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Sample records for accuracy selected thermodynamic

  1. On the Accuracy of Genomic Selection

    PubMed Central

    Rabier, Charles-Elie; Barre, Philippe; Asp, Torben; Charmet, Gilles; Mangin, Brigitte

    2016-01-01

    Genomic selection is focused on prediction of breeding values of selection candidates by means of high density of markers. It relies on the assumption that all quantitative trait loci (QTLs) tend to be in strong linkage disequilibrium (LD) with at least one marker. In this context, we present theoretical results regarding the accuracy of genomic selection, i.e., the correlation between predicted and true breeding values. Typically, for individuals (so-called test individuals), breeding values are predicted by means of markers, using marker effects estimated by fitting a ridge regression model to a set of training individuals. We present a theoretical expression for the accuracy; this expression is suitable for any configurations of LD between QTLs and markers. We also introduce a new accuracy proxy that is free of the QTL parameters and easily computable; it outperforms the proxies suggested in the literature, in particular, those based on an estimated effective number of independent loci (Me). The theoretical formula, the new proxy, and existing proxies were compared for simulated data, and the results point to the validity of our approach. The calculations were also illustrated on a new perennial ryegrass set (367 individuals) genotyped for 24,957 single nucleotide polymorphisms (SNPs). In this case, most of the proxies studied yielded similar results because of the lack of markers for coverage of the entire genome (2.7 Gb). PMID:27322178

  2. Accuracy Based Generation of Thermodynamic Properties for Light Water in RELAP5-3D

    SciTech Connect

    Cliff B. Davis

    2010-09-01

    RELAP5-3D interpolates to obtain thermodynamic properties for use in its internal calculations. The accuracy of the interpolation was determined for the original steam tables currently used by the code. This accuracy evaluation showed that the original steam tables are generally detailed enough to allow reasonably accurate interpolations in most areas needed for typical analyses of nuclear reactors cooled by light water. However, there were some regions in which the original steam tables were judged to not provide acceptable accurate results. Revised steam tables were created that used a finer thermodynamic mesh between 4 and 21 MPa and 530 and 640 K. The revised steam tables solved most of the problems observed with the original steam tables. The accuracies of the original and revised steam tables were compared throughout the thermodynamic grid.

  3. Thermodynamics in rotating systems—analysis of selected examples

    NASA Astrophysics Data System (ADS)

    Güémez, J.; Fiolhais, M.

    2014-01-01

    We solve a set of selected exercises on rotational motion requiring a mechanical and thermodynamical analysis. When non-conservative forces or thermal effects are present, a complete study must use the first law of thermodynamics together with Newton’s second law. The latter is here better expressed in terms of an ‘angular’ impulse-momentum equation (Poinsot-Euler equation), or, equivalently, in terms of a ‘rotational’ pseudo-work-energy equation. Thermodynamical aspects in rotational systems, when e.g. frictional forces are present or when there is a variation of the rotational kinetic energy due to internal sources of energy, are discussed.

  4. Is there a link between selectivity and binding thermodynamics profiles?

    PubMed

    Tarcsay, Ákos; Keserű, György M

    2015-01-01

    Thermodynamics of ligand binding is influenced by the interplay between enthalpy and entropy contributions of the binding event. The impact of these binding free energy components, however, is not limited to the primary target only. Here, we investigate the relationship between binding thermodynamics and selectivity profiles by combining publicly available data from broad off-target assay profiling and the corresponding thermodynamics measurements. Our analysis indicates that compounds binding their primary targets with higher entropy contributions tend to hit more off-targets compared with those ligands that demonstrated enthalpy-driven binding.

  5. Assessing genomic selection prediction accuracy in a dynamic barley breeding

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Genomic selection is a method to improve quantitative traits in crops and livestock by estimating breeding values of selection candidates using phenotype and genome-wide marker data sets. Prediction accuracy has been evaluated through simulation and cross-validation, however validation based on prog...

  6. Toward Improved Force-Field Accuracy through Sensitivity Analysis of Host-Guest Binding Thermodynamics.

    PubMed

    Yin, Jian; Fenley, Andrew T; Henriksen, Niel M; Gilson, Michael K

    2015-08-13

    Improving the capability of atomistic computer models to predict the thermodynamics of noncovalent binding is critical for successful structure-based drug design, and the accuracy of such calculations remains limited by nonoptimal force field parameters. Ideally, one would incorporate protein-ligand affinity data into force field parametrization, but this would be inefficient and costly. We now demonstrate that sensitivity analysis can be used to efficiently tune Lennard-Jones parameters of aqueous host-guest systems for increasingly accurate calculations of binding enthalpy. These results highlight the promise of a comprehensive use of calorimetric host-guest binding data, along with existing validation data sets, to improve force field parameters for the simulation of noncovalent binding, with the ultimate goal of making protein-ligand modeling more accurate and hence speeding drug discovery.

  7. The Signatures of Selection for Translational Accuracy in Plant Genes

    PubMed Central

    Porceddu, Andrea; Zenoni, Sara; Camiolo, Salvatore

    2013-01-01

    Little is known about the natural selection of synonymous codons within the coding sequences of plant genes. We analyzed the distribution of synonymous codons within plant coding sequences and found that preferred codons tend to encode the more conserved and functionally important residues of plant proteins. This was consistent among several synonymous codon families and applied to genes with different expression profiles and functions. Most of the randomly chosen alternative sets of codons scored weaker associations than the actual sets of preferred codons, suggesting that codon position within plant genes and codon usage bias have coevolved to maximize translational accuracy. All these findings are consistent with the mistranslation-induced protein misfolding theory, which predicts the natural selection of highly preferred codons more frequently at sites where translation errors could compromise protein folding or functionality. Our results will provide an important insight in future studies of protein folding, molecular evolution, and transgene design for optimal expression. PMID:23695187

  8. Accuracy of selected techniques for estimating ice-affected streamflow

    USGS Publications Warehouse

    Walker, John F.

    1991-01-01

    This paper compares the accuracy of selected techniques for estimating streamflow during ice-affected periods. The techniques are classified into two categories - subjective and analytical - depending on the degree of judgment required. Discharge measurements have been made at three streamflow-gauging sites in Iowa during the 1987-88 winter and used to established a baseline streamflow record for each site. Using data based on a simulated six-week field-tip schedule, selected techniques are used to estimate discharge during the ice-affected periods. For the subjective techniques, three hydrographers have independently compiled each record. Three measures of performance are used to compare the estimated streamflow records with the baseline streamflow records: the average discharge for the ice-affected period, and the mean and standard deviation of the daily errors. Based on average ranks for three performance measures and the three sites, the analytical and subjective techniques are essentially comparable. For two of the three sites, Kruskal-Wallis one-way analysis of variance detects significant differences among the three hydrographers for the subjective methods, indicating that the subjective techniques are less consistent than the analytical techniques. The results suggest analytical techniques may be viable tools for estimating discharge during periods of ice effect, and should be developed further and evaluated for sites across the United States.

  9. Selective Effect of Physical Fatigue on Motor Imagery Accuracy

    PubMed Central

    Di Rienzo, Franck; Collet, Christian; Hoyek, Nady; Guillot, Aymeric

    2012-01-01

    While the use of motor imagery (the mental representation of an action without overt execution) during actual training sessions is usually recommended, experimental studies examining the effect of physical fatigue on subsequent motor imagery performance are sparse and yielded divergent findings. Here, we investigated whether physical fatigue occurring during an intense sport training session affected motor imagery ability. Twelve swimmers (nine males, mean age 15.5 years) conducted a 45 min physically-fatiguing protocol where they swam from 70% to 100% of their maximal aerobic speed. We tested motor imagery ability immediately before and after fatigue state. Participants randomly imagined performing a swim turn using internal and external visual imagery. Self-reports ratings, imagery times and electrodermal responses, an index of alertness from the autonomic nervous system, were the dependent variables. Self-reports ratings indicated that participants did not encounter difficulty when performing motor imagery after fatigue. However, motor imagery times were significantly shortened during posttest compared to both pretest and actual turn times, thus indicating reduced timing accuracy. Looking at the selective effect of physical fatigue on external visual imagery did not reveal any difference before and after fatigue, whereas significantly shorter imagined times and electrodermal responses (respectively 15% and 48% decrease, p<0.001) were observed during the posttest for internal visual imagery. A significant correlation (r = 0.64; p<0.05) was observed between motor imagery vividness (estimated through imagery questionnaire) and autonomic responses during motor imagery after fatigue. These data support that unlike local muscle fatigue, physical fatigue occurring during intense sport training sessions is likely to affect motor imagery accuracy. These results might be explained by the updating of the internal representation of the motor sequence, due to temporary

  10. Thermodynamic properties and phase equilibria of selected Heusler compounds

    NASA Astrophysics Data System (ADS)

    Yin, Ming

    Heusler compounds are ternary intermetallics with many promising properties such as spin polarization and magnetic shape memory effect. A better understanding of their thermodynamic properties facilitates future design and development. Therefore, standard enthalpies of formation and heat capacities from room temperature to 1500 K of selected Heusler compounds X2YZ (X = Co, Fe, Ni, Pd, Rh, Ru; Y = Co, Cu, Fe, Hf, Mn, Ni, Ti, V, Zr; Z = Al, Ga, In, Si, Ge, Sn) and half-Heusler compounds XYSn (X = Au, Co, Fe, Ir, Ni, Pd, Pt, Rh; Y = Hf, Mn, Ti, Zr) were measured using high temperature direct reaction calorimetry. The measured standard enthalpies of formation were compared with those predicted from ab initio calculations and the extended semi-empirical Miedema's model. Trends in standard enthalpy of formation with respect to the periodic classification of elements were discussed. The effect of a fourth element (Co, Cu, Fe, Pd; Ti, V; Al, Ga, In, Si, Ge) on the standard enthalpy of formation of Ni2MnSn was also investigated. Lattice parameters of the compounds with an L21 structure were determined using X-ray powder diffraction analysis. Differential scanning calorimetry was used to determine melting points and phase transformation temperatures. Phase relationships were investigated using scanning electron microscopy with an energy dispersive spectrometer. The isothermal section of the Fe-Sn-Ti ternary system at 873 K was established using equilibrated alloys. Three ternary compounds including the Heusler compound Fe2SnTi were observed. A new ternary compound Fe5Sn9Ti 6 was reported and the crystal structure of FeSnTi2 was determined for the first time.

  11. Accuracy of Genomic Selection in a Rice Synthetic Population Developed for Recurrent Selection Breeding.

    PubMed

    Grenier, Cécile; Cao, Tuong-Vi; Ospina, Yolima; Quintero, Constanza; Châtel, Marc Henri; Tohme, Joe; Courtois, Brigitte; Ahmadi, Nourollah

    2015-01-01

    Genomic selection (GS) is a promising strategy for enhancing genetic gain. We investigated the accuracy of genomic estimated breeding values (GEBV) in four inter-related synthetic populations that underwent several cycles of recurrent selection in an upland rice-breeding program. A total of 343 S2:4 lines extracted from those populations were phenotyped for flowering time, plant height, grain yield and panicle weight, and genotyped with an average density of one marker per 44.8 kb. The relative effect of the linkage disequilibrium (LD) and minor allele frequency (MAF) thresholds for selecting markers, the relative size of the training population (TP) and of the validation population (VP), the selected trait and the genomic prediction models (frequentist and Bayesian) on the accuracy of GEBVs was investigated in 540 cross validation experiments with 100 replicates. The effect of kinship between the training and validation populations was tested in an additional set of 840 cross validation experiments with a single genomic prediction model. LD was high (average r2 = 0.59 at 25 kb) and decreased slowly, distribution of allele frequencies at individual loci was markedly skewed toward unbalanced frequencies (MAF average value 15.2% and median 9.6%), and differentiation between the four synthetic populations was low (FST ≤0.06). The accuracy of GEBV across all cross validation experiments ranged from 0.12 to 0.54 with an average of 0.30. Significant differences in accuracy were observed among the different levels of each factor investigated. Phenotypic traits had the biggest effect, and the size of the incidence matrix had the smallest. Significant first degree interaction was observed for GEBV accuracy between traits and all the other factors studied, and between prediction models and LD, MAF and composition of the TP. The potential of GS to accelerate genetic gain and breeding options to increase the accuracy of predictions are discussed. PMID:26313446

  12. Accuracy of Genomic Selection in a Rice Synthetic Population Developed for Recurrent Selection Breeding.

    PubMed

    Grenier, Cécile; Cao, Tuong-Vi; Ospina, Yolima; Quintero, Constanza; Châtel, Marc Henri; Tohme, Joe; Courtois, Brigitte; Ahmadi, Nourollah

    2015-01-01

    Genomic selection (GS) is a promising strategy for enhancing genetic gain. We investigated the accuracy of genomic estimated breeding values (GEBV) in four inter-related synthetic populations that underwent several cycles of recurrent selection in an upland rice-breeding program. A total of 343 S2:4 lines extracted from those populations were phenotyped for flowering time, plant height, grain yield and panicle weight, and genotyped with an average density of one marker per 44.8 kb. The relative effect of the linkage disequilibrium (LD) and minor allele frequency (MAF) thresholds for selecting markers, the relative size of the training population (TP) and of the validation population (VP), the selected trait and the genomic prediction models (frequentist and Bayesian) on the accuracy of GEBVs was investigated in 540 cross validation experiments with 100 replicates. The effect of kinship between the training and validation populations was tested in an additional set of 840 cross validation experiments with a single genomic prediction model. LD was high (average r2 = 0.59 at 25 kb) and decreased slowly, distribution of allele frequencies at individual loci was markedly skewed toward unbalanced frequencies (MAF average value 15.2% and median 9.6%), and differentiation between the four synthetic populations was low (FST ≤0.06). The accuracy of GEBV across all cross validation experiments ranged from 0.12 to 0.54 with an average of 0.30. Significant differences in accuracy were observed among the different levels of each factor investigated. Phenotypic traits had the biggest effect, and the size of the incidence matrix had the smallest. Significant first degree interaction was observed for GEBV accuracy between traits and all the other factors studied, and between prediction models and LD, MAF and composition of the TP. The potential of GS to accelerate genetic gain and breeding options to increase the accuracy of predictions are discussed.

  13. Accuracy of Genomic Selection in a Rice Synthetic Population Developed for Recurrent Selection Breeding

    PubMed Central

    Ospina, Yolima; Quintero, Constanza; Châtel, Marc Henri; Tohme, Joe; Courtois, Brigitte

    2015-01-01

    Genomic selection (GS) is a promising strategy for enhancing genetic gain. We investigated the accuracy of genomic estimated breeding values (GEBV) in four inter-related synthetic populations that underwent several cycles of recurrent selection in an upland rice-breeding program. A total of 343 S2:4 lines extracted from those populations were phenotyped for flowering time, plant height, grain yield and panicle weight, and genotyped with an average density of one marker per 44.8 kb. The relative effect of the linkage disequilibrium (LD) and minor allele frequency (MAF) thresholds for selecting markers, the relative size of the training population (TP) and of the validation population (VP), the selected trait and the genomic prediction models (frequentist and Bayesian) on the accuracy of GEBVs was investigated in 540 cross validation experiments with 100 replicates. The effect of kinship between the training and validation populations was tested in an additional set of 840 cross validation experiments with a single genomic prediction model. LD was high (average r2 = 0.59 at 25 kb) and decreased slowly, distribution of allele frequencies at individual loci was markedly skewed toward unbalanced frequencies (MAF average value 15.2% and median 9.6%), and differentiation between the four synthetic populations was low (FST ≤0.06). The accuracy of GEBV across all cross validation experiments ranged from 0.12 to 0.54 with an average of 0.30. Significant differences in accuracy were observed among the different levels of each factor investigated. Phenotypic traits had the biggest effect, and the size of the incidence matrix had the smallest. Significant first degree interaction was observed for GEBV accuracy between traits and all the other factors studied, and between prediction models and LD, MAF and composition of the TP. The potential of GS to accelerate genetic gain and breeding options to increase the accuracy of predictions are discussed. PMID:26313446

  14. Free Radical Halogenation, Selectivity, and Thermodynamics: The Polanyi Principle and Hammond's Postulate

    ERIC Educational Resources Information Center

    Scala, Alfred A.

    2004-01-01

    The underlying ideas of the Polanyi principle and Hammond's postulate in relation to the simple free halogenation reactions and their selectivity and thermodynamics is presented. The results indicate that the chlorine atom exhibits a slightly less selectivity in the liquid phase as compared to in the gas phase.

  15. A thermodynamic study of selective solvation in solvent mixtures.

    PubMed

    Cabot, Rafel; Hunter, Christopher A

    2010-04-21

    Changes in the (31)P NMR chemical shift of tri-n-butylphosphine oxide have been measured as function of solvent composition in a number of binary solvent mixtures. The data were analysed using a model that separates the contributions of specific H-bond interactions with the first solvation shell and the non-specific effects of the bulk solvent on the chemical shift. This allowed measurement of equilibrium constants between differently solvated states of the probe and hence thermodynamic quantification of preferential solvation in the binary mixtures. The results are analysed in the context of the electrostatic solvent competition model, which assumes that solvent effects on intermolecular interactions can be interpreted based on the exchange of specific functional group contacts, with minimal involvement of the bulk solvent. The thermodynamic measurements of preferential solvation were used to determine the H-bond donor parameter alpha for cyclohexane, n-octane, n-dodecane, benzene, 1,4-dioxane, carbon tetrachloride, acetone, dichloromethane, dimethyl sulfoxide and chloroform. For solvents where the H-bond donor parameters have been measured as solutes in carbon tetrachloride solution, the H-bond donor parameters measured here for the same compounds as solvents are practically identical, i.e. solute and solvent H-bond parameters are directly interchangable. For alkanes, the experimental H-bond donor parameter is significantly larger than expected based on calculated molecular electrostatic potential surfaces. This might suggest an increase in the relative importance of van der Waals interactions when electrostatic effects are weak. PMID:20449502

  16. Selecting fillers on emotional appearance improves lineup identification accuracy.

    PubMed

    Flowe, Heather D; Klatt, Thimna; Colloff, Melissa F

    2014-12-01

    Mock witnesses sometimes report using criminal stereotypes to identify a face from a lineup, a tendency known as criminal face bias. Faces are perceived as criminal-looking if they appear angry. We tested whether matching the emotional appearance of the fillers to an angry suspect can reduce criminal face bias. In Study 1, mock witnesses (n = 226) viewed lineups in which the suspect had an angry, happy, or neutral expression, and we varied whether the fillers matched the expression. An additional group of participants (n = 59) rated the faces on criminal and emotional appearance. As predicted, mock witnesses tended to identify suspects who appeared angrier and more criminal-looking than the fillers. This tendency was reduced when the lineup fillers matched the emotional appearance of the suspect. Study 2 extended the results, testing whether the emotional appearance of the suspect and fillers affects recognition memory. Participants (n = 1,983) studied faces and took a lineup test in which the emotional appearance of the target and fillers was varied between subjects. Discrimination accuracy was enhanced when the fillers matched an angry target's emotional appearance. We conclude that lineup member emotional appearance plays a critical role in the psychology of lineup identification. The fillers should match an angry suspect's emotional appearance to improve lineup identification accuracy.

  17. Thermodynamics of selected trace elements in the Jovian atmosphere

    NASA Technical Reports Server (NTRS)

    Fegley, B., Jr.; Lewis, J. S.

    1979-01-01

    The thermochemistry of several hundred compounds of twelve selected trace elements (Ge, Se, Ga, As, Te, Pb, Sn, Cd, Sb, Tl, In, and Bi) has been investigated for solar composition material along a Jupiter adiabat. The results indicate that AsF3, InBr, TlI, and SbS, in addition to CO, PH3, GeH4, AsH3, H2Se, HCl, HF, and H3BO3 proposed by Barshay and Lewis (1978), may be potential chemical tracers of atmospheric dynamics. The reported observation of GeH4 is interpreted on the basis of new calculations as implying rapid vertical transport from levels where the temperature is greater than or equal to 800 K. Upper limits are also set on the abundances of many gaseous compounds of the elements investigated.

  18. Thermodynamic guiding principles in selective synthesis of strontium iridate Ruddlesden-Popper epitaxial films

    NASA Astrophysics Data System (ADS)

    Nishio, Kazunori; Hwang, Harold Y.; Hikita, Yasuyuki

    2016-03-01

    We demonstrate the selective fabrication of Ruddlesden-Popper (RP) type SrIrO3, Sr3Ir2O7, and Sr2IrO4 epitaxial thin films from a single SrIrO3 target using pulsed laser deposition (PLD). We identified that the growth conditions stabilizing each phase directly map onto the phase diagram expected from thermodynamic equilibria. This approach allows precise cation stoichiometry control as evidenced by the stabilization of single phase Sr3Ir2O7 for the first time, overcoming the close thermodynamic stability between neighboring RP phases. Despite the non-equilibrium nature of PLD, these results highlight the importance of thermodynamic guiding principles to strategically synthesize the targeted phase in complex oxide thin films.

  19. Use of Thermodynamic Modeling for Selection of Electrolyte for Electrorefining of Magnesium from Aluminum Alloy Melts

    NASA Astrophysics Data System (ADS)

    Gesing, Adam J.; Das, Subodh K.

    2016-06-01

    With United States Department of Energy Advanced Research Project Agency funding, experimental proof-of-concept was demonstrated for RE-12TM electrorefining process of extraction of desired amount of Mg from recycled scrap secondary Al molten alloys. The key enabling technology for this process was the selection of the suitable electrolyte composition and operating temperature. The selection was made using the FactSage thermodynamic modeling software and the light metal, molten salt, and oxide thermodynamic databases. Modeling allowed prediction of the chemical equilibria, impurity contents in both anode and cathode products, and in the electrolyte. FactSage also provided data on the physical properties of the electrolyte and the molten metal phases including electrical conductivity and density of the molten phases. Further modeling permitted selection of electrode and cell construction materials chemically compatible with the combination of molten metals and the electrolyte.

  20. Does feature selection improve classification accuracy? Impact of sample size and feature selection on classification using anatomical magnetic resonance images.

    PubMed

    Chu, Carlton; Hsu, Ai-Ling; Chou, Kun-Hsien; Bandettini, Peter; Lin, Chingpo

    2012-03-01

    There are growing numbers of studies using machine learning approaches to characterize patterns of anatomical difference discernible from neuroimaging data. The high-dimensionality of image data often raises a concern that feature selection is needed to obtain optimal accuracy. Among previous studies, mostly using fixed sample sizes, some show greater predictive accuracies with feature selection, whereas others do not. In this study, we compared four common feature selection methods. 1) Pre-selected region of interests (ROIs) that are based on prior knowledge. 2) Univariate t-test filtering. 3) Recursive feature elimination (RFE), and 4) t-test filtering constrained by ROIs. The predictive accuracies achieved from different sample sizes, with and without feature selection, were compared statistically. To demonstrate the effect, we used grey matter segmented from the T1-weighted anatomical scans collected by the Alzheimer's disease Neuroimaging Initiative (ADNI) as the input features to a linear support vector machine classifier. The objective was to characterize the patterns of difference between Alzheimer's disease (AD) patients and cognitively normal subjects, and also to characterize the difference between mild cognitive impairment (MCI) patients and normal subjects. In addition, we also compared the classification accuracies between MCI patients who converted to AD and MCI patients who did not convert within the period of 12 months. Predictive accuracies from two data-driven feature selection methods (t-test filtering and RFE) were no better than those achieved using whole brain data. We showed that we could achieve the most accurate characterizations by using prior knowledge of where to expect neurodegeneration (hippocampus and parahippocampal gyrus). Therefore, feature selection does improve the classification accuracies, but it depends on the method adopted. In general, larger sample sizes yielded higher accuracies with less advantage obtained by using

  1. Accuracy-rate tradeoffs: how do enzymes meet demands of selectivity and catalytic efficiency?

    PubMed

    Tawfik, Dan S

    2014-08-01

    I discuss some physico-chemical and evolutionary aspects of enzyme accuracy (selectivity, specificity) and speed (turnover rate, processivity). Accuracy can be a beneficial side-product of active-sites being refined to proficiently convert a given substrate into one product. However, exclusion of undesirable, non-cognate substrates is also an explicitly evolved trait that may come with a cost. I define two schematic mechanisms. Ground-state discrimination applies to enzymes where selectivity is achieved primarily at the level of substrate binding. Exemplified by DNA methyltransferases and the ribosome, ground-state discrimination imposes strong accuracy-rate tradeoffs. Alternatively, transition-state discrimination, applies to relatively small substrates where substrate binding and chemistry are efficiently coupled, and evokes weaker tradeoffs. Overall, the mechanistic, structural and evolutionary basis of enzymatic accuracy-rate tradeoffs merits deeper understanding.

  2. Effects of implant angulation, material selection, and impression technique on impression accuracy: a preliminary laboratory study.

    PubMed

    Rutkunas, Vygandas; Sveikata, Kestutis; Savickas, Raimondas

    2012-01-01

    The aim of this preliminary laboratory study was to evaluate the effects of 5- and 25-degree implant angulations in simulated clinical casts on an impression's accuracy when using different impression materials and tray selections. A convenience sample of each implant angulation group was selected for both open and closed trays in combination with one polyether and two polyvinyl siloxane impression materials. The influence of material and technique appeared to be significant for both 5- and 25-degree angulations (P < .05), and increased angulation tended to decrease impression accuracy. The open-tray technique was more accurate with highly nonaxially oriented implants for the small sample size investigated.

  3. Accuracy and responses of genomic selection on key traits in apple breeding

    PubMed Central

    Muranty, Hélène; Troggio, Michela; Sadok, Inès Ben; Rifaï, Mehdi Al; Auwerkerken, Annemarie; Banchi, Elisa; Velasco, Riccardo; Stevanato, Piergiorgio; van de Weg, W Eric; Di Guardo, Mario; Kumar, Satish; Laurens, François; Bink, Marco C A M

    2015-01-01

    The application of genomic selection in fruit tree crops is expected to enhance breeding efficiency by increasing prediction accuracy, increasing selection intensity and decreasing generation interval. The objectives of this study were to assess the accuracy of prediction and selection response in commercial apple breeding programmes for key traits. The training population comprised 977 individuals derived from 20 pedigreed full-sib families. Historic phenotypic data were available on 10 traits related to productivity and fruit external appearance and genotypic data for 7829 SNPs obtained with an Illumina 20K SNP array. From these data, a genome-wide prediction model was built and subsequently used to calculate genomic breeding values of five application full-sib families. The application families had genotypes at 364 SNPs from a dedicated 512 SNP array, and these genotypic data were extended to the high-density level by imputation. These five families were phenotyped for 1 year and their phenotypes were compared to the predicted breeding values. Accuracy of genomic prediction across the 10 traits reached a maximum value of 0.5 and had a median value of 0.19. The accuracies were strongly affected by the phenotypic distribution and heritability of traits. In the largest family, significant selection response was observed for traits with high heritability and symmetric phenotypic distribution. Traits that showed non-significant response often had reduced and skewed phenotypic variation or low heritability. Among the five application families the accuracies were uncorrelated to the degree of relatedness to the training population. The results underline the potential of genomic prediction to accelerate breeding progress in outbred fruit tree crops that still need to overcome long generation intervals and extensive phenotyping costs. PMID:26744627

  4. Estimation of accuracies and expected genetic change from selection for selection indexes that use multiple-trait predictions of breeding values.

    PubMed

    Barwick, S A; Tier, B; Swan, A A; Henzell, A L

    2013-10-01

    Procedures are described for estimating selection index accuracies for individual animals and expected genetic change from selection for the general case where indexes of EBVs predict an aggregate breeding objective of traits that may or may not have been measured. Index accuracies for the breeding objective are shown to take an important general form, being able to be expressed as the product of the accuracy of the index function of true breeding values and the accuracy with which that function predicts the breeding objective. When the accuracies of the individual EBVs of the index are known, prediction error variances (PEVs) and covariances (PECs) for the EBVs within animal are able to be well approximated, and index accuracies and expected genetic change from selection estimated with high accuracy. The procedures are suited to routine use in estimating index accuracies in genetic evaluation, and for providing important information, without additional modelling, on the directions in which a population will move under selection.

  5. The influence of feature selection methods on accuracy, stability and interpretability of molecular signatures.

    PubMed

    Haury, Anne-Claire; Gestraud, Pierre; Vert, Jean-Philippe

    2011-01-01

    Biomarker discovery from high-dimensional data is a crucial problem with enormous applications in biology and medicine. It is also extremely challenging from a statistical viewpoint, but surprisingly few studies have investigated the relative strengths and weaknesses of the plethora of existing feature selection methods. In this study we compare 32 feature selection methods on 4 public gene expression datasets for breast cancer prognosis, in terms of predictive performance, stability and functional interpretability of the signatures they produce. We observe that the feature selection method has a significant influence on the accuracy, stability and interpretability of signatures. Surprisingly, complex wrapper and embedded methods generally do not outperform simple univariate feature selection methods, and ensemble feature selection has generally no positive effect. Overall a simple Student's t-test seems to provide the best results.

  6. Assessing the accuracy of selectivity as a basis for solvent screening in extractive distillation processes

    SciTech Connect

    Momoh, S.O. )

    1991-01-01

    An important parameter for consideration in the screening of solvents for an extractive distillation process is selectivity at infinite dilution. The higher the selectivity, the better the solvent. This paper assesses the accuracy of using selectivity as a basis for solvent screening in extractive distillation processes. Three types of binary mixtures that are usually separated by an extractive distillation process are chosen for investigation. Having determined the optimum solvent feed rate to be two times the feed rate of the binary mixture, the total annual costs of extractive distillation processes for each of the chosen mixtures and for various solvents are carried out. The solvents are ranked on the basis of the total annual cost (obtained by design and costing equations) for the extractive distillation processes, and this ranking order is compared with that of selectivity at infinite dilution as determined by the UNIFAC method. This matching of selectivity with total annual cost does not produce a very good correlation.

  7. Thermodynamic and Kinetic Studies for Intensifying Selective Decomposition of Zinc Ferrite

    NASA Astrophysics Data System (ADS)

    Han, Junwei; Liu, Wei; Qin, Wenqing; Jiao, Fen; Wang, Dawei; Liang, Chao

    2016-01-01

    A novel method to intensify the selective decomposition of zinc ferrite by a roasting process including reduction and magnetization stages was proposed. The relevant thermodynamic analysis with HSC [enthalpy (H), entropy (S) and heat capacity (C)] Chemistry 5.0 and experimental research on a laboratory scale were investigated. The thermodynamic calculations show that increasing the temperature and the CO amount promote not only the decomposition of zinc ferrite but also the formation of wustite, which can be converted to magnetite using sufficient CO2 at 823 K. The experimental results indicate that the zinc ferrite was decomposed into zinc oxide and wustite by reduction roasting under a gas mixture of 20% CO, 20% CO2 and 60% N2 at 1023 K for 90 min, and the decomposition degree of zinc ferrite reached 94%. Then, the generated wustite was transformed into magnetite by magnetization roasting under CO2 atmosphere at 823 K for 75 min, after which the selective extraction of zinc from zinc ferrite could be well achieved by low acid leaching. Increasing temperature and time were conducive to the magnetization within low temperature range, but when the temperature was above 823 K the zinc ferrite could be regenerated.

  8. Thermodynamic and Kinetic Studies for Intensifying Selective Decomposition of Zinc Ferrite

    NASA Astrophysics Data System (ADS)

    Han, Junwei; Liu, Wei; Qin, Wenqing; Jiao, Fen; Wang, Dawei; Liang, Chao

    2016-09-01

    A novel method to intensify the selective decomposition of zinc ferrite by a roasting process including reduction and magnetization stages was proposed. The relevant thermodynamic analysis with HSC [enthalpy (H), entropy (S) and heat capacity (C)] Chemistry 5.0 and experimental research on a laboratory scale were investigated. The thermodynamic calculations show that increasing the temperature and the CO amount promote not only the decomposition of zinc ferrite but also the formation of wustite, which can be converted to magnetite using sufficient CO2 at 823 K. The experimental results indicate that the zinc ferrite was decomposed into zinc oxide and wustite by reduction roasting under a gas mixture of 20% CO, 20% CO2 and 60% N2 at 1023 K for 90 min, and the decomposition degree of zinc ferrite reached 94%. Then, the generated wustite was transformed into magnetite by magnetization roasting under CO2 atmosphere at 823 K for 75 min, after which the selective extraction of zinc from zinc ferrite could be well achieved by low acid leaching. Increasing temperature and time were conducive to the magnetization within low temperature range, but when the temperature was above 823 K the zinc ferrite could be regenerated.

  9. Interactive FORTRAN IV computer programs for the thermodynamic and transport properties of selected cryogens (fluids pack)

    NASA Technical Reports Server (NTRS)

    Mccarty, R. D.

    1980-01-01

    The thermodynamic and transport properties of selected cryogens had programmed into a series of computer routines. Input variables are any two of P, rho or T in the single phase regions and either P or T for the saturated liquid or vapor state. The output is pressure, density, temperature, entropy, enthalpy for all of the fluids and in most cases specific heat capacity and speed of sound. Viscosity and thermal conductivity are also given for most of the fluids. The programs are designed for access by remote terminal; however, they have been written in a modular form to allow the user to select either specific fluids or specific properties for particular needs. The program includes properties for hydrogen, helium, neon, nitrogen, oxygen, argon, and methane. The programs include properties for gaseous and liquid states usually from the triple point to some upper limit of pressure and temperature which varies from fluid to fluid.

  10. Cooperative thermodynamic control of selectivity in the self-assembly of rare earth metal-ligand helices.

    PubMed

    Johnson, Amber M; Young, Michael C; Zhang, Xing; Julian, Ryan R; Hooley, Richard J

    2013-11-27

    Metal-selective self-assembly with rare-earth cations is possible with suitable rigid, symmetrical bis-tridentate ligands. Kinetically controlled formation is initially observed, with smaller cations preferentially incorporated. Over time, the more thermodynamically favorable complexes with larger metals are formed. This thermodynamic control is a cooperative supramolecular phenomenon and only occurs upon multiple-metal-based self-assembly: single-metal ML3 analogues do not show reversible selectivity. The selectivity is dependent on small variations in lanthanide ionic radius and occurs despite identical coordination-ligand coordination geometries and minor size differences in the rare-earth metals.

  11. Improvement of olfactometric measurement accuracy and repeatability by optimization of panel selection procedures.

    PubMed

    Capelli, L; Sironi, S; Del Rosso, R; Céntola, P; Bonati, S

    2010-01-01

    The EN 13725:2003, which standardizes the determination of odour concentration by dynamic olfactometry, fixes the limits for panel selection in terms of individual threshold towards a reference gas (n-butanol in nitrogen) and of standard deviation of the responses. Nonetheless, laboratories have some degrees of freedom in developing their own procedures for panel selection and evaluation. Most Italian olfactometric laboratories use a similar procedure for panel selection, based on the repeated analysis of samples of n-butanol at a concentration of 60 ppm. The first part of this study demonstrates that this procedure may originate a sort of "smartening" of the assessors, which means that they become able to guess the right answers in order to maintain their qualification as panel members, independently from their real olfactory perception. For this reason, the panel selection procedure has been revised with the aim of making it less repetitive, therefore preventing the possibility for panel members to be able to guess the best answers in order to comply with the selection criteria. The selection of new panel members and the screening of the active ones according to this revised procedure proved this new procedure to be more selective than the "standard" one. Finally, the results of the tests with n-butanol conducted after the introduction of the revised procedure for panel selection and regular verification showed an effective improvement of the laboratory measurement performances in terms of accuracy and precision.

  12. Improvement of olfactometric measurement accuracy and repeatability by optimization of panel selection procedures.

    PubMed

    Capelli, L; Sironi, S; Del Rosso, R; Céntola, P; Bonati, S

    2010-01-01

    The EN 13725:2003, which standardizes the determination of odour concentration by dynamic olfactometry, fixes the limits for panel selection in terms of individual threshold towards a reference gas (n-butanol in nitrogen) and of standard deviation of the responses. Nonetheless, laboratories have some degrees of freedom in developing their own procedures for panel selection and evaluation. Most Italian olfactometric laboratories use a similar procedure for panel selection, based on the repeated analysis of samples of n-butanol at a concentration of 60 ppm. The first part of this study demonstrates that this procedure may originate a sort of "smartening" of the assessors, which means that they become able to guess the right answers in order to maintain their qualification as panel members, independently from their real olfactory perception. For this reason, the panel selection procedure has been revised with the aim of making it less repetitive, therefore preventing the possibility for panel members to be able to guess the best answers in order to comply with the selection criteria. The selection of new panel members and the screening of the active ones according to this revised procedure proved this new procedure to be more selective than the "standard" one. Finally, the results of the tests with n-butanol conducted after the introduction of the revised procedure for panel selection and regular verification showed an effective improvement of the laboratory measurement performances in terms of accuracy and precision. PMID:20220249

  13. Thermodynamic selectivity of functional agents on zeolite for sodium dodecyl sulfate sequestration.

    PubMed

    Leng, Ling; Wang, Jian; Qiu, Xianxiu; Zhao, Yanxiang; Yip, Yuk-Wang; Law, Ga-Lai; Shih, Kaimin; Zhou, Zhengyuan; Lee, Po-Heng

    2016-11-15

    This study proposes a thermodynamic approach to effectively select functional agents onto zeolite for sodium dodecyl sulfate (SDS) sequestration in greywater reuse. We combine isothermal titration calorimetry (ITC) and quantum chemistry simulation (QCS) to identify the interactions between SDS and agents at the molecular level. Three potential agents, cetyl trimethyl ammonium bromide (CTAB), N,N,N-trimethyltetradecan-1-aminium bromide (C14TAB), and 14-hydroxy-N,N,N-trimethyltetradecan-1-aminium bromide (C14HTAB), differ in carbon chain length and hydrophilic groups. The ITC titration of SDS with CTAB released the highest heat, followed by those with C14TAB and C14HTAB, as was the same trend for the amounts of SDS adsorbed by the respective functionalized-zeolites. Results suggest that the favorable SDS sorption occurred at the bilayer CTAB-zeolite is driven by enthalpy as similar as the SDS…CTAB interaction found, regardless of the contribution from electrostatic and/or hydrophobic behaviors, while the declined sorption is entropy-driven via the predominant hydrophobic interaction onto the monolayer CTAB-zeolite. The data presented here interpret the nature of molecularly thermodynamic quantities and enable the manipulation of sorption capacity optimization. PMID:27399145

  14. Bottom-up coarse-grained models with predictive accuracy and transferability for both structural and thermodynamic properties of heptane-toluene mixtures

    NASA Astrophysics Data System (ADS)

    Dunn, Nicholas J. H.; Noid, W. G.

    2016-05-01

    This work investigates the promise of a "bottom-up" extended ensemble framework for developing coarse-grained (CG) models that provide predictive accuracy and transferability for describing both structural and thermodynamic properties. We employ a force-matching variational principle to determine system-independent, i.e., transferable, interaction potentials that optimally model the interactions in five distinct heptane-toluene mixtures. Similarly, we employ a self-consistent pressure-matching approach to determine a system-specific pressure correction for each mixture. The resulting CG potentials accurately reproduce the site-site rdfs, the volume fluctuations, and the pressure equations of state that are determined by all-atom (AA) models for the five mixtures. Furthermore, we demonstrate that these CG potentials provide similar accuracy for additional heptane-toluene mixtures that were not included their parameterization. Surprisingly, the extended ensemble approach improves not only the transferability but also the accuracy of the calculated potentials. Additionally, we observe that the required pressure corrections strongly correlate with the intermolecular cohesion of the system-specific CG potentials. Moreover, this cohesion correlates with the relative "structure" within the corresponding mapped AA ensemble. Finally, the appendix demonstrates that the self-consistent pressure-matching approach corresponds to minimizing an appropriate relative entropy.

  15. Thermodynamics of protein-ligand interactions as a reference for computational analysis: how to assess accuracy, reliability and relevance of experimental data.

    PubMed

    Krimmer, Stefan G; Klebe, Gerhard

    2015-09-01

    For a conscientious interpretation of thermodynamic parameters (Gibbs free energy, enthalpy and entropy) obtained by isothermal titration calorimetry (ITC), it is necessary to first evaluate the experimental setup and conditions at which the data were measured. The data quality must be assessed and the precision and accuracy of the measured parameters must be estimated. This information provides the basis at which level discussion of the data is appropriate, and allows insight into the significance of comparisons with other data. The aim of this article is to provide the reader with basic understanding of the ITC technique and the experimental practices commonly applied, in order to foster an appreciation for how much measured thermodynamic parameters can deviate from ideal, error-free values. Particular attention is paid to the shape of the recorded isotherm (c-value), the influence of the applied buffer used for the reaction (protonation reactions, pH), the chosen experimental settings (temperature), impurities of protein and ligand, sources of systematic errors (solution concentration, solution activity, and device calibration) and to the applied analysis software. Furthermore, we comment on enthalpy-entropy compensation, heat capacities and van't Hoff enthalpies. PMID:26376645

  16. Thermodynamics of protein-ligand interactions as a reference for computational analysis: how to assess accuracy, reliability and relevance of experimental data.

    PubMed

    Krimmer, Stefan G; Klebe, Gerhard

    2015-09-01

    For a conscientious interpretation of thermodynamic parameters (Gibbs free energy, enthalpy and entropy) obtained by isothermal titration calorimetry (ITC), it is necessary to first evaluate the experimental setup and conditions at which the data were measured. The data quality must be assessed and the precision and accuracy of the measured parameters must be estimated. This information provides the basis at which level discussion of the data is appropriate, and allows insight into the significance of comparisons with other data. The aim of this article is to provide the reader with basic understanding of the ITC technique and the experimental practices commonly applied, in order to foster an appreciation for how much measured thermodynamic parameters can deviate from ideal, error-free values. Particular attention is paid to the shape of the recorded isotherm (c-value), the influence of the applied buffer used for the reaction (protonation reactions, pH), the chosen experimental settings (temperature), impurities of protein and ligand, sources of systematic errors (solution concentration, solution activity, and device calibration) and to the applied analysis software. Furthermore, we comment on enthalpy-entropy compensation, heat capacities and van't Hoff enthalpies.

