated regions of oncogenes and model sequences. Kinetic and equilibrium analyses of the hairpin to G-quadruplex conformational transition of purified RNA as well as during co-transcriptional folding indicate that tRNA significantly shifts the equilibrium toward the hairpin conformer. The enhancement of relative translation efficiency in a reporter gene assay is shown to be due to the tRNA-mediated shift in hairpin-G-quadruplex equilibrium of oncogenic mRNAs. Our findings suggest that tRNA is a possible therapeutic target in diseases in which RNA conformational equilibria is dysregulated. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical Energy Release in Several Recently Discovered Detonation and Deflagration Flows

NASA Astrophysics Data System (ADS)

Tarver, Craig M.

2010-10-01

Several recent experiments on complex detonation and deflagration flows are analyzed in terms of the chemical energy release required to sustain these flows. The observed double cellular structures in detonating gaseous nitromethane-oxygen and NO2-fuel (H2, CH4, and C2H6) mixtures are explained by the amplification of two distinct pressure wave frequencies by two exothermic reactions, the faster reaction forming vibrationally excited NO* and the slower reaction forming highly vibrationally excited N2**. The establishment of a Chapman-Jouguet (C-J) deflagration behind a weak shock wave, the C-J detonation established after a head-on collision with a shock front, and the C-J detonation conditions established in reactive supersonic flows are quantitatively calculated using the chemical energy release of a H2 + Cl2 mixture. For these three reactive flows, these calculations illustrate that different fractions of the exothermic chemical energy are used to sustain steady-state propagation. C-J detonation calculations on the various initial states using the CHEETAH chemical equilibrium code are shown to be in good agreement with experimental detonation velocity measurements for the head-on collision and supersonic flow detonations.

NNEPEQ: Chemical equilibrium version of the Navy/NASA Engine Program

NASA Technical Reports Server (NTRS)

Fishbach, Laurence H.; Gordon, Sanford

1988-01-01

The Navy NASA Engine Program, NNEP, currently is in use at a large number of government agencies, commercial companies and universities. This computer code has bee used extensively to calculate the design and off-design (matched) performance of a broad range of turbine engines, ranging from subsonic turboprops to variable cycle engines for supersonic transports. Recently, there has been increased interest in applications for which NNEP was not capable of simulating, namely, high Mach applications, alternate fuels including cryogenics, and cycles such as the gas generator air-turbo-rocker (ATR). In addition, there is interest in cycles employing ejectors such as for military fighters. New engine component models had to be created for incorporation into NNEP, and it was found necessary to include chemical dissociation effects of high temperature gases. The incorporation of these extended capabilities into NNEP is discussed and some of the effects of these changes are illustrated.

Radiative Viscous Shock Layer Analysis of Fire, Apollo, and PAET Flight Data

NASA Technical Reports Server (NTRS)

Balakrishnan, A.; Park, Chul; Green, Michael J.

1986-01-01

Equilibrium, radiating viscous shock layer solutions are obtained for a number of trajectory points of the Fire II, Apollo 4, and PAET experimental flight vehicles. Convective heating rates calculated by a benchmark code agree well with two engineering correlations, except at high altitudes corresponding to low densities. Calculated radiation intensities are compared with the flight radiometer data and with inviscid flow results. Differences as great as 70% are observed between measured data and the viscous calculations. Because of boundary-layer absorption, viscous effects reduce the intensity to the wall by as much as 30% compared with inviscid intensities. Preliminary chemical and thermal nonequilibrium flow calculations along a stagnation streamline for a PAET trajectory predict an enhancement to the radiation owing to the chemical relaxation. Stagnation point solutions are also presented for future aeroassisted orbital transfer vehicle geometries with nose radii of 0.3-15 m.

Radiative viscous-shock-layer analysis of Fire, Apollo, and PAET flight data

NASA Technical Reports Server (NTRS)

Balakrishnan, A.; Park, C.; Green, M. J.

1985-01-01

Equilibrium, radiating viscous-shock-layer solutions are obtained for a number of trajectory points of the Fire II, Apollo 4, and PAET experimental flight vehicles. Convective heating rates calculated by a benchmark code agree well, except at high altitudes corresponding to low densities, with two engineering correlations. Calculated radiation intensities are compared with the flight radiometer data and with inviscid flow results. Differences as great as 70 percent are observed between measured data and the viscous calculations. Viscous effects reduce the intensity toward the wall, because of boundary-layer absorption, by as much as 30 percent, compared with inviscid intensities. Preliminary chemical and thermal nonequilibrium flow calculations along a stagnation streamline for a PAET trajectory predict enhancement of radiation owing to chemical relaxation. Stagnation point solutions are also presented for future air-assisted orbital transfer vehicle geometries with nose radii ranging from 0.3 to 15 m.

NNEPEQ - Chemical equilibrium version of the Navy/NASA Engine Program

NASA Technical Reports Server (NTRS)

Fishbach, L. H.; Gordon, S.

1989-01-01

The Navy NASA Engine Program, NNEP, currently is in use at a large number of government agencies, commercial companies and universities. This computer code has been used extensively to calculate the design and off-design (matched) performance of a broad range of turbine engines, ranging from subsonic turboprops to variable cycle engines for supersonic transports. Recently, there has been increased interest in applications for which NNEP was not capable of simulating, namely, high Mach applications, alternate fuels including cryogenics, and cycles such as the gas generator air-turbo-rocker (ATR). In addition, there is interest in cycles employing ejectors such as for military fighters. New engine component models had to be created for incorporation into NNEP, and it was found necessary to include chemical dissociation effects of high temperature gases. The incorporation of these extended capabilities into NNEP is discussed and some of the effects of these changes are illustrated.

Effect of inert propellant injection on Mars ascent vehicle performance

NASA Technical Reports Server (NTRS)

Colvin, James E.; Landis, Geoffrey A.

1992-01-01

A Mars ascent vehicle is limited in performance by the propellant which can be brought from Earth. In some cases the vehicle performance can be improved by injecting inert gas into the engine, if the inert gas is available as an in-situ resource and does not have to be brought from Earth. Carbon dioxide, nitrogen, and argon are constituents of the Martian atmosphere which could be separated by compressing the atmosphere, without any chemical processing step. The effect of inert gas injection on rocket engine performance was analyzed with a numerical combustion code that calculated chemical equilibrium for engines of varying combustion chamber pressure, expansion ratio, oxidizer/fuel ratio, and inert injection fraction. Results of this analysis were applied to several candidate missions to determine how the required mass of return propellant needed in low Earth orbit could be decreased using inert propellant injection.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rasouli, C.; Abbasi Davani, F., E-mail: fabbasidavani@gmail.com

A series of experiments and numerical calculations have been done on the Damavand tokamak for accurate determination of equilibrium parameters, such as the plasma boundary position and shape. For this work, the pickup coils of the Damavand tokamak were recalibrated and after that a plasma boundary shape identification code was developed for analyzing the experimental data, such as magnetic probes and coils currents data. The plasma boundary position, shape and other parameters are determined by the plasma shape identification code. A free-boundary equilibrium code was also generated for comparison with the plasma boundary shape identification results and determination of requiredmore » fields to obtain elongated plasma in the Damavand tokamak.« less

Non-equilibrium synergistic effects in atmospheric pressure plasmas.

PubMed

Guo, Heng; Zhang, Xiao-Ning; Chen, Jian; Li, He-Ping; Ostrikov, Kostya Ken

2018-03-19

Non-equilibrium is one of the important features of an atmospheric gas discharge plasma. It involves complicated physical-chemical processes and plays a key role in various actual plasma processing. In this report, a novel complete non-equilibrium model is developed to reveal the non-equilibrium synergistic effects for the atmospheric-pressure low-temperature plasmas (AP-LTPs). It combines a thermal-chemical non-equilibrium fluid model for the quasi-neutral plasma region and a simplified sheath model for the electrode sheath region. The free-burning argon arc is selected as a model system because both the electrical-thermal-chemical equilibrium and non-equilibrium regions are involved simultaneously in this arc plasma system. The modeling results indicate for the first time that it is the strong and synergistic interactions among the mass, momentum and energy transfer processes that determine the self-consistent non-equilibrium characteristics of the AP-LTPs. An energy transfer process related to the non-uniform spatial distributions of the electron-to-heavy-particle temperature ratio has also been discovered for the first time. It has a significant influence for self-consistently predicting the transition region between the "hot" and "cold" equilibrium regions of an AP-LTP system. The modeling results would provide an instructive guidance for predicting and possibly controlling the non-equilibrium particle-energy transportation process in various AP-LTPs in future.

Inventory Control: A Small Electronic Device for Studying Chemical Kinetics.

ERIC Educational Resources Information Center

Perez-Rodriguez, A. L.; Calvo-Aguilar, J. L.

1984-01-01

Shows how the rate of reaction can be studied using a simple electronic device that overcomes the difficulty students encounter in solving the differential equations describing chemical equilibrium. The device, used in conjunction with an oscilloscope, supplies the voltages that represent the chemical variables that take part in the equilibrium.…

Understanding Chemical Equilibrium Using Entropy Analysis: The Relationship between [delta]S[subscript tot](sys[superscript o]) and the Equilibrium Constant

ERIC Educational Resources Information Center

Bindel, Thomas H.

2010-01-01

Entropy analyses as a function of the extent of reaction are presented for a number of physicochemical processes, including vaporization of a liquid, dimerization of nitrogen dioxide, and the autoionization of water. Graphs of the total entropy change versus the extent of reaction give a visual representation of chemical equilibrium and the second…

Understanding Chemical Equilibrium: The Role of Gas Phases and Mixing Contributions in the Minimum of Free Energy Plots

ERIC Educational Resources Information Center

Tomba, J. Pablo

2017-01-01

The use of free energy plots to understand the concept of thermodynamic equilibrium has been shown to be of great pedagogical value in materials science. Although chemical equilibrium is also amenable to this kind of analysis, it is not part of the agenda of materials science textbooks. Something similar is found in chemistry branches, where free…

CET89 - CHEMICAL EQUILIBRIUM WITH TRANSPORT PROPERTIES, 1989

NASA Technical Reports Server (NTRS)

Mcbride, B.

1994-01-01

Scientists and engineers need chemical equilibrium composition data to calculate the theoretical thermodynamic properties of a chemical system. This information is essential in the design and analysis of equipment such as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical processing equipment. The substantial amount of numerical computation required to obtain equilibrium compositions and transport properties for complex chemical systems led scientists at NASA's Lewis Research Center to develop CET89, a program designed to calculate the thermodynamic and transport properties of these systems. CET89 is a general program which will calculate chemical equilibrium compositions and mixture properties for any chemical system with available thermodynamic data. Generally, mixtures may include condensed and gaseous products. CET89 performs the following operations: it 1) obtains chemical equilibrium compositions for assigned thermodynamic states, 2) calculates dilute-gas transport properties of complex chemical mixtures, 3) obtains Chapman-Jouguet detonation properties for gaseous species, 4) calculates incident and reflected shock properties in terms of assigned velocities, and 5) calculates theoretical rocket performance for both equilibrium and frozen compositions during expansion. The rocket performance function allows the option of assuming either a finite area or an infinite area combustor. CET89 accommodates problems involving up to 24 reactants, 20 elements, and 600 products (400 of which may be condensed). The program includes a library of thermodynamic and transport properties in the form of least squares coefficients for possible reaction products. It includes thermodynamic data for over 1300 gaseous and condensed species and transport data for 151 gases. The subroutines UTHERM and UTRAN convert thermodynamic and transport data to unformatted form for faster processing. The program conforms to the FORTRAN 77 standard, except for some input in NAMELIST format. It requires about 423 KB memory, and is designed to be used on mainframe, workstation, and mini computers. Due to its memory requirements, this program does not readily lend itself to implementation on MS-DOS based machines.

Foundations of atmospheric pressure non-equilibrium plasmas

NASA Astrophysics Data System (ADS)

Bruggeman, Peter J.; Iza, Felipe; Brandenburg, Ronny

2017-12-01

Non-equilibrium plasmas have been intensively studied over the past century in the context of material processing, environmental remediation, ozone generation, excimer lamps and plasma display panels. Research on atmospheric pressure non-equilibrium plasmas intensified over the last two decades leading to a large variety of plasma sources that have been developed for an extended application range including chemical conversion, medicine, chemical analysis and disinfection. The fundamental understanding of these discharges is emerging but there remain a lot of unexplained phenomena in these intrinsically complex plasmas. The properties of non-equilibrium plasmas at atmospheric pressure span over a huge range of electron densities as well as heavy particle and electron temperatures. This paper provides an overview of the key underlying processes that are important for the generation and stabilization of atmospheric pressure non-equilibrium plasmas. The unique physical and chemical properties of theses discharges are also summarized.

A Mechanical Analogue for Chemical Potential, Extent of Reaction, and the Gibbs Energy.

ERIC Educational Resources Information Center

Glass, Samuel V.; DeKock, Roger L.

1998-01-01

Presents an analogy that relates the one-dimensional mechanical equilibrium of a rigid block between two Hooke's law springs and the chemical equilibrium of two perfect gases using ordinary materials. (PVD)

Adaptive Chemical Networks under Non-Equilibrium Conditions: The Evaporating Droplet.

PubMed

Armao, Joseph J; Lehn, Jean-Marie

2016-10-17

Non-volatile solutes in an evaporating drop experience an out-of-equilibrium state due to non-linear concentration effects and complex flow patterns. Here, we demonstrate a small molecule chemical reaction network that undergoes a rapid adaptation response to the out-of-equilibrium conditions inside the droplet leading to control over the molecular constitution and spatial arrangement of the deposition pattern. Adaptation results in a pronounced coffee stain effect and coupling to chemical concentration gradients within the drop is demonstrated. Amplification and suppression of network species are readily identifiable with confocal fluorescence microscopy. We anticipate that these observations will contribute to the design and exploration of out-of-equilibrium chemical systems, as well as be useful towards the development of point-of-care medical diagnostics and controlled deposition of small molecules through inkjet printing. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Non-equilibrium assembly of microtubules: from molecules to autonomous chemical robots.

PubMed

Hess, H; Ross, Jennifer L

2017-09-18

Biological systems have evolved to harness non-equilibrium processes from the molecular to the macro scale. It is currently a grand challenge of chemistry, materials science, and engineering to understand and mimic biological systems that have the ability to autonomously sense stimuli, process these inputs, and respond by performing mechanical work. New chemical systems are responding to the challenge and form the basis for future responsive, adaptive, and active materials. In this article, we describe a particular biochemical-biomechanical network based on the microtubule cytoskeletal filament - itself a non-equilibrium chemical system. We trace the non-equilibrium aspects of the system from molecules to networks and describe how the cell uses this system to perform active work in essential processes. Finally, we discuss how microtubule-based engineered systems can serve as testbeds for autonomous chemical robots composed of biological and synthetic components.

Computer model of one-dimensional equilibrium controlled sorption processes

USGS Publications Warehouse

Grove, D.B.; Stollenwerk, K.G.

1984-01-01

A numerical solution to the one-dimensional solute-transport equation with equilibrium-controlled sorption and a first-order irreversible-rate reaction is presented. The computer code is written in FORTRAN language, with a variety of options for input and output for user ease. Sorption reactions include Langmuir, Freundlich, and ion-exchange, with or without equal valance. General equations describing transport and reaction processes are solved by finite-difference methods, with nonlinearities accounted for by iteration. Complete documentation of the code, with examples, is included. (USGS)

Reactive Fluid Flow and Applications to Diagenesis, Mineral Deposits, and Crustal Rocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rye, Danny M.; Bolton, Edward W.

2002-11-04

The objective is to initiate new: modeling of coupled fluid flow and chemical reactions of geologic environments; experimental and theoretical studies of water-rock reactions; collection and interpretation of stable isotopic and geochemical field data at many spatial scales of systems involving fluid flow and reaction in environments ranging from soils to metamorphic rocks. Theoretical modeling of coupled fluid flow and chemical reactions, involving kinetics, has been employed to understand the differences between equilibrium, steady-state, and non-steady-state behavior of the chemical evolution of open fluid-rock systems. The numerical codes developed in this project treat multi-component, finite-rate reactions combined with advective andmore » dispersive transport in multi-dimensions. The codes incorporate heat, mass, and isotopic transfer in both porous and fractured media. Experimental work has obtained the kinetic rate laws of pertinent silicate-water reactions and the rates of Sr release during chemical weathering. Ab-initio quantum mechanical techniques have been applied to obtain the kinetics and mechanisms of silicate surface reactions and isotopic exchange between water and dissolved species. Geochemical field-based studies were carried out on the Wepawaug metamorphic schist, on the Irish base-metal sediment-hosted ore system, in the Dalradian metamorphic complex in Scotland, and on weathering in the Columbia River flood basalts. The geochemical and isotopic field data, and the experimental and theoretical rate data, were used as constraints on the numerical models and to determine the length and time scales relevant to each of the field areas.« less

Achieving Chemical Equilibrium: The Role of Imposed Conditions in the Ammonia Formation Reaction

ERIC Educational Resources Information Center

Tellinghuisen, Joel

2006-01-01

Under conditions of constant temperature T and pressure P, chemical equilibrium occurs in a closed system (fixed mass) when the Gibbs free energy G of the reaction mixture is minimized. However, when chemical reactions occur under other conditions, other thermodynamic functions are minimized or maximized. For processes at constant T and volume V,…

GENESIS: new self-consistent models of exoplanetary spectra

NASA Astrophysics Data System (ADS)

Gandhi, Siddharth; Madhusudhan, Nikku

2017-12-01

We are entering the era of high-precision and high-resolution spectroscopy of exoplanets. Such observations herald the need for robust self-consistent spectral models of exoplanetary atmospheres to investigate intricate atmospheric processes and to make observable predictions. Spectral models of plane-parallel exoplanetary atmospheres exist, mostly adapted from other astrophysical applications, with different levels of sophistication and accuracy. There is a growing need for a new generation of models custom-built for exoplanets and incorporating state-of-the-art numerical methods and opacities. The present work is a step in this direction. Here we introduce GENESIS, a plane-parallel, self-consistent, line-by-line exoplanetary atmospheric modelling code that includes (a) formal solution of radiative transfer using the Feautrier method, (b) radiative-convective equilibrium with temperature correction based on the Rybicki linearization scheme, (c) latest absorption cross-sections, and (d) internal flux and external irradiation, under the assumptions of hydrostatic equilibrium, local thermodynamic equilibrium and thermochemical equilibrium. We demonstrate the code here with cloud-free models of giant exoplanetary atmospheres over a range of equilibrium temperatures, metallicities, C/O ratios and spanning non-irradiated and irradiated planets, with and without thermal inversions. We provide the community with theoretical emergent spectra and pressure-temperature profiles over this range, along with those for several known hot Jupiters. The code can generate self-consistent spectra at high resolution and has the potential to be integrated into general circulation and non-equilibrium chemistry models as it is optimized for efficiency and convergence. GENESIS paves the way for high-fidelity remote sensing of exoplanetary atmospheres at high resolution with current and upcoming observations.

The efficiency of driving chemical reactions by a physical non-equilibrium is kinetically controlled.

PubMed

Göppel, Tobias; Palyulin, Vladimir V; Gerland, Ulrich

2016-07-27

An out-of-equilibrium physical environment can drive chemical reactions into thermodynamically unfavorable regimes. Under prebiotic conditions such a coupling between physical and chemical non-equilibria may have enabled the spontaneous emergence of primitive evolutionary processes. Here, we study the coupling efficiency within a theoretical model that is inspired by recent laboratory experiments, but focuses on generic effects arising whenever reactant and product molecules have different transport coefficients in a flow-through system. In our model, the physical non-equilibrium is represented by a drift-diffusion process, which is a valid coarse-grained description for the interplay between thermophoresis and convection, as well as for many other molecular transport processes. As a simple chemical reaction, we consider a reversible dimerization process, which is coupled to the transport process by different drift velocities for monomers and dimers. Within this minimal model, the coupling efficiency between the non-equilibrium transport process and the chemical reaction can be analyzed in all parameter regimes. The analysis shows that the efficiency depends strongly on the Damköhler number, a parameter that measures the relative timescales associated with the transport and reaction kinetics. Our model and results will be useful for a better understanding of the conditions for which non-equilibrium environments can provide a significant driving force for chemical reactions in a prebiotic setting.

A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions.

PubMed

Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C; Brooks, Scott C; Pace, Molly N; Kim, Young-Jin; Jardine, Philip M; Watson, David B

2007-06-16

This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

A Pseudo-Temporal Multi-Grid Relaxation Scheme for Solving the Parabolized Navier-Stokes Equations

NASA Technical Reports Server (NTRS)

White, J. A.; Morrison, J. H.

1999-01-01

A multi-grid, flux-difference-split, finite-volume code, VULCAN, is presented for solving the elliptic and parabolized form of the equations governing three-dimensional, turbulent, calorically perfect and non-equilibrium chemically reacting flows. The space marching algorithms developed to improve convergence rate and or reduce computational cost are emphasized. The algorithms presented are extensions to the class of implicit pseudo-time iterative, upwind space-marching schemes. A full approximate storage, full multi-grid scheme is also described which is used to accelerate the convergence of a Gauss-Seidel relaxation method. The multi-grid algorithm is shown to significantly improve convergence on high aspect ratio grids.

Computer codes for thermal analysis of a solid rocket motor nozzle

NASA Technical Reports Server (NTRS)

Chauhan, Rajinder Singh

1988-01-01

A number of computer codes are available for performing thermal analysis of solid rocket motor nozzles. Aerotherm Chemical Equilibrium (ACE) computer program can be used to perform one-dimensional gas expansion to determine the state of the gas at each location of a nozzle. The ACE outputs can be used as input to a computer program called Momentum/Energy Integral Technique (MEIT) for predicting boundary layer development development, shear, and heating on the surface of the nozzle. The output from MEIT can be used as input to another computer program called Aerotherm Charring Material Thermal Response and Ablation Program (CMA). This program is used to calculate oblation or decomposition response of the nozzle material. A code called Failure Analysis Nonlinear Thermal and Structural Integrated Code (FANTASTIC) is also likely to be used for performing thermal analysis of solid rocket motor nozzles after the program is duly verified. A part of the verification work on FANTASTIC was done by using one and two dimension heat transfer examples with known answers. An attempt was made to prepare input for performing thermal analysis of the CCT nozzle using the FANTASTIC computer code. The CCT nozzle problem will first be solved by using ACE, MEIT, and CMA. The same problem will then be solved using FANTASTIC. These results will then be compared for verification of FANTASTIC.

Computer program determines chemical equilibria in complex systems

NASA Technical Reports Server (NTRS)

Gordon, S.; Zeleznik, F. J.

1966-01-01

Computer program numerically solves nonlinear algebraic equations for chemical equilibrium based on iteration equations independent of choice of components. This program calculates theoretical performance for frozen and equilibrium composition during expansion and Chapman-Jouguet flame properties, studies combustion, and designs hardware.

Algorithm For Hypersonic Flow In Chemical Equilibrium

NASA Technical Reports Server (NTRS)

Palmer, Grant

1989-01-01

Implicit, finite-difference, shock-capturing algorithm calculates inviscid, hypersonic flows in chemical equilibrium. Implicit formulation chosen because overcomes limitation on mathematical stability encountered in explicit formulations. For dynamical portion of problem, Euler equations written in conservation-law form in Cartesian coordinate system for two-dimensional or axisymmetric flow. For chemical portion of problem, equilibrium state of gas at each point in computational grid determined by minimizing local Gibbs free energy, subject to local conservation of molecules, atoms, ions, and total enthalpy. Major advantage: resulting algorithm naturally stable and captures strong shocks without help of artificial-dissipation terms to damp out spurious numerical oscillations.

Computer Program for Calculation of Complex Chemical Equilibrium Compositions, Rocket Performance, Incident and Reflected Shocks, and Chapman-Jouguet Detonations. Interim Revision, March 1976

NASA Technical Reports Server (NTRS)

Gordon, S.; Mcbride, B. J.

1976-01-01

A detailed description of the equations and computer program for computations involving chemical equilibria in complex systems is given. A free-energy minimization technique is used. The program permits calculations such as (1) chemical equilibrium for assigned thermodynamic states (T,P), (H,P), (S,P), (T,V), (U,V), or (S,V), (2) theoretical rocket performance for both equilibrium and frozen compositions during expansion, (3) incident and reflected shock properties, and (4) Chapman-Jouguet detonation properties. The program considers condensed species as well as gaseous species.

3D equilibrium reconstruction with islands

NASA Astrophysics Data System (ADS)

Cianciosa, M.; Hirshman, S. P.; Seal, S. K.; Shafer, M. W.

2018-04-01

This paper presents the development of a 3D equilibrium reconstruction tool and the results of the first-ever reconstruction of an island equilibrium. The SIESTA non-nested equilibrium solver has been coupled to the V3FIT 3D equilibrium reconstruction code. Computed from a coupled VMEC and SIESTA model, synthetic signals are matched to measured signals by finding an optimal set of equilibrium parameters. By using the normalized pressure in place of normalized flux, non-equilibrium quantities needed by diagnostic signals can be efficiently mapped to the equilibrium. The effectiveness of this tool is demonstrated by reconstructing an island equilibrium of a DIII-D inner wall limited L-mode case with an n = 1 error field applied. Flat spots in Thomson and ECE temperature diagnostics show the reconstructed islands have the correct size and phase. ).

First-principles Monte Carlo simulations of reaction equilibria in compressed vapors

DOE PAGES

Fetisov, Evgenii O.; Kuo, I-Feng William; Knight, Chris; ...

2016-06-13

Predictive modeling of reaction equilibria presents one of the grand challenges in the field of molecular simulation. Difficulties in the study of such systems arise from the need (i) to accurately model both strong, short-ranged interactions leading to the formation of chemical bonds and weak interactions arising from the environment, and (ii) to sample the range of time scales involving frequent molecular collisions, slow diffusion, and infrequent reactive events. Here we present a novel reactive first-principles Monte Carlo (RxFPMC) approach that allows for investigation of reaction equilibria without the need to prespecify a set of chemical reactions and their ideal-gasmore » equilibrium constants. We apply RxFPMC to investigate a nitrogen/oxygen mixture at T = 3000 K and p = 30 GPa, i.e., conditions that are present in atmospheric lightning strikes and explosions. The RxFPMC simulations show that the solvation environment leads to a significantly enhanced NO concentration that reaches a maximum when oxygen is present in slight excess. In addition, the RxFPMC simulations indicate the formation of NO 2 and N 2O in mole fractions approaching 1%, whereas N 3 and O 3 are not observed. Lastly, the equilibrium distributions obtained from the RxFPMC simulations agree well with those from a thermochemical computer code parametrized to experimental data.« less

First-principles Monte Carlo simulations of reaction equilibria in compressed vapors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fetisov, Evgenii O.; Kuo, I-Feng William; Knight, Chris

Predictive modeling of reaction equilibria presents one of the grand challenges in the field of molecular simulation. Difficulties in the study of such systems arise from the need (i) to accurately model both strong, short-ranged interactions leading to the formation of chemical bonds and weak interactions arising from the environment, and (ii) to sample the range of time scales involving frequent molecular collisions, slow diffusion, and infrequent reactive events. Here we present a novel reactive first-principles Monte Carlo (RxFPMC) approach that allows for investigation of reaction equilibria without the need to prespecify a set of chemical reactions and their ideal-gasmore » equilibrium constants. We apply RxFPMC to investigate a nitrogen/oxygen mixture at T = 3000 K and p = 30 GPa, i.e., conditions that are present in atmospheric lightning strikes and explosions. The RxFPMC simulations show that the solvation environment leads to a significantly enhanced NO concentration that reaches a maximum when oxygen is present in slight excess. In addition, the RxFPMC simulations indicate the formation of NO 2 and N 2O in mole fractions approaching 1%, whereas N 3 and O 3 are not observed. Lastly, the equilibrium distributions obtained from the RxFPMC simulations agree well with those from a thermochemical computer code parametrized to experimental data.« less

Cantera and Cantera Electrolyte Thermodynamics Objects

DOE Office of Scientific and Technical Information (OSTI.GOV)

John Hewson, Harry Moffat

Cantera is a suite of object-oriented software tools for problems involving chemical kinetics, thermodynamics, and/or transport processes. It is a multi-organizational effort to create and formulate high quality 0D and 1D constitutive modeling tools for reactive transport codes.Institutions involved with the effort include Sandia, MIT, Colorado School of Mines, U. Texas, NASA, and Oak Ridge National Labs. Specific to Sandia's contributions, the Cantera Electrolyte Thermo Objects (CETO) packages is comprised of add-on routines for Cantera that handle electrolyte thermochemistry and reactions within the overall Cantera package. Cantera is a C++ Cal Tech code that handles gas phase species transport, reaction,more » and thermodynamics. With this addition, Cantera can be extended to handle problems involving liquid phase reactions and transport in electrolyte systems, and phase equilibrium problemsinvolving concentrated electrolytes and gas/solid phases. A full treatment of molten salt thermodynamics and transport has also been implemented in CETO. The routines themselves consist of .cpp and .h files containing C++ objects that are derived from parent Cantera objects representing thermodynamic functions. They are linked unto the main Cantera libraries when requested by the user. As an addendum to the main thermodynamics objects, several utility applications are provided. The first is multiphase Gibbs free energy minimizer based on the vcs algorithm, called vcs_cantera. This code allows for the calculation of thermodynamic equilibrium in multiple phases at constant temperature and pressure. Note, a similar code capability exists already in Cantera. This version follows the same algorithm, but gas a different code-base starting point, and is used as a research tool for algorithm development. The second program, cttables, prints out tables of thermodynamic and kinetic information for thermodynamic and kinetic objects within Cantera. This program serves as a "Get the numbers out" utility for Cantera, and as such it is very useful as a verification tool. These add-on utilities are encapsulated into a directory structure named cantera_apps, whose installation uses autoconf and also utilizes Cantera's application environment (i.e., they utilize Cantera as a library).« less

Chemical equilibrium of ablation materials including condensed species

NASA Technical Reports Server (NTRS)

Stroud, C. W.; Brinkley, K. L.

1975-01-01

Equilibrium is determined by finding chemical composition with minimum free energy. Method of steepest descent is applied to quadratic representation of free-energy surface. Solution is initiated by selecting arbitrary set of mole fractions, from which point on free-energy surface is computed.

Chemistry Resolved Kinetic Flow Modeling of TATB Based Explosives

NASA Astrophysics Data System (ADS)

Vitello, Peter; Fried, Lawrence; Howard, Mike; Levesque, George; Souers, Clark

2011-06-01

Detonation waves in insensitive, TATB based explosives are believed to have multi-time scale regimes. The initial burn rate of such explosives has a sub-microsecond time scale. However, significant late-time slow release in energy is believed to occur due to diffusion limited growth of carbon. In the intermediate time scale concentrations of product species likely change from being in equilibrium to being kinetic rate controlled. We use the thermo-chemical code CHEETAH linked to ALE hydrodynamics codes to model detonations. We term our model chemistry resolved kinetic flow as CHEETAH tracks the time dependent concentrations of individual species in the detonation wave and calculate EOS values based on the concentrations. A validation suite of model simulations compared to recent high fidelity metal push experiments at ambient and cold temperatures has been developed. We present here a study of multi-time scale kinetic rate effects for these experiments. Prepared by LLNL under Contract DE-AC52-07NA27344.

Theoretical and computer models of detonation in solid explosives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tarver, C.M.; Urtiew, P.A.

1997-10-01

Recent experimental and theoretical advances in understanding energy transfer and chemical kinetics have led to improved models of detonation waves in solid explosives. The Nonequilibrium Zeldovich - von Neumann - Doring (NEZND) model is supported by picosecond laser experiments and molecular dynamics simulations of the multiphonon up-pumping and internal vibrational energy redistribution (IVR) processes by which the unreacted explosive molecules are excited to the transition state(s) preceding reaction behind the leading shock front(s). High temperature, high density transition state theory calculates the induction times measured by laser interferometric techniques. Exothermic chain reactions form product gases in highly excited vibrational states,more » which have been demonstrated to rapidly equilibrate via supercollisions. Embedded gauge and Fabry-Perot techniques measure the rates of reaction product expansion as thermal and chemical equilibrium is approached. Detonation reaction zone lengths in carbon-rich condensed phase explosives depend on the relatively slow formation of solid graphite or diamond. The Ignition and Growth reactive flow model based on pressure dependent reaction rates and Jones-Wilkins-Lee (JWL) equations of state has reproduced this nanosecond time resolved experimental data and thus has yielded accurate average reaction zone descriptions in one-, two- and three- dimensional hydrodynamic code calculations. The next generation reactive flow model requires improved equations of state and temperature dependent chemical kinetics. Such a model is being developed for the ALE3D hydrodynamic code, in which heat transfer and Arrhenius kinetics are intimately linked to the hydrodynamics.« less

Non-equilibrium reaction rates in chemical kinetic equations

NASA Astrophysics Data System (ADS)

Gorbachev, Yuriy

2018-05-01

Within the recently proposed asymptotic method for solving the Boltzmann equation for chemically reacting gas mixture, the chemical kinetic equations has been derived. Corresponding one-temperature non-equilibrium reaction rates are expressed in terms of specific heat capacities of the species participate in the chemical reactions, bracket integrals connected with the internal energy transfer in inelastic non-reactive collisions and energy transfer coefficients. Reactions of dissociation/recombination of homonuclear and heteronuclear diatomic molecules are considered. It is shown that all reaction rates are the complex functions of the species densities, similarly to the unimolecular reaction rates. For determining the rate coefficients it is recommended to tabulate corresponding bracket integrals, additionally to the equilibrium rate constants. Correlation of the obtained results with the irreversible thermodynamics is established.

Do high school chemistry examinations inhibit deeper level understanding of dynamic reversible chemical reactions?

NASA Astrophysics Data System (ADS)

Wheeldon, R.; Atkinson, R.; Dawes, A.; Levinson, R.

2012-07-01

Background and purpose : Chemistry examinations can favour the deployment of algorithmic procedures like Le Chatelier's Principle (LCP) rather than reasoning using chemical principles. This study investigated the explanatory resources which high school students use to answer equilibrium problems and whether the marks given for examination answers require students to use approaches beyond direct application of LCP. Sample : The questionnaire was administered to 162 students studying their first year of advanced chemistry (age 16/17) in three high achieving London high schools. Design and methods : The students' explanations of reversible chemical systems were inductively coded to identify the explanatory approaches used and interviews with 13 students were used to check for consistency. AS level examination questions on reversible reactions were analysed to identify the types of explanations sought and the students' performance in these examinations was compared to questionnaire answers. Results : 19% of students used a holistic explanatory approach: when the rates of forward and reverse reactions are correctly described, recognising their simultaneous and mutually dependent nature. 36% used a mirrored reactions approach when the connected nature of the forward and reverse reactions is identified, but not their mutual dependency. 42% failed to recognize the interdependence of forward and reverse reactions (reactions not connected approach). Only 4% of marks for AS examination questions on reversible chemical systems asked for responses which went beyond either direct application of LCP or recall of equilibrium knowledge. 37% of students attained an A grade in their AS national examinations. Conclusions : Examinations favour the application of LCP making it possible to obtain the highest grade with little understanding of reversible chemical systems beyond a direct application of this algorithm. Therefore students' understanding may be attenuated so that they are unable to use kinetic sub-micro level ideas which will support the building of deeper energetic conceptions at university.

Treatment of Chemical Equilibrium without Using Thermodynamics or Statistical Mechanics.

ERIC Educational Resources Information Center

Nelson, P. G.

1986-01-01

Discusses the conventional approaches to teaching about chemical equilibrium in advanced physical chemistry courses. Presents an alternative approach to the treatment of this concept by using Boltzmann's distribution law. Lists five advantages to using this method as compared with the other approaches. (TW)

Activity Enhancement Based on the Chemical Equilibrium of Multiple-Subunit Nitrile Hydratase from Bordetella petrii.

PubMed

Liu, Yi; Liu, Ping; Lin, Lu; Zhao, Yueqin; Zhong, Wenjuan; Wu, Lunjie; Zhou, Zhemin; Sun, Weifeng

2016-09-01

The maturation mechanism of nitrile hydratase (NHase) of Pseudomonas putida NRRL-18668 was discovered and named as "self-subunit swapping." Since the NHase of Bordetella petrii DSM 12804 is similar to that of P. putida, the NHase maturation of B. petrii is proposed to be the same as that of P. putida. However, there is no further information on the application of NHase according to these findings. We successfully rapidly purified NHase and its activator through affinity his tag, and found that the cell extracts of NHase possessed multiple types of protein ingredients including α, β, α2β2, and α(P14K)2 who were in a state of chemical equilibrium. Furthermore, the activity was significantly enhanced through adding extra α(P14K)2 to the cell extracts of NHase according to the chemical equilibrium. Our findings are useful for the activity enhancement of multiple-subunit enzyme and for the first time significantly increased the NHase activity according to the chemical equilibrium.

Implicit Coupling Approach for Simulation of Charring Carbon Ablators

NASA Technical Reports Server (NTRS)

Chen, Yih-Kanq; Gokcen, Tahir

2013-01-01

This study demonstrates that coupling of a material thermal response code and a flow solver with nonequilibrium gas/surface interaction for simulation of charring carbon ablators can be performed using an implicit approach. The material thermal response code used in this study is the three-dimensional version of Fully Implicit Ablation and Thermal response program, which predicts charring material thermal response and shape change on hypersonic space vehicles. The flow code solves the reacting Navier-Stokes equations using Data Parallel Line Relaxation method. Coupling between the material response and flow codes is performed by solving the surface mass balance in flow solver and the surface energy balance in material response code. Thus, the material surface recession is predicted in flow code, and the surface temperature and pyrolysis gas injection rate are computed in material response code. It is demonstrated that the time-lagged explicit approach is sufficient for simulations at low surface heating conditions, in which the surface ablation rate is not a strong function of the surface temperature. At elevated surface heating conditions, the implicit approach has to be taken, because the carbon ablation rate becomes a stiff function of the surface temperature, and thus the explicit approach appears to be inappropriate resulting in severe numerical oscillations of predicted surface temperature. Implicit coupling for simulation of arc-jet models is performed, and the predictions are compared with measured data. Implicit coupling for trajectory based simulation of Stardust fore-body heat shield is also conducted. The predicted stagnation point total recession is compared with that predicted using the chemical equilibrium surface assumption

A new nuclide transport model in soil in the GENII-LIN health physics code

NASA Astrophysics Data System (ADS)

Teodori, F.

2017-11-01

The nuclide soil transfer model, originally included in the GENII-LIN software system, was intended for residual contamination from long term activities and from waste form degradation. Short life nuclides were supposed absent or at equilibrium with long life parents. Here we present an enhanced soil transport model, where short life nuclide contributions are correctly accounted. This improvement extends the code capabilities to handle incidental release of contaminant to soil, by evaluating exposure since the very beginning of the contamination event, before the radioactive decay chain equilibrium is reached.

Thermodynamic equilibrium-air correlations for flowfield applications

NASA Technical Reports Server (NTRS)

Zoby, E. V.; Moss, J. N.

1981-01-01

Equilibrium-air thermodynamic correlations have been developed for flowfield calculation procedures. A comparison between the postshock results computed by the correlation equations and detailed chemistry calculations is very good. The thermodynamic correlations are incorporated in an approximate inviscid flowfield code with a convective heating capability for the purpose of defining the thermodynamic environment through the shock layer. Comparisons of heating rates computed by the approximate code and a viscous-shock-layer method are good. In addition to presenting the thermodynamic correlations, the impact of several viscosity models on the convective heat transfer is demonstrated.

Rapid computation of chemical equilibrium composition - An application to hydrocarbon combustion

NASA Technical Reports Server (NTRS)

Erickson, W. D.; Prabhu, R. K.

1986-01-01

A scheme for rapidly computing the chemical equilibrium composition of hydrocarbon combustion products is derived. A set of ten governing equations is reduced to a single equation that is solved by the Newton iteration method. Computation speeds are approximately 80 times faster than the often used free-energy minimization method. The general approach also has application to many other chemical systems.

Convective Dynamics and Disequilibrium Chemistry in the Atmospheres of Giant Planets and Brown Dwarfs

NASA Astrophysics Data System (ADS)

Bordwell, Baylee; Brown, Benjamin P.; Oishi, Jeffrey S.

2018-02-01

Disequilibrium chemical processes significantly affect the spectra of substellar objects. To study these effects, dynamical disequilibrium has been parameterized using the quench and eddy diffusion approximations, but little work has been done to explore how these approximations perform under realistic planetary conditions in different dynamical regimes. As a first step toward addressing this problem, we study the localized, small-scale convective dynamics of planetary atmospheres by direct numerical simulation of fully compressible hydrodynamics with reactive tracers using the Dedalus code. Using polytropically stratified, plane-parallel atmospheres in 2D and 3D, we explore the quenching behavior of different abstract chemical species as a function of the dynamical conditions of the atmosphere as parameterized by the Rayleigh number. We find that in both 2D and 3D, chemical species quench deeper than would be predicted based on simple mixing-length arguments. Instead, it is necessary to employ length scales based on the chemical equilibrium profile of the reacting species in order to predict quench points and perform chemical kinetics modeling in 1D. Based on the results of our simulations, we provide a new length scale, derived from the chemical scale height, that can be used to perform these calculations. This length scale is simple to calculate from known chemical data and makes reasonable predictions for our dynamical simulations.

3D equilibrium reconstruction with islands

DOE PAGES

Cianciosa, M.; Hirshman, S. P.; Seal, S. K.; ...

2018-02-15

This study presents the development of a 3D equilibrium reconstruction tool and the results of the first-ever reconstruction of an island equilibrium. The SIESTA non-nested equilibrium solver has been coupled to the V3FIT 3D equilibrium reconstruction code. Computed from a coupled VMEC and SIESTA model, synthetic signals are matched to measured signals by finding an optimal set of equilibrium parameters. By using the normalized pressure in place of normalized flux, non-equilibrium quantities needed by diagnostic signals can be efficiently mapped to the equilibrium. The effectiveness of this tool is demonstrated by reconstructing an island equilibrium of a DIII-D inner wallmore » limited L-mode case with an n = 1 error field applied. Finally, flat spots in Thomson and ECE temperature diagnostics show the reconstructed islands have the correct size and phase.« less

3D equilibrium reconstruction with islands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cianciosa, M.; Hirshman, S. P.; Seal, S. K.

This study presents the development of a 3D equilibrium reconstruction tool and the results of the first-ever reconstruction of an island equilibrium. The SIESTA non-nested equilibrium solver has been coupled to the V3FIT 3D equilibrium reconstruction code. Computed from a coupled VMEC and SIESTA model, synthetic signals are matched to measured signals by finding an optimal set of equilibrium parameters. By using the normalized pressure in place of normalized flux, non-equilibrium quantities needed by diagnostic signals can be efficiently mapped to the equilibrium. The effectiveness of this tool is demonstrated by reconstructing an island equilibrium of a DIII-D inner wallmore » limited L-mode case with an n = 1 error field applied. Finally, flat spots in Thomson and ECE temperature diagnostics show the reconstructed islands have the correct size and phase.« less

Development of 19F-NMR chemical shift detection of DNA B-Z equilibrium using 19F-NMR.

PubMed

Nakamura, S; Yang, H; Hirata, C; Kersaudy, F; Fujimoto, K

2017-06-28

Various DNA conformational changes are in correlation with biological events. In particular, DNA B-Z equilibrium showed a high correlation with translation and transcription. In this study, we developed a DNA probe containing 5-trifluoromethylcytidine or 5-trifluoromethylthymidine to detect DNA B-Z equilibrium using 19 F-NMR. Its probe enabled the quantitative detection of B-, Z-, and ss-DNA based on 19 F-NMR chemical shift change.

Self-organization of grafted polyelectrolyte layers via the coupling of chemical equilibrium and physical interactions.

PubMed

Tagliazucchi, Mario; de la Cruz, Mónica Olvera; Szleifer, Igal

2010-03-23

The competition between chemical equilibrium, for example protonation, and physical interactions determines the molecular organization and functionality of biological and synthetic systems. Charge regulation by displacement of acid-base equilibrium induced by changes in the local environment provides a feedback mechanism that controls the balance between electrostatic, van der Waals, steric interactions and molecular organization. Which strategies do responsive systems follow to globally optimize chemical equilibrium and physical interactions? We address this question by theoretically studying model layers of end-grafted polyacids. These layers spontaneously form self-assembled aggregates, presenting domains of controlled local pH and whose morphologies can be manipulated by the composition of the solution in contact with the film. Charge regulation stabilizes micellar domains over a wide range of pH by reducing the local charge in the aggregate at the cost of chemical free energy and gaining in hydrophobic interactions. This balance determines the boundaries between different aggregate morphologies. We show that a qualitatively new form of organization arises from the coupling between physical interactions and protonation equilibrium. This optimization strategy presents itself with polyelectrolytes coexisting in two different and well-defined protonation states. Our results underline the need of considering the coupling between chemical equilibrium and physical interactions due to their highly nonadditive behavior. The predictions provide guidelines for the creation of responsive polymer layers presenting self-organized patterns with functional properties and they give insights for the understanding of competing interactions in highly inhomogeneous and constrained environments such as those relevant in nanotechnology and those responsible for biological cells function.

Chemical Equilibrium and Polynomial Equations: Beware of Roots.

ERIC Educational Resources Information Center

Smith, William R.; Missen, Ronald W.

1989-01-01

Describes two easily applied mathematical theorems, Budan's rule and Rolle's theorem, that in addition to Descartes's rule of signs and intermediate-value theorem, are useful in chemical equilibrium. Provides examples that illustrate the use of all four theorems. Discusses limitations of the polynomial equation representation of chemical…

Problem Solving and Chemical Equilibrium: Successful versus Unsuccessful Performance.

ERIC Educational Resources Information Center

Camacho, Moises; Good, Ron

1989-01-01

Describes the problem-solving behaviors of experts and novices engaged in solving seven chemical equilibrium problems. Lists 27 behavioral tendencies of successful and unsuccessful problem solvers. Discusses several implications for a problem solving theory, think-aloud techniques, adequacy of the chemistry domain, and chemistry instruction.…

Numerical solution of Space Shuttle Orbiter flow field including real gas effects

NASA Technical Reports Server (NTRS)

Prabhu, D. K.; Tannehill, J. C.

1984-01-01

The hypersonic, laminar flow around the Space Shuttle Orbiter has been computed for both an ideal gas (gamma = 1.2) and equilibrium air using a real-gas, parabolized Navier-Stokes code. This code employs a generalized coordinate transformation; hence, it places no restrictions on the orientation of the solution surfaces. The initial solution in the nose region was computed using a 3-D, real-gas, time-dependent Navier-Stokes code. The thermodynamic and transport properties of equilibrium air were obtained from either approximate curve fits or a table look-up procedure. Numerical results are presented for flight conditions corresponding to the STS-3 trajectory. The computed surface pressures and convective heating rates are compared with data from the STS-3 flight.

Modelling of chemical degradation of blended cement-based materials by leaching cycles with Callovo-Oxfordian porewater

NASA Astrophysics Data System (ADS)

Olmeda, Javier; Henocq, Pierre; Giffaut, Eric; Grivé, Mireia

2017-06-01

The present work describes a thermodynamic model based on pore water replacement cycles to simulate the chemical evolution of blended cement (BFS + FA) by interaction with external Callovo-Oxfordian (COx) pore water. In the framework of the radioactive waste management, the characterization of the radionuclide behaviour (solubility/speciation, adsorption) in cementitious materials needs to be done for several chemical degradation states (I to IV). In particular, in the context of the deep geological radioactive waste disposal project (Cigéo), cement-based materials will be chemically evolved with time in contact with the host-rock (COx formation). The objective of this study is to provide an equilibrium solution composition for each degradation state for a CEM-V cement-based material to support the adsorption and diffusion experiments reproducing any state of degradation. Calculations have been performed at 25 °C using the geochemical code PhreeqC and an up-to-date thermodynamic database (ThermoChimie v.9.0.b) coupled to SIT approach for ionic strength correction. The model replicates experimental data with accuracy. The approach followed in this study eases the analysis of the chemical evolution in both aqueous and solid phase to obtain a fast assessment of the geochemical effects associated to an external water intrusion of variable composition on concrete structures.

High speed turbulent reacting flows: DNS and LES

NASA Technical Reports Server (NTRS)

Givi, Peyman

1990-01-01

Work on understanding the mechanisms of mixing and reaction in high speed turbulent reacting flows was continued. Efforts, in particular, were concentrated on taking advantage of modern computational methods to simulate high speed turbulent flows. In doing so, two methodologies were used: large eddy simulations (LES) and direct numerical simulations (DNS). In the work related with LES the objective is to study the behavior of the probability density functions (pdfs) of scalar properties within the subgrid in reacting turbulent flows. The data base obtained by DNS for a detailed study of the pdf characteristics within the subgrid was used. Simulations are performed for flows under various initializations to include the effects of compressibility on mixing and chemical reactions. In the work related with DNS, a two-dimensional temporally developing high speed mixing layer under the influence of a second-order non-equilibrium chemical reaction of the type A + B yields products + heat was considered. Simulations were performed with different magnitudes of the convective Mach numbers and with different chemical kinetic parameters for the purpose of examining the isolated effects of the compressibility and the heat released by the chemical reactions on the structure of the layer. A full compressible code was developed and utilized, so that the coupling between mixing and chemical reactions is captured in a realistic manner.

Thermodynamics and Kinetics of Chemical Equilibrium in Solution.

ERIC Educational Resources Information Center

Leenson, I. A.

1986-01-01

Discusses theory of thermodynamics of the equilibrium in solution and dissociation-dimerization kinetics. Describes experimental procedure including determination of molar absorptivity and equilibrium constant, reaction enthalpy, and kinetics of the dissociation-dimerization reaction. (JM)

Prediction of chemical speciation in stabilized/solidified wastes using a general chemical equilibrium model. Part 1: Chemical representation of cementitious binders

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, J.Y.; Batchelor, B.

1999-03-01

Chemical equilibrium models are useful to evaluate stabilized/solidified waste. A general equilibrium model, SOLTEQ, a modified version of MINTEQA2 for S/S, was applied to predict the chemical speciations in the stabilized/solidified waste form. A method was developed to prepare SOLTEQ input data that can chemically represent various stabilized/solidified binders. Taylor`s empirical model was used to describe partitioning of alkali ions. As a result, SOLTEQ could represent chemical speciation in pure binder systems such as ordinary Portland cement and ordinary Portland cement + fly ash. Moreover, SOLTEQ could reasonably describe the effects on the chemical speciation due to variations in water-to-cement,more » fly ash contents, and hydration times of various binder systems. However, this application of SOLTEQ was not accurate in predicting concentrations of Ca, Si, and SO{sub 4} ions, due to uncertainties in the CSH solubility model and K{sub sp} values of cement hydrates at high pH values.« less

Teaching Chemical Equilibrium with the Jigsaw Technique

ERIC Educational Resources Information Center

Doymus, Kemal

2008-01-01

This study investigates the effect of cooperative learning (jigsaw) versus individual learning methods on students' understanding of chemical equilibrium in a first-year general chemistry course. This study was carried out in two different classes in the department of primary science education during the 2005-2006 academic year. One of the classes…

Computer program determines chemical composition of physical system at equilibrium

NASA Technical Reports Server (NTRS)

Kwong, S. S.

1966-01-01

FORTRAN 4 digital computer program calculates equilibrium composition of complex, multiphase chemical systems. This is a free energy minimization method with solution of the problem reduced to mathematical operations, without concern for the chemistry involved. Also certain thermodynamic properties are determined as byproducts of the main calculations.

Control of Chemical Equilibrium by Solvent: A Basis for Teaching Physical Chemistry of Solutions

ERIC Educational Resources Information Center

Prezhdo, Oleg V.; Craig, Colleen F.; Fialkov, Yuriy; Prezhdo, Victor V.

2007-01-01

The study demonstrates that the solvent present in a system can highly alter and control the chemical equilibrium of a system. The results show that the dipole moment and polarizibility of a system can be highly altered by using different mixed solvents.

Learning of Chemical Equilibrium through Modelling-Based Teaching

ERIC Educational Resources Information Center

Maia, Poliana Flavia; Justi, Rosaria

2009-01-01

This paper presents and discusses students' learning process of chemical equilibrium from a modelling-based approach developed from the use of the "Model of Modelling" diagram. The investigation was conducted in a regular classroom (students 14-15 years old) and aimed at discussing how modelling-based teaching can contribute to students…

Strategies Reported Used by Instructors to Address Student Alternate Conceptions in Chemical Equilibrium

ERIC Educational Resources Information Center

Piquette, Jeff S.; Heikkinen, Henry W.

2005-01-01

This study explores general-chemistry instructors' awareness of and ability to identify and address common student learning obstacles in chemical equilibrium. Reported instructor strategies directed at remediating student alternate conceptions were investigated and compared with successful, literature-based conceptual change methods. Fifty-two…

Teaching the Concept of Gibbs Energy Minimization through Its Application to Phase-Equilibrium Calculation

ERIC Educational Resources Information Center

Privat, Romain; Jaubert, Jean-Noe¨l; Berger, Etienne; Coniglio, Lucie; Lemaitre, Ce´cile; Meimaroglou, Dimitrios; Warth, Vale´rie

2016-01-01

Robust and fast methods for chemical or multiphase equilibrium calculation are routinely needed by chemical-process engineers working on sizing or simulation aspects. Yet, while industrial applications essentially require calculation tools capable of discriminating between stable and nonstable states and converging to nontrivial solutions,…

Evaluating role of interactive visualization tool in improving students' conceptual understanding of chemical equilibrium

NASA Astrophysics Data System (ADS)

Sampath Kumar, Bharath

The purpose of this study is to examine the role of partnering visualization tool such as simulation towards development of student's concrete conceptual understanding of chemical equilibrium. Students find chemistry concepts abstract, especially at the microscopic level. Chemical equilibrium is one such topic. While research studies have explored effectiveness of low tech instructional strategies such as analogies, jigsaw, cooperative learning, and using modeling blocks, fewer studies have explored the use of visualization tool such as simulations in the context of dynamic chemical equilibrium. Research studies have identified key reasons behind misconceptions such as lack of systematic understanding of foundational chemistry concepts, failure to recognize the system is dynamic, solving numerical problems on chemical equilibrium in an algorithmic fashion, erroneous application Le Chatelier's principle (LCP) etc. Kress et al. (2001) suggested that external representation in the form of visualization is more than a tool for learning, because it enables learners to make meanings or express their ideas which cannot be readily done so through a verbal representation alone. Mixed method study design was used towards data collection. The qualitative portion of the study is aimed towards understanding the change in student's mental model before and after the intervention. A quantitative instrument was developed based on common areas of misconceptions identified by research studies. A pilot study was conducted prior to the actual study to obtain feedback from students on the quantitative instrument and the simulation. Participants for the pilot study were sampled from a single general chemistry class. Following the pilot study, the research study was conducted with a total of 27 students (N=15 in experimental group and N=12 in control group). Prior to participating in the study, students have completed their midterm test on the topic of chemical equilibrium. Qualitative interviews pre and post revealed students' mental model or thought process towards chemical equilibrium. Simulations used in the study were developed using the SCRATCH software platform. In order to test the effect of visualization tool on students' conceptual understanding of chemical equilibrium, an ANCOVA analysis was conducted. Results from a one-factor ANCOVA showed posttest scores were significantly higher for the experimental group (Mpostadj. = 7.27 SDpost = 1.387) relative to the control group (Mpostadj. = 2.67, SDpost = 1.371) after adjusting for pretest scores, F (1,24) = 71.82, MSE = 1.497, p = 0.03, eta 2p = 0.75, d = 3.33. Cohen's d was converted to an attenuated effect size d* using the procedure outlined in Thompson (2006). The adjusted (for pretest scores) group mean difference estimate without measure error correction for the posttest scores and the pretest scores was 4.2 with a Cohen's d = 3.04. An alternate approach reported in Cho and Preacher (2015) was used to determine effect size. The adjusted (for pretest scores) group mean difference estimate with measurement error correction only for the posttest scores (but not with measurement error correction for the pretest scores) was 4.99 with a Cohen's d = 3.61. Finally, the adjusted (for pretest scores) group mean difference estimate with measurement error correction for both pretest and posttest scores was 4.23 with a Cohen's d = 3.07. From a quantitative perspective, these effect size indicate a strong relationship between the experimental intervention provided and students' conceptual understanding of chemical equilibrium concepts. That is, those students who received the experimental intervention had exceptionally higher. KEYWORDS: Chemical Equilibrium, Visualization, Alternate Conceptions, Ontological Shift. Simulations.

Remarks on the chemical Fokker-Planck and Langevin equations: Nonphysical currents at equilibrium.

PubMed

Ceccato, Alessandro; Frezzato, Diego

2018-02-14

The chemical Langevin equation and the associated chemical Fokker-Planck equation are well-known continuous approximations of the discrete stochastic evolution of reaction networks. In this work, we show that these approximations suffer from a physical inconsistency, namely, the presence of nonphysical probability currents at the thermal equilibrium even for closed and fully detailed-balanced kinetic schemes. An illustration is given for a model case.

Equilibrium Partitioning Sediment Benchmarks (ESBs) for the ...

EPA Pesticide Factsheets

This document describes procedures to determine the concentrations of nonionic organic chemicals in sediment interstitial waters. In previous ESB documents, the general equilibrium partitioning (EqP) approach was chosen for the derivation of sediment benchmarks because it accounts for the varying bioavailability of chemicals in different sediments and allows for the incorporation of the appropriate biological effects concentration. This provides for the derivation of benchmarks that are causally linked to the specific chemical, applicable across sediments, and appropriately protective of benthic organisms.  This equilibrium partitioning sediment benchmark (ESB) document was prepared by scientists from the Atlantic Ecology Division, Mid-Continent Ecology Division, and Western Ecology Division, the Office of Water, and private consultants. The document describes procedures to determine the interstitial water concentrations of nonionic organic chemicals in contaminated sediments. Based on these concentrations, guidance is provided on the derivation of toxic units to assess whether the sediments are likely to cause adverse effects to benthic organisms. The equilibrium partitioning (EqP) approach was chosen because it is based on the concentrations of chemical(s) that are known to be harmful and bioavailable in the environment.  This document, and five others published over the last nine years, will be useful for the Program Offices, including Superfund, a

The Yambo code: a comprehensive tool to perform ab-initio simulations of equilibrium and out-of-equilibrium properties

NASA Astrophysics Data System (ADS)

Marini, Andrea

Density functional theory and many-body perturbation theory methods (such as GW and Bethe-Selpether equation) are standard approaches to the equilibrium ground and excited state properties of condensed matter systems, surfaces, molecules and other several kind of materials. At the same time ultra-fast optical spectroscopy is becoming a widely used and powerful tool for the observation of the out-of-equilibrium dynamical processes. In this case the theoretical tools (such as the Baym-Kadanoff equation) are well known but, only recently, have been merged with the ab-Initio approach. And, for this reason, highly parallel and efficient codes are lacking. Nevertheless, the combination of these two areas of research represents, for the ab-initio community, a challenging prespective as it requires the development of advanced theoretical, methodological and numerical tools. Yambo is a popular community software implementing the above methods using plane-waves and pseudo-potentials. Yambo is available to the community as open-source software, and oriented to high-performance computing. The Yambo project aims at making the simulation of these equilibrium and out-of-equilibrium complex processes available to a wide community of users. Indeed the code is used, in practice, in many countries and well beyond the European borders. Yambo is a member of the suite of codes of the MAX European Center of Excellence (Materials design at the exascale) . It is also used by the user facilities of the European Spectroscopy Facility and of the NFFA European Center (nanoscience foundries & fine analysis). In this talk I will discuss some recent numerical and methodological developments that have been implemented in Yambo towards to exploitation of next generation HPC supercomputers. In particular, I will present the hybrid MPI+OpenMP parallelization and the specific case of the response function calculation. I will also discuss the future plans of the Yambo project and its potential use as tool for science dissemination, also in third world countries. Etsf, MAX European Center of Excellence and NFFA European Center.

Supersonic flow of chemically reacting gas-particle mixtures. Volume 1: A theoretical analysis and development of the numerical solution

NASA Technical Reports Server (NTRS)

Penny, M. M.; Smith, S. D.; Anderson, P. G.; Sulyma, P. R.; Pearson, M. L.

1976-01-01

A numerical solution for chemically reacting supersonic gas-particle flows in rocket nozzles and exhaust plumes was described. The gas-particle flow solution is fully coupled in that the effects of particle drag and heat transfer between the gas and particle phases are treated. Gas and particles exchange momentum via the drag exerted on the gas by the particles. Energy is exchanged between the phases via heat transfer (convection and/or radiation). Thermochemistry calculations (chemical equilibrium, frozen or chemical kinetics) were shown to be uncoupled from the flow solution and, as such, can be solved separately. The solution to the set of governing equations is obtained by utilizing the method of characteristics. The equations cast in characteristic form are shown to be formally the same for ideal, frozen, chemical equilibrium and chemical non-equilibrium reacting gas mixtures. The particle distribution is represented in the numerical solution by a finite distribution of particle sizes.

Principal component analysis acceleration of rovibrational coarse-grain models for internal energy excitation and dissociation

NASA Astrophysics Data System (ADS)

Bellemans, Aurélie; Parente, Alessandro; Magin, Thierry

2018-04-01

The present work introduces a novel approach for obtaining reduced chemistry representations of large kinetic mechanisms in strong non-equilibrium conditions. The need for accurate reduced-order models arises from compression of large ab initio quantum chemistry databases for their use in fluid codes. The method presented in this paper builds on existing physics-based strategies and proposes a new approach based on the combination of a simple coarse grain model with Principal Component Analysis (PCA). The internal energy levels of the chemical species are regrouped in distinct energy groups with a uniform lumping technique. Following the philosophy of machine learning, PCA is applied on the training data provided by the coarse grain model to find an optimally reduced representation of the full kinetic mechanism. Compared to recently published complex lumping strategies, no expert judgment is required before the application of PCA. In this work, we will demonstrate the benefits of the combined approach, stressing its simplicity, reliability, and accuracy. The technique is demonstrated by reducing the complex quantum N2(g+1Σ) -N(S4u ) database for studying molecular dissociation and excitation in strong non-equilibrium. Starting from detailed kinetics, an accurate reduced model is developed and used to study non-equilibrium properties of the N2(g+1Σ) -N(S4u ) system in shock relaxation simulations.

Solute transport with multiple equilibrium-controlled or kinetically controlled chemical reactions

USGS Publications Warehouse

Friedly, John C.; Rubin, Jacob

1992-01-01

A new approach is applied to the problem of modeling solute transport accompanied by many chemical reactions. The approach, based on concepts of the concentration space and its stoichiometric subspaces, uses elements of the subspaces as primary dependent variables. It is shown that the resulting model equations are compact in form, isolate the chemical reaction expressions from flow expressions, and can be used for either equilibrium or kinetically controlled reactions. The implications of the results on numerical algorithms for solving the equations are discussed. The application of the theory is illustrated throughout with examples involving a simple but broadly representative set of reactions previously considered in the literature. Numerical results are presented for four interconnected reactions: a homogeneous complexation reaction, two sorption reactions, and a dissolution/precipitation reaction. Three cases are considered: (1) four kinetically controlled reactions, (2) four equilibrium-controlled reactions, and (3) a system with two kinetically controlled reactions and two equilibrium-controlled reactions.

Computer program to solve two-dimensional shock-wave interference problems with an equilibrium chemically reacting air model

NASA Technical Reports Server (NTRS)

Glass, Christopher E.

1990-01-01

The computer program EASI, an acronym for Equilibrium Air Shock Interference, was developed to calculate the inviscid flowfield, the maximum surface pressure, and the maximum heat flux produced by six shock wave interference patterns on a 2-D, cylindrical configuration. Thermodynamic properties of the inviscid flowfield are determined using either an 11-specie, 7-reaction equilibrium chemically reacting air model or a calorically perfect air model. The inviscid flowfield is solved using the integral form of the conservation equations. Surface heating calculations at the impingement point for the equilibrium chemically reacting air model use variable transport properties and specific heat. However, for the calorically perfect air model, heating rate calculations use a constant Prandtl number. Sample calculations of the six shock wave interference patterns, a listing of the computer program, and flowcharts of the programming logic are included.

Computer program to solve two-dimensional shock-wave interference problems with an equilibrium chemically reacting air model

NASA Astrophysics Data System (ADS)

Glass, Christopher E.

1990-08-01

The computer program EASI, an acronym for Equilibrium Air Shock Interference, was developed to calculate the inviscid flowfield, the maximum surface pressure, and the maximum heat flux produced by six shock wave interference patterns on a 2-D, cylindrical configuration. Thermodynamic properties of the inviscid flowfield are determined using either an 11-specie, 7-reaction equilibrium chemically reacting air model or a calorically perfect air model. The inviscid flowfield is solved using the integral form of the conservation equations. Surface heating calculations at the impingement point for the equilibrium chemically reacting air model use variable transport properties and specific heat. However, for the calorically perfect air model, heating rate calculations use a constant Prandtl number. Sample calculations of the six shock wave interference patterns, a listing of the computer program, and flowcharts of the programming logic are included.

Confinement properties of tokamak plasmas with extended regions of low magnetic shear

NASA Astrophysics Data System (ADS)

Graves, J. P.; Cooper, W. A.; Kleiner, A.; Raghunathan, M.; Neto, E.; Nicolas, T.; Lanthaler, S.; Patten, H.; Pfefferle, D.; Brunetti, D.; Lutjens, H.

2017-10-01

Extended regions of low magnetic shear can be advantageous to tokamak plasmas. But the core and edge can be susceptible to non-resonant ideal fluctuations due to the weakened restoring force associated with magnetic field line bending. This contribution shows how saturated non-linear phenomenology, such as 1 / 1 Long Lived Modes, and Edge Harmonic Oscillations associated with QH-modes, can be modelled accurately using the non-linear stability code XTOR, the free boundary 3D equilibrium code VMEC, and non-linear analytic theory. That the equilibrium approach is valid is particularly valuable because it enables advanced particle confinement studies to be undertaken in the ordinarily difficult environment of strongly 3D magnetic fields. The VENUS-LEVIS code exploits the Fourier description of the VMEC equilibrium fields, such that full Lorenzian and guiding centre approximated differential operators in curvilinear angular coordinates can be evaluated analytically. Consequently, the confinement properties of minority ions such as energetic particles and high Z impurities can be calculated accurately over slowing down timescales in experimentally relevant 3D plasmas.

A General Method for Automatic Computation of Equilibrium Compositions and Theoretical Rocket Performance of Propellants

NASA Technical Reports Server (NTRS)

Gordon, Sanford; Zeleznik, Frank J.; Huff, Vearl N.

1959-01-01

A general computer program for chemical equilibrium and rocket performance calculations was written for the IBM 650 computer with 2000 words of drum storage, 60 words of high-speed core storage, indexing registers, and floating point attachments. The program is capable of carrying out combustion and isentropic expansion calculations on a chemical system that may include as many as 10 different chemical elements, 30 reaction products, and 25 pressure ratios. In addition to the equilibrium composition, temperature, and pressure, the program calculates specific impulse, specific impulse in vacuum, characteristic velocity, thrust coefficient, area ratio, molecular weight, Mach number, specific heat, isentropic exponent, enthalpy, entropy, and several thermodynamic first derivatives.

Numerical study of chemically reacting viscous flow relevant to pulsed detonation engines

NASA Astrophysics Data System (ADS)

Yi, Tae-Hyeong

2005-11-01

A computational fluid dynamics code for two-dimensional, multi-species, laminar Navier-Stokes equations is developed to simulate a recently proposed engine concept for a pulsed detonation based propulsion system and to investigate the feasibility of the engine of the concept. The governing equations that include transport phenomena such as viscosity, thermal conduction and diffusion are coupled with chemical reactions. The gas is assumed to be thermally perfect and in chemically non-equilibrium. The stiffness due to coupling the fluid dynamics and the chemical kinetics is properly taken care of by using a time-operator splitting method and a variable coefficient ordinary differential equation solver. A second-order Roe scheme with a minmod limiter is explicitly used for space descretization, while a second-order, two-step Runge-Kutta method is used for time descretization. In space integration, a finite volume method and a cell-centered scheme are employed. The first-order derivatives in the equations of transport properties are discretized by a central differencing with Green's theorem. Detailed chemistry is involved in this study. Two chemical reaction mechanisms are extracted from GRI-Mech, which are forty elementary reactions with thirteen species for a hydrogen-air mixture and twenty-seven reactions with eight species for a hydrogen-oxygen mixture. The code is ported to a high-performance parallel machine with Message-Passing Interface. Code validation is performed with chemical kinetic modeling for a stoichiometric hydrogen-air mixture, an one-dimensional detonation tube, a two-dimensional, inviscid flow over a wedge and a viscous flow over a flat plate. Detonation is initiated using a numerically simulated arc-ignition or shock-induced ignition system. Various freestream conditions are utilized to study the propagation of the detonation in the proposed concept of the engine. Investigation of the detonation propagation is performed for a pulsed detonation rocket and a supersonic combustion chamber. For a pulsed detonation rocket case, the detonation tube is embedded in a mixing chamber where an initiator is added to the main detonation chamber. Propagating detonation waves in a supersonic combustion chamber is investigated for one- and two-dimensional cases. The detonation initiated by an arc and a shock wave is studied in the inviscid and viscous flow, respectively. Various features including a detonation-shock interaction, a detonation diffraction, a base flow and a vortex are observed.

A kinetic and equilibrium analysis of silicon carbide chemical vapor deposition on monofilaments

NASA Technical Reports Server (NTRS)

Gokoglu, S. A.; Kuczmarski, M. A.

1993-01-01

Chemical kinetics of atmospheric pressure silicon carbide (SiC) chemical vapor deposition (CVD) from dilute silane and propane source gases in hydrogen is numerically analyzed in a cylindrical upflow reactor designed for CVD on monofilaments. The chemical composition of the SiC deposit is assessed both from the calculated total fluxes of carbon and silicon and from chemical equilibrium considerations for the prevailing temperatures and species concentrations at and along the filament surface. The effects of gas and surface chemistry on the evolution of major gas phase species are considered in the analysis.

Electrochemical Transfer of S Between Molten Steel and Molten Slag

NASA Astrophysics Data System (ADS)

Kim, Dong-Hyun; Kim, Wook; Kang, Youn-Bae

2018-06-01

S transfer between molten steel and molten slag was investigated in view of the electrochemical character of S transfer. C-saturated molten steel containing S was allowed to react with CaO-SiO2-Al2O3-MgO slag at 1673 K (1400 °C) until the two phases arrive at a chemical equilibrium. The application of an electric field of constant current through graphite electrodes lowered the S content in the molten steel below its chemical equilibrium level, and the system arrived at a new equilibrium level (electrochemical equilibrium). However, subsequent shutting off of the electric field did not lead to the system reverting to the original chemical equilibrium: reversion of S was observed but to a limited extent. The application of an electric field of opposite direction or flowing of CO gas allowed significant reversion of S. Side reactions (decomposition of oxide components) were observed, and these were considered to be coupled to the transfer of S. An electrochemical reaction mechanism was proposed based on the experimental observations found in the present study.

Design of an ammonia closed-loop storage system in a CSP power plant with a power tower cavity receiver

NASA Astrophysics Data System (ADS)

Abdiwe, Ramadan; Haider, Markus

2017-06-01

In this study the thermochemical system using ammonia as energy storage carrier is investigated and a transient mathematical model using MATLAB software was developed to predict the behavior of the ammonia closed-loop storage system including but not limited to the ammonia solar reactor and the ammonia synthesis reactor. The MATLAB model contains transient mass and energy balances as well as chemical equilibrium model for each relevant system component. For the importance of the dissociation and formation processes in the system, a Computational Fluid Dynamics (CFD) simulation on the ammonia solar and synthesis reactors has been performed. The CFD commercial package FLUENT is used for the simulation study and all the important mechanisms for packed bed reactors are taken into account, such as momentum, heat and mass transfer, and chemical reactions. The FLUENT simulation reveals the profiles inside both reactors and compared them with the profiles from the MATLAB code.

Multi-GPU unsteady 2D flow simulation coupled with a state-to-state chemical kinetics

NASA Astrophysics Data System (ADS)

Tuttafesta, Michele; Pascazio, Giuseppe; Colonna, Gianpiero

2016-10-01

In this work we are presenting a GPU version of a CFD code for high enthalpy reacting flow, using the state-to-state approach. In supersonic and hypersonic flows, thermal and chemical non-equilibrium is one of the fundamental aspects that must be taken into account for the accurate characterization of the plasma and state-to-state kinetics is the most accurate approach used for this kind of problems. This model consists in writing a continuity equation for the population of each vibrational level of the molecules in the mixture, determining at the same time the species densities and the distribution of the population in internal levels. An explicit scheme is employed here to integrate the governing equations, so as to exploit the GPU structure and obtain an efficient algorithm. The best performances are obtained for reacting flows in state-to-state approach, reaching speedups of the order of 100, thanks to the use of an operator splitting scheme for the kinetics equations.

Retrieval Analysis of the Emission Spectrum of WASP-12b: Sensitivity of Outcomes to Prior Assumptions and Implications for Formation History

NASA Astrophysics Data System (ADS)

Oreshenko, Maria; Lavie, Baptiste; Grimm, Simon L.; Tsai, Shang-Min; Malik, Matej; Demory, Brice-Olivier; Mordasini, Christoph; Alibert, Yann; Benz, Willy; Quanz, Sascha P.; Trotta, Roberto; Heng, Kevin

2017-09-01

We analyze the emission spectrum of the hot Jupiter WASP-12b using our HELIOS-R retrieval code and HELIOS-K opacity calculator. When interpreting Hubble and Spitzer data, the retrieval outcomes are found to be prior-dominated. When the prior distributions of the molecular abundances are assumed to be log-uniform, the volume mixing ratio of HCN is found to be implausibly high. A VULCAN chemical kinetics model of WASP-12b suggests that chemical equilibrium is a reasonable assumption even when atmospheric mixing is implausibly rigorous. Guided by (exo)planet formation theory, we set Gaussian priors on the elemental abundances of carbon, oxygen, and nitrogen with the Gaussian peaks being centered on the measured C/H, O/H, and N/H values of the star. By enforcing chemical equilibrium, we find substellar O/H and stellar to slightly superstellar C/H for the dayside atmosphere of WASP-12b. The superstellar carbon-to-oxygen ratio is just above unity, regardless of whether clouds are included in the retrieval analysis, consistent with Madhusudhan et al. Furthermore, whether a temperature inversion exists in the atmosphere depends on one’s assumption for the Gaussian width of the priors. Our retrieved posterior distributions are consistent with the formation of WASP-12b in a solar-composition protoplanetary disk, beyond the water iceline, via gravitational instability or pebble accretion (without core erosion) and migration inward to its present orbital location via a disk-free mechanism, and are inconsistent with both in situ formation and core accretion with disk migration, as predicted by Madhusudhan et al. We predict that the interpretation of James Webb Space Telescope WASP-12b data will not be prior-dominated.