  17. Thermodynamic analysis of the selective chlorination of electric arc furnace dust.

    PubMed

    Pickles, C A

    2009-07-30

    The remelting of automobile scrap in an electric arc furnace (EAF) results in the production of a dust, which contains high concentrations of the oxides of zinc, iron, calcium and other metals. Typically, the lead and zinc are of commercial value, while the other metals are not worth recovering. At the present time, EAF dusts are treated in high temperature Waelz rotary kiln-type processes, where the lead and zinc oxides are selectively reduced and simultaneously reoxidized and a crude zinc oxide is produced. Another alternative processing route is selective chlorination, in which the non-ferrous metals are preferentially chlorinated to their gaseous chlorides and in this manner separated from the iron. In the present research, a detailed thermodynamic analysis of this chlorination process has been performed and the following factors were investigated; temperature, amount of chlorine, lime content, silica content, presence of an inert gas and the oxygen potential. High lead and zinc recoveries as gaseous chlorides could be achieved but some of the iron oxide was also chlorinated. Additionally, the calcium oxide in the dust consumes chlorine, but this can be minimized by adding silica, which results in the formation of stable calcium silicates. The optimum conditions were determined for a typical dust composition. The selectivities achieved with chlorination were lower than those for reduction, as reported in the literature, but there are other advantages such as the potential recovery of copper.

  18. Comparative accuracy of the Albedo, transmission and absorption for selected radiative transfer approximations

    NASA Technical Reports Server (NTRS)

    King, M. D.; HARSHVARDHAN

    1986-01-01

    Illustrations of both the relative and absolute accuracy of eight different radiative transfer approximations as a function of optical thickness, solar zenith angle and single scattering albedo are given. Computational results for the plane albedo, total transmission and fractional absorption were obtained for plane-parallel atmospheres composed of cloud particles. These computations, which were obtained using the doubling method, are compared with comparable results obtained using selected radiative transfer approximations. Comparisons were made between asymptotic theory for thick layers and the following widely used two stream approximations: Coakley-Chylek's models 1 and 2, Meador-Weaver, Eddington, delta-Eddington, PIFM and delta-discrete ordinates.

  19. Predicted accuracy of and response to genomic selection for new traits in dairy cattle.

    PubMed

    Calus, M P L; de Haas, Y; Pszczola, M; Veerkamp, R F

    2013-02-01

    Genomic selection relaxes the requirement of traditional selection tools to have phenotypic measurements on close relatives of all selection candidates. This opens up possibilities to select for traits that are difficult or expensive to measure. The objectives of this paper were to predict accuracy of and response to genomic selection for a new trait, considering that only a cow reference population of moderate size was available for the new trait, and that selection simultaneously targeted an index and this new trait. Accuracy for and response to selection were deterministically evaluated for three different breeding goals. Single trait selection for the new trait based only on a limited cow reference population of up to 10 000 cows, showed that maximum genetic responses of 0.20 and 0.28 genetic standard deviation (s.d.) per year can be achieved for traits with a heritability of 0.05 and 0.30, respectively. Adding information from the index based on a reference population of 5000 bulls, and assuming a genetic correlation of 0.5, increased genetic response for both heritability levels by up to 0.14 genetic s.d. per year. The scenario with simultaneous selection for the new trait and the index, yielded a substantially lower response for the new trait, especially when the genetic correlation with the index was negative. Despite the lower response for the index, whenever the new trait had considerable economic value, including the cow reference population considerably improved the genetic response for the new trait. For scenarios with a zero or negative genetic correlation with the index and equal economic value for the index and the new trait, a reference population of 2000 cows increased genetic response for the new trait with at least 0.10 and 0.20 genetic s.d. per year, for heritability levels of 0.05 and 0.30, respectively. We conclude that for new traits with a very small or positive genetic correlation with the index, and a high positive economic value

  20. Individual variation in exploratory behaviour improves speed and accuracy of collective nest selection by Argentine ants

    PubMed Central

    Hui, Ashley; Pinter-Wollman, Noa

    2014-01-01

    Collective behaviours are influenced by the behavioural composition of the group. For example, a collective behaviour may emerge from the average behaviour of the group's constituents, or be driven by a few key individuals that catalyse the behaviour of others in the group. When ant colonies collectively relocate to a new nest site, there is an inherent trade-off between the speed and accuracy of their decision of where to move due to the time it takes to gather information. Thus, variation among workers in exploratory behaviour, which allows gathering information about potential new nest sites, may impact the ability of a colony to move quickly into a suitable new nest. The invasive Argentine ant, Linepithema humile, expands its range locally through the dispersal and establishment of propagules: groups of ants and queens. We examine whether the success of these groups in rapidly finding a suitable nest site is affected by their behavioural composition. We compared nest choice speed and accuracy among groups of all-exploratory, all-nonexploratory and half-exploratory–half-nonexploratory individuals. We show that exploratory individuals improve both the speed and accuracy of collective nest choice, and that exploratory individuals have additive, not synergistic, effects on nest site selection. By integrating an examination of behaviour into the study of invasive species we shed light on the mechanisms that impact the progression of invasion. PMID:25018558

  1. [Analysis on the accuracy of simple selection method of Fengshi (GB 31)].

    PubMed

    Li, Zhixing; Zhang, Haihua; Li, Suhe

    2015-12-01

    To explore the accuracy of simple selection method of Fengshi (GB 31). Through the study of the ancient and modern data,the analysis and integration of the acupuncture books,the comparison of the locations of Fengshi (GB 31) by doctors from all dynasties and the integration of modern anatomia, the modern simple selection method of Fengshi (GB 31) is definite, which is the same as the traditional way. It is believed that the simple selec tion method is in accord with the human-oriented thought of TCM. Treatment by acupoints should be based on the emerging nature and the individual difference of patients. Also, it is proposed that Fengshi (GB 31) should be located through the integration between the simple method and body surface anatomical mark.

  2. Group-Item and Directed Scanning: Examining Preschoolers' Accuracy and Efficiency in Two Augmentative Communication Symbol Selection Methods

    ERIC Educational Resources Information Center

    White, Aubrey Randall; Carney, Edward; Reichle, Joe

    2010-01-01

    Purpose: The current investigation compared directed scanning and group-item scanning among typically developing 4-year-old children. Of specific interest were their accuracy, selection speed, and efficiency of cursor movement in selecting colored line drawn symbols representing object vocabulary. Method: Twelve 4-year-olds made selections in both…

  3. Effects of machining accuracy on frequency response properties of thick-screen frequency selective surface

    NASA Astrophysics Data System (ADS)

    Fang, Chunyi; Gao, Jinsong; Xin, Chen

    2012-10-01

    Electromagnetic theory shows that a thick-screen frequency selective surface (FSS) has many advantages in its frequency response characteristics. In addition, it can be used to make a stealth radome. Therefore, we research in detail how machining accuracy affects the frequency response properties of the FSS in the gigahertz range. Specifically, by using the least squares method applied to machining data, the effects of different machining precision in the samples can be calculated thus obtaining frequency response curves which were verified by testing in the near-field in a microwave dark room. The results show that decreasing roughness and flatness variation leads to an increase in the bandwidth and that an increase in spacing error leads to the center frequency drifting lower. Finally, an increase in aperture error leads to an increase in bandwidth. Therefore, the conclusion is that machining accuracy should be controlled and that a spatial error less than 0.05 mm is required in order to avoid unwanted center frequency drift and a transmittance decrease.

  4. Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

    SciTech Connect

    Arnold, John

    2015-01-21

    The uranyl cation (UO₂²⁺) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

  5. Thermodynamic analysis of the selective carbothermic reduction of electric arc furnace dust.

    PubMed

    Pickles, C A

    2008-01-31

    Electric arc furnace (EAF) dust, which is produced as a result of the melting of automobile scrap in an electric arc furnace, contains considerable amounts of zinc and lead, which are of significant economic value. Typically, the other major components are iron oxide and calcium oxide with minor amounts of other metal oxides. In this research, a detailed thermodynamic study of the pyrometallurgical processing of the dust, using carbon as a reducing agent was performed. The SOLGASMIX solver of Outokumpu HSC Chemistry((R)) 5.1 was used to calculate the equilibrium composition under reducing conditions. The control input dust composition was as follows (in mass percent): 8.100% CaO, 8.250% 2CaO.SiO(2), 11.200% CaCO(3), 8.830% CaO.Fe(2)O(3), 7.840% Fe(3)O(4), 3.770% PbO, 38.150% ZnFe(2)O(4) and 13.860% ZnO. Selective reduction and separation of both the zinc and the lead as metallic vapours, from the iron, in oxide form, was examined. The separation of the zinc or the lead from the iron, was defined quantitatively in terms of the selectivity factor (logbeta) as follows. Equation [see the text] where the subscript symbols refer to the metal being present in gaseous (g), metallic solid (m), solid oxide (o) or metallic liquid (l) form, respectively. The standard calculations were performed for one hundred grams of dust at atmospheric pressure. The variables investigated were as follows; temperature in the range of 1273-1873K, reactant ratio (i.e. moles of carbon per gram of dust), dust composition, addition of inert gas and reduced total pressure. The calculated values were in reasonable agreement with those from previously published studies and also industrial results.

  6. On the importance of thermodynamic investigations for the re-assessment of selected ternary Fe-base systems

    NASA Astrophysics Data System (ADS)

    Presoly, P.; Bernhard, C.

    2016-07-01

    Reliable thermodynamic data are essential for the design and the production of new alloying systems. Particularly, the knowledge of the high-temperature phase transformations (TLiquid, TSolid, TPerit, Tγ→δ) are important for the solidification and the further processing. Investigations of selected commercial Dual-Phase, TRIP and high-Mn TWIP steels by DTA/DSC measurements show that the experimental results differ significantly from the calculation results of thermodynamic databases with respect to the phase transformation temperature and sequence. Based on these findings, it is very important to identify the defective subsystems of complex alloys in order to optimise the thermodynamic databases. In order to verify a quaternary system, e.g. the Fe-C-Si-Mn system, it is important to check the corresponding ternary subsystems. This was performed by DSC measurements of selected model alloys. By doing so, it was found that in Si- and Mn-alloyed Dual-Phase steels the thermodynamic description of the Fe-Si-Mn system is currently inadequate. This is a very important result, since all new designed steel grades for the automotive industry are based on a Fe-C-Si-Mn matrix.

  7. Balancing accuracy and efficiency in selecting vibrational configuration interaction basis states using vibrational perturbation theory

    NASA Astrophysics Data System (ADS)

    Sibaev, Marat; Crittenden, Deborah L.

    2016-08-01

    This work describes the benchmarking of a vibrational configuration interaction (VCI) algorithm that combines the favourable computational scaling of VPT2 with the algorithmic robustness of VCI, in which VCI basis states are selected according to the magnitude of their contribution to the VPT2 energy, for the ground state and fundamental excited states. Particularly novel aspects of this work include: expanding the potential to 6th order in normal mode coordinates, using a double-iterative procedure in which configuration selection and VCI wavefunction updates are performed iteratively (micro-iterations) over a range of screening threshold values (macro-iterations), and characterisation of computational resource requirements as a function of molecular size. Computational costs may be further reduced by a priori truncation of the VCI wavefunction according to maximum extent of mode coupling, along with discarding negligible force constants and VCI matrix elements, and formulating the wavefunction in a harmonic oscillator product basis to enable efficient evaluation of VCI matrix elements. Combining these strategies, we define a series of screening procedures that scale as O ( Nmode 6 ) - O ( Nmode 9 ) in run time and O ( Nmode 6 ) - O ( Nmode 7 ) in memory, depending on the desired level of accuracy. Our open-source code is freely available for download from http://www.sourceforge.net/projects/pyvci-vpt2.

  8. Polymorph selection and nanocrystallite rearrangement of calcium carbonate in carboxymethyl chitosan aqueous solution: Thermodynamic and kinetic analysis

    SciTech Connect

    Zhao, Donghui; Zhu, Yingchun; Li, Fang; Ruan, Qichao; Zhang, Shengmao; Zhang, Linlin; Xu, Fangfang

    2010-01-15

    In this article, the polymorph selection of calcium carbonate has been successfully achieved in water-soluble carboxymethyl chitosan aqueous solution at different temperatures (25-95 {sup o}C). Vaterite is formed in carboxymethyl chitosan solution 25 {sup o}C accompanied with trace of calcite, whereas pure aragonite is obtained at 95 {sup o}C. Scanning electron microscopy and transmission electron microscopy analyses show that the products are formed from the recrystallization of nanometer crystallites. Thermodynamic and kinetic analyses reveal that the polymorph of calcium carbonate is controlled and selected by kinetics in various temperatures. As a heterogeneous nucleator and stabilizing agent, carboxymethyl chitosan changes the nucleation and growth of calcium carbonate from thermodynamic into kinetic control. Under kinetic limitation, the reaction rate of aragonite increases along with the elevating of temperature and surpasses the rate of vaterite above 327 K.

  9. Increased prediction accuracy in wheat breeding trials using a marker × environment interaction genomic selection model.

    PubMed

    Lopez-Cruz, Marco; Crossa, Jose; Bonnett, David; Dreisigacker, Susanne; Poland, Jesse; Jannink, Jean-Luc; Singh, Ravi P; Autrique, Enrique; de los Campos, Gustavo

    2015-04-01

    Genomic selection (GS) models use genome-wide genetic information to predict genetic values of candidates of selection. Originally, these models were developed without considering genotype × environment interaction(G×E). Several authors have proposed extensions of the single-environment GS model that accommodate G×E using either covariance functions or environmental covariates. In this study, we model G×E using a marker × environment interaction (M×E) GS model; the approach is conceptually simple and can be implemented with existing GS software. We discuss how the model can be implemented by using an explicit regression of phenotypes on markers or using co-variance structures (a genomic best linear unbiased prediction-type model). We used the M×E model to analyze three CIMMYT wheat data sets (W1, W2, and W3), where more than 1000 lines were genotyped using genotyping-by-sequencing and evaluated at CIMMYT's research station in Ciudad Obregon, Mexico, under simulated environmental conditions that covered different irrigation levels, sowing dates and planting systems. We compared the M×E model with a stratified (i.e., within-environment) analysis and with a standard (across-environment) GS model that assumes that effects are constant across environments (i.e., ignoring G×E). The prediction accuracy of the M×E model was substantially greater of that of an across-environment analysis that ignores G×E. Depending on the prediction problem, the M×E model had either similar or greater levels of prediction accuracy than the stratified analyses. The M×E model decomposes marker effects and genomic values into components that are stable across environments (main effects) and others that are environment-specific (interactions). Therefore, in principle, the interaction model could shed light over which variants have effects that are stable across environments and which ones are responsible for G×E. The data set and the scripts required to reproduce the analysis are

  10. Increased Prediction Accuracy in Wheat Breeding Trials Using a Marker × Environment Interaction Genomic Selection Model

    PubMed Central

    Lopez-Cruz, Marco; Crossa, Jose; Bonnett, David; Dreisigacker, Susanne; Poland, Jesse; Jannink, Jean-Luc; Singh, Ravi P.; Autrique, Enrique; de los Campos, Gustavo

    2015-01-01

    Genomic selection (GS) models use genome-wide genetic information to predict genetic values of candidates of selection. Originally, these models were developed without considering genotype × environment interaction(G×E). Several authors have proposed extensions of the single-environment GS model that accommodate G×E using either covariance functions or environmental covariates. In this study, we model G×E using a marker × environment interaction (M×E) GS model; the approach is conceptually simple and can be implemented with existing GS software. We discuss how the model can be implemented by using an explicit regression of phenotypes on markers or using co-variance structures (a genomic best linear unbiased prediction-type model). We used the M×E model to analyze three CIMMYT wheat data sets (W1, W2, and W3), where more than 1000 lines were genotyped using genotyping-by-sequencing and evaluated at CIMMYT’s research station in Ciudad Obregon, Mexico, under simulated environmental conditions that covered different irrigation levels, sowing dates and planting systems. We compared the M×E model with a stratified (i.e., within-environment) analysis and with a standard (across-environment) GS model that assumes that effects are constant across environments (i.e., ignoring G×E). The prediction accuracy of the M×E model was substantially greater of that of an across-environment analysis that ignores G×E. Depending on the prediction problem, the M×E model had either similar or greater levels of prediction accuracy than the stratified analyses. The M×E model decomposes marker effects and genomic values into components that are stable across environments (main effects) and others that are environment-specific (interactions). Therefore, in principle, the interaction model could shed light over which variants have effects that are stable across environments and which ones are responsible for G×E. The data set and the scripts required to reproduce the analysis

  11. Accuracy of genomic selection for age at puberty in a multi-breed population of tropically adapted beef cattle.

    PubMed

    Farah, M M; Swan, A A; Fortes, M R S; Fonseca, R; Moore, S S; Kelly, M J

    2016-02-01

    Genomic selection is becoming a standard tool in livestock breeding programs, particularly for traits that are hard to measure. Accuracy of genomic selection can be improved by increasing the quantity and quality of data and potentially by improving analytical methods. Adding genotypes and phenotypes from additional breeds or crosses often improves the accuracy of genomic predictions but requires specific methodology. A model was developed to incorporate breed composition estimated from genotypes into genomic selection models. This method was applied to age at puberty data in female beef cattle (as estimated from age at first observation of a corpus luteum) from a mix of Brahman and Tropical Composite beef cattle. In this dataset, the new model incorporating breed composition did not increase the accuracy of genomic selection. However, the breeding values exhibited slightly less bias (as assessed by deviation of regression of phenotype on genomic breeding values from the expected value of 1). Adding additional Brahman animals to the Tropical Composite analysis increased the accuracy of genomic predictions and did not affect the accuracy of the Brahman predictions. PMID:26490440

  12. Analysis of elevated temperature data for thermodynamic properties of selected radionuclides

    SciTech Connect

    Wruck, D.A.; Palmer, C.E.A.

    1997-08-01

    This report is a review of chemical thermodynamic data for Ni, Zr, Tc, U, Np, Pu and Am in aqueous solutions at elevated temperatures. Thermodynamic data for aqueous reactions over the temperature range 20-150{degrees}C are needed for geochemical modeling studies of the Yucca Mountain Project. The present review is focused on the aqueous complexes relevant to expected conditions in the Yucca Mountain region: primarily the hydroxide, carbonate, sulfate and fluoride complexes with the metal ions. Existing thermodynamic data are evaluated, and means of extrapolating 25{degrees}C data to the temperatures of interest are discussed. There will be a separate review of solubility data for relevant Ni, Zr, Tc, Np, Pu and Am compounds.

  13. Thermodynamic analysis of lignocellulosic biofuel production via a biochemical process: guiding technology selection and research focus.

    PubMed

    Sohel, M Imroz; Jack, Michael W

    2011-02-01

    The aim of this paper is to present an exergy analysis of bioethanol production process from lignocellulosic feedstock via a biochemical process to asses the overall thermodynamic efficiency and identify the main loss processes. The thermodynamic efficiency of the biochemical process was found to be 35% and the major inefficiencies of this process were identified as: the combustion of lignin for process heat and power production and the simultaneous scarification and co-fermentation process accounting for 67% and 27% of the lost exergy, respectively. These results were also compared with a previous analysis of a thermochemical process for producing biofuel. Despite fundamental differences, the biochemical and thermochemical processes considered here had similar levels of thermodynamic efficiency. Process heat and power production was the major contributor to exergy loss in both of the processes. Unlike the thermochemical process, the overall efficiency of the biochemical process largely depends on how the lignin is utilized. PMID:21036607

  14. Thermodynamic analysis of lignocellulosic biofuel production via a biochemical process: guiding technology selection and research focus.

    PubMed

    Sohel, M Imroz; Jack, Michael W

    2011-02-01

    The aim of this paper is to present an exergy analysis of bioethanol production process from lignocellulosic feedstock via a biochemical process to asses the overall thermodynamic efficiency and identify the main loss processes. The thermodynamic efficiency of the biochemical process was found to be 35% and the major inefficiencies of this process were identified as: the combustion of lignin for process heat and power production and the simultaneous scarification and co-fermentation process accounting for 67% and 27% of the lost exergy, respectively. These results were also compared with a previous analysis of a thermochemical process for producing biofuel. Despite fundamental differences, the biochemical and thermochemical processes considered here had similar levels of thermodynamic efficiency. Process heat and power production was the major contributor to exergy loss in both of the processes. Unlike the thermochemical process, the overall efficiency of the biochemical process largely depends on how the lignin is utilized.

  15. Trp(359) regulates flavin thermodynamics and coenzyme selectivity in Mycobacterium tuberculosis FprA.

    PubMed

    Neeli, Rajasekhar; Sabri, Muna; McLean, Kirsty J; Dunford, Adrian J; Scrutton, Nigel S; Leys, David; Munro, Andrew W

    2008-05-01

    Mtb (Mycobacterium tuberculosis) FprA (flavoprotein reductase A) is an NAD(P)H-dependent FAD-binding reductase that is structurally related to mammalian adrenodoxin reductase, and which supports the catalytic function of Mtb cytochrome P450s. Trp(359), proximal to the FAD, was investigated in light of its potential role in controlling coenzyme interactions, as observed for similarly located aromatic residues in diflavin reductases. Phylogenetic analysis indicated that a tryptophan residue corresponding to Trp(359) is conserved across FprA-type enzymes and in adrenodoxin reductases. W359A/H mutants of Mtb FprA were generated, expressed and the proteins characterized to define the role of Trp(359). W359A/H mutants exhibited perturbed UV-visible absorption/fluorescence properties. The FAD semiquinone formed in wild-type NADPH-reduced FprA was destabilized in the W359A/H mutants, which also had more positive FAD midpoint reduction potentials (-168/-181 mV respectively, versus the standard hydrogen electrode, compared with -230 mV for wild-type FprA). The W359A/H mutants had lower ferricyanide reductase k(cat) and NAD(P)H K(m) values, but this led to improvements in catalytic efficiency (k(cat)/K(m)) with NADH as reducing coenzyme (9.6/18.8 muM(-1).min(-1) respectively, compared with 5.7 muM(-1).min(-1) for wild-type FprA). Stopped-flow spectroscopy revealed NAD(P)H-dependent FAD reduction as rate-limiting in steady-state catalysis, and to be retarded in mutants (e.g. limiting rate constants for NADH-dependent FAD reduction were 25.4 s(-1) for wild-type FprA and 4.8 s(-1)/13.4 s(-1) for W359A/H mutants). Diminished mutant FAD content (particularly in W359H FprA) highlighted the importance of Trp(359) for flavin stability. The results demonstrate that the conserved Trp(359) is critical in regulating FprA FAD binding, thermodynamic properties, catalytic efficiency and coenzyme selectivity.

  16. The effects of relatedness and GxE interaction on prediction accuracies in genomic selection: a study in cassava

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Prior to implementation of genomic selection, an evaluation of the potential accuracy of prediction can be obtained by cross validation. In this procedure, a population with both phenotypes and genotypes is split into training and validation sets. The prediction model is fitted using the training se...

  17. Screening Accuracy of Level 2 Autism Spectrum Disorder Rating Scales: A Review of Selected Instruments

    ERIC Educational Resources Information Center

    Norris, Megan; Lecavalier, Luc

    2010-01-01

    The goal of this review was to examine the state of Level 2, caregiver-completed rating scales for the screening of Autism Spectrum Disorders (ASDs) in individuals above the age of three years. We focused on screening accuracy and paid particular attention to comparison groups. Inclusion criteria required that scales be developed post ICD-10, be…

  18. Genomic selection accuracy for grain quality traits in biparental wheat populations

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Genomic selection (GS) is a promising tool for plant and animal breeding that uses genome wide molecular marker data to capture small and large effect quantitative trait loci and predict the genetic value of selection candidates. Genomic selection has been shown previously to have higher prediction ...

  19. Selecting polymers for two-phase partitioning bioreactors (TPPBs): Consideration of thermodynamic affinity, crystallinity, and glass transition temperature.

    PubMed

    Bacon, Stuart L; Peterson, Eric C; Daugulis, Andrew J; Parent, J Scott

    2015-01-01

    Two-phase partitioning bioreactor technology involves the use of a secondary immiscible phase to lower the concentration of cytotoxic solutes in the fermentation broth to subinhibitory levels. Although polymeric absorbents have attracted recent interest due to their low cost and biocompatibility, material selection requires the consideration of properties beyond those of small molecule absorbents (i.e., immiscible organic solvents). These include a polymer's (1) thermodynamic affinity for the target compound, (2) degree of crystallinity (wc ), and (3) glass transition temperature (Tg ). We have examined the capability of three thermodynamic models to predict the partition coefficient (PC) for n-butyric acid, a fermentation product, in 15 polymers. Whereas PC predictions for amorphous materials had an average absolute deviation (AAD) of ≥16%, predictions for semicrystalline polymers were less accurate (AAD ≥ 30%). Prediction errors were associated with uncertainties in determining the degree of crystallinity within a polymer and the effect of absorbed water on n-butyric acid partitioning. Further complications were found to arise for semicrystalline polymers, wherein strongly interacting solutes increased the polymer's absorptive capacity by actually dissolving the crystalline fraction. Finally, we determined that diffusion limitations may occur for polymers operating near their Tg , and that the Tg can be reduced by plasticization by water and/or solute. This study has demonstrated the impact of basic material properties that affects the performance of polymers as sequestering phases in TPPBs, and reflects the additional complexity of polymers that must be taken into account in material selection. PMID:26259846

  20. Selecting polymers for two-phase partitioning bioreactors (TPPBs): Consideration of thermodynamic affinity, crystallinity, and glass transition temperature.

    PubMed

    Bacon, Stuart L; Peterson, Eric C; Daugulis, Andrew J; Parent, J Scott

    2015-01-01

    Two-phase partitioning bioreactor technology involves the use of a secondary immiscible phase to lower the concentration of cytotoxic solutes in the fermentation broth to subinhibitory levels. Although polymeric absorbents have attracted recent interest due to their low cost and biocompatibility, material selection requires the consideration of properties beyond those of small molecule absorbents (i.e., immiscible organic solvents). These include a polymer's (1) thermodynamic affinity for the target compound, (2) degree of crystallinity (wc ), and (3) glass transition temperature (Tg ). We have examined the capability of three thermodynamic models to predict the partition coefficient (PC) for n-butyric acid, a fermentation product, in 15 polymers. Whereas PC predictions for amorphous materials had an average absolute deviation (AAD) of ≥16%, predictions for semicrystalline polymers were less accurate (AAD ≥ 30%). Prediction errors were associated with uncertainties in determining the degree of crystallinity within a polymer and the effect of absorbed water on n-butyric acid partitioning. Further complications were found to arise for semicrystalline polymers, wherein strongly interacting solutes increased the polymer's absorptive capacity by actually dissolving the crystalline fraction. Finally, we determined that diffusion limitations may occur for polymers operating near their Tg , and that the Tg can be reduced by plasticization by water and/or solute. This study has demonstrated the impact of basic material properties that affects the performance of polymers as sequestering phases in TPPBs, and reflects the additional complexity of polymers that must be taken into account in material selection.

  1. Differential Water Thermodynamics Determine PI3K-Beta/Delta Selectivity for Solvent-Exposed Ligand Modifications.

    PubMed

    Robinson, Daniel; Bertrand, Thomas; Carry, Jean-Christophe; Halley, Frank; Karlsson, Andreas; Mathieu, Magali; Minoux, Hervé; Perrin, Marc-Antoine; Robert, Benoit; Schio, Laurent; Sherman, Woody

    2016-05-23

    Phosphoinositide 3-kinases (PI3Ks) are involved in important cellular functions and represent desirable targets for drug discovery efforts, especially related to oncology; however, the four PI3K subtypes (α, β, γ, and δ) have highly similar binding sites, making the design of selective inhibitors challenging. A series of inhibitors with selectivity toward the β subtype over δ resulted in compound 3(S), which has entered a phase I/Ib clinical trial for patients with advanced PTEN-deficient cancer. Interestingly, X-ray crystallography revealed that the modifications making inhibitor 3(S) and related compounds selective toward the β-isoform do not interact directly with either PI3Kβ or PI3Kδ, thereby confounding rationalization of the SAR. Here, we apply explicit solvent molecular dynamics and solvent thermodynamic analysis using WaterMap in an effort to understand the unusual affinity and selectivity trends. We find that differences in solvent energetics and water networks, which are modulated upon binding of different ligands, explain the experimental affinity and selectivity trends. This study highlights the critical role of water molecules in molecular recognition and the importance of considering water networks in drug discovery efforts to rationalize and improve selectivity. PMID:27144736

  2. Accuracy of initial codon selection by aminoacyl-tRNAs on the mRNA-programmed bacterial ribosome

    PubMed Central

    Zhang, Jingji; Ieong, Ka-Weng; Johansson, Magnus; Ehrenberg, Måns

    2015-01-01

    We used a cell-free system with pure Escherichia coli components to study initial codon selection of aminoacyl-tRNAs in ternary complex with elongation factor Tu and GTP on messenger RNA-programmed ribosomes. We took advantage of the universal rate-accuracy trade-off for all enzymatic selections to determine how the efficiency of initial codon readings decreased linearly toward zero as the accuracy of discrimination against near-cognate and wobble codon readings increased toward the maximal asymptote, the d value. We report data on the rate-accuracy variation for 7 cognate, 7 wobble, and 56 near-cognate codon readings comprising about 15% of the genetic code. Their d values varied about 400-fold in the 200–80,000 range depending on type of mismatch, mismatch position in the codon, and tRNA isoacceptor type. We identified error hot spots (d = 200) for U:G misreading in second and U:U or G:A misreading in third codon position by His-tRNAHis and, as also seen in vivo, Glu-tRNAGlu. We suggest that the proofreading mechanism has evolved to attenuate error hot spots in initial selection such as those found here. PMID:26195797

  3. Feature Selection Has a Large Impact on One-Class Classification Accuracy for MicroRNAs in Plants

    PubMed Central

    Yousef, Malik; Saçar Demirci, Müşerref Duygu; Khalifa, Waleed; Allmer, Jens

    2016-01-01

    MicroRNAs (miRNAs) are short RNA sequences involved in posttranscriptional gene regulation. Their experimental analysis is complicated and, therefore, needs to be supplemented with computational miRNA detection. Currently computational miRNA detection is mainly performed using machine learning and in particular two-class classification. For machine learning, the miRNAs need to be parametrized and more than 700 features have been described. Positive training examples for machine learning are readily available, but negative data is hard to come by. Therefore, it seems prerogative to use one-class classification instead of two-class classification. Previously, we were able to almost reach two-class classification accuracy using one-class classifiers. In this work, we employ feature selection procedures in conjunction with one-class classification and show that there is up to 36% difference in accuracy among these feature selection methods. The best feature set allowed the training of a one-class classifier which achieved an average accuracy of ~95.6% thereby outperforming previous two-class-based plant miRNA detection approaches by about 0.5%. We believe that this can be improved upon in the future by rigorous filtering of the positive training examples and by improving current feature clustering algorithms to better target pre-miRNA feature selection. PMID:27190509

  4. Thermodynamic and kinetic studies of the gating behavior of a K+- selective channel from the sarcoplasmic reticulum membrane

    PubMed Central

    1980-01-01

    A voltage-dependent, K+-selective ionic channel from sarcoplasmic reticulum of rabbit skeletal muscle has been studied in a planar phospholipid bilayer membrane. The puppose of this work is to study the mechanism by which the channel undergoes transitions between its conducting and nonconducting states. Thermodynamic studies show that the "open" and "closed" states of the channel exist in a voltage- dependent equilibrium, and that the channel displays only a single open state; the channel conductance is 120 pmho in 0.1 M K+. The channel's gating process follows single exponential kinetics at all voltages tested, and the individual opening and closing rate constants are exponentially dependent on voltage. The individual rate constants may also be determined from a stochastic analysis of channel fluctuations among multiple conductance levels. Neither the thermodynamic nor the kinetic parameters of gating depend on the absolute concentration of channels in the bilayer. The results are taken as evidence that the channel gates by an unusually simple two-state conformational mechanism in which the equivalent of 1.1 net charges are moved across the membrane during the formation of the open channel. PMID:6255061

  5. The effect of tray selection on the accuracy of elastomeric impression materials.

    PubMed

    Gordon, G E; Johnson, G H; Drennon, D G

    1990-01-01

    This study evaluated the accuracy of reproduction of stone casts made from impressions using different tray and impression materials. The tray materials used were an acrylic resin, a thermoplastic, and a plastic. The impression materials used were an additional silicone, a polyether, and a polysulfide. Impressions were made of a stainless steel master die that simulated crown preparations for a fixed partial denture and an acrylic resin model with cross-arch and anteroposterior landmarks in stainless steel that typify clinical intra-arch distances. Impressions of the fixed partial denture simulation were made with all three impression materials and all three tray types. Impressions of the cross-arch and anteroposterior landmarks were made by using all three tray types with only the addition reaction silicone impression material. Impressions were poured at 1 hour with a type IV dental stone. Data were analyzed by using ANOVA with a sample size of five. Results indicated that custom-made trays of acrylic resin and the thermoplastic material performed similarly regarding die accuracy and produced clinically acceptable casts. The stock plastic tray consistently produced casts with greater dimensional change than the two custom trays. PMID:2404101

  6. Impact of marker ascertainment bias on genomic selection accuracy and estimates of genetic diversity

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Genome-wide molecular markers are readily being applied to evaluate genetic diversity in germplasm collections and for making genomic selections in breeding programs. To accurately predict phenotypes and assay genetic diversity, molecular markers should assay a representative sample of the polymorp...

  7. Imputation of unordered markers and the impact on genomic selection accuracy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Genomic selection, a breeding method that promises to accelerate rates of genetic gain, requires dense, genome-wide marker data. Sequence-based genotyping methods can generate de novo large numbers of markers. However, without a reference genome, these markers are unordered and typically have a lar...

  8. Imputation of unordered markers and the impact on genomic selection accuracy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Genomic selection, a breeding method that promises to accelerate rates of genetic gain, requires dense, genome-wide marker data. Genotyping-by-sequencing can generate a large number of de novo markers. However, without a reference genome, these markers are unordered and typically have a large propo...

  9. Thermodynamics-Based Selection and Design of Creep-Resistant Cast Mg Alloys

    NASA Astrophysics Data System (ADS)

    Abaspour, Saeideh; Cáceres, Carlos H.

    2015-12-01

    Atomic level thermodynamics arguments that account for the generally weak age hardening response while suggesting that extending the athermal regime through short-range order (SRO) is a most feasible path to increasing the creep strength of many current alloys are presented. The tendency, or otherwise, of many solutes to develop SRO in dilute solid solutions rationalizes a number of observations in current multicomponent Mg alloys, and in particular the retention of linear strain hardening at high temperatures, while it disputes the viability of several micromechanisms often considered active, such as pinning of edge dislocations by mobile solute clouds, dynamic precipitation of thermally stable precipitates, or atomic size effects on the diffusivity. Potential solutes are sorted out and ranked based on the sign and value of the enthalpy of mixing of binary solid solutions using the Miedema phenomenological scheme. Due to their large negative energy of mixing and reasonable solubility (>1 at. pct) at ~473 K (~200 °C), Y and Gd appear as the best candidates to increase the creep strength through SRO, followed by Nd and Ca, in close agreement with data reported in the literature. The feasibility of enhancing the age hardening response through homogeneously nucleated, coherent precipitates, in some cases despite the negative energy of mixing of the alloy, or via internally ordered precipitates mimicking those present in Mg-Th alloys is considered by making parallels with the Al-Zn and the Al-Cu alloy systems. The possible optimization of the strengthening of high pressure die cast alloys combining SRO and intergranular eutectics or of heat-treatable cast alloys through internally ordered precipitates and SRO is discussed.

  10. Uranium(VI) Binding Forms in Selected Human Body Fluids: Thermodynamic Calculations versus Spectroscopic Measurements.

    PubMed

    Osman, Alfatih A A; Geipel, Gerhard; Barkleit, Astrid; Bernhard, Gert

    2015-02-16

    Human exposure to uranium increasingly becomes a subject of interest in many scientific disciplines such as environmental medicine, toxicology, and radiation protection. Knowledge about uranium chemical binding forms(speciation) in human body fluids can be of great importance to understand not only its biokinetics but also its relevance in risk assessment and in designing decorporation therapy in the case of accidental overexposure. In this study, thermodynamic calculations of uranium speciation in relevant simulated and original body fluids were compared with spectroscopic data after ex-situ uranium addition. For the first time, experimental data on U(VI) speciation in body fluids (saliva, sweat, urine) was obtained by means of cryogenic time-resolved laser-induced fluorescence spectroscopy (cryo-TRLFS) at 153 K. By using the time dependency of fluorescence decay and the band positions of the emission spectra, various uranyl complexes were demonstrated in the studied samples. The variations of the body fluids in terms of chemical composition, pH, and ionic strength resulted in different binding forms of U(VI). The speciation of U(VI) in saliva and in urine was affected by the presence of bioorganic ligands, whereas in sweat, the distribution depends mainly on inorganic ligands. We also elucidated the role of biological buffers, i.e., phosphate (H(2)PO(4−)/HPO(4)(2−)) on U(VI) distribution, and the system Ca(2+)/UO(2)(2+)/PO(4)(3−) was discussed in detail in both saliva and urine. The theoretical speciation calculations of the main U(VI) species in the investigated body fluids were significantly consistent with the spectroscopic data. Laser fluorescence spectroscopy showed success and reliability for direct determination of U(VI) in such biological matrices with the possibility for further improvement.

  11. Bayesian approach increases accuracy when selecting cowpea genotypes with high adaptability and phenotypic stability.

    PubMed

    Barroso, L M A; Teodoro, P E; Nascimento, M; Torres, F E; Dos Santos, A; Corrêa, A M; Sagrilo, E; Corrêa, C C G; Silva, F A; Ceccon, G

    2016-01-01

    This study aimed to verify that a Bayesian approach could be used for the selection of upright cowpea genotypes with high adaptability and phenotypic stability, and the study also evaluated the efficiency of using informative and minimally informative a priori distributions. Six trials were conducted in randomized blocks, and the grain yield of 17 upright cowpea genotypes was assessed. To represent the minimally informative a priori distributions, a probability distribution with high variance was used, and a meta-analysis concept was adopted to represent the informative a priori distributions. Bayes factors were used to conduct comparisons between the a priori distributions. The Bayesian approach was effective for selection of upright cowpea genotypes with high adaptability and phenotypic stability using the Eberhart and Russell method. Bayes factors indicated that the use of informative a priori distributions provided more accurate results than minimally informative a priori distributions. PMID:26985961

  12. Bayesian approach increases accuracy when selecting cowpea genotypes with high adaptability and phenotypic stability.

    PubMed

    Barroso, L M A; Teodoro, P E; Nascimento, M; Torres, F E; Dos Santos, A; Corrêa, A M; Sagrilo, E; Corrêa, C C G; Silva, F A; Ceccon, G

    2016-03-11

    This study aimed to verify that a Bayesian approach could be used for the selection of upright cowpea genotypes with high adaptability and phenotypic stability, and the study also evaluated the efficiency of using informative and minimally informative a priori distributions. Six trials were conducted in randomized blocks, and the grain yield of 17 upright cowpea genotypes was assessed. To represent the minimally informative a priori distributions, a probability distribution with high variance was used, and a meta-analysis concept was adopted to represent the informative a priori distributions. Bayes factors were used to conduct comparisons between the a priori distributions. The Bayesian approach was effective for selection of upright cowpea genotypes with high adaptability and phenotypic stability using the Eberhart and Russell method. Bayes factors indicated that the use of informative a priori distributions provided more accurate results than minimally informative a priori distributions.

  13. Accuracy of travel time distribution (TTD) models as affected by TTD complexity, observation errors, and model and tracer selection

    USGS Publications Warehouse

    Green, Christopher T.; Zhang, Yong; Jurgens, Bryant C.; Starn, J. Jeffrey; Landon, Matthew K.

    2014-01-01

    Analytical models of the travel time distribution (TTD) from a source area to a sample location are often used to estimate groundwater ages and solute concentration trends. The accuracies of these models are not well known for geologically complex aquifers. In this study, synthetic datasets were used to quantify the accuracy of four analytical TTD models as affected by TTD complexity, observation errors, model selection, and tracer selection. Synthetic TTDs and tracer data were generated from existing numerical models with complex hydrofacies distributions for one public-supply well and 14 monitoring wells in the Central Valley, California. Analytical TTD models were calibrated to synthetic tracer data, and prediction errors were determined for estimates of TTDs and conservative tracer (NO3−) concentrations. Analytical models included a new, scale-dependent dispersivity model (SDM) for two-dimensional transport from the watertable to a well, and three other established analytical models. The relative influence of the error sources (TTD complexity, observation error, model selection, and tracer selection) depended on the type of prediction. Geological complexity gave rise to complex TTDs in monitoring wells that strongly affected errors of the estimated TTDs. However, prediction errors for NO3− and median age depended more on tracer concentration errors. The SDM tended to give the most accurate estimates of the vertical velocity and other predictions, although TTD model selection had minor effects overall. Adding tracers improved predictions if the new tracers had different input histories. Studies using TTD models should focus on the factors that most strongly affect the desired predictions.

  14. Improved localization accuracy in double-helix point spread function super-resolution fluorescence microscopy using selective-plane illumination

    NASA Astrophysics Data System (ADS)

    Yu, Jie; Cao, Bo; Li, Heng; Yu, Bin; Chen, Danni; Niu, Hanben

    2014-09-01

    Recently, three-dimensional (3D) super resolution imaging of cellular structures in thick samples has been enabled with the wide-field super-resolution fluorescence microscopy based on double helix point spread function (DH-PSF). However, when the sample is Epi-illuminated, much background fluorescence from those excited molecules out-of-focus will reduce the signal-to-noise ratio (SNR) of the image in-focus. In this paper, we resort to a selective-plane illumination strategy, which has been used for tissue-level imaging and single molecule tracking, to eliminate out-of-focus background and to improve SNR and the localization accuracy of the standard DH-PSF super-resolution imaging in thick samples. We present a novel super-resolution microscopy that combine selective-plane illumination and DH-PSF. The setup utilizes a well-defined laser light sheet which theoretical thickness is 1.7μm (FWHM) at 640nm excitation wavelength. The image SNR of DH-PSF microscopy between selective-plane illumination and Epi-illumination are compared. As we expect, the SNR of the DH-PSF microscopy based selective-plane illumination is increased remarkably. So, 3D localization precision of DH-PSF would be improved significantly. We demonstrate its capabilities by studying 3D localizing of single fluorescent particles. These features will provide high thick samples compatibility for future biomedical applications.

  15. AMES Stereo Pipeline Derived DEM Accuracy Experiment Using LROC-NAC Stereopairs and Weighted Spatial Dependence Simulation for Lunar Site Selection

    NASA Astrophysics Data System (ADS)

    Laura, J. R.; Miller, D.; Paul, M. V.

    2012-03-01

    An accuracy assessment of AMES Stereo Pipeline derived DEMs for lunar site selection using weighted spatial dependence simulation and a call for outside AMES derived DEMs to facilitate a statistical precision analysis.

  16. Phase selection during the crystallization of metal-organic frameworks; thermodynamic and kinetic factors in the lithium tartrate system.

    PubMed

    Yeung, Hamish Hei-Man; Cheetham, Anthony Kevin

    2014-01-01

    We report the phase behaviour of chiral, racemic and meso-lithium tartrate frameworks, which was examined as a function of solvent system, temperature and ligand isomer. Through our comprehensive investigation of this system of 14 diverse phases, we have gained detailed insight into the effect of synthesis conditions on product structure, and elucidated the thermodynamic and kinetic factors involved in phase selection. Reactions in ethanol between lithium acetate and chiral, racemic and meso-tartaric acids give rise to anhydrous kinetic products; polymorphs with higher entropy tend to appear at high temperatures. Reactions at room temperature in water-ethanol mixtures give rise to hydrated kinetic products, including two new crystal structures, [Li2(D,L-tartrate)(H2O)2]n in P1 and [Li2(meso-tartrate)(H2O)(0.5)]n in C222(1), whose structures are contrasted with known anhydrous products. Reactions at elevated temperatures in water-ethanol mixtures result in the formation of low enthalpy, anhydrous products and, furthermore, the global minimum energy structure appears at high temperatures in all cases owing to in situ ligand isomerization.

  17. The Role of Some Selected Psychological and Personality Traits of the Rater in the Accuracy of Self- and Peer-Assessment

    ERIC Educational Resources Information Center

    AlFallay, Ibrahim

    2004-01-01

    This paper investigates the role of some selected psychological and personality traits of learners of English as a foreign language in the accuracy of self- and peer-assessments. The selected traits were motivation types, self-esteem, anxiety, motivational intensity, and achievement. 78 students of English as a foreign language participated in…

  18. Mutations in a conserved region of RNA polymerase II influence the accuracy of mRNA start site selection.

    PubMed Central

    Hekmatpanah, D S; Young, R A

    1991-01-01

    A sensitive phenotypic assay has been used to identify mutations affecting transcription initiation in the genes encoding the two large subunits of Saccharomyces cerevisiae RNA polymerase II (RPB1 and RPB2). The rpb1 and rpb2 mutations alter the ratio of transcripts initiated at two adjacent start sites of a delta-insertion promoter. Of a large number of rpb1 and rpb2 mutations screened, only a few affect transcription initiation patterns at delta-insertion promoters, and these mutations are in close proximity to each other within both RPB1 and RPB2. The two rpb1 mutations alter amino acid residues within homology block G, a region conserved in the large subunits of all RNA polymerases. The three strong rpb2 mutations alter adjacent amino acids. At a wild-type promoter, the rpb1 mutations affect the accuracy of mRNA start site selection by producing a small but detectable increase in the 5'-end heterogeneity of transcripts. These RNA polymerase II mutations implicate specific portions of the enzyme in aspects of transcription initiation. Images PMID:1922077

  19. Thermodynamic modelling of supercritical water gasification: investigating the effect of biomass composition to aid in the selection of appropriate feedstock material.

    PubMed

    Louw, Jeanne; Schwarz, Cara E; Knoetze, Johannes H; Burger, Andries J

    2014-12-01

    A process model developed in Aspen Plus®, was used for the thermodynamic modelling of supercritical water gasification (SCWG) using a wide variety of biomass materials as feedstock. The influence of the composition of the biomass material (in terms of carbon, hydrogen and oxygen content) on various performance indicators (such as gas yields, cold gas efficiency, calorific value of product gas and heat of reaction), were determined at various temperatures (600, 700 and 800°C) and biomass feed concentrations (5, 15 and 25wt.%). Generalised contour plots, based on the biomass composition, were developed for these performance indicators to provide the thermodynamic limits at various operating conditions. These plots can aid in the selection or screening of potential biomass materials and appropriate operating conditions for SCWG prior to conducting experimental work.

  20. Thermodynamic modelling of supercritical water gasification: investigating the effect of biomass composition to aid in the selection of appropriate feedstock material.

    PubMed

    Louw, Jeanne; Schwarz, Cara E; Knoetze, Johannes H; Burger, Andries J

    2014-12-01

    A process model developed in Aspen Plus®, was used for the thermodynamic modelling of supercritical water gasification (SCWG) using a wide variety of biomass materials as feedstock. The influence of the composition of the biomass material (in terms of carbon, hydrogen and oxygen content) on various performance indicators (such as gas yields, cold gas efficiency, calorific value of product gas and heat of reaction), were determined at various temperatures (600, 700 and 800°C) and biomass feed concentrations (5, 15 and 25wt.%). Generalised contour plots, based on the biomass composition, were developed for these performance indicators to provide the thermodynamic limits at various operating conditions. These plots can aid in the selection or screening of potential biomass materials and appropriate operating conditions for SCWG prior to conducting experimental work. PMID:25463777

  1. Clock accuracy and precision evolve as a consequence of selection for adult emergence in a narrow window of time in fruit flies Drosophila melanogaster.

    PubMed

    Kannan, Nisha N; Vaze, Koustubh M; Sharma, Vijay Kumar

    2012-10-15

    Although circadian clocks are believed to have evolved under the action of periodic selection pressures (selection on phasing) present in the geophysical environment, there is very little rigorous and systematic empirical evidence to support this. In the present study, we examined the effect of selection for adult emergence in a narrow window of time on the circadian rhythms of fruit flies Drosophila melanogaster. Selection was imposed in every generation by choosing flies that emerged during a 1 h window of time close to the emergence peak of baseline/control flies under 12 h:12 h light:dark cycles. To study the effect of selection on circadian clocks we estimated several quantifiable features that reflect inter- and intra-individual variance in adult emergence and locomotor activity rhythms. The results showed that with increasing generations, incidence of adult emergence and activity of adult flies during the 1 h selection window increased gradually in the selected populations. Flies from the selected populations were more homogenous in their clock period, were more coherent in their phase of entrainment, and displayed enhanced accuracy and precision in their emergence and activity rhythms compared with controls. These results thus suggest that circadian clocks in D. melanogaster evolve enhanced accuracy and precision when subjected to selection for emergence in a narrow window of time.

  2. Solvent effect on the complex formation of a crown ether derivative with sodium and potassium ions. Thermodynamic background of selectivity

    NASA Astrophysics Data System (ADS)

    Li, Yin; Huszthy, Péter; Móczár, Ildikó; Szemenyei, Balázs; Kunsági-Máté, Sándor

    2013-01-01

    The complexation properties of dimethyl-pyridino-18-crown-6 ether (M2P18C6) with Na+ and K+ in different primary alcohols including methanol (MeOH), ethanol (EtOH) and n-propanol (n-PrOH) were investigated by UV-vis spectroscopy. Stability constants and thermodynamic parameters have been determined applying the van't Hoff theory. In the cases of both Na+ and K+ the stability constants increase with decreasing permittivity of the solvent used. M2P18C6 always exhibits better affinity to K+ in each alcoholic solution compared to Na+. Thermodynamic studies suggest that in both cases there is a correlation between the permittivity of the solvent and the enthalpy and entropy change of complex formation.

  3. Structure-thermodynamics-antioxidant activity relationships of selected natural phenolic acids and derivatives: an experimental and theoretical evaluation.

    PubMed

    Chen, Yuzhen; Xiao, Huizhi; Zheng, Jie; Liang, Guizhao

    2015-01-01

    Phenolic acids and derivatives have potential biological functions, however, little is known about the structure-activity relationships and the underlying action mechanisms of these phenolic acids to date. Herein we investigate the structure-thermodynamics-antioxidant relationships of 20 natural phenolic acids and derivatives using DPPH• scavenging assay, density functional theory calculations at the B3LYP/6-311++G(d,p) levels of theory, and quantitative structure-activity relationship (QSAR) modeling. Three main working mechanisms (HAT, SETPT and SPLET) are explored in four micro-environments (gas-phase, benzene, water and ethanol). Computed thermodynamics parameters (BDE, IP, PDE, PA and ETE) are compared with the experimental radical scavenging activities against DPPH•. Available theoretical and experimental investigations have demonstrated that the extended delocalization and intra-molecular hydrogen bonds are the two main contributions to the stability of the radicals. The C = O or C = C in COOH, COOR, C = CCOOH and C = CCOOR groups, and orthodiphenolic functionalities are shown to favorably stabilize the specific radical species to enhance the radical scavenging activities, while the presence of the single OH in the ortho position of the COOH group disfavors the activities. HAT is the thermodynamically preferred mechanism in the gas phase and benzene, whereas SPLET in water and ethanol. Furthermore, our QSAR models robustly represent the structure-activity relationships of these explored compounds in polar media. PMID:25803685

  4. Structure-thermodynamics-antioxidant activity relationships of selected natural phenolic acids and derivatives: an experimental and theoretical evaluation.

    PubMed

    Chen, Yuzhen; Xiao, Huizhi; Zheng, Jie; Liang, Guizhao

    2015-01-01

    Phenolic acids and derivatives have potential biological functions, however, little is known about the structure-activity relationships and the underlying action mechanisms of these phenolic acids to date. Herein we investigate the structure-thermodynamics-antioxidant relationships of 20 natural phenolic acids and derivatives using DPPH• scavenging assay, density functional theory calculations at the B3LYP/6-311++G(d,p) levels of theory, and quantitative structure-activity relationship (QSAR) modeling. Three main working mechanisms (HAT, SETPT and SPLET) are explored in four micro-environments (gas-phase, benzene, water and ethanol). Computed thermodynamics parameters (BDE, IP, PDE, PA and ETE) are compared with the experimental radical scavenging activities against DPPH•. Available theoretical and experimental investigations have demonstrated that the extended delocalization and intra-molecular hydrogen bonds are the two main contributions to the stability of the radicals. The C = O or C = C in COOH, COOR, C = CCOOH and C = CCOOR groups, and orthodiphenolic functionalities are shown to favorably stabilize the specific radical species to enhance the radical scavenging activities, while the presence of the single OH in the ortho position of the COOH group disfavors the activities. HAT is the thermodynamically preferred mechanism in the gas phase and benzene, whereas SPLET in water and ethanol. Furthermore, our QSAR models robustly represent the structure-activity relationships of these explored compounds in polar media.

  5. A quantitative method for evaluating numerical simulation accuracy of time-transient Lamb wave propagation with its applications to selecting appropriate element size and time step.

    PubMed

    Wan, Xiang; Xu, Guanghua; Zhang, Qing; Tse, Peter W; Tan, Haihui

    2016-01-01

    Lamb wave technique has been widely used in non-destructive evaluation (NDE) and structural health monitoring (SHM). However, due to the multi-mode characteristics and dispersive nature, Lamb wave propagation behavior is much more complex than that of bulk waves. Numerous numerical simulations on Lamb wave propagation have been conducted to study its physical principles. However, few quantitative studies on evaluating the accuracy of these numerical simulations were reported. In this paper, a method based on cross correlation analysis for quantitatively evaluating the simulation accuracy of time-transient Lamb waves propagation is proposed. Two kinds of error, affecting the position and shape accuracies are firstly identified. Consequently, two quantitative indices, i.e., the GVE (group velocity error) and MACCC (maximum absolute value of cross correlation coefficient) derived from cross correlation analysis between a simulated signal and a reference waveform, are proposed to assess the position and shape errors of the simulated signal. In this way, the simulation accuracy on the position and shape is quantitatively evaluated. In order to apply this proposed method to select appropriate element size and time step, a specialized 2D-FEM program combined with the proposed method is developed. Then, the proper element size considering different element types and time step considering different time integration schemes are selected. These results proved that the proposed method is feasible and effective, and can be used as an efficient tool for quantitatively evaluating and verifying the simulation accuracy of time-transient Lamb wave propagation. PMID:26315506

  6. Canopy Temperature and Vegetation Indices from High-Throughput Phenotyping Improve Accuracy of Pedigree and Genomic Selection for Grain Yield in Wheat

    PubMed Central

    Rutkoski, Jessica; Poland, Jesse; Mondal, Suchismita; Autrique, Enrique; Pérez, Lorena González; Crossa, José; Reynolds, Matthew; Singh, Ravi

    2016-01-01

    Genomic selection can be applied prior to phenotyping, enabling shorter breeding cycles and greater rates of genetic gain relative to phenotypic selection. Traits measured using high-throughput phenotyping based on proximal or remote sensing could be useful for improving pedigree and genomic prediction model accuracies for traits not yet possible to phenotype directly. We tested if using aerial measurements of canopy temperature, and green and red normalized difference vegetation index as secondary traits in pedigree and genomic best linear unbiased prediction models could increase accuracy for grain yield in wheat, Triticum aestivum L., using 557 lines in five environments. Secondary traits on training and test sets, and grain yield on the training set were modeled as multivariate, and compared to univariate models with grain yield on the training set only. Cross validation accuracies were estimated within and across-environment, with and without replication, and with and without correcting for days to heading. We observed that, within environment, with unreplicated secondary trait data, and without correcting for days to heading, secondary traits increased accuracies for grain yield by 56% in pedigree, and 70% in genomic prediction models, on average. Secondary traits increased accuracy slightly more when replicated, and considerably less when models corrected for days to heading. In across-environment prediction, trends were similar but less consistent. These results show that secondary traits measured in high-throughput could be used in pedigree and genomic prediction to improve accuracy. This approach could improve selection in wheat during early stages if validated in early-generation breeding plots. PMID:27402362

  7. Thermodynamic Diagrams

    NASA Astrophysics Data System (ADS)

    Chaston, Scot

    1999-02-01

    Thermodynamic data such as equilibrium constants, standard cell potentials, molar enthalpies of formation, and standard entropies of substances can be a very useful basis for an organized presentation of knowledge in diverse areas of applied chemistry. Thermodynamic data can become particularly useful when incorporated into thermodynamic diagrams that are designed to be easy to recall, to serve as a basis for reconstructing previous knowledge, and to determine whether reactions can occur exergonically or only with the help of an external energy source. Few students in our chemistry-based courses would want to acquire the depth of knowledge or rigor of professional thermodynamicists. But they should nevertheless learn how to make good use of thermodynamic data in their professional occupations that span the chemical, biological, environmental, and medical laboratory fields. This article discusses examples of three thermodynamic diagrams that have been developed for this purpose. They are the thermodynamic energy account (TEA), the total entropy scale, and the thermodynamic scale diagrams. These diagrams help in the teaching and learning of thermodynamics by bringing the imagination into the process of developing a better understanding of abstract thermodynamic functions, and by allowing the reader to keep track of specialist thermodynamic discourses in the literature.

  8. Thermodynamics of statistical inference by cells.

    PubMed

    Lang, Alex H; Fisher, Charles K; Mora, Thierry; Mehta, Pankaj

    2014-10-01

    The deep connection between thermodynamics, computation, and information is now well established both theoretically and experimentally. Here, we extend these ideas to show that thermodynamics also places fundamental constraints on statistical estimation and learning. To do so, we investigate the constraints placed by (nonequilibrium) thermodynamics on the ability of biochemical signaling networks to estimate the concentration of an external signal. We show that accuracy is limited by energy consumption, suggesting that there are fundamental thermodynamic constraints on statistical inference.

  9. The equation of state for stellar envelopes. IV - Thermodynamic quantities and selected ionization fractions for six elemental mixes

    NASA Technical Reports Server (NTRS)

    Mihalas, Dimitri; Hummer, D. G.; Mihalas, Barbara Weibel; Daeppen, Werner

    1990-01-01

    The free-energy minimization technique in the form developed in the preceding papers in this series is employed to evaluate thermodynamic quantities and ionization fractions on a fine temperature and density grid for six astrophysical mixtures of 15 elements. The mixtures range from that appropriate to super-metal-rich stars, through solar abundance, to that for extreme Population II objects. In this paper, the results for solar abundances are summarized in a form that is illustrative and which facilitates comparison with the results from other equation of state calculations.

  10. Measurements of thermodynamic and optical properties of selected aqueous organic and organic-inorganic mixtures of atmospheric relevance.

    PubMed

    Lienhard, Daniel M; Bones, David L; Zuend, Andreas; Krieger, Ulrich K; Reid, Jonathan P; Peter, Thomas

    2012-10-11

    Atmospheric aerosol particles can exhibit liquid solution concentrations supersaturated with respect to the dissolved organic and inorganic species and supercooled with respect to ice. In this study, thermodynamic and optical properties of sub- and supersaturated aqueous solutions of atmospheric interest are presented. The density, refractive index, water activity, ice melting temperatures, and homogeneous ice freezing temperatures of binary aqueous solutions containing L(+)-tartaric acid, tannic acid, and levoglucosan and ternary aqueous solutions containing levoglucosan and one of the salts NH(4)HSO(4), (NH(4))(2)SO(4), and NH(4)NO(3) have been measured in the supersaturated concentration range for the first time. In addition, the density and refractive index of binary aqueous citric acid and raffinose solutions and the glass transition temperatures of binary aqueous L(+)-tartaric acid and levoglucosan solutions have been measured. The data presented here are derived from experiments on single levitated microdroplets and bulk solutions and should find application in thermodynamic and atmospheric aerosol models as well as in food science applications.

  11. Thermodynamic data for modeling acid mine drainage problems: compilation and estimation of data for selected soluble iron-sulfate minerals

    USGS Publications Warehouse

    Hemingway, Bruch S.; Seal, Robert R., II; Chou, I-Ming

    2002-01-01

    Enthalpy of formation, Gibbs energy of formation, and entropy values have been compiled from the literature for the hydrated ferrous sulfate minerals melanterite, rozenite, and szomolnokite, and a variety of other hydrated sulfate compounds. On the basis of this compilation, it appears that there is no evidence for an excess enthalpy of mixing for sulfate-H2O systems, except for the first H2O molecule of crystallization. The enthalpy and Gibbs energy of formation of each H2O molecule of crystallization, except the first, in the iron(II) sulfate - H2O system is -295.15 and -238.0 kJ?mol-1, respectively. The absence of an excess enthalpy of mixing is used as the basis for estimating thermodynamic values for a variety of ferrous, ferric, and mixed-valence sulfate salts of relevance to acid-mine drainage systems.

  12. Accuracy and cut-off point selection in three-class classification problems using a generalization of the Youden index.

    PubMed

    Nakas, Christos T; Alonzo, Todd A; Yiannoutsos, Constantin T

    2010-12-10

    We study properties of the index J(3), defined as the accuracy, or the maximum correct classification, for a given three-class classification problem. Specifically, using J(3) one can assess the discrimination between the three distributions and obtain an optimal pair of cut-off points c(1)

  13. Interfacial engineering of solution-processed Ni nanochain-SiOx (x < 2) cermets towards thermodynamically stable, anti-oxidation solar selective absorbers

    NASA Astrophysics Data System (ADS)

    Yu, Xiaobai; Wang, Xiaoxin; Zhang, Qinglin; Liu, Jifeng

    2016-04-01

    Cermet solar thermal selective absorber coatings are an important component of high-efficiency concentrated solar power (CSP) receivers. The oxidation of the metal nanoparticles in cermet solar absorbers is a great challenge for vacuum-free operation. Recently, we have demonstrated that oxidation is kinetically retarded in solution processed, high-optical-performance Ni nanochain-SiOx cermet system compared to conventional Ni-Al2O3 system when annealed in air at 450-600 °C for several hours. However, for long-term, high-temperature applications in CSP systems, thermodynamically stable antioxidation behavior is highly desirable, which requires new mechanisms beyond kinetically reducing the oxidation rate. Towards this goal, in this paper, we demonstrate that pre-operation annealing of Ni nanochain-SiOx cermets at 900 °C in N2 forms the thermodynamically stable orthorhombic phase of NiSi at the Ni/SiOx interfaces, leading to self-terminated oxidation at 550 °C in air due to this interfacial engineering. In contrast, pre-operation annealing at a lower temperature of 750 °C in N2 (as conducted in our previous work) cannot achieve interfacial NiSi formation directly, and further annealing in air at 450-600 °C for >4 h only leads to the formation of the less stable (metastable) hexagonal phase of NiSi. Therefore, the high-temperature pre-operation annealing is critical to form the desirable orthorhombic phase of NiSi at Ni/SiOx interfaces towards thermodynamically stable antioxidation behavior. Remarkably, with this improved interfacial engineering, the oxidation of 80-nm-diameter Ni nanochain-SiOx saturates after annealing at 550 °C in air for 12 h. Additional annealing at 550 °C in air for as long as 20 h (i.e., 32 h air annealing at >550 °C in total) has almost no further impact on the structural or optical properties of the coatings, the latter being very sensitive to any interfacial changes due to the localized surface plasmon resonances of the metal

  14. ZCURVE 3.0: identify prokaryotic genes with higher accuracy as well as automatically and accurately select essential genes.

    PubMed

    Hua, Zhi-Gang; Lin, Yan; Yuan, Ya-Zhou; Yang, De-Chang; Wei, Wen; Guo, Feng-Biao

    2015-07-01

    In 2003, we developed an ab initio program, ZCURVE 1.0, to find genes in bacterial and archaeal genomes. In this work, we present the updated version (i.e. ZCURVE 3.0). Using 422 prokaryotic genomes, the average accuracy was 93.7% with the updated version, compared with 88.7% with the original version. Such results also demonstrate that ZCURVE 3.0 is comparable with Glimmer 3.02 and may provide complementary predictions to it. In fact, the joint application of the two programs generated better results by correctly finding more annotated genes while also containing fewer false-positive predictions. As the exclusive function, ZCURVE 3.0 contains one post-processing program that can identify essential genes with high accuracy (generally >90%). We hope ZCURVE 3.0 will receive wide use with the web-based running mode. The updated ZCURVE can be freely accessed from http://cefg.uestc.edu.cn/zcurve/ or http://tubic.tju.edu.cn/zcurveb/ without any restrictions. PMID:25977299

  15. ZCURVE 3.0: identify prokaryotic genes with higher accuracy as well as automatically and accurately select essential genes.

    PubMed

    Hua, Zhi-Gang; Lin, Yan; Yuan, Ya-Zhou; Yang, De-Chang; Wei, Wen; Guo, Feng-Biao

    2015-07-01

    In 2003, we developed an ab initio program, ZCURVE 1.0, to find genes in bacterial and archaeal genomes. In this work, we present the updated version (i.e. ZCURVE 3.0). Using 422 prokaryotic genomes, the average accuracy was 93.7% with the updated version, compared with 88.7% with the original version. Such results also demonstrate that ZCURVE 3.0 is comparable with Glimmer 3.02 and may provide complementary predictions to it. In fact, the joint application of the two programs generated better results by correctly finding more annotated genes while also containing fewer false-positive predictions. As the exclusive function, ZCURVE 3.0 contains one post-processing program that can identify essential genes with high accuracy (generally >90%). We hope ZCURVE 3.0 will receive wide use with the web-based running mode. The updated ZCURVE can be freely accessed from http://cefg.uestc.edu.cn/zcurve/ or http://tubic.tju.edu.cn/zcurveb/ without any restrictions.

  16. An Analysis of the Selected Materials Used in Step Measurements During Pre-Fits of Thermal Protection System Tiles and the Accuracy of Measurements Made Using These Selected Materials

    NASA Technical Reports Server (NTRS)

    Kranz, David William

    2010-01-01

    The goal of this research project was be to compare and contrast the selected materials used in step measurements during pre-fits of thermal protection system tiles and to compare and contrast the accuracy of measurements made using these selected materials. The reasoning for conducting this test was to obtain a clearer understanding to which of these materials may yield the highest accuracy rate of exacting measurements in comparison to the completed tile bond. These results in turn will be presented to United Space Alliance and Boeing North America for their own analysis and determination. Aerospace structures operate under extreme thermal environments. Hot external aerothermal environments in high Mach number flights lead to high structural temperatures. The differences between tile heights from one to another are very critical during these high Mach reentries. The Space Shuttle Thermal Protection System is a very delicate and highly calculated system. The thermal tiles on the ship are measured to within an accuracy of .001 of an inch. The accuracy of these tile measurements is critical to a successful reentry of an orbiter. This is why it is necessary to find the most accurate method for measuring the height of each tile in comparison to each of the other tiles. The test results indicated that there were indeed differences in the selected materials used in step measurements during prefits of Thermal Protection System Tiles and that Bees' Wax yielded a higher rate of accuracy when compared to the baseline test. In addition, testing for experience level in accuracy yielded no evidence of difference to be found. Lastly the use of the Trammel tool over the Shim Pack yielded variable difference for those tests.

  17. Use of Selected Goodness-of-Fit Statistics to Assess the Accuracy of a Model of Henry Hagg Lake, Oregon

    NASA Astrophysics Data System (ADS)

    Rounds, S. A.; Sullivan, A. B.

    2004-12-01

    Assessing a model's ability to reproduce field data is a critical step in the modeling process. For any model, some method of determining goodness-of-fit to measured data is needed to aid in calibration and to evaluate model performance. Visualizations and graphical comparisons of model output are an excellent way to begin that assessment. At some point, however, model performance must be quantified. Goodness-of-fit statistics, including the mean error (ME), mean absolute error (MAE), root mean square error, and coefficient of determination, typically are used to measure model accuracy. Statistical tools such as the sign test or Wilcoxon test can be used to test for model bias. The runs test can detect phase errors in simulated time series. Each statistic is useful, but each has its limitations. None provides a complete quantification of model accuracy. In this study, a suite of goodness-of-fit statistics was applied to a model of Henry Hagg Lake in northwest Oregon. Hagg Lake is a man-made reservoir on Scoggins Creek, a tributary to the Tualatin River. Located on the west side of the Portland metropolitan area, the Tualatin Basin is home to more than 450,000 people. Stored water in Hagg Lake helps to meet the agricultural and municipal water needs of that population. Future water demands have caused water managers to plan for a potential expansion of Hagg Lake, doubling its storage to roughly 115,000 acre-feet. A model of the lake was constructed to evaluate the lake's water quality and estimate how that quality might change after raising the dam. The laterally averaged, two-dimensional, U.S. Army Corps of Engineers model CE-QUAL-W2 was used to construct the Hagg Lake model. Calibrated for the years 2000 and 2001 and confirmed with data from 2002 and 2003, modeled parameters included water temperature, ammonia, nitrate, phosphorus, algae, zooplankton, and dissolved oxygen. Several goodness-of-fit statistics were used to quantify model accuracy and bias. Model

  18. A thermodynamic approach for selecting operating conditions in the design of reversible solid oxide cell energy systems

    NASA Astrophysics Data System (ADS)

    Wendel, Christopher H.; Kazempoor, Pejman; Braun, Robert J.

    2016-01-01

    Reversible solid oxide cell (ReSOC) systems are being increasingly considered for electrical energy storage, although much work remains before they can be realized, including cell materials development and system design optimization. These systems store electricity by generating a synthetic fuel in electrolysis mode and subsequently recover electricity by electrochemically oxidizing the stored fuel in fuel cell mode. System thermal management is improved by promoting methane synthesis internal to the ReSOC stack. Within this strategy, the cell-stack operating conditions are highly impactful on system performance and optimizing these parameters to suit both operating modes is critical to achieving high roundtrip efficiency. Preliminary analysis shows the thermoneutral voltage to be a useful parameter for analyzing ReSOC systems and the focus of this study is to quantitatively examine how it is affected by ReSOC operating conditions. The results reveal that the thermoneutral voltage is generally reduced by increased pressure, and reductions in temperature, fuel utilization, and hydrogen-to-carbon ratio. Based on the thermodynamic analysis, many different combinations of these operating conditions are expected to promote efficient energy storage. Pressurized systems can achieve high efficiency at higher temperature and fuel utilization, while non-pressurized systems may require lower stack temperature and suffer from reduced energy density.

  19. Accuracy of genomic prediction for BCWD resistance in rainbow trout using different genotyping platforms and genomic selection models

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In this study, we aimed to (1) predict genomic estimated breeding value (GEBV) for bacterial cold water disease (BCWD) resistance by genotyping training (n=583) and validation samples (n=53) with two genotyping platforms (24K RAD-SNP and 49K SNP) and using different genomic selection (GS) models (Ba...

  20. Performance, Accuracy, Data Delivery, and Feedback Methods in Order Selection: A Comparison of Voice, Handheld, and Paper Technologies

    ERIC Educational Resources Information Center

    Ludwig, Timothy D.; Goomas, David T.

    2007-01-01

    Field study was conducted in auto-parts after-market distribution centers where selectors used handheld computers to receive instructions and feedback about their product selection process. A wireless voice-interaction technology was then implemented in a multiple baseline fashion across three departments of a warehouse (N = 14) and was associated…

  1. Improving accuracy of overhanging structures for selective laser melting through reliability characterization of single track formation on thick powder beds

    NASA Astrophysics Data System (ADS)

    Mohanty, Sankhya; Hattel, Jesper H.

    2016-04-01

    Repeatability and reproducibility of parts produced by selective laser melting is a standing issue, and coupled with a lack of standardized quality control presents a major hindrance towards maturing of selective laser melting as an industrial scale process. Consequently, numerical process modelling has been adopted towards improving the predictability of the outputs from the selective laser melting process. Establishing the reliability of the process, however, is still a challenge, especially in components having overhanging structures. In this paper, a systematic approach towards establishing reliability of overhanging structure production by selective laser melting has been adopted. A calibrated, fast, multiscale thermal model is used to simulate the single track formation on a thick powder bed. Single tracks are manufactured on a thick powder bed using same processing parameters, but at different locations in a powder bed and in different laser scanning directions. The difference in melt track widths and depths captures the effect of changes in incident beam power distribution due to location and processing direction. The experimental results are used in combination with numerical model, and subjected to uncertainty and reliability analysis. Cumulative probability distribution functions obtained for melt track widths and depths are found to be coherent with observed experimental values. The technique is subsequently extended for reliability characterization of single layers produced on a thick powder bed without support structures, by determining cumulative probability distribution functions for average layer thickness, sample density and thermal homogeneity.

  2. Thermodynamic holography.

    PubMed

    Wei, Bo-Bo; Jiang, Zhan-Feng; Liu, Ren-Bao

    2015-01-01

    The holographic principle states that the information about a volume of a system is encoded on the boundary surface of the volume. Holography appears in many branches of physics, such as optics, electromagnetism, many-body physics, quantum gravity, and string theory. Here we show that holography is also an underlying principle in thermodynamics, a most important foundation of physics. The thermodynamics of a system is fully determined by its partition function. We prove that the partition function of a finite but arbitrarily large system is an analytic function on the complex plane of physical parameters, and therefore the partition function in a region on the complex plane is uniquely determined by its values along the boundary. The thermodynamic holography has applications in studying thermodynamics of nano-scale systems (such as molecule engines, nano-generators and macromolecules) and provides a new approach to many-body physics. PMID:26478214

  3. Thermodynamic holography

    PubMed Central

    Wei, Bo-Bo; Jiang, Zhan-Feng; Liu, Ren-Bao

    2015-01-01

    The holographic principle states that the information about a volume of a system is encoded on the boundary surface of the volume. Holography appears in many branches of physics, such as optics, electromagnetism, many-body physics, quantum gravity, and string theory. Here we show that holography is also an underlying principle in thermodynamics, a most important foundation of physics. The thermodynamics of a system is fully determined by its partition function. We prove that the partition function of a finite but arbitrarily large system is an analytic function on the complex plane of physical parameters, and therefore the partition function in a region on the complex plane is uniquely determined by its values along the boundary. The thermodynamic holography has applications in studying thermodynamics of nano-scale systems (such as molecule engines, nano-generators and macromolecules) and provides a new approach to many-body physics. PMID:26478214

  4. Thermodynamic Analysis of the Selectivity Enhancement Obtained by Using Smart Hydrogels That Are Zwitterionic When Detecting Glucose With Boronic Acid Moieties

    PubMed Central

    Horkay, F.; Cho, S. H.; Tathireddy, P.; Rieth, L.; Solzbacher, F.; Magda, J.

    2011-01-01

    Because the boronic acid moiety reversibly binds to sugar molecules and has low cytotoxicity, boronic acid-containing hydrogels are being used in a variety of implantable glucose sensors under development, including sensors based on optical, fluorescence, and swelling pressure measurements. However, some method of glucose selectivity enhancement is often necessary, because isolated boronic acid molecules have a binding constant with glucose that is some forty times smaller than their binding constant with fructose, the second most abundant sugar in the human body. In many cases, glucose selectivity enhancement is obtained by incorporating pendant tertiary amines into the hydrogel network, thereby giving rise to a hydrogel that is zwitterionic at physiological pH. However, the mechanism by which incorporation of tertiary amines confers selectivity enhancement is poorly understood. In order to clarify this mechanism, we use the osmotic deswelling technique to compare the thermodynamic interactions of glucose and fructose with a zwitterionic smart hydrogel containing boronic acid moieties. We also investigate the change in the structure of the hydrogel that occurs when it binds to glucose or to fructose using the technique of small angle neutron scattering. PMID:22190765

  5. Thermodynamics of Resource Recycling.

    ERIC Educational Resources Information Center

    Hauserman, W. B.

    1988-01-01

    Evaluates the overall economic efficiency of a closed resource cycle. Uses elementary thermodynamic definitions of overall thermal efficiency for determining an economically quantifiable basis. Selects aluminum for investigation and includes a value-entropy diagram for a closed aluminum cycle. (MVL)

  6. Variable selection procedures before partial least squares regression enhance the accuracy of milk fatty acid composition predicted by mid-infrared spectroscopy.

    PubMed

    Gottardo, P; Penasa, M; Lopez-Villalobos, N; De Marchi, M

    2016-10-01

    Mid-infrared spectroscopy is a high-throughput technique that allows the prediction of milk quality traits on a large-scale. The accuracy of prediction achievable using partial least squares (PLS) regression is usually high for fatty acids (FA) that are more abundant in milk, whereas it decreases for FA that are present in low concentrations. Two variable selection methods, uninformative variable elimination or a genetic algorithm combined with PLS regression, were used in the present study to investigate their effect on the accuracy of prediction equations for milk FA profile expressed either as a concentration on total identified FA or a concentration in milk. For FA expressed on total identified FA, the coefficient of determination of cross-validation from PLS alone was low (0.25) for the prediction of polyunsaturated FA and medium (0.70) for saturated FA. The coefficient of determination increased to 0.54 and 0.95 for polyunsaturated and saturated FA, respectively, when FA were expressed on a milk basis and using PLS alone. Both algorithms before PLS regression improved the accuracy of prediction for FA, especially for FA that are usually difficult to predict; for example, the improvement with respect to the PLS regression ranged from 9 to 80%. In general, FA were better predicted when their concentrations were expressed on a milk basis. These results might favor the use of prediction equations in the dairy industry for genetic purposes and payment system. PMID:27522434

  7. Assessment of exercise-induced minor muscle lesions: the accuracy of Cyriax's diagnosis by selective tension paradigm.

    PubMed

    Franklin, M E; Conner-Kerr, T; Chamness, M; Chenier, T C; Kelly, R R; Hodge, T

    1996-09-01

    The Cyriax selective tension assessment paradigm is commonly used by clinicians for the diagnosis of soft tissue lesions; however, studies have not demonstrated that it is a valid method. The purpose of this study was to examine the construct validity of the active motion, passive motion, resisted movement, and palpation components of the Cyriax selective tension diagnosis paradigm in subjects with an exercise-induced minor hamstring muscle lesion. Nine female subjects with a mean age of 23.6 years (SD = 4.7) and a mass of 57.3 kg (SD = 10.7) performed two sets of 20 maximal eccentric isokinetic knee flexor contractions designed to induce a minor muscle lesion of the hamstrings. Active range of motion, passive range of motion, knee extension end-feel pain relative to resistance sequence, knee flexor isometric strength, pain perception during knee flexor resisted movement testing, and palpation pain of the hamstrings were assessed at 0, 5, 2, 12, 24, 48, and 72 hours postexercise and compared with Cyriax's hypothesized selective tension paradigm results. Consistent with Cyriax's paradigm, passive range of motion remained unchanged, and perceived pain of the hamstrings increased with resistance testing at 12, 24, 48, and 72 hours postexercise when compared with baseline. In addition, palpation pain of the hamstrings was significantly elevated at 48 and 72 hours after exercise (p < 0.05). In contrast of Cyriax's paradigm, active range of motion was significantly reduced over time (p < 0.05), with the least amount of motion compared to baseline (85%) occurring at 48 hours postexercise. Further, resisted movement testing found significant knee flexor isometric strength reductions over time (p < 0.05), with the greatest reductions (33%) occurring at 48 hours postexercise. According to Cyriax, when a minor muscle lesion is tested, it should be strong and painful; however, none of the postexercise time frames exhibited results that were strong and painful. This study

  8. Tailor-made biocatalysts: combining thermodynamics, organic synthesis, molecular biology, biochemistry and microbiology for the design of enzyme selections

    PubMed Central

    Jestin, Jean-Luc

    2012-01-01

    A general strategy for the isolation of catalysts for given chemical reactions was designed. A first link between genes and their corresponding proteins was established by phage display: using Darwin's principles on evolution based on selection and amplification, rare protein molecules can then be selected for function from a large repertoire prior to their characterization by sequencing of their genes. A second link was created between enzymes and their products. By making use of the chelate effect and of Inovirus particles as a chemical, affinity chromatography for the reaction product is then sufficient to isolate among 106 to 1011 proteins and their genes, the rare ones coding for catalysts of interest. The strategy for the parallel processing of information on the catalytic activity of variants from a large protein repertoire is highlighted in this review. PMID:24688654

  9. Retentivity, selectivity and thermodynamic behavior of polycyclic aromatic hydrocarbons on charge-transfer and hypercrosslinked stationary phases under conditions of normal phase high performance liquid chromatography.

    PubMed

    Jiang, Ping; Lucy, Charles A

    2016-03-11

    Charge-transfer and hypercrosslinked polystyrene phases offer retention and separation for polycyclic aromatic hydrocarbons (PAHs) and thus have potential for petroleum analysis. The size, shape and planarity selectivity for PAH standards on charge-transfer (DNAP column) and hypercrosslinked polystyrene (HC-Tol and 5HGN columns) phases are different under normal phase liquid chromatography (NPLC). The HC-Tol column behaves like a conventional NPLC column with low retention of PAHs. Retention of PAHs on the DNAP and 5HGN are strong and increases with the number of aromatic rings. The main retention mechanism is through π-π interactions and dipole-induced dipole interaction. Thermodynamics indicates that the retention mechanism of PAHs remains unchanged over the temperature range 20-60°C. In addition, on either DNAP or 5HGN column, both linear and bent PAHs are retained through the same mechanism. But DNAP possesses smaller π-π interaction and higher planarity selectivity than 5HGN for PAHs. This is suggestive that DNAP interacts with PAHs through a disordered phase arrangement, while 5HGN behaves as an ordered adsorption phase.

  10. Stochastic thermodynamics

    NASA Astrophysics Data System (ADS)

    Eichhorn, Ralf; Aurell, Erik

    2014-04-01

    'Stochastic thermodynamics as a conceptual framework combines the stochastic energetics approach introduced a decade ago by Sekimoto [1] with the idea that entropy can consistently be assigned to a single fluctuating trajectory [2]'. This quote, taken from Udo Seifert's [3] 2008 review, nicely summarizes the basic ideas behind stochastic thermodynamics: for small systems, driven by external forces and in contact with a heat bath at a well-defined temperature, stochastic energetics [4] defines the exchanged work and heat along a single fluctuating trajectory and connects them to changes in the internal (system) energy by an energy balance analogous to the first law of thermodynamics. Additionally, providing a consistent definition of trajectory-wise entropy production gives rise to second-law-like relations and forms the basis for a 'stochastic thermodynamics' along individual fluctuating trajectories. In order to construct meaningful concepts of work, heat and entropy production for single trajectories, their definitions are based on the stochastic equations of motion modeling the physical system of interest. Because of this, they are valid even for systems that are prevented from equilibrating with the thermal environment by external driving forces (or other sources of non-equilibrium). In that way, the central notions of equilibrium thermodynamics, such as heat, work and entropy, are consistently extended to the non-equilibrium realm. In the (non-equilibrium) ensemble, the trajectory-wise quantities acquire distributions. General statements derived within stochastic thermodynamics typically refer to properties of these distributions, and are valid in the non-equilibrium regime even beyond the linear response. The extension of statistical mechanics and of exact thermodynamic statements to the non-equilibrium realm has been discussed from the early days of statistical mechanics more than 100 years ago. This debate culminated in the development of linear response

  11. Methodology of Thermodynamics

    ERIC Educational Resources Information Center

    Mohan, Gyan

    1969-01-01

    Presents a systematization of the mathematical formulae in thermodynamics. From the set of thermodynamic variables, four equations are derived which contain the total mathematical jargon of thermodynamics. (LC)

  12. Thermodynamic Basis of Selectivity in the Interactions of Tissue Inhibitors of Metalloproteinases N-domains with Matrix Metalloproteinases-1, -3, and -14.