Retrieval Analysis of the Emission Spectrum of WASP-12b: Sensitivity of Outcomes to Prior Assumptions and Implications for Formation History

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oreshenko, Maria; Lavie, Baptiste; Grimm, Simon L.

We analyze the emission spectrum of the hot Jupiter WASP-12b using our HELIOS-R retrieval code and HELIOS-K opacity calculator. When interpreting Hubble and Spitzer data, the retrieval outcomes are found to be prior-dominated. When the prior distributions of the molecular abundances are assumed to be log-uniform, the volume mixing ratio of HCN is found to be implausibly high. A VULCAN chemical kinetics model of WASP-12b suggests that chemical equilibrium is a reasonable assumption even when atmospheric mixing is implausibly rigorous. Guided by (exo)planet formation theory, we set Gaussian priors on the elemental abundances of carbon, oxygen, and nitrogen with themore » Gaussian peaks being centered on the measured C/H, O/H, and N/H values of the star. By enforcing chemical equilibrium, we find substellar O/H and stellar to slightly superstellar C/H for the dayside atmosphere of WASP-12b. The superstellar carbon-to-oxygen ratio is just above unity, regardless of whether clouds are included in the retrieval analysis, consistent with Madhusudhan et al. Furthermore, whether a temperature inversion exists in the atmosphere depends on one’s assumption for the Gaussian width of the priors. Our retrieved posterior distributions are consistent with the formation of WASP-12b in a solar-composition protoplanetary disk, beyond the water iceline, via gravitational instability or pebble accretion (without core erosion) and migration inward to its present orbital location via a disk-free mechanism, and are inconsistent with both in situ formation and core accretion with disk migration, as predicted by Madhusudhan et al. We predict that the interpretation of James Webb Space Telescope WASP-12b data will not be prior-dominated.« less

A Computer Oriented Scheme for Coding Chemicals in the Field of Biomedicine.

ERIC Educational Resources Information Center

Bobka, Marilyn E.; Subramaniam, J.B.

The chemical coding scheme of the Medical Coding Scheme (MCS), developed for use in the Comparative Systems Laboratory (CSL), is outlined and evaluated in this report. The chemical coding scheme provides a classification scheme and encoding method for drugs and chemical terms. Using the scheme complicated chemical structures may be expressed…

Systematic Approach to Calculate the Concentration of Chemical Species in Multi-Equilibrium Problems

ERIC Educational Resources Information Center

Baeza-Baeza, Juan Jose; Garcia-Alvarez-Coque, Maria Celia

2011-01-01

A general systematic approach is proposed for the numerical calculation of multi-equilibrium problems. The approach involves several steps: (i) the establishment of balances involving the chemical species in solution (e.g., mass balances, charge balance, and stoichiometric balance for the reaction products), (ii) the selection of the unknowns (the…

Quantum-chemical calculations and electron diffraction study of the equilibrium molecular structure of vitamin K3

NASA Astrophysics Data System (ADS)

Khaikin, L. S.; Tikhonov, D. S.; Grikina, O. E.; Rykov, A. N.; Stepanov, N. F.

2014-05-01

The equilibrium molecular structure of 2-methyl-1,4-naphthoquinone (vitamin K3) having C s symmetry is experimentally characterized for the first time by means of gas-phase electron diffraction using quantum-chemical calculations and data on the vibrational spectra of related compounds.

An Evaluation of the Venous Equilibrium Model for Hepatic Clearance using Isolated Perfused Rainbow Trout Livers

EPA Science Inventory

The venous equilibrium model is widely used to describe hepatic clearance (CLH) of chemicals metabolized by the liver. If chemical delivery to the tissue does not limit CLH, this model predicts that CLH will approximately equal the product of intrinsic metabolic clearance and a t...

Student Misconceptions in Chemical Equilibrium as Related to Cognitive Level and Achievement.

ERIC Educational Resources Information Center

Wheeler, Alan E.; Kass, Heidi

Reported is an investigation to determine the nature and extent of student misconceptions in chemical equilibrium and to ascertain the degree to which certain misconceptions are related to chemistry achievement and to performance on specific tasks involving cognitive transformations characteristic of the concrete and formal operational stages of…

Using Think-Aloud Protocols to Investigate Secondary School Chemistry Teachers' Misconceptions about Chemical Equilibrium

ERIC Educational Resources Information Center

Cheung, Derek

2009-01-01

Secondary school chemistry teachers' understanding of chemical equilibrium was investigated through interviews using the think-aloud technique. The interviews were conducted with twelve volunteer chemistry teachers in Hong Kong. Their teaching experience ranged from 3 to 18 years. They were asked to predict what would happen to the equilibrium…

NEBULAR: Spectrum synthesis for mixed hydrogen-helium gas in ionization equilibrium

NASA Astrophysics Data System (ADS)

Schirmer, Mischa

2016-08-01

NEBULAR synthesizes the spectrum of a mixed hydrogen helium gas in collisional ionization equilibrium. It is not a spectral fitting code, but it can be used to resample a model spectrum onto the wavelength grid of a real observation. It supports a wide range of temperatures and densities. NEBULAR includes free-free, free-bound, two-photon and line emission from HI, HeI and HeII. The code will either return the composite model spectrum, or, if desired, the unrescaled atomic emission coefficients. It is written in C++ and depends on the GNU Scientific Library (GSL).

A numerical code for a three-dimensional magnetospheric MHD equilibrium model

NASA Technical Reports Server (NTRS)

Voigt, G.-H.

1992-01-01

Two dimensional and three dimensional MHD equilibrium models were begun for Earth's magnetosphere. The original proposal was motivated by realizing that global, purely data based models of Earth's magnetosphere are inadequate for studying the underlying plasma physical principles according to which the magnetosphere evolves on the quasi-static convection time scale. Complex numerical grid generation schemes were established for a 3-D Poisson solver, and a robust Grad-Shafranov solver was coded for high beta MHD equilibria. Thus, the effects were calculated of both the magnetopause geometry and boundary conditions on the magnetotail current distribution.

A THC Simulator for Modeling Fluid-Rock Interactions

NASA Astrophysics Data System (ADS)

Hamidi, Sahar; Galvan, Boris; Heinze, Thomas; Miller, Stephen

2014-05-01

Fluid-rock interactions play an essential role in many earth processes, from a likely influence on earthquake nucleation and aftershocks, to enhanced geothermal system, carbon capture and storage (CCS), and underground nuclear waste repositories. In THC models, two-way interactions between different processes (thermal, hydraulic and chemical) are present. Fluid flow influences the permeability of the rock especially if chemical reactions are taken into account. On one hand solute concentration influences fluid properties while, on the other hand, heat can affect further chemical reactions. Estimating heat production from a naturally fractured geothermal systems remains a complex problem. Previous works are typically based on a local thermal equilibrium assumption and rarely consider the salinity. The dissolved salt in fluid affects the hydro- and thermodynamical behavior of the system by changing the hydraulic properties of the circulating fluid. Coupled thermal-hydraulic-chemical models (THC) are important for investigating these processes, but what is needed is a coupling to mechanics to result in THMC models. Although similar models currently exist (e.g. PFLOTRAN), our objective here is to develop algorithms for implementation using the Graphics Processing Unit (GPU) computer architecture to be run on GPU clusters. To that aim, we present a two-dimensional numerical simulation of a fully coupled non-isothermal non-reactive solute flow. The thermal part of the simulation models heat transfer processes for either local thermal equilibrium or nonequilibrium cases, and coupled to a non-reactive mass transfer described by a non-linear diffusion/dispersion model. The flow process of the model includes a non-linear Darcian flow for either saturated or unsaturated scenarios. For the unsaturated case, we use the Richards' approximation for a mixture of liquid and gas phases. Relative permeability and capillary pressure are determined by the van Genuchten relations. Permeability of rock is controlled by porosity, which is itself related to effective stress. The theoretical model is solved using explicit finite differences, and runs in parallel mode with OpenMP. The code is fully modular so that any combination of current THC processes, one- and two-phase, can be chosen. Future developments will include dissolution and precipitation of chemical components in addition to chemical erosion.

Bioconcentration of lipophilic compounds by some aquatic organisms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hawker, D.W.; Connell, D.W.

1986-04-01

With nondegradable, lipophilic compounds having log P values ranging from 2 to 6, direct linear relationships have been found between the logarithms of the equilibrium bioconcentration factors, and also reciprocal clearance rate constants, with log P for daphnids and molluscs. These relationships permit calculation of the times required for equilibrium and significant bioconcentration of lipophilic chemicals. Compared with fish, these time periods are successively shorter for molluscs, then daphnids. The equilibrium biotic concentration was found to decrease with increasing chemical hydrophobicity for both molluscs and daphnids. Also, new linear relationships between the logarithm of the bioconcentration factor and log Pmore » were found for compounds not attaining equilibrium within finite exposure times.« less

The Lack of Chemical Equilibrium does not Preclude the Use of the Classical Nucleation Theory in Circumstellar Outflows

NASA Technical Reports Server (NTRS)

Paquette, John A.; Nuth, Joseph A., III

2011-01-01

Classical nucleation theory has been used in models of dust nucleation in circumstellar outflows around oxygen-rich asymptotic giant branch stars. One objection to the application of classical nucleation theory (CNT) to astrophysical systems of this sort is that an equilibrium distribution of clusters (assumed by CNT) is unlikely to exist in such conditions due to a low collision rate of condensable species. A model of silicate grain nucleation and growth was modified to evaluate the effect of a nucleation flux orders of magnitUde below the equilibrium value. The results show that a lack of chemical equilibrium has only a small effect on the ultimate grain distribution.

Code Verification Results of an LLNL ASC Code on Some Tri-Lab Verification Test Suite Problems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, S R; Bihari, B L; Salari, K

As scientific codes become more complex and involve larger numbers of developers and algorithms, chances for algorithmic implementation mistakes increase. In this environment, code verification becomes essential to building confidence in the code implementation. This paper will present first results of a new code verification effort within LLNL's B Division. In particular, we will show results of code verification of the LLNL ASC ARES code on the test problems: Su Olson non-equilibrium radiation diffusion, Sod shock tube, Sedov point blast modeled with shock hydrodynamics, and Noh implosion.

Three model space experiments on chemical reactions. [Gibbs adsorption, equilibrium shift and electrodeposition

NASA Technical Reports Server (NTRS)

Grodzka, P.; Facemire, B.

1977-01-01

Three investigations conducted aboard Skylab IV and Apollo-Soyuz involved phenomena that are of interest to the biochemistry community. The formaldehyde clock reaction and the equilibrium shift reaction experiments conducted aboard Apollo Soyuz demonstrate the effect of low-g foams or air/liquid dispersions on reaction rate and chemical equilibrium. The electrodeposition reaction experiment conducted aboard Skylab IV demonstrate the effect of a low-g environment on an electrochemical displacement reaction. The implications of the three space experiments for various applications are considered.

Derivation of the chemical-equilibrium rate coefficient using scattering theory

NASA Technical Reports Server (NTRS)

Mickens, R. E.

1977-01-01

Scattering theory is applied to derive the equilibrium rate coefficient for a general homogeneous chemical reaction involving ideal gases. The reaction rate is expressed in terms of the product of a number of normalized momentum distribution functions, the product of the number of molecules with a given internal energy state, and the spin-averaged T-matrix elements. An expression for momentum distribution at equilibrium for an arbitrary molecule is presented, and the number of molecules with a given internal-energy state is represented by an expression which includes the partition function.

Chemical bonding and the equilibrium composition of Grignard reagents in ethereal solutions.

PubMed

Henriques, André M; Barbosa, André G H

2011-11-10

A thorough analysis of the electronic structure and thermodynamic aspects of Grignard reagents and its associated equilibrium composition in ethereal solutions is performed. Considering methylmagnesium halides containing fluorine, chlorine, and bromine, we studied the neutral, charged, and radical species associated with their chemical equilibrium in solution. The ethereal solvents considered, tetrahydrofuran (THF) and ethyl ether (Et(2)O), were modeled using the polarizable continuum model (PCM) and also by explicit coordination to the Mg atoms in a cluster. The chemical bonding of the species that constitute the Grignard reagent is analyzed in detail with generalized valence bond (GVB) wave functions. Equilibrium constants were calculated with the DFT/M06 functional and GVB wave functions, yielding similar results. According to our calculations and existing kinetic and electrochemical evidence, the species R(•), R(-), (•)MgX, and RMgX(2)(-) must be present in low concentration in the equilibrium. We conclude that depending on the halogen, a different route must be followed to produce the relevant equilibrium species in each case. Chloride and bromide must preferably follow a "radical-based" pathway, and fluoride must follow a "carbanionic-based" pathway. These different mechanisms are contrasted against the available experimental results and are proven to be consistent with the existing thermodynamic data on the Grignard reagent equilibria.

BLT-EC (Breach, Leach and Transport-Equilibrium Chemistry) data input guide. A computer model for simulating release and coupled geochemical transport of contaminants from a subsurface disposal facility

DOE Office of Scientific and Technical Information (OSTI.GOV)

MacKinnon, R.J.; Sullivan, T.M.; Kinsey, R.R.

1997-05-01

The BLT-EC computer code has been developed, implemented, and tested. BLT-EC is a two-dimensional finite element computer code capable of simulating the time-dependent release and reactive transport of aqueous phase species in a subsurface soil system. BLT-EC contains models to simulate the processes (container degradation, waste-form performance, transport, chemical reactions, and radioactive production and decay) most relevant to estimating the release and transport of contaminants from a subsurface disposal system. Water flow is provided through tabular input or auxiliary files. Container degradation considers localized failure due to pitting corrosion and general failure due to uniform surface degradation processes. Waste-form performancemore » considers release to be limited by one of four mechanisms: rinse with partitioning, diffusion, uniform surface degradation, and solubility. Transport considers the processes of advection, dispersion, diffusion, chemical reaction, radioactive production and decay, and sources (waste form releases). Chemical reactions accounted for include complexation, sorption, dissolution-precipitation, oxidation-reduction, and ion exchange. Radioactive production and decay in the waste form is simulated. To improve the usefulness of BLT-EC, a pre-processor, ECIN, which assists in the creation of chemistry input files, and a post-processor, BLTPLOT, which provides a visual display of the data have been developed. BLT-EC also includes an extensive database of thermodynamic data that is also accessible to ECIN. This document reviews the models implemented in BLT-EC and serves as a guide to creating input files and applying BLT-EC.« less

GRIZZLY Model of Multi-Reactive Species Diffusion, Moisture/Heat Transfer and Alkali-Silica Reaction for Simulating Concrete Aging and Degradation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Hai; Spencer, Benjamin W.; Cai, Guowei

Concrete is widely used in the construction of nuclear facilities because of its structural strength and its ability to shield radiation. The use of concrete in nuclear power plants for containment and shielding of radiation and radioactive materials has made its performance crucial for the safe operation of the facility. As such, when life extension is considered for nuclear power plants, it is critical to have accurate and reliable predictive tools to address concerns related to various aging processes of concrete structures and the capacity of structures subjected to age-related degradation. The goal of this report is to document themore » progress of the development and implementation of a fully coupled thermo-hydro-mechanical-chemical model in GRIZZLY code with the ultimate goal to reliably simulate and predict long-term performance and response of aged NPP concrete structures subjected to a number of aging mechanisms including external chemical attacks and volume-changing chemical reactions within concrete structures induced by alkali-silica reactions and long-term exposure to irradiation. Based on a number of survey reports of concrete aging mechanisms relevant to nuclear power plants and recommendations from researchers in concrete community, we’ve implemented three modules during FY15 in GRIZZLY code, (1) multi-species reactive diffusion model within cement materials; (2) coupled moisture and heat transfer model in concrete; and (3) anisotropic, stress-dependent, alkali-silica reaction induced swelling model. The multi-species reactive diffusion model was implemented with the objective to model aging of concrete structures subjected to aggressive external chemical attacks (e.g., chloride attack, sulfate attack, etc.). It considers multiple processes relevant to external chemical attacks such as diffusion of ions in aqueous phase within pore spaces, equilibrium chemical speciation reactions and kinetic mineral dissolution/precipitation. The moisture/heat transfer module was implemented to simulate long-term spatial and temporal evolutions of the moisture and temperature fields within concrete structures at both room and elevated temperatures. The ASR swelling model implemented in GRIZZLY code can simulate anisotropic expansions of ASR gel under either uniaxial, biaxial and triaxial stress states, and can be run simultaneously with the moisture/heat transfer model and coupled with various elastic/inelastic solid mechanics models that were implemented in GRIZZLY code previously. This report provides detailed descriptions of the governing equations, constitutive equations and numerical algorithms of the three modules implemented in GRIZZLY during FY15, simulation results of example problems and model validation results by comparing simulations with available experimental data reported in the literature. The close match between the experiments and simulations clearly demonstrate the potential of GRIZZLY code for reliable evaluation and prediction of long-term performance and response of aged concrete structures in nuclear power plants.« less

The temporal evolution of magnesium isotope fractionation during hydromagnesite dissolution, precipitation, and at equilibrium

NASA Astrophysics Data System (ADS)

Oelkers, Eric H.; Berninger, Ulf-Niklas; Pérez-Fernàndez, Andrea; Chmeleff, Jérôme; Mavromatis, Vasileios

2018-04-01

This study provides experimental evidence of the resetting of the magnesium (Mg) isotope signatures of hydromagnesite in the presence of an aqueous fluid during its congruent dissolution, precipitation, and at equilibrium at ambient temperatures over month-long timescales. All experiments were performed in batch reactors in aqueous sodium carbonate buffer solutions having a pH from 7.8 to 9.2. The fluid phase in all experiments attained bulk chemical equilibrium within analytical uncertainty with hydromagnesite within several days, but the experiments were allowed to continue for up to 575 days. During congruent hydromagnesite dissolution, the fluid first became enriched in isotopically light Mg compared to the dissolving hydromagnesite, but this Mg isotope composition became heavier after the fluid attained chemical equilibrium with the mineral. The δ26Mg composition of the fluid was up to ∼0.35‰ heavier than the initial dissolving hydromagnesite at the end of the dissolution experiments. Hydromagnesite precipitation was provoked during one experiment by increasing the reaction temperature from 4 to 50 °C. The δ26Mg composition of the fluid increased as hydromagnesite precipitated and continued to increase after the fluid attained bulk equilibrium with this phase. These observations are consistent with the hypothesis that mineral-fluid equilibrium is dynamic (i.e. dissolution and precipitation occur at equal, non-zero rates at equilibrium). Moreover the results presented in this study confirm (1) that the transfer of material from the solid to the fluid phase may not be conservative during stoichiometric dissolution, and (2) that the isotopic compositions of carbonate minerals can evolve even when the mineral is in bulk chemical equilibrium with its coexisting fluid. This latter observation suggests that the preservation of isotopic signatures of carbonate minerals in the geological record may require a combination of the isolation of fluid-mineral system from external chemical input and/or the existence of a yet to be defined dissolution/precipitation inhibition mechanism.

A New Multimedia Application for Teaching and Learning Chemical Equilibrium

ERIC Educational Resources Information Center

Ollino, Mario; Aldoney, Jenny; Domínguez, Ana M.; Merino, Cristian

2018-01-01

This study presents a method for teaching the subject of chemical equilibrium in which students engage in self-learning mediated by the use of a new multimedia animation (SEQ-alfa©). This method is presented together with evidence supporting its advantages. At a microscopic level, the simulator shows the mutual transformation of A molecules into B…

Exploring the Use of Multiple Analogical Models when Teaching and Learning Chemical Equilibrium

ERIC Educational Resources Information Center

Harrison, Allan G.; De Jong, Onno

2005-01-01

This study describes the multiple analogical models used to introduce and teach Grade 12 chemical equilibrium. We examine the teacher's reasons for using models, explain each model's development during the lessons, and analyze the understandings students derived from the models. A case study approach was used and the data were drawn from the…

Some Considerations on the Fundamentals of Chemical Kinetics: Steady State, Quasi-Equilibrium, and Transition State Theory

ERIC Educational Resources Information Center

Perez-Benito, Joaquin F.

2017-01-01

The elementary reaction sequence A ? I ? Products is the simplest mechanism for which the steady-state and quasi-equilibrium kinetic approximations can be applied. The exact integrated solutions for this chemical system allow inferring the conditions that must fulfill the rate constants for the different approximations to hold. A graphical…

Functional Fixedness and Functional Reduction as Common Sense Reasonings in Chemical Equilibrium and in Geometry and Polarity of Molecules.

ERIC Educational Resources Information Center

Furio, C.; Calatayud, M. L.; Barcenas, S. L.; Padilla, O. M.

2000-01-01

Focuses on learning difficulties in procedural knowledge, and assesses the procedural difficulties of grade 12 and first- and third-year university students based on common sense reasoning in two areas of chemistry--chemical equilibrium and geometry, and polarity of molecules. (Contains 55 references.) (Author/YDS)

Argumentation Practices in Classroom: Pre-Service Teachers' Conceptual Understanding of Chemical Equilibrium

ERIC Educational Resources Information Center

Kaya, Ebru

2013-01-01

This study examines the impact of argumentation practices on pre-service teachers' understanding of chemical equilibrium. The sample consisted of 100 pre-service teachers in two classes of a public university. One of these classes was assigned as experimental and the other as control group, randomly. In the experimental group, the subject of…

A time-accurate implicit method for chemical non-equilibrium flows at all speeds

NASA Technical Reports Server (NTRS)

Shuen, Jian-Shun

1992-01-01

A new time accurate coupled solution procedure for solving the chemical non-equilibrium Navier-Stokes equations over a wide range of Mach numbers is described. The scheme is shown to be very efficient and robust for flows with velocities ranging from M less than or equal to 10(exp -10) to supersonic speeds.

A Simple Method to Calculate the Temperature Dependence of the Gibbs Energy and Chemical Equilibrium Constants

ERIC Educational Resources Information Center

Vargas, Francisco M.

2014-01-01

The temperature dependence of the Gibbs energy and important quantities such as Henry's law constants, activity coefficients, and chemical equilibrium constants is usually calculated by using the Gibbs-Helmholtz equation. Although, this is a well-known approach and traditionally covered as part of any physical chemistry course, the required…

A Teaching Sequence for Learning the Concept of Chemical Equilibrium in Secondary School Education

ERIC Educational Resources Information Center

Ghirardi, Marco; Marchetti, Fabio; Pettinari, Claudio; Regis, Alberto; Roletto, Ezio

2014-01-01

A novel didactic sequence is proposed for the teaching of chemical equilibrium. This teaching sequence takes into account the historical and epistemological evolution of the concept, the alternative conceptions and learning difficulties highlighted by teaching science and research in education, and the need to focus on both the students'…

The Effect of a Conceptual Change Approach on Understanding of Students' Chemical Equilibrium Concepts

ERIC Educational Resources Information Center

Atasoy, Basri; Akkus, Huseyin; Kadayifci, Hakki

2009-01-01

The purpose of this study was to compare the effects of a conceptual change approach over traditional instruction on tenth-grade students' conceptual achievement in understanding chemical equilibrium. The study was conducted in two classes of the same teacher with participation of a total of 44 tenth-grade students. In this study, a…

Determination of Students' Alternative Conceptions about Chemical Equilibrium: A Review of Research and the Case of Turkey

ERIC Educational Resources Information Center

Ozmen, Haluk

2008-01-01

This study aims to determine prospective science student teachers' alternative conceptions of the chemical equilibrium concept. A 13-item pencil and paper, two-tier multiple choice diagnostic instrument, the Test to Identify Students' Alternative Conceptions (TISAC), was developed and administered to 90 second-semester science student teachers…

Implementation of Finite Rate Chemistry Capability in OVERFLOW

NASA Technical Reports Server (NTRS)

Olsen, M. E.; Venkateswaran, S.; Prabhu, D. K.

2004-01-01

An implementation of both finite rate and equilibrium chemistry have been completed for the OVERFLOW code, a chimera capable, complex geometry flow code widely used to predict transonic flow fields. The implementation builds on the computational efficiency and geometric generality of the solver.

Assessment of Stable Isotope Distribution in Complex Systems

NASA Astrophysics Data System (ADS)

He, Y.; Cao, X.; Wang, J.; Bao, H.

2017-12-01

Biomolecules in living organisms have the potential to approach chemical steady state and even apparent isotope equilibrium because enzymatic reactions are intrinsically reversible. If an apparent local equilibrium can be identified, enzymatic reversibility and its controlling factors may be quantified, which helps to understand complex biochemical processes. Earlier research on isotope fractionation tends to focus on specific process and compare mostly two different chemical species. Using linear regression, "Thermodynamic order", which refers to correlated δ13C and 13β values, has been proposed to be present among many biomolecules by Galimov et al. However, the concept "thermodynamic order" they proposed and the approach they used has been questioned. Here, we propose that the deviation of a complex system from its equilibrium state can be rigorously described as a graph problem as is applied in discrete mathematics. The deviation of isotope distribution from equilibrium state and apparent local isotope equilibrium among a subset of biomolecules can be assessed using an apparent fractionation difference matrix (|Δα|). Applying the |Δα| matrix analysis to earlier published data of amino acids, we show the existence of apparent local equilibrium among different amino acids in potato and a kind of green alga. The existence of apparent local equilibrium is in turn consistent with the notion that enzymatic reactions can be reversible even in living systems. The result also implies that previous emphasis on external carbon source intake may be misplaced when studying isotope distribution in physiology. In addition to the identification of local equilibrium among biomolecules, the difference matrix approach has the potential to explore chemical or isotope equilibrium state in extraterrestrial bodies, to distinguish living from non-living systems, and to classify living species. This approach will benefit from large numbers of systematic data and advanced pattern recognition techniques.

Verification of the ideal magnetohydrodynamic response at rational surfaces in the VMEC code

DOE PAGES

Lazerson, Samuel A.; Loizu, Joaquim; Hirshman, Steven; ...

2016-01-13

The VMEC nonlinear ideal MHD equilibrium code [S. P. Hirshman and J. C. Whitson, Phys. Fluids 26, 3553 (1983)] is compared against analytic linear ideal MHD theory in a screw-pinch-like configuration. The focus of such analysis is to verify the ideal MHD response at magnetic surfaces which possess magnetic transform (ι) which is resonant with spectral values of the perturbed boundary harmonics. A large aspect ratio circular cross section zero-beta equilibrium is considered. This equilibrium possess a rational surface with safety factor q = 2 at a normalized flux value of 0.5. A small resonant boundary perturbation is introduced, excitingmore » a response at the resonant rational surface. The code is found to capture the plasma response as predicted by a newly developed analytic theory that ensures the existence of nested flux surfaces by allowing for a jump in rotational transform (ι=1/q). The VMEC code satisfactorily reproduces these theoretical results without the necessity of an explicit transform discontinuity (Δι) at the rational surface. It is found that the response across the rational surfaces depends upon both radial grid resolution and local shear (dι/dΦ, where ι is the rotational transform and Φ the enclosed toroidal flux). Calculations of an implicit Δι suggest that it does not arise due to numerical artifacts (attributed to radial finite differences in VMEC) or existence conditions for flux surfaces as predicted by linear theory (minimum values of Δι). Scans of the rotational transform profile indicate that for experimentally relevant levels of transform shear the response becomes increasing localised. Furthermore, careful examination of a large experimental tokamak equilibrium, with applied resonant fields, indicates that this shielding response is present, suggesting the phenomena is not limited to this verification exercise.« less

Prediction of the effects of soil-based countermeasures on soil solution chemistry of soils contaminated with radiocesium using the hydrogeochemical code PHREEQC.

PubMed

Hormann, Volker; Kirchner, Gerald

2002-04-22

For agriculturally used areas, which are contaminated by the debris from a nuclear accident, the use of chemical amendmends (e.g. potassium chloride and lime) is among the most common soil-based countermeasures. These countermeasures are intended to reduce the plant uptake of radionuclides (mainly 137Cs and 90Sr) by competitive inhibition by chemically similar ions. So far, the impacts of countermeasures on soil solution composition - and thus, their effectiveness - have almost exclusively been established experimentally, since they depend on mineral composition and chemical characteristics of the soil affected. In this study, which focuses on caesium contamination, the well-established code PHREEQC was used as a geochemical model to calculate the changes in the ionic compositions of soil solutions, which result from the application of potassium or ammonium in batch equilibrium experiments. The simple ion exchange model used by PHREEQC was improved by taking into account selective sorption of Cs+, NH4+ and K+ by clay minerals. Calculations were performed with three different initial soil solution compositions, corresponding to particular soil types (loam, sand, peat). For loamy and sandy soils, our calculational results agree well with experimental data reported by Nisbet (Effectiveness of soil-based countermeasures six months and one year after contamination of five diverse soil types with caesium-134 and strontium-90. Contract Report NRPB-M546, National Radiation Protection Board, Chilton, 1995.). For peat, discrepancies were found indicating that for organic soils a reliable set of exchange constants of the relevant cations still has to be determined experimentally. For cesium, however, these discrepancies almost disappeared if selective sites were assumed to be inaccessible. Additionally, results of sensitivity analyses are presented by which the influence of the main soil parameters on Cs+ concentrations in solution after soil treatment has been systematically studied. It is shown that calculating the impacts of soil-based chemical countermeasures on soil solution chemistry using geochemical codes such as PHREEQC offers an attractive alternative to establishing these impacts by often time-consuming and site-specific experiments.

CFD analysis of laboratory scale phase equilibrium cell operation

NASA Astrophysics Data System (ADS)

Jama, Mohamed Ali; Nikiforow, Kaj; Qureshi, Muhammad Saad; Alopaeus, Ville

2017-10-01

For the modeling of multiphase chemical reactors or separation processes, it is essential to predict accurately chemical equilibrium data, such as vapor-liquid or liquid-liquid equilibria [M. Šoóš et al., Chem. Eng. Process.: Process Intensif. 42(4), 273-284 (2003)]. The instruments used in these experiments are typically designed based on previous experiences, and their operation verified based on known equilibria of standard components. However, mass transfer limitations with different chemical systems may be very different, potentially falsifying the measured equilibrium compositions. In this work, computational fluid dynamics is utilized to design and analyze laboratory scale experimental gas-liquid equilibrium cell for the first time to augment the traditional analysis based on plug flow assumption. Two-phase dilutor cell, used for measuring limiting activity coefficients at infinite dilution, is used as a test case for the analysis. The Lagrangian discrete model is used to track each bubble and to study the residence time distribution of the carrier gas bubbles in the dilutor cell. This analysis is necessary to assess whether the gas leaving the cell is in equilibrium with the liquid, as required in traditional analysis of such apparatus. Mass transfer for six different bio-oil compounds is calculated to determine the approach equilibrium concentration. Also, residence times assuming plug flow and ideal mixing are used as reference cases to evaluate the influence of mixing on the approach to equilibrium in the dilutor. Results show that the model can be used to predict the dilutor operating conditions for which each of the studied gas-liquid systems reaches equilibrium.

CFD analysis of laboratory scale phase equilibrium cell operation.

PubMed

Jama, Mohamed Ali; Nikiforow, Kaj; Qureshi, Muhammad Saad; Alopaeus, Ville

2017-10-01

For the modeling of multiphase chemical reactors or separation processes, it is essential to predict accurately chemical equilibrium data, such as vapor-liquid or liquid-liquid equilibria [M. Šoóš et al., Chem. Eng. Process Intensif. 42(4), 273-284 (2003)]. The instruments used in these experiments are typically designed based on previous experiences, and their operation verified based on known equilibria of standard components. However, mass transfer limitations with different chemical systems may be very different, potentially falsifying the measured equilibrium compositions. In this work, computational fluid dynamics is utilized to design and analyze laboratory scale experimental gas-liquid equilibrium cell for the first time to augment the traditional analysis based on plug flow assumption. Two-phase dilutor cell, used for measuring limiting activity coefficients at infinite dilution, is used as a test case for the analysis. The Lagrangian discrete model is used to track each bubble and to study the residence time distribution of the carrier gas bubbles in the dilutor cell. This analysis is necessary to assess whether the gas leaving the cell is in equilibrium with the liquid, as required in traditional analysis of such apparatus. Mass transfer for six different bio-oil compounds is calculated to determine the approach equilibrium concentration. Also, residence times assuming plug flow and ideal mixing are used as reference cases to evaluate the influence of mixing on the approach to equilibrium in the dilutor. Results show that the model can be used to predict the dilutor operating conditions for which each of the studied gas-liquid systems reaches equilibrium.

Chemical reactions simulated by ground-water-quality models

USGS Publications Warehouse

Grove, David B.; Stollenwerk, Kenneth G.

1987-01-01

Recent literature concerning the modeling of chemical reactions during transport in ground water is examined with emphasis on sorption reactions. The theory of transport and reactions in porous media has been well documented. Numerous equations have been developed from this theory, to provide both continuous and sequential or multistep models, with the water phase considered for both mobile and immobile phases. Chemical reactions can be either equilibrium or non-equilibrium, and can be quantified in linear or non-linear mathematical forms. Non-equilibrium reactions can be separated into kinetic and diffusional rate-limiting mechanisms. Solutions to the equations are available by either analytical expressions or numerical techniques. Saturated and unsaturated batch, column, and field studies are discussed with one-dimensional, laboratory-column experiments predominating. A summary table is presented that references the various kinds of models studied and their applications in predicting chemical concentrations in ground waters.

REACTION OF AMINO-ACIDS AND PEPTIDE BONDS WITH FORMALDEHYDE AS MEASURED BY CHANGES IN THE ULTRA-VIOLET SPECTRA,

DTIC Science & Technology

AMINO ACIDS , CHEMICAL REACTIONS), (*PEPTIDES, CHEMICAL REACTIONS), (*FORMALDEHYDE, CHEMICAL REACTIONS), (*ULTRAVIOLET SPECTROSCOPY, PROTEINS), ABSORPTION SPECTRA, CHEMICAL BONDS, AMIDES, CHEMICAL EQUILIBRIUM, REACTION KINETICS

Conversion of Chemical Reaction Energy into Useful Work in the Van't Hoff Equilibrium Box

ERIC Educational Resources Information Center

Bazhin, N. M.; Parmon, V. N.

2007-01-01

The ideal van't Hoff equilibrium box is described in detail. It shows that van't Hoff equilibrium box divided in two parts can simultaneously produce heat and useful work without violation of the first law of thermodynamics.

LeChâtelier's Principle in the Sciences

NASA Astrophysics Data System (ADS)

Thomsen, Volker B. E.

2000-02-01

LeChâtelier's principle of chemical equilibrium is actually a very general statement about systems in equilibrium and their behavior when subjected to external force or stress. Although one almost never finds mention of his name or law in other sciences, analogous principles and concepts do exist. In this note we examine some of the similar forms taken by this chemical principle in the fields of physics, geology, biology, and economics. Lenz's law in physics is an example of electromagnetic equilibrium and the geological principle of isostatic uplift concerns mechanical equilibrium. Both are strictly consequences of conservation of energy. LeChâtelier's principle deals with thermodynamic equilibrium and involves both the first and second laws of thermodynamics. The concept of homeostasis in biology and the economic law of supply and demand are both equilibrium-like principles, but involve systems in the steady state. However, all these principles involve the stability of the system under consideration and the analogies presented may be useful in the teaching of LeChâtelier's principle.

Chemical Equilibrium And Transport (CET)

NASA Technical Reports Server (NTRS)

Mcbride, B. J.

1991-01-01

Powerful, machine-independent program calculates theoretical thermodynamic properties of chemical systems. Aids in design of compressors, turbines, engines, heat exchangers, and chemical processing equipment.

Combined LAURA-UPS hypersonic solution procedure

NASA Technical Reports Server (NTRS)

Wood, William A.; Thompson, Richard A.

1993-01-01

A combined solution procedure for hypersonic flowfields around blunted slender bodies was implemented using a thin-layer Navier-Stokes code (LAURA) in the nose region and a parabolized Navier-Stokes code (UPS) on the after body region. Perfect gas, equilibrium air, and non-equilibrium air solutions to sharp cones and a sharp wedge were obtained using UPS alone as a preliminary step. Surface heating rates are presented for two slender bodies with blunted noses, having used LAURA to provide a starting solution to UPS downstream of the sonic line. These are an 8 deg sphere-cone in Mach 5, perfect gas, laminar flow at 0 and 4 deg angles of attack and the Reentry F body at Mach 20, 80,000 ft equilibrium gas conditions for 0 and 0.14 deg angles of attack. The results indicate that this procedure is a timely and accurate method for obtaining aerothermodynamic predictions on slender hypersonic vehicles.

Extension of the SIESTA MHD equilibrium code to free-plasma-boundary problems

DOE PAGES

Peraza-Rodriguez, Hugo; Reynolds-Barredo, J. M.; Sanchez, Raul; ...

2017-08-28

Here, SIESTA is a recently developed MHD equilibrium code designed to perform fast and accurate calculations of ideal MHD equilibria for three-dimensional magnetic configurations. Since SIESTA does not assume closed magnetic surfaces, the solution can exhibit magnetic islands and stochastic regions. In its original implementation SIESTA addressed only fixed-boundary problems. That is, the shape of the plasma edge, assumed to be a magnetic surface, was kept fixed as the solution iteratively converges to equilibrium. This condition somewhat restricts the possible applications of SIESTA. In this paper we discuss an extension that will enable SIESTA to address free-plasma-boundary problems, opening upmore » the possibility of investigating problems in which the plasma boundary is perturbed either externally or internally. As an illustration, SIESTA is applied to a configuration of the W7-X stellarator.« less

Extension of the SIESTA MHD equilibrium code to free-plasma-boundary problems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peraza-Rodriguez, Hugo; Reynolds-Barredo, J. M.; Sanchez, Raul

Here, SIESTA is a recently developed MHD equilibrium code designed to perform fast and accurate calculations of ideal MHD equilibria for three-dimensional magnetic configurations. Since SIESTA does not assume closed magnetic surfaces, the solution can exhibit magnetic islands and stochastic regions. In its original implementation SIESTA addressed only fixed-boundary problems. That is, the shape of the plasma edge, assumed to be a magnetic surface, was kept fixed as the solution iteratively converges to equilibrium. This condition somewhat restricts the possible applications of SIESTA. In this paper we discuss an extension that will enable SIESTA to address free-plasma-boundary problems, opening upmore » the possibility of investigating problems in which the plasma boundary is perturbed either externally or internally. As an illustration, SIESTA is applied to a configuration of the W7-X stellarator.« less

Chemical compatibility of some ceramic matrix composite structures with fusion reactor helium coolant at high temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perez, F.J.; Ghoniem, N.M.

The thermodynamic stability of SiC/SiC composite structures proposed for fusion applications is presented in this paper. Minimization of the free energy for reacting species in the temperature range 773-1273 K is achieved by utilizing the NASA-Lewis Chemical Equilibrium Thermodynamics Code (CET). The chemical stability of the matrix (SiC), as well as several potential fiber coatings are studied. Helium coolant is assumed to contain O{sub 2} and water moisture impurities in the range 100-1000 ppm. The work is applied to recent Magnetic and Inertial Confinement Conceptual designs. The present study indicated that the upper useful temperature limit for SiC/SiC composites, frommore » the standpoint of high-temperature corrosion, will be in the neighborhood of 1273 K. Up to this temperature, corrosion of SiC is shown to be negligible. The main mechanism of weight loss will be by evaporation to the plasma side. The presence of a protective SiO{sub 2} condensed phase is discussed, and is shown to result in further reduction of high-temperature corrosion. The thermodynamic stability of C and BN is shown to be very poor under typical fusion reactor conditions. Further development of chemically stable interface materials is required.« less

Group Contribution Methods for Phase Equilibrium Calculations.

PubMed

Gmehling, Jürgen; Constantinescu, Dana; Schmid, Bastian

2015-01-01

The development and design of chemical processes are carried out by solving the balance equations of a mathematical model for sections of or the whole chemical plant with the help of process simulators. For process simulation, besides kinetic data for the chemical reaction, various pure component and mixture properties are required. Because of the great importance of separation processes for a chemical plant in particular, a reliable knowledge of the phase equilibrium behavior is required. The phase equilibrium behavior can be calculated with the help of modern equations of state or g(E)-models using only binary parameters. But unfortunately, only a very small part of the experimental data for fitting the required binary model parameters is available, so very often these models cannot be applied directly. To solve this problem, powerful predictive thermodynamic models have been developed. Group contribution methods allow the prediction of the required phase equilibrium data using only a limited number of group interaction parameters. A prerequisite for fitting the required group interaction parameters is a comprehensive database. That is why for the development of powerful group contribution methods almost all published pure component properties, phase equilibrium data, excess properties, etc., were stored in computerized form in the Dortmund Data Bank. In this review, the present status, weaknesses, advantages and disadvantages, possible applications, and typical results of the different group contribution methods for the calculation of phase equilibria are presented.

Benchmarking gyrokinetic simulations in a toroidal flux-tube

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Y.; Parker, S. E.; Wan, W.

2013-09-15

A flux-tube model is implemented in the global turbulence code GEM [Y. Chen and S. E. Parker, J. Comput. Phys. 220, 839 (2007)] in order to facilitate benchmarking with Eulerian codes. The global GEM assumes the magnetic equilibrium to be completely given. The initial flux-tube implementation simply selects a radial location as the center of the flux-tube and a radial size of the flux-tube, sets all equilibrium quantities (B, ∇B, etc.) to be equal to the values at the center of the flux-tube, and retains only a linear radial profile of the safety factor needed for boundary conditions. This implementationmore » shows disagreement with Eulerian codes in linear simulations. An alternative flux-tube model based on a complete local equilibrium solution of the Grad-Shafranov equation [J. Candy, Plasma Phys. Controlled Fusion 51, 105009 (2009)] is then implemented. This results in better agreement between Eulerian codes and the particle-in-cell (PIC) method. The PIC algorithm based on the v{sub ||}-formalism [J. Reynders, Ph.D. dissertation, Princeton University, 1992] and the gyrokinetic ion/fluid electron hybrid model with kinetic electron closure [Y. Chan and S. E. Parker, Phys. Plasmas 18, 055703 (2011)] are also implemented in the flux-tube geometry and compared with the direct method for both the ion temperature gradient driven modes and the kinetic ballooning modes.« less

Nighttime Ozone Chemical Equilibrium in the Mesopause Region

NASA Astrophysics Data System (ADS)

Kulikov, M. Yu.; Belikovich, M. V.; Grygalashvyly, M.; Sonnemann, G. R.; Ermakova, T. S.; Nechaev, A. A.; Feigin, A. M.

2018-03-01

We examine the applicability of the assumption that nighttime ozone is in photochemical equilibrium. The analysis is based on calculations with a 3-D chemical transport model. These data are used to determine the ratio of correct (calculated) O3 density to its equilibrium value for the conditions of the nighttime mesosphere depending on the altitude, latitude, and month in the annual cycle. The results obtained demonstrate that the retrieval of O and H distributions using the assumption of photochemical ozone equilibrium may lead to a significant error below 81-87 km depending on season. Possible modifications of the currently used approach that allow improving the quality of retrieval of O and H mesospheric distributions from satellite-based observations are discussed.

Dynamical coupling between magnetic equilibrium and transport in tokamak scenario modelling, with application to current ramps

NASA Astrophysics Data System (ADS)

Fable, E.; Angioni, C.; Ivanov, A. A.; Lackner, K.; Maj, O.; Medvedev, S. Yu; Pautasso, G.; Pereverzev, G. V.; Treutterer, W.; the ASDEX Upgrade Team

2013-07-01

The modelling of tokamak scenarios requires the simultaneous solution of both the time evolution of the plasma kinetic profiles and of the magnetic equilibrium. Their dynamical coupling involves additional complications, which are not present when the two physical problems are solved separately. Difficulties arise in maintaining consistency in the time evolution among quantities which appear in both the transport and the Grad-Shafranov equations, specifically the poloidal and toroidal magnetic fluxes as a function of each other and of the geometry. The required consistency can be obtained by means of iteration cycles, which are performed outside the equilibrium code and which can have different convergence properties depending on the chosen numerical scheme. When these external iterations are performed, the stability of the coupled system becomes a concern. In contrast, if these iterations are not performed, the coupled system is numerically stable, but can become physically inconsistent. By employing a novel scheme (Fable E et al 2012 Nucl. Fusion submitted), which ensures stability and physical consistency among the same quantities that appear in both the transport and magnetic equilibrium equations, a newly developed version of the ASTRA transport code (Pereverzev G V et al 1991 IPP Report 5/42), which is coupled to the SPIDER equilibrium code (Ivanov A A et al 2005 32nd EPS Conf. on Plasma Physics (Tarragona, 27 June-1 July) vol 29C (ECA) P-5.063), in both prescribed- and free-boundary modes is presented here for the first time. The ASTRA-SPIDER coupled system is then applied to the specific study of the modelling of controlled current ramp-up in ASDEX Upgrade discharges.

Equilibrium sampling of environmental pollutants in fish: comparison with lipid-normalized concentrations and homogenization effects on chemical activity.

PubMed

Jahnke, Annika; Mayer, Philipp; Adolfsson-Erici, Margaretha; McLachlan, Michael S

2011-07-01

Equilibrium sampling of organic pollutants into the silicone polydimethylsiloxane (PDMS) has recently been applied in biological tissues including fish. Pollutant concentrations in PDMS can then be multiplied with lipid/PDMS distribution coefficients (D(Lipid,PDMS) ) to obtain concentrations in fish lipids. In the present study, PDMS thin films were used for equilibrium sampling of polychlorinated biphenyls (PCBs) in intact tissue of two eels and one salmon. A classical exhaustive extraction technique to determine lipid-normalized PCB concentrations, which assigns the body burden of the chemical to the lipid fraction of the fish, was additionally applied. Lipid-based PCB concentrations obtained by equilibrium sampling were 85 to 106% (Norwegian Atlantic salmon), 108 to 128% (Baltic Sea eel), and 51 to 83% (Finnish lake eel) of those determined using total extraction. This supports the validity of the equilibrium sampling technique, while at the same time confirming that the fugacity capacity of these lipid-rich tissues for PCBs was dominated by the lipid fraction. Equilibrium sampling was also applied to homogenates of the same fish tissues. The PCB concentrations in the PDMS were 1.2 to 2.0 times higher in the homogenates (statistically significant in 18 of 21 cases, p < 0.05), indicating that homogenization increased the chemical activity of the PCBs and decreased the fugacity capacity of the tissue. This observation has implications for equilibrium sampling and partition coefficients determined using tissue homogenates. Copyright © 2011 SETAC.

Surface-dependent chemical equilibrium constants and capacitances for bare and 3-cyanopropyldimethylchlorosilane coated silica nanochannels.

PubMed

Andersen, Mathias Bækbo; Frey, Jared; Pennathur, Sumita; Bruus, Henrik

2011-01-01

We present a combined theoretical and experimental analysis of the solid-liquid interface of fused-silica nanofabricated channels with and without a hydrophilic 3-cyanopropyldimethylchlorosilane (cyanosilane) coating. We develop a model that relaxes the assumption that the surface parameters C(1), C(2), and pK(+) are constant and independent of surface composition. Our theoretical model consists of three parts: (i) a chemical equilibrium model of the bare or coated wall, (ii) a chemical equilibrium model of the buffered bulk electrolyte, and (iii) a self-consistent Gouy-Chapman-Stern triple-layer model of the electrochemical double layer coupling these two equilibrium models. To validate our model, we used both pH-sensitive dye-based capillary filling experiments as well as electro-osmotic current-monitoring measurements. Using our model we predict the dependence of ζ potential, surface charge density, and capillary filling length ratio on ionic strength for different surface compositions, which can be difficult to achieve otherwise. Copyright © 2010 Elsevier Inc. All rights reserved.

An X-Ray Analysis Database of Photoionization Cross Sections Including Variable Ionization

NASA Technical Reports Server (NTRS)

Wang, Ping; Cohen, David H.; MacFarlane, Joseph J.; Cassinelli, Joseph P.

1997-01-01

Results of research efforts in the following areas are discussed: review of the major theoretical and experimental data of subshell photoionization cross sections and ionization edges of atomic ions to assess the accuracy of the data, and to compile the most reliable of these data in our own database; detailed atomic physics calculations to complement the database for all ions of 17 cosmically abundant elements; reconciling the data from various sources and our own calculations; and fitting cross sections with functional approximations and incorporating these functions into a compact computer code.Also, efforts included adapting an ionization equilibrium code, tabulating results, and incorporating them into the overall program and testing the code (both ionization equilibrium and opacity codes) with existing observational data. The background and scientific applications of this work are discussed. Atomic physics cross section models and calculations are described. Calculation results are compared with available experimental data and other theoretical data. The functional approximations used for fitting cross sections are outlined and applications of the database are discussed.

A transformation theory of stochastic evolution in Red Moon methodology to time evolution of chemical reaction process in the full atomistic system.

PubMed

Suzuki, Yuichi; Nagaoka, Masataka

2017-05-28

Atomistic information of a whole chemical reaction system, e.g., instantaneous microscopic molecular structures and orientations, offers important and deeper insight into clearly understanding unknown chemical phenomena. In accordance with the progress of a number of simultaneous chemical reactions, the Red Moon method (a hybrid Monte Carlo/molecular dynamics reaction method) is capable of simulating atomistically the chemical reaction process from an initial state to the final one of complex chemical reaction systems. In the present study, we have proposed a transformation theory to interpret the chemical reaction process of the Red Moon methodology as the time evolution process in harmony with the chemical kinetics. For the demonstration of the theory, we have chosen the gas reaction system in which the reversible second-order reaction H 2 + I 2  ⇌ 2HI occurs. First, the chemical reaction process was simulated from the initial configurational arrangement containing a number of H 2 and I 2 molecules, each at 300 K, 500 K, and 700 K. To reproduce the chemical equilibrium for the system, the collision frequencies for the reactions were taken into consideration in the theoretical treatment. As a result, the calculated equilibrium concentrations [H 2 ] eq and equilibrium constants K eq at all the temperatures were in good agreement with their corresponding experimental values. Further, we applied the theoretical treatment for the time transformation to the system and have shown that the calculated half-life τ's of [H 2 ] reproduce very well the analytical ones at all the temperatures. It is, therefore, concluded that the application of the present theoretical treatment with the Red Moon method makes it possible to analyze reasonably the time evolution of complex chemical reaction systems to chemical equilibrium at the atomistic level.

The generation of meaningful information in molecular systems.

PubMed

Wills, Peter R

2016-03-13

The physico-chemical processes occurring inside cells are under the computational control of genetic (DNA) and epigenetic (internal structural) programming. The origin and evolution of genetic information (nucleic acid sequences) is reasonably well understood, but scant attention has been paid to the origin and evolution of the molecular biological interpreters that give phenotypic meaning to the sequence information that is quite faithfully replicated during cellular reproduction. The near universality and age of the mapping from nucleotide triplets to amino acids embedded in the functionality of the protein synthetic machinery speaks to the early development of a system of coding which is still extant in every living organism. We take the origin of genetic coding as a paradigm of the emergence of computation in natural systems, focusing on the requirement that the molecular components of an interpreter be synthesized autocatalytically. Within this context, it is seen that interpreters of increasing complexity are generated by series of transitions through stepped dynamic instabilities (non-equilibrium phase transitions). The early phylogeny of the amino acyl-tRNA synthetase enzymes is discussed in such terms, leading to the conclusion that the observed optimality of the genetic code is a natural outcome of the processes of self-organization that produced it. © 2016 The Author(s).

Simulations for Teaching Chemical Equilibrium

NASA Astrophysics Data System (ADS)

Huddle, Penelope A.; White, Margaret Dawn; Rogers, Fiona

2000-07-01

This paper outlines a systematic approach to teaching chemical equilibrium using simulation experiments that address most known alternate conceptions in the topic. Graphs drawn using the data from the simulations are identical to those obtained using real experimental data for reactions that go to equilibrium. This allows easy mapping of the analogy to the target. The requirements for the simulations are simple and inexpensive, making them accessible to even the poorest schools. The simulations can be adapted for all levels, from pupils who are first encountering equilibrium through students in tertiary education to qualified teachers who have experienced difficulty in teaching the topic. The simulations were piloted on four very different audiences. Minor modifications were then made before the Equilibrium Games as reported in this paper were tested on three groups of subjects: a Grade 12 class, college students, and university Chemistry I students. Marked improvements in understanding of the concept were shown in two of the three sets of subjects.

Navier-Stokes simulation of real gas flows in nozzles

NASA Technical Reports Server (NTRS)

Nagaraj, N.; Lombard, C. K.

1987-01-01

Air flow in a hypersonic nozzle causes real gas effects due to reaction among the species constituting air. Such reactions may be in chemical equilibrium or in chemical nonequilibrium. Here using the CSCM upwind scheme for the compressible Navier-Stokes equations, the real gas flowfield in an arcjet nozzle is computed for both the equilibrium case and the nonequilibrium case. A hypersonic nozzle flow arising from a pebble bed heated plenum is also computed for the equilibrium situation. Between the equilibrium cases, the chemistry is treated by two different schemes and comments are made as to computational complexity. For the nonequilibrium case, a full set of seventeen reactions and full implicit coupling of five species with gasdynamics is employed to compute the flowfield. For all cases considered here the gas is assumed to be a calorically imperfect mixture of ideal gases in thermal equilibrium.

One-dimensional thermohydraulic code THESEUS and its application to chilldown process simulation in two-phase hydrogen flows

NASA Astrophysics Data System (ADS)

Papadimitriou, P.; Skorek, T.

THESUS is a thermohydraulic code for the calculation of steady state and transient processes of two-phase cryogenic flows. The physical model is based on four conservation equations with separate liquid and gas phase mass conservation equations. The thermohydraulic non-equilibrium is calculated by means of evaporation and condensation models. The mechanical non-equilibrium is modeled by a full-range drift-flux model. Also heat conduction in solid structures and heat exchange for the full spectrum of heat transfer regimes can be simulated. Test analyses of two-channel chilldown experiments and comparisons with the measured data have been performed.

PARVMEC: An Efficient, Scalable Implementation of the Variational Moments Equilibrium Code

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seal, Sudip K; Hirshman, Steven Paul; Wingen, Andreas

The ability to sustain magnetically confined plasma in a state of stable equilibrium is crucial for optimal and cost-effective operations of fusion devices like tokamaks and stellarators. The Variational Moments Equilibrium Code (VMEC) is the de-facto serial application used by fusion scientists to compute magnetohydrodynamics (MHD) equilibria and study the physics of three dimensional plasmas in confined configurations. Modern fusion energy experiments have larger system scales with more interactive experimental workflows, both demanding faster analysis turnaround times on computational workloads that are stressing the capabilities of sequential VMEC. In this paper, we present PARVMEC, an efficient, parallel version of itsmore » sequential counterpart, capable of scaling to thousands of processors on distributed memory machines. PARVMEC is a non-linear code, with multiple numerical physics modules, each with its own computational complexity. A detailed speedup analysis supported by scaling results on 1,024 cores of a Cray XC30 supercomputer is presented. Depending on the mode of PARVMEC execution, speedup improvements of one to two orders of magnitude are reported. PARVMEC equips fusion scientists for the first time with a state-of-theart capability for rapid, high fidelity analyses of magnetically confined plasmas at unprecedented scales.« less

Hidden Structural Codes in Protein Intrinsic Disorder.

PubMed

Borkosky, Silvia S; Camporeale, Gabriela; Chemes, Lucía B; Risso, Marikena; Noval, María Gabriela; Sánchez, Ignacio E; Alonso, Leonardo G; de Prat Gay, Gonzalo

2017-10-17

Intrinsic disorder is a major structural category in biology, accounting for more than 30% of coding regions across the domains of life, yet consists of conformational ensembles in equilibrium, a major challenge in protein chemistry. Anciently evolved papillomavirus genomes constitute an unparalleled case for sequence to structure-function correlation in cases in which there are no folded structures. E7, the major transforming oncoprotein of human papillomaviruses, is a paradigmatic example among the intrinsically disordered proteins. Analysis of a large number of sequences of the same viral protein allowed for the identification of a handful of residues with absolute conservation, scattered along the sequence of its N-terminal intrinsically disordered domain, which intriguingly are mostly leucine residues. Mutation of these led to a pronounced increase in both α-helix and β-sheet structural content, reflected by drastic effects on equilibrium propensities and oligomerization kinetics, and uncovers the existence of local structural elements that oppose canonical folding. These folding relays suggest the existence of yet undefined hidden structural codes behind intrinsic disorder in this model protein. Thus, evolution pinpoints conformational hot spots that could have not been identified by direct experimental methods for analyzing or perturbing the equilibrium of an intrinsically disordered protein ensemble.

The Effect of Context-Based Chemical Equilibrium on Grade 11 Students' Learning, Motivation and Constructivist Learning Environment

ERIC Educational Resources Information Center

ilhan, Nail; Yildirim, Ali; Yilmaz, Sibel Sadi

2016-01-01

In recent years, many countries have adopted a context-based approach for designing science curricula for education at all levels. The aim of this study was to determine the effectiveness of a Context-Based Chemistry Course (CBCC) as compared with traditional/existing instruction, on 11th grade students' learning about chemical equilibrium,…

The Effectiveness of Conceptual Change Texts in Remediating High School Students' Alternative Conceptions Concerning Chemical Equilibrium

ERIC Educational Resources Information Center

Ozmen, Haluk

2007-01-01

This study investigated the effectiveness of conceptual change texts in remediating high school students' alternative conceptions concerning chemical equilibrium. A quasi-experimental design was used in this study. The subjects for this study consisted of a total 78 tenth-grade students, 38 of them in the experimental group and 40 of them in the…

Composition and Thermodynamic Properties of Air in Chemical Equilibrium

NASA Technical Reports Server (NTRS)

Moeckel, W E; Weston, Kenneth C

1958-01-01

Charts have been prepared relating the thermodynamic properties of air in chemical equilibrium for temperatures to 15,000 degrees k and for pressures 10(-5) to 10 (plus 4) atmospheres. Also included are charts showing the composition of air, the isentropic exponent, and the speed of sound. These charts are based on thermodynamic data calculated by the National Bureau of Standards.

The Effect of Cooperative Learning Approach Based on Conceptual Change Condition on Students' Understanding of Chemical Equilibrium Concepts

ERIC Educational Resources Information Center

Bilgin, Ibrahim; Geban, Omer

2006-01-01

The purpose of this study is to investigate the effects of the cooperative learning approach based on conceptual change conditions over traditional instruction on 10th grade students' conceptual understanding and achievement of computational problems related to chemical equilibrium concepts. The subjects of this study consisted of 87 tenth grade…

Analogies in the Teaching of Chemical Equilibrium: A Synthesis/Analysis of the Literature

ERIC Educational Resources Information Center

Raviolo, Andres; Garritz, Andoni

2009-01-01

This paper presents a thorough literature review of the analogies used to teach chemical equilibrium. The main objective is to compile all the analogies that have been found to be of service to the teacher and the student. Additionally, we categorize and analyze analogies in relation to the following aspects: representation of the dynamic nature…

Multi-Species Fluxes for the Parallel Quiet Direct Simulation (QDS) Method

NASA Astrophysics Data System (ADS)

Cave, H. M.; Lim, C.-W.; Jermy, M. C.; Krumdieck, S. P.; Smith, M. R.; Lin, Y.-J.; Wu, J.-S.

2011-05-01

Fluxes of multiple species are implemented in the Quiet Direct Simulation (QDS) scheme for gas flows. Each molecular species streams independently. All species are brought to local equilibrium at the end of each time step. The multi species scheme is compared to DSMC simulation, on a test case of a Mach 20 flow of a xenon/helium mixture over a forward facing step. Depletion of the heavier species in the bow shock and the near-wall layer are seen. The multi-species QDS code is then used to model the flow in a pulsed-pressure chemical vapour deposition reactor set up for carbon film deposition. The injected gas is a mixture of methane and hydrogen. The temporal development of the spatial distribution of methane over the substrate is tracked.

A Massively Parallel Particle Code for Rarefied Ionized and Neutral Gas Flows in Earth and Planetary Atmospheres, Ionospheres and Magnetospheres

NASA Technical Reports Server (NTRS)

Combi, Michael R.

2004-01-01

In order to understand the global structure, dynamics, and physical and chemical processes occurring in the upper atmospheres, exospheres, and ionospheres of the Earth, the other planets, comets and planetary satellites and their interactions with their outer particles and fields environs, it is often necessary to address the fundamentally non-equilibrium aspects of the physical environment. These are regions where complex chemistry, energetics, and electromagnetic field influences are important. Traditional approaches are based largely on hydrodynamic or magnetohydrodynamic MHD) formulations and are very important and highly useful. However, these methods often have limitations in rarefied physical regimes where the molecular collision rates and ion gyrofrequencies are small and where interactions with ionospheres and upper neutral atmospheres are important.

Some pungent arguments against the physico-chemical theories of the origin of the genetic code and corroborating the coevolution theory.

PubMed

Di Giulio, Massimo

2017-02-07

Whereas it is extremely easy to prove that "if the biosynthetic relationships between amino acids were fundamental in the structuring of the genetic code, then their physico-chemical properties might also be revealed in the genetic code table"; it is, on the contrary, impossible to prove that "if the physico-chemical properties of amino acids were fundamental in the structuring of the genetic code, then the presence of the biosynthetic relationships between amino acids should not be revealed in the genetic code". And, given that in the genetic code table are mirrored both the biosynthetic relationships between amino acids and their physico-chemical properties, all this would be a test that would falsify the physico-chemical theories of the origin of the genetic code. That is to say, if the physico-chemical properties of amino acids had a fundamental role in organizing the genetic code, then we would not have duly revealed the presence - in the genetic code - of the biosynthetic relationships between amino acids, and on the contrary this has been observed. Therefore, this falsifies the physico-chemical theories of genetic code origin. Whereas, the coevolution theory of the origin of the genetic code would be corroborated by this analysis, because it would be able to give a description of evolution of the genetic code more coherent with the indisputable empirical observations that link both the biosynthetic relationships of amino acids and their physico-chemical properties to the evolutionary organization of the genetic code. Copyright © 2016 Elsevier Ltd. All rights reserved.

Generic reactive transport codes as flexible tools to integrate soil organic matter degradation models with water, transport and geochemistry in soils

NASA Astrophysics Data System (ADS)

Jacques, Diederik; Gérard, Fréderic; Mayer, Uli; Simunek, Jirka; Leterme, Bertrand

2016-04-01

A large number of organic matter degradation, CO2 transport and dissolved organic matter models have been developed during the last decades. However, organic matter degradation models are in many cases strictly hard-coded in terms of organic pools, degradation kinetics and dependency on environmental variables. The scientific input of the model user is typically limited to the adjustment of input parameters. In addition, the coupling with geochemical soil processes including aqueous speciation, pH-dependent sorption and colloid-facilitated transport are not incorporated in many of these models, strongly limiting the scope of their application. Furthermore, the most comprehensive organic matter degradation models are combined with simplified representations of flow and transport processes in the soil system. We illustrate the capability of generic reactive transport codes to overcome these shortcomings. The formulations of reactive transport codes include a physics-based continuum representation of flow and transport processes, while biogeochemical reactions can be described as equilibrium processes constrained by thermodynamic principles and/or kinetic reaction networks. The flexibility of these type of codes allows for straight-forward extension of reaction networks, permits the inclusion of new model components (e.g.: organic matter pools, rate equations, parameter dependency on environmental conditions) and in such a way facilitates an application-tailored implementation of organic matter degradation models and related processes. A numerical benchmark involving two reactive transport codes (HPx and MIN3P) demonstrates how the process-based simulation of transient variably saturated water flow (Richards equation), solute transport (advection-dispersion equation), heat transfer and diffusion in the gas phase can be combined with a flexible implementation of a soil organic matter degradation model. The benchmark includes the production of leachable organic matter and inorganic carbon in the aqueous and gaseous phases, as well as different decomposition functions with first-order, linear dependence or nonlinear dependence on a biomass pool. In addition, we show how processes such as local bioturbation (bio-diffusion) can be included implicitly through a Fickian formulation of transport of soil organic matter. Coupling soil organic matter models with generic and flexible reactive transport codes offers a valuable tool to enhance insights into coupled physico-chemical processes at different scales within the scope of C-biogeochemical cycles, possibly linked with other chemical elements such as plant nutrients and pollutants.

Analysis of non-equilibrium phenomena in inductively coupled plasma generators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, W.; Panesi, M., E-mail: mpanesi@illinois.edu; Lani, A.

This work addresses the modeling of non-equilibrium phenomena in inductively coupled plasma discharges. In the proposed computational model, the electromagnetic induction equation is solved together with the set of Navier-Stokes equations in order to compute the electromagnetic and flow fields, accounting for their mutual interaction. Semi-classical statistical thermodynamics is used to determine the plasma thermodynamic properties, while transport properties are obtained from kinetic principles, with the method of Chapman and Enskog. Particle ambipolar diffusive fluxes are found by solving the Stefan-Maxwell equations with a simple iterative method. Two physico-mathematical formulations are used to model the chemical reaction processes: (1) Amore » Local Thermodynamics Equilibrium (LTE) formulation and (2) a thermo-chemical non-equilibrium (TCNEQ) formulation. In the TCNEQ model, thermal non-equilibrium between the translational energy mode of the gas and the vibrational energy mode of individual molecules is accounted for. The electronic states of the chemical species are assumed in equilibrium with the vibrational temperature, whereas the rotational energy mode is assumed to be equilibrated with translation. Three different physical models are used to account for the coupling of chemistry and energy transfer processes. Numerical simulations obtained with the LTE and TCNEQ formulations are used to characterize the extent of non-equilibrium of the flow inside the Plasmatron facility at the von Karman Institute. Each model was tested using different kinetic mechanisms to assess the sensitivity of the results to variations in the reaction parameters. A comparison of temperatures and composition profiles at the outlet of the torch demonstrates that the flow is in non-equilibrium for operating conditions characterized by pressures below 30 000 Pa, frequency 0.37 MHz, input power 80 kW, and mass flow 8 g/s.« less

Analysis of non-equilibrium phenomena in inductively coupled plasma generators

NASA Astrophysics Data System (ADS)

Zhang, W.; Lani, A.; Panesi, M.

2016-07-01

This work addresses the modeling of non-equilibrium phenomena in inductively coupled plasma discharges. In the proposed computational model, the electromagnetic induction equation is solved together with the set of Navier-Stokes equations in order to compute the electromagnetic and flow fields, accounting for their mutual interaction. Semi-classical statistical thermodynamics is used to determine the plasma thermodynamic properties, while transport properties are obtained from kinetic principles, with the method of Chapman and Enskog. Particle ambipolar diffusive fluxes are found by solving the Stefan-Maxwell equations with a simple iterative method. Two physico-mathematical formulations are used to model the chemical reaction processes: (1) A Local Thermodynamics Equilibrium (LTE) formulation and (2) a thermo-chemical non-equilibrium (TCNEQ) formulation. In the TCNEQ model, thermal non-equilibrium between the translational energy mode of the gas and the vibrational energy mode of individual molecules is accounted for. The electronic states of the chemical species are assumed in equilibrium with the vibrational temperature, whereas the rotational energy mode is assumed to be equilibrated with translation. Three different physical models are used to account for the coupling of chemistry and energy transfer processes. Numerical simulations obtained with the LTE and TCNEQ formulations are used to characterize the extent of non-equilibrium of the flow inside the Plasmatron facility at the von Karman Institute. Each model was tested using different kinetic mechanisms to assess the sensitivity of the results to variations in the reaction parameters. A comparison of temperatures and composition profiles at the outlet of the torch demonstrates that the flow is in non-equilibrium for operating conditions characterized by pressures below 30 000 Pa, frequency 0.37 MHz, input power 80 kW, and mass flow 8 g/s.

Stagnation-point heat-transfer rate predictions at aeroassist flight conditions

NASA Technical Reports Server (NTRS)

Gupta, Roop N.; Jones, Jim J.; Rochelle, William C.

1992-01-01

The results are presented for the stagnation-point heat-transfer rates used in the design process of the Aeroassist Flight Experiment (AFE) vehicle over its entire aeropass trajectory. The prediction methods used in this investigation demonstrate the application of computational fluid dynamics (CFD) techniques to a wide range of flight conditions and their usefulness in a design process. The heating rates were computed by a viscous-shock-layer (VSL) code at the lower altitudes and by a Navier-Stokes (N-S) code for the higher altitude cases. For both methods, finite-rate chemically reacting gas was considered, and a temperature-dependent wall-catalysis model was used. The wall temperature for each case was assumed to be radiative equilibrium temperature, based on total heating. The radiative heating was estimated by using a correlation equation. Wall slip was included in the N-S calculation method, and this method implicitly accounts for shock slip. The N-S/VSL combination of projection methods was established by comparison with the published benchmark flow-field code LAURA results at lower altitudes, and the direct simulation Monte Carlo results at higher altitude cases. To obtain the design heating rate over the entire forward face of the vehicle, a boundary-layer method (BLIMP code) that employs reacting chemistry and surface catalysis was used. The ratio of the VSL or N-S method prediction to that obtained from the boundary-layer method code at the stagnation point is used to define an adjustment factor, which accounts for the errors involved in using the boundary-layer method.

Observable Signatures of Wind-driven Chemistry with a Fully Consistent Three-dimensional Radiative Hydrodynamics Model of HD 209458b

NASA Astrophysics Data System (ADS)

Drummond, B.; Mayne, N. J.; Manners, J.; Carter, A. L.; Boutle, I. A.; Baraffe, I.; Hébrard, É.; Tremblin, P.; Sing, D. K.; Amundsen, D. S.; Acreman, D.

2018-03-01

We present a study of the effect of wind-driven advection on the chemical composition of hot-Jupiter atmospheres using a fully consistent 3D hydrodynamics, chemistry, and radiative transfer code, the Met Office Unified Model (UM). Chemical modeling of exoplanet atmospheres has primarily been restricted to 1D models that cannot account for 3D dynamical processes. In this work, we couple a chemical relaxation scheme to the UM to account for the chemical interconversion of methane and carbon monoxide. This is done consistently with the radiative transfer meaning that departures from chemical equilibrium are included in the heating rates (and emission) and hence complete the feedback between the dynamics, thermal structure, and chemical composition. In this Letter, we simulate the well studied atmosphere of HD 209458b. We find that the combined effect of horizontal and vertical advection leads to an increase in the methane abundance by several orders of magnitude, which is directly opposite to the trend found in previous works. Our results demonstrate the need to include 3D effects when considering the chemistry of hot-Jupiter atmospheres. We calculate transmission and emission spectra, as well as the emission phase curve, from our simulations. We conclude that gas-phase nonequilibrium chemistry is unlikely to explain the model–observation discrepancy in the 4.5 μm Spitzer/IRAC channel. However, we highlight other spectral regions, observable with the James Webb Space Telescope, where signatures of wind-driven chemistry are more prominant.

Silicone passive equilibrium samplers as 'chemometers' in eels and sediments of a Swedish lake.

PubMed

Jahnke, Annika; Mayer, Philipp; McLachlan, Michael S; Wickström, Håkan; Gilbert, Dorothea; MacLeod, Matthew

2014-03-01

Passive equilibrium samplers deployed in two or more media of a system and allowed to come to equilibrium can be viewed as 'chemometers' that reflect the difference in chemical activities of contaminants between the media. We applied silicone-based equilibrium samplers to measure relative chemical activities of seven 'indicator' polychlorinated biphenyls (PCBs) and hexachlorobenzene in eels and sediments from a Swedish lake. Chemical concentrations in eels and sediments were also measured using exhaustive extraction methods. Lipid-normalized concentrations in eels were higher than organic carbon-normalized concentrations in sediments, with biota-sediment accumulation factors (BSAFs) of five PCBs ranging from 2.7 to 12.7. In contrast, chemical activities of the same pollutants inferred by passive sampling were 3.5 to 31.3 times lower in eels than in sediments. The apparent contradiction between BSAFs and activity ratios is consistent with the sorptive capacity of lipids exceeding that of sediment organic carbon from this ecosystem by up to 50-fold. Factors that may contribute to the elevated activity in sediments are discussed, including slower response of sediments than water to reduced emissions, sediment diagenesis and sorption to phytoplankton. The 'chemometer' approach has the potential to become a powerful tool to study the thermodynamic controls on persistent organic chemicals in the environment and should be extended to other environmental compartments.