    PubMed

    Zou, Haiyin; Wu, Ying; Brew, Keith

    2016-05-20

    The four tissue inhibitors of metalloproteinases (TIMPs) are potent inhibitors of the many matrixins (MMPs), except that TIMP1 weakly inhibits some MMPs, including MMP14. The broad-spectrum inhibition of MMPs by TIMPs and their N-domains (NTIMPs) is consistent with the previous isothermal titration calorimetric finding that their interactions are entropy-driven but differ in contributions from solvent and conformational entropy (ΔSsolv, ΔSconf), estimated using heat capacity changes (ΔCp). Selective engineered NTIMPs have potential applications for treating MMP-related diseases, including cancer and cardiomyopathy. Here we report isothermal titration calorimetric studies of the effects of selectivity-modifying mutations in NTIMP1 and NTIMP2 on the thermodynamics of their interactions with MMP1, MMP3, and MMP14. The weak inhibition of MMP14 by NTIMP1 reflects a large conformational entropy penalty for binding. The T98L mutation, peripheral to the NTIMP1 reactive site, enhances binding by increasing ΔSsolv but also reduces ΔSconf However, the same mutation increases NTIMP1 binding to MMP3 in an interaction that has an unusual positive ΔCp This indicates a decrease in solvent entropy compensated by increased conformational entropy, possibly reflecting interactions involving alternative conformers. The NTIMP2 mutant, S2D/S4A is a selective MMP1 inhibitor through electrostatic effects of a unique MMP-1 arginine. Asp-2 increases reactive site polarity, reducing ΔCp, but increases conformational entropy to maintain strong binding to MMP1. There is a strong negative correlation between ΔSsolv and ΔSconf for all characterized interactions, but the data for each MMP have characteristic ranges, reflecting intrinsic differences in the structures and dynamics of their free and inhibitor-bound forms. PMID:27033700

  13. Influence of Raw Image Preprocessing and Other Selected Processes on Accuracy of Close-Range Photogrammetric Systems According to Vdi 2634

    NASA Astrophysics Data System (ADS)

    Reznicek, J.; Luhmann, T.; Jepping, C.

    2016-06-01

    This paper examines the influence of raw image preprocessing and other selected processes on the accuracy of close-range photogrammetric measurement. The examined processes and features includes: raw image preprocessing, sensor unflatness, distance-dependent lens distortion, extending the input observations (image measurements) by incorporating all RGB colour channels, ellipse centre eccentricity and target detecting. The examination of each effect is carried out experimentally by performing the validation procedure proposed in the German VDI guideline 2634/1. The validation procedure is based on performing standard photogrammetric measurements of high-accurate calibrated measuring lines (multi-scale bars) with known lengths (typical uncertainty = 5 μm at 2 sigma). The comparison of the measured lengths with the known values gives the maximum length measurement error LME, which characterize the accuracy of the validated photogrammetric system. For higher reliability the VDI test field was photographed ten times independently with the same configuration and camera settings. The images were acquired with the metric ALPA 12WA camera. The tests are performed on all ten measurements which gives the possibility to measure the repeatability of the estimated parameters as well. The influences are examined by comparing the quality characteristics of the reference and tested settings.

  14. Descriptive thermodynamics

    NASA Astrophysics Data System (ADS)

    Ford, David; Huntsman, Steven

    2006-06-01

    Thermodynamics (in concert with its sister discipline, statistical physics) can be regarded as a data reduction scheme based on partitioning a total system into a subsystem and a bath that weakly interact with each other. Whereas conventionally, the systems investigated require this form of data reduction in order to facilitate prediction, a different problem also occurs, in the context of communication networks, markets, etc. Such “empirically accessible” systems typically overwhelm observers with the sort of information that in the case of (say) a gas is effectively unobtainable. What is required for such complex interacting systems is not prediction (this may be impossible when humans besides the observer are responsible for the interactions) but rather, description as a route to understanding. Still, the need for a thermodynamical data reduction scheme remains. In this paper, we show how an empirical temperature can be computed for finite, empirically accessible systems, and further outline how this construction allows the age-old science of thermodynamics to be fruitfully applied to them.

  15. Nanoscopic Thermodynamics.

    PubMed

    Qi, Weihong

    2016-09-20

    Conventional thermodynamics for bulk substances encounters challenges when one considers materials on the nanometer scale. Quantities such as entropy, enthalpy, free energy, melting temperature, ordering temperature, Debye temperature, and specific heat no longer remain constant but change with the crystal dimension, size, and morphology. Often, one phenomenon is associated with a variety of theories from different perspectives. Still, a model that can reconcile the size and shape dependence of the thermal properties of the nanoscaled substances remains one of the goals of nanoscience and nanotechnology. This Account highlights the nanoscopic thermodynamics for nanoparticles, nanowires, and nanofilms, with particular emphasis on the bond energy model. The central idea is that the atomic cohesive energy determines the thermodynamic performance of a substance and the cohesive energy varies with the atomic coordination environment. It is the cohesive energy difference between the core and the shell that dictates the nanoscopic thermodynamics. This bond energy model rationalizes the following: (i) how the surface dangling bonds depress the melting temperature, entropy, and enthalpy; (ii) how the order-disorder transition of the nanoparticles depends on particle size and how their stability may vary when they are embedded in an appropriate matrix; (iii) predictions of the existence of face-centered cubic structures of Ti, Zr, and Hf at small size; (iv) how two elements that are immiscible in the bulk can form an alloy on the nanoscale, where the critical size can be predicted. The model has enabled us to reproduce the size and shape dependence of a number of physical properties, such as melting temperature, melting entropy, melting enthalpy, ordering temperature, Gibbs free energy, and formation heat, among others, for materials such as Pd, Au, Ag, Cu, Ni, Sn, Pb, In, Bi, Al, Ti, Zr, Hf, In-Al, Ag-Ni, Co-Pt, Cu-Ag, Cu-Ni, Au-Ni, Ag-Pt, and Au-Pt on the nanometer scale

  16. Natural thermodynamics

    NASA Astrophysics Data System (ADS)

    Annila, Arto

    2016-02-01

    The principle of increasing entropy is derived from statistical physics of open systems assuming that quanta of actions, as undividable basic build blocks, embody everything. According to this tenet, all systems evolve from one state to another either by acquiring quanta from their surroundings or by discarding quanta to the surroundings in order to attain energetic balance in least time. These natural processes result in ubiquitous scale-free patterns: skewed distributions that accumulate in a sigmoid manner and hence span log-log scales mostly as straight lines. Moreover, the equation for least-time motions reveals that evolution is by nature a non-deterministic process. Although the obtained insight in thermodynamics from the notion of quanta in motion yields nothing new, it accentuates that contemporary comprehension is impaired when modeling evolution as a computable process by imposing conservation of energy and thereby ignoring that quantum of actions are the carriers of energy from the system to its surroundings.

  17. The relative accuracy of standard estimators for macrofaunal abundance and species richness derived from selected intertidal transect designs used to sample exposed sandy beaches

    NASA Astrophysics Data System (ADS)

    Schoeman, transect designs used to sample exposed sandy beaches D. S.; Wheeler, M.; Wait, M.

    2003-10-01

    In order to ensure that patterns detected in field samples reflect real ecological processes rather than methodological idiosyncrasies, it is important that researchers attempt to understand the consequences of the sampling and analytical designs that they select. This is especially true for sandy beach ecology, which has lagged somewhat behind ecological studies of other intertidal habitats. This paper investigates the performance of routine estimators of macrofaunal abundance and species richness, which are variables that have been widely used to infer predictable patterns of biodiversity across a gradient of beach types. To do this, a total of six shore-normal strip transects were sampled on three exposed, oceanic sandy beaches in the Eastern Cape, South Africa. These transects comprised contiguous quadrats arranged linearly between the spring high and low water marks. Using simple Monte Carlo simulation techniques, data collected from the strip transects were used to assess the accuracy of parameter estimates from different sampling strategies relative to their true values (macrofaunal abundance ranged 595-1369 individuals transect -1; species richness ranged 12-21 species transect -1). Results indicated that estimates from the various transect methods performed in a similar manner both within beaches and among beaches. Estimates for macrofaunal abundance tended to be negatively biased, especially at levels of sampling effort most commonly reported in the literature, and accuracy decreased with decreasing sampling effort. By the same token, estimates for species richness were always negatively biased and were also characterised by low precision. Furthermore, triplicate transects comprising a sampled area in the region of 4 m 2 (as has been previously recommended) are expected to miss more than 30% of the species that occur on the transect. Surprisingly, for both macrofaunal abundance and species richness, estimates based on data from transects sampling quadrats

  18. Genomic selection and association mapping in rice (Oryza sativa): effect of trait genetic architecture, training population composition, marker number and statistical model on accuracy of rice genomic selection in elite, tropical rice breeding lines.

    PubMed

    Spindel, Jennifer; Begum, Hasina; Akdemir, Deniz; Virk, Parminder; Collard, Bertrand; Redoña, Edilberto; Atlin, Gary; Jannink, Jean-Luc; McCouch, Susan R

    2015-02-01

    Genomic Selection (GS) is a new breeding method in which genome-wide markers are used to predict the breeding value of individuals in a breeding population. GS has been shown to improve breeding efficiency in dairy cattle and several crop plant species, and here we evaluate for the first time its efficacy for breeding inbred lines of rice. We performed a genome-wide association study (GWAS) in conjunction with five-fold GS cross-validation on a population of 363 elite breeding lines from the International Rice Research Institute's (IRRI) irrigated rice breeding program and herein report the GS results. The population was genotyped with 73,147 markers using genotyping-by-sequencing. The training population, statistical method used to build the GS model, number of markers, and trait were varied to determine their effect on prediction accuracy. For all three traits, genomic prediction models outperformed prediction based on pedigree records alone. Prediction accuracies ranged from 0.31 and 0.34 for grain yield and plant height to 0.63 for flowering time. Analyses using subsets of the full marker set suggest that using one marker every 0.2 cM is sufficient for genomic selection in this collection of rice breeding materials. RR-BLUP was the best performing statistical method for grain yield where no large effect QTL were detected by GWAS, while for flowering time, where a single very large effect QTL was detected, the non-GS multiple linear regression method outperformed GS models. For plant height, in which four mid-sized QTL were identified by GWAS, random forest produced the most consistently accurate GS models. Our results suggest that GS, informed by GWAS interpretations of genetic architecture and population structure, could become an effective tool for increasing the efficiency of rice breeding as the costs of genotyping continue to decline. PMID:25689273

  19. Genomic Selection and Association Mapping in Rice (Oryza sativa): Effect of Trait Genetic Architecture, Training Population Composition, Marker Number and Statistical Model on Accuracy of Rice Genomic Selection in Elite, Tropical Rice Breeding Lines

    PubMed Central

    Spindel, Jennifer; Begum, Hasina; Akdemir, Deniz; Virk, Parminder; Collard, Bertrand; Redoña, Edilberto; Atlin, Gary; Jannink, Jean-Luc; McCouch, Susan R.

    2015-01-01

    Genomic Selection (GS) is a new breeding method in which genome-wide markers are used to predict the breeding value of individuals in a breeding population. GS has been shown to improve breeding efficiency in dairy cattle and several crop plant species, and here we evaluate for the first time its efficacy for breeding inbred lines of rice. We performed a genome-wide association study (GWAS) in conjunction with five-fold GS cross-validation on a population of 363 elite breeding lines from the International Rice Research Institute's (IRRI) irrigated rice breeding program and herein report the GS results. The population was genotyped with 73,147 markers using genotyping-by-sequencing. The training population, statistical method used to build the GS model, number of markers, and trait were varied to determine their effect on prediction accuracy. For all three traits, genomic prediction models outperformed prediction based on pedigree records alone. Prediction accuracies ranged from 0.31 and 0.34 for grain yield and plant height to 0.63 for flowering time. Analyses using subsets of the full marker set suggest that using one marker every 0.2 cM is sufficient for genomic selection in this collection of rice breeding materials. RR-BLUP was the best performing statistical method for grain yield where no large effect QTL were detected by GWAS, while for flowering time, where a single very large effect QTL was detected, the non-GS multiple linear regression method outperformed GS models. For plant height, in which four mid-sized QTL were identified by GWAS, random forest produced the most consistently accurate GS models. Our results suggest that GS, informed by GWAS interpretations of genetic architecture and population structure, could become an effective tool for increasing the efficiency of rice breeding as the costs of genotyping continue to decline. PMID:25689273

  20. Genomic selection and association mapping in rice (Oryza sativa): effect of trait genetic architecture, training population composition, marker number and statistical model on accuracy of rice genomic selection in elite, tropical rice breeding lines.

    PubMed

    Spindel, Jennifer; Begum, Hasina; Akdemir, Deniz; Virk, Parminder; Collard, Bertrand; Redoña, Edilberto; Atlin, Gary; Jannink, Jean-Luc; McCouch, Susan R

    2015-02-01

    Genomic Selection (GS) is a new breeding method in which genome-wide markers are used to predict the breeding value of individuals in a breeding population. GS has been shown to improve breeding efficiency in dairy cattle and several crop plant species, and here we evaluate for the first time its efficacy for breeding inbred lines of rice. We performed a genome-wide association study (GWAS) in conjunction with five-fold GS cross-validation on a population of 363 elite breeding lines from the International Rice Research Institute's (IRRI) irrigated rice breeding program and herein report the GS results. The population was genotyped with 73,147 markers using genotyping-by-sequencing. The training population, statistical method used to build the GS model, number of markers, and trait were varied to determine their effect on prediction accuracy. For all three traits, genomic prediction models outperformed prediction based on pedigree records alone. Prediction accuracies ranged from 0.31 and 0.34 for grain yield and plant height to 0.63 for flowering time. Analyses using subsets of the full marker set suggest that using one marker every 0.2 cM is sufficient for genomic selection in this collection of rice breeding materials. RR-BLUP was the best performing statistical method for grain yield where no large effect QTL were detected by GWAS, while for flowering time, where a single very large effect QTL was detected, the non-GS multiple linear regression method outperformed GS models. For plant height, in which four mid-sized QTL were identified by GWAS, random forest produced the most consistently accurate GS models. Our results suggest that GS, informed by GWAS interpretations of genetic architecture and population structure, could become an effective tool for increasing the efficiency of rice breeding as the costs of genotyping continue to decline.

  1. Advances in thermodynamics

    SciTech Connect

    Sieniutycz, S. ); Salamon, P. )

    1990-01-01

    This book covers: nonequilibrium thermodynamics for solar energy applications; finite-time thermodynamics as applied to solar power conversion; thermodynamics and economics; exergy analysis; and an analysis of cumulative exergy consumption and exergy losses.

  2. CODATA thermodynamic tables

    SciTech Connect

    Garvin, D.; Parker, V.B.; White, H.J. Jr.

    1987-01-01

    Recommended values are presented for chemical thermodynamic properties of selected compounds of calcium and their mixtures. These have been prepared in accord with a previously developed plan and as a test of it. All values in the present table are mutually consistent and are consistent with the CODATA Key Values for Thermodynamics. The values are recommended for general use. This work has been an activity of the CODATA Task Group on Chemical Thermodynamic Tables. The evaluated data are for common compounds of calcium (element, oxide, hydroxide, peroxide, fluoride, sulfate, nitrate and carbonate, their hydrates and their ions in aqueous solution) and for three systems: Ca-Mg, CaCl/sub 2/-KCl and CaCl/sub 2/-H/sub 2/O. Forty one tables of thermal functions (heat capacity, entropy, enthalpy, and Gibbs energy functions) are given for those compounds of magnesium, calcium and potassium for which the properties have been evaluated in this work. Twenty four tables of thermal functions are given for auxiliary substances. Each table spans the temperature range 0 to 4000 K, to the extent that data are available. Formation properties at 298.15 K (enthalpy and Gibbs energy of formation) are given for 68 compounds of calcium, magnesium and potassium plus the relevant values for 54 auxiliary substances.

  3. The accuracy of selected land use and land cover maps at scales of 1:250,000 and 1:100,000

    USGS Publications Warehouse

    Fitzpatrick-Lins, Katherine

    1980-01-01

    Land use and land cover maps produced by the U.S. Geological Survey are found to meet or exceed the established standard of accuracy. When analyzed using a point sampling technique and binomial probability theory, several maps, illustrative of those produced for different parts of the country, were found to meet or exceed accuracies of 85 percent. Those maps tested were Tampa, Fla., Portland, Me., Charleston, W. Va., and Greeley, Colo., published at a scale of 1:250,000, and Atlanta, Ga., and Seattle and Tacoma, Wash., published at a scale of 1:100,000. For each map, the values were determined by calculating the ratio of the total number of points correctly interpreted to the total number of points sampled. Six of the seven maps tested have accuracies of 85 percent or better at the 95-percent lower confidence limit. When the sample data for predominant categories (those sampled with a significant number of points) were grouped together for all maps, accuracies of those predominant categories met the 85-percent accuracy criterion, with one exception. One category, Residential, had less than 85-percent accuracy at the 95-percent lower confidence limit. Nearly all residential land sampled was mapped correctly, but some areas of other land uses were mapped incorrectly as Residential.

  4. Thermodynamics of Radiation Modes

    ERIC Educational Resources Information Center

    Pina, Eduardo; de la Selva, Sara Maria Teresa

    2010-01-01

    We study the equilibrium thermodynamics of the electromagnetic radiation in a cavity of a given volume and temperature. We found three levels of description, the thermodynamics of one mode, the thermodynamics of the distribution of frequencies in a band by summing over the frequencies in it and the global thermodynamics by summing over all the…

  5. Statistical thermodynamics of clustered populations.

    PubMed

    Matsoukas, Themis

    2014-08-01

    We present a thermodynamic theory for a generic population of M individuals distributed into N groups (clusters). We construct the ensemble of all distributions with fixed M and N, introduce a selection functional that embodies the physics that governs the population, and obtain the distribution that emerges in the scaling limit as the most probable among all distributions consistent with the given physics. We develop the thermodynamics of the ensemble and establish a rigorous mapping to regular thermodynamics. We treat the emergence of a so-called giant component as a formal phase transition and show that the criteria for its emergence are entirely analogous to the equilibrium conditions in molecular systems. We demonstrate the theory by an analytic model and confirm the predictions by Monte Carlo simulation.

  6. The Role of Selected Lexical Factors on Confrontation Naming Accuracy, Speed, and Fluency in Adults Who Do and Do Not Stutter

    ERIC Educational Resources Information Center

    Newman, Rochelle S.; Ratner, Nan Bernstein

    2007-01-01

    Purpose: The purpose of this study was to investigate whether lexical access in adults who stutter (AWS) differs from that in people who do not stutter. Specifically, the authors examined the role of 3 lexical factors on naming speed, accuracy, and fluency: word frequency, neighborhood density, and neighborhood frequency. If stuttering results…

  7. Measuring Thermodynamic Length

    SciTech Connect

    Crooks, Gavin E

    2007-09-07

    Thermodynamic length is a metric distance between equilibrium thermodynamic states. Among other interesting properties, this metric asymptotically bounds the dissipation induced by a finite time transformation of a thermodynamic system. It is also connected to the Jensen-Shannon divergence, Fisher information, and Rao's entropy differential metric. Therefore, thermodynamic length is of central interestin understanding matter out of equilibrium. In this Letter, we will consider how to denethermodynamic length for a small system described by equilibrium statistical mechanics and how to measure thermodynamic length within a computer simulation. Surprisingly, Bennett's classic acceptance ratio method for measuring free energy differences also measures thermodynamic length.

  8. Use of thermodynamic sorption models to derive radionuclide Kd values for performance assessment: Selected results and recommendations of the NEA sorption project

    USGS Publications Warehouse

    Ochs, M.; Davis, J.A.; Olin, M.; Payne, T.E.; Tweed, C.J.; Askarieh, M.M.; Altmann, S.

    2006-01-01

    For the safe final disposal and/or long-term storage of radioactive wastes, deep or near-surface underground repositories are being considered world-wide. A central safety feature is the prevention, or sufficient retardation, of radionuclide (RN) migration to the biosphere. To this end, radionuclide sorption is one of the most important processes. Decreasing the uncertainty in radionuclide sorption may contribute significantly to reducing the overall uncertainty of a performance assessment (PA). For PA, sorption is typically characterised by distribution coefficients (Kd values). The conditional nature of Kd requires different estimates of this parameter for each set of geochemical conditions of potential relevance in a RN's migration pathway. As it is not feasible to measure sorption for every set of conditions, the derivation of Kd for PA must rely on data derived from representative model systems. As a result, uncertainty in Kd is largely caused by the need to derive values for conditions not explicitly addressed in experiments. The recently concluded NEA Sorption Project [1] showed that thermodynamic sorption models (TSMs) are uniquely suited to derive K d as a function of conditions, because they allow a direct coupling of sorption with variable solution chemistry and mineralogy in a thermodynamic framework. The results of the project enable assessment of the suitability of various TSM approaches for PA-relevant applications as well as of the potential and limitations of TSMs to model RN sorption in complex systems. ?? by Oldenbourg Wissenschaftsverlag.

  9. Thermodynamics of binding of structurally similar ligands to histone deacetylase 8 sheds light on challenges in the rational design of potent and isozyme-selective inhibitors of the enzyme.

    PubMed

    Singh, Raushan K; Suzuki, Takayoshi; Mandal, Tanmay; Balsubramanian, Narayanaganesh; Haldar, Manas; Mueller, Dustin J; Strode, Jerrod A; Cook, Gregory; Mallik, Sanku; Srivastava, D K

    2014-12-01

    Among the different histone deacetylase (HDAC) isozymes, HDAC8 is the most highly malleable enzyme, and it exhibits the potential to accommodate structurally diverse ligands (albeit with moderate binding affinities) in its active site pocket. To probe the molecular basis of this feature, we performed detailed thermodynamic studies of the binding of structurally similar ligands, which differed with respect to the "cap", "linker", and "metal-binding" regions of the suberoylanilide hydroxamic acid (SAHA) pharmacophore, to HDAC8. The experimental data revealed that although the enthalpic (ΔH°) and entropic (ΔS°) changes for the binding of individual SAHA analogues to HDAC8 were substantially different, their binding free energies (ΔG°) were markedly similar, conforming to a strong enthalpy-entropy compensation effect. This effect was further observed in the temperature-dependent thermodynamics of binding of all SAHA analogues to the enzyme. Notably, in contrast to other metalloenzymes, our isothermal titration calorimetry experiments (performed in different buffers of varying ionization enthalpies) suggest that depending on the ligand, its zinc-binding group may or may not be deprotonated upon the binding to HDAC8. Furthermore, the heat capacity changes (ΔCp°) associated with the ligand binding to HDAC8 markedly differed from one SAHA analogue to the other, and such features could primarily be rationalized in light of the dynamic flexibility in the enzyme structure in conjunction with the reorganization of the active site resident water molecules. Arguments are presented that although the binding thermodynamic features described above would facilitate identification of weak to moderately tight-binding HDAC8 inhibitors (by a high-throughput and/or virtual screening of libraries of small molecules), they would pose major challenges for the structure-based rational design of highly potent and isozyme-selective inhibitors of human HDAC8.

  10. Thermodynamics of Binding of Structurally Similar Ligands to Histone Deacetylase 8 Sheds Light on Challenges in the Rational Design of Potent and Isozyme-Selective Inhibitors of the Enzyme

    PubMed Central

    2015-01-01

    Among the different histone deacetylase (HDAC) isozymes, HDAC8 is the most highly malleable enzyme, and it exhibits the potential to accommodate structurally diverse ligands (albeit with moderate binding affinities) in its active site pocket. To probe the molecular basis of this feature, we performed detailed thermodynamic studies of the binding of structurally similar ligands, which differed with respect to the “cap”, “linker”, and “metal-binding” regions of the suberoylanilide hydroxamic acid (SAHA) pharmacophore, to HDAC8. The experimental data revealed that although the enthalpic (ΔH°) and entropic (ΔS°) changes for the binding of individual SAHA analogues to HDAC8 were substantially different, their binding free energies (ΔG°) were markedly similar, conforming to a strong enthalpy–entropy compensation effect. This effect was further observed in the temperature-dependent thermodynamics of binding of all SAHA analogues to the enzyme. Notably, in contrast to other metalloenzymes, our isothermal titration calorimetry experiments (performed in different buffers of varying ionization enthalpies) suggest that depending on the ligand, its zinc-binding group may or may not be deprotonated upon the binding to HDAC8. Furthermore, the heat capacity changes (ΔCp°) associated with the ligand binding to HDAC8 markedly differed from one SAHA analogue to the other, and such features could primarily be rationalized in light of the dynamic flexibility in the enzyme structure in conjunction with the reorganization of the active site resident water molecules. Arguments are presented that although the binding thermodynamic features described above would facilitate identification of weak to moderately tight-binding HDAC8 inhibitors (by a high-throughput and/or virtual screening of libraries of small molecules), they would pose major challenges for the structure-based rational design of highly potent and isozyme-selective inhibitors of human HDAC8. PMID:25407689

  11. Thermodynamics of binding of structurally similar ligands to histone deacetylase 8 sheds light on challenges in the rational design of potent and isozyme-selective inhibitors of the enzyme.

    PubMed

    Singh, Raushan K; Suzuki, Takayoshi; Mandal, Tanmay; Balsubramanian, Narayanaganesh; Haldar, Manas; Mueller, Dustin J; Strode, Jerrod A; Cook, Gregory; Mallik, Sanku; Srivastava, D K

    2014-12-01

    Among the different histone deacetylase (HDAC) isozymes, HDAC8 is the most highly malleable enzyme, and it exhibits the potential to accommodate structurally diverse ligands (albeit with moderate binding affinities) in its active site pocket. To probe the molecular basis of this feature, we performed detailed thermodynamic studies of the binding of structurally similar ligands, which differed with respect to the "cap", "linker", and "metal-binding" regions of the suberoylanilide hydroxamic acid (SAHA) pharmacophore, to HDAC8. The experimental data revealed that although the enthalpic (ΔH°) and entropic (ΔS°) changes for the binding of individual SAHA analogues to HDAC8 were substantially different, their binding free energies (ΔG°) were markedly similar, conforming to a strong enthalpy-entropy compensation effect. This effect was further observed in the temperature-dependent thermodynamics of binding of all SAHA analogues to the enzyme. Notably, in contrast to other metalloenzymes, our isothermal titration calorimetry experiments (performed in different buffers of varying ionization enthalpies) suggest that depending on the ligand, its zinc-binding group may or may not be deprotonated upon the binding to HDAC8. Furthermore, the heat capacity changes (ΔCp°) associated with the ligand binding to HDAC8 markedly differed from one SAHA analogue to the other, and such features could primarily be rationalized in light of the dynamic flexibility in the enzyme structure in conjunction with the reorganization of the active site resident water molecules. Arguments are presented that although the binding thermodynamic features described above would facilitate identification of weak to moderately tight-binding HDAC8 inhibitors (by a high-throughput and/or virtual screening of libraries of small molecules), they would pose major challenges for the structure-based rational design of highly potent and isozyme-selective inhibitors of human HDAC8. PMID:25407689

  12. Thermodynamics: Frontiers and Foundations.

    SciTech Connect

    JEFFERY,; LEWINS, D.

    2009-07-27

    Version 00 Dr. J.D. Lewins has now released the following new book for free distribution: Thermodynamics: Frontiers and Foundations, Preface by Sir Alan Cottrell Introduction 1. Four-Square Foundations: The Laws of Thermodynamics 2. Maximum Entropy and Minimum Energy: The Master Functions and Equations 3. Ideal Gases and their Applications 4. Real Fluids and Some Applications 5. Van der Waals: A Model for Real Fluids 6. Surface Tension: Bubbles and Drops 7. Inert and Reactive Mixtures; An introduction to Chemical Thermodynamics 8. Radiation Thermodynamics: Solar Power Potential 9. Outposts of the Empire 10. A Glimpse into Statistical Thermodynamics Envoi

  13. Thermodynamics: Frontiers and Foundations.

    2009-07-27

    Version 00 Dr. J.D. Lewins has now released the following new book for free distribution: Thermodynamics: Frontiers and Foundations, Preface by Sir Alan Cottrell Introduction 1. Four-Square Foundations: The Laws of Thermodynamics 2. Maximum Entropy and Minimum Energy: The Master Functions and Equations 3. Ideal Gases and their Applications 4. Real Fluids and Some Applications 5. Van der Waals: A Model for Real Fluids 6. Surface Tension: Bubbles and Drops 7. Inert and Reactive Mixtures;more » An introduction to Chemical Thermodynamics 8. Radiation Thermodynamics: Solar Power Potential 9. Outposts of the Empire 10. A Glimpse into Statistical Thermodynamics Envoi« less

  14. Effect of optical digitizer selection on the application accuracy of a surgical localization system-a quantitative comparison between the OPTOTRAK and flashpoint tracking systems

    NASA Technical Reports Server (NTRS)

    Li, Q.; Zamorano, L.; Jiang, Z.; Gong, J. X.; Pandya, A.; Perez, R.; Diaz, F.

    1999-01-01

    Application accuracy is a crucial factor for stereotactic surgical localization systems, in which space digitization camera systems are one of the most critical components. In this study we compared the effect of the OPTOTRAK 3020 space digitization system and the FlashPoint Model 3000 and 5000 3D digitizer systems on the application accuracy for interactive localization of intracranial lesions. A phantom was mounted with several implantable frameless markers which were randomly distributed on its surface. The target point was digitized and the coordinates were recorded and compared with reference points. The differences from the reference points represented the deviation from the "true point." The root mean square (RMS) was calculated to show the differences, and a paired t-test was used to analyze the results. The results with the phantom showed that, for 1-mm sections of CT scans, the RMS was 0.76 +/- 0. 54 mm for the OPTOTRAK system, 1.23 +/- 0.53 mm for the FlashPoint Model 3000 3D digitizer system, and 1.00 +/- 0.42 mm for the FlashPoint Model 5000 system. These preliminary results showed that there is no significant difference between the three tracking systems, and, from the quality point of view, they can all be used for image-guided surgery procedures. Copyright 1999 Wiley-Liss, Inc.

  15. Effect of optical digitizer selection on the application accuracy of a surgical localization system-a quantitative comparison between the OPTOTRAK and flashpoint tracking systems.

    PubMed

    Li, Q; Zamorano, L; Jiang, Z; Gong, J X; Pandya, A; Perez, R; Diaz, F

    1999-01-01

    Application accuracy is a crucial factor for stereotactic surgical localization systems, in which space digitization camera systems are one of the most critical components. In this study we compared the effect of the OPTOTRAK 3020 space digitization system and the FlashPoint Model 3000 and 5000 3D digitizer systems on the application accuracy for interactive localization of intracranial lesions. A phantom was mounted with several implantable frameless markers which were randomly distributed on its surface. The target point was digitized and the coordinates were recorded and compared with reference points. The differences from the reference points represented the deviation from the "true point." The root mean square (RMS) was calculated to show the differences, and a paired t-test was used to analyze the results. The results with the phantom showed that, for 1-mm sections of CT scans, the RMS was 0.76 +/- 0. 54 mm for the OPTOTRAK system, 1.23 +/- 0.53 mm for the FlashPoint Model 3000 3D digitizer system, and 1.00 +/- 0.42 mm for the FlashPoint Model 5000 system. These preliminary results showed that there is no significant difference between the three tracking systems, and, from the quality point of view, they can all be used for image-guided surgery procedures. PMID:10631374

  16. Kinetic, equilibrium and thermodynamic studies on sorption of uranium and thorium from aqueous solutions by a selective impregnated resin containing carminic acid.

    PubMed

    Rahmani-Sani, Abolfazl; Hosseini-Bandegharaei, Ahmad; Hosseini, Seyyed-Hossein; Kharghani, Keivan; Zarei, Hossein; Rastegar, Ayoob

    2015-04-01

    In this work, the removal of uranium and thorium ions from aqueous solutions was studied by solid-liquid extraction using an advantageous extractant-impregnated resin (EIR) prepared by loading carminic acid (CA) onto Amberlite XAD-16 resin beads. Batch sorption experiments using CA/XAD-16 beads for the removal of U(VI) and Th(IV) ions were carried out as a function of several parameters, like equilibration time, metal ion concentration, etc. The equilibrium data obtained from the sorption experiments were adjusted to the Langmuir isotherm model and the calculated maximum sorption capacities in terms of monolayer sorption were in agreement with those obtained from the experiments. The experimental data on the sorption behavior of both metal ions onto the EIR beads fitted well in both Bangham and intra-particle diffusion kinetic models, indicating that the intra-particle diffusion is the rate-controlling step. The thermodynamic studies at different temperatures revealed the feasibility and the spontaneous nature of the sorption process for both uranium and thorium ions. PMID:25576783

  17. Kinetic, equilibrium and thermodynamic studies on sorption of uranium and thorium from aqueous solutions by a selective impregnated resin containing carminic acid.

    PubMed

    Rahmani-Sani, Abolfazl; Hosseini-Bandegharaei, Ahmad; Hosseini, Seyyed-Hossein; Kharghani, Keivan; Zarei, Hossein; Rastegar, Ayoob

    2015-04-01

    In this work, the removal of uranium and thorium ions from aqueous solutions was studied by solid-liquid extraction using an advantageous extractant-impregnated resin (EIR) prepared by loading carminic acid (CA) onto Amberlite XAD-16 resin beads. Batch sorption experiments using CA/XAD-16 beads for the removal of U(VI) and Th(IV) ions were carried out as a function of several parameters, like equilibration time, metal ion concentration, etc. The equilibrium data obtained from the sorption experiments were adjusted to the Langmuir isotherm model and the calculated maximum sorption capacities in terms of monolayer sorption were in agreement with those obtained from the experiments. The experimental data on the sorption behavior of both metal ions onto the EIR beads fitted well in both Bangham and intra-particle diffusion kinetic models, indicating that the intra-particle diffusion is the rate-controlling step. The thermodynamic studies at different temperatures revealed the feasibility and the spontaneous nature of the sorption process for both uranium and thorium ions.

  18. Thermodynamic properties for bunsenite, NiO, magnetite, Fe3O4, and hematite, Fe2O3, with comments on selected oxygen buffer reactions

    USGS Publications Warehouse

    Hemingway, B.S.

    1990-01-01

    Smoothed values of the heat capacities and derived thermodynamic functions are given for bunsenite, magnetite, and hematite for the temperature interval 298.15 to 1800 K. The Gibbs free energy for the reaction Ni + 0.5O2 = NiO is given by the equation ??rG0T = -238.39 + 0.1146T - 3.72 ?? 10-3T ln T and is valid from 298.15 K to 1700 K. The Gibbs free energy (in kJ) of the reaction 2 magnetite + 3 quartz = 3 fayalite + O2 may be calculated from the equation ??rG0T = 474.155 - 0.16120 T in kJ and between 800 and 1400 K. The Gibbs free energy (in kJ) of the reaction 6 hematite = 4 magnetite + O2 may be calculated from the following equations: ??rG0T = 496.215 - 0.27114T, ??rG0T = 514.690 - 0.29753T, ??rG0T = 501.348 - 0.2854T. -from Author

  19. Thermodynamical Aspects in Heavy Ion Reactions

    NASA Astrophysics Data System (ADS)

    Bruno, M.; Cannata, F.; D'Agostino, M.; de Sanctis, J.; Fabbri, S.; Fuschini, E.; Geraci, E.; Guiot, B.; Vannini, G.; Verondini, E.; Gulminelli, F.; Chomaz, Ph.; Casini, G.; Chiari, M.; Nannini, A.; Barlini, S.; Gramegna, F.; Kravchuk, V.; Lanchais, A.; Vannucci, L.; Moroni, A.; Ordine, A.; Abbondanno, U.; Margagliotti, G. V.

    2005-12-01

    The excited nuclear systems formed in heavy ion collisions can be studied from a thermodynamical point of view. Charged finite systems have different behaviors with respect to infinite ones. After experimental selection of such equilibrated systems the extraction of thermodynamic coordinates is performed. Different signals compatible with a liquid-gas phase transition have been obtained. In particular a bimodal distribution of the asymmetry between the first two heaviest fragments is presented. Abnormally large fluctuations, which in thermodynamic equilibrium are associated to a negative branch of the heat capacity give indications of a first order phase transition. Perspectives for new generation experiments are indicated.

  20. Thermodynamic Model of Afterburning in Explosions

    SciTech Connect

    Kuhl, A L; Howard, M; Fried, L

    2003-04-23

    Thermodynamic states encountered during afterburning of explosion products gases in air were analyzed with the Cheetah code. Results are displayed in the form of Le Chatelier diagrams: the locus of states of specific internal energy versus temperature, for six different condensed explosives charges. Accuracy of the results was confirmed by comparing the fuel and products curves with the heats of detonation and combustion, and species composition as measured in bomb calorimeter experiments. Results were fit with analytic functions u = f ( T ) suitable for specifying the thermodynamic properties required for gas-dynamic models of afterburning in explosions.

  1. BACCHUS: Brussels Automatic Code for Characterizing High accUracy Spectra

    NASA Astrophysics Data System (ADS)

    Masseron, Thomas; Merle, Thibault; Hawkins, Keith

    2016-05-01

    BACCHUS (Brussels Automatic Code for Characterizing High accUracy Spectra) derives stellar parameters (Teff, log g, metallicity, microturbulence velocity and rotational velocity), equivalent widths, and abundances. The code includes on the fly spectrum synthesis, local continuum normalization, estimation of local S/N, automatic line masking, four methods for abundance determinations, and a flagging system aiding line selection. BACCHUS relies on the grid of MARCS model atmospheres, Masseron's model atmosphere thermodynamic structure interpolator, and the radiative transfer code Turbospectrum (ascl:1205.004).

  2. Validation of selected analytical methods using accuracy profiles to assess the impact of a Tobacco Heating System on indoor air quality.

    PubMed

    Mottier, Nicolas; Tharin, Manuel; Cluse, Camille; Crudo, Jean-René; Lueso, María Gómez; Goujon-Ginglinger, Catherine G; Jaquier, Anne; Mitova, Maya I; Rouget, Emmanuel G R; Schaller, Mathieu; Solioz, Jennifer

    2016-09-01

    Studies in environmentally controlled rooms have been used over the years to assess the impact of environmental tobacco smoke on indoor air quality. As new tobacco products are developed, it is important to determine their impact on air quality when used indoors. Before such an assessment can take place it is essential that the analytical methods used to assess indoor air quality are validated and shown to be fit for their intended purpose. Consequently, for this assessment, an environmentally controlled room was built and seven analytical methods, representing eighteen analytes, were validated. The validations were carried out with smoking machines using a matrix-based approach applying the accuracy profile procedure. The performances of the methods were compared for all three matrices under investigation: background air samples, the environmental aerosol of Tobacco Heating System THS 2.2, a heat-not-burn tobacco product developed by Philip Morris International, and the environmental tobacco smoke of a cigarette. The environmental aerosol generated by the THS 2.2 device did not have any appreciable impact on the performances of the methods. The comparison between the background and THS 2.2 environmental aerosol samples generated by smoking machines showed that only five compounds were higher when THS 2.2 was used in the environmentally controlled room. Regarding environmental tobacco smoke from cigarettes, the yields of all analytes were clearly above those obtained with the other two air sample types. PMID:27343591

  3. Validation of selected analytical methods using accuracy profiles to assess the impact of a Tobacco Heating System on indoor air quality.

    PubMed

    Mottier, Nicolas; Tharin, Manuel; Cluse, Camille; Crudo, Jean-René; Lueso, María Gómez; Goujon-Ginglinger, Catherine G; Jaquier, Anne; Mitova, Maya I; Rouget, Emmanuel G R; Schaller, Mathieu; Solioz, Jennifer

    2016-09-01

    Studies in environmentally controlled rooms have been used over the years to assess the impact of environmental tobacco smoke on indoor air quality. As new tobacco products are developed, it is important to determine their impact on air quality when used indoors. Before such an assessment can take place it is essential that the analytical methods used to assess indoor air quality are validated and shown to be fit for their intended purpose. Consequently, for this assessment, an environmentally controlled room was built and seven analytical methods, representing eighteen analytes, were validated. The validations were carried out with smoking machines using a matrix-based approach applying the accuracy profile procedure. The performances of the methods were compared for all three matrices under investigation: background air samples, the environmental aerosol of Tobacco Heating System THS 2.2, a heat-not-burn tobacco product developed by Philip Morris International, and the environmental tobacco smoke of a cigarette. The environmental aerosol generated by the THS 2.2 device did not have any appreciable impact on the performances of the methods. The comparison between the background and THS 2.2 environmental aerosol samples generated by smoking machines showed that only five compounds were higher when THS 2.2 was used in the environmentally controlled room. Regarding environmental tobacco smoke from cigarettes, the yields of all analytes were clearly above those obtained with the other two air sample types.

  4. Calixarene and resorcarene based receptors: from structural and thermodynamic studies to the synthesis of a new mercury(II) selective material.

    PubMed

    de Namor, Angela F Danil; Aparicio-Aragon, Walther; Nwogu, Nwanyinnaya; El Gamouz, Abdelaziz; Piro, Oscar E; Castellano, Eduardo E

    2011-06-01

    Materials used in current technological approaches for the removal of mercury lack selectivity. Given that this is one of the main features of supramolecular chemistry, receptors based on calix[4]arene and calix[4]resorcarene containing functional groups able to interact selectively with polluting ions while discriminating against biologically essential ones were designed. Thus two receptors, a partially functionalized calix[4]arene derivative, namely, 5,11,17,23-tetra-tert-butyl [25-27-bis(diethyl thiophosphate amino)dihydroxy] calix[4]arene (1) and a fully functionalized calix[4]resorcarene, 4,6,10,12,16,18,22,24-diethyl thiophosphate calix[4]resorcarene (2) are introduced. Mercury(II) was the identified target due to the environmental and health problems associated with its presence in water Thus following the synthesis and characterization of 1 and 2 in solution ((1)HNMR) and in the solid state (X-ray crystallography) the sequence of experimental events leading to cation complexation studies in acetonitrile and methanol ((1)H NMR, conductance, potentiometric, and calorimetric measurements) with the aim of assessing their behavior as mercury selective receptors are described. The cation selectivity pattern observed in acetonitrile follows the sequence Hg(II) > Cu(II) > Ag(I). In methanol 1 is also selective for Hg(II) relative to Ag(I) but no interaction takes place between this receptor and Cu(II) in this solvent. Based on previous results and experimental facts shown in this paper, it is concluded that the complexation observed with Cu(II) in acetonitrile occurs through the acetonitrile-receptor adduct rather than through the free ligand. Receptor 2 has an enhanced capacity for uptaking Hg(II) but forms metalate complexes with Cu(II). These studies in solution guided the inmobilization of receptor 1 into a silica support to produce a new and recyclable material for the removal of Hg(II) from water. An assessment on its capacity to extract this cation from

  5. Thermodynamic constraints on fluctuation phenomena

    NASA Astrophysics Data System (ADS)

    Maroney, O. J. E.