The Nature of the Interplay among Components of Pedagogical Content Knowledge in Reaction Rate and Chemical Equilibrium Topics of Novice and Experienced Chemistry Teachers

ERIC Educational Resources Information Center

Akin, Fatma Nur; Uzuntiryaki-Kondakci, Esen

2018-01-01

We examined the interactions among pedagogical content knowledge (PCK) components of novice and experienced chemistry teachers in teaching reaction rate and chemical equilibrium topics in this qualitative multiple-case design study. For this aim, three chemistry teachers who had different levels of teaching experience in chemistry teaching were…

Exploring the Impact of Argumentation on Pre-Service Science Teachers' Conceptual Understanding of Chemical Equilibrium

ERIC Educational Resources Information Center

Aydeniz, Mehmet; Dogan, Alev

2016-01-01

This study examines the impact of argumentation on pre-service science teachers' (PST) conceptual understanding of chemical equilibrium. The sample consisted of 57 first-year PSTs enrolled in a teacher education program in Turkey. Thirty two of the 57 PSTs who participated in this study were in the experimental group and 25 in the control group.…

Studying Equilibrium in the Chemical Reaction between Ferric and Iodide Ions in Solution Using a Simple and Inexpensive Approach

ERIC Educational Resources Information Center

Nikolaychuk, Pavel Anatolyevich; Kuvaeva, Alyona Olegovna

2016-01-01

A laboratory experiment on the study of the chemical equilibrium based on the reaction between ferric and iodide ions in solution with the formation of ferrous ions, free iodine, and triiodide ions is developed. The total concentration of iodide and triiodide ions in the reaction mixture during the reaction is determined by the argentometric…

Reviewing Some Crucial Concepts of Gibbs Energy in Chemical Equilibrium Using a Computer-Assisted, Guided-Problem-Solving Approach

ERIC Educational Resources Information Center

Borge, Javier

2015-01-01

G, G°, [delta][subscript r]G, [delta][subscript r]G°, [delta]G, and [delta]G° are essential quantities to master the chemical equilibrium. Although the number of publications devoted to explaining these items is extremely high, it seems that they do not produce the desired effect because some articles and textbooks are still being written with…

The effects of using screencasting as a multimedia pre-training tool to manage the intrinsic cognitive load of chemical equilibrium instruction for advanced high school chemistry students

NASA Astrophysics Data System (ADS)

Musallam, Ramsey

Chemistry is a complex knowledge domain. Specifically, research notes that Chemical Equilibrium presents greater cognitive challenges than other topics in chemistry. Cognitive Load Theory describes the impact a subject, and the learning environment, have on working memory. Intrinsic load is the facet of Cognitive Load Theory that explains the complexity innate to complex subjects. The purpose of this study was to build on the limited research into intrinsic cognitive load, by examining the effects of using multimedia screencasts as a pre-training technique to manage the intrinsic cognitive load of chemical equilibrium instruction for advanced high school chemistry students. A convenience sample of 62 fourth-year high school students enrolled in an advanced chemistry course from a co-ed high school in urban San Francisco were given a chemical equilibrium concept pre-test. Upon conclusion of the pre-test, students were randomly assigned to two groups: pre-training and no pre-training. The pre-training group received a 10 minute and 52 second pre-training screencast that provided definitions, concepts and an overview of chemical equilibrium. After pre-training both group received the same 50-minute instructional lecture. After instruction, all students were given a chemical equilibrium concept post-test. Independent sample t-tests were conducted to examine differences in performance and intrinsic load. No significant differences in performance or intrinsic load, as measured by ratings of mental effort, were observed on the pre-test. Significant differences in performance, t(60)=3.70, p=.0005, and intrinsic load, t(60)=5.34, p=.0001, were observed on the post-test. A significant correlation between total performance scores and total mental effort ratings was also observed, r(60)=-0.44, p=.0003. Because no significant differences in prior knowledge were observed, it can be concluded that pre-training was successful at reducing intrinsic load. Moreover, a significant correlation between performance and mental effort strengthens the argument that performance measures can be used to approximate intrinsic cognitive load.

Barium isotope fractionation during witherite (BaCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; van Zuilen, Kirsten; Purgstaller, Bettina; Baldermann, Andre; Nägler, Thomas F.; Dietzel, Martin

2016-10-01

This study examines the behavior of Ba isotope fractionation between witherite and fluid during mineral dissolution, precipitation and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 10-2 M NaCl solution where the pH was adjusted by continuous bubbling of a water saturated gas phase of CO2 or atmospheric air. During witherite dissolution no Ba isotope fractionation was observed between solid and fluid. In contrast, during witherite precipitation, caused by a pH increase, a preferential uptake of the lighter 134Ba isotopomer in the solid phase was observed. In this case, the isotope fractionation factor αwitherite-fluid is calculated to be 0.99993 ± 0.00004 (or Δ137/134Bawitherite-fluid ≈ -0.07 ± 0.04‰, 2 sd). The most interesting feature of this study, however, is that after the attainment of chemical equilibrium, the Ba isotope composition of the aqueous phase is progressively becoming lighter, indicating a continuous exchange of Ba2+ ions between witherite and fluid. Mass balance calculations indicate that the detachment of Ba from the solid is not only restricted to the outer surface layer of the solid, but affects several (∼7 unit cells) subsurface layers of the crystal. This observation comes in excellent agreement with the concept of a dynamic system at chemical equilibrium in a mineral-fluid system, denoting that the time required for the achievement of isotopic equilibrium in the witherite-fluid system is longer compared to that observed for chemical equilibrium. Overall, these results indicate that the isotopic composition of Ba bearing carbonates in natural environments may be altered due to changes in fluid composition without a net dissolution/precipitation to be observed.

Convergence to equilibrium of renormalised solutions to nonlinear chemical reaction–diffusion systems

NASA Astrophysics Data System (ADS)

Fellner, Klemens; Tang, Bao Quoc

2018-06-01

The convergence to equilibrium for renormalised solutions to nonlinear reaction-diffusion systems is studied. The considered reaction-diffusion systems arise from chemical reaction networks with mass action kinetics and satisfy the complex balanced condition. By applying the so-called entropy method, we show that if the system does not have boundary equilibria, i.e. equilibrium states lying on the boundary of R_+^N, then any renormalised solution converges exponentially to the complex balanced equilibrium with a rate, which can be computed explicitly up to a finite-dimensional inequality. This inequality is proven via a contradiction argument and thus not explicitly. An explicit method of proof, however, is provided for a specific application modelling a reversible enzyme reaction by exploiting the specific structure of the conservation laws. Our approach is also useful to study the trend to equilibrium for systems possessing boundary equilibria. More precisely, to show the convergence to equilibrium for systems with boundary equilibria, we establish a sufficient condition in terms of a modified finite-dimensional inequality along trajectories of the system. By assuming this condition, which roughly means that the system produces too much entropy to stay close to a boundary equilibrium for infinite time, the entropy method shows exponential convergence to equilibrium for renormalised solutions to complex balanced systems with boundary equilibria.

Stochastic pumping of non-equilibrium steady-states: how molecules adapt to a fluctuating environment.

PubMed

Astumian, R D

2018-01-11

In the absence of input energy, a chemical reaction in a closed system ineluctably relaxes toward an equilibrium state governed by a Boltzmann distribution. The addition of a catalyst to the system provides a way for more rapid equilibration toward this distribution, but the catalyst can never, in and of itself, drive the system away from equilibrium. In the presence of external fluctuations, however, a macromolecular catalyst (e.g., an enzyme) can absorb energy and drive the formation of a steady state between reactant and product that is not determined solely by their relative energies. Due to the ubiquity of non-equilibrium steady states in living systems, the development of a theory for the effects of external fluctuations on chemical systems has been a longstanding focus of non-equilibrium thermodynamics. The theory of stochastic pumping has provided insight into how a non-equilibrium steady-state can be formed and maintained in the presence of dissipation and kinetic asymmetry. This effort has been greatly enhanced by a confluence of experimental and theoretical work on synthetic molecular machines designed explicitly to harness external energy to drive non-equilibrium transport and self-assembly.

Development and application of the GIM code for the Cyber 203 computer

NASA Technical Reports Server (NTRS)

Stainaker, J. F.; Robinson, M. A.; Rawlinson, E. G.; Anderson, P. G.; Mayne, A. W.; Spradley, L. W.

1982-01-01

The GIM computer code for fluid dynamics research was developed. Enhancement of the computer code, implicit algorithm development, turbulence model implementation, chemistry model development, interactive input module coding and wing/body flowfield computation are described. The GIM quasi-parabolic code development was completed, and the code used to compute a number of example cases. Turbulence models, algebraic and differential equations, were added to the basic viscous code. An equilibrium reacting chemistry model and implicit finite difference scheme were also added. Development was completed on the interactive module for generating the input data for GIM. Solutions for inviscid hypersonic flow over a wing/body configuration are also presented.

A thermal NO(x) prediction model - Scalar computation module for CFD codes with fluid and kinetic effects

NASA Technical Reports Server (NTRS)

Mcbeath, Giorgio; Ghorashi, Bahman; Chun, Kue

1993-01-01

A thermal NO(x) prediction model is developed to interface with a CFD, k-epsilon based code. A converged solution from the CFD code is the input to the postprocessing model for prediction of thermal NO(x). The model uses a decoupled analysis to estimate the equilibrium level of (NO(x))e which is the constant rate limit. This value is used to estimate the flame (NO(x)) and in turn predict the rate of formation at each node using a two-step Zeldovich mechanism. The rate is fixed on the NO(x) production rate plot by estimating the time to reach equilibrium by a differential analysis based on the reaction: O + N2 = NO + N. The rate is integrated in the nonequilibrium time space based on the residence time at each node in the computational domain. The sum of all nodal predictions yields the total NO(x) level.

PROCEDURES FOR THE DERIVATION OF EQUILIBRIUM PARTITIONING SEDIMENT BENCHMARKS (ESBS) FOR THE PROTECTION OF BENTHIC ORGANISMS: COMPENDIUM OF TIER 2 VALUES FOR NONIONIC ORGANICS

EPA Science Inventory

This equilibrium partitioning sediment benchmark (ESB) document describes procedures to derive concentrations for 32 nonionic organic chemicals in sediment which are protective of the presence of freshwater and marine benthic organisms. The equilibrium partitioning (EqP) approach...

Development of an R-based wrapper code for the computation of hydrochemical predominance diagrams based on PHREEQC modeling outputs

NASA Astrophysics Data System (ADS)

Mork, M. W.; Kracht, O.

2012-04-01

When investigating stability relations in aquatic solutions or rock-water interactions, the number of dissolved species and mineral phases involved can be overwhelming. To facilitate an overview about equilibrium relationships and how chemical elements are distributed between different aqueous ions, complexes, and solids, predominance diagrams are a widely used tool in aquatic chemistry. In the simplest approach, the predominance field boundaries can be calculated based on a set of mass action equations and log K values for the reactions between different species. Example given, for the popular redox diagram (pe-pH diagram), half cell reactions according to Nernst's equation can be used (Garrels & Christ 1965). In such case, boundaries between different species are "equal-activity" lines. However, for boundaries between solids and dissolved species a specific concentration needs to be stipulated, and the same applies if other components than those displayed in the diagram are involved in the possible reactions. In such case, the predominance field boundaries depend on the actual concentration values chosen. An alternative approach can be the computation of predominance diagrams using the full speciation obtained from a geochemical speciation program, which then needs to be coupled with an external wrapper code for appropriate control and data pre- and post-processing. In this way, the distribution of different species can be based on the consideration of complete chemical analysis obtained from laboratory investigations. We present the results of a student semester-project that aimed to develop and test an external wrapper program for the computation of pe-pH diagrams based on modeling outputs obtained with PHREEQC (Parkhurst & Appelo 1999). We have chosen PHREEQC for this core task as a geochemical calculation module, because of its capabilities to simulate a wide range of equilibrium reactions between water and minerals. Due to the intended final users, a free and extensible simulation platform was considered important. The wrapper program was created in the R environment which is freely available under the GNU General Public License (R Development Core Team 2011). The wrapper reads in analytical data in the standard PHREEQC input file format and then iterates over a systematic selection of pe and pH values. These data are transferred to PHREEQC for the calculation of a corresponding set of hydrochemical speciations based on thermodynamic equilibrium. The results of the PHREEQC simulations are subsequently analyzed by a postprocessor function in order to derive a two-dimensional representation of the dominant aquatic species in the pe-pH plane. In this step, the most abundant species at each grid point is identified as the predominant one. To investigate the utility of the program, differences in the speciation of iron were calculated from chemical compositions of water samples from one of our current field sites (Gardermoen / Øvre Romerike aquifer in S-Norway).

Molecular simulations of Crussard curves of detonation product mixtures at chemical equilibrium: Microscopic calculation of the Chapman-Jouguet state

NASA Astrophysics Data System (ADS)

Bourasseau, Emeric; Dubois, Vincent; Desbiens, Nicolas; Maillet, Jean-Bernard

2007-06-01

The simultaneous use of the Reaction Ensemble Monte Carlo (ReMC) method and the Adaptative Erpenbeck EOS (AE-EOS) method allows us to calculate direclty the thermodynamical and chemical equilibrium of a mixture on the hugoniot curve. The ReMC method allow to reach chemical equilibrium of detonation products and the AE-EOS method constraints ths system to satisfy the Hugoniot relation. Once the Crussard curve of detonation products has been established, CJ state properties may be calculated. An additional NPT simulation is performed at CJ conditions in order to compute derivative thermodynamic quantities like Cp, Cv, Gruneisen gama, sound velocity, and compressibility factor. Several explosives has been studied, of which PETN, nitromethane, tetranitromethane, and hexanitroethane. In these first simulations, solid carbon is eventually treated using an EOS.

A project based on multi-configuration Dirac-Fock calculations for plasma spectroscopy

NASA Astrophysics Data System (ADS)

Comet, M.; Pain, J.-C.; Gilleron, F.; Piron, R.

2017-09-01

We present a project dedicated to hot plasma spectroscopy based on a Multi-Configuration Dirac-Fock (MCDF) code, initially developed by J. Bruneau. The code is briefly described and the use of the transition state method for plasma spectroscopy is detailed. Then an opacity code for local-thermodynamic-equilibrium plasmas using MCDF data, named OPAMCDF, is presented. Transition arrays for which the number of lines is too large to be handled in a Detailed Line Accounting (DLA) calculation can be modeled within the Partially Resolved Transition Array method or using the Unresolved Transition Arrays formalism in jj-coupling. An improvement of the original Partially Resolved Transition Array method is presented which gives a better agreement with DLA computations. Comparisons with some absorption and emission experimental spectra are shown. Finally, the capability of the MCDF code to compute atomic data required for collisional-radiative modeling of plasma at non local thermodynamic equilibrium is illustrated. In addition to photoexcitation, this code can be used to calculate photoionization, electron impact excitation and ionization cross-sections as well as autoionization rates in the Distorted-Wave or Close Coupling approximations. Comparisons with cross-sections and rates available in the literature are discussed.

Simulations in support of the T4B experiment

NASA Astrophysics Data System (ADS)

Qerushi, Artan; Ross, Patrick; Lohff, Chriss; Raymond, Anthony; Montecalvo, Niccolo

2017-10-01

Simulations in support of the T4B experiment are presented. These include a Grad-Shafranov equilibrium solver and equilibrium reconstruction from flux-loop measurements, collision radiative models for plasma spectroscopy (determination of electron density and temperature from line ratios) and fast ion test particle codes for neutral beam - plasma coupling. ©2017 Lockheed Martin Corporation. All Rights Reserved.

Radiation calculation in non-equilibrium shock layer

NASA Astrophysics Data System (ADS)

Dubois, Joanne

2005-05-01

The purpose of the work was to investigate confidence in radiation predictions on an entry probe body in high temperature conditions taking the Huygens probe as an example. Existing engineering flowfield codes for shock tube and blunt body simulations were used and updated when necessary to compute species molar fractions and flow field parameters. An interface to the PARADE radiation code allowed radiative emission estimates to the body surface to be made. A validation of the radiative models in equilibrium conditions was first made with published data and by comparison with shock tube test case data from the IUSTI TCM2 facility with Titan like atmosphere test gas. Further verifications were made in non-equilibrium with published computations. These comparisons were initially made using a Boltzmann assumption for the electronic states of CN. An attempt was also made to use pseudo species for the individual electronic states of CN. Assumptions made in this analysis are described and a further comparison with shock tube data undertaken. Several CN radiation datasets have been used, and while improvements to the modelling tools have been made, it seems that considerable uncertainty remains in the modelling of the non-equilibrium emission using simple engineering methods.

Characterization of the conformational equilibrium between the two major substates of RNase A using NMR chemical shifts.

PubMed

Camilloni, Carlo; Robustelli, Paul; De Simone, Alfonso; Cavalli, Andrea; Vendruscolo, Michele

2012-03-07

Following the recognition that NMR chemical shifts can be used for protein structure determination, rapid advances have recently been made in methods for extending this strategy for proteins and protein complexes of increasing size and complexity. A remaining major challenge is to develop approaches to exploit the information contained in the chemical shifts about conformational fluctuations in native states of proteins. In this work we show that it is possible to determine an ensemble of conformations representing the free energy surface of RNase A using chemical shifts as replica-averaged restraints in molecular dynamics simulations. Analysis of this surface indicates that chemical shifts can be used to characterize the conformational equilibrium between the two major substates of this protein. © 2012 American Chemical Society

Sensitivity of equilibrium profile reconstruction to motional Stark effect measurements

NASA Astrophysics Data System (ADS)

Batha, S. H.; Levinton, F. M.; Hirshman, S. P.; Bell, M. G.; Wieland, R. M.

1996-09-01

The magnetic-field pitch-angle profile, gamma p(R) identical to tan-1(Bpol/Btor), is measured on TFTR using a motional Stark effect (MSE) polarimeter. Measured pitch angle profiles, along with kinetic profiles and external magnetic measurements, are used to compute a self-consistent equilibrium using the free-boundary variational moments equilibrium code VMEC. Uncertainties in the q profile due to uncertainties in gamma P(R), magnetic measurements and kinetic measurements are found to be small. Subsequent uncertainties in the VMEC-calculated current density and shear profiles are also small

Internal Flow Thermal/Fluid Modeling of STS-107 Port Wing in Support of the Columbia Accident Investigation Board

NASA Technical Reports Server (NTRS)

Sharp, John R.; Kittredge, Ken; Schunk, Richard G.

2003-01-01

As part of the aero-thermodynamics team supporting the Columbia Accident Investigation Board (CAB), the Marshall Space Flight Center was asked to perform engineering analyses of internal flows in the port wing. The aero-thermodynamics team was split into internal flow and external flow teams with the support being divided between shorter timeframe engineering methods and more complex computational fluid dynamics. In order to gain a rough order of magnitude type of knowledge of the internal flow in the port wing for various breach locations and sizes (as theorized by the CAB to have caused the Columbia re-entry failure), a bulk venting model was required to input boundary flow rates and pressures to the computational fluid dynamics (CFD) analyses. This paper summarizes the modeling that was done by MSFC in Thermal Desktop. A venting model of the entire Orbiter was constructed in FloCAD based on Rockwell International s flight substantiation analyses and the STS-107 reentry trajectory. Chemical equilibrium air thermodynamic properties were generated for SINDA/FLUINT s fluid property routines from a code provided by Langley Research Center. In parallel, a simplified thermal mathematical model of the port wing, including the Thermal Protection System (TPS), was based on more detailed Shuttle re-entry modeling previously done by the Dryden Flight Research Center. Once the venting model was coupled with the thermal model of the wing structure with chemical equilibrium air properties, various breach scenarios were assessed in support of the aero-thermodynamics team. The construction of the coupled model and results are presented herein.

When do particle ratios freeze out in relativistic heavy ion collisions?

NASA Astrophysics Data System (ADS)

Humanic, Thomas; Bellwied, Rene

1999-10-01

The systematics of CERN SPS data for transverse mass distributions have been shown to imply that thermal equilibrium is achieved at freeze out in these collisions. This conclusion is based on the observation that for p+p, S+S, and Pb+Pb collisions freeze out occurs at a single temperature for all particle species measured if one assumes a certain uniform expansion velocity after hadronization for each colliding system [1]. A recent final- state rescattering calculation for SPS Pb+Pb collisions has shown that these systematics can be described as a consequence of particle rescattering where the system is assumed initially (i.e. at hadronization) to have a common temperature for all particles and no initial expansion velocity [2]. In addition to kinetic observables, it is equally interesting to investigate the time dependence of particle abundances through particle ratios in such a calculation. Two questions immediately arise: 1) is chemical equilibrium established in these collisions, and 2) when does chemical freeze out occur with respect to thermal freeze out for different particle ratios? How rescattering influences particle ratios is clearly of interest if one would like to deduce information about the hadronization stage of the collision from particle ratios measured at freeze out. For the present work we will show results for strange and non-strange particle ratios within the context of a version of the dynamic transport code used in Ref. [2]. [1] NA44 colaboration, I.G. Bearden et al., Phys. Rev. Lett. 78,2080(1997), [2] T. J. Humanic, Phys. Rev. C 57,866(1998)

Exact results in nonequilibrium statistical mechanics: Formalism and applications in chemical kinetics and single-molecule free energy estimation

NASA Astrophysics Data System (ADS)

Adib, Artur B.

In the last two decades or so, a collection of results in nonequilibrium statistical mechanics that departs from the traditional near-equilibrium framework introduced by Lars Onsager in 1931 has been derived, yielding new fundamental insights into far-from-equilibrium processes in general. Apart from offering a more quantitative statement of the second law of thermodynamics, some of these results---typified by the so-called "Jarzynski equality"---have also offered novel means of estimating equilibrium quantities from nonequilibrium processes, such as free energy differences from single-molecule "pulling" experiments. This thesis contributes to such efforts by offering three novel results in nonequilibrium statistical mechanics: (a) The entropic analog of the Jarzynski equality; (b) A methodology for estimating free energies from "clamp-and-release" nonequilibrium processes; and (c) A directly measurable symmetry relation in chemical kinetics similar to (but more general than) chemical detailed balance. These results share in common the feature of remaining valid outside Onsager's near-equilibrium regime, and bear direct applicability in protein folding kinetics as well as in single-molecule free energy estimation.

Progress Toward an Efficient and General CFD Tool for Propulsion Design/Analysis

NASA Technical Reports Server (NTRS)

Cox, C. F.; Cinnella, P.; Westmoreland, S.

1996-01-01

The simulation of propulsive flows inherently involves chemical activity. Recent years have seen substantial strides made in the development of numerical schemes for reacting flowfields, in particular those involving finite-rate chemistry. However, finite-rate calculations are computationally intensive and require knowledge of the actual kinetics, which are not always known with sufficient accuracy. Alternatively, flow simulations based on the assumption of local chemical equilibrium are capable of obtaining physically reasonable results at far less computational cost. The present study summarizes the development of efficient numerical techniques for the simulation of flows in local chemical equilibrium, whereby a 'Black Box' chemical equilibrium solver is coupled to the usual gasdynamic equations. The generalization of the methods enables the modelling of any arbitrary mixture of thermally perfect gases, including air, combustion mixtures and plasmas. As demonstration of the potential of the methodologies, several solutions, involving reacting and perfect gas flows, will be presented. Included is a preliminary simulation of the SSME startup transient. Future enhancements to the proposed techniques will be discussed, including more efficient finite-rate and hybrid (partial equilibrium) schemes. The algorithms that have been developed and are being optimized provide for an efficient and general tool for the design and analysis of propulsion systems.

Preparing "Chameleon Balls" from Natural Plants: Simple Handmade pH Indicator and Teaching Material for Chemical Equilibrium

NASA Astrophysics Data System (ADS)

Kanda, Naoki; Asano, Takayuki; Itoh, Toshiyuki; Onoda, Makoto

1995-12-01

Anthocyanins are found in the flowers and fruits of natural plants. Since their color depends on pH, they are sometines used as a pH indicator. Since these sequences are reversible, they are also useful in demonstrating chemical equilibrium in the repetitive color changes of anthocyanins from flowers by controlling pH conditions. We prepared the polysaccharide beads conatining water extracts of red cabbage as calcium alginate. The beads showed a clear red color under acidic conditions, turned blue at neutral pH of 7, and orange-yellow at pH of 13. This color change could be demonstrated over and over. Because the color changes of these polysaccharide beads depended darmatically on pH, junior high students in science classes called them "chameleon balls" when we demonstrated this reaction for them. In this paper we describe how polysaccharide beads, which are made from calcium alginate with natural pigments, served as a teaching tool for the chemical equilibrium of anthocyanins under different pH conditions. Preparation of the chameleon ball is very easy. The most important thing is that making the chameleon ball is great fun. The ball should therefore be viewed not only as a handmade pH indicator but also an interesting teaching tool of the chemical equilibrium reaction.

Argumentation Practices in Classroom: Pre-service teachers' conceptual understanding of chemical equilibrium

NASA Astrophysics Data System (ADS)

Kaya, Ebru

2013-05-01

This study examines the impact of argumentation practices on pre-service teachers' understanding of chemical equilibrium. The sample consisted of 100 pre-service teachers in two classes of a public university. One of these classes was assigned as experimental and the other as control group, randomly. In the experimental group, the subject of chemical equilibrium was taught by using argumentative practices and the participants were encouraged to participate in the lessons actively. However, the instructor taught the same subject by using the lecturing method without engaging argumentative activities in the control group. The Chemical Equilibrium Concept Test and Written Argumentation Survey were administered to all participants to assess their conceptual understanding and the quality of their arguments, respectively. The analysis of covariance results indicate that argumentation practices significantly improved conceptual understanding of the experimental group when compared to the control group. Furthermore, the results show that the pre-service teachers exposed to argumentative practices constructed more quality arguments than those in the control group after the instruction. Based on these results, it can be concluded that the instruction based on argumentative practices is effective in concept teaching in science education. Therefore, argumentation should be explicitly taught in teacher education besides elementary and secondary education.

A Newton method for the magnetohydrodynamic equilibrium equations

NASA Astrophysics Data System (ADS)

Oliver, Hilary James

We have developed and implemented a (J, B) space Newton method to solve the full nonlinear three dimensional magnetohydrodynamic equilibrium equations in toroidal geometry. Various cases have been run successfully, demonstrating significant improvement over Picard iteration, including a 3D stellarator equilibrium at β = 2%. The algorithm first solves the equilibrium force balance equation for the current density J, given a guess for the magnetic field B. This step is taken from the Picard-iterative PIES 3D equilibrium code. Next, we apply Newton's method to Ampere's Law by expansion of the functional J(B), which is defined by the first step. An analytic calculation in magnetic coordinates, of how the Pfirsch-Schlüter currents vary in the plasma in response to a small change in the magnetic field, yields the Newton gradient term (analogous to ∇f . δx in Newton's method for f(x) = 0). The algorithm is computationally feasible because we do this analytically, and because the gradient term is flux surface local when expressed in terms of a vector potential in an Ar=0 gauge. The equations are discretized by a hybrid spectral/offset grid finite difference technique, and leading order radial dependence is factored from Fourier coefficients to improve finite- difference accuracy near the polar-like origin. After calculating the Newton gradient term we transfer the equation from the magnetic grid to a fixed background grid, which greatly improves the code's performance.

Prediction of hydrodynamics and chemistry of confined turbulent methane-air flames with attention to formation of oxides of nitrogen

NASA Technical Reports Server (NTRS)

Elghobashi, S.; Spalding, D. B.; Srivatsa, S. K.

1977-01-01

A formulation of the governing partial differential equations for fluid flow and reacting chemical species in a tubular combustor is presented. A numerical procedure for the solution of the governing differential equations is described, and models for chemical equilibrium and chemical kinetics calculations are presented. The chemical equilibrium model is used to characterize the hydrocarbon reactions. The chemical kinetics model is used to predict the concentrations of the oxides of nitrogen. The combustor consists of a cylindrical duct of varying cross sections with concentric streams of gaseous fuel and air entering the duct at one end. Four sample cases with specified inlet and boundary conditions are considered, and the results are discussed

Ab Initio Infrared and Raman Spectra.

DTIC Science & Technology

1982-08-01

equilibrium and non -equilibrium systems. It b pointed out that a similar ab !ni- te QFC molecular dynamic approach could be used to compute other types of...applied to -2- equilibrium and non -equilibrium system. It is pointed out that a similar oh im- ib QFCT molecular dynamic approach could be used to...desire to be able to experimentally identify and understand transient species or states (such as those existing during the course of chemical

Effect of a Perturbation on the Chemical Equilibrium: Comparison with Le Châtelier's Principle

NASA Astrophysics Data System (ADS)

Martínez Torres, Emilio

2007-03-01

This article develops a general thermodynamic treatment to predict the direction of shift in a chemical equilibrium when it is subjected to a stress. This treatment gives an inequality that relates the change in the perturbed variable and the change that the equilibrium shift produces in the conjugated variable. To illustrate the generality of this approach, it has been applied to predict the direction of shift caused by changes of pressure, volume, and amount of substance. In this last case, the well-known unexpected shift in the ammonia synthesis equilibrium upon addition of nitrogen is easily explained. From the above referred inequality and the stability criteria of thermodynamics some conclusions have been obtained about the direction of shift in terms of extensive and extensive variables. This article is suitable for physical chemistry courses.

Modeling the Non-Equilibrium Process of the Chemical Adsorption of Ammonia on GaN(0001) Reconstructed Surfaces Based on Steepest-Entropy-Ascent Quantum Thermodynamics.

PubMed

Kusaba, Akira; Li, Guanchen; von Spakovsky, Michael R; Kangawa, Yoshihiro; Kakimoto, Koichi

2017-08-15

Clearly understanding elementary growth processes that depend on surface reconstruction is essential to controlling vapor-phase epitaxy more precisely. In this study, ammonia chemical adsorption on GaN(0001) reconstructed surfaces under metalorganic vapor phase epitaxy (MOVPE) conditions (3Ga-H and N ad -H + Ga-H on a 2 × 2 unit cell) is investigated using steepest-entropy-ascent quantum thermodynamics (SEAQT). SEAQT is a thermodynamic-ensemble based, first-principles framework that can predict the behavior of non-equilibrium processes, even those far from equilibrium where the state evolution is a combination of reversible and irreversible dynamics. SEAQT is an ideal choice to handle this problem on a first-principles basis since the chemical adsorption process starts from a highly non-equilibrium state. A result of the analysis shows that the probability of adsorption on 3Ga-H is significantly higher than that on N ad -H + Ga-H. Additionally, the growth temperature dependence of these adsorption probabilities and the temperature increase due to the heat of reaction is determined. The non-equilibrium thermodynamic modeling applied can lead to better control of the MOVPE process through the selection of preferable reconstructed surfaces. The modeling also demonstrates the efficacy of DFT-SEAQT coupling for determining detailed non-equilibrium process characteristics with a much smaller computational burden than would be entailed with mechanics-based, microscopic-mesoscopic approaches.

Modeling the Non-Equilibrium Process of the Chemical Adsorption of Ammonia on GaN(0001) Reconstructed Surfaces Based on Steepest-Entropy-Ascent Quantum Thermodynamics

PubMed Central

Kusaba, Akira; von Spakovsky, Michael R.; Kangawa, Yoshihiro; Kakimoto, Koichi

2017-01-01

Clearly understanding elementary growth processes that depend on surface reconstruction is essential to controlling vapor-phase epitaxy more precisely. In this study, ammonia chemical adsorption on GaN(0001) reconstructed surfaces under metalorganic vapor phase epitaxy (MOVPE) conditions (3Ga-H and Nad-H + Ga-H on a 2 × 2 unit cell) is investigated using steepest-entropy-ascent quantum thermodynamics (SEAQT). SEAQT is a thermodynamic-ensemble based, first-principles framework that can predict the behavior of non-equilibrium processes, even those far from equilibrium where the state evolution is a combination of reversible and irreversible dynamics. SEAQT is an ideal choice to handle this problem on a first-principles basis since the chemical adsorption process starts from a highly non-equilibrium state. A result of the analysis shows that the probability of adsorption on 3Ga-H is significantly higher than that on Nad-H + Ga-H. Additionally, the growth temperature dependence of these adsorption probabilities and the temperature increase due to the heat of reaction is determined. The non-equilibrium thermodynamic modeling applied can lead to better control of the MOVPE process through the selection of preferable reconstructed surfaces. The modeling also demonstrates the efficacy of DFT-SEAQT coupling for determining detailed non-equilibrium process characteristics with a much smaller computational burden than would be entailed with mechanics-based, microscopic-mesoscopic approaches. PMID:28809816

Earth's Core-Mantle equilibrium and a heat sink at the Core Mantle Boundary

NASA Astrophysics Data System (ADS)

Alfe, D.; Pozzo, M.; Davies, C. J.; Gubbins, D.

2016-12-01

Chemical equilibrium between the two sides of the core mantle boundary (CMB) has longbeen debated. If the core is well mixed and in equilibrium with the inner coredisequilibrium at the CMB seems inevitable. Indeed, a number of experiments pointto a possible non-equilibrium configuration in which the core liquid iron mixture wouldbe undersaturated in oxygen. As discussed by several authors, this chemical imbalancecould result in the formation of an oxygen rich layer at the top of the core, and astratification, which could explain a seismic anomaly claimed by some authors.Here we have revisited the core-mantle equilibrium by calculating the chemical potentialof FeO in both liquid iron mixtures and solid Periclase at CMB conditions, usingfirst principles methods based on quantum mechanics and standard statistical mechanics.We find that FeO is favoured in the liquid mixture, with an equilibrium O concentrationthat is much larger than that of the bulk core. In addition, we find that the heat ofreaction of the FeO dissolution form the mantle to the core is positive, making thereaction endothermic, and therefore providing a heat sink at the top of the core.The power lost in the heat sink depends on the rate of FeO dissolution, and we discussa scenario which could result in a heat sink of several TW. This sink would absorbsome of the heat conducted along the core adiabat and reduce the CMB heat flux.

Modeling of laser induced air plasma and shock wave dynamics using 2D-hydrodynamic simulations

NASA Astrophysics Data System (ADS)

Paturi, Prem Kiran; S, Sai Shiva; Chelikani, Leela; Ikkurthi, Venkata Ramana; C. D., Sijoy; Chaturvedi, Shashank; Acrhem, University Of Hyderabad Team; Computational Analysis Division, Bhabha Atomic Research Centre, Visakhapatnam Team

2017-06-01

The laser induced air plasma dynamics and the SW evolution modeled using the two dimensional hydrodynamic code by considering two different EOS: ideal gas EOS with charge state effects taken into consideration and Chemical Equilibrium applications (CEA) EOS considering the chemical kinetics of different species will be presented. The inverse bremsstrahlung absorption process due to electron-ion and electron-neutrals is considered for the laser-air interaction process for both the models. The numerical results obtained with the two models were compared with that of the experimental observations over the time scales of 200 - 4000 ns at an input laser intensity of 2.3 ×1010 W/cm2. The comparison shows that the plasma and shock dynamics differ significantly for two EOS considered. With the ideas gas EOS the asymmetric expansion and the subsequent plasma dynamics have been well reproduced as observed in the experiments, whereas with the CEA model these processes were not reproduced due to the laser energy absorption occurring mostly at the focal volume. ACRHEM team thank DRDO, India for funding.

Finite-beta equilibria for Wendelstein 7-X configurations using the Princeton Iterative Equilibrium Solver code

NASA Astrophysics Data System (ADS)

Arndt, S.; Merkel, P.; Monticello, D. A.; Reiman, A. H.

1999-04-01

Fixed- and free-boundary equilibria for Wendelstein 7-X (W7-X) [W. Lotz et al., Plasma Physics and Controlled Nuclear Fusion Research 1990 (Proc. 13th Int. Conf. Washington, DC, 1990), (International Atomic Energy Agency, Vienna, 1991), Vol. 2, p. 603] configurations are calculated using the Princeton Iterative Equilibrium Solver (PIES) [A. H. Reiman et al., Comput. Phys. Commun., 43, 157 (1986)] to deal with magnetic islands and stochastic regions. Usually, these W7-X configurations require a large number of iterations for PIES convergence. Here, two methods have been successfully tested in an attempt to decrease the number of iterations needed for convergence. First, periodic sequences of different blending parameters are used. Second, the initial guess is vastly improved by using results of the Variational Moments Equilibrium Code (VMEC) [S. P. Hirshmann et al., Phys. Fluids 26, 3553 (1983)]. Use of these two methods have allowed verification of the Hamada condition and tendency of "self-healing" of islands has been observed.

Modeling MHD Equilibrium and Dynamics with Non-Axisymmetric Resistive Walls in LTX and HBT-EP

NASA Astrophysics Data System (ADS)

Hansen, C.; Levesque, J.; Boyle, D. P.; Hughes, P.

2017-10-01

In experimental magnetized plasmas, currents in the first wall, vacuum vessel, and other conducting structures can have a strong influence on plasma shape and dynamics. These effects are complicated by the 3D nature of these structures, which dictate available current paths. Results from simulations to study the effect of external currents on plasmas in two different experiments will be presented: 1) The arbitrary geometry, 3D extended MHD code PSI-Tet is applied to study linear and non-linear plasma dynamics in the High Beta Tokamak (HBT-EP) focusing on toroidal asymmetries in the adjustable conducting wall. 2) Equilibrium reconstructions of the Lithium Tokamak eXperiment (LTX) in the presence of non-axisymmetric eddy currents. An axisymmetric model is used to reconstruct the plasma equilibrium, using the PSI-Tri code, along with a set of fixed 3D eddy current distributions in the first wall and vacuum vessel [C. Hansen et al., PoP Apr. 2017]. Simulations of detailed experimental geometries are enabled by use of the PSI-Tet code, which employs a high order finite element method on unstructured tetrahedral grids that are generated directly from CAD models. Further development of PSI-Tet and PSI-Tri will also be presented. This work supported by US DOE contract DE-SC0016256.