    2009-12-01

    The relationships among reversible Carnot cycles, the absence of perpetual motion machines, and the existence of a nondecreasing globally unique entropy function form the starting point of many textbook presentations of the foundations of thermodynamics. However, the thermal fluctuation phenomena associated with statistical mechanics has been argued to restrict the domain of validity of this basis of the second law of thermodynamics. Here we demonstrate that fluctuation phenomena can be incorporated into the traditional presentation, extending rather than restricting the domain of validity of the phenomenologically motivated second law. Consistency conditions lead to constraints upon the possible spectrum of thermal fluctuations. In a special case this uniquely selects the Gibbs canonical distribution and more generally incorporates the Tsallis distributions. No particular model of microscopic dynamics need be assumed.

  6. Thermodynamic constraints on fluctuation phenomena.

    PubMed

    Maroney, O J E

    2009-12-01

    The relationships among reversible Carnot cycles, the absence of perpetual motion machines, and the existence of a nondecreasing globally unique entropy function form the starting point of many textbook presentations of the foundations of thermodynamics. However, the thermal fluctuation phenomena associated with statistical mechanics has been argued to restrict the domain of validity of this basis of the second law of thermodynamics. Here we demonstrate that fluctuation phenomena can be incorporated into the traditional presentation, extending rather than restricting the domain of validity of the phenomenologically motivated second law. Consistency conditions lead to constraints upon the possible spectrum of thermal fluctuations. In a special case this uniquely selects the Gibbs canonical distribution and more generally incorporates the Tsallis distributions. No particular model of microscopic dynamics need be assumed.

  7. Thermodynamics and combustion modeling

    NASA Technical Reports Server (NTRS)

    Zeleznik, Frank J.

    1986-01-01

    Modeling fluid phase phenomena blends the conservation equations of continuum mechanics with the property equations of thermodynamics. The thermodynamic contribution becomes especially important when the phenomena involve chemical reactions as they do in combustion systems. The successful study of combustion processes requires (1) the availability of accurate thermodynamic properties for both the reactants and the products of reaction and (2) the computational capabilities to use the properties. A discussion is given of some aspects of the problem of estimating accurate thermodynamic properties both for reactants and products of reaction. Also, some examples of the use of thermodynamic properties for modeling chemically reacting systems are presented. These examples include one-dimensional flow systems and the internal combustion engine.

  8. Assessing the impact of end-member selection on the accuracy of satellite-based spatial variability models for actual evapotranspiration estimation

    NASA Astrophysics Data System (ADS)

    Long, Di; Singh, Vijay P.

    2013-05-01

    This study examines the impact of end-member (i.e., hot and cold extremes) selection on the performance and mechanisms of error propagation in satellite-based spatial variability models for estimating actual evapotranspiration, using the triangle, surface energy balance algorithm for land (SEBAL), and mapping evapotranspiration with high resolution and internalized calibration (METRIC) models. These models were applied to the soil moisture-atmosphere coupling experiment site in central Iowa on two Landsat Thematic Mapper/Enhanced Thematic Mapper Plus acquisition dates in 2002. Evaporative fraction (EF, defined as the ratio of latent heat flux to availability energy) estimates from the three models at field and watershed scales were examined using varying end-members. Results show that the end-members fundamentally determine the magnitudes of EF retrievals at both field and watershed scales. The hot and cold extremes exercise a similar impact on the discrepancy between the EF estimates and the ground-based measurements, i.e., given a hot (cold) extreme, the EF estimates tend to increase with increasing temperature of cold (hot) extreme, and decrease with decreasing temperature of cold (hot) extreme. The coefficient of determination between the EF estimates and the ground-based measurements depends principally on the capability of remotely sensed surface temperature (Ts) to capture EF (i.e., depending on the correlation between Ts and EF measurements), being slightly influenced by the end-members. Varying the end-members does not substantially affect the standard deviation and skewness of the EF frequency distributions from the same model at the watershed scale. However, different models generate markedly different EF frequency distributions due to differing model physics, especially the limiting edges of EF defined in the remotely sensed vegetation fraction (fc) and Ts space. In general, the end-members cannot be properly determined because (1) they do not

  9. Thermodynamic estimation: Ionic materials

    SciTech Connect

    Glasser, Leslie

    2013-10-15

    Thermodynamics establishes equilibrium relations among thermodynamic parameters (“properties”) and delineates the effects of variation of the thermodynamic functions (typically temperature and pressure) on those parameters. However, classical thermodynamics does not provide values for the necessary thermodynamic properties, which must be established by extra-thermodynamic means such as experiment, theoretical calculation, or empirical estimation. While many values may be found in the numerous collected tables in the literature, these are necessarily incomplete because either the experimental measurements have not been made or the materials may be hypothetical. The current paper presents a number of simple and relible estimation methods for thermodynamic properties, principally for ionic materials. The results may also be used as a check for obvious errors in published values. The estimation methods described are typically based on addition of properties of individual ions, or sums of properties of neutral ion groups (such as “double” salts, in the Simple Salt Approximation), or based upon correlations such as with formula unit volumes (Volume-Based Thermodynamics). - Graphical abstract: Thermodynamic properties of ionic materials may be readily estimated by summation of the properties of individual ions, by summation of the properties of ‘double salts’, and by correlation with formula volume. Such estimates may fill gaps in the literature, and may also be used as checks of published values. This simplicity arises from exploitation of the fact that repulsive energy terms are of short range and very similar across materials, while coulombic interactions provide a very large component of the attractive energy in ionic systems. Display Omitted - Highlights: • Estimation methods for thermodynamic properties of ionic materials are introduced. • Methods are based on summation of single ions, multiple salts, and correlations. • Heat capacity, entropy

  10. Thermodynamic temperature by primary radiometry.

    PubMed

    Anhalt, Klaus; Machin, Graham

    2016-03-28

    Above the freezing temperature of silver (1234.93 K), the International Temperature Scale of 1990 (ITS-90) gives a temperature, T90, in terms of a defining fixed-point blackbody and Planck's law of thermal radiation in ratio form. Alternatively, by using Planck's law directly, thermodynamic temperature can be determined by applying radiation detectors calibrated in absolute terms for their spectral responsivity. With the advent of high-quality semiconductor photodiodes and the development of high-accuracy cryogenic radiometers during the last two decades radiometric detector standards with very small uncertainties in the range of 0.01-0.02% have been developed for direct, absolute radiation thermometry with uncertainties comparable to those for the realization of the ITS-90. This article gives an overview of a number of design variants of different types of radiometer used for primary radiometry and describes their calibration. Furthermore, details and requirements regarding the experimental procedure for obtaining low uncertainty thermodynamic temperatures with these radiometers are presented, noting that such radiometers can also be used at temperatures well below the silver point. Finally, typical results obtained by these methods are reviewed. PMID:26903102

  11. Generalizing thermodynamic properties of bulk single-walled carbon nanotubes

    SciTech Connect

    Rodriguez, Kenneth R. Nanney, Warren A.; Maddux, Cassandra J.A.; Martínez, Hernán L.; Malone, Marvin A.; Coe, James V.

    2014-12-15

    The enthalpy and Gibbs free energy thermodynamical potentials of single walled carbon nanotubes were studied of all types (armchairs, zig-zags, chirals (n>m), and chiral (nthermodynamic potentials were obtained using a previously demonstrated robust method based on semi-empirical PM3 calculations and an extrapolated cluster approach. Those values were used to study the relationship between the thermodynamic potentials and the diameter of the nanotube. Results of this study led to the proposal of a single equation for the thermodynamical potential of ΔH{sub AB}{sup 298 K} or ΔG{sub AB}{sup 298 K} (assembly of nanotubes from atoms) versus the chiral vector indexes n and m for any given nanotube. The equations show a good level of accuracy in predicting thermodynamic potentials for practical applications.

  12. Generalizing thermodynamic properties of bulk single-walled carbon nanotubes

    PubMed Central

    Rodriguez, Kenneth R.; Nanney, Warren A.; A. Maddux, Cassandra J.; Martínez, Hernán L.

    2014-01-01

    The enthalpy and Gibbs free energy thermodynamical potentials of single walled carbon nanotubes were studied of all types (armchairs, zig-zags, chirals (n>m), and chiral (nthermodynamic potentials were obtained using a previously demonstrated robust method based on semi-empirical PM3 calculations and an extrapolated cluster approach. Those values were used to study the relationship between the thermodynamic potentials and the diameter of the nanotube. Results of this study led to the proposal of a single equation for the thermodynamical potential of ΔHAB298 K or ΔGAB298 K (assembly of nanotubes from atoms) versus the chiral vector indexes n and m for any given nanotube. The equations show a good level of accuracy in predicting thermodynamic potentials for practical applications. PMID:25874156

  13. Generalizing thermodynamic properties of bulk single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Rodriguez, Kenneth R.; Malone, Marvin A.; Nanney, Warren A.; A. Maddux, Cassandra J.; Coe, James V.; Martínez, Hernán L.

    2014-12-01

    The enthalpy and Gibbs free energy thermodynamical potentials of single walled carbon nanotubes were studied of all types (armchairs, zig-zags, chirals (n>m), and chiral (nthermodynamic potentials were obtained using a previously demonstrated robust method based on semi-empirical PM3 calculations and an extrapolated cluster approach. Those values were used to study the relationship between the thermodynamic potentials and the diameter of the nanotube. Results of this study led to the proposal of a single equation for the thermodynamical potential of Δ HAB 298 K or Δ GAB 298 K (assembly of nanotubes from atoms) versus the chiral vector indexes n and m for any given nanotube. The equations show a good level of accuracy in predicting thermodynamic potentials for practical applications.

  14. Genomic selection & association mapping in rice: effect of trait genetic architecture, training population composition, marker number & statistical model on accuracy of rice genomic selection in elite, tropical rice breeding

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Genomic Selection (GS) is a new breeding method in which genome-wide markers are used to predict the breeding value of individuals in a breeding population. GS has been shown to improve breeding efficiency in dairy cattle and several crop plant species, and here we evaluate for the first time its ef...

  15. Predictive thermodynamics for ionic solids and liquids.

    PubMed

    Glasser, Leslie; Jenkins, H Donald Brooke

    2016-08-21

    The application of thermodynamics is simple, even if the theory may appear intimidating. We describe tools, developed over recent years, which make it easy to estimate often elusive thermodynamic parameter values, generally (but not exclusively) for ionic materials, both solid and liquid, as well as for their solid hydrates and solvates. The tools are termed volume-based thermodynamics (VBT) and thermodynamic difference rules (TDR), supplemented by the simple salt approximation (SSA) and single-ion values for volume, Vm, heat capacity, , entropy, , formation enthalpy, ΔfH°, and Gibbs formation energy, ΔfG°. These tools can be applied to provide values of thermodynamic and thermomechanical properties such as standard enthalpy of formation, ΔfH°, standard entropy, , heat capacity, Cp, Gibbs function of formation, ΔfG°, lattice potential energy, UPOT, isothermal expansion coefficient, α, and isothermal compressibility, β, and used to suggest the thermodynamic feasibility of reactions among condensed ionic phases. Because many of these methods yield results largely independent of crystal structure, they have been successfully extended to the important and developing class of ionic liquids as well as to new and hypothesised materials. Finally, these predictive methods are illustrated by application to K2SnCl6, for which known experimental results are available for comparison. A selection of applications of VBT and TDR is presented which have enabled input, usually in the form of thermodynamics, to be brought to bear on a range of topical problems. Perhaps the most significant advantage of VBT and TDR methods is their inherent simplicity in that they do not require a high level of computational expertise nor expensive high-performance computation tools - a spreadsheet will usually suffice - yet the techniques are extremely powerful and accessible to non-experts. The connection between formula unit volume, Vm, and standard thermodynamic parameters represents a

  16. Predictive thermodynamics for ionic solids and liquids.

    PubMed

    Glasser, Leslie; Jenkins, H Donald Brooke

    2016-08-21

    The application of thermodynamics is simple, even if the theory may appear intimidating. We describe tools, developed over recent years, which make it easy to estimate often elusive thermodynamic parameter values, generally (but not exclusively) for ionic materials, both solid and liquid, as well as for their solid hydrates and solvates. The tools are termed volume-based thermodynamics (VBT) and thermodynamic difference rules (TDR), supplemented by the simple salt approximation (SSA) and single-ion values for volume, Vm, heat capacity, , entropy, , formation enthalpy, ΔfH°, and Gibbs formation energy, ΔfG°. These tools can be applied to provide values of thermodynamic and thermomechanical properties such as standard enthalpy of formation, ΔfH°, standard entropy, , heat capacity, Cp, Gibbs function of formation, ΔfG°, lattice potential energy, UPOT, isothermal expansion coefficient, α, and isothermal compressibility, β, and used to suggest the thermodynamic feasibility of reactions among condensed ionic phases. Because many of these methods yield results largely independent of crystal structure, they have been successfully extended to the important and developing class of ionic liquids as well as to new and hypothesised materials. Finally, these predictive methods are illustrated by application to K2SnCl6, for which known experimental results are available for comparison. A selection of applications of VBT and TDR is presented which have enabled input, usually in the form of thermodynamics, to be brought to bear on a range of topical problems. Perhaps the most significant advantage of VBT and TDR methods is their inherent simplicity in that they do not require a high level of computational expertise nor expensive high-performance computation tools - a spreadsheet will usually suffice - yet the techniques are extremely powerful and accessible to non-experts. The connection between formula unit volume, Vm, and standard thermodynamic parameters represents a

  17. Electrochemical thermodynamic measurement system

    DOEpatents

    Reynier, Yvan; Yazami, Rachid; Fultz, Brent T.

    2009-09-29

    The present invention provides systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and electrochemical energy storage and conversion systems. Systems and methods of the present invention are configured for simultaneously collecting a suite of measurements characterizing a plurality of interconnected electrochemical and thermodynamic parameters relating to the electrode reaction state of advancement, voltage and temperature. Enhanced sensitivity provided by the present methods and systems combined with measurement conditions that reflect thermodynamically stabilized electrode conditions allow very accurate measurement of thermodynamic parameters, including state functions such as the Gibbs free energy, enthalpy and entropy of electrode/electrochemical cell reactions, that enable prediction of important performance attributes of electrode materials and electrochemical systems, such as the energy, power density, current rate and the cycle life of an electrochemical cell.

  18. Thermodynamics: A Stirling effort

    NASA Astrophysics Data System (ADS)

    Horowitz, Jordan M.; Parrondo, Juan M. R.

    2012-02-01

    The realization of a single-particle Stirling engine pushes thermodynamics into stochastic territory where fluctuations dominate, and points towards a better understanding of energy transduction at the microscale.

  19. Thermodynamics and Frozen Foods.

    ERIC Educational Resources Information Center

    Kerr, William L.; Reid, David S.

    1993-01-01

    The heat content of a food at a given temperature can be described by the thermodynamic property of enthalpy. Presents a method to construct a simple calorimeter for measuring the enthalpy changes of different foods during freezing. (MDH)

  20. Relative Accuracy Evaluation

    PubMed Central

    Zhang, Yan; Wang, Hongzhi; Yang, Zhongsheng; Li, Jianzhong

    2014-01-01

    The quality of data plays an important role in business analysis and decision making, and data accuracy is an important aspect in data quality. Thus one necessary task for data quality management is to evaluate the accuracy of the data. And in order to solve the problem that the accuracy of the whole data set is low while a useful part may be high, it is also necessary to evaluate the accuracy of the query results, called relative accuracy. However, as far as we know, neither measure nor effective methods for the accuracy evaluation methods are proposed. Motivated by this, for relative accuracy evaluation, we propose a systematic method. We design a relative accuracy evaluation framework for relational databases based on a new metric to measure the accuracy using statistics. We apply the methods to evaluate the precision and recall of basic queries, which show the result's relative accuracy. We also propose the method to handle data update and to improve accuracy evaluation using functional dependencies. Extensive experimental results show the effectiveness and efficiency of our proposed framework and algorithms. PMID:25133752

  1. Accuracy in optical overlay metrology

    NASA Astrophysics Data System (ADS)

    Bringoltz, Barak; Marciano, Tal; Yaziv, Tal; DeLeeuw, Yaron; Klein, Dana; Feler, Yoel; Adam, Ido; Gurevich, Evgeni; Sella, Noga; Lindenfeld, Ze'ev; Leviant, Tom; Saltoun, Lilach; Ashwal, Eltsafon; Alumot, Dror; Lamhot, Yuval; Gao, Xindong; Manka, James; Chen, Bryan; Wagner, Mark

    2016-03-01

    In this paper we discuss the mechanism by which process variations determine the overlay accuracy of optical metrology. We start by focusing on scatterometry, and showing that the underlying physics of this mechanism involves interference effects between cavity modes that travel between the upper and lower gratings in the scatterometry target. A direct result is the behavior of accuracy as a function of wavelength, and the existence of relatively well defined spectral regimes in which the overlay accuracy and process robustness degrades (`resonant regimes'). These resonances are separated by wavelength regions in which the overlay accuracy is better and independent of wavelength (we term these `flat regions'). The combination of flat and resonant regions forms a spectral signature which is unique to each overlay alignment and carries certain universal features with respect to different types of process variations. We term this signature the `landscape', and discuss its universality. Next, we show how to characterize overlay performance with a finite set of metrics that are available on the fly, and that are derived from the angular behavior of the signal and the way it flags resonances. These metrics are used to guarantee the selection of accurate recipes and targets for the metrology tool, and for process control with the overlay tool. We end with comments on the similarity of imaging overlay to scatterometry overlay, and on the way that pupil overlay scatterometry and field overlay scatterometry differ from an accuracy perspective.

  2. Stereotype Accuracy: Toward Appreciating Group Differences.

    ERIC Educational Resources Information Center

    Lee, Yueh-Ting, Ed.; And Others

    The preponderance of scholarly theory and research on stereotypes assumes that they are bad and inaccurate, but understanding stereotype accuracy and inaccuracy is more interesting and complicated than simpleminded accusations of racism or sexism would seem to imply. The selections in this collection explore issues of the accuracy of stereotypes…

  3. THERMODYNAMIC PROPERTIES OF SELECTED HFC REFRIGERANTS

    EPA Science Inventory

    Hydrofluorocarbon (HFC) refrigerants are possible alternatives to replace ozone-depleting chlorofluorocarbon and hydrochlorofluorocarbon (HCFC) refrigerants. The flammability of a proposed new refrigerant is a major consideration in assessing its utility for a particular applicat...

  4. Thermodynamics of Biological Processes

    PubMed Central

    Garcia, Hernan G.; Kondev, Jane; Orme, Nigel; Theriot, Julie A.; Phillips, Rob

    2012-01-01

    There is a long and rich tradition of using ideas from both equilibrium thermodynamics and its microscopic partner theory of equilibrium statistical mechanics. In this chapter, we provide some background on the origins of the seemingly unreasonable effectiveness of ideas from both thermodynamics and statistical mechanics in biology. After making a description of these foundational issues, we turn to a series of case studies primarily focused on binding that are intended to illustrate the broad biological reach of equilibrium thinking in biology. These case studies include ligand-gated ion channels, thermodynamic models of transcription, and recent applications to the problem of bacterial chemotaxis. As part of the description of these case studies, we explore a number of different uses of the famed Monod–Wyman–Changeux (MWC) model as a generic tool for providing a mathematical characterization of two-state systems. These case studies should provide a template for tailoring equilibrium ideas to other problems of biological interest. PMID:21333788

  5. Thermodynamics of graphene

    NASA Astrophysics Data System (ADS)

    Rusanov, A. I.

    2014-12-01

    The 21st century has brought a lot of new results related to graphene. Apparently, graphene has been characterized from all points of view except surface science and, especially, surface thermodynamics. This report aims to close this gap. Since graphene is the first real two-dimensional solid, a general formulation of the thermodynamics of two-dimensional solid bodies is given. The two-dimensional chemical potential tensor coupled with stress tensor is introduced, and fundamental equations are derived for energy, free energy, grand thermodynamic potential (in the classical and hybrid forms), enthalpy, and Gibbs energy. The fundamentals of linear boundary phenomena are formulated with explaining the concept of a dividing line, the mechanical and thermodynamic line tensions, line energy and other linear properties with necessary thermodynamic equations. The one-dimensional analogs of the Gibbs adsorption equation and Shuttleworth-Herring relation are presented. The general thermodynamic relationships are illustrated with calculations based on molecular theory. To make the reader sensible of the harmony of chemical and van der Waals forces in graphene, the remake of the classical graphite theory is presented with additional variable combinations of graphene sheets. The calculation of the line energy of graphene is exhibited including contributions both from chemical bonds and van der Waals forces (expectedly, the latter are considerably smaller than the former). The problem of graphene holes originating from migrating vacancies is discussed on the basis of the Gibbs-Curie principle. An important aspect of line tension is the planar sheet/nanotube transition where line tension acts as a driving force. Using the bending stiffness of graphene, the possible radius range is estimated for achiral (zigzag and armchair) nanotubes.

  6. Thermodynamics of ABC transporters.

    PubMed

    Zhang, Xuejun C; Han, Lei; Zhao, Yan

    2016-01-01

    ABC transporters form the largest of all transporter families, and their structural study has made tremendous progress over recent years. However, despite such advances, the precise mechanisms that determine the energy-coupling between ATP hydrolysis and the conformational changes following substrate binding remain to be elucidated. Here, we present our thermodynamic analysis for both ABC importers and exporters, and introduce the two new concepts of differential-binding energy and elastic conformational energy into the discussion. We hope that the structural analysis of ABC transporters will henceforth take thermodynamic aspects of transport mechanisms into account as well.

  7. Viscoplasticity: A thermodynamic formulation

    NASA Technical Reports Server (NTRS)

    Freed, A. D.; Chaboche, J. L.

    1989-01-01

    A thermodynamic foundation using the concept of internal state variables is given for a general theory of viscoplasticity, as it applies to initially isotropic materials. Three fundamental internal state variables are admitted. They are: a tensor valued back stress for kinematic effects, and the scalar valued drag and yield strengths for isotropic effects. All three are considered to phenomenologically evolve according to competitive processes between strain hardening, strain induced dynamic recovery, and time induced static recovery. Within this phenomenological framework, a thermodynamically admissible set of evolution equations is put forth. This theory allows each of the three fundamental internal variables to be composed as a sum of independently evolving constituents.

  8. Beyond Equilibrium Thermodynamics

    NASA Astrophysics Data System (ADS)

    Öttinger, Hans Christian

    2005-01-01

    Beyond Equilibrium Thermodynamics fills a niche in the market by providing a comprehensive introduction to a new, emerging topic in the field. The importance of non-equilibrium thermodynamics is addressed in order to fully understand how a system works, whether it is in a biological system like the brain or a system that develops plastic. In order to fully grasp the subject, the book clearly explains the physical concepts and mathematics involved, as well as presenting problems and solutions; over 200 exercises and answers are included. Engineers, scientists, and applied mathematicians can all use the book to address their problems in modelling, calculating, and understanding dynamic responses of materials.

  9. Black Hole Thermodynamics in an Undergraduate Thermodynamics Course.

    ERIC Educational Resources Information Center

    Parker, Barry R.; McLeod, Robert J.

    1980-01-01

    An analogy, which has been drawn between black hole physics and thermodynamics, is mathematically broadened in this article. Equations similar to the standard partial differential relations of thermodynamics are found for black holes. The results can be used to supplement an undergraduate thermodynamics course. (Author/SK)

  10. Liquid chromatography-high resolution/ high accuracy (tandem) mass spectrometry-based identification of in vivo generated metabolites of the selective androgen receptor modulator ACP-105 for doping control purposes.

    PubMed

    Thevis, Mario; Thomas, Andreas; Piper, Thomas; Krug, Oliver; Delahaut, Philippe; Schänzer, Wilhelm

    2014-01-01

    Selective androgen receptor modulators (SARMs) represent an emerging class of therapeutics which have been prohibited in sport as anabolic agents according to the regulations of the World Anti-Doping Agency (WADA) since 2008. Within the past three years, numerous adverse analytical findings with SARMs in routine doping control samples have been reported despite missing clinical approval of these substances. Hence, preventive doping research concerning the metabolism and elimination of new therapeutic entities of the class of SARMs are vital for efficient and timely sports drug testing programs as banned compounds are most efficiently screened when viable targets (for example, characteristic metabolites) are identified. In the present study, the metabolism of ACP-105, a novel SARM drug candidate, was studied in vivo in rats. Following oral administration, urine samples were collected over a period of seven days and analyzed for metabolic products by Liquid chromatography-high resolution/high accuracy (tandem) mass spectrometry. Samples were subjected to enzymatic hydrolysis prior to liquid-liquid extraction and a total of seven major phase-I metabolites were detected, three of which were attributed to monohydroxylated and four to bishydroxylated ACP-105. The hydroxylation sites were assigned by means of diagnostic product ions and respective dissociation pathways of the analytes following positive or negative ionization and collisional activation as well as selective chemical derivatization. The identified metabolites were used as target compounds to investigate their traceability in a rat elimination urine samples study and monohydroxylated and bishydroxylated species were detectable for up to four and six days post-administration, respectively.

  11. Program Computes Thermodynamic Functions

    NASA Technical Reports Server (NTRS)

    Mcbride, Bonnie J.; Gordon, Sanford

    1994-01-01

    PAC91 is latest in PAC (Properties and Coefficients) series. Two principal features are to provide means of (1) generating theoretical thermodynamic functions from molecular constants and (2) least-squares fitting of these functions to empirical equations. PAC91 written in FORTRAN 77 to be machine-independent.

  12. Focus on stochastic thermodynamics

    NASA Astrophysics Data System (ADS)

    Van den Broeck, Christian; Sasa, Shin-ichi; Seifert, Udo

    2016-02-01

    We introduce the thirty papers collected in this ‘focus on’ issue. The contributions explore conceptual issues within and around stochastic thermodynamics, use this framework for the theoretical modeling and experimental investigation of specific systems, and provide further perspectives on and for this active field.

  13. Thermodynamics in dynamical spacetimes

    NASA Astrophysics Data System (ADS)

    Tresguerres, Romualdo

    2014-03-01

    We derive a general formulation of the laws of irreversible thermodynamics in the presence of electromagnetism and gravity. For the handling of macroscopic material media, we use as a guide the field equations and the Noether identities of fundamental matter as deduced in the framework of gauge theories of the Poincaré ⊗ U(1) group.

  14. On Teaching Thermodynamics

    ERIC Educational Resources Information Center

    Debbasch, F.

    2011-01-01

    The logical structure of classical thermodynamics is presented in a modern, geometrical manner. The first and second law receive clear, operatively oriented statements and the Gibbs free energy extremum principle is fully discussed. Applications relevant to chemistry, such as phase transitions, dilute solutions theory and, in particular, the law…

  15. Thermodynamics of Dilute Solutions.

    ERIC Educational Resources Information Center

    Jancso, Gabor; Fenby, David V.

    1983-01-01

    Discusses principles and definitions related to the thermodynamics of dilute solutions. Topics considered include dilute solution, Gibbs-Duhem equation, reference systems (pure gases and gaseous mixtures, liquid mixtures, dilute solutions), real dilute solutions (focusing on solute and solvent), terminology, standard states, and reference systems.…

  16. Fluctuating Thermodynamics for Biological Processes

    NASA Astrophysics Data System (ADS)

    Ham, Sihyun

    Because biomolecular processes are largely under thermodynamic control, dynamic extension of thermodynamics is necessary to uncover the mechanisms and driving factors of fluctuating processes. The fluctuating thermodynamics technology presented in this talk offers a practical means for the thermodynamic characterization of conformational dynamics in biomolecules. The use of fluctuating thermodynamics has the potential to provide a comprehensive picture of fluctuating phenomena in diverse biological processes. Through the application of fluctuating thermodynamics, we provide a thermodynamic perspective on the misfolding and aggregation of the various proteins associated with human diseases. In this talk, I will present the detailed concepts and applications of the fluctuating thermodynamics technology for elucidating biological processes. This work was supported by Samsung Science and Technology Foundation under Project Number SSTF-BA1401-13.

  17. Practical thermodynamics of Yukawa systems at strong coupling.

    PubMed

    Khrapak, Sergey A; Kryuchkov, Nikita P; Yurchenko, Stanislav O; Thomas, Hubertus M

    2015-05-21

    Simple practical approach to estimate thermodynamic properties of strongly coupled Yukawa systems, in both fluid and solid phases, is presented. The accuracy of the approach is tested by extensive comparison with direct computer simulation results (for fluids and solids) and the recently proposed shortest-graph method (for solids). Possible applications to other systems of softly repulsive particles are briefly discussed. PMID:26001480

  18. Practical thermodynamics of Yukawa systems at strong coupling

    SciTech Connect

    Khrapak, Sergey A.; Kryuchkov, Nikita P.; Yurchenko, Stanislav O.; Thomas, Hubertus M.

    2015-05-21

    Simple practical approach to estimate thermodynamic properties of strongly coupled Yukawa systems, in both fluid and solid phases, is presented. The accuracy of the approach is tested by extensive comparison with direct computer simulation results (for fluids and solids) and the recently proposed shortest-graph method (for solids). Possible applications to other systems of softly repulsive particles are briefly discussed.

  19. Thermodynamic Curvature and Black Holes

    NASA Astrophysics Data System (ADS)

    Ruppeiner, George

    In my talk, I will discuss black hole thermodynamics, particularly what happens when you add thermodynamic curvature to the mix. Although black hole thermodynamics is a little off the main theme of this workshop, I hope nevertheless that my message will be of some interest to researchers in supersymmetry and supergravity.

  20. Thermodynamics of perfect fluids from scalar field theory

    NASA Astrophysics Data System (ADS)

    Ballesteros, Guillermo; Comelli, Denis; Pilo, Luigi

    2016-07-01

    The low-energy dynamics of relativistic continuous media is given by a shift-symmetric effective theory of four scalar fields. These scalars describe the embedding in spacetime of the medium and play the role of Stückelberg fields for spontaneously broken spatial and time translations. Perfect fluids are selected imposing a stronger symmetry group or reducing the field content to a single scalar. We explore the relation between the field theory description of perfect fluids to thermodynamics. By drawing the correspondence between the allowed operators at leading order in derivatives and the thermodynamic variables, we find that a complete thermodynamic picture requires the four Stückelberg fields. We show that thermodynamic stability plus the null-energy condition imply dynamical stability. We also argue that a consistent thermodynamic interpretation is not possible if any of the shift symmetries is explicitly broken.

  1. GEOSPATIAL DATA ACCURACY ASSESSMENT

    EPA Science Inventory

    The development of robust accuracy assessment methods for the validation of spatial data represent's a difficult scientific challenge for the geospatial science community. The importance and timeliness of this issue is related directly to the dramatic escalation in the developmen...

  2. Classification accuracy improvement

    NASA Technical Reports Server (NTRS)

    Kistler, R.; Kriegler, F. J.

    1977-01-01

    Improvements made in processing system designed for MIDAS (prototype multivariate interactive digital analysis system) effects higher accuracy in classification of pixels, resulting in significantly-reduced processing time. Improved system realizes cost reduction factor of 20 or more.

  3. Overlay accuracy fundamentals

    NASA Astrophysics Data System (ADS)

    Kandel, Daniel; Levinski, Vladimir; Sapiens, Noam; Cohen, Guy; Amit, Eran; Klein, Dana; Vakshtein, Irina

    2012-03-01

    Currently, the performance of overlay metrology is evaluated mainly based on random error contributions such as precision and TIS variability. With the expected shrinkage of the overlay metrology budget to < 0.5nm, it becomes crucial to include also systematic error contributions which affect the accuracy of the metrology. Here we discuss fundamental aspects of overlay accuracy and a methodology to improve accuracy significantly. We identify overlay mark imperfections and their interaction with the metrology technology, as the main source of overlay inaccuracy. The most important type of mark imperfection is mark asymmetry. Overlay mark asymmetry leads to a geometrical ambiguity in the definition of overlay, which can be ~1nm or less. It is shown theoretically and in simulations that the metrology may enhance the effect of overlay mark asymmetry significantly and lead to metrology inaccuracy ~10nm, much larger than the geometrical ambiguity. The analysis is carried out for two different overlay metrology technologies: Imaging overlay and DBO (1st order diffraction based overlay). It is demonstrated that the sensitivity of DBO to overlay mark asymmetry is larger than the sensitivity of imaging overlay. Finally, we show that a recently developed measurement quality metric serves as a valuable tool for improving overlay metrology accuracy. Simulation results demonstrate that the accuracy of imaging overlay can be improved significantly by recipe setup optimized using the quality metric. We conclude that imaging overlay metrology, complemented by appropriate use of measurement quality metric, results in optimal overlay accuracy.

  4. Dynamically tunable transformation thermodynamics

    NASA Astrophysics Data System (ADS)

    García-Meca, Carlos; Barceló, Carlos

    2016-04-01

    Recently, the introduction of transformation thermodynamics has provided a way to design thermal media that alter the flow of heat according to any spatial deformation, enabling the construction of novel devices such as thermal cloaks or concentrators. However, in its current version, this technique only allows static deformations of space. Here, we develop a space–time theory of transformation thermodynamics that incorporates the possibility of performing time-varying deformations. This extra freedom greatly widens the range of achievable effects, providing an additional degree of control for heat management applications. As an example, we design a reconfigurable thermal cloak that can be opened and closed dynamically, therefore being able to gradually adjust the temperature distribution of a given region.

  5. Canonical fluid thermodynamics

    NASA Technical Reports Server (NTRS)

    Schmid, L. A.

    1972-01-01

    The space-time integral of the thermodynamic pressure plays the role of the thermodynamic potential for compressible, adiabatic flow in the sense that the pressure integral for stable flow is less than for all slightly different flows. This stability criterion can be converted into a variational minimum principle by requiring the molar free-enthalpy and the temperature, which are the arguments of the pressure function, to be generalized velocities, that is, the proper-time derivatives of scalar spare-time functions which are generalized coordinates in the canonical formalism. In a fluid context, proper-time differentiation must be expressed in terms of three independent quantities that specify the fluid velocity. This can be done in several ways, all of which lead to different variants (canonical transformations) of the same constraint-free action integral whose Euler-Lagrange equations are just the well-known equations of motion for adiabatic compressible flow.

  6. Thermodynamic analysis of spectra

    SciTech Connect

    Mitchell, G. E.; Shriner, J. F. Jr.

    2008-04-04

    Although random matrix theory had its initial application to neutron resonances, there is a relative scarcity of suitable nuclear data. The primary reason for this is the sensitivity of the standard measures used to evaluate spectra--the spectra must be essential pure (no state with a different symmetry) and complete (no states missing). Additional measures that are less sensitive to these experimental limitations are of significant value. The standard measure for long range order is the {delta}{sub 3} statistic. In the original paper that introduced this statistic, Dyson and Mehta also attempted to evaluate spectra with thermodynamic variables obtained from the circular orthogonal ensemble. We consider the thermodynamic 'internal energy' and evaluate its sensitivity to experimental limitations such as missing and spurious levels. Monte Carlo simulations suggest that the internal energy is less sensitive to mistakes than is {delta}{sub 3}, and thus the internal energy can serve as a addition to the tool kit for evaluating experimental spectra.

  7. Thermodynamics of nuclear transport

    NASA Astrophysics Data System (ADS)

    Wang, Ching-Hao; Mehta, Pankaj; Elbaum, Michael

    Molecular transport across the nuclear envelope is important for eukaryotes for gene expression and signaling. Experimental studies have revealed that nuclear transport is inherently a nonequilibrium process and actively consumes energy. In this work we present a thermodynamics theory of nuclear transport for a major class of nuclear transporters that are mediated by the small GTPase Ran. We identify the molecular elements responsible for powering nuclear transport, which we term the ``Ran battery'' and find that the efficiency of transport, measured by the cargo nuclear localization ratio, is limited by competition between cargo molecules and RanGTP to bind transport receptors, as well as the amount of NTF2 (i.e. RanGDP carrier) available to circulate the energy flow. This picture complements our current understanding of nuclear transport by providing a comprehensive thermodynamics framework to decipher the underlying biochemical machinery. Pm and CHW were supported by a Simons Investigator in the Mathematical Modeling in Living Systems grant (to PM).

  8. Advances in computational solvation thermodynamics

    NASA Astrophysics Data System (ADS)

    Wyczalkowski, Matthew A.

    The aim of this thesis is to develop improved methods for calculating the free energy, entropy and enthalpy of solvation from molecular simulations. Solvation thermodynamics of model compounds provides quantitative measurements used to analyze the stability of protein conformations in aqueous milieus. Solvation free energies govern the favorability of the solvation process, while entropy and enthalpy decompositions give insight into the molecular mechanisms by which the process occurs. Computationally, a coupling parameter lambda modulates solute-solvent interactions to simulate an insertion process, and multiple lengthy simulations at a fixed lambda value are typically required for free energy calculations to converge; entropy and enthalpy decompositions generally take 10-100 times longer. This thesis presents three advances which accelerate the convergence of such calculations: (1) Development of entropy and enthalpy estimators which combine data from multiple simulations; (2) Optimization of lambda schedules, or the set of parameter values associated with each simulation; (3) Validation of Hamiltonian replica exchange, a technique which swaps lambda values between two otherwise independent simulations. Taken together, these techniques promise to increase the accuracy and precision of free energy, entropy and enthalpy calculations. Improved estimates, in turn, can be used to investigate the validity and limits of existing solvation models and refine force field parameters, with the goal of understanding better the collapse transition and aggregation behavior of polypeptides.

  9. Contact symmetries and Hamiltonian thermodynamics

    SciTech Connect

    Bravetti, A.; Lopez-Monsalvo, C.S.; Nettel, F.

    2015-10-15

    It has been shown that contact geometry is the proper framework underlying classical thermodynamics and that thermodynamic fluctuations are captured by an additional metric structure related to Fisher’s Information Matrix. In this work we analyse several unaddressed aspects about the application of contact and metric geometry to thermodynamics. We consider here the Thermodynamic Phase Space and start by investigating the role of gauge transformations and Legendre symmetries for metric contact manifolds and their significance in thermodynamics. Then we present a novel mathematical characterization of first order phase transitions as equilibrium processes on the Thermodynamic Phase Space for which the Legendre symmetry is broken. Moreover, we use contact Hamiltonian dynamics to represent thermodynamic processes in a way that resembles the classical Hamiltonian formulation of conservative mechanics and we show that the relevant Hamiltonian coincides with the irreversible entropy production along thermodynamic processes. Therefore, we use such property to give a geometric definition of thermodynamically admissible fluctuations according to the Second Law of thermodynamics. Finally, we show that the length of a curve describing a thermodynamic process measures its entropy production.

  10. Spacecraft attitude determination accuracy from mission experience

    NASA Technical Reports Server (NTRS)

    Brasoveanu, D.; Hashmall, J.

    1994-01-01

    This paper summarizes a compilation of attitude determination accuracies attained by a number of satellites supported by the Goddard Space Flight Center Flight Dynamics Facility. The compilation is designed to assist future mission planners in choosing and placing attitude hardware and selecting the attitude determination algorithms needed to achieve given accuracy requirements. The major goal of the compilation is to indicate realistic accuracies achievable using a given sensor complement based on mission experience. It is expected that the use of actual spacecraft experience will make the study especially useful for mission design. A general description of factors influencing spacecraft attitude accuracy is presented. These factors include determination algorithms, inertial reference unit characteristics, and error sources that can affect measurement accuracy. Possible techniques for mitigating errors are also included. Brief mission descriptions are presented with the attitude accuracies attained, grouped by the sensor pairs used in attitude determination. The accuracies for inactive missions represent a compendium of missions report results, and those for active missions represent measurements of attitude residuals. Both three-axis and spin stabilized missions are included. Special emphasis is given to high-accuracy sensor pairs, such as two fixed-head star trackers (FHST's) and fine Sun sensor plus FHST. Brief descriptions of sensor design and mode of operation are included. Also included are brief mission descriptions and plots summarizing the attitude accuracy attained using various sensor complements.

  11. Statistical Thermodynamics and Microscale Thermophysics

    NASA Astrophysics Data System (ADS)

    Carey, Van P.

    1999-08-01

    Many exciting new developments in microscale engineering are based on the application of traditional principles of statistical thermodynamics. In this text Van Carey offers a modern view of thermodynamics, interweaving classical and statistical thermodynamic principles and applying them to current engineering systems. He begins with coverage of microscale energy storage mechanisms from a quantum mechanics perspective and then develops the fundamental elements of classical and statistical thermodynamics. Subsequent chapters discuss applications of equilibrium statistical thermodynamics to solid, liquid, and gas phase systems. The remainder of the book is devoted to nonequilibrium thermodynamics of transport phenomena and to nonequilibrium effects and noncontinuum behavior at the microscale. Although the text emphasizes mathematical development, Carey includes many examples and exercises to illustrate how the theoretical concepts are applied to systems of scientific and engineering interest. In the process he offers a fresh view of statistical thermodynamics for advanced undergraduate and graduate students, as well as practitioners, in mechanical, chemical, and materials engineering.

  12. The discovery of thermodynamics

    NASA Astrophysics Data System (ADS)

    Weinberger, Peter

    2013-07-01

    Based on the idea that a scientific journal is also an "agora" (Greek: market place) for the exchange of ideas and scientific concepts, the history of thermodynamics between 1800 and 1910 as documented in the Philosophical Magazine Archives is uncovered. Famous scientists such as Joule, Thomson (Lord Kelvin), Clausius, Maxwell or Boltzmann shared this forum. Not always in the most friendly manner. It is interesting to find out, how difficult it was to describe in a scientific (mathematical) language a phenomenon like "heat", to see, how long it took to arrive at one of the fundamental principles in physics: entropy. Scientific progress started from the simple rule of Boyle and Mariotte dating from the late eighteenth century and arrived in the twentieth century with the concept of probabilities. Thermodynamics was the driving intellectual force behind the industrial revolution, behind the enormous social changes caused by this revolution. The history of thermodynamics is a fascinating story, which also gives insights into the mechanism that seem to govern science.

  13. Nonequilibrium thermodynamics of nucleation

    SciTech Connect

    Schweizer, M.; Sagis, L. M. C.

    2014-12-14

    We present a novel approach to nucleation processes based on the GENERIC framework (general equation for the nonequilibrium reversible-irreversible coupling). Solely based on the GENERIC structure of time-evolution equations and thermodynamic consistency arguments of exchange processes between a metastable phase and a nucleating phase, we derive the fundamental dynamics for this phenomenon, based on continuous Fokker-Planck equations. We are readily able to treat non-isothermal nucleation even when the nucleating cores cannot be attributed intensive thermodynamic properties. In addition, we capture the dynamics of the time-dependent metastable phase being continuously expelled from the nucleating phase, and keep rigorous track of the volume corrections to the dynamics. Within our framework the definition of a thermodynamic nuclei temperature is manifest. For the special case of nucleation of a gas phase towards its vapor-liquid coexistence, we illustrate that our approach is capable of reproducing recent literature results obtained by more microscopic considerations for the suppression of the nucleation rate due to nonisothermal effects.

  14. Accuracy potentials for large space antenna structures

    NASA Technical Reports Server (NTRS)

    Hedgepeth, J. M.

    1980-01-01

    The relationships among materials selection, truss design, and manufacturing techniques in the interest of surface accuracies for large space antennas are discussed. Among the antenna configurations considered are: tetrahedral truss, pretensioned truss, and geodesic dome and radial rib structures. Comparisons are made of the accuracy achievable by truss and dome structure types for a wide variety of diameters, focal lengths, and wavelength of radiated signal, taking into account such deforming influences as solar heating-caused thermal transients and thermal gradients.

  15. Thermodynamic Model of Aluminum Combustion in SDF Explosions

    SciTech Connect

    Kuhl, . L

    2006-06-19

    Thermodynamic states encountered during combustion of Aluminum powder in Shock-Dispersed-Fuel (SDF) explosions were analyzed with the Cheetah code. Results are displayed in the Le Chatelier diagram: the locus of states of specific internal energy versus temperature. Accuracy of the results was confirmed by comparing the fuel and products curves with the heats of detonation and combustion, and species composition as measured in bomb calorimeter experiments. Results were fit with analytic functions u = f(T) suitable for specifying the thermodynamic properties required for gas-dynamic models of combustion in explosions.

  16. Actinide thermodynamic predictions. 3. Thermodynamics of compounds and aquo ions of the 2+, 3+ and 4+ oxidation states and standard electrode potentials at 298. 15 K

    SciTech Connect

    Bratsch, S.G.; Lagowski, J.J.

    1986-01-16

    A modified ionic model is applied to selected actinide thermodynamic measurements to allow the evaluation of gas-phase ion thermodynamics across the actinide series. These are used to predict the thermodynamic properties of a number of actinide compounds and aquo ions at 298.15 K. General guidelines are offered for predicting the relative stabilities of actinide(II), -(III), and -(IV) compounds in various chemical environments. 40 references, 6 figures, 8 tables.

  17. Thermodynamics of Thermoelectric Materials

    NASA Astrophysics Data System (ADS)

    Doak, Jeff W.

    One challenge facing society is the responsible use of our energy resources. Increasing the efficiency of energy generation provides one path to solving this challenge. One commonality among most current energy generation methods is that waste heat is generated during the generation process. Thermoelectrics can provide a solution to increasing the efficiency of power generation and automotive systems by converting waste heat directly to electricity. The current barrier to implementation of thermoelectric systems is the low efficiencies of underlying thermoelectric materials. The efficiency of a thermoelectric material depends on the electronic and thermal transport properties of the material; a good thermoelectric material should be an electronic conductor and a thermal insulator, traits which generally oppose one another. The thermal properties of a thermoelectric material can be improved by forming nanoscale precipitates with the material which scatter phonons, reducing the thermal conductivity. The electronic properties of a thermoelectric material can be improved by doping the material to increase the electronic conductivity or by alloying the material to favorably alter its band structure. The ability of these chemical modifications to affect the thermoelectric efficiency of material are ultimately governed by the chemical thermodynamics of the system. PbTe is a prototypical thermoelectric material: Alloying PbTe with PbS (or other materials) creates nanostructures which scatter phonons and reduce the lattice thermal conductivity. Doping PbTe with Na increases the hole concentration, increasing the electronic conductivity. In this work, we investigate the thermodynamics of PbTe and similar systems using first principles to understand the underlying mechanisms controlling the formation of nanostructures and the amount of doping allowed in these systems. In this work we: 1) investigate the thermodynamics of pseudo-binary alloys of IV--VI systems to identify the

  18. Thermodynamic properties of selected uranium compounds and aqueous species at 298.15 K and 1 bar and at higher temperatures; preliminary models for the origin of coffinite deposits

    USGS Publications Warehouse

    Hemingway, B.S.

    1982-01-01

    Thermodynamic values for 110 uranium-bearing phases and 28 aqueous uranium solution species (298.15 K and l bar) are tabulated based upon evaluated experimental data (largely from calorimetric experiments) and estimated values. Molar volume data are given for most of the solid phases. Thermodynamic values for 16 uranium-bearing phases are presented for higher temperatures in the form of and as a supplement to U.S. Geological Survey Bulletin 1452 (Robie et al., 1979). The internal consistency of the thermodynamic values reported herein is dependent upon the reliability of the experimental results for several uranium phases that have been used as secondary calorimetric reference phases. The data for the reference phases and for those phases evaluated with respect to the secondary reference phases are discussed. A preliminary model for coffinite formation has been proposed together with an estimate of the free energy of formation of coffinite. Free energy values are estimated for several other uranium-bearing silicate phases that have been reported as secondary uranium phases associated with uranium ore deposits and that could be expected to develop wherever uranium is leached by groundwaters.

  19. RNA Thermodynamic Structural Entropy

    PubMed Central

    Garcia-Martin, Juan Antonio; Clote, Peter

    2015-01-01

    Conformational entropy for atomic-level, three dimensional biomolecules is known experimentally to play an important role in protein-ligand discrimination, yet reliable computation of entropy remains a difficult problem. Here we describe the first two accurate and efficient algorithms to compute the conformational entropy for RNA secondary structures, with respect to the Turner energy model, where free energy parameters are determined from UV absorption experiments. An algorithm to compute the derivational entropy for RNA secondary structures had previously been introduced, using stochastic context free grammars (SCFGs). However, the numerical value of derivational entropy depends heavily on the chosen context free grammar and on the training set used to estimate rule probabilities. Using data from the Rfam database, we determine that both of our thermodynamic methods, which agree in numerical value, are substantially faster than the SCFG method. Thermodynamic structural entropy is much smaller than derivational entropy, and the correlation between length-normalized thermodynamic entropy and derivational entropy is moderately weak to poor. In applications, we plot the structural entropy as a function of temperature for known thermoswitches, such as the repression of heat shock gene expression (ROSE) element, we determine that the correlation between hammerhead ribozyme cleavage activity and total free energy is improved by including an additional free energy term arising from conformational entropy, and we plot the structural entropy of windows of the HIV-1 genome. Our software RNAentropy can compute structural entropy for any user-specified temperature, and supports both the Turner’99 and Turner’04 energy parameters. It follows that RNAentropy is state-of-the-art software to compute RNA secondary structure conformational entropy. Source code is available at https://github.com/clotelab/RNAentropy/; a full web server is available at http

  20. RNA Thermodynamic Structural Entropy.

    PubMed

    Garcia-Martin, Juan Antonio; Clote, Peter

    2015-01-01

    Conformational entropy for atomic-level, three dimensional biomolecules is known experimentally to play an important role in protein-ligand discrimination, yet reliable computation of entropy remains a difficult problem. Here we describe the first two accurate and efficient algorithms to compute the conformational entropy for RNA secondary structures, with respect to the Turner energy model, where free energy parameters are determined from UV absorption experiments. An algorithm to compute the derivational entropy for RNA secondary structures had previously been introduced, using stochastic context free grammars (SCFGs). However, the numerical value of derivational entropy depends heavily on the chosen context free grammar and on the training set used to estimate rule probabilities. Using data from the Rfam database, we determine that both of our thermodynamic methods, which agree in numerical value, are substantially faster than the SCFG method. Thermodynamic structural entropy is much smaller than derivational entropy, and the correlation between length-normalized thermodynamic entropy and derivational entropy is moderately weak to poor. In applications, we plot the structural entropy as a function of temperature for known thermoswitches, such as the repression of heat shock gene expression (ROSE) element, we determine that the correlation between hammerhead ribozyme cleavage activity and total free energy is improved by including an additional free energy term arising from conformational entropy, and we plot the structural entropy of windows of the HIV-1 genome. Our software RNAentropy can compute structural entropy for any user-specified temperature, and supports both the Turner'99 and Turner'04 energy parameters. It follows that RNAentropy is state-of-the-art software to compute RNA secondary structure conformational entropy. Source code is available at https://github.com/clotelab/RNAentropy/; a full web server is available at http

  1. Interfacial solvation thermodynamics.

    PubMed

    Ben-Amotz, Dor

    2016-10-19

    Previous studies have reached conflicting conclusions regarding the interplay of cavity formation, polarizability, desolvation, and surface capillary waves in driving the interfacial adsorptions of ions and molecules at air-water interfaces. Here we revisit these questions by combining exact potential distribution results with linear response theory and other physically motivated approximations. The results highlight both exact and approximate compensation relations pertaining to direct (solute-solvent) and indirect (solvent-solvent) contributions to adsorption thermodynamics, of relevance to solvation at air-water interfaces, as well as a broader class of processes linked to the mean force potential between ions, molecules, nanoparticles, proteins, and biological assemblies. PMID:27545849

  2. Stochastic thermodynamics of resetting

    NASA Astrophysics Data System (ADS)

    Fuchs, Jaco; Goldt, Sebastian; Seifert, Udo

    2016-03-01

    Stochastic dynamics with random resetting leads to a non-equilibrium steady state. Here, we consider the thermodynamics of resetting by deriving the first and second law for resetting processes far from equilibrium. We identify the contributions to the entropy production of the system which arise due to resetting and show that they correspond to the rate with which information is either erased or created. Using Landauer's principle, we derive a bound on the amount of work that is required to maintain a resetting process. We discuss different regimes of resetting, including a Maxwell demon scenario where heat is extracted from a bath at constant temperature.

  3. Interfacial solvation thermodynamics

    NASA Astrophysics Data System (ADS)

    Ben-Amotz, Dor

    2016-10-01

    Previous studies have reached conflicting conclusions regarding the interplay of cavity formation, polarizability, desolvation, and surface capillary waves in driving the interfacial adsorptions of ions and molecules at air-water interfaces. Here we revisit these questions by combining exact potential distribution results with linear response theory and other physically motivated approximations. The results highlight both exact and approximate compensation relations pertaining to direct (solute-solvent) and indirect (solvent-solvent) contributions to adsorption thermodynamics, of relevance to solvation at air-water interfaces, as well as a broader class of processes linked to the mean force potential between ions, molecules, nanoparticles, proteins, and biological assemblies.

  4. Thermodynamics of paracrystalline silicon

    SciTech Connect

    Voyles, P. M.; Treacy, M. M. J.; Gibson, J. M.

    2000-05-09

    Fluctuation microscopy experiments have shown that the as-deposited structure of amorphous silicon thin films is paracrystalline. A paracrystal consists of small (< 3 nm in diameter) topologically crystalline grains separated by a disordered matrix. Here the authors consider the thermodynamics of paracrystalline silicon as a function of the grain size and the temperature. They offer a simple model that qualitatively explains the observed metastability of the ordered structure at low temperature (300 K), the relaxation towards a more disordered structure at intermediate temperatures (600 K), and the recrystallization at high temperatures (1,000 K).

  5. Dynamics versus thermodynamics

    NASA Astrophysics Data System (ADS)

    Berdichevsky, V. L.

    1991-05-01

    An effort is made to characterize the ways in which the approaches of statistical mechanics and thermodynamics can be useful in the study of the dynamic behavior of structures. This meditation proceeds through consideration of such wide-ranging and deliberately provocative questions as: 'What are to be considered values in a stress-distribution function?' and 'How many degrees-of-freedom has a beam?'; it then gives attention to the hierarchy of vibrations, the interaction of the mechanism of dissipation with invisible degrees of freedom, and a plausible view of vibrations for the case of small dissipation.

  6. Thermodynamics of Rubber Elasticity

    NASA Astrophysics Data System (ADS)

    Pellicer, J.; Manzanares, J. A.; Zúñiga, J.; Utrillas, P.; Fernández, J.

    2001-02-01

    A thermodynamic study of an isotropic rubber band under uniaxial stress is presented on the basis of its equation of state. The behavior of the rubber band is compared with both that of an ideal elastomer and that of an ideal gas, considering the generalized Joule's law as the ideality criterion. First, the thermal expansion of rubber at constant stress and the change in the stress with temperature at constant length are described. Thermoelastic inversion is then considered, and the experimental observations are easily rationalized. Finally, the temperature changes observed in the adiabatic stretching of a rubber band are evaluated from the decrease of entropy with length.

  7. On thermodynamic and microscopic reversibility

    SciTech Connect

    Crooks, Gavin E.

    2011-07-12

    The word 'reversible' has two (apparently) distinct applications in statistical thermodynamics. A thermodynamically reversible process indicates an experimental protocol for which the entropy change is zero, whereas the principle of microscopic reversibility asserts that the probability of any trajectory of a system through phase space equals that of the time reversed trajectory. However, these two terms are actually synonymous: a thermodynamically reversible process is microscopically reversible, and vice versa.

  8. Thermodynamics of Accelerating Black Holes

    NASA Astrophysics Data System (ADS)

    Appels, Michael; Gregory, Ruth; KubizÅák, David

    2016-09-01

    We address a long-standing problem of describing the thermodynamics of an accelerating black hole. We derive a standard first law of black hole thermodynamics, with the usual identification of entropy proportional to the area of the event horizon—even though the event horizon contains a conical singularity. This result not only extends the applicability of black hole thermodynamics to realms previously not anticipated, it also opens a possibility for studying novel properties of an important class of exact radiative solutions of Einstein equations describing accelerated objects. We discuss the thermodynamic volume, stability, and phase structure of these black holes.

  9. Predictive thermodynamics for condensed phases.

    PubMed

    Glasser, Leslie; Jenkins, H Donald Brooke

    2005-10-01

    Thermodynamic information is central to assessment of the stability and reactivity of materials. However, because of both the demanding nature of experimental thermodynamics and the virtually unlimited number of conceivable compounds, experimental data is often unavailable or, for hypothetical materials, necessarily impossible to obtain. We describe simple procedures for thermodynamic prediction for condensed phases, both ionic and organic covalent, principally via formula unit volumes (or density); our volume-based approach (VBT) provides a new thermodynamic tool for such assessment. These methods, being independent of detailed knowledge of crystal structures, are applicable to liquids and amorphous materials as well as to crystalline solids. Examples of their use are provided. PMID:16172676

  10. Thermodynamics of Error Correction

    NASA Astrophysics Data System (ADS)

    Sartori, Pablo; Pigolotti, Simone

    2015-10-01

    Information processing at the molecular scale is limited by thermal fluctuations. This can cause undesired consequences in copying information since thermal noise can lead to errors that can compromise the functionality of the copy. For example, a high error rate during DNA duplication can lead to cell death. Given the importance of accurate copying at the molecular scale, it is fundamental to understand its thermodynamic features. In this paper, we derive a universal expression for the copy error as a function of entropy production and work dissipated by the system during wrong incorporations. Its derivation is based on the second law of thermodynamics; hence, its validity is independent of the details of the molecular machinery, be it any polymerase or artificial copying device. Using this expression, we find that information can be copied in three different regimes. In two of them, work is dissipated to either increase or decrease the error. In the third regime, the protocol extracts work while correcting errors, reminiscent of a Maxwell demon. As a case study, we apply our framework to study a copy protocol assisted by kinetic proofreading, and show that it can operate in any of these three regimes. We finally show that, for any effective proofreading scheme, error reduction is limited by the chemical driving of the proofreading reaction.

  11. Thermodynamics of geothermal fluids

    SciTech Connect

    Rogers, P.S.Z.

    1981-03-01

    A model to predict the thermodynamic properties of geothermal brines, based on a minimum amount of experimental data on a few key systems, is tested. Volumetric properties of aqueous sodium chloride, taken from the literature, are represented by a parametric equation over the range 0 to 300{sup 0}C and 1 bar to 1 kbar. Density measurements at 20 bar needed to complete the volumetric description also are presented. The pressure dependence of activity and thermal properties, derived from the volumetric equation, can be used to complete an equation of state for sodium chloride solutions. A flow calorimeter, used to obtain heat capacity data at high temperatures and pressures, is described. Heat capacity measurements, from 30 to 200{sup 0}C and 1 bar to 200 bar, are used to derive values for the activity coefficient and other thermodynamic properties of sodium sulfate solutions as a function of temperature. Literature data on the solubility of gypsum in mixed electrolyte solutions have been used to evaluate model parameters for calculating gypsum solubility in seawater and natural brines. Predictions of strontium and barium sulfate solubility in seawater also are given.

  12. Thermodynamics. [algebraic structure

    NASA Technical Reports Server (NTRS)

    Zeleznik, F. J.

    1976-01-01

    The fundamental structure of thermodynamics is purely algebraic, in the sense of atopological, and it is also independent of partitions, composite systems, the zeroth law, and entropy. The algebraic structure requires the notion of heat, but not the first law. It contains a precise definition of entropy and identifies it as a purely mathematical concept. It also permits the construction of an entropy function from heat measurements alone when appropriate conditions are satisfied. Topology is required only for a discussion of the continuity of thermodynamic properties, and then the weak topology is the relevant topology. The integrability of the differential form of the first law can be examined independently of Caratheodory's theorem and his inaccessibility axiom. Criteria are established by which one can determine when an integrating factor can be made intensive and the pseudopotential extensive and also an entropy. Finally, a realization of the first law is constructed which is suitable for all systems whether they are solids or fluids, whether they do or do not exhibit chemical reactions, and whether electromagnetic fields are or are not present.

  13. Thermodynamics of diffusion

    NASA Astrophysics Data System (ADS)

    Matuszak, Daniel

    Diffusion is the migration of molecules in the reference frame of a system's center of mass and it is a physical process that occurs in all chemical and biological systems. Diffusion generally involves intermolecular interactions that lead to clustering, adsorption, and phase transitions; as such, it is difficult to describe theoretically on a molecular level in systems containing both intermolecular repulsions and attractions. This work describes a simple thermodynamic approach that accounts for intermolecular attractions and repulsions (much like how the van der Waals equation does) to model and help provide an understanding of diffusion. The approach is an extension of the equilibrium Lattice Density Functional Theory of Aranovich and Donohue; it was developed with Mason and Lonsdale's guidelines on how to construct and test a transport theory. In the framework of lattice fluids, this new approach gives (a) correct equilibrium limits, (b) Fickian behavior for non-interacting systems, (c) correct departures from Fickian behavior in non-ideal systems, (d) the correct Maxwell-Stefan formulation, (e) symmetry behavior upon re-labeling species, (f) reasonable non-equilibrium phase behavior, (g) agreement with Molecular Dynamics simulations, (h) agreement with the theory of non-equilibrium thermodynamics, (i) a vanishing diffusive flux at the critical point, and (j) other qualitatively-correct behaviors when applied to problems in porous membranes and in packed beds.

  14. Biochemical Thermodynamics under near Physiological Conditions

    ERIC Educational Resources Information Center

    Mendez, Eduardo

    2008-01-01

    The recommendations for nomenclature and tables in Biochemical Thermodynamics approved by IUBMB and IUPAC in 1994 can be easily introduced after the chemical thermodynamic formalism. Substitution of the usual standard thermodynamic properties by the transformed ones in the thermodynamic equations, and the use of appropriate thermodynamic tables…

  15. Enzyme-Inhibitor Association Thermodynamics

    PubMed Central

    Resat, Haluk; Marrone, Tami J.; McCammon, J. Andrew

    1997-01-01

    Studying the thermodynamics of biochemical association reactions at the microscopic level requires efficient sampling of the configurations of the reactants and solvent as a function of the reaction pathways. In most cases, the associating ligand and receptor have complementary interlocking shapes. Upon association, loosely connected or disconnected solvent cavities at and around the binding site are formed. Disconnected solvent regions lead to severe statistical sampling problems when simulations are performed with explicit solvent. It was recently proposed that, when such limitations are encountered, they might be overcome by the use of the grand canonical ensemble. Here we investigate one such case and report the association free energy profile (potential of mean force) between trypsin and benzamidine along a chosen reaction coordinate as calculated using the grand canonical Monte Carlo method. The free energy profile is also calculated for a continuum solvent model using the Poisson equation, and the results are compared to the explicit water simulations. The comparison shows that the continuum solvent approach is surprisingly successful in reproducing the explicit solvent simulation results. The Monte Carlo results are analyzed in detail with respect to solvation structure. In the binding site channel there are waters bridging the carbonyl oxygen groups of Asp189 with the NH2 groups of benzamidine, which are displaced upon inhibitor binding. A similar solvent-bridging configuration has been seen in the crystal structure of trypsin complexed with bovine pancreatic trypsin inhibitor. The predicted locations of other internal waters are in very good agreement with the positions found in the crystal structures, which supports the accuracy of the simulations. ImagesFIGURE 5 PMID:9017183

  16. Quantum chemical approach to estimating the thermodynamics of metabolic reactions.

    PubMed

    Jinich, Adrian; Rappoport, Dmitrij; Dunn, Ian; Sanchez-Lengeling, Benjamin; Olivares-Amaya, Roberto; Noor, Elad; Even, Arren Bar; Aspuru-Guzik, Alán

    2014-11-12

    Thermodynamics plays an increasingly important role in modeling and engineering metabolism. We present the first nonempirical computational method for estimating standard Gibbs reaction energies of metabolic reactions based on quantum chemistry, which can help fill in the gaps in the existing thermodynamic data. When applied to a test set of reactions from core metabolism, the quantum chemical approach is comparable in accuracy to group contribution methods for isomerization and group transfer reactions and for reactions not including multiply charged anions. The errors in standard Gibbs reaction energy estimates are correlated with the charges of the participating molecules. The quantum chemical approach is amenable to systematic improvements and holds potential for providing thermodynamic data for all of metabolism.

  17. Thermodynamics and Spontaneity

    NASA Astrophysics Data System (ADS)

    Ochs, Raymond S.

    1996-10-01

    Despite the importance of thermodynamics as the foundation of chemistry, most students emerge from introductory courses with only a dim understanding of this subject. Generally students recognize that the information is significant, yet do not assimilate it into later studies, especially in applied fields such as biology and biochemistry. A clear sense of the problem is reflected in a number of other contributions to this Journal (e.g., 1 - 6). Most (1 - 4, 6) recommend increased rigor in derivation of equations. This may appeal to students in advanced courses in chemical thermodynamics, but not to most. A few other suggestions are to introduce the subject earlier in general chemistry courses (2) or to provide innovative ways to visualize reaction changes (3). I suggest that the problem lies at another level entirely: the meanings of the terms are not clear. Recently, MacNeal (7) introduced the concept of mathsemantics, the joining of mathematics with a deep understanding of the sense (semantics) in which it operates. For example, the author argues that not only can we add apples and oranges (yielding total fruit), but that anything less than such a synthesis is trivial. Mathematics is hard, not because of the actual mathematical part of the problem but because of the semantics. As discussed thoroughly by Weinburg (8), the very names we affix to ideas dominate how we think about them. A similar reorientation would benefit chemical education. By way of example, the word "spontaneous" is widely used in thermodynamics, presumably because the word is familiar and assists understanding of this subject. In the following, I will provide evidence that this word has contributed more to the obfuscation of chemical ideas than it has helped elucidate them. Literature Cited 1. Redlich, O. J. Chem. Educ. 1975, 52, 374 - 376. 2. Bergquist, W.; Heikkinen, H. J. Chem. Educ. 1990, 67, 1000 - 1003. 3. Macomber, R. S. J. Chem. Educ. 1994, 71, 311 - 312. 4. Sanchez, K. S.; Vergenz, R

  18. New Horizons in Thermodynamics

    NASA Astrophysics Data System (ADS)

    Hayward, Geoffrey Gordon

    1991-02-01

    This thesis collects five papers which treat the theory of horizon thermodynamics and its applications to cosmology. In the first paper I consider general, spherically symmetric spacetimes with cosmological and black hole horizons. I find that a state of thermal equilibrium may exist in classical manifolds with two horizons so long as a matter distribution is present. I calculate the Euclidean action for non-classical manifolds with and without boundary and relate it to the grand canonical weighting factor. I find that the mean thermal energy of the cosmological horizon is negative. In the second paper I derive the first law of thermodynamics for bounded, static, spherically symmetric spacetimes which include a matter distribution and either a black hole or cosmological horizon. I calculate heat capacities associated with matter/horizon systems and find that they may be positive or negative depending on the matter configuration. I discuss the case in which the cosmological constant is allowed to vary and conclude that the Hawking/Coleman mechanisms for explaining the low value of the cosmological constant are not well formulated. In the third paper, co-authored by Jorma Louko, we analyze variational principles for non-smooth metrics. These principles give insight to the problem of constructing minisuperspace path integrals in horizon statistical mechanics and quantum cosmology. We demonstrate that smoothness conditions can be derived from the variational principle as equations of motion. We suggest a new prescription for minisuperspace path integrals on the manifold | D times S^2. In the fourth paper, I examine the contribution of the horizon energy density to black hole temperature. I show the existence of positive heat capacity solutions in the small mass regime. In the fifth paper, co-authored by Diego Pavon we investigate the role of primordial black holes in the very early universe under SU(3) times SU(2) times U (1), SU(5), and their supersymmetric

  19. Computing the Free Energy Barriers for Less by Sampling with a Coarse Reference Potential while Retaining Accuracy of the Target Fine Model.

    PubMed

    Plotnikov, Nikolay V

    2014-08-12

    Proposed in this contribution is a protocol for calculating fine-physics (e.g., ab initio QM/MM) free-energy surfaces at a high level of accuracy locally (e.g., only at reactants and at the transition state for computing the activation barrier) from targeted fine-physics sampling and extensive exploratory coarse-physics sampling. The full free-energy surface is still computed but at a lower level of accuracy from coarse-physics sampling. The method is analytically derived in terms of the umbrella sampling and the free-energy perturbation methods which are combined with the thermodynamic cycle and the targeted sampling strategy of the paradynamics approach. The algorithm starts by computing low-accuracy fine-physics free-energy surfaces from the coarse-physics sampling in order to identify the reaction path and to select regions for targeted sampling. Thus, the algorithm does not rely on the coarse-physics minimum free-energy reaction path. Next, segments of high-accuracy free-energy surface are computed locally at selected regions from the targeted fine-physics sampling and are positioned relative to the coarse-physics free-energy shifts. The positioning is done by averaging the free-energy perturbations computed with multistep linear response approximation method. This method is analytically shown to provide results of the thermodynamic integration and the free-energy interpolation methods, while being extremely simple in implementation. Incorporating the metadynamics sampling to the algorithm is also briefly outlined. The application is demonstrated by calculating the B3LYP//6-31G*/MM free-energy barrier for an enzymatic reaction using a semiempirical PM6/MM reference potential. These modifications allow computing the activation free energies at a significantly reduced computational cost but at the same level of accuracy compared to computing full potential of mean force.

  20. Optimal design of robot accuracy compensators

    SciTech Connect

    Zhuang, H.; Roth, Z.S. . Robotics Center and Electrical Engineering Dept.); Hamano, Fumio . Dept. of Electrical Engineering)

    1993-12-01

    The problem of optimal design of robot accuracy compensators is addressed. Robot accuracy compensation requires that actual kinematic parameters of a robot be previously identified. Additive corrections of joint commands, including those at singular configurations, can be computed without solving the inverse kinematics problem for the actual robot. This is done by either the damped least-squares (DLS) algorithm or the linear quadratic regulator (LQR) algorithm, which is a recursive version of the DLS algorithm. The weight matrix in the performance index can be selected to achieve specific objectives, such as emphasizing end-effector's positioning accuracy over orientation accuracy or vice versa, or taking into account proximity to robot joint travel limits and singularity zones. The paper also compares the LQR and the DLS algorithms in terms of computational complexity, storage requirement, and programming convenience. Simulation results are provided to show the effectiveness of the algorithms.

  1. Thermodynamics from Car to Kitchen

    ERIC Educational Resources Information Center

    Auty, Geoff

    2014-01-01

    The historical background to the laws of thermodynamics is explained using examples we can all observe in the world around us, focusing on motorised transport, refrigeration and solar heating. This is not to be considered as an academic article. The purpose is to improve understanding of thermodynamics rather than impart new knowledge, and for…

  2. Thermodynamic analysis of conductive filaments

    NASA Astrophysics Data System (ADS)

    Karpov, V.; Niraula, D.; Karpov, I.

    2016-08-01

    We present a thermodynamic theory of the conductive filament growth and dissolution in random access memory describing the observed features of their current-voltage (IV) characteristics. Our theory is based on the self-consisted Fokker-Planck approach reducing the filament kinetics to its thermodynamics. Expressing the observed IV features through material parameters, our results pave a way to device improvements.

  3. Thermodynamics--A Practical Subject.

    ERIC Educational Resources Information Center

    Jones, Hugh G.

    1984-01-01

    Provides a simplified, synoptic overview of the area of thermodynamics, enumerating and explaining the four basic laws, and introducing the mathematics involved in a stepwise fashion. Discusses such basic tools of thermodynamics as enthalpy, entropy, Helmholtz free energy, and Gibbs free energy, and their uses in problem solving. (JM)

  4. Ch. 33 Modeling: Computational Thermodynamics

    SciTech Connect

    Besmann, Theodore M

    2012-01-01

    This chapter considers methods and techniques for computational modeling for nuclear materials with a focus on fuels. The basic concepts for chemical thermodynamics are described and various current models for complex crystalline and liquid phases are illustrated. Also included are descriptions of available databases for use in chemical thermodynamic studies and commercial codes for performing complex equilibrium calculations.

  5. High Accuracy Fuel Flowmeter, Phase 1

    NASA Technical Reports Server (NTRS)

    Mayer, C.; Rose, L.; Chan, A.; Chin, B.; Gregory, W.

    1983-01-01

    Technology related to aircraft fuel mass - flowmeters was reviewed to determine what flowmeter types could provide 0.25%-of-point accuracy over a 50 to one range in flowrates. Three types were selected and were further analyzed to determine what problem areas prevented them from meeting the high accuracy requirement, and what the further development needs were for each. A dual-turbine volumetric flowmeter with densi-viscometer and microprocessor compensation was selected for its relative simplicity and fast response time. An angular momentum type with a motor-driven, spring-restrained turbine and viscosity shroud was selected for its direct mass-flow output. This concept also employed a turbine for fast response and a microcomputer for accurate viscosity compensation. The third concept employed a vortex precession volumetric flowmeter and was selected for its unobtrusive design. Like the turbine flowmeter, it uses a densi-viscometer and microprocessor for density correction and accurate viscosity compensation.

  6. Thermodynamics and cement science

    SciTech Connect

    Damidot, D.; Lothenbach, B.; Herfort, D.; Glasser, F.P.

    2011-07-15

    Thermodynamics applied to cement science has proved to be very valuable. One of the most striking findings has been the extent to which the hydrate phases, with one conspicuous exception, achieve equilibrium. The important exception is the persistence of amorphous C-S-H which is metastable with respect to crystalline calcium silicate hydrates. Nevertheless C-S-H can be included in the scope of calculations. As a consequence, from comparison of calculation and experiment, it appears that kinetics is not necessarily an insuperable barrier to engineering the phase composition of a hydrated Portland cement. Also the sensitivity of the mineralogy of the AFm and AFt phase compositions to the presence of calcite and to temperature has been reported. This knowledge gives a powerful incentive to develop links between the mineralogy and engineering properties of hydrated cement paste and, of course, anticipates improvements in its performance leading to decreasing the environmental impacts of cement production.

  7. The thermodynamic brain.

    PubMed

    Donnelly, Joseph; Czosnyka, Marek

    2014-01-01

    Apart from its complex functionality, the brain is a robust thermodynamic machine; the tissue metabolic rate is high and it is thermally shielded by a skull. Therefore, if there is no high-volume blood flow to cool and stabilize the brain temperature, the possibility of unstable behavior seems to be high. Inflowing arterial blood is normally cooler than the brain tissue temperature, and outflowing venous blood is normally warmer than arterial blood but cooler than the brain tissue. Brain blood flow can thus be understood as a cooler for the brain. Pros and cons of clinical measurement, with clear indication for a multimodal monitoring approach, are discussed along with a brief review of basic facts known about temperature, cerebral blood flow and volume, intracranial pressure, and compartmental compliances of the brain. PMID:25672816

  8. Thermodynamics of Protein Aggregation

    NASA Astrophysics Data System (ADS)

    Osborne, Kenneth L.; Barz, Bogdan; Bachmann, Michael; Strodel, Birgit

    Amyloid protein aggregation characterizes many neurodegenerative disorders, including Alzheimer's, Parkinson's, and Creutz- feldt-Jakob disease. Evidence suggests that amyloid aggregates may share similar aggregation pathways, implying simulation of full-length amyloid proteins is not necessary for understanding amyloid formation. In this study we simulate GNNQQNY, the N-terminal prion-determining domain of the yeast protein Sup35 to investigate the thermodynamics of structural transitions during aggregation. We use a coarse-grained model with replica-exchange molecular dynamics to investigate the association of 3-, 6-, and 12-chain GNNQQNY systems and we determine the aggregation pathway by studying aggregation states of GN- NQQNY. We find that the aggregation of the hydrophilic GNNQQNY sequence is mainly driven by H-bond formation, leading to the formation of /3-sheets from the very beginning of the assembly process. Condensation (aggregation) and ordering take place simultaneously, which is underpinned by the occurrence of a single heat capacity peak only.

  9. Modern problems of thermodynamics

    NASA Astrophysics Data System (ADS)

    Novikov, I. I.

    2012-12-01

    The role of energy and methods of its saving for the development of human society and life are analyzed. The importance of future use of space energy flows and energy of water and air oceans is emphasized. The authors consider the idea of the unit for production of electric energy and pure substances using sodium chloride which reserves are limitless on the planet. Looking retrospectively at the development of power engineering from the elementary fire to modern electric power station, we see that the used method of heat production, namely by direct interaction of fuel and oxidizer, is the simplest. However, it may be possible to combust coal, i.e., carbon in salt melt, for instance, sodium chloride that would be more rational and efficient. If the stated problems are solved positively, we would master all energy properties of the substance; and this is the main problem of thermodynamics being one of the sciences on energy.

  10. A Hamiltonian approach to Thermodynamics

    NASA Astrophysics Data System (ADS)

    Baldiotti, M. C.; Fresneda, R.; Molina, C.

    2016-10-01

    In the present work we develop a strictly Hamiltonian approach to Thermodynamics. A thermodynamic description based on symplectic geometry is introduced, where all thermodynamic processes can be described within the framework of Analytic Mechanics. Our proposal is constructed on top of a usual symplectic manifold, where phase space is even dimensional and one has well-defined Poisson brackets. The main idea is the introduction of an extended phase space where thermodynamic equations of state are realized as constraints. We are then able to apply the canonical transformation toolkit to thermodynamic problems. Throughout this development, Dirac's theory of constrained systems is extensively used. To illustrate the formalism, we consider paradigmatic examples, namely, the ideal, van der Waals and Clausius gases.

  11. Thermodynamic aspects of vitrification.

    PubMed

    Wowk, Brian

    2010-02-01

    Vitrification is a process in which a liquid begins to behave as a solid during cooling without any substantial change in molecular arrangement or thermodynamic state variables. The physical phenomenon of vitrification is relevant to both cryopreservation by freezing, in which cells survive in glass between ice crystals, and cryopreservation by vitrification in which a whole sample is vitrified. The change from liquid to solid behavior is called the glass transition. It is coincident with liquid viscosity reaching 10(13) Poise during cooling, which corresponds to a shear stress relaxation time of several minutes. The glass transition can be understood on a molecular level as a loss of rotational and translational degrees of freedom over a particular measurement timescale, leaving only bond vibration within a fixed molecular structure. Reduced freedom of molecular movement results in decreased heat capacity and thermal expansivity in glass relative to the liquid state. In cryoprotectant solutions, the change from liquid to solid properties happens over a approximately 10 degrees C temperature interval centered on a glass transition temperature, typically near -120 degrees C (+/-10 degrees C) for solutions used for vitrification. Loss of freedom to quickly rearrange molecular position causes liquids to depart from thermodynamic equilibrium as they turn into a glass during vitrification. Residual molecular mobility below the glass transition temperature allows glass to very slowly contract, release heat, and decrease entropy during relaxation toward equilibrium. Although diffusion is practically non-existent below the glass transition temperature, small local movements of molecules related to relaxation have consequences for cryobiology. In particular, ice nucleation in supercooled vitrification solutions occurs at remarkable speed until at least 15 degrees C below the glass transition temperature. PMID:19538955

  12. Thermodynamics of feldspathoid solutions

    NASA Astrophysics Data System (ADS)

    Sack, Richard O.; Ghiorso, Mark S.

    We have developed models for the thermody-namic properties of nephelines, kalsilites, and leucites in the simple system NaAlSiO4-KAlSiO4-Ca0.5AlSiO4-SiO2-H2O that are consistent with all known constraints on subsolidus equilibria and thermodynamic properties, and have integrated them into the existing MELTS software package. The model for nepheline is formulated for the simplifying assumptions that (1) a molecular mixing-type approximation describes changes in the configurational entropy associated with the coupled exchange substitutions □Si?NaAl and □Ca? Na2 and that (2) Na+ and K+ display long-range non-convergent ordering between a large cation and the three small cation sites in the Na4Al4Si4O16 formula unit. Notable features of the model include the prediction that the mineral tetrakalsilite (``panunzite'', sensu stricto) results from anti-ordering of Na and K between the large cation and the three small cation sites in the nepheline structure at high temperatures, an average dT/dP slope of about 55°/kbar for the reaction over the temperature and pressure ranges 800-1050 °C and 500-5000 bars, roughly symmetric (i.e. quadratic) solution behavior of the K-Na substitution along joins between fully ordered components in nepheline, and large positive Gibbs energies for the nepheline reciprocal reactions and and for the leucite reciprocal reaction

  13. High accuracy OMEGA timekeeping

    NASA Technical Reports Server (NTRS)

    Imbier, E. A.

    1982-01-01

    The Smithsonian Astrophysical Observatory (SAO) operates a worldwide satellite tracking network which uses a combination of OMEGA as a frequency reference, dual timing channels, and portable clock comparisons to maintain accurate epoch time. Propagational charts from the U.S. Coast Guard OMEGA monitor program minimize diurnal and seasonal effects. Daily phase value publications of the U.S. Naval Observatory provide corrections to the field collected timing data to produce an averaged time line comprised of straight line segments called a time history file (station clock minus UTC). Depending upon clock location, reduced time data accuracies of between two and eight microseconds are typical.

  14. Fluorination utilizing thermodynamically unstable fluorides and fluoride salts thereof

    SciTech Connect

    Bartlett, Neil; Whalen, J. Marc; Chacon, Lisa

    2000-12-12

    A method for fluorinating a carbon compound or cationic carbon compound utilizes a fluorination agent selected from thermodynamically unstable nickel fluorides and salts thereof in liquid anhydrous hydrogen fluoride. The desired carbon compound or cationic organic compound to undergo fluorination is selected and reacted with the fluorination agent by contacting the selected organic or cationic organic compound and the chosen fluorination agent in a reaction vessel for a desired reaction time period at room temperature or less.

  15. Evaluating the accuracy of SHAPE-directed RNA secondary structure predictions.

    PubMed

    Sükösd, Zsuzsanna; Swenson, M Shel; Kjems, Jørgen; Heitsch, Christine E

    2013-03-01

    Recent advances in RNA structure determination include using data from high-throughput probing experiments to improve thermodynamic prediction accuracy. We evaluate the extent and nature of improvements in data-directed predictions for a diverse set of 16S/18S ribosomal sequences using a stochastic model of experimental SHAPE data. The average accuracy for 1000 data-directed predictions always improves over the original minimum free energy (MFE) structure. However, the amount of improvement varies with the sequence, exhibiting a correlation with MFE accuracy. Further analysis of this correlation shows that accurate MFE base pairs are typically preserved in a data-directed prediction, whereas inaccurate ones are not. Thus, the positive predictive value of common base pairs is consistently higher than the directed prediction accuracy. Finally, we confirm sequence dependencies in the directability of thermodynamic predictions and investigate the potential for greater accuracy improvements in the worst performing test sequence.

  16. The thermodynamic properties of benzothiazole and benzoxazole

    SciTech Connect

    Steele, W.V.; Chirico, R.D.; Knipmeyer, S.E.; Nguyen, A.

    1991-08-01

    This research program, funded by the Department of Energy, Office of Fossil Energy, Advanced Extraction and Process Technology, provides accurate experimental thermochemical and thermophysical properties for key'' organic diheteroatom-containing compounds present in heavy petroleum feedstocks, and applies the experimental information to thermodynamic analyses of key hydrodesulfurization, hydrodenitrogenation, and hydrodeoxygenation reaction networks. Thermodynamic analyses, based on accurate information, provide insights for the design of cost-effective methods of heteroatom removal. The results reported here, and in a companion report to be completed, will point the way to the development of new methods of heteroatom removal from heavy petroleum. Measurements leading to the calculation of the ideal-gas thermodynamic properties are reported for benzothiazole and benzoxazole. Experimental methods included combustion calorimetry, adiabatic heat-capacity calorimetry, comparative ebulliometry, inclinded-piston gauge manometry, and differential-scanning calorimetry (d.s.c). Critical property estimates are made for both compounds. Entropies, enthalpies, and Gibbs energies of formation were derived for the ideal gas for both compounds for selected temperatures between 280 K and near 650 K. The Gibbs energies of formation will be used in a subsequent report in thermodynamic calculations to study the reaction pathways for the removal of the heteratoms by hydrogenolysis. The results obtained in this research are compared with values present in the literature. The failure of a previous adiabatic heat capacity study to see the phase transition in benzothiazole is noted. Literature vibrational frequency assignments were used to calculate ideal gas entropies in the temperature range reported here for both compounds. Resulting large deviations show the need for a revision of those assignments. 68 refs., 6 figs., 15 tabs.