Computational design of an experimental laser-powered thruster

NASA Technical Reports Server (NTRS)

Jeng, San-Mou; Litchford, Ronald; Keefer, Dennis

1988-01-01

An extensive numerical experiment, using the developed computer code, was conducted to design an optimized laser-sustained hydrogen plasma thruster. The plasma was sustained using a 30 kW CO2 laser beam operated at 10.6 micrometers focused inside the thruster. The adopted physical model considers two-dimensional compressible Navier-Stokes equations coupled with the laser power absorption process, geometric ray tracing for the laser beam, and the thermodynamically equilibrium (LTE) assumption for the plasma thermophysical and optical properties. A pressure based Navier-Stokes solver using body-fitted coordinate was used to calculate the laser-supported rocket flow which consists of both recirculating and transonic flow regions. The computer code was used to study the behavior of laser-sustained plasmas within a pipe over a wide range of forced convection and optical arrangements before it was applied to the thruster design, and these theoretical calculations agree well with existing experimental results. Several different throat size thrusters operated at 150 and 300 kPa chamber pressure were evaluated in the numerical experiment. It is found that the thruster performance (vacuum specific impulse) is highly dependent on the operating conditions, and that an adequately designed laser-supported thruster can have a specific impulse around 1500 sec. The heat loading on the wall of the calculated thrusters were also estimated, and it is comparable to heat loading on the conventional chemical rocket. It was also found that the specific impulse of the calculated thrusters can be reduced by 200 secs due to the finite chemical reaction rate.

Extension of a Kinetic Approach to Chemical Reactions to Electronic Energy Levels and Reactions Involving Charged Species with Application to DSMC Simulations

NASA Technical Reports Server (NTRS)

Liechty, Derek S.

2014-01-01

The ability to compute rarefied, ionized hypersonic flows is becoming more important as missions such as Earth reentry, landing high mass payloads on Mars, and the exploration of the outer planets and their satellites are being considered. Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties are extended in the current work to include electronic energy level transitions and reactions involving charged particles. These extensions are shown to agree favorably with reported transition and reaction rates from the literature for near-equilibrium conditions. Also, the extensions are applied to the second flight of the Project FIRE flight experiment at 1634 seconds with a Knudsen number of 0.001 at an altitude of 76.4 km. In order to accomplish this, NASA's direct simulation Monte Carlo code DAC was rewritten to include the ability to simulate charge-neutral ionized flows, take advantage of the recently introduced chemistry model, and to include the extensions presented in this work. The 1634 second data point was chosen for comparisons to be made in order to include a CFD solution. The Knudsen number at this point in time is such that the DSMC simulations are still tractable and the CFD computations are at the edge of what is considered valid because, although near-transitional, the flow is still considered to be continuum. It is shown that the inclusion of electronic energy levels in the DSMC simulation is necessary for flows of this nature and is required for comparison to the CFD solution. The flow field solutions are also post-processed by the nonequilibrium radiation code HARA to compute the radiative portion.

Converting Panax ginseng DNA and chemical fingerprints into two-dimensional barcode.

PubMed

Cai, Yong; Li, Peng; Li, Xi-Wen; Zhao, Jing; Chen, Hai; Yang, Qing; Hu, Hao

2017-07-01

In this study, we investigated how to convert the Panax ginseng DNA sequence code and chemical fingerprints into a two-dimensional code. In order to improve the compression efficiency, GATC2Bytes and digital merger compression algorithms are proposed. HPLC chemical fingerprint data of 10 groups of P. ginseng from Northeast China and the internal transcribed spacer 2 (ITS2) sequence code as the DNA sequence code were ready for conversion. In order to convert such data into a two-dimensional code, the following six steps were performed: First, the chemical fingerprint characteristic data sets were obtained through the inflection filtering algorithm. Second, precompression processing of such data sets is undertaken. Third, precompression processing was undertaken with the P. ginseng DNA (ITS2) sequence codes. Fourth, the precompressed chemical fingerprint data and the DNA (ITS2) sequence code were combined in accordance with the set data format. Such combined data can be compressed by Zlib, an open source data compression algorithm. Finally, the compressed data generated a two-dimensional code called a quick response code (QR code). Through the abovementioned converting process, it can be found that the number of bytes needed for storing P. ginseng chemical fingerprints and its DNA (ITS2) sequence code can be greatly reduced. After GTCA2Bytes algorithm processing, the ITS2 compression rate reaches 75% and the chemical fingerprint compression rate exceeds 99.65% via filtration and digital merger compression algorithm processing. Therefore, the overall compression ratio even exceeds 99.36%. The capacity of the formed QR code is around 0.5k, which can easily and successfully be read and identified by any smartphone. P. ginseng chemical fingerprints and its DNA (ITS2) sequence code can form a QR code after data processing, and therefore the QR code can be a perfect carrier of the authenticity and quality of P. ginseng information. This study provides a theoretical basis for the development of a quality traceability system of traditional Chinese medicine based on a two-dimensional code.

LSENS - GENERAL CHEMICAL KINETICS AND SENSITIVITY ANALYSIS CODE

NASA Technical Reports Server (NTRS)

Bittker, D. A.

1994-01-01

LSENS has been developed for solving complex, homogeneous, gas-phase, chemical kinetics problems. The motivation for the development of this program is the continuing interest in developing detailed chemical reaction mechanisms for complex reactions such as the combustion of fuels and pollutant formation and destruction. A reaction mechanism is the set of all elementary chemical reactions that are required to describe the process of interest. Mathematical descriptions of chemical kinetics problems constitute sets of coupled, nonlinear, first-order ordinary differential equations (ODEs). The number of ODEs can be very large because of the numerous chemical species involved in the reaction mechanism. Further complicating the situation are the many simultaneous reactions needed to describe the chemical kinetics of practical fuels. For example, the mechanism describing the oxidation of the simplest hydrocarbon fuel, methane, involves over 25 species participating in nearly 100 elementary reaction steps. Validating a chemical reaction mechanism requires repetitive solutions of the governing ODEs for a variety of reaction conditions. Analytical solutions to the systems of ODEs describing chemistry are not possible, except for the simplest cases, which are of little or no practical value. Consequently, there is a need for fast and reliable numerical solution techniques for chemical kinetics problems. In addition to solving the ODEs describing chemical kinetics, it is often necessary to know what effects variations in either initial condition values or chemical reaction mechanism parameters have on the solution. Such a need arises in the development of reaction mechanisms from experimental data. The rate coefficients are often not known with great precision and in general, the experimental data are not sufficiently detailed to accurately estimate the rate coefficient parameters. The development of a reaction mechanism is facilitated by a systematic sensitivity analysis which provides the relationships between the predictions of a kinetics model and the input parameters of the problem. LSENS provides for efficient and accurate chemical kinetics computations and includes sensitivity analysis for a variety of problems, including nonisothermal conditions. LSENS replaces the previous NASA general chemical kinetics codes GCKP and GCKP84. LSENS is designed for flexibility, convenience and computational efficiency. A variety of chemical reaction models can be considered. The models include static system, steady one-dimensional inviscid flow, reaction behind an incident shock wave including boundary layer correction, and the perfectly stirred (highly backmixed) reactor. In addition, computations of equilibrium properties can be performed for the following assigned states, enthalpy and pressure, temperature and pressure, internal energy and volume, and temperature and volume. For static problems LSENS computes sensitivity coefficients with respect to the initial values of the dependent variables and/or the three rates coefficient parameters of each chemical reaction. To integrate the ODEs describing chemical kinetics problems, LSENS uses the packaged code LSODE, the Livermore Solver for Ordinary Differential Equations, because it has been shown to be the most efficient and accurate code for solving such problems. The sensitivity analysis computations use the decoupled direct method, as implemented by Dunker and modified by Radhakrishnan. This method has shown greater efficiency and stability with equal or better accuracy than other methods of sensitivity analysis. LSENS is written in FORTRAN 77 with the exception of the NAMELIST extensions used for input. While this makes the code fairly machine independent, execution times on IBM PC compatibles would be unacceptable to most users. LSENS has been successfully implemented on a Sun4 running SunOS and a DEC VAX running VMS. With minor modifications, it should also be easily implemented on other platforms with FORTRAN compilers which support NAMELIST input. LSENS required 4Mb of RAM under SunOS 4.1.1 and 3.4Mb of RAM under VMS 5.5.1. The standard distribution medium for LSENS is a .25 inch streaming magnetic tape cartridge (QIC-24) in UNIX tar format. It is also available on a 1600 BPI 9-track magnetic tape or a TK50 tape cartridge in DEC VAX BACKUP format. Alternate distribution media and formats are available upon request. LSENS was developed in 1992.

Nonequilibrium radiation and chemistry models for aerocapture vehicle flowfields

NASA Technical Reports Server (NTRS)

Carlson, Leland A.

1994-01-01

The primary accomplishments of the project were as follows: (1) From an overall standpoint, the primary accomplishment of this research was the development of a complete gasdynamic-radiatively coupled nonequilibrium viscous shock layer solution method for axisymmetric blunt bodies. This method can be used for rapid engineering modeling of nonequilibrium re-entry flowfields over a wide range of conditions. (2) Another significant accomplishment was the development of an air radiation model that included local thermodynamic nonequilibrium (LTNE) phenomena. (3) As part of this research, three electron-electronic energy models were developed. The first was a quasi-equilibrium electron (QEE) model which determined an effective free electron temperature and assumed that the electronic states were in equilibrium with the free electrons. The second was a quasi-equilibrium electron-electronic (QEEE) model which computed an effective electron-electronic temperature. The third model was a full electron-electronic (FEE) differential equation model which included convective, collisional, viscous, conductive, vibrational coupling, and chemical effects on electron-electronic energy. (4) Since vibration-dissociation coupling phenomena as well as vibrational thermal nonequilibrium phenomena are important in the nonequilibrium zone behind a shock front, a vibrational energy and vibration-dissociation coupling model was developed and included in the flowfield model. This model was a modified coupled vibrational dissociation vibrational (MCVDV) model and also included electron-vibrational coupling. (5) Another accomplishment of the project was the usage of the developed models to investigate radiative heating. (6) A multi-component diffusion model which properly models the multi-component nature of diffusion in complex gas mixtures such as air, was developed and incorporated into the blunt body model. (7) A model was developed to predict the magnitude and characteristics of the shock wave precursor ahead of vehicles entering the Earth's atmosphere. (8) Since considerable data exists for radiating nonequilibrium flow behind normal shock waves, a normal shock wave version of the blunt body code was developed. (9) By comparing predictions from the models and codes with available normal shock data and the flight data of Fire II, it is believed that the developed flowfield and nonequilibrium radiation models have been essentially validated for engineering applications.

SPECIES - EVALUATING THERMODYNAMIC PROPERTIES, TRANSPORT PROPERTIES & EQUILIBRIUM CONSTANTS OF AN 11-SPECIES AIR MODEL

NASA Technical Reports Server (NTRS)

Thompson, R. A.

1994-01-01

Accurate numerical prediction of high-temperature, chemically reacting flowfields requires a knowledge of the physical properties and reaction kinetics for the species involved in the reacting gas mixture. Assuming an 11-species air model at temperatures below 30,000 degrees Kelvin, SPECIES (Computer Codes for the Evaluation of Thermodynamic Properties, Transport Properties, and Equilibrium Constants of an 11-Species Air Model) computes values for the species thermodynamic and transport properties, diffusion coefficients and collision cross sections for any combination of the eleven species, and reaction rates for the twenty reactions normally occurring. The species represented in the model are diatomic nitrogen, diatomic oxygen, atomic nitrogen, atomic oxygen, nitric oxide, ionized nitric oxide, the free electron, ionized atomic nitrogen, ionized atomic oxygen, ionized diatomic nitrogen, and ionized diatomic oxygen. Sixteen subroutines compute the following properties for both a single species, interaction pair, or reaction, and an array of all species, pairs, or reactions: species specific heat and static enthalpy, species viscosity, species frozen thermal conductivity, diffusion coefficient, collision cross section (OMEGA 1,1), collision cross section (OMEGA 2,2), collision cross section ratio, and equilibrium constant. The program uses least squares polynomial curve-fits of the most accurate data believed available to provide the requested values more quickly than is possible with table look-up methods. The subroutines for computing transport coefficients and collision cross sections use additional code to correct for any electron pressure when working with ionic species. SPECIES was developed on a SUN 3/280 computer running the SunOS 3.5 operating system. It is written in standard FORTRAN 77 for use on any machine, and requires roughly 92K memory. The standard distribution medium for SPECIES is a 5.25 inch 360K MS-DOS format diskette. The contents of the diskettes are compressed using the PKWARE archiving tools. The utility to unarchive the files, PKUNZIP.EXE, is included. This program was last updated in 1991. SUN and SunOS are registered trademarks of Sun Microsystems, Inc.

Evolution of light hydrocarbon gases in subsurface processes: Constraints from chemical equilibrium

NASA Astrophysics Data System (ADS)

Sugisaki, Ryuichi; Nagamine, Koichiro

1995-06-01

The behaviour of CH 4, C 2H 6 and C 3H 8 in subsurface processes such as magma intrusion, volcanic gas discharge and natural gas generation have been examined from the viewpoint of chemical equilibrium. It seems that equilibrium among these three hydrocarbons is attainable at about 200°C. When a system at high temperatures is cooled, re-equilibration is continued until a low temperature is reached. The rate at which re-equilibration is achieved, however, steadily diminishes and, below 200°C, the reaction between the hydrocarbons stops and the gas composition at this time is frozen in, and it remains unchanged in a metastable state for a long period of geological time. Natural gas compositions from various fields have shown that, when a hydrocarbon system out of chemical equilibrium is heated, it gradually approaches equilibrium above 150°C. On the way towards equilibration, compositions of thermogenic gases apparently temporarily show a thermodynamic equilibrium constant at a temperature that is higher than the real equilibrium temperature expected from the ambient temperature of the samples; in contrast, biogenic gases indicate a lower temperature. In lower temperature regions, kinetic effects probably control the gas composition; the compositions are essentially subjected to genetic processes operating on the gases (such as pyrolysis of organic material and bacterial activity) and they fluctuate substantially. Examination of volcanic gases and pyrolysis experimental data, however, have suggested that the equilibration rate of these hydrocarbons is sluggish in comparison with that of reactive inorganic species such as H 2S and SO 2. The view presented in this study will be helpful in understanding the genetic processes that create oil and gas and the migration of these hydrocarbons and in interpreting the origins of magmatic gases.

Chemical computing with reaction-diffusion processes.

PubMed

Gorecki, J; Gizynski, K; Guzowski, J; Gorecka, J N; Garstecki, P; Gruenert, G; Dittrich, P

2015-07-28

Chemical reactions are responsible for information processing in living organisms. It is believed that the basic features of biological computing activity are reflected by a reaction-diffusion medium. We illustrate the ideas of chemical information processing considering the Belousov-Zhabotinsky (BZ) reaction and its photosensitive variant. The computational universality of information processing is demonstrated. For different methods of information coding constructions of the simplest signal processing devices are described. The function performed by a particular device is determined by the geometrical structure of oscillatory (or of excitable) and non-excitable regions of the medium. In a living organism, the brain is created as a self-grown structure of interacting nonlinear elements and reaches its functionality as the result of learning. We discuss whether such a strategy can be adopted for generation of chemical information processing devices. Recent studies have shown that lipid-covered droplets containing solution of reagents of BZ reaction can be transported by a flowing oil. Therefore, structures of droplets can be spontaneously formed at specific non-equilibrium conditions, for example forced by flows in a microfluidic reactor. We describe how to introduce information to a droplet structure, track the information flow inside it and optimize medium evolution to achieve the maximum reliability. Applications of droplet structures for classification tasks are discussed. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

NMR spectroscopic studies of a TAT-derived model peptide in imidazolium-based ILs: influence on chemical shifts and the cis/trans equilibrium state.

PubMed

Wiedemann, Christoph; Ohlenschläger, Oliver; Mrestani-Klaus, Carmen; Bordusa, Frank

2017-09-13

NMR spectroscopy was used to study systematically the impact of imidazolium-based ionic liquid (IL) solutions on a TAT-derived model peptide containing Xaa-Pro peptide bonds. The selected IL anions cover a wide range of the Hofmeister series of ions. Based on highly resolved one- and two-dimensional NMR spectra individual 1 H and 13 C peptide chemical shift differences were analysed and a classification of IL anions according to the Hofmeister series was derived. The observed chemical shift changes indicate significant interactions between the peptide and the ILs. In addition, we examined the impact of different ILs towards the cis/trans equilibrium state of the Xaa-Pro peptide bonds. In this context, the IL cations appear to be of exceptional importance for inducing an alteration of the native cis/trans equilibrium state of Xaa-Pro bonds in favour of the trans-isomers.

Coupling microscopic and mesoscopic scales to simulate chemical equilibrium between a nanometric carbon cluster and detonation products fluid.

PubMed

Bourasseau, Emeric; Maillet, Jean-Bernard

2011-04-21

This paper presents a new method to obtain chemical equilibrium properties of detonation products mixtures including a solid carbon phase. In this work, the solid phase is modelled through a mesoparticle immersed in the fluid, such that the heterogeneous character of the mixture is explicitly taken into account. Inner properties of the clusters are taken from an equation of state obtained in a previous work, and interaction potential between the nanocluster and the fluid particles is derived from all-atoms simulations using the LCBOPII potential (Long range Carbon Bond Order Potential II). It appears that differences in chemical equilibrium results obtained with this method and the "composite ensemble method" (A. Hervouet et al., J. Phys. Chem. B, 2008, 112.), where fluid and solid phases are considered as non-interacting, are not significant, underlining the fact that considering the inhomogeneity of such system is crucial.

Chemical kinetics on extrasolar planets.

PubMed

Moses, Julianne I

2014-04-28

Chemical kinetics plays an important role in controlling the atmospheric composition of all planetary atmospheres, including those of extrasolar planets. For the hottest exoplanets, the composition can closely follow thermochemical-equilibrium predictions, at least in the visible and infrared photosphere at dayside (eclipse) conditions. However, for atmospheric temperatures approximately <2000K, and in the uppermost atmosphere at any temperature, chemical kinetics matters. The two key mechanisms by which kinetic processes drive an exoplanet atmosphere out of equilibrium are photochemistry and transport-induced quenching. I review these disequilibrium processes in detail, discuss observational consequences and examine some of the current evidence for kinetic processes on extrasolar planets.

Mesoscale simulations of shockwave energy dissipation via chemical reactions.

PubMed

Antillon, Edwin; Strachan, Alejandro

2015-02-28

We use a particle-based mesoscale model that incorporates chemical reactions at a coarse-grained level to study the response of materials that undergo volume-reducing chemical reactions under shockwave-loading conditions. We find that such chemical reactions can attenuate the shockwave and characterize how the parameters of the chemical model affect this behavior. The simulations show that the magnitude of the volume collapse and velocity at which the chemistry propagates are critical to weaken the shock, whereas the energetics in the reactions play only a minor role. Shock loading results in transient states where the material is away from local equilibrium and, interestingly, chemical reactions can nucleate under such non-equilibrium states. Thus, the timescales for equilibration between the various degrees of freedom in the material affect the shock-induced chemistry and its ability to attenuate the propagating shock.

PROCEDURES FOR THE DERIVATION OF EQUILIBRIUM ...

EPA Pesticide Factsheets

This equilibrium partitioning sediment benchmark (ESB) document describes procedures to derive concentrations for 32 nonionic organic chemicals in sediment which are protective of the presence of freshwater and marine benthic organisms. The equilibrium partitioning (EqP) approach was chosen because it accounts for the varying biological availability of chemicals in different sediments and allows for the incorporation of the appropriate biological effects concentration. This provides for the derivation of benchmarks that are causally linked to the specific chemical, applicable across sediments, and appropriately protective of benthic organisms. EqP can be used to calculate ESBs for any toxicity endpoint for which there are water-only toxicity data; it is not limited to any single effect endpoint. For the purposes of this document, ESBs for 32 nonionic organic chemicals, including several low molecular weight aliphatic and aromatic compounds, pesticides, and phthalates, were derived using Final Chronic Values (FCV) from Water Quality Criteria (WQC) or Secondary Chronic Values (SCV) derived from existing toxicological data using the Great Lakes Water Quality Initiative (GLI) or narcosis theory approaches. These values are intended to be the concentration of each chemical in water that is protective of the presence of aquatic life. For nonionic organic chemicals demonstrating a narcotic mode of action, ESBs derived using the GLI approach specifically for fres

Machine learning predictions of molecular properties: Accurate many-body potentials and nonlocality in chemical space

DOE PAGES

Hansen, Katja; Biegler, Franziska; Ramakrishnan, Raghunathan; ...

2015-06-04

Simultaneously accurate and efficient prediction of molecular properties throughout chemical compound space is a critical ingredient toward rational compound design in chemical and pharmaceutical industries. Aiming toward this goal, we develop and apply a systematic hierarchy of efficient empirical methods to estimate atomization and total energies of molecules. These methods range from a simple sum over atoms, to addition of bond energies, to pairwise interatomic force fields, reaching to the more sophisticated machine learning approaches that are capable of describing collective interactions between many atoms or bonds. In the case of equilibrium molecular geometries, even simple pairwise force fields demonstratemore » prediction accuracy comparable to benchmark energies calculated using density functional theory with hybrid exchange-correlation functionals; however, accounting for the collective many-body interactions proves to be essential for approaching the “holy grail” of chemical accuracy of 1 kcal/mol for both equilibrium and out-of-equilibrium geometries. This remarkable accuracy is achieved by a vectorized representation of molecules (so-called Bag of Bonds model) that exhibits strong nonlocality in chemical space. The same representation allows us to predict accurate electronic properties of molecules, such as their polarizability and molecular frontier orbital energies.« less

Stability of high-speed boundary layers in oxygen including chemical non-equilibrium effects

NASA Astrophysics Data System (ADS)

Klentzman, Jill; Tumin, Anatoli

2013-11-01

The stability of high-speed boundary layers in chemical non-equilibrium is examined. A parametric study varying the edge temperature and the wall conditions is conducted for boundary layers in oxygen. The edge Mach number and enthalpy ranges considered are relevant to the flight conditions of reusable hypersonic cruise vehicles. Both viscous and inviscid stability formulations are used and the results compared to gain insight into the effects of viscosity and thermal conductivity on the stability. It is found that viscous effects have a strong impact on the temperature and mass fraction perturbations in the critical layer and in the viscous sublayer near the wall. Outside of these areas, the perturbations closely match in the viscous and inviscid models. The impact of chemical non-equilibrium on the stability is investigated by analyzing the effects of the chemical source term in the stability equations. The chemical source term is found to influence the growth rate of the second Mack mode instability but not have much of an effect on the mass fraction eigenfunction for the flow parameters considered. This work was supported by the AFOSR/NASA/National Center for Hypersonic Laminar-Turbulent Transition Research.

Machine Learning Predictions of Molecular Properties: Accurate Many-Body Potentials and Nonlocality in Chemical Space

PubMed Central

2015-01-01

Simultaneously accurate and efficient prediction of molecular properties throughout chemical compound space is a critical ingredient toward rational compound design in chemical and pharmaceutical industries. Aiming toward this goal, we develop and apply a systematic hierarchy of efficient empirical methods to estimate atomization and total energies of molecules. These methods range from a simple sum over atoms, to addition of bond energies, to pairwise interatomic force fields, reaching to the more sophisticated machine learning approaches that are capable of describing collective interactions between many atoms or bonds. In the case of equilibrium molecular geometries, even simple pairwise force fields demonstrate prediction accuracy comparable to benchmark energies calculated using density functional theory with hybrid exchange-correlation functionals; however, accounting for the collective many-body interactions proves to be essential for approaching the “holy grail” of chemical accuracy of 1 kcal/mol for both equilibrium and out-of-equilibrium geometries. This remarkable accuracy is achieved by a vectorized representation of molecules (so-called Bag of Bonds model) that exhibits strong nonlocality in chemical space. In addition, the same representation allows us to predict accurate electronic properties of molecules, such as their polarizability and molecular frontier orbital energies. PMID:26113956

Molecular finite-size effects in stochastic models of equilibrium chemical systems.

PubMed

Cianci, Claudia; Smith, Stephen; Grima, Ramon

2016-02-28

The reaction-diffusion master equation (RDME) is a standard modelling approach for understanding stochastic and spatial chemical kinetics. An inherent assumption is that molecules are point-like. Here, we introduce the excluded volume reaction-diffusion master equation (vRDME) which takes into account volume exclusion effects on stochastic kinetics due to a finite molecular radius. We obtain an exact closed form solution of the RDME and of the vRDME for a general chemical system in equilibrium conditions. The difference between the two solutions increases with the ratio of molecular diameter to the compartment length scale. We show that an increase in the fraction of excluded space can (i) lead to deviations from the classical inverse square root law for the noise-strength, (ii) flip the skewness of the probability distribution from right to left-skewed, (iii) shift the equilibrium of bimolecular reactions so that more product molecules are formed, and (iv) strongly modulate the Fano factors and coefficients of variation. These volume exclusion effects are found to be particularly pronounced for chemical species not involved in chemical conservation laws. Finally, we show that statistics obtained using the vRDME are in good agreement with those obtained from Brownian dynamics with excluded volume interactions.

Prediction of hydrodynamics and chemistry of confined turbulent methane-air frames in a two concentric tube combustor

NASA Technical Reports Server (NTRS)

Markatos, N. C.; Spalding, D. B.; Srivatsa, S. K.

1978-01-01

A formulation of the governing partial differential equations for fluid flow and reacting chemical species in a two-concentric-tube combustor is presented. A numerical procedure for the solution of the governing differential equations is described and models for chemical-equilibrium and chemical-kinetics calculations are presented. The chemical-equilibrium model is used to characterize the hydrocarbon reactions. The chemical-kinetics model is used to predict the concentrations of the oxides of nitrogen. The combustor considered consists of two coaxial ducts. Concentric streams of gaseous fuel and air enter the inlet duct at one end; the flow then reverses and flows out through the outer duct. Two sample cases with specified inlet and boundary conditions are considered and the results are discussed.

Efficiency of muscle contraction. The chemimechanic equilibrium

NASA Astrophysics Data System (ADS)

Becker, E. W.

1991-10-01

Although muscle contraction is one of the principal themes of biological research, the exact mechanism whereby the chemical free energy of ATP hydrolysis is converted into mechanical work remains elusive. The high thermodynamic efficiency of the process, above all, is difficult to explain on the basis of present theories. A model of the elementary effect in muscle contraction is proposed which aims at high thermodynamic efficiency based on an approximate equilibrium between chemical and mechanical forces throughout the transfer of free energy. The experimental results described in the literature support the assumption that chemimechanic equilibrium is approximated by a free energy transfer system based on the binding of divalent metal ions to the myosin light chains. Muscle contraction demonstrated without light chains is expected to proceed with a considerably lower efficiency. Free energy transfer systems based on the binding of ions to proteins seem to be widespread in the cell. By establishing an approximate chemimechanic equilibrium, they could facilitate biological reactions considerably and save large amounts of free energy. The concept of chemimechanic equilibrium is seen as a supplementation to the concept of chemiosmotic equilibrium introduced for the membrane transport by P. Mitchell.

Thermodynamics of stoichiometric biochemical networks in living systems far from equilibrium.

PubMed

Qian, Hong; Beard, Daniel A

2005-04-22

The principles of thermodynamics apply to both equilibrium and nonequilibrium biochemical systems. The mathematical machinery of the classic thermodynamics, however, mainly applies to systems in equilibrium. We introduce a thermodynamic formalism for the study of metabolic biochemical reaction (open, nonlinear) networks in both time-dependent and time-independent nonequilibrium states. Classical concepts in equilibrium thermodynamics-enthalpy, entropy, and Gibbs free energy of biochemical reaction systems-are generalized to nonequilibrium settings. Chemical motive force, heat dissipation rate, and entropy production (creation) rate, key concepts in nonequilibrium systems, are introduced. Dynamic equations for the thermodynamic quantities are presented in terms of the key observables of a biochemical network: stoichiometric matrix Q, reaction fluxes J, and chemical potentials of species mu without evoking empirical rate laws. Energy conservation and the Second Law are established for steady-state and dynamic biochemical networks. The theory provides the physiochemical basis for analyzing large-scale metabolic networks in living organisms.

Spectral Quasi-Equilibrium Manifold for Chemical Kinetics.

PubMed

Kooshkbaghi, Mahdi; Frouzakis, Christos E; Boulouchos, Konstantinos; Karlin, Iliya V

2016-05-26

The Spectral Quasi-Equilibrium Manifold (SQEM) method is a model reduction technique for chemical kinetics based on entropy maximization under constraints built by the slowest eigenvectors at equilibrium. The method is revisited here and discussed and validated through the Michaelis-Menten kinetic scheme, and the quality of the reduction is related to the temporal evolution and the gap between eigenvalues. SQEM is then applied to detailed reaction mechanisms for the homogeneous combustion of hydrogen, syngas, and methane mixtures with air in adiabatic constant pressure reactors. The system states computed using SQEM are compared with those obtained by direct integration of the detailed mechanism, and good agreement between the reduced and the detailed descriptions is demonstrated. The SQEM reduced model of hydrogen/air combustion is also compared with another similar technique, the Rate-Controlled Constrained-Equilibrium (RCCE). For the same number of representative variables, SQEM is found to provide a more accurate description.

Computer codes for the evaluation of thermodynamic and transport properties for equilibrium air to 30000 K

NASA Technical Reports Server (NTRS)

Thompson, Richard A.; Lee, Kam-Pui; Gupta, Roop N.

1991-01-01

The computer codes developed here provide self-consistent thermodynamic and transport properties for equilibrium air for temperatures from 500 to 30000 K over a temperature range of 10 (exp -4) to 10 (exp -2) atm. These properties are computed through the use of temperature dependent curve fits for discrete values of pressure. Interpolation is employed for intermediate values of pressure. The curve fits are based on mixture values calculated from an 11-species air model. Individual species properties used in the mixture relations are obtained from a recent study by the present authors. A review and discussion of the sources and accuracy of the curve fitted data used herein are given in NASA RP 1260.

Validation of extended magnetohydrodynamic simulations of the HIT-SI3 experiment using the NIMROD code

NASA Astrophysics Data System (ADS)

Morgan, K. D.; Jarboe, T. R.; Hossack, A. C.; Chandra, R. N.; Everson, C. J.

2017-12-01

The HIT-SI3 experiment uses a set of inductively driven helicity injectors to apply a non-axisymmetric current drive on the edge of the plasma, driving an axisymmetric spheromak equilibrium in a central confinement volume. These helicity injectors drive a non-axisymmetric perturbation that oscillates in time, with relative temporal phasing of the injectors modifying the mode structure of the applied perturbation. A set of three experimental discharges with different perturbation spectra are modelled using the NIMROD extended magnetohydrodynamics code, and comparisons are made to both magnetic and fluid measurements. These models successfully capture the bulk dynamics of both the perturbation and the equilibrium, though disagreements related to the pressure gradients experimentally measured exist.

Traceability and Quality Control in Traditional Chinese Medicine: From Chemical Fingerprint to Two-Dimensional Barcode.

PubMed

Cai, Yong; Li, Xiwen; Li, Mei; Chen, Xiaojia; Hu, Hao; Ni, Jingyun; Wang, Yitao

2015-01-01

Chemical fingerprinting is currently a widely used tool that enables rapid and accurate quality evaluation of Traditional Chinese Medicine (TCM). However, chemical fingerprints are not amenable to information storage, recognition, and retrieval, which limit their use in Chinese medicine traceability. In this study, samples of three kinds of Chinese medicines were randomly selected and chemical fingerprints were then constructed by using high performance liquid chromatography. Based on chemical data, the process of converting the TCM chemical fingerprint into two-dimensional code is presented; preprocess and filtering algorithm are also proposed aiming at standardizing the large amount of original raw data. In order to know which type of two-dimensional code (2D) is suitable for storing data of chemical fingerprints, current popular types of 2D codes are analyzed and compared. Results show that QR Code is suitable for recording the TCM chemical fingerprint. The fingerprint information of TCM can be converted into data format that can be stored as 2D code for traceability and quality control.

A quantitative speciation model for the adsorption of organic pollutants on activated carbon.

PubMed

Grivé, M; García, D; Domènech, C; Richard, L; Rojo, I; Martínez, X; Rovira, M

2013-01-01

Granular activated carbon (GAC) is commonly used as adsorbent in water treatment plants given its high capacity for retaining organic pollutants in aqueous phase. The current knowledge on GAC behaviour is essentially empirical, and no quantitative description of the chemical relationships between GAC surface groups and pollutants has been proposed. In this paper, we describe a quantitative model for the adsorption of atrazine onto GAC surface. The model is based on results of potentiometric titrations and three types of adsorption experiments which have been carried out in order to determine the nature and distribution of the functional groups on the GAC surface, and evaluate the adsorption characteristics of GAC towards atrazine. Potentiometric titrations have indicated the existence of at least two different families of chemical groups on the GAC surface, including phenolic- and benzoic-type surface groups. Adsorption experiments with atrazine have been satisfactorily modelled with the geochemical code PhreeqC, assuming that atrazine is sorbed onto the GAC surface in equilibrium (log Ks = 5.1 ± 0.5). Independent thermodynamic calculations suggest a possible adsorption of atrazine on a benzoic derivative. The present work opens a new approach for improving the adsorption capabilities of GAC towards organic pollutants by modifying its chemical properties.

40 CFR 61.341 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... to industrial organic chemicals, organic pesticide products, pharmaceutical preparations, paint and allied products, fertilizers, and agricultural chemicals. Examples of chemical manufacturing plants...). Maximum organic vapor pressure means the equilibrium partial pressure exerted by the waste at the...

Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns.

PubMed

Dousset, S; Thevenot, M; Pot, V; Simunek, J; Andreux, F

2007-12-07

In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due to higher preferential flow and lower fraction of equilibrium sorption sites.

Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns

NASA Astrophysics Data System (ADS)

Dousset, S.; Thevenot, M.; Pot, V.; Šimunek, J.; Andreux, F.

2007-12-01

In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due to higher preferential flow and lower fraction of equilibrium sorption sites.

Regenerable biocide delivery unit, volume 2

NASA Technical Reports Server (NTRS)

Atwater, James E.; Wheeler, Richard R., Jr.

1992-01-01

Source code for programs dealing with the following topics are presented: (1) life cycle test stand-parametric test stand control (in BASIC); (2) simultaneous aqueous iodine equilibria-true equilibrium (in C); (3) simultaneous aqueous iodine equilibria-pseudo-equilibrium (in C); (4) pseudo-(fast)-equilibrium with iodide initially present (in C); (5) solution of simultaneous iodine rate expressions (Mathematica); (6) 2nd order kinetics of I2-formic acid in humidity condensate (Mathematica); (7) prototype RMCV onboard microcontroller (CAMBASIC); (8) prototype RAM data dump to PC (in BASIC); and (9) prototype real time data transfer to PC (in BASIC).

Impact of rainfall intensity on the transport of two herbicides in undisturbed grassed filter strip soil cores

NASA Astrophysics Data System (ADS)

Pot, V.; Šimůnek, J.; Benoit, P.; Coquet, Y.; Yra, A.; Martínez-Cordón, M.-J.

2005-12-01

Two series of displacement experiments with isoproturon and metribuzin herbicides were performed on two undisturbed grassed filter strip soil cores, under unsaturated steady-state flow conditions. Several rainfall intensities (0.070, 0.147, 0.161, 0.308 and 0.326 cm h - 1 ) were used. A water tracer (bromide) was simultaneously injected in each displacement experiment. A descriptive analysis of experimental breakthrough curves of bromide and herbicides combined with a modeling analysis showed an impact of rainfall intensity on the solute transport. Two contrasting physical non-equilibrium transport processes occurred. Multiple (three) porosity domains contributed to flow at the highest rainfall intensities, including preferential flow through macropore pathways. Macropores were not active any longer at intermediate and lowest velocities, and the observed preferential transport was described using dual-porosity-type models with a zero or low flow in the matrix domain. Chemical non-equilibrium transport of herbicides was found at all rainfall intensities. Significantly higher estimated values of degradation rate parameters as compared to batch data were correlated with the degree of non-equilibrium sorption. Experimental breakthrough curves were analyzed using different physical and chemical equilibrium and non-equilibrium transport models: convective-dispersive model (CDE), dual-porosity model (MIM), dual-permeability model (DP), triple-porosity, dual permeability model (DP-MIM); each combined with both chemical instantaneous and kinetic sorption.

Chemistry and Chemical Equilibrium Dynamics of BMAA and Its Carbamate Adducts

PubMed Central

Diaz-parga, Pedro

2018-01-01

Beta-N-methylamino-L-alanine (BMAA) has been demonstrated to contribute to the onset of the ALS/Parkinsonism-dementia complex (ALS/PDC) and is implicated in the progression of other neurodegenerative diseases. While the role of BMAA in these diseases is still debated, one of the suggested mechanisms involves the activation of excitatory glutamate receptors. In particular, the excitatory effects of BMAA are shown to be dependent on the presence of bicarbonate ions, which in turn forms carbamate adducts in physiological conditions. The formation of carbamate adducts from BMAA and bicarbonate is similar to the formation of carbamate adducts from non-proteinogenic amino acids. Structural, chemical, and biological information related to non-proteinogenic amino acids provide insight into the formation of and possible neurological action of BMAA. This article reviews the carbamate formation of BMAA in the presence of bicarbonate ions, with a particular focus on how the chemical equilibrium of BMAA carbamate adducts may affect the molecular mechanism of its function. Highlights of nuclear magnetic resonance (NMR)-based studies on the equilibrium process between free BMAA and its adducts are presented. The role of divalent metals on the equilibrium process is also explored. The formation and the equilibrium process of carbamate adducts of BMAA may answer questions on their neuroactive potency and provide strong motivation for further investigations into other toxic mechanisms. PMID:28921378

Chemistry and Chemical Equilibrium Dynamics of BMAA and Its Carbamate Adducts.