  17. The thermodynamic properties of benzothiazole and benzoxazole

    NASA Astrophysics Data System (ADS)

    Steele, W. V.; Chirico, R. D.; Knipmeyer, S. E.; Nguyen, A.

    1991-08-01

    This research program, funded by the Department of Energy, Office of Fossil Energy, Advanced Extraction and Process Technology, provides accurate experimental thermochemical and thermophysical properties for key organic diheteroatom-containing compounds present in heavy petroleum feedstocks, and applies the experimental information to thermodynamic analyses of key hydrodesulfurization, hydrodenitrogenation, and hydrodeoxygenation reaction networks. Thermodynamic analyses, based on accurate information, provide insights for the design of cost-effective methods of heteroatom removal. The results reported here, and in a companion report to be completed, will point the way to the development of new methods of heteroatom removal from heavy petroleum. Measurements leading to the calculation of the ideal-gas thermodynamic properties are reported for benzothiazole and benzoxazole. Experimental methods included combustion calorimetry, adiabatic heat-capacity calorimetry, comparative ebulliometry, inclinded-piston gauge manometry, and differential-scanning calorimetry (d.s.c). Critical property estimates are made for both compounds. Entropies, enthalpies, and Gibbs energies of formation were derived for the ideal gas for both compounds for selected temperatures between 280 K and near 650 K. The Gibbs energies of formation will be used in a subsequent report in thermodynamic calculations to study the reaction pathways for the removal of the heteratoms by hydrogenolysis. The results obtained in this research are compared with values present in the literature. The failure of a previous adiabatic heat capacity study to see the phase transition in benzothiazole is noted. Literature vibrational frequency assignments were used to calculate ideal gas entropies in the temperature range reported here for both compounds. Resulting large deviations show the need for a revision of those assignments.

  18. Thermodynamic tabulations for selected phases in the system CaO-Al2O3-SiO2-H2 at 101.325 kPa (1 atm) between 273.15 and 1800 K

    USGS Publications Warehouse

    Haas, John L.; Robinson, Glipin R.; Hemingway, Bruch S.

    1981-01-01

    The standard thermodynamic properties of phases in the lime‐alumina‐silica‐ water system between 273.15 and 1800 K at 101.325 kPa (1 atm) were evalated from published experimental data. Phases included in the compilation are boehmite, diaspore, gibbsite, kaolinite, dickite, halloysite, andalusite, kyanite, sillimanite, Ca‐Al cliniopyroxene, anorthite, gehlenite, grossular, prehnite, zoisite, margarite, wollastonite, cyclowollastonite ( = pseudowollastonite), larnite, Ca olivine, hatrurite, and rankinite. The properties include heat capacity, entropy, relative enthalpy, and the Gibbs energy function of the phases and the enthalpies, Gibbs energies, and equilibrium constants for formation both from the elements and the oxides. Tabulated values are given at 50 K intervals with the 2‐sigma confidence limit at 250 K intervals. Summaries for each phase give the temperature‐ dependent functions for heat capacity, entropy, and relative enthalpy and the experimental data used in the final evaluation.

  19. Thermodynamic Metrics and Optimal Paths

    SciTech Connect

    Sivak, David; Crooks, Gavin

    2012-05-08

    A fundamental problem in modern thermodynamics is how a molecular-scale machine performs useful work, while operating away from thermal equilibrium without excessive dissipation. To this end, we derive a friction tensor that induces a Riemannian manifold on the space of thermodynamic states. Within the linear-response regime, this metric structure controls the dissipation of finite-time transformations, and bestows optimal protocols with many useful properties. We discuss the connection to the existing thermodynamic length formalism, and demonstrate the utility of this metric by solving for optimal control parameter protocols in a simple nonequilibrium model.

  20. Stochastic thermodynamics of information processing

    NASA Astrophysics Data System (ADS)

    Cardoso Barato, Andre

    2015-03-01

    We consider two recent advancements on theoretical aspects of thermodynamics of information processing. First we show that the theory of stochastic thermodynamics can be generalized to include information reservoirs. These reservoirs can be seen as a sequence of bits which has its Shannon entropy changed due to the interaction with the system. Second we discuss bipartite systems, which provide a convenient description of Maxwell's demon. Analyzing a special class of bipartite systems we show that they can be used to study cellular information processing, allowing for the definition of an entropic rate that quantifies how much a cell learns about a fluctuating external environment and that is bounded by the thermodynamic entropy production.

  1. Actinide Thermodynamics at Elevated Temperatures

    SciTech Connect

    Friese, Judah I.; Rao, Linfeng; Xia, Yuanxian; Bachelor, Paula P.; Tian, Guoxin

    2007-11-16

    The postclosure chemical environment in the proposed Yucca Mountain repository is expected to experience elevated temperatures. Predicting migration of actinides is possible if sufficient, reliable thermodynamic data on hydrolysis and complexation are available for these temperatures. Data are scarce and scattered for 25 degrees C, and nonexistent for elevated temperatures. This collaborative project between LBNL and PNNL collects thermodynamic data at elevated temperatures on actinide complexes with inorganic ligands that may be present in Yucca Mountain. The ligands include hydroxide, fluoride, sulfate, phosphate and carbonate. Thermodynamic parameters of complexation, including stability constants, enthalpy, entropy and heat capacity of complexation, are measured with a variety of techniques including solvent extraction, potentiometry, spectrophotometry and calorimetry

  2. The Thermodynamic Properties of Cubanite

    NASA Technical Reports Server (NTRS)

    Berger, E. L.; Lauretta, D. S.; Keller, L. P.

    2012-01-01

    CuFe2S3 exists in two polymorphs, a low-temperature orthorhombic form (cubanite) and a high-temperature cubic form (isocubanite). Cubanite has been identified in the CI-chondrite and Stardust collections. However, the thermodynamic properties of cubanite have neither been measured nor estimated. Our derivation of a thermodynamic model for cubanite allows constraints to be placed on the formation conditions. This data, along with the temperature constraint afforded by the crystal structure, can be used to assess the environments in which cubanite formation is (or is not) thermodynamically favored.

  3. Taming catalysts in quantum thermodynamics

    NASA Astrophysics Data System (ADS)

    Skrzypczyk, Paul

    2015-08-01

    Auxiliary quantum systems which can be borrowed to help facilitate thermodynamic processes but must be returned almost undisturbed—i.e. catalysts—are very powerful objects in quantum thermodynamics. In fact, they appear almost too powerful, since they allow for any state transformation to be carried out while being disturbed by an arbitrarily small amount. In their recent paper Ng et al (2015 New J. Phys. 17 085004) show how to tame catalysts in quantum thermodynamics by placing additional physical constraints on them, in terms of dimension and energy.

  4. CRC handbook of applied thermodynamics

    SciTech Connect

    Palmer, D.A. . Research and Development Dept.)

    1987-01-01

    This book feature an overview of the importance of physical properties and thermodynamics; and the use of thermodynamics to predict the extent of reaction in proposed new chemical combinations. The use of special types of data and prediction methods to develop flowsheets for probing projects; and sources of critically evaluated data, dividing the published works into three categories depending on quality are given. Methods of doing one's own critical evaluation of literature, a list of known North American contract experimentalist with the types of data measured by each, methods for measuring equilibrium data, and thermodynamic concepts to carry out process optimization are also featured.

  5. Thermodynamics and Structure of Plutonium Alloys

    SciTech Connect

    Allen, P G; Turchi, P A; Gallegos, G F

    2004-01-30

    The goal of this project was to investigate the chemical and structural effects of gallium and impurity elements, iron and nickel, on the phase behavior and crystallography of Pu-Ga alloys. This was done utilizing a theoretical chemical approach to predict binary and ternary alloy energetics, phase stability, and transformations. The modeling results were validated with experimental data derived from the synthesis of selected alloys and advanced characterization tools. The ultimate goal of this work was to develop a robust predictive capability for studying the thermodynamics and the structure-properties relationships in complex materials of high relevance to the Laboratory and DOE mission.

  6. The use of thermodynamic and kinetic data in drug discovery: decisive insight or increasing the puzzlement?

    PubMed

    Klebe, Gerhard

    2015-02-01

    The prime property to rate the success of hit-to-lead-to-drug optimization in drug discovery is binding affinity. Rational approaches try to relate this property with structure. Affinity can be linked to the thermodynamic property, Gibbs free energy of binding, which itself factorizes into enthalpy and entropy. With respect to kinetic properties, affinity can be associated with the ratio of koff and kon of complex formation. Do these features help to obtain better insight into affinity? The present viewpoint assesses our current understanding of thermodynamics- or kinetics-structure relationships and questions the accuracy of data collected to learn about the thermodynamic and kinetic basis to comprehend affinity.

  7. The application of the thermodynamic perturbation theory to study the hydrophobic hydration

    PubMed Central

    Mohorič, Tomaž; Urbic, Tomaz; Hribar-Lee, Barbara

    2013-01-01

    The thermodynamic perturbation theory was tested against newly obtained Monte Carlo computer simulations to describe the major features of the hydrophobic effect in a simple 3D-Mercedes-Benz water model: the temperature and hydrophobe size dependence on entropy, enthalpy, and free energy of transfer of a simple hydrophobic solute into water. An excellent agreement was obtained between the theoretical and simulation results. Further, the thermodynamic perturbation theory qualitatively correctly (with respect to the experimental data) describes the solvation thermodynamics under conditions where the simulation results are difficult to obtain with good enough accuracy, e.g., at high pressures. PMID:23862923

  8. The application of the thermodynamic perturbation theory to study the hydrophobic hydration

    NASA Astrophysics Data System (ADS)

    Mohorič, Tomaž; Urbic, Tomaz; Hribar-Lee, Barbara

    2013-07-01

    The thermodynamic perturbation theory was tested against newly obtained Monte Carlo computer simulations to describe the major features of the hydrophobic effect in a simple 3D-Mercedes-Benz water model: the temperature and hydrophobe size dependence on entropy, enthalpy, and free energy of transfer of a simple hydrophobic solute into water. An excellent agreement was obtained between the theoretical and simulation results. Further, the thermodynamic perturbation theory qualitatively correctly (with respect to the experimental data) describes the solvation thermodynamics under conditions where the simulation results are difficult to obtain with good enough accuracy, e.g., at high pressures.

  9. The application of the thermodynamic perturbation theory to study the hydrophobic hydration.

    PubMed

    Mohoric, Tomaz; Urbic, Tomaz; Hribar-Lee, Barbara

    2013-07-14

    The thermodynamic perturbation theory was tested against newly obtained Monte Carlo computer simulations to describe the major features of the hydrophobic effect in a simple 3D-Mercedes-Benz water model: the temperature and hydrophobe size dependence on entropy, enthalpy, and free energy of transfer of a simple hydrophobic solute into water. An excellent agreement was obtained between the theoretical and simulation results. Further, the thermodynamic perturbation theory qualitatively correctly (with respect to the experimental data) describes the solvation thermodynamics under conditions where the simulation results are difficult to obtain with good enough accuracy, e.g., at high pressures.

  10. The application of the thermodynamic perturbation theory to study the hydrophobic hydration.

    PubMed

    Mohoric, Tomaz; Urbic, Tomaz; Hribar-Lee, Barbara

    2013-07-14

    The thermodynamic perturbation theory was tested against newly obtained Monte Carlo computer simulations to describe the major features of the hydrophobic effect in a simple 3D-Mercedes-Benz water model: the temperature and hydrophobe size dependence on entropy, enthalpy, and free energy of transfer of a simple hydrophobic solute into water. An excellent agreement was obtained between the theoretical and simulation results. Further, the thermodynamic perturbation theory qualitatively correctly (with respect to the experimental data) describes the solvation thermodynamics under conditions where the simulation results are difficult to obtain with good enough accuracy, e.g., at high pressures. PMID:23862923

  11. Thermodynamic black di-rings

    SciTech Connect

    Iguchi, Hideo; Mishima, Takashi

    2010-10-15

    Previously the five dimensional S{sup 1}-rotating black rings have been superposed in a concentric way by some solitonic methods, and regular systems of two S{sup 1}-rotating black rings were constructed by the authors and then Evslin and Krishnan (we called these solutions 'black di-rings'). In this place we show some characteristics of the solutions of five dimensional black di-rings, especially in thermodynamic equilibrium. After the summary of the di-ring expressions and their physical quantities, first we comment on the equivalence of the two different solution sets of the black di-rings. Then the existence of thermodynamic black di-rings is shown, in which both isothermality and isorotation between the inner black ring and the outer black ring are realized. We also give detailed analysis of peculiar properties of the thermodynamic black di-ring including discussion about a certain kind of thermodynamic stability (instability) of the system.

  12. Thermodynamic efficiency of solar concentrators.

    PubMed

    Shatz, Narkis; Bortz, John; Winston, Roland

    2010-04-26

    The optical thermodynamic efficiency is a comprehensive metric that takes into account all loss mechanisms associated with transferring flux from the source to the target phase space, which may include losses due to inadequate design, non-ideal materials, fabrication errors, and less than maximal concentration. We discuss consequences of Fermat's principle of geometrical optics and review étendue dilution and optical loss mechanisms associated with nonimaging concentrators. We develop an expression for the optical thermodynamic efficiency which combines the first and second laws of thermodynamics. As such, this metric is a gold standard for evaluating the performance of nonimaging concentrators. We provide examples illustrating the use of this new metric for concentrating photovoltaic systems for solar power applications, and in particular show how skewness mismatch limits the attainable optical thermodynamic efficiency. PMID:20588573

  13. Thermodynamic efficiency of solar concentrators.

    PubMed

    Shatz, Narkis; Bortz, John; Winston, Roland

    2010-04-26

    The optical thermodynamic efficiency is a comprehensive metric that takes into account all loss mechanisms associated with transferring flux from the source to the target phase space, which may include losses due to inadequate design, non-ideal materials, fabrication errors, and less than maximal concentration. We discuss consequences of Fermat's principle of geometrical optics and review étendue dilution and optical loss mechanisms associated with nonimaging concentrators. We develop an expression for the optical thermodynamic efficiency which combines the first and second laws of thermodynamics. As such, this metric is a gold standard for evaluating the performance of nonimaging concentrators. We provide examples illustrating the use of this new metric for concentrating photovoltaic systems for solar power applications, and in particular show how skewness mismatch limits the attainable optical thermodynamic efficiency. PMID:20607882

  14. Quantifying uncertainties in first-principles alloy thermodynamics using cluster expansions

    NASA Astrophysics Data System (ADS)

    Aldegunde, Manuel; Zabaras, Nicholas; Kristensen, Jesper

    2016-10-01

    The cluster expansion is a popular surrogate model for alloy modeling to avoid costly quantum mechanical simulations. As its practical implementations require approximations, its use trades efficiency for accuracy. Furthermore, the coefficients of the model need to be determined from some known data set (training set). These two sources of error, if not quantified, decrease the confidence we can put in the results obtained from the surrogate model. This paper presents a framework for the determination of the cluster expansion coefficients using a Bayesian approach, which allows for the quantification of uncertainties in the predictions. In particular, a relevance vector machine is used to automatically select the most relevant terms of the model while retaining an analytical expression for the predictive distribution. This methodology is applied to two binary alloys, SiGe and MgLi, including the temperature dependence in their effective cluster interactions. The resulting cluster expansions are used to calculate the uncertainty in several thermodynamic quantities: ground state line, including the uncertainty in which structures are thermodynamically stable at 0 K, phase diagrams and phase transitions. The uncertainty in the ground state line is found to be of the order of meV/atom, showing that the cluster expansion is reliable to ab initio level accuracy even with limited data. We found that the uncertainty in the predicted phase transition temperature increases when including the temperature dependence of the effective cluster interactions. Also, the use of the bond stiffness versus bond length approximation to calculate temperature dependent properties from a reduced set of alloy configurations showed similar uncertainty to the approach where all training configurations are considered but at a much reduced computational cost.

  15. Simulating Metabolism with Statistical Thermodynamics

    SciTech Connect

    Cannon, William R.

    2014-08-04

    Kinetic probabilities of state are usually based on empirical measurements, while thermodynamic state probabilities are based on the assumption that chemical species are distributed to according to a multinomial Boltzmann distribution. While the use of kinetic simulations is desirable, obtaining all the mass action rate constants necessary to carry out kinetic simulations is an overwhelming challenge. Here, the kinetic probability of a state is compared in depth to the thermodynamic probability of a state for sets of coupled reactions. The entropic and energetic contributions to thermodynamic stable states are described and compared to entropic and energetic contributions of kinetic steady states. It is shown that many kinetic steady states are possible for a system of coupled reactions depending on the relative values of the mass action rate constants, but only one of these corresponds to a thermodynamically stable state. Furthermore, the thermodynamic stable state corresponds to a minimum free energy state. The use of thermodynamic simulations of state to model metabolic processes is attractive, since metabolite levels and energy requirements of pathways can be evaluated using only standard free energies of formation as parameters in the probability distribution. In chemical physics, the assumption of a Boltzmann distribution is the basis of transition state theory for modeling transitory species. Application to stable species, such as those found in metabolic processes, is a less severe assumption that would enable the use of simulations of state.

  16. Thermodynamic Analysis of Biodegradation Pathways

    PubMed Central

    Finley, Stacey D.; Broadbelt, Linda J.

    2014-01-01

    Microorganisms provide a wealth of biodegradative potential in the reduction and elimination of xenobiotic compounds in the environment. One useful metric to evaluate potential biodegradation pathways is thermodynamic feasibility. However, experimental data for the thermodynamic properties of xenobiotics is scarce. The present work uses a group contribution method to study the thermodynamic properties of the University of Minnesota Biocatalysis/Biodegradation Database. The Gibbs free energies of formation and reaction are estimated for 914 compounds (81%) and 902 reactions (75%), respectively, in the database. The reactions are classified based on the minimum and maximum Gibbs free energy values, which accounts for uncertainty in the free energy estimates and a feasible concentration range relevant to biodegradation. Using the free energy estimates, the cumulative free energy change of 89 biodegradation pathways (51%) in the database could be estimated. A comparison of the likelihood of the biotransformation rules in the Pathway Prediction System and their thermodynamic feasibility was then carried out. This analysis revealed that when evaluating the feasibility of biodegradation pathways, it is important to consider the thermodynamic topology of the reactions in the context of the complete pathway. Group contribution is shown to be a viable tool for estimating, a priori, the thermodynamic feasibility and the relative likelihood of alternative biodegradation reactions. This work offers a useful tool to a broad range of researchers interested in estimating the feasibility of the reactions in existing or novel biodegradation pathways. PMID:19288443

  17. Thermodynamics of firms' growth.

    PubMed

    Zambrano, Eduardo; Hernando, Alberto; Fernández Bariviera, Aurelio; Hernando, Ricardo; Plastino, Angelo

    2015-11-01

    The distribution of firms' growth and firms' sizes is a topic under intense scrutiny. In this paper, we show that a thermodynamic model based on the maximum entropy principle, with dynamical prior information, can be constructed that adequately describes the dynamics and distribution of firms' growth. Our theoretical framework is tested against a comprehensive database of Spanish firms, which covers, to a very large extent, Spain's economic activity, with a total of 1,155,142 firms evolving along a full decade. We show that the empirical exponent of Pareto's law, a rule often observed in the rank distribution of large-size firms, is explained by the capacity of economic system for creating/destroying firms, and that can be used to measure the health of a capitalist-based economy. Indeed, our model predicts that when the exponent is larger than 1, creation of firms is favoured; when it is smaller than 1, destruction of firms is favoured instead; and when it equals 1 (matching Zipf's law), the system is in a full macroeconomic equilibrium, entailing 'free' creation and/or destruction of firms. For medium and smaller firm sizes, the dynamical regime changes, the whole distribution can no longer be fitted to a single simple analytical form and numerical prediction is required. Our model constitutes the basis for a full predictive framework regarding the economic evolution of an ensemble of firms. Such a structure can be potentially used to develop simulations and test hypothetical scenarios, such as economic crisis or the response to specific policy measures.

  18. Thermodynamics of firms' growth

    PubMed Central

    Zambrano, Eduardo; Hernando, Alberto; Hernando, Ricardo; Plastino, Angelo

    2015-01-01

    The distribution of firms' growth and firms' sizes is a topic under intense scrutiny. In this paper, we show that a thermodynamic model based on the maximum entropy principle, with dynamical prior information, can be constructed that adequately describes the dynamics and distribution of firms' growth. Our theoretical framework is tested against a comprehensive database of Spanish firms, which covers, to a very large extent, Spain's economic activity, with a total of 1 155 142 firms evolving along a full decade. We show that the empirical exponent of Pareto's law, a rule often observed in the rank distribution of large-size firms, is explained by the capacity of economic system for creating/destroying firms, and that can be used to measure the health of a capitalist-based economy. Indeed, our model predicts that when the exponent is larger than 1, creation of firms is favoured; when it is smaller than 1, destruction of firms is favoured instead; and when it equals 1 (matching Zipf's law), the system is in a full macroeconomic equilibrium, entailing ‘free’ creation and/or destruction of firms. For medium and smaller firm sizes, the dynamical regime changes, the whole distribution can no longer be fitted to a single simple analytical form and numerical prediction is required. Our model constitutes the basis for a full predictive framework regarding the economic evolution of an ensemble of firms. Such a structure can be potentially used to develop simulations and test hypothetical scenarios, such as economic crisis or the response to specific policy measures. PMID:26510828

  19. Thermodynamics of firms' growth.

    PubMed

    Zambrano, Eduardo; Hernando, Alberto; Fernández Bariviera, Aurelio; Hernando, Ricardo; Plastino, Angelo

    2015-11-01

    The distribution of firms' growth and firms' sizes is a topic under intense scrutiny. In this paper, we show that a thermodynamic model based on the maximum entropy principle, with dynamical prior information, can be constructed that adequately describes the dynamics and distribution of firms' growth. Our theoretical framework is tested against a comprehensive database of Spanish firms, which covers, to a very large extent, Spain's economic activity, with a total of 1,155,142 firms evolving along a full decade. We show that the empirical exponent of Pareto's law, a rule often observed in the rank distribution of large-size firms, is explained by the capacity of economic system for creating/destroying firms, and that can be used to measure the health of a capitalist-based economy. Indeed, our model predicts that when the exponent is larger than 1, creation of firms is favoured; when it is smaller than 1, destruction of firms is favoured instead; and when it equals 1 (matching Zipf's law), the system is in a full macroeconomic equilibrium, entailing 'free' creation and/or destruction of firms. For medium and smaller firm sizes, the dynamical regime changes, the whole distribution can no longer be fitted to a single simple analytical form and numerical prediction is required. Our model constitutes the basis for a full predictive framework regarding the economic evolution of an ensemble of firms. Such a structure can be potentially used to develop simulations and test hypothetical scenarios, such as economic crisis or the response to specific policy measures. PMID:26510828

  20. Reticence, Accuracy and Efficacy

    NASA Astrophysics Data System (ADS)

    Oreskes, N.; Lewandowsky, S.

    2015-12-01

    James Hansen has cautioned the scientific community against "reticence," by which he means a reluctance to speak in public about the threat of climate change. This may contribute to social inaction, with the result that society fails to respond appropriately to threats that are well understood scientifically. Against this, others have warned against the dangers of "crying wolf," suggesting that reticence protects scientific credibility. We argue that both these positions are missing an important point: that reticence is not only a matter of style but also of substance. In previous work, Bysse et al. (2013) showed that scientific projections of key indicators of climate change have been skewed towards the low end of actual events, suggesting a bias in scientific work. More recently, we have shown that scientific efforts to be responsive to contrarian challenges have led scientists to adopt the terminology of a "pause" or "hiatus" in climate warming, despite the lack of evidence to support such a conclusion (Lewandowsky et al., 2015a. 2015b). In the former case, scientific conservatism has led to under-estimation of climate related changes. In the latter case, the use of misleading terminology has perpetuated scientific misunderstanding and hindered effective communication. Scientific communication should embody two equally important goals: 1) accuracy in communicating scientific information and 2) efficacy in expressing what that information means. Scientists should strive to be neither conservative nor adventurous but to be accurate, and to communicate that accurate information effectively.

  1. Thermodynamic properties and environmental chemistry of chromium

    SciTech Connect

    Schmidt, R.L.

    1984-07-01

    Values of standard entropy, standard enthalpy of formation, and standard free energy of formation for Cr and its solid and aqueous species are tabulated in this report. These values were selected or recalculated after careful evaluation of the best available current thermochemical data. The basis for selection of data centered on conformation with the recent studies of Vasil'ev et al. (1977a,b, 1978, 1980, 1981) for Cr/sup 3 +/ data and O'Hare and Boerio (1975) for CrO/sub 4//sup 2 -/ data. The thermodynamic data presented in this report will be incorporated into the data base of the geochemical computer model, MINTEQ. The distribution of Cr in the environment among its aqueous inorganic species is, according to the thermodynamic data, highly dependent upon pH and Eh and the presence of complexing ligands. The speciation of Cr in natural waters is also controlled by reduction and complexation by organic matter, adsorption and oxidation by Mn-oxide in suspended particulate matter and sediment, and reduction by H/sub 2/S released from anoxic sediments. 89 references, 8 figures, 11 tables.

  2. High accuracy fuel flowmeter

    NASA Technical Reports Server (NTRS)

    1986-01-01

    All three flowmeter concepts (vortex, dual turbine, and angular momentum) were subjected to experimental and analytical investigation to determine the potential portotype performance. The three concepts were subjected to a comprehensive rating. Eight parameters of performance were evaluated on a zero-to-ten scale, weighted, and summed. The relative ratings of the vortex, dual turbine, and angular momentum flowmeters are 0.71, 1.00, and 0.95, respectively. The dual turbine flowmeter concept was selected as the primary candidate and the angular momentum flowmeter as the secondary candidate for prototype development and evaluation.

  3. Landauer's blowtorch effect as a thermodynamic cross process: Brownian cooling.

    PubMed

    Das, Moupriya; Das, Debojyoti; Barik, Debashis; Ray, Deb Shankar

    2015-11-01

    The local heating of a selected region in a double-well potential alters the relative stability of the two wells and gives rise to an enhancement of population transfer to the cold well. We show that this Landauer's blowtorch effect may be considered in the spirit of a thermodynamic cross process linearly connecting the flux of particles and the thermodynamic force associated with the temperature difference and consequently ensuring the existence of a reverse cross effect. This reverse effect is realized by directing the thermalized particles in a double-well potential by application of an external bias from one well to the other, which suffers cooling. PMID:26651642

  4. Electrochemistry of the Zinc-Silver Oxide System. Part 1: Thermodynamic Studies Using Commercial Miniature Cells.

    ERIC Educational Resources Information Center

    Smith, Michael J.; Vincent, Colin A.

    1989-01-01

    Uses reversible electrochemical cells near equilibrium to study basic thermodynamic concepts such as maximum work and free energy. Selects sealed, miniature, commercial cells to obtain accurate measurement of enthalpy, entropy, and Gibbs free energy. (MVL)

  5. EOS mapping accuracy study

    NASA Technical Reports Server (NTRS)

    Forrest, R. B.; Eppes, T. A.; Ouellette, R. J.

    1973-01-01

    Studies were performed to evaluate various image positioning methods for possible use in the earth observatory satellite (EOS) program and other earth resource imaging satellite programs. The primary goal is the generation of geometrically corrected and registered images, positioned with respect to the earth's surface. The EOS sensors which were considered were the thematic mapper, the return beam vidicon camera, and the high resolution pointable imager. The image positioning methods evaluated consisted of various combinations of satellite data and ground control points. It was concluded that EOS attitude control system design must be considered as a part of the image positioning problem for EOS, along with image sensor design and ground image processing system design. Study results show that, with suitable efficiency for ground control point selection and matching activities during data processing, extensive reliance should be placed on use of ground control points for positioning the images obtained from EOS and similar programs.

  6. Nonequilibrium thermodynamics of an interface

    NASA Astrophysics Data System (ADS)

    Schweizer, Marco; Öttinger, Hans Christian; Savin, Thierry

    2016-05-01

    Interfacial thermodynamics has deep ramifications in understanding the boundary conditions of transport theories. We present a formulation of local equilibrium for interfaces that extends the thermodynamics of the "dividing surface," as introduced by Gibbs, to nonequilibrium settings such as evaporation or condensation. By identifying the precise position of the dividing surface in the interfacial region with a gauge degree of freedom, we exploit gauge-invariance requirements to consistently define the intensive variables for the interface. The model is verified under stringent conditions by employing high-precision nonequilibrium molecular-dynamics simulations of a coexisting vapor-liquid Lennard-Jones fluid. We conclude that the interfacial temperature is determined using the surface tension as a "thermometer," and it can be significantly different from the temperatures of the adjacent phases. Our findings lay foundations for nonequilibrium interfacial thermodynamics.

  7. Non-hermitian quantum thermodynamics

    NASA Astrophysics Data System (ADS)

    Gardas, Bartłomiej; Deffner, Sebastian; Saxena, Avadh

    2016-03-01

    Thermodynamics is the phenomenological theory of heat and work. Here we analyze to what extent quantum thermodynamic relations are immune to the underlying mathematical formulation of quantum mechanics. As a main result, we show that the Jarzynski equality holds true for all non-hermitian quantum systems with real spectrum. This equality expresses the second law of thermodynamics for isothermal processes arbitrarily far from equilibrium. In the quasistatic limit however, the second law leads to the Carnot bound which is fulfilled even if some eigenenergies are complex provided they appear in conjugate pairs. Furthermore, we propose two setups to test our predictions, namely with strongly interacting excitons and photons in a semiconductor microcavity and in the non-hermitian tight-binding model.

  8. Analyze distillation columns with thermodynamics

    SciTech Connect

    Ognisty, T.P. )

    1995-02-01

    In a distillation column, heat supplies the work for separating the components of a feed stream into products. Distillation columns consume some 95% of the total energy used in separations. This amounts to roughly 3% of the energy consumed in the US. Since distillation is so energy intensive and requires significant capital outlays, an endless quest to improve the economics has continued since the beginning of the industry. By analyzing the thermodynamics of a distillation column, an engineer can quantify the thermodynamic efficiency of the process, identify the regions where energy can be better utilized, and define the minimum targets for energy consumption. This article reviews the principles of distillation column thermodynamics and outlines the analysis of lost work profiles and column heat profiles. It then illustrates these concepts through three examples.

  9. Non-hermitian quantum thermodynamics.

    PubMed

    Gardas, Bartłomiej; Deffner, Sebastian; Saxena, Avadh

    2016-01-01

    Thermodynamics is the phenomenological theory of heat and work. Here we analyze to what extent quantum thermodynamic relations are immune to the underlying mathematical formulation of quantum mechanics. As a main result, we show that the Jarzynski equality holds true for all non-hermitian quantum systems with real spectrum. This equality expresses the second law of thermodynamics for isothermal processes arbitrarily far from equilibrium. In the quasistatic limit however, the second law leads to the Carnot bound which is fulfilled even if some eigenenergies are complex provided they appear in conjugate pairs. Furthermore, we propose two setups to test our predictions, namely with strongly interacting excitons and photons in a semiconductor microcavity and in the non-hermitian tight-binding model. PMID:27003686

  10. Non-hermitian quantum thermodynamics

    PubMed Central

    Gardas, Bartłomiej; Deffner, Sebastian; Saxena, Avadh

    2016-01-01

    Thermodynamics is the phenomenological theory of heat and work. Here we analyze to what extent quantum thermodynamic relations are immune to the underlying mathematical formulation of quantum mechanics. As a main result, we show that the Jarzynski equality holds true for all non-hermitian quantum systems with real spectrum. This equality expresses the second law of thermodynamics for isothermal processes arbitrarily far from equilibrium. In the quasistatic limit however, the second law leads to the Carnot bound which is fulfilled even if some eigenenergies are complex provided they appear in conjugate pairs. Furthermore, we propose two setups to test our predictions, namely with strongly interacting excitons and photons in a semiconductor microcavity and in the non-hermitian tight-binding model. PMID:27003686

  11. Non-hermitian quantum thermodynamics

    DOE PAGES

    Gardas, Bartłomiej; Deffner, Sebastian; Saxena, Avadh

    2016-03-22

    Thermodynamics is the phenomenological theory of heat and work. Here we analyze to what extent quantum thermodynamic relations are immune to the underlying mathematical formulation of quantum mechanics. As a main result, we show that the Jarzynski equality holds true for all non-hermitian quantum systems with real spectrum. This equality expresses the second law of thermodynamics for isothermal processes arbitrarily far from equilibrium. In the quasistatic limit however, the second law leads to the Carnot bound which is fulfilled even if some eigenenergies are complex provided they appear in conjugate pairs. Lastly, we propose two setups to test our predictions,more » namely with strongly interacting excitons and photons in a semiconductor microcavity and in the non-hermitian tight-binding model.« less

  12. Nonequilibrium thermodynamics of an interface.

    PubMed

    Schweizer, Marco; Öttinger, Hans Christian; Savin, Thierry

    2016-05-01

    Interfacial thermodynamics has deep ramifications in understanding the boundary conditions of transport theories. We present a formulation of local equilibrium for interfaces that extends the thermodynamics of the "dividing surface," as introduced by Gibbs, to nonequilibrium settings such as evaporation or condensation. By identifying the precise position of the dividing surface in the interfacial region with a gauge degree of freedom, we exploit gauge-invariance requirements to consistently define the intensive variables for the interface. The model is verified under stringent conditions by employing high-precision nonequilibrium molecular-dynamics simulations of a coexisting vapor-liquid Lennard-Jones fluid. We conclude that the interfacial temperature is determined using the surface tension as a "thermometer," and it can be significantly different from the temperatures of the adjacent phases. Our findings lay foundations for nonequilibrium interfacial thermodynamics.

  13. Nonequilibrium thermodynamics of an interface.

    PubMed

    Schweizer, Marco; Öttinger, Hans Christian; Savin, Thierry

    2016-05-01

    Interfacial thermodynamics has deep ramifications in understanding the boundary conditions of transport theories. We present a formulation of local equilibrium for interfaces that extends the thermodynamics of the "dividing surface," as introduced by Gibbs, to nonequilibrium settings such as evaporation or condensation. By identifying the precise position of the dividing surface in the interfacial region with a gauge degree of freedom, we exploit gauge-invariance requirements to consistently define the intensive variables for the interface. The model is verified under stringent conditions by employing high-precision nonequilibrium molecular-dynamics simulations of a coexisting vapor-liquid Lennard-Jones fluid. We conclude that the interfacial temperature is determined using the surface tension as a "thermometer," and it can be significantly different from the temperatures of the adjacent phases. Our findings lay foundations for nonequilibrium interfacial thermodynamics. PMID:27300960

  14. Thermodynamics from a scaling Hamiltonian

    NASA Astrophysics Data System (ADS)

    Del Pino, L. A.; Troncoso, P.; Curilef, S.

    2007-11-01

    There are problems with defining the thermodynamic limit of systems with long-range interactions; as a result, the thermodynamic behavior of these types of systems is anomalous. In the present work, we review some concepts from both extensive and nonextensive thermodynamic perspectives. We use a model, whose Hamiltonian takes into account spins ferromagnetically coupled in a chain via a power law that decays at large interparticle distance r as 1/rα for α⩾0 . Here, we review old nonextensive scaling. In addition, we propose a Hamiltonian scaled by 2((N/2)1-α-1)/(1-α) that explicitly includes symmetry of the lattice and dependence on the size N of the system. The approach enabled us to improve upon previous results. A numerical test is conducted through Monte Carlo simulations. In the model, periodic boundary conditions are adopted to eliminate surface effects.

  15. Landsat classification accuracy assessment procedures

    USGS Publications Warehouse

    Mead, R. R.; Szajgin, John

    1982-01-01

    A working conference was held in Sioux Falls, South Dakota, 12-14 November, 1980 dealing with Landsat classification Accuracy Assessment Procedures. Thirteen formal presentations were made on three general topics: (1) sampling procedures, (2) statistical analysis techniques, and (3) examples of projects which included accuracy assessment and the associated costs, logistical problems, and value of the accuracy data to the remote sensing specialist and the resource manager. Nearly twenty conference attendees participated in two discussion sessions addressing various issues associated with accuracy assessment. This paper presents an account of the accomplishments of the conference.

  16. CRC handbook of applied thermodynamics

    SciTech Connect

    Palmer, D.A. . Research and Development Dept.)

    1987-01-01

    The emphasis of this book is on applied thermodynamics, featuring the stage of development of a process rather than the logical development of thermodynamic principles. It is organized according to the types of problems encountered in industry, such as probing research, process assessment, and process development. The applied principles presented can be used in most areas of industry including oil and gas production and processing, chemical processing, power generation, polymer production, food processing, synthetic fuels production, specialty chemicals and pharmaceuticals production, bioengineered processes, etc.

  17. Thermodynamic Properties of Nitrogen Including Liquid and Vapor Phases from 63K to 2000K with Pressures to 10,000 Bar

    NASA Technical Reports Server (NTRS)

    Jacobsen, Richard T.; Stewart, Richard B.

    1973-01-01

    Tables of thermodynamic properties of nitrogen are presented for the liquid and vapor phases for temperatures from the freezing line to 2000K and pressures to 10,000 bar. The tables include values of density, internal energy, enthalpy, entropy, isochoric heat capacity, isobaric heat capacity velocity of sound, the isotherm derivative, and the isochor derivative. The thermodynamic property tables are based on an equation of state, P=P (p,T), which accurately represents liquid and gaseous nitrogen for the range of pressures and temperatures covered by the tables. Comparisons of property values calculated from the equation of state with measured values for P-p-T, heat capacity, enthalpy, latent heat, and velocity of sound are included to illustrate the agreement between the experimental data and the tables of properties presented here. The coefficients of the equation of state were determined by a weighted least squares fit to selected P-p-T data and, simultaneously, to isochoric heat capacity data determined by corresponding states analysis from oxygen data, and to data which define the phase equilibrium criteria for the saturated liquid and the saturated vapor. The vapor pressure equation, melting curve equation, and an equation to represent the ideal gas heat capacity are also presented. Estimates of the accuracy of the equation of state, the vapor pressure equation, and the ideal gas heat capacity equation are given. The equation of state, derivatives of the equation, and the integral functions for calculating derived thermodynamic properties are included.

  18. Quantum-thermodynamic treatment of intrinsic anharmonicity; Wallace's theorem revisited

    NASA Astrophysics Data System (ADS)

    Jacobs, Michel H. G.; de Jong, Bernard H. W. S.

    2005-12-01

    Wallace (in Thermodynamics of crystals, 1972) developed a theorem, rooted in rigid lattice dynamics, which incorporates intrinsic anharmonic effects in solids. The practical application of this theorem in mineral physics is computationally involved and this is the main reason for the theorem not getting the attention it deserves. Because intrinsic anharmonicity is an important issue at the extreme conditions in planetary mantles, we derived a method which removes the computational obstacles in applying this theorem. We extended the theorem to incorporate details of the phonon spectrum and tested our algorithm on forsterite (Mg2SiO4). Using a least squares inversion technique applied to all available experimental data, we show that it results in an accurate representation of thermodynamic properties and sound wave velocities of Mg2SiO4 in its complete pressure-temperature stability range. We also show that the accuracy of our results is not significantly affected by the use of a different equation of state.

  19. Thermodynamics of water entry in hydrophobic channels of carbon nanotubes.

    PubMed

    Kumar, Hemant; Mukherjee, Biswaroop; Lin, Shiang-Tai; Dasgupta, Chandan; Sood, A K; Maiti, Prabal K

    2011-03-28

    Experiments and computer simulations demonstrate that water spontaneously fills the hydrophobic cavity of a carbon nanotube. To gain a quantitative thermodynamic understanding of this phenomenon, we use the recently developed two phase thermodynamics method to compute translational and rotational entropies of confined water molecules inside single-walled carbon nanotubes and show that the increase in energy of a water molecule inside the nanotube is compensated by the gain in its rotational entropy. The confined water is in equilibrium with the bulk water and the Helmholtz free energy per water molecule of confined water is the same as that in the bulk within the accuracy of the simulation results. A comparison of translational and rotational spectra of water molecules confined in carbon nanotubes with that of bulk water shows significant shifts in the positions of the spectral peaks that are directly related to the tube radius.

  20. Simplified curve fits for the thermodynamic properties of equilibrium air

    NASA Technical Reports Server (NTRS)

    Srinivasan, S.; Tannehill, J. C.; Weilmuenster, K. J.

    1987-01-01

    New, improved curve fits for the thermodynamic properties of equilibrium air have been developed. The curve fits are for pressure, speed of sound, temperature, entropy, enthalpy, density, and internal energy. These curve fits can be readily incorporated into new or existing computational fluid dynamics codes if real gas effects are desired. The curve fits are constructed from Grabau-type transition functions to model the thermodynamic surfaces in a piecewise manner. The accuracies and continuity of these curve fits are substantially improved over those of previous curve fits. These improvements are due to the incorporation of a small number of additional terms in the approximating polynomials and careful choices of the transition functions. The ranges of validity of the new curve fits are temperatures up to 25 000 K and densities from 10 to the -7 to 10 to the 3d power amagats.

  1. Test Expectancy Affects Metacomprehension Accuracy

    ERIC Educational Resources Information Center

    Thiede, Keith W.; Wiley, Jennifer; Griffin, Thomas D.

    2011-01-01

    Background: Theory suggests that the accuracy of metacognitive monitoring is affected by the cues used to judge learning. Researchers have improved monitoring accuracy by directing attention to more appropriate cues; however, this is the first study to more directly point students to more appropriate cues using instructions regarding tests and…

  2. Thermodynamic properties of minerals

    USGS Publications Warehouse

    Robie, Richard A.