PubMed

Diaz-Parga, Pedro; Goto, Joy J; Krishnan, V V

2018-01-01

Beta-N-methylamino-L-alanine (BMAA) has been demonstrated to contribute to the onset of the ALS/Parkinsonism-dementia complex (ALS/PDC) and is implicated in the progression of other neurodegenerative diseases. While the role of BMAA in these diseases is still debated, one of the suggested mechanisms involves the activation of excitatory glutamate receptors. In particular, the excitatory effects of BMAA are shown to be dependent on the presence of bicarbonate ions, which in turn forms carbamate adducts in physiological conditions. The formation of carbamate adducts from BMAA and bicarbonate is similar to the formation of carbamate adducts from non-proteinogenic amino acids. Structural, chemical, and biological information related to non-proteinogenic amino acids provide insight into the formation of and possible neurological action of BMAA. This article reviews the carbamate formation of BMAA in the presence of bicarbonate ions, with a particular focus on how the chemical equilibrium of BMAA carbamate adducts may affect the molecular mechanism of its function. Highlights of nuclear magnetic resonance (NMR)-based studies on the equilibrium process between free BMAA and its adducts are presented. The role of divalent metals on the equilibrium process is also explored. The formation and the equilibrium process of carbamate adducts of BMAA may answer questions on their neuroactive potency and provide strong motivation for further investigations into other toxic mechanisms.

Transferring mixtures of chemicals from sediment to a bioassay using silicone-based passive sampling and dosing.

PubMed

Mustajärvi, Lukas; Eriksson-Wiklund, Ann-Kristin; Gorokhova, Elena; Jahnke, Annika; Sobek, Anna

2017-11-15

Environmental mixtures of chemicals consist of a countless number of compounds with unknown identity and quantity. Yet, chemical regulation is mainly built around the assessment of single chemicals. Existing frameworks for assessing the toxicity of mixtures require that both the chemical composition and quantity are known. Quantitative analyses of the chemical composition of environmental mixtures are however extremely challenging and resource-demanding. Bioassays may therefore serve as a useful approach for investigating the combined toxicity of environmental mixtures of chemicals in a cost-efficient and holistic manner. In this study, an unknown environmental mixture of bioavailable semi-hydrophobic to hydrophobic chemicals was sampled from a contaminated sediment in a coastal Baltic Sea area using silicone polydimethylsiloxane (PDMS) as an equilibrium passive sampler. The chemical mixture was transferred to a PDMS-based passive dosing system, and its applicability was demonstrated using green algae Tetraselmis suecica in a cell viability assay. The proportion of dead cells increased significantly with increasing exposure level and in a dose-response manner. At an ambient concentration, the proportion of dead cells in the population was nearly doubled compared to the control; however, the difference was non-significant due to high inter-replicate variability and a low number of replicates. The validation of the test system regarding equilibrium sampling, loading efficiency into the passive dosing polymer, stability of the mixture composition, and low algal mortality in control treatments demonstrates that combining equilibrium passive sampling and passive dosing is a promising tool for investigating the toxicity of bioavailable semi-hydrophobic and hydrophobic chemicals in complex environmental mixtures.

HCN production from impact ejecta on the early Earth

NASA Astrophysics Data System (ADS)

Parkos, Devon; Pikus, Aaron; Alexeenko, Alina; Melosh, H. J.

2016-11-01

Major impact events have drastically altered the evolution of life on Earth. The reentry of ejecta formed from these events can trigger widespread chemical changes to the atmosphere on a global scale. This mechanism was proposed as a source of HCN during the Late Heavy Bombardment (LHB), 4.1 to 3.8 billion years ago. Significant concentrations of HCN in surface water could directly lead to adenine formation, a precursor for RNA. This work uses the Direct Simulation Monte Carlo (DSMC) method to examine the production of CN and HCN due to the reentry of impact ejecta. We use the Statistical Modeling in Low-Density Environment (SMILE) code, which utilizes the Total Collisional Energy (TCE) model for reactions. The collisions are described by the Variable Soft Sphere (VSS) and Larsen-Borgnakke (LB) models. We compare this nonequilibrium production to equilibrium concentrations from bulk atmospheric heating. The equilibrium HCN yield for a 1023 J impact is 7.0×104 moles, corresponding to a 2.5×1014 molecules per m2 surface deposition. We find that additional CN and HCN is produced under thermochemical nonequilibrium, particularly at higher altitudes. The total nonequilibrium yield for a 1023 J impact is 1.2×106 moles of HCN, a value 17 times the equilibrium result. This corresponds to a surface deposition of 1.4×1015 molecules per m2. This increase in production indicates that thermochemical nonequilibrium effects play a strong role in HCN from impact ejecta, and must be considered when investigating impacts as a plausible mechanism for significant adenine production during the LHB.

CFD Code Development for Combustor Flows

NASA Technical Reports Server (NTRS)

Norris, Andrew

2003-01-01

During the lifetime of this grant, work has been performed in the areas of model development, code development, code validation and code application. For model development, this has included the PDF combustion module, chemical kinetics based on thermodynamics, neural network storage of chemical kinetics, ILDM chemical kinetics and assumed PDF work. Many of these models were then implemented in the code, and in addition many improvements were made to the code, including the addition of new chemistry integrators, property evaluation schemes, new chemistry models and turbulence-chemistry interaction methodology. Validation of all new models and code improvements were also performed, while application of the code to the ZCET program and also the NPSS GEW combustor program were also performed. Several important items remain under development, including the NOx post processing, assumed PDF model development and chemical kinetic development. It is expected that this work will continue under the new grant.

Nada: A new code for studying self-gravitating tori around black holes

NASA Astrophysics Data System (ADS)

Montero, Pedro J.; Font, José A.; Shibata, Masaru

2008-09-01

We present a new two-dimensional numerical code called Nada designed to solve the full Einstein equations coupled to the general relativistic hydrodynamics equations. The code is mainly intended for studies of self-gravitating accretion disks (or tori) around black holes, although it is also suitable for regular spacetimes. Concerning technical aspects the Einstein equations are formulated and solved in the code using a formulation of the standard 3+1 Arnowitt-Deser-Misner canonical formalism system, the so-called Baumgarte-Shapiro Shibata-Nakamura approach. A key feature of the code is that derivative terms in the spacetime evolution equations are computed using a fourth-order centered finite difference approximation in conjunction with the Cartoon method to impose the axisymmetry condition under Cartesian coordinates (the choice in Nada), and the puncture/moving puncture approach to carry out black hole evolutions. Correspondingly, the general relativistic hydrodynamics equations are written in flux-conservative form and solved with high-resolution, shock-capturing schemes. We perform and discuss a number of tests to assess the accuracy and expected convergence of the code, namely, (single) black hole evolutions, shock tubes, and evolutions of both spherical and rotating relativistic stars in equilibrium, the gravitational collapse of a spherical relativistic star leading to the formation of a black hole. In addition, paving the way for specific applications of the code, we also present results from fully general relativistic numerical simulations of a system formed by a black hole surrounded by a self-gravitating torus in equilibrium.

Reacting Chemistry Based Burn Model for Explosive Hydrocodes

NASA Astrophysics Data System (ADS)

Schwaab, Matthew; Greendyke, Robert; Steward, Bryan

2017-06-01

Currently, in hydrocodes designed to simulate explosive material undergoing shock-induced ignition, the state of the art is to use one of numerous reaction burn rate models. These burn models are designed to estimate the bulk chemical reaction rate. Unfortunately, these models are largely based on empirical data and must be recalibrated for every new material being simulated. We propose that the use of an equilibrium Arrhenius rate reacting chemistry model in place of these empirically derived burn models will improve the accuracy for these computational codes. Such models have been successfully used in codes simulating the flow physics around hypersonic vehicles. A reacting chemistry model of this form was developed for the cyclic nitramine RDX by the Naval Research Laboratory (NRL). Initial implementation of this chemistry based burn model has been conducted on the Air Force Research Laboratory's MPEXS multi-phase continuum hydrocode. In its present form, the burn rate is based on the destruction rate of RDX from NRL's chemistry model. Early results using the chemistry based burn model show promise in capturing deflagration to detonation features more accurately in continuum hydrocodes than previously achieved using empirically derived burn models.

Multivariable optimization of liquid rocket engines using particle swarm algorithms

NASA Astrophysics Data System (ADS)

Jones, Daniel Ray

Liquid rocket engines are highly reliable, controllable, and efficient compared to other conventional forms of rocket propulsion. As such, they have seen wide use in the space industry and have become the standard propulsion system for launch vehicles, orbit insertion, and orbital maneuvering. Though these systems are well understood, historical optimization techniques are often inadequate due to the highly non-linear nature of the engine performance problem. In this thesis, a Particle Swarm Optimization (PSO) variant was applied to maximize the specific impulse of a finite-area combustion chamber (FAC) equilibrium flow rocket performance model by controlling the engine's oxidizer-to-fuel ratio and de Laval nozzle expansion and contraction ratios. In addition to the PSO-controlled parameters, engine performance was calculated based on propellant chemistry, combustion chamber pressure, and ambient pressure, which are provided as inputs to the program. The performance code was validated by comparison with NASA's Chemical Equilibrium with Applications (CEA) and the commercially available Rocket Propulsion Analysis (RPA) tool. Similarly, the PSO algorithm was validated by comparison with brute-force optimization, which calculates all possible solutions and subsequently determines which is the optimum. Particle Swarm Optimization was shown to be an effective optimizer capable of quick and reliable convergence for complex functions of multiple non-linear variables.

Effects of Non-Equilibrium Chemistry and Darcy-Forchheimer Flow of Pyrolysis Gas for a Charring Ablator

NASA Technical Reports Server (NTRS)

Chen, Yih-Kanq; Milos, Frank S.

2011-01-01

The Fully Implicit Ablation and Thermal Response code, FIAT, simulates pyrolysis and ablation of thermal protection materials and systems. The governing equations, which include energy conservation, a three-component decomposition model, and a surface energy balance, are solved with a moving grid. This work describes new modeling capabilities that are added to a special version of FIAT. These capabilities include a time-dependent pyrolysis gas flow momentum equation with Darcy-Forchheimer terms and pyrolysis gas species conservation equations with finite-rate homogeneous chemical reactions. The total energy conservation equation is also enhanced for consistency with these new additions. Parametric studies are performed using this enhanced version of FIAT. Two groups of analyses of Phenolic Impregnated Carbon Ablator (PICA) are presented. In the first group, an Orion flight environment for a proposed Lunar-return trajectory is considered. In the second group, various test conditions for arcjet models are examined. The central focus of these parametric studies is to understand the effect of pyrolysis gas momentum transfer on PICA material in-depth thermal responses with finite-rate, equilibrium, or frozen homogeneous gas chemistry. Results are presented, discussed, and compared with those predicted by the baseline PICA/FIAT ablation and thermal response model developed by the Orion Thermal Protection System Advanced Development Project.

Development of a 1.5D plasma transport code for coupling to full orbit runaway electron simulations

NASA Astrophysics Data System (ADS)

Lore, J. D.; Del Castillo-Negrete, D.; Baylor, L.; Carbajal, L.

2017-10-01

A 1.5D (1D radial transport + 2D equilibrium geometry) plasma transport code is being developed to simulate runaway electron generation, mitigation, and avoidance by coupling to the full-orbit kinetic electron transport code KORC. The 1.5D code solves the time-dependent 1D flux surface averaged transport equations with sources for plasma density, pressure, and poloidal magnetic flux, along with the Grad-Shafranov equilibrium equation for the 2D flux surface geometry. Disruption mitigation is simulated by introducing an impurity neutral gas `pellet', with impurity densities and electron cooling calculated from ionization, recombination, and line emission rate coefficients. Rapid cooling of the electrons increases the resistivity, inducing an electric field which can be used as an input to KORC. The runaway electron current is then included in the parallel Ohm's law in the transport equations. The 1.5D solver will act as a driver for coupled simulations to model effects such as timescales for thermal quench, runaway electron generation, and pellet impurity mixtures for runaway avoidance. Current progress on the code and details of the numerical algorithms will be presented. Work supported by the US DOE under DE-AC05-00OR22725.

Computational methods for reactive transport modeling: An extended law of mass-action, xLMA, method for multiphase equilibrium calculations

NASA Astrophysics Data System (ADS)

Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg; Saar, Martin O.

2016-10-01

We present an extended law of mass-action (xLMA) method for multiphase equilibrium calculations and apply it in the context of reactive transport modeling. This extended LMA formulation differs from its conventional counterpart in that (i) it is directly derived from the Gibbs energy minimization (GEM) problem (i.e., the fundamental problem that describes the state of equilibrium of a chemical system under constant temperature and pressure); and (ii) it extends the conventional mass-action equations with Lagrange multipliers from the Gibbs energy minimization problem, which can be interpreted as stability indices of the chemical species. Accounting for these multipliers enables the method to determine all stable phases without presuming their types (e.g., aqueous, gaseous) or their presence in the equilibrium state. Therefore, the here proposed xLMA method inherits traits of Gibbs energy minimization algorithms that allow it to naturally detect the phases present in equilibrium, which can be single-component phases (e.g., pure solids or liquids) or non-ideal multi-component phases (e.g., aqueous, melts, gaseous, solid solutions, adsorption, or ion exchange). Moreover, our xLMA method requires no technique that tentatively adds or removes reactions based on phase stability indices (e.g., saturation indices for minerals), since the extended mass-action equations are valid even when their corresponding reactions involve unstable species. We successfully apply the proposed method to a reactive transport modeling problem in which we use PHREEQC and GEMS as alternative backends for the calculation of thermodynamic properties such as equilibrium constants of reactions, standard chemical potentials of species, and activity coefficients. Our tests show that our algorithm is efficient and robust for demanding applications, such as reactive transport modeling, where it converges within 1-3 iterations in most cases. The proposed xLMA method is implemented in Reaktoro, a unified open-source framework for modeling chemically reactive systems.

Investigation of the n  =  1 resistive wall modes in the ITER high-mode confinement

NASA Astrophysics Data System (ADS)

Zheng, L. J.; Kotschenreuther, M. T.; Valanju, P.

2017-06-01

The n  =  1 resistive wall mode (RWM) stability of ITER high-mode confinement is investigated with bootstrap current included for equilibrium, together with the rotation and diamagnetic drift effects for stability. Here, n is the toroidal mode number. We use the CORSICA code for computing the free boundary equilibrium and AEGIS code for stability. We find that the inclusion of bootstrap current for equilibrium is critical. It can reduce the local magnetic shear in the pedestal, so that the infernal mode branches can develop. Consequently, the n  =  1 modes become unstable without a stabilizing wall at a considerably lower beta limit, driven by the steep pressure gradient in the pedestal. Typical values of the wall position stabilize the ideal mode, but give rise to the ‘pedestal’ resistive wall modes. We find that the rotation can contribute a stabilizing effect on RWMs and the diamagnetic drift effects can further improve the stability in the co-current rotation case. But, generally speaking, the rotation stabilization effects are not as effective as the case without including the bootstrap current effects on equilibrium. We also find that the diamagnetic drift effects are actually destabilizing when there is a counter-current rotation.

radEq Add-On Module for CFD Solver Loci-CHEM

NASA Technical Reports Server (NTRS)

McCloud, Peter

2013-01-01

Loci-CHEM to be applied to flow velocities where surface radiation due to heating from compression and friction becomes significant. The module adds a radiation equilibrium boundary condition to the computational fluid dynamics (CFD) code to produce accurate results. The module expanded the upper limit for accurate CFD solutions of Loci-CHEM from Mach 4 to Mach 10 based on Space Shuttle Orbiter Re-Entry trajectories. Loci-CHEM already has a very promising architecture and performance, but absence of radiation equilibrium boundary condition limited the application of Loci-CHEM to below Mach 4. The immediate advantage of the add-on module is that it allows Loci-CHEM to work with supersonic flows up to Mach 10. This transformed Loci-CHEM from a rocket engine- heritage CFD code with general subsonic and low-supersonic applications, to an aeroheating code with hypersonic applications. The follow-on advantage of the module is that it is a building block for additional add-on modules that will solve for the heating generated at Mach numbers higher than 10.

Energy spectrum of 208Pb(n,x) reactions

NASA Astrophysics Data System (ADS)

Tel, E.; Kavun, Y.; Özdoǧan, H.; Kaplan, A.

2018-02-01

Fission and fusion reactor technologies have been investigated since 1950's on the world. For reactor technology, fission and fusion reaction investigations are play important role for improve new generation technologies. Especially, neutron reaction studies have an important place in the development of nuclear materials. So neutron effects on materials should study as theoretically and experimentally for improve reactor design. For this reason, Nuclear reaction codes are very useful tools when experimental data are unavailable. For such circumstances scientists created many nuclear reaction codes such as ALICE/ASH, CEM95, PCROSS, TALYS, GEANT, FLUKA. In this study we used ALICE/ASH, PCROSS and CEM95 codes for energy spectrum calculation of outgoing particles from Pb bombardment by neutron. While Weisskopf-Ewing model has been used for the equilibrium process in the calculations, full exciton, hybrid and geometry dependent hybrid nuclear reaction models have been used for the pre-equilibrium process. The calculated results have been discussed and compared with the experimental data taken from EXFOR.

Reaction rates of oxygen with hemoglobin measured by non-equilibrium facilitated oxygen diffusion through hemoglobin solutions.

PubMed

Bouwer, S T; Hoofd, L; Kreuzer, F

2001-02-16

The purpose of this study was to verify the concept of non-equilibrium facilitated oxygen diffusion. This work succeeds our previous study, where facilitated oxygen diffusion by hemoglobin was measured at conditions of chemical equilibrium, and which yielded diffusion coefficients of hemoglobin and of oxygen. In the present work chemical non-equilibrium was induced using very thin diffusion layers. As a result, facilitation was decreased as predicted by theory. Thus, this work presents the first experimental demonstration of non-equilibrium facilitated oxygen diffusion. In addition, association and dissociation rate parameters of the reaction between oxygen and bovine and human hemoglobin were calculated and the effect of the homotropic and heterotropic interactions on each rate parameter was demonstrated. The results indicate that the homotropic interaction--which leads to increasing oxygen affinity with increasing oxygenation--is predominantly due to an increase in the association rate. The heterotropic interaction--which leads to decreasing oxygen affinity by anionic ligands--appears to be effected in two ways. Cl- increases the dissociation rate. In contrast, 2,3-diphosphoglycerate decreases the association rate.

Equilibrium chemical vapor deposition growth of Bernal-stacked bilayer graphene.

PubMed

Zhao, Pei; Kim, Sungjin; Chen, Xiao; Einarsson, Erik; Wang, Miao; Song, Yenan; Wang, Hongtao; Chiashi, Shohei; Xiang, Rong; Maruyama, Shigeo

2014-11-25

Using ethanol as the carbon source, self-limiting growth of AB-stacked bilayer graphene (BLG) has been achieved on Cu via an equilibrium chemical vapor deposition (CVD) process. We found that during this alcohol catalytic CVD (ACCVD) a source-gas pressure range exists to break the self-limitation of monolayer graphene on Cu, and at a certain equilibrium state it prefers to form uniform BLG with a high surface coverage of ∼94% and AB-stacking ratio of nearly 100%. More importantly, once the BLG is completed, this growth shows a self-limiting manner, and an extended ethanol flow time does not result in additional layers. We investigate the mechanism of this equilibrium BLG growth using isotopically labeled (13)C-ethanol and selective surface aryl functionalization, and results reveal that during the equilibrium ACCVD process a continuous substitution of graphene flakes occurs to the as-formed graphene and the BLG growth follows a layer-by-layer epitaxy mechanism. These phenomena are significantly in contrast to those observed for previously reported BLG growth using methane as precursor.

Retrieving the Molecular Composition of Planet-Forming Material: An Accurate Non-LTE Radiative Transfer Code for JWST

NASA Astrophysics Data System (ADS)

Pontoppidan, Klaus

Based on the observed distributions of exoplanets and dynamical models of their evolution, the primary planet-forming regions of protoplanetary disks are thought to span distances of 1-20 AU from typical stars. A key observational challenge of the next decade will be to understand the links between the formation of planets in protoplanetary disks and the chemical composition of exoplanets. Potentially habitable planets in particular are likely formed by solids growing within radii of a few AU, augmented by unknown contributions from volatiles formed at larger radii of 10-50 AU. The basic chemical composition of these inner disk regions is characterized by near- to far-infrared (2-200 micron) emission lines from molecular gas at temperatures of 50-1500 K. A critical step toward measuring the chemical composition of planet-forming regions is therefore to convert observed infrared molecular line fluxes, profiles and images to gas temperatures, densities and molecular abundances. However, current techniques typically employ approximate radiative transfer methods and assumptions of local thermodynamic equilibrium (LTE) to retrieve abundances, leading to uncertainties of orders of magnitude and inconclusive comparisons to chemical models. Ultimately, the scientific impact of the high quality spectroscopic data expected from the James Webb Space Telescope (JWST) will be limited by the availability of radiative transfer tools for infrared molecular lines. We propose to develop a numerically accurate, non-LTE 3D line radiative transfer code, needed to interpret mid-infrared molecular line observations of protoplanetary and debris disks in preparation for the James Webb Space Telescope (JWST). This will be accomplished by adding critical functionality to the existing Monte Carlo code LIME, which was originally developed to support (sub)millimeter interferometric observations. In contrast to existing infrared codes, LIME calculates the exact statistical balance of arbitrary collections of molecular lines, and does not use large velocity gradient (LVG) or escape probability approximations. However, to use LIME for infrared line radiative transfer, new functionality must be added and tested, such as dust scattering, UV fluorescence, and interfaces with public state-of-the art 3D dust radiative transfer codes (e.g., RADMC3D) and thermo-chemical codes (e.g, ProDiMo). Infrared transitions of molecules expected to be ubiquitous in JWST spectra currently do not have good databases applicable to astrophysical modeling and protoplanetary disks, including water, OH, CO2, NH3, CH4, HCN, etc. Obtaining accurate solutions of the non-LTE line transfer problem in 3D in the infrared is computationally intensive. We propose to benchmark the new code relative to existing, approximate methods to determine whether they are accurate, and under what conditions. We will also create conversion tables between mid-infrared line strengths of water, OH, CH4, NH3, CH3OH, CO2 and other species expected to be observed with JWST, and their relative abundances in planet-forming regions. We propose to apply the new IR-LIME to retrieve molecular abundances from archival and new spectroscopic observations with Spitzer/Herschel/Keck/VLT of CO, water, OH and organic molecules, and to publish comprehensive tables of retrieved molecular abundances in protoplanetary disks. The proposed research is relevant to the XRP call, since it addresses a critical step in inferring the chemical abundances of planet-forming material, which in turn can be compared to the observed compositions of exoplanets, thereby improving our understanding of the origins of exoplanetary systems. The proposed research is particularly timely as the first JWST science data are expected to become available toward the end of the three-year duration of the project.

A Unified Kinetics and Equilibrium Experiment: Rate Law, Activation Energy, and Equilibrium Constant for the Dissociation of Ferroin

ERIC Educational Resources Information Center

Sattar, Simeen

2011-01-01

Tris(1,10-phenanthroline)iron(II) is the basis of a suite of four experiments spanning 5 weeks. Students determine the rate law, activation energy, and equilibrium constant for the dissociation of the complex ion in acid solution and base dissociation constant for phenanthroline. The focus on one chemical system simplifies a daunting set of…

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lazerson, Samuel A.; Loizu, Joaquim; Hirshman, Steven

The VMEC nonlinear ideal MHD equilibrium code [S. P. Hirshman and J. C. Whitson, Phys. Fluids 26, 3553 (1983)] is compared against analytic linear ideal MHD theory in a screw-pinch-like configuration. The focus of such analysis is to verify the ideal MHD response at magnetic surfaces which possess magnetic transform (ι) which is resonant with spectral values of the perturbed boundary harmonics. A large aspect ratio circular cross section zero-beta equilibrium is considered. This equilibrium possess a rational surface with safety factor q = 2 at a normalized flux value of 0.5. A small resonant boundary perturbation is introduced, excitingmore » a response at the resonant rational surface. The code is found to capture the plasma response as predicted by a newly developed analytic theory that ensures the existence of nested flux surfaces by allowing for a jump in rotational transform (ι=1/q). The VMEC code satisfactorily reproduces these theoretical results without the necessity of an explicit transform discontinuity (Δι) at the rational surface. It is found that the response across the rational surfaces depends upon both radial grid resolution and local shear (dι/dΦ, where ι is the rotational transform and Φ the enclosed toroidal flux). Calculations of an implicit Δι suggest that it does not arise due to numerical artifacts (attributed to radial finite differences in VMEC) or existence conditions for flux surfaces as predicted by linear theory (minimum values of Δι). Scans of the rotational transform profile indicate that for experimentally relevant levels of transform shear the response becomes increasing localised. Furthermore, careful examination of a large experimental tokamak equilibrium, with applied resonant fields, indicates that this shielding response is present, suggesting the phenomena is not limited to this verification exercise.« less

Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Harrison, Anna L.; Eisenhauer, Anton; Dietzel, Martin

2017-12-01

In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 0.01 M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1 atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3 - δ88/86Srfluid = -0.05 ± 0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985 ± 0.00003 corresponding to Δ88/86SrSrCO3-fluid = -0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7-8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr isotopes as environmental proxies in aquatic environments.

PyNeb: a new tool for analyzing emission lines. I. Code description and validation of results

NASA Astrophysics Data System (ADS)

Luridiana, V.; Morisset, C.; Shaw, R. A.

2015-01-01

Analysis of emission lines in gaseous nebulae yields direct measures of physical conditions and chemical abundances and is the cornerstone of nebular astrophysics. Although the physical problem is conceptually simple, its practical complexity can be overwhelming since the amount of data to be analyzed steadily increases; furthermore, results depend crucially on the input atomic data, whose determination also improves each year. To address these challenges we created PyNeb, an innovative code for analyzing emission lines. PyNeb computes physical conditions and ionic and elemental abundances and produces both theoretical and observational diagnostic plots. It is designed to be portable, modular, and largely customizable in aspects such as the atomic data used, the format of the observational data to be analyzed, and the graphical output. It gives full access to the intermediate quantities of the calculation, making it possible to write scripts tailored to the specific type of analysis one wants to carry out. In the case of collisionally excited lines, PyNeb works by solving the equilibrium equations for an n-level atom; in the case of recombination lines, it works by interpolation in emissivity tables. The code offers a choice of extinction laws and ionization correction factors, which can be complemented by user-provided recipes. It is entirely written in the python programming language and uses standard python libraries. It is fully vectorized, making it apt for analyzing huge amounts of data. The code is stable and has been benchmarked against IRAF/NEBULAR. It is public, fully documented, and has already been satisfactorily used in a number of published papers.

Non-equilibrium effects in high temperature chemical reactions

NASA Technical Reports Server (NTRS)

Johnson, Richard E.

1987-01-01

Reaction rate data were collected for chemical reactions occurring at high temperatures during reentry of space vehicles. The principle of detailed balancing is used in modeling kinetics of chemical reactions at high temperatures. Although this principle does not hold for certain transient or incubation times in the initial phase of the reaction, it does seem to be valid for the rates of internal energy transitions that occur within molecules and atoms. That is, for every rate of transition within the internal energy states of atoms or molecules, there is an inverse rate that is related through an equilibrium expression involving the energy difference of the transition.

Intermittent Fermi-Pasta-Ulam Dynamics at Equilibrium

NASA Astrophysics Data System (ADS)

Campbell, David; Danieli, Carlo; Flach, Sergej

The equilibrium value of an observable defines a manifold in the phase space of an ergodic and equipartitioned many-body syste. A typical trajectory pierces that manifold infinitely often as time goes to infinity. We use these piercings to measure both the relaxation time of the lowest frequency eigenmode of the Fermi-Pasta-Ulam chain, as well as the fluctuations of the subsequent dynamics in equilibrium. We show that previously obtained scaling laws for equipartition times are modified at low energy density due to an unexpected slowing down of the relaxation. The dynamics in equilibrium is characterized by a power-law distribution of excursion times far off equilibrium, with diverging variance. The long excursions arise from sticky dynamics close to regular orbits in the phase space. Our method is generalizable to large classes of many-body systems. The authors acknowledge financial support from IBS (Project Code IBS-R024-D1).

Sorptive capacity of membrane lipids, storage lipids, and proteins: a preliminary study of partitioning of organochlorines in lean fish from a PCB-contaminated freshwater lake.

PubMed

Mäenpää, Kimmo; Leppänen, Matti T; Figueiredo, Kaisa; Tigistu-Sahle, Feven; Käkelä, Reijo

2015-01-01

Knowledge on the internal distribution of halogenated organic chemicals (HOCs) would improve our understanding of dose-effect relationships and subsequently improve risk assessment of contaminated sites. Herein, we determine the concentrations of HOCs based on equilibrium partitioning in storage lipids, membrane lipids, and proteins in field-contaminated fish using equilibrium sampling devices. The study shows the importance of protein as a sorptive phase in lean fish. Our results provide a basis for using species-specific equilibrium partitioning coefficients between sorptive tissues and fish internal water as a substitute for K(ow) in, for example, upgrading models that simulate food-chain accumulation of the chemical.

Viscous-shock-layer solutions for turbulent flow of radiating gas mixtures in chemical equilibrium

NASA Technical Reports Server (NTRS)

Anderson, E. C.; Moss, J. N.

1975-01-01

The viscous-shock-layer equations for hypersonic laminar and turbulent flows of radiating or nonradiating gas mixtures in chemical equilibrium are presented for two-dimensional and axially-symmetric flow fields. Solutions were obtained using an implicit finite-difference scheme and results are presented for hypersonic flow over spherically-blunted cone configurations at freestream conditions representative of entry into the atmosphere of Venus. These data are compared with solutions obtained using other methods of analysis.

Viscous shock layer solutions for turbulent flow of radiating gas mixtures in chemical equilibrium

NASA Technical Reports Server (NTRS)

Anderson, E. C.; Moss, J. N.

1975-01-01

The viscous shock layer equations for hypersonic laminar and turbulent flows of radiating or nonradiating gas mixtures in chemical equilibrium are presented for two-dimensional and axially symmetric flow fields. Solutions are obtained using an implicit finite difference scheme and results are presented for hypersonic flow over spherically blunted cone configurations at free stream conditions representative of entry into the atmosphere of Venus. These data are compared with solutions obtained using other methods of analysis.

Near-equilibrium chemical vapor deposition of high-quality single-crystal graphene directly on various dielectric substrates.

PubMed

Chen, Jianyi; Guo, Yunlong; Jiang, Lili; Xu, Zhiping; Huang, Liping; Xue, Yunzhou; Geng, Dechao; Wu, Bin; Hu, Wenping; Yu, Gui; Liu, Yunqi

2014-03-05

By using near-equilibrium chemical vapor deposition, it is demonstrated that high-quality single-crystal graphene can be grown on dielectric substrates. The maximum size is about 11 μm. The carrier mobility can reach about 5650 cm(2) V(-1) s(-1) , which is comparable to those of some metal-catalyzed graphene crystals, reflecting the good quality of the graphene lattice. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An unstructured shock-fitting solver for hypersonic plasma flows in chemical non-equilibrium

NASA Astrophysics Data System (ADS)

Pepe, R.; Bonfiglioli, A.; D'Angola, A.; Colonna, G.; Paciorri, R.

2015-11-01

A CFD solver, using Residual Distribution Schemes on unstructured grids, has been extended to deal with inviscid chemical non-equilibrium flows. The conservative equations have been coupled with a kinetic model for argon plasma which includes the argon metastable state as independent species, taking into account electron-atom and atom-atom processes. Results in the case of an hypersonic flow around an infinite cylinder, obtained by using both shock-capturing and shock-fitting approaches, show higher accuracy of the shock-fitting approach.

Transient Macroscopic Chemistry in the DSMC Method

NASA Astrophysics Data System (ADS)

Goldsworthy, M. J.; Macrossan, M. N.; Abdel-Jawad, M.

2008-12-01

In the Direct Simulation Monte Carlo method, a combination of statistical and deterministic procedures applied to a finite number of `simulator' particles are used to model rarefied gas-kinetic processes. Traditionally, chemical reactions are modelled using information from specific colliding particle pairs. In the Macroscopic Chemistry Method (MCM), the reactions are decoupled from the specific particle pairs selected for collisions. Information from all of the particles within a cell is used to determine a reaction rate coefficient for that cell. MCM has previously been applied to steady flow DSMC simulations. Here we show how MCM can be used to model chemical kinetics in DSMC simulations of unsteady flow. Results are compared with a collision-based chemistry procedure for two binary reactions in a 1-D unsteady shock-expansion tube simulation and during the unsteady development of 2-D flow through a cavity. For the shock tube simulation, close agreement is demonstrated between the two methods for instantaneous, ensemble-averaged profiles of temperature and species mole fractions. For the cavity flow, a high degree of thermal non-equilibrium is present and non-equilibrium reaction rate correction factors are employed in MCM. Very close agreement is demonstrated for ensemble averaged mole fraction contours predicted by the particle and macroscopic methods at three different flow-times. A comparison of the accumulated number of net reactions per cell shows that both methods compute identical numbers of reaction events. For the 2-D flow, MCM required similar CPU and memory resources to the particle chemistry method. The Macroscopic Chemistry Method is applicable to any general DSMC code using any viscosity or non-reacting collision models and any non-reacting energy exchange models. MCM can be used to implement any reaction rate formulations, whether these be from experimental or theoretical studies.

Traceability and Quality Control in Traditional Chinese Medicine: From Chemical Fingerprint to Two-Dimensional Barcode

PubMed Central

Cai, Yong; Li, Xiwen; Li, Mei; Chen, Xiaojia; Ni, Jingyun; Wang, Yitao

2015-01-01

Chemical fingerprinting is currently a widely used tool that enables rapid and accurate quality evaluation of Traditional Chinese Medicine (TCM). However, chemical fingerprints are not amenable to information storage, recognition, and retrieval, which limit their use in Chinese medicine traceability. In this study, samples of three kinds of Chinese medicines were randomly selected and chemical fingerprints were then constructed by using high performance liquid chromatography. Based on chemical data, the process of converting the TCM chemical fingerprint into two-dimensional code is presented; preprocess and filtering algorithm are also proposed aiming at standardizing the large amount of original raw data. In order to know which type of two-dimensional code (2D) is suitable for storing data of chemical fingerprints, current popular types of 2D codes are analyzed and compared. Results show that QR Code is suitable for recording the TCM chemical fingerprint. The fingerprint information of TCM can be converted into data format that can be stored as 2D code for traceability and quality control. PMID:26089936

Las Palmeras Molecular Dynamics: A flexible and modular molecular dynamics code

NASA Astrophysics Data System (ADS)

Davis, Sergio; Loyola, Claudia; González, Felipe; Peralta, Joaquín

2010-12-01

Las Palmeras Molecular Dynamics (LPMD) is a highly modular and extensible molecular dynamics (MD) code using interatomic potential functions. LPMD is able to perform equilibrium MD simulations of bulk crystalline solids, amorphous solids and liquids, as well as non-equilibrium MD (NEMD) simulations such as shock wave propagation, projectile impacts, cluster collisions, shearing, deformation under load, heat conduction, heterogeneous melting, among others, which involve unusual MD features like non-moving atoms and walls, unstoppable atoms with constant-velocity, and external forces like electric fields. LPMD is written in C++ as a compromise between efficiency and clarity of design, and its architecture is based on separate components or plug-ins, implemented as modules which are loaded on demand at runtime. The advantage of this architecture is the ability to completely link together the desired components involved in the simulation in different ways at runtime, using a user-friendly control file language which describes the simulation work-flow. As an added bonus, the plug-in API (Application Programming Interface) makes it possible to use the LPMD components to analyze data coming from other simulation packages, convert between input file formats, apply different transformations to saved MD atomic trajectories, and visualize dynamical processes either in real-time or as a post-processing step. Individual components, such as a new potential function, a new integrator, a new file format, new properties to calculate, new real-time visualizers, and even a new algorithm for handling neighbor lists can be easily coded, compiled and tested within LPMD by virtue of its object-oriented API, without the need to modify the rest of the code. LPMD includes already several pair potential functions such as Lennard-Jones, Morse, Buckingham, MCY and the harmonic potential, as well as embedded-atom model (EAM) functions such as the Sutton-Chen and Gupta potentials. Integrators to choose include Euler (if only for demonstration purposes), Verlet and Velocity Verlet, Leapfrog and Beeman, among others. Electrostatic forces are treated as another potential function, by default using the plug-in implementing the Ewald summation method. Program summaryProgram title: LPMD Catalogue identifier: AEHG_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEHG_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU General Public License version 3 No. of lines in distributed program, including test data, etc.: 509 490 No. of bytes in distributed program, including test data, etc.: 6 814 754 Distribution format: tar.gz Programming language: C++ Computer: 32-bit and 64-bit workstation Operating system: UNIX RAM: Minimum 1024 bytes Classification: 7.7 External routines: zlib, OpenGL Nature of problem: Study of Statistical Mechanics and Thermodynamics of condensed matter systems, as well as kinetics of non-equilibrium processes in the same systems. Solution method: Equilibrium and non-equilibrium molecular dynamics method, Monte Carlo methods. Restrictions: Rigid molecules are not supported. Polarizable atoms and chemical bonds (proteins) either. Unusual features: The program is able to change the temperature of the simulation cell, the pressure, cut regions of the cell, color the atoms by properties, even during the simulation. It is also possible to fix the positions and/or velocity of groups of atoms. Visualization of atoms and some physical properties during the simulation. Additional comments: The program does not only perform molecular dynamics and Monte Carlo simulations, it is also able to filter and manipulate atomic configurations, read and write different file formats, convert between them, evaluate different structural and dynamical properties. Running time: 50 seconds on a 1000-step simulation of 4000 argon atoms, running on a single 2.67 GHz Intel processor.

Predicting radiative heat transfer in thermochemical nonequilibrium flow fields. Theory and user's manual for the LORAN code

NASA Technical Reports Server (NTRS)

Chambers, Lin Hartung

1994-01-01

The theory for radiation emission, absorption, and transfer in a thermochemical nonequilibrium flow is presented. The expressions developed reduce correctly to the limit at equilibrium. To implement the theory in a practical computer code, some approximations are used, particularly the smearing of molecular radiation. Details of these approximations are presented and helpful information is included concerning the use of the computer code. This user's manual should benefit both occasional users of the Langley Optimized Radiative Nonequilibrium (LORAN) code and those who wish to use it to experiment with improved models or properties.

Three dimensional equilibrium solutions for a current-carrying reversed-field pinch plasma with a close-fitting conducting shell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koliner, J. J.; Boguski, J., E-mail: boguski@wisc.edu; Anderson, J. K.

2016-03-15

In order to characterize the Madison Symmetric Torus (MST) reversed-field pinch (RFP) plasmas that bifurcate to a helical equilibrium, the V3FIT equilibrium reconstruction code was modified to include a conducting boundary. RFP plasmas become helical at a high plasma current, which induces large eddy currents in MST's thick aluminum shell. The V3FIT conducting boundary accounts for the contribution from these eddy currents to external magnetic diagnostic coil signals. This implementation of V3FIT was benchmarked against MSTFit, a 2D Grad-Shafranov solver, for axisymmetric plasmas. The two codes both fit B{sub θ} measurement loops around the plasma minor diameter with qualitative agreementmore » between each other and the measured field. Fits in the 3D case converge well, with q-profile and plasma shape agreement between two distinct toroidal locking phases. Greater than 60% of the measured n = 5 component of B{sub θ} at r = a is due to eddy currents in the shell, as calculated by the conducting boundary model.« less

Three dimensional equilibrium solutions for a current-carrying reversed-field pinch plasma with a close-fitting conducting shell

DOE PAGES

Koliner, J. J.; Boguski, J.; Anderson, J. K.; ...

2016-03-25

In order to characterize the Madison Symmetric Torus (MST) reversed-field pinch(RFP)plasmas that bifurcate to a helical equilibrium, the V3FIT equilibrium reconstruction code was modified to include a conducting boundary. RFPplasmas become helical at a high plasma current, which induces large eddy currents in MST's thick aluminum shell. The V3FIT conducting boundary accounts for the contribution from these eddy currents to external magnetic diagnostic coil signals. This implementation of V3FIT was benchmarked against MSTFit, a 2D Grad-Shafranov solver, for axisymmetric plasmas. The two codes both fit B measurement loops around the plasma minor diameter with qualitative agreement between each other andmore » the measured field. Fits in the 3D case converge well, with q-profile and plasma shape agreement between two distinct toroidal locking phases. Greater than 60% of the measured n = 5 component of B at r = a is due to eddy currents in the shell, as calculated by the conducting boundary model.« less

HO-CHUNK: Radiation Transfer code

NASA Astrophysics Data System (ADS)

Whitney, Barbara A.; Wood, Kenneth; Bjorkman, J. E.; Cohen, Martin; Wolff, Michael J.

2017-11-01

HO-CHUNK calculates radiative equilibrium temperature solution, thermal and PAH/vsg emission, scattering and polarization in protostellar geometries. It is useful for computing spectral energy distributions (SEDs), polarization spectra, and images.

A Study of Interactions between Mixing and Chemical Reaction Using the Rate-Controlled Constrained-Equilibrium Method

NASA Astrophysics Data System (ADS)

Hadi, Fatemeh; Janbozorgi, Mohammad; Sheikhi, M. Reza H.; Metghalchi, Hameed

2016-10-01

The rate-controlled constrained-equilibrium (RCCE) method is employed to study the interactions between mixing and chemical reaction. Considering that mixing can influence the RCCE state, the key objective is to assess the accuracy and numerical performance of the method in simulations involving both reaction and mixing. The RCCE formulation includes rate equations for constraint potentials, density and temperature, which allows taking account of mixing alongside chemical reaction without splitting. The RCCE is a dimension reduction method for chemical kinetics based on thermodynamics laws. It describes the time evolution of reacting systems using a series of constrained-equilibrium states determined by RCCE constraints. The full chemical composition at each state is obtained by maximizing the entropy subject to the instantaneous values of the constraints. The RCCE is applied to a spatially homogeneous constant pressure partially stirred reactor (PaSR) involving methane combustion in oxygen. Simulations are carried out over a wide range of initial temperatures and equivalence ratios. The chemical kinetics, comprised of 29 species and 133 reaction steps, is represented by 12 RCCE constraints. The RCCE predictions are compared with those obtained by direct integration of the same kinetics, termed detailed kinetics model (DKM). The RCCE shows accurate prediction of combustion in PaSR with different mixing intensities. The method also demonstrates reduced numerical stiffness and overall computational cost compared to DKM.

An Excel-based tool for evaluating and visualizing geothermobarometry data

NASA Astrophysics Data System (ADS)

Hora, John Milan; Kronz, Andreas; Möller-McNett, Stefan; Wörner, Gerhard

2013-07-01

Application of geothermobarometry based on equilibrium exchange of chemical components between two mineral phases in natural samples frequently leads to the dilemma of either: (1) relying on relatively few measurements where there is a high likelihood of equilibrium, or (2) using many analysis pairs, where a significant proportion may not be useful and must be filtered out. The second approach leads to the challenges of (1) evaluation of equilibrium for large numbers of analysis pairs, (2) finding patterns in the dataset where multiple populations exist, and (3) visualizing relationships between calculated temperatures and compositional and textural parameters. Given the limitations of currently-used thermobarometry spreadsheets, we redesign them in a way that eliminates tedium by automating data importing, quality control and calculations, while making all results visible in a single view. Rather than using a traditional spreadsheet layout, we array the calculations in a grid. Each color-coded grid node contains the calculated temperature result corresponding to the intersection of two analyses given in the corresponding column and row. We provide Microsoft Excel templates for some commonly-used thermometers, that can be modified for use with any geothermometer or geobarometer involving two phases. Conditional formatting and ability to sort according to any chosen parameter simplifies pattern recognition, while tests for equilibrium can be incorporated into grid calculations. A case study of rhyodacite domes at Parinacota volcano, Chile, indicates a single population of Fe-Ti oxide temperatures, despite Mg-Mn compositional variability. Crystal zoning and differing thermal histories are, however, evident as a bimodal population of plagioclase-amphibole temperatures. Our approach aids in identification of suspect analyses and xenocrysts and visualization of links between temperature and phase composition. This facilitates interpretation of whether heat transfer was accompanied by bulk mass transfer, and to what degree diffusion has homogenized calculated temperature results in hybrid magmas.

Conceptual model analysis of interaction at a concrete-Boom Clay interface

NASA Astrophysics Data System (ADS)

Liu, Sanheng; Jacques, Diederik; Govaerts, Joan; Wang, Lian

In many concepts for deep disposal of high-level radioactive waste, cementitious materials are used in the engineered barriers. For example, in Belgium the engineered barrier system is based on a considerable amount of cementitious materials as buffer and backfill in the so-called supercontainer embedded in the hosting geological formation. A potential hosting formation is Boom Clay. Insight in the interaction between the high-pH pore water of the cementitious materials and neutral-pH Boom Clay pore water is required. Two problems are quite common for modeling of such a system. The first one is the computational cost due to the long timescale model assessments envisaged for the deep disposal system. Also a very fine grid (in sub-millimeter), especially at interfaces has to be used in order to accurately predict the evolution of the system. The second one is whether to use equilibrium or kinetic reaction models. The objectives of this paper are twofold. First, we develop an efficient coupled reactive transport code for this diffusion-dominated system by making full use of multi-processors/cores computers. Second, we investigate how sensitive the system is to chemical reaction models especially when pore clogging due to mineral precipitation is considered within the cementitious system. To do this, we selected two portlandite dissolution models, i.e., equilibrium (fastest) and diffusion-controlled model with precipitation of a calcite layer around portlandite particles (diffusion-controlled dissolution). The results show that with shrinking core model portlandite dissolution and calcite precipitation are much slower than with the equilibrium model. Also diffusion-controlled dissolution smooths out dissolution fronts compared to the equilibrium model. However, only a slight difference with respect to the clogging time can be found even though we use a very small diffusion coefficient (10-20 m2/s) in the precipitated calcite layer.

Laboratory and modeling studies of chemistry in dense molecular clouds

NASA Technical Reports Server (NTRS)

Huntress, W. T., Jr.; Prasad, S. S.; Mitchell, G. F.

1980-01-01

A chemical evolutionary model with a large number of species and a large chemical library is used to examine the principal chemical processes in interstellar clouds. Simple chemical equilibrium arguments show the potential for synthesis of very complex organic species by ion-molecule radiative association reactions.

Insights: Simple Models for Teaching Equilibrium and Le Chatelier's Principle.

ERIC Educational Resources Information Center

Russell, Joan M.

1988-01-01

Presents three models that have been effective for teaching chemical equilibrium and Le Chatelier's principle: (1) the liquid transfer model, (2) the fish model, and (3) the teeter-totter model. Explains each model and its relation to Le Chatelier's principle. (MVL)

Visualising the equilibrium distribution and mobility of organic contaminants in soil using the chemical partitioning space.

PubMed

Wong, Fiona; Wania, Frank

2011-06-01

Assessing the behaviour of organic chemicals in soil is a complex task as it is governed by the physical chemical properties of the chemicals, the characteristics of the soil as well as the ambient conditions of the environment. The chemical partitioning space, defined by the air-water partition coefficient (K(AW)) and the soil organic carbon-water partition coefficient (K(OC)), was employed to visualize the equilibrium distribution of organic contaminants between the air-filled pores, the pore water and the solid phases of the bulk soil and the relative importance of the three transport processes removing contaminants from soil (evaporation, leaching and particle erosion). The partitioning properties of twenty neutral organic chemicals (i.e. herbicides, pharmaceuticals, polychlorinated biphenyls and volatile chemicals) were estimated using poly-parameter linear free energy relationships and superimposed onto these maps. This allows instantaneous estimation of the equilibrium phase distribution and mobility of neutral organic chemicals in soil. Although there is a link between the major phase and the dominant transport process, such that chemicals found in air-filled pore space are subject to evaporation, those in water-filled pore space undergo leaching and those in the sorbed phase are associated with particle erosion, the partitioning coefficient thresholds for distribution and mobility can often deviate by many orders of magnitude. In particular, even a small fraction of chemical in pore water or pore air allows for evaporation and leaching to dominate over solid phase transport. Multiple maps that represent soils that differ in the amount and type of soil organic matter, water saturation, temperature, depth of surface soil horizon, and mineral matters were evaluated.

[Thermodynamics of the origin of life, evolution and aging].

PubMed

Gladyshev, G P

2014-01-01

Briefly discusses the history of the search of thermodynamic approach to explain the origin of life, evolution and aging of living beings. The origin of life is the result of requirement by the quasi-equilibrium hierarchical thermodynamics, in particular, the supramolecular thermodynamics. The evolution and aging of living beings is accompanied with changes of chemical and supramolecular compositions of living bodies, as well as with changes in the composition and structure of all hierarchies of the living world. The thermodynamic principle of substance stability predicts the existence of a single genetic code in our universe. The thermodynamic theory optimizes physiology and medicine and recommends antiaging diets and medicines. Hierarchical thermodynamics forms the design diversity of culture and art. The thermodynamic theory of origin of life, evolution and aging is the development of Clausius-Gibbs thermodynamics. Hierarchical thermodynamics is the mirror of Darwin-Wallace's-theory.

BurnMan: Towards a multidisciplinary toolkit for reproducible deep Earth science

NASA Astrophysics Data System (ADS)

Myhill, R.; Cottaar, S.; Heister, T.; Rose, I.; Unterborn, C. T.; Dannberg, J.; Martin-Short, R.

2016-12-01

BurnMan (www.burnman.org) is an open-source toolbox to compute thermodynamic and thermoelastic properties as a function of pressure and temperature using published mineral physical parameters and equations-of-state. The framework is user-friendly, written in Python, and modular, allowing the user to implement their own equations of state, endmember and solution model libraries, geotherms, and averaging schemes. Here we introduce various new modules, which can be used to: Fit thermodynamic variables to data from high pressure static and shock wave experiments, Calculate equilibrium assemblages given a bulk composition, pressure and temperature, Calculate chemical potentials and oxygen fugacities for given assemblages Compute 3D synthetic seismic models using output from geodynamic models and compare these results with global seismic tomographic models, Create input files for synthetic seismogram codes. Users can contribute scripts that reproduce the results from peer-reviewed articles and practical demonstrations (e.g. Cottaar et al., 2014).

Nozzle Numerical Analysis Of The Scimitar Engine

NASA Astrophysics Data System (ADS)

Battista, F.; Marini, M.; Cutrone, L.

2011-05-01

This work describes part of the activities on the LAPCAT-II A2 vehicle, in which starting from the available conceptual vehicle design and the related pre- cooled turbo-ramjet engine called SCIMITAR, well- thought assumptions made for performance figures of different components during the iteration process within LAPCAT-I will be assessed in more detail. In this paper it is presented a numerical analysis aimed at the design optimization of the nozzle contour of the LAPCAT A2 SCIMITAR engine designed by Reaction Engines Ltd. (REL) (see Figure 1). In particular, nozzle shape optimization process is presented for cruise conditions. All the computations have been carried out by using the CIRA C3NS code in non equilibrium conditions. The effect of considering detailed or reduced chemical kinetic schemes has been analyzed with a particular focus on the production of pollutants. An analysis of engine performance parameters, such as thrust and combustion efficiency has been carried out.

Laser-heated thruster

NASA Technical Reports Server (NTRS)

Kemp, N. H.; Lewis, P. F.

1980-01-01

The development of a computer program for the design of the thrust chamber for a CW laser heated thruster was examined. Hydrodgen was employed as the propellant gas and high temperature absorber. The laser absorption coefficient of the mixture/laser radiation combination is given in temperature and species densities. Radiative and absorptive properties are given to determine radiation from such gas mixtures. A computer code for calculating the axisymmetric channel flow of a gas mixture in chemical equilibrium, and laser energy absorption and convective and radiative heating is described. It is concluded that: (1) small amounts of cesium seed substantially increase the absorption coefficient of hydrogen; (2) cesium is a strong radiator and contributes greatly to radiation of cesium seeded hydrogen; (3) water vapor is a poor absorber; and (4) for 5.3mcm radiation, both H2O/CO and NO/CO seeded hydrogen mixtures are good absorbers.

Formation of nitric acid hydrates - A chemical equilibrium approach

NASA Technical Reports Server (NTRS)

Smith, Roland H.

1990-01-01

Published data are used to calculate equilibrium constants for reactions of the formation of nitric acid hydrates over the temperature range 190 to 205 K. Standard enthalpies of formation and standard entropies are calculated for the tri- and mono-hydrates. These are shown to be in reasonable agreement with earlier calorimetric measurements. The formation of nitric acid trihydrate in the polar stratosphere is discussed in terms of these equilibrium constants.

Spontaneity and Equilibrium: Why "?G < 0 Denotes a Spontaneous Process" and "?G = 0 Means the System Is at Equilibrium" Are Incorrect

ERIC Educational Resources Information Center

Raff, Lionel M.

2014-01-01

The fundamental criteria for chemical reactions to be spontaneous in a given direction are generally incorrectly stated as ?G < 0 or ?A < 0 in most introductory chemistry textbooks and even in some more advanced texts. Similarly, the criteria for equilibrium are also misstated as being ?G = 0 or ?A = 0. Following a brief review of the…

Plasma Jet Interactions with Liquids in Partial Fulfillment of an NRL Karles Fellowship

DTIC Science & Technology

2015-11-30

deposition), modify (e.g., chemical functionalization), and etch (in Si technology) materials. In low- pressure non- equilibrium discharge plasmas... equilibrium discharge plasmas, associated with the above processes, the electron population is much more energetic than both the ions and neutral gas...to be crucial to the advancements of these fields1, 2. Background: Atmospheric-pressure, non- equilibrium (APNE) plasmas, like low-pressure plasmas

Net Reaction Rate and Neutrino Cooling Rate for the Urca Process in Departure from Chemical Equilibrium in the Crust of Fast-accreting Neutron Stars

NASA Astrophysics Data System (ADS)

Wang, Wei-Hua; Huang, Xi; Zheng, Xiao-Ping

We discuss the effect of compression on Urca shells in the ocean and crust of accreting neutron stars, especially in superbursting sources. We find that Urca shells may be deviated from chemical equilibrium in neutron stars which accrete at several tenths of the local Eddington accretion rate. The deviation depends on the energy threshold of the parent and daughter nuclei, the transition strength, the temperature, and the local accretion rate. In a typical crust model of accreting neutron stars, the chemical departures range from a few tenths of kBT to tens of kBT for various Urca pairs. If the Urca shell can exist in crusts of accreting neutron stars, compression may enhance the net neutrino cooling rate by a factor of about 1-2 relative to the neutrino emissivity in chemical equilibrium. For some cases, such as Urca pairs with small energy thresholds and/or weak transition strength, the large chemical departure may result in net heating rather than cooling, although the released heat can be small. Strong Urca pairs in the deep crust are hard to be deviated even in neutron stars accreting at the local Eddington accretion rate.

Exploring the use of multiple analogical models when teaching and learning chemical equilibrium

NASA Astrophysics Data System (ADS)

Harrison, Allan G.; de Jong, Onno

2005-12-01

This study describes the multiple analogical models used to introduce and teach Grade 12 chemical equilibrium. We examine the teacher's reasons for using models, explain each model's development during the lessons, and analyze the understandings students derived from the models. A case study approach was used and the data were drawn from the observation of three consecutive Grade 12 lessons on chemical equilibrium, pre- and post-lesson interviews, and delayed student interviews. The key analogical models used in teaching were: the school dance; the sugar in a teacup; the pot of curry; and the busy highway. The lesson and interview data were subject to multiple, independent analyses and yielded the following outcomes: The teacher planned to use the students' prior knowledge wherever possible and he responded to student questions with stories and extended and enriched analogies. He planned to discuss where each analogy broke down but did not. The students enjoyed the teaching but built variable mental models of equilibrium and some of their analogical mappings were unreliable. A female student disliked masculine analogies, other students tended to see elements of the multiple models in isolation, and some did not recognize all the analogical mappings embedded in the teaching plan. Most students learned that equilibrium reactions are dynamic, occur in closed systems, and the forward and reverse reactions are balanced. We recommend the use of multiple analogies like these and insist that teachers always show where the analogy breaks down and carefully negotiate the conceptual outcomes.

Finite-deformation phase-field chemomechanics for multiphase, multicomponent solids

NASA Astrophysics Data System (ADS)

Svendsen, Bob; Shanthraj, Pratheek; Raabe, Dierk

2018-03-01

The purpose of this work is the development of a framework for the formulation of geometrically non-linear inelastic chemomechanical models for a mixture of multiple chemical components diffusing among multiple transforming solid phases. The focus here is on general model formulation. No specific model or application is pursued in this work. To this end, basic balance and constitutive relations from non-equilibrium thermodynamics and continuum mixture theory are combined with a phase-field-based description of multicomponent solid phases and their interfaces. Solid phase modeling is based in particular on a chemomechanical free energy and stress relaxation via the evolution of phase-specific concentration fields, order-parameter fields (e.g., related to chemical ordering, structural ordering, or defects), and local internal variables. At the mixture level, differences or contrasts in phase composition and phase local deformation in phase interface regions are treated as mixture internal variables. In this context, various phase interface models are considered. In the equilibrium limit, phase contrasts in composition and local deformation in the phase interface region are determined via bulk energy minimization. On the chemical side, the equilibrium limit of the current model formulation reduces to a multicomponent, multiphase, generalization of existing two-phase binary alloy interface equilibrium conditions (e.g., KKS). On the mechanical side, the equilibrium limit of one interface model considered represents a multiphase generalization of Reuss-Sachs conditions from mechanical homogenization theory. Analogously, other interface models considered represent generalizations of interface equilibrium conditions consistent with laminate and sharp-interface theory. In the last part of the work, selected existing models are formulated within the current framework as special cases and discussed in detail.

Significance of vapor phase chemical reactions on CVD rates predicted by chemically frozen and local thermochemical equilibrium boundary layer theories

NASA Technical Reports Server (NTRS)

Gokoglu, Suleyman A.

1988-01-01

This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.

Calculation of the relative metastabilities of proteins using the CHNOSZ software package

PubMed Central

Dick, Jeffrey M

2008-01-01

Background Proteins of various compositions are required by organisms inhabiting different environments. The energetic demands for protein formation are a function of the compositions of proteins as well as geochemical variables including temperature, pressure, oxygen fugacity and pH. The purpose of this study was to explore the dependence of metastable equilibrium states of protein systems on changes in the geochemical variables. Results A software package called CHNOSZ implementing the revised Helgeson-Kirkham-Flowers (HKF) equations of state and group additivity for ionized unfolded aqueous proteins was developed. The program can be used to calculate standard molal Gibbs energies and other thermodynamic properties of reactions and to make chemical speciation and predominance diagrams that represent the metastable equilibrium distributions of proteins. The approach takes account of the chemical affinities of reactions in open systems characterized by the chemical potentials of basis species. The thermodynamic database included with the package permits application of the software to mineral and other inorganic systems as well as systems of proteins or other biomolecules. Conclusion Metastable equilibrium activity diagrams were generated for model cell-surface proteins from archaea and bacteria adapted to growth in environments that differ in temperature and chemical conditions. The predicted metastable equilibrium distributions of the proteins can be compared with the optimal growth temperatures of the organisms and with geochemical variables. The results suggest that a thermodynamic assessment of protein metastability may be useful for integrating bio- and geochemical observations. PMID:18834534

3D Equilibrium Effects Due to RMP Application on DIII-D

DOE Office of Scientific and Technical Information (OSTI.GOV)

S. Lazerson, E. Lazarus, S. Hudson, N. Pablant and D. Gates

2012-06-20

The mitigation and suppression of edge localized modes (ELMs) through application of resonant magnetic perturbations (RMPs) in Tokamak plasmas is a well documented phenomenon [1]. Vacuum calculations suggest the formation of edge islands and stochastic regions when RMPs are applied to the axisymmetric equilibria. Self-consistent calculations of the plasma equilibrium with the VMEC [2] and SPEC [3] codes have been performed for an up-down symmetric shot (142603) in DIII-D. In these codes, a self-consistent calculation of the plasma response due to the RMP coils is calculated. The VMEC code globally enforces the constraints of ideal MHD; consequently, a continuously nestedmore » family of flux surfaces is enforced throughout the plasma domain. This approach necessarily precludes the observation of islands or field-line chaos. The SPEC code relaxes the constraints of ideal MHD locally, and allows for islands and field line chaos at or near the rational surfaces. Equilibria with finite pressure gradients are approximated by a set of discrete "ideal-interfaces" at the most irrational flux surfaces and where the strongest pressure gradients are observed. Both the VMEC and SPEC calculations are initialized from EFIT reconstructions of the plasma that are consistent with the experimental pressure and current profiles. A 3D reconstruction using the STELLOPT code, which fits VMEC equilibria to experimental measurements, has also been performed. Comparisons between the equilibria generated by the 3D codes and between STELLOPT and EFIT are presented.« less

3D Equilibrium Effects Due to RMP Application on DIII-D

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lazerson, S.; Lazarus, E.; Hudson, S.

2012-06-20

The mitigation and suppression of edge localized modes (ELMs) through application of resonant magnetic perturbations (RMPs) in Tokamak plasmas is a well documented phenomenon. Vacuum calculations suggest the formation of edge islands and stochastic regions when RMPs are applied to the axisymmetric equilibria. Self-consistent calculations of the plasma equilibrium with the VMEC and SPEC codes have been performed for an up-down symmetric shot in DIII-D. In these codes, a self-consistent calculation of the plasma response due to the RMP coils is calculated. The VMEC code globally enforces the constraints of ideal MHD; consequently, a continuously nested family of flux surfacesmore » is enforced throughout the plasma domain. This approach necessarily precludes the observation of islands or field-line chaos. The SPEC code relaxes the constraints of ideal MHD locally, and allows for islands and field line chaos at or near the rational surfaces. Equilibria with finite pressure gradients are approximated by a set of discrete "ideal-interfaces" at the most irrational flux surfaces and where the strongest pressure gradients are observed. Both the VMEC and SPEC calculations are initialized from EFIT reconstructions of the plasma that are consistent with the experimental pressure and current profiles. A 3D reconstruction using the STELLOPT code, which fits VMEC equilibria to experimental measurements, has also been performed. Comparisons between the equilibria generated by the 3D codes and between STELLOPT and EFIT are presented.« less

Equilibrium chemical reaction of supersonic hydrogen-air jets (the ALMA computer program)

NASA Technical Reports Server (NTRS)

Elghobashi, S.

1977-01-01

The ALMA (axi-symmetrical lateral momentum analyzer) program is concerned with the computation of two dimensional coaxial jets with large lateral pressure gradients. The jets may be free or confined, laminar or turbulent, reacting or non-reacting. Reaction chemistry is equilibrium.

A procedure to find thermodynamic equilibrium constants for CO2 and CH4 adsorption on activated carbon.

PubMed

Trinh, T T; van Erp, T S; Bedeaux, D; Kjelstrup, S; Grande, C A

2015-03-28

Thermodynamic equilibrium for adsorption means that the chemical potential of gas and adsorbed phase are equal. A precise knowledge of the chemical potential is, however, often lacking, because the activity coefficient of the adsorbate is not known. Adsorption isotherms are therefore commonly fitted to ideal models such as the Langmuir, Sips or Henry models. We propose here a new procedure to find the activity coefficient and the equilibrium constant for adsorption which uses the thermodynamic factor. Instead of fitting the data to a model, we calculate the thermodynamic factor and use this to find first the activity coefficient. We show, using published molecular simulation data, how this procedure gives the thermodynamic equilibrium constant and enthalpies of adsorption for CO2(g) on graphite. We also use published experimental data to find similar thermodynamic properties of CO2(g) and of CH4(g) adsorbed on activated carbon. The procedure gives a higher accuracy in the determination of enthalpies of adsorption than ideal models do.

Viscous-shock-layer solutions with coupled radiation and ablation injection for earth entry

NASA Technical Reports Server (NTRS)

Gupta, Roop N.; Lee, Kam-Pui; Moos, James N.; Sutton, Kenneth

1990-01-01

Results are obtained for the forebody of a planetary exploration vehicle entering the earth's atmosphere. A viscous-shock-layer analysis is used assuming the flow to be laminar and in chemical equilibrium. Presented results include coupled radiation and ablation injection. This study further includes the effect of different transport and thermodynamic properties and radiation models. A Lewis number of 1.4 appears adequate for the radiation-dominated flows. Five velocities corresponding to different possible trajectory points at an altitude of 70 km have been further analyzed in detail. Sublimation and radiative equilibrium wall temperatures are employed for cases with and without coupled injection, respectively. For the cases analyzed here, the mass injection rates are small. However, the rates could become large if a lower altitude is used for aerobraking and/or the body size is increased. A comparison of the equilibrium results with finite-rate chemistry calculation shows the flowfield to be in chemical equilibrium.

Reactive solute transport in streams: 1. Development of an equilibrium- based model

USGS Publications Warehouse

Runkel, Robert L.; Bencala, Kenneth E.; Broshears, Robert E.; Chapra, Steven C.

1996-01-01

An equilibrium-based solute transport model is developed for the simulation of trace metal fate and transport in streams. The model is formed by coupling a solute transport model with a chemical equilibrium submodel based on MINTEQ. The solute transport model considers the physical processes of advection, dispersion, lateral inflow, and transient storage, while the equilibrium submodel considers the speciation and complexation of aqueous species, precipitation/dissolution and sorption. Within the model, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (water-borne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach.

Sparse Partial Equilibrium Tables in Chemically Resolved Reactive Flow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vitello, P; Fried, L E; Pudliner, B

2003-07-14

The detonation of an energetic material is the result of a complex interaction between kinetic chemical reactions and hydrodynamics. Unfortunately, little is known concerning the detailed chemical kinetics of detonations in energetic materials. CHEETAH uses rate laws to treat species with the slowest chemical reactions, while assuming other chemical species are in equilibrium. CHEETAH supports a wide range of elements and condensed detonation products and can also be applied to gas detonations. A sparse hash table of equation of state values, called the ''cache'' is used in CHEETAH to enhance the efficiency of kinetic reaction calculations. For large-scale parallel hydrodynamicmore » calculations, CHEETAH uses MPI communication to updates to the cache. We present here details of the sparse caching model used in the CHEETAH. To demonstrate the efficiency of modeling using a sparse cache model we consider detonations in energetic materials.« less

Sparse Partial Equilibrium Tables in Chemically Resolved Reactive Flow

NASA Astrophysics Data System (ADS)

Vitello, Peter; Fried, Laurence E.; Pudliner, Brian; McAbee, Tom

2004-07-01

The detonation of an energetic material is the result of a complex interaction between kinetic chemical reactions and hydrodynamics. Unfortunately, little is known concerning the detailed chemical kinetics of detonations in energetic materials. CHEETAH uses rate laws to treat species with the slowest chemical reactions, while assuming other chemical species are in equilibrium. CHEETAH supports a wide range of elements and condensed detonation products and can also be applied to gas detonations. A sparse hash table of equation of state values is used in CHEETAH to enhance the efficiency of kinetic reaction calculations. For large-scale parallel hydrodynamic calculations, CHEETAH uses parallel communication to updates to the cache. We present here details of the sparse caching model used in the CHEETAH coupled to an ALE hydrocode. To demonstrate the efficiency of modeling using a sparse cache model we consider detonations in energetic materials.

Analysis of a two-dimensional type 6 shock-interference pattern using a perfect-gas code and a real-gas code

NASA Technical Reports Server (NTRS)

Bertin, J. J.; Graumann, B. W.

1973-01-01

Numerical codes were developed to calculate the two dimensional flow field which results when supersonic flow encounters double wedge configurations whose angles are such that a type 4 pattern occurs. The flow field model included the shock interaction phenomena for a delta wing orbiter. Two numerical codes were developed, one which used the perfect gas relations and a second which incorporated a Mollier table to define equilibrium air properties. The two codes were used to generate theoretical surface pressure and heat transfer distributions for velocities from 3,821 feet per second to an entry condition of 25,000 feet per second.

Inviscid flux-splitting algorithms for real gases with non-equilibrium chemistry

NASA Technical Reports Server (NTRS)

Shuen, Jian-Shun; Liou, Meng-Sing; Van Leer, Bram

1990-01-01

Formulations of inviscid flux splitting algorithms for chemical nonequilibrium gases are presented. A chemical system for air dissociation and recombination is described. Numerical results for one-dimensional shock tube and nozzle flows of air in chemical nonequilibrium are examined.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsai, Shang-Min; Grosheintz, Luc; Kitzmann, Daniel

We present an open-source and validated chemical kinetics code for studying hot exoplanetary atmospheres, which we name VULCAN. It is constructed for gaseous chemistry from 500 to 2500 K, using a reduced C–H–O chemical network with about 300 reactions. It uses eddy diffusion to mimic atmospheric dynamics and excludes photochemistry. We have provided a full description of the rate coefficients and thermodynamic data used. We validate VULCAN by reproducing chemical equilibrium and by comparing its output versus the disequilibrium-chemistry calculations of Moses et al. and Rimmer and Helling. It reproduces the models of HD 189733b and HD 209458b by Mosesmore » et al., which employ a network with nearly 1600 reactions. We also use VULCAN to examine the theoretical trends produced when the temperature–pressure profile and carbon-to-oxygen ratio are varied. Assisted by a sensitivity test designed to identify the key reactions responsible for producing a specific molecule, we revisit the quenching approximation and find that it is accurate for methane but breaks down for acetylene, because the disequilibrium abundance of acetylene is not directly determined by transport-induced quenching, but is rather indirectly controlled by the disequilibrium abundance of methane. Therefore we suggest that the quenching approximation should be used with caution and must always be checked against a chemical kinetics calculation. A one-dimensional model atmosphere with 100 layers, computed using VULCAN, typically takes several minutes to complete. VULCAN is part of the Exoclimes Simulation Platform (ESP; exoclime.net) and publicly available at https://github.com/exoclime/VULCAN.« less

A tightly coupled non-equilibrium model for inductively coupled radio-frequency plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Munafò, A., E-mail: munafo@illinois.edu; Alfuhaid, S. A., E-mail: alfuhai2@illinois.edu; Panesi, M., E-mail: mpanesi@illinois.edu

2015-10-07

The objective of the present work is the development of a tightly coupled magneto-hydrodynamic model for inductively coupled radio-frequency plasmas. Non Local Thermodynamic Equilibrium (NLTE) effects are described based on a hybrid State-to-State approach. A multi-temperature formulation is used to account for thermal non-equilibrium between translation of heavy-particles and vibration of molecules. Excited electronic states of atoms are instead treated as separate pseudo-species, allowing for non-Boltzmann distributions of their populations. Free-electrons are assumed Maxwellian at their own temperature. The governing equations for the electro-magnetic field and the gas properties (e.g., chemical composition and temperatures) are written as a coupled systemmore » of time-dependent conservation laws. Steady-state solutions are obtained by means of an implicit Finite Volume method. The results obtained in both LTE and NLTE conditions over a broad spectrum of operating conditions demonstrate the robustness of the proposed coupled numerical method. The analysis of chemical composition and temperature distributions along the torch radius shows that: (i) the use of the LTE assumption may lead to an inaccurate prediction of the thermo-chemical state of the gas, and (ii) non-equilibrium phenomena play a significant role close the walls, due to the combined effects of Ohmic heating and macroscopic gradients.« less

A CO2-Silica Geothermometer for Low Temperature Geothermal Resource Assessment, with Application to Resources in the Safford Basin, Arizona

DOE Office of Scientific and Technical Information (OSTI.GOV)

Witcher, James C.; Stone, Claudia

1983-11-01

Geothermics is the study of the earth's heat energy, it's affect on subsurface temperature distribution, it's physical and chemical sources, and it's role in dynamic geologic processes. The term, geothermometry, is applied to the determination of equilibrium temperatures of natural chemical systems, including rock, mineral, and liquid phases. An assemblage of minerals or a chemical system whose phase composition is a function of temperature and pressure can be used as a geothermometer. Thus a geothermometer is useful to determine the formation temperature of rock or the last equilibrium temperature of a flowing aqueous solution such as ground water and hydrothermalmore » fluids.« less

Development and Assessment of a Computer-Based Equation of State for Equilibrium Air

DTIC Science & Technology

2013-09-01

for very low energies. However, the ideal gas EOS is appropriate for atmospheric flight at subsonic, transonic, and low supersonic flight speeds...Flow Properties About Blunt Bodies Moving at Supersonic Speeds in an Equilibrium Gas ,” NASA TR R-204, July 1964. 21. Tannehill, John C., and Mugge...changes are made. 15. Subject Terms Air, thermodynamic properties, equation of state, chemical equilibrium, real- gas 16. SECURITY CLASSIFICATION

Modeling of 3D magnetic equilibrium effects on edge turbulence stability during RMP ELM suppression in tokamaks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilcox, R. S.; Wingen, Andreas; Cianciosa, Mark R.

Some recent experimental observations have found turbulent fluctuation structures that are non-axisymmetric in a tokamak with applied 3D fields. Here, two fluid resistive effects are shown to produce changes relevant to turbulent transport in the modeled 3D magnetohydrodynamic (MHD) equilibrium of tokamak pedestals with these 3D fields applied. Ideal MHD models are insufficient to reproduce the relevant effects. By calculating the ideal 3D equilibrium using the VMEC code, the geometric shaping parameters that determine linear turbulence stability, including the normal curvature and local magnetic shear, are shown to be only weakly modified by applied 3D fields in the DIII-D tokamak.more » These ideal MHD effects are therefore not sufficient to explain the observed changes to fluctuations and transport. Using the M3D-C1 code to model the 3D equilibrium, density is shown to be redistributed on flux surfaces in the pedestal when resistive two fluid effects are included, while islands are screened by rotation in this region. Furthermore, the redistribution of density results in density and pressure gradient scale lengths that vary within pedestal flux surfaces between different helically localized flux tubes. This would produce different drive terms for trapped electron mode and kinetic ballooning mode turbulence, the latter of which is expected to be the limiting factor for pedestal pressure gradients in DIII-D.« less