    1962-01-01

    In the ten years since the publication of the national Bureau of Standards comprehensive tables of thermochemical properties, by Rossini and other (1952), a very large body of modern calorimetric and equilibrium data has become available. Because of the complex interrelations among many thermochemical data and the necessity for internal consistency among these values, a complete revision of this standard reference is required. This is also true of the summaries of thermochemical data for the sulfides (Richardson and Jeffes 1952) and for the oxides (Coughlin 1954). The following tables present critically selected values for the heat and free energy of formation, the logarithm of the equilibrium constant of formation Log Kf, the entropy and the molar volume, at 298.15°K (25.0°C) and one atmosphere for minerals.

  3. Superfluid thermodynamic cycle refrigerator

    DOEpatents

    Swift, Gregory W.; Kotsubo, Vincent Y.

    1992-01-01

    A cryogenic refrigerator cools a heat source by cyclically concentrating and diluting the amount of .sup.3 He in a single phase .sup.3 He-.sup.4 He solution. The .sup.3 He in superfluid .sup.4 He acts in a manner of an ideal gas in a vacuum. Thus, refrigeration is obtained using any conventional thermal cycle, but preferably a Stirling or Carnot cycle. A single phase solution of liquid .sup.3 He at an initial concentration in superfluid .sup.4 He is contained in a first variable volume connected to a second variable volume through a superleak device that enables free passage of .sup.4 He while restricting passage of .sup.3 He. The .sup.3 He is compressed (concentrated) and expanded (diluted) in a phased manner to carry out the selected thermal cycle to remove heat from the heat load for cooling below 1 K.

  4. Superfluid thermodynamic cycle refrigerator

    DOEpatents

    Swift, G.W.; Kotsubo, V.Y.

    1992-12-22

    A cryogenic refrigerator cools a heat source by cyclically concentrating and diluting the amount of [sup 3]He in a single phase [sup 3]He-[sup 4]He solution. The [sup 3]He in superfluid [sup 4]He acts in a manner of an ideal gas in a vacuum. Thus, refrigeration is obtained using any conventional thermal cycle, but preferably a Stirling or Carnot cycle. A single phase solution of liquid [sup 3]He at an initial concentration in superfluid [sup 4]He is contained in a first variable volume connected to a second variable volume through a superleak device that enables free passage of [sup 4]He while restricting passage of [sup 3]He. The [sup 3]He is compressed (concentrated) and expanded (diluted) in a phased manner to carry out the selected thermal cycle to remove heat from the heat load for cooling below 1 K. 12 figs.

  5. A paradigm shift in patterning foundation from frequency multiplication to edge-placement accuracy: a novel processing solution by selective etching and alternating-material self-aligned multiple patterning

    NASA Astrophysics Data System (ADS)

    Han, Ting; Liu, Hongyi; Chen, Yijian

    2016-03-01

    Overlay errors, cut/block and line/space critical-dimension (CD) variations are the major sources of the edge-placement errors (EPE) in the cut/block patterning processes of complementary lithography when IC technology is scaled down to sub-10nm half pitch (HP). In this paper, we propose and discuss a modular technology to reduce the EPE effect by combining selective etching and alternating-material (dual-material) self-aligned multiple patterning (altSAMP) processes. Preliminary results of altSAMP process development and material screening experiment are reported and possible material candidates are suggested. A geometrical cut-process yield model considering the joint effect of overlay errors, cut-hole and line CD variations is developed to analyze its patterning performance. In addition to the contributions from the above three process variations, the impacts of key control parameters (such as cut-hole overhang and etching selectivity) on the patterning yield are examined. It is shown that the optimized altSAMP patterning process significantly improves the patterning yield compared with conventional SAMP processes, especially when the half pitch of device patterns is driven down to 7 nm and below.

  6. Thermodynamics of electrochemical lithium storage.

    PubMed

    Maier, Joachim

    2013-05-01

    The thermodynamics of electrochemical lithium storage are examined by taking into account that it is the point defects that enable storage. While the Li defects are mobile, most of the other point defects have to be considered as frozen owing to the performance temperature being low compared to the melting point of the electrode materials. The defect chemistry needs to be considered to fully understand equilibrium charge/discharge curves. On this basis, single phase and multiphase storage mechanisms can be discussed in terms of theoretical storage capacity and theoretical voltage. Of paramount interest in the field of Li batteries are metastable materials, in particular nanocrystalline and amorphous materials. The thermodynamics of storage and voltage, also at interfaces, thus deserve a special treatment. The relationship between reversible cell voltage and lithium content is derived for the novel job-sharing mechanism. With respect to the classic storage modes, thermodynamic differences for cathodes and anodes are elaborated with a special attention being paid to the search for new materials. As this contribution concentrates on the equilibrium state, current-related phenomena (irreversible thermodynamics) are only briefly touched upon. PMID:23630067

  7. Simulating Metabolism with Statistical Thermodynamics

    PubMed Central

    Cannon, William R.

    2014-01-01

    New methods are needed for large scale modeling of metabolism that predict metabolite levels and characterize the thermodynamics of individual reactions and pathways. Current approaches use either kinetic simulations, which are difficult to extend to large networks of reactions because of the need for rate constants, or flux-based methods, which have a large number of feasible solutions because they are unconstrained by the law of mass action. This report presents an alternative modeling approach based on statistical thermodynamics. The principles of this approach are demonstrated using a simple set of coupled reactions, and then the system is characterized with respect to the changes in energy, entropy, free energy, and entropy production. Finally, the physical and biochemical insights that this approach can provide for metabolism are demonstrated by application to the tricarboxylic acid (TCA) cycle of Escherichia coli. The reaction and pathway thermodynamics are evaluated and predictions are made regarding changes in concentration of TCA cycle intermediates due to 10- and 100-fold changes in the ratio of NAD+:NADH concentrations. Finally, the assumptions and caveats regarding the use of statistical thermodynamics to model non-equilibrium reactions are discussed. PMID:25089525

  8. A Simple Statistical Thermodynamics Experiment

    ERIC Educational Resources Information Center

    LoPresto, Michael C.

    2010-01-01

    Comparing the predicted and actual rolls of combinations of both two and three dice can help to introduce many of the basic concepts of statistical thermodynamics, including multiplicity, probability, microstates, and macrostates, and demonstrate that entropy is indeed a measure of randomness, that disordered states (those of higher entropy) are…

  9. THERMODYNAMICS USED IN ENVIRONMENTAL ENGINEERING

    EPA Science Inventory

    Thermodynamics is a science in which energy transformations are studied as well as their relationships to the changes in the chemical properties of a system. It is the fundamental basis of many engineering fields. The profession of environmental engineering is no exception. In pa...

  10. Thermodynamics on the Molality Scale

    ERIC Educational Resources Information Center

    Canagaratna, Sebastian G.; Maheswaran, M.

    2013-01-01

    For physical measurements, the compositions of solutions, especially electrolyte solutions, are expressed in terms of molality rather than mole fractions. The development of the necessary thermodynamic equations directly in terms of molality is not common in textbooks, and the treatment in the literature is not very systematic. We develop a…

  11. Some Considerations about Thermodynamic Cycles

    ERIC Educational Resources Information Center

    da Silva, M. F. Ferreira

    2012-01-01

    After completing their introductory studies on thermodynamics at the university level, typically in a second-year university course, most students show a number of misconceptions. In this work, we identify some of those erroneous ideas and try to explain their origins. We also give a suggestion to attack the problem through a systematic and…

  12. Thermodynamics of electrochemical lithium storage.

    PubMed

    Maier, Joachim

    2013-05-01

    The thermodynamics of electrochemical lithium storage are examined by taking into account that it is the point defects that enable storage. While the Li defects are mobile, most of the other point defects have to be considered as frozen owing to the performance temperature being low compared to the melting point of the electrode materials. The defect chemistry needs to be considered to fully understand equilibrium charge/discharge curves. On this basis, single phase and multiphase storage mechanisms can be discussed in terms of theoretical storage capacity and theoretical voltage. Of paramount interest in the field of Li batteries are metastable materials, in particular nanocrystalline and amorphous materials. The thermodynamics of storage and voltage, also at interfaces, thus deserve a special treatment. The relationship between reversible cell voltage and lithium content is derived for the novel job-sharing mechanism. With respect to the classic storage modes, thermodynamic differences for cathodes and anodes are elaborated with a special attention being paid to the search for new materials. As this contribution concentrates on the equilibrium state, current-related phenomena (irreversible thermodynamics) are only briefly touched upon.

  13. Conservation laws and thermodynamic efficiencies.

    PubMed

    Benenti, Giuliano; Casati, Giulio; Wang, Jiao

    2013-02-15

    We show that generic systems with a single relevant conserved quantity reach the Carnot efficiency in the thermodynamic limit. Such a general result is illustrated by means of a diatomic chain of hard-point elastically colliding particles where the total momentum is the only relevant conserved quantity.

  14. Analogy between Thermodynamics and Mechanics.

    ERIC Educational Resources Information Center

    Peterson, Mark A.

    1979-01-01

    Establishes and illustrates a formal analogy between the motion of a particle and the "motion" of the equilibrium state of a homogeneous system in a quasistatic process. The purpose is to show that there is a much larger set of natural coordinate transformations in thermodynamics. (GA)

  15. Thermodynamics of Oligonucleotide Duplex Melting

    ERIC Educational Resources Information Center

    Schreiber-Gosche, Sherrie; Edwards, Robert A.

    2009-01-01

    Melting temperatures of oligonucleotides are useful for a number of molecular biology applications, such as the polymerase chain reaction (PCR). Although melting temperatures are often calculated with simplistic empirical equations, application of thermodynamics provides more accurate melting temperatures and an opportunity for students to apply…

  16. Bullet trajectory reconstruction - Methods, accuracy and precision.

    PubMed

    Mattijssen, Erwin J A T; Kerkhoff, Wim

    2016-05-01

    Based on the spatial relation between a primary and secondary bullet defect or on the shape and dimensions of the primary bullet defect, a bullet's trajectory prior to impact can be estimated for a shooting scene reconstruction. The accuracy and precision of the estimated trajectories will vary depending on variables such as, the applied method of reconstruction, the (true) angle of incidence, the properties of the target material and the properties of the bullet upon impact. This study focused on the accuracy and precision of estimated bullet trajectories when different variants of the probing method, ellipse method, and lead-in method are applied on bullet defects resulting from shots at various angles of incidence on drywall, MDF and sheet metal. The results show that in most situations the best performance (accuracy and precision) is seen when the probing method is applied. Only for the lowest angles of incidence the performance was better when either the ellipse or lead-in method was applied. The data provided in this paper can be used to select the appropriate method(s) for reconstruction and to correct for systematic errors (accuracy) and to provide a value of the precision, by means of a confidence interval of the specific measurement. PMID:27044032

  17. A thermodynamic review of cryogenic refrigeration cycles for liquefaction of natural gas

    NASA Astrophysics Data System (ADS)

    Chang, Ho-Myung

    2015-12-01

    A thermodynamic review is presented on cryogenic refrigeration cycles for the liquefaction process of natural gas. The main purpose of this review is to examine the thermodynamic structure of various cycles and provide a theoretical basis for selecting a cycle in accordance with different needs and design criteria. Based on existing or proposed liquefaction processes, sixteen ideal cycles are selected and the optimal conditions to achieve their best thermodynamic performance are investigated. The selected cycles include standard and modified versions of Joule-Thomson (JT) cycle, Brayton cycle, and their combined cycle with pure refrigerants (PR) or mixed refrigerants (MR). Full details of the cycles are presented and discussed in terms of FOM (figure of merit) and thermodynamic irreversibility. In addition, a new method of nomenclature is proposed to clearly identify the structure of cycles by abbreviation.

  18. Thermodynamic aspects of heat pipe operation

    NASA Technical Reports Server (NTRS)

    Richter, Robert; Gottschlich, Joseph

    1990-01-01

    An expanded heat pipe operating model is described which includes thermodynamic and heat transfer considerations to reconcile disparities between actual and theoretical heat pipe performances. The analysis shows that thermodynamic considerations can explain the observed heat pipe performance limitations. A full understanding of thermodynamic processes could lead to advanced concepts for thermal transport devices.

  19. Transposed critical temperature Rankine thermodynamic cycle

    SciTech Connect

    Pope, W.L.; Doyle, P.A.

    1980-04-01

    The transposed critical temperature (TPCT) is shown to be an extremely important thermodynamic property in the selection of the working fluid and turbine states for optimized geothermal power plants operating on a closed organic (binary) Rankine cycle. When the optimum working fluid composition and process states are determined for given source and sink conditions (7 parameter optimization), turbine inlet states are found to be consistently adjacent to the low pressure side of the working fluids' TPCT line on pressure-enthalpy coordinates. Although the TPCT concepts herein may find numerous future applications in high temperature, advanced cycles for fossil or nuclear fired steam power plants and in supercritical organic Rankine heat recovery bottoming cycles for Diesel engines, this discussion is limited to moderate temperature (150 to 250/sup 0/C) closed simple organic Rankine cycle geothermal power plants. Conceptual design calculations pertinent to the first geothermal binary cycle Demonstration Plant are included.

  20. The thermodynamic properties of thianthrene and phenoxathiin

    SciTech Connect

    Steele, W.V.; Chirico, R.D.; Knipmeyer, S.E.; Nguyen, A.

    1993-04-01

    Measurements leading to the calculation of the ideal-gas thermodynamic properties are reported for thianthrene (Chemical Abstracts registry number [92-85-3]) and phenoxathiin (registry number [262-20-41]). Experimental methods included combustion calorimetry, adiabatic heat-capacity calorimetry, vibrating-tube densitometry, comparative ebulliometry, inclined-piston gauge manometry, and differential-scanning calorimetry (d.s.c.). Critical properties were estimated for both materials based on the measurement results. Entropies, enthalpies, and Gibbs energies of formation were derived for the ideal gas for both compounds for selected temperatures between 298.15 K and 700 K. The property-measurement results reported here for thianthrene and phenoxathiin provide the first experimental gas-phase Gibbs energies of formation for tricyclic diheteroatom-containing molecules.

  1. The thermodynamic properties of thianthrene and phenoxathiin

    NASA Astrophysics Data System (ADS)

    Steele, W. V.; Chirico, R. D.; Knipmeyer, S. E.; Nguyen, A.

    1993-04-01

    Measurements leading to the calculation of the ideal-gas thermodynamic properties are reported for thianthrene and phenoxathiin. Experimental methods included combustion calorimetry, adiabatic heat-capacity calorimetry, vibrating-tube densitometry, comparative ebulliometry, inclined-piston gauge manometry, and differential-scanning calorimetry (d.s.c.). Critical properties were estimated for both materials based on the measurement results. Entropies, enthalpies, and Gibbs energies of formation were derived for the ideal gas for both compounds for selected temperatures between 298.15 K and 700 K. The property-measurement results reported here for thianthrene and phenoxathiin provide the first experimental gas-phase Gibbs energies of formation for tricyclic diheteroatom-containing molecules.

  2. Thermodynamics and statistical mechanics. [thermodynamic properties of gases

    NASA Technical Reports Server (NTRS)

    1976-01-01

    The basic thermodynamic properties of gases are reviewed and the relations between them are derived from the first and second laws. The elements of statistical mechanics are then formulated and the partition function is derived. The classical form of the partition function is used to obtain the Maxwell-Boltzmann distribution of kinetic energies in the gas phase and the equipartition of energy theorem is given in its most general form. The thermodynamic properties are all derived as functions of the partition function. Quantum statistics are reviewed briefly and the differences between the Boltzmann distribution function for classical particles and the Fermi-Dirac and Bose-Einstein distributions for quantum particles are discussed.

  3. When Does Choice of Accuracy Measure Alter Imputation Accuracy Assessments?

    PubMed

    Ramnarine, Shelina; Zhang, Juan; Chen, Li-Shiun; Culverhouse, Robert; Duan, Weimin; Hancock, Dana B; Hartz, Sarah M; Johnson, Eric O; Olfson, Emily; Schwantes-An, Tae-Hwi; Saccone, Nancy L

    2015-01-01

    Imputation, the process of inferring genotypes for untyped variants, is used to identify and refine genetic association findings. Inaccuracies in imputed data can distort the observed association between variants and a disease. Many statistics are used to assess accuracy; some compare imputed to genotyped data and others are calculated without reference to true genotypes. Prior work has shown that the Imputation Quality Score (IQS), which is based on Cohen's kappa statistic and compares imputed genotype probabilities to true genotypes, appropriately adjusts for chance agreement; however, it is not commonly used. To identify differences in accuracy assessment, we compared IQS with concordance rate, squared correlation, and accuracy measures built into imputation programs. Genotypes from the 1000 Genomes reference populations (AFR N = 246 and EUR N = 379) were masked to match the typed single nucleotide polymorphism (SNP) coverage of several SNP arrays and were imputed with BEAGLE 3.3.2 and IMPUTE2 in regions associated with smoking behaviors. Additional masking and imputation was conducted for sequenced subjects from the Collaborative Genetic Study of Nicotine Dependence and the Genetic Study of Nicotine Dependence in African Americans (N = 1,481 African Americans and N = 1,480 European Americans). Our results offer further evidence that concordance rate inflates accuracy estimates, particularly for rare and low frequency variants. For common variants, squared correlation, BEAGLE R2, IMPUTE2 INFO, and IQS produce similar assessments of imputation accuracy. However, for rare and low frequency variants, compared to IQS, the other statistics tend to be more liberal in their assessment of accuracy. IQS is important to consider when evaluating imputation accuracy, particularly for rare and low frequency variants. PMID:26458263

  4. Thermodynamic properties of modified gravity theories

    NASA Astrophysics Data System (ADS)

    Bamba, Kazuharu

    2016-06-01

    We review thermodynamic properties of modified gravity theories, such as F(R) gravity and f(T) gravity, where R is the scalar curvature and T is the torsion scalar in teleparallelism. In particular, we explore the equivalence between the equations of motion for modified gravity theories and the Clausius relation in thermodynamics. In addition, thermodynamics of the cosmological apparent horizon is investigated in f(T) gravity. We show both equilibrium and nonequilibrium descriptions of thermodynamics. It is demonstrated that the second law of thermodynamics in the universe can be met, when the temperature of the outside of the apparent horizon is equivalent to that of the inside of it.

  5. Thermodynamic model of nonequilibrium phase transitions.

    PubMed

    Martyushev, L M; Konovalov, M S

    2011-07-01

    Within the scope of a thermodynamic description using the maximum entropy production principle, transitions from one nonequilibrium (kinetic) regime to another are considered. It is shown that in the case when power-law dependencies of thermodynamic flux on force are similar for two regimes, only a transition accompanied by a positive jump of thermodynamic flux is possible between them. It is found that the difference in powers of the dependencies of thermodynamic fluxes on forces results in a number of interesting nonequilibrium transitions between kinetic regimes, including the reentrant one with a negative jump of thermodynamic flux. PMID:21867119

  6. Impact of Atmospheric Infrared Sounder (AIRS) Thermodynamic Profiles on Regional Precipitation Forecasting

    NASA Technical Reports Server (NTRS)

    Chou, S.-H.; Zavodsky, B. T.; Jedloved, G. J.

    2010-01-01

    In data sparse regions, remotely-sensed observations can be used to improve analyses and lead to better forecasts. One such source comes from the Atmospheric Infrared Sounder (AIRS), which together with the Advanced Microwave Sounding Unit (AMSU), provides temperature and moisture profiles in clear and cloudy regions with accuracy which approaches that of radiosondes. The purpose of this paper is to describe an approach to assimilate AIRS thermodynamic profile data into a regional configuration of the Advanced Research WRF (ARW) model using WRF-Var. Quality indicators are used to select only the highest quality temperature and moisture profiles for assimilation in clear and partly cloudy regions, and uncontaminated portions of retrievals above clouds in overcast regions. Separate error characteristics for land and water profiles are also used in the assimilation process. Assimilation results indicate that AIRS profiles produce an analysis closer to in situ observations than the background field. Forecasts from a 37-day case study period in the winter of 2007 show that AIRS profile data can lead to improvements in 6-h cumulative precipitation forecasts resulting from improved thermodynamic fields. Additionally, in a convective heavy rainfall event from February 2007, assimilation of AIRS profiles produces a more unstable boundary layer resulting in enhanced updrafts in the model. These updrafts produce a squall line and precipitation totals that more closely reflect ground-based observations than a no AIRS control forecast. The location of available high-quality AIRS profiles ahead of approaching storm systems is found to be of paramount importance to the amount of impact the observations will have on the resulting forecasts.

  7. Thermodynamics of combined cycle plant

    NASA Astrophysics Data System (ADS)

    Crane, R. I.

    The fundamental thermodynamics of power plants including definitions of performance criteria and an introduction to exergy are reviewed, and treatments of simplified performance calculations for the components which form the major building blocks and a gas/steam combined cycle plant are given: the gas turbine, the heat recovery steam generator, and the remainder of the steam plant. Efficiency relationships and energy and exergy analyses of combined cycle plant are presented, with examples. Among the aspects considered are gas turbine performance characteristics and fuels, temperature differences for heat recovery, multiple steam pressures and reheat, supplementary firing and feed water heating. Attention is drawn to points of thermodynamic interest arising from applications of combined cycle plant to repowering of existing steam plant and to combined heat and power (cogeneration); some advances, including coal firing, are also introduced.

  8. The 4th Thermodynamic Principle?

    SciTech Connect

    Montero Garcia, Jose de la Luz; Novoa Blanco, Jesus Francisco

    2007-04-28

    It should be emphasized that the 4th Principle above formulated is a thermodynamic principle and, at the same time, is mechanical-quantum and relativist, as it should inevitably be and its absence has been one of main the theoretical limitations of the physical theory until today.We show that the theoretical discovery of Dimensional Primitive Octet of Matter, the 4th Thermodynamic Principle, the Quantum Hexet of Matter, the Global Hexagonal Subsystem of Fundamental Constants of Energy and the Measurement or Connected Global Scale or Universal Existential Interval of the Matter is that it is possible to be arrived at a global formulation of the four 'forces' or fundamental interactions of nature. The Einstein's golden dream is possible.

  9. Thermodynamic effects on developed cavitation

    NASA Technical Reports Server (NTRS)

    Holl, J. W.; Billet, M. L.; Weir, D. S.

    1975-01-01

    The results of an investigation of thermodynamic effects are presented. Distributions of temperature and pressure in a developed cavity were measured for zero- and quarter-caliber ogives. A semiempirical entrainment theory was developed to correlate the measured temperature depression in the cavity. This theory correlates the maximum temperature depression expressed in dimensionless form as the Jakob number in terms of the dimensionless numbers of Nusselt, Reynolds, Froude, and Peclet, and dimensionless cavity length, L/D. The results show that in general, the temperature depression increases with L/D and temperature and the cavitation number based on measured cavity pressure is a function of L/D for a given model contour, independent of the thermodynamic effect.

  10. Thermodynamics of stochastic Turing machines.

    PubMed

    Strasberg, Philipp; Cerrillo, Javier; Schaller, Gernot; Brandes, Tobias

    2015-10-01

    In analogy to Brownian computers we explicitly show how to construct stochastic models which mimic the behavior of a general-purpose computer (a Turing machine). Our models are discrete state systems obeying a Markovian master equation, which are logically reversible and have a well-defined and consistent thermodynamic interpretation. The resulting master equation, which describes a simple one-step process on an enormously large state space, allows us to thoroughly investigate the thermodynamics of computation for this situation. Especially in the stationary regime we can well approximate the master equation by a simple Fokker-Planck equation in one dimension. We then show that the entropy production rate at steady state can be made arbitrarily small, but the total (integrated) entropy production is finite and grows logarithmically with the number of computational steps. PMID:26565165

  11. Dissipation Bound for Thermodynamic Control.

    PubMed

    Machta, Benjamin B

    2015-12-31

    Biological and engineered systems operate by coupling function to the transfer of heat and/or particles down a thermal or chemical gradient. In idealized deterministically driven systems, thermodynamic control can be exerted reversibly, with no entropy production, as long as the rate of the protocol is made slow compared to the equilibration time of the system. Here we consider fully realizable, entropically driven systems where the control parameters themselves obey rules that are reversible and that acquire directionality in time solely through dissipation. We show that when such a system moves in a directed way through thermodynamic space, it must produce entropy that is on average larger than its generalized displacement as measured by the Fisher information metric. This distance measure is subextensive but cannot be made small by slowing the rate of the protocol. PMID:26764981

  12. Dissipation Bound for Thermodynamic Control

    NASA Astrophysics Data System (ADS)

    Machta, Benjamin B.

    2015-12-01

    Biological and engineered systems operate by coupling function to the transfer of heat and/or particles down a thermal or chemical gradient. In idealized deterministically driven systems, thermodynamic control can be exerted reversibly, with no entropy production, as long as the rate of the protocol is made slow compared to the equilibration time of the system. Here we consider fully realizable, entropically driven systems where the control parameters themselves obey rules that are reversible and that acquire directionality in time solely through dissipation. We show that when such a system moves in a directed way through thermodynamic space, it must produce entropy that is on average larger than its generalized displacement as measured by the Fisher information metric. This distance measure is subextensive but cannot be made small by slowing the rate of the protocol.

  13. Thermodynamic Model of Spatial Memory

    NASA Astrophysics Data System (ADS)

    Kaufman, Miron; Allen, P.

    1998-03-01

    We develop and test a thermodynamic model of spatial memory. Our model is an application of statistical thermodynamics to cognitive science. It is related to applications of the statistical mechanics framework in parallel distributed processes research. Our macroscopic model allows us to evaluate an entropy associated with spatial memory tasks. We find that older adults exhibit higher levels of entropy than younger adults. Thurstone's Law of Categorical Judgment, according to which the discriminal processes along the psychological continuum produced by presentations of a single stimulus are normally distributed, is explained by using a Hooke spring model of spatial memory. We have also analyzed a nonlinear modification of the ideal spring model of spatial memory. This work is supported by NIH/NIA grant AG09282-06.

  14. A thermodynamically stable nanophase material.

    PubMed

    Lin, Zhang; Gilbert, Benjamin; Liu, Quanlin; Ren, Guoqiang; Huang, Feng

    2006-05-10

    Nanoparticles are metastable relative to the equivalent bulk material due to the positive excess interfacial free energy (IFE). Previous studies have shown that, with increasing surface interaction strength, the IFE diminishes but remains positive. We describe an experimental multicomponent system in which a nanoscale ZnS material is thermodynamically favored and can be formed at the expense of bulk ZnS. In 17 M sodium hydroxide solution, at 230 degrees C, both 3 nm ZnS nanoparticles and bulk ZnS are transformed into sheetlike nanocrystals with a ZnS polytype structure. Our results are theoretically compatible with the concept of a negative IFE, although not with the assumption of constant interface composition. We clarify the meaning of an effective negative IFE and present the necessary conditions for strong chemical surface interactions to stabilize nanoscale inorganic materials relative to bulk matter. Our results show that synthesis methods employing thermodynamic controls can produce nanomaterials with novel morphology.

  15. Nonequilibrium thermodynamics of pressure solution

    NASA Astrophysics Data System (ADS)

    Lehner, F. K.; Bataille, J.

    1984-01-01

    This paper is concerned with the thermodynamic theory of solution and precipitation processes in wet crustal rocks and with the mechanism of steady pressure-solution slip in ‘contact zones,’ such as grain-to-grain contacts, fracture surfaces, and permeable gouge layers, that are infiltrated by a mobile aqueous solution phase. A local dissipation jump condition at the phase boundary is fundamental to identifying the thermodynamic force driving the solution and precipitation process and is used here in setting up linear phenomenological relations to model near-equilibrium phase transformation kinetics. The local thermodynamic equilibrium of a stressed pure solid in contact with its melt or solution phase is governed by Gibbs's relation, which is rederived here, in a manner emphasizing its independence of constitutive assumptions for the solid while neglecting surface tension and diffusion in the solid. Fluid-infiltrated contact zones, such as those formed by rough surfaces, cannot generally be in thermodynamic equilibrium, especially during an ongoing process of pressure-solution slip, and the existing equilibrium formulations are incorrect in overlooking dissipative processes tending to eliminate fluctuations in superficial free energies due to stress concentrations near asperities, defects, or impurities. Steady pressure-solution slip is likely to exhibit a nonlinear dependence of slip rate on shear stress and effective normal stress, due to a dependence of the contact-zone state on the latter. Given that this dependence is negligible within some range, linear relations for pressure-solution slip can be derived for the limiting cases of diffusion-controlled and interface-reaction-controlled rates. A criterion for rate control by one of these mechanisms is set by the magnitude of the dimensionless quantity kδ/2C pD, where k is the interfacial transfer coefficient, δ is the mean diffusion path length, C p is the solubility at pressure p, and D is the mass

  16. Gluon Thermodynamics at Intermediate Coupling

    SciTech Connect

    Andersen, Jens O.; Strickland, Michael; Su Nan

    2010-03-26

    We calculate the thermodynamic functions of Yang-Mills theory to three-loop order using the hard-thermal-loop perturbation theory reorganization of finite temperature quantum field theory. We show that at three-loop order hard-thermal-loop perturbation theory is compatible with lattice results for the pressure, energy density, and entropy down to temperatures T{approx}2-3T{sub c}.

  17. WATEQ3 geochemical model: thermodynamic data for several additional solids

    SciTech Connect

    Krupka, K.M.; Jenne, E.A.

    1982-09-01

    Geochemical models such as WATEQ3 can be used to model the concentrations of water-soluble pollutants that may result from the disposal of nuclear waste and retorted oil shale. However, for a model to competently deal with these water-soluble pollutants, an adequate thermodynamic data base must be provided that includes elements identified as important in modeling these pollutants. To this end, several minerals and related solid phases were identified that were absent from the thermodynamic data base of WATEQ3. In this study, the thermodynamic data for the identified solids were compiled and selected from several published tabulations of thermodynamic data. For these solids, an accepted Gibbs free energy of formation, ..delta..G/sup 0//sub f,298/, was selected for each solid phase based on the recentness of the tabulated data and on considerations of internal consistency with respect to both the published tabulations and the existing data in WATEQ3. For those solids not included in these published tabulations, Gibbs free energies of formation were calculated from published solubility data (e.g., lepidocrocite), or were estimated (e.g., nontronite) using a free-energy summation method described by Mattigod and Sposito (1978). The accepted or estimated free energies were then combined with internally consistent, ancillary thermodynamic data to calculate equilibrium constants for the hydrolysis reactions of these minerals and related solid phases. Including these values in the WATEQ3 data base increased the competency of this geochemical model in applications associated with the disposal of nuclear waste and retorted oil shale. Additional minerals and related solid phases that need to be added to the solubility submodel will be identified as modeling applications continue in these two programs.

  18. Thermodynamic equilibrium at heterogeneous pressure

    NASA Astrophysics Data System (ADS)

    Vrijmoed, J. C.; Podladchikov, Y. Y.

    2015-07-01

    Recent advances in metamorphic petrology point out the importance of grain-scale pressure variations in high-temperature metamorphic rocks. Pressure derived from chemical zonation using unconventional geobarometry based on equal chemical potentials fits mechanically feasible pressure variations. Here, a thermodynamic equilibrium method is presented that predicts chemical zoning as a result of pressure variations by Gibbs energy minimization. Equilibrium thermodynamic prediction of the chemical zoning in the case of pressure heterogeneity is done by constrained Gibbs minimization using linear programming techniques. In addition to constraining the system composition, a certain proportion of the system is constrained at a specified pressure. Input pressure variations need to be discretized, and each discrete pressure defines an additional constraint for the minimization. The Gibbs minimization method provides identical results to a geobarometry approach based on chemical potentials, thus validating the inferred pressure gradient. The thermodynamic consistency of the calculation is supported by the similar result obtained from two different approaches. In addition, the method can be used for multi-component, multi-phase systems of which several applications are given. A good fit to natural observations in multi-phase, multi-component systems demonstrates the possibility to explain phase assemblages and zoning by spatial pressure variations at equilibrium as an alternative to pressure variation in time due to disequilibrium.

  19. Thermodynamical Structure of Protoplanetary Disks

    NASA Astrophysics Data System (ADS)

    Hirose, S.; Turner, N.

    2009-12-01

    The thermodynamics of protoplanetary disks determines chemical and physical evolution of dust and gas in the disks, and thus is relevant for understanding the origin and formation of planetary systems. In this paper, the thermodynamical structure of protoplanetary disks around low-mass stars is studied using three-dimensional radiation magnetohydrodynamic (MHD) simulations. Local patches of the disk are modeled using the shearing box approximation with vertical gravity. For simplicity, the dust and gas are well mixed and have the same temperature, and ideal MHD is assumed. The frequency-integrated radiation field is evolved using the flux-limited diffusion approximation, adopting thermally averaged opacities. The heating arises from the dissipation of MHD turbulence driven by magnetorotational instability due to differential rotation of the disk, and the cooling comes from infrared radiation losses. Irradiation by the central star is treated by injecting appropriate amount of thermal energy near the disk photosphere for visible lights. The results indicate the heating is more concentrated in the disk atmosphere than in the classical model. The single-point heating rate in the atmosphere fluctuates by orders of magnitude over time intervals comparable to the orbital period due to magnetic reconnection and shocks, while the patch of disk overall sustains dynamical and thermodynamical equilibrium over many cooling times. We will discuss implications of our numerical results for line and continuum emission from protoplanetary disks.

  20. Thermodynamics of Oligonucleotide Duplex Melting

    NASA Astrophysics Data System (ADS)

    Schreiber-Gosche, Sherrie; Edwards, Robert A.

    2009-05-01

    Melting temperatures of oligonucleotides are useful for a number of molecular biology applications, such as the polymerase chain reaction (PCR). Although melting temperatures are often calculated with simplistic empirical equations, application of thermodynamics provides more accurate melting temperatures and an opportunity for students to apply rigorous thermodynamic analysis to an important biochemical problem. Because the stacking of base pairs on top of one another is a significant factor in the energetics of oligonucleotide melting, several investigators have applied van't Hoff analysis to melting temperature data using a nearest-neighbor model and have obtained entropies and enthalpies for the stacking of bases. The present article explains how the equilibrium constant for the dissociation of strands from double-stranded oligonucleotides can be expressed in terms of the total strand concentration and thus how the total strand concentration influences the melting temperature. It also presents a simplified analysis based on the entropies and enthalpies of stacking that is manually tractable so that students can work examples to help them understand the thermodynamics of oligonucleotide melting.

  1. Thermodynamic States in Explosion Fields

    SciTech Connect

    Kuhl, A L

    2010-03-12

    We investigate the thermodynamic states occurring in explosion fields from condensed explosive charges. These states are often modeled with a Jones-Wilkins-Lee (JWL) function. However, the JWL function is not a Fundamental Equation of Thermodynamics, and therefore cannot give a complete specification of such states. We use the Cheetah code of Fried to study the loci of states of the expanded detonation products gases from C-4 charges, and their combustion products air. In the Le Chatelier Plane of specific-internal-energy versus temperature, these loci are fit with a Quadratic Model function u(T), which has been shown to be valid for T < 3,000 K and p < 1k-bar. This model is used to derive a Fundamental Equation u(v,s) for C-4. Given u(v,s), one can use Maxwell's Relations to derive all other thermodynamic functions, such as temperature: T(v,s), pressure: p(v,s), enthalpy: h(v,s), Gibbs free energy: g(v,s) and Helmholz free energy: f(v,s); these loci are displayed in figures for C-4. Such complete equations of state are needed for numerical simulations of blast waves from explosive charges, and their reflections from surfaces.

  2. Thermodynamical journey in plant biology

    PubMed Central

    Barbacci, Adelin; Magnenet, Vincent; Lahaye, Marc

    2015-01-01

    Nonequilibrium irreversible thermodynamics constitute a meaningful point of view suitable to explore life with a rich paradigm. This analytical framework can be used to span the gap from molecular processes to plant function and shows great promise to create a holistic description of life. Since living organisms dissipate energy, exchange entropy and matter with their environment, they can be assimilated to dissipative structures. This concept inherited from nonequilibrium thermodynamics has four properties which defines a scale independent framework suitable to provide a simpler and more comprehensive view of the highly complex plant biology. According to this approach, a biological function is modeled as a cascade of dissipative structures. Each dissipative structure, corresponds to a biological process, which is initiated by the amplification of a fluctuation. Evolution of the process leads to the breakage of the system symmetry and to the export of entropy. Exporting entropy to the surrounding environment corresponds to collecting information about it. Biological actors which break the symmetry of the system and which store information are by consequence, key actors on which experiments and data analysis focus most. This paper aims at illustrating properties of dissipative structure through familiar examples and thus initiating the dialogue between nonequilibrium thermodynamics and plant biology. PMID:26175747

  3. Thermodynamic curvature and ensemble nonequivalence

    NASA Astrophysics Data System (ADS)

    Bravetti, Alessandro; Nettel, Francisco

    2014-08-01

    In this work we consider thermodynamic geometries defined as Hessians of different potentials and derive some useful formulas that show their complementary role in the description of thermodynamic systems with 2 degrees of freedom that show ensemble nonequivalence. From the expressions derived for the metrics, we can obtain the curvature scalars in a very simple and compact form. We explain here the reason why each curvature scalar diverges over the line of divergence of one of the specific heats. This application is of special interest in the study of changes of stability in black holes as defined by Davies. From these results we are able to prove on a general footing a conjecture first formulated by Liu, Lü, Luo, and Shao stating that different Hessian metrics can correspond to different behaviors in the various ensembles. We study the case of two thermodynamic dimensions. Moreover, comparing our result with the more standard turning point method developed by Poincaré, we obtain that the divergence of the scalar curvature of the Hessian metric of one potential exactly matches the change of stability in the corresponding ensemble.

  4. Accuracy assessment of NLCD 2006 land cover and impervious surface

    USGS Publications Warehouse

    Wickham, James D.; Stehman, Stephen V.; Gass, Leila; Dewitz, Jon; Fry, Joyce A.; Wade, Timothy G.

    2013-01-01

    Release of NLCD 2006 provides the first wall-to-wall land-cover change database for the conterminous United States from Landsat Thematic Mapper (TM) data. Accuracy assessment of NLCD 2006 focused on four primary products: 2001 land cover, 2006 land cover, land-cover change between 2001 and 2006, and impervious surface change between 2001 and 2006. The accuracy assessment was conducted by selecting a stratified random sample of pixels with the reference classification interpreted from multi-temporal high resolution digital imagery. The NLCD Level II (16 classes) overall accuracies for the 2001 and 2006 land cover were 79% and 78%, respectively, with Level II user's accuracies exceeding 80% for water, high density urban, all upland forest classes, shrubland, and cropland for both dates. Level I (8 classes) accuracies were 85% for NLCD 2001 and 84% for NLCD 2006. The high overall and user's accuracies for the individual dates translated into high user's accuracies for the 2001–2006 change reporting themes water gain and loss, forest loss, urban gain, and the no-change reporting themes for water, urban, forest, and agriculture. The main factor limiting higher accuracies for the change reporting themes appeared to be difficulty in distinguishing the context of grass. We discuss the need for more research on land-cover change accuracy assessment.

  5. Development of a Stirling System Dynamic Model With Enhanced Thermodynamics

    NASA Technical Reports Server (NTRS)

    Regan, Timothy F.; Lewandowski, Edward J.

    2005-01-01

    The Stirling Convertor System Dynamic Model developed at NASA Glenn Research Center is a software model developed from first principles that includes the mechanical and mounting dynamics, the thermodynamics, the linear alternator, and the controller of a free-piston Stirling power convertor, along with the end user load. As such it represents the first detailed modeling tool for fully integrated Stirling convertor-based power systems. The thermodynamics of the model were originally a form of the isothermal Stirling cycle. In some situations it may be desirable to improve the accuracy of the Stirling cycle portion of the model. An option under consideration is to enhance the SDM thermodynamics by coupling the model with Gedeon Associates Sage simulation code. The result will be a model that gives a more accurate prediction of the performance and dynamics of the free-piston Stirling convertor. A method of integrating the Sage simulation code with the System Dynamic Model is described. Results of SDM and Sage simulation are compared to test data. Model parameter estimation and model validation are discussed.

  6. Thermodynamic Modeling of the YO(l.5)-ZrO2 System

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan S.; Liu, Zi-Kui; Kaufman, Larry; Zhang, Fan

    2003-01-01

    The YO1.5-ZrO2 system consists of five solid solutions, one liquid solution, and one intermediate compound. A thermodynamic description of this system is developed, which allows calculation of the phase diagram and thermodynamic properties. Two different solution models are used-a neutral species model with YO1.5 and ZrO2 as the components and a charged species model with Y(+3), Zr(+4), O(-2), and vacancies as components. For each model, regular and sub-regular solution parameters are derived fiom selected equilibrium phase and thermodynamic data.

  7. High accuracy autonomous navigation using the global positioning system (GPS)

    NASA Technical Reports Server (NTRS)

    Truong, Son H.; Hart, Roger C.; Shoan, Wendy C.; Wood, Terri; Long, Anne C.; Oza, Dipak H.; Lee, Taesul

    1997-01-01

    The application of global positioning system (GPS) technology to the improvement of the accuracy and economy of spacecraft navigation, is reported. High-accuracy autonomous navigation algorithms are currently being qualified in conjunction with the GPS attitude determination flyer (GADFLY) experiment for the small satellite technology initiative Lewis spacecraft. Preflight performance assessments indicated that these algorithms are able to provide a real time total position accuracy of better than 10 m and a velocity accuracy of better than 0.01 m/s, with selective availability at typical levels. It is expected that the position accuracy will be increased to 2 m if corrections are provided by the GPS wide area augmentation system.

  8. Thermodynamic Studies for Drug Design and Screening

    PubMed Central

    Garbett, Nichola C.; Chaires, Jonathan B.

    2012-01-01

    Introduction A key part of drug design and development is the optimization of molecular interactions between an engineered drug candidate and its binding target. Thermodynamic characterization provides information about the balance of energetic forces driving binding interactions and is essential for understanding and optimizing molecular interactions. Areas covered This review discusses the information that can be obtained from thermodynamic measurements and how this can be applied to the drug development process. Current approaches for the measurement and optimization of thermodynamic parameters are presented, specifically higher throughput and calorimetric methods. Relevant literature for this review was identified in part by bibliographic searches for the period 2004 – 2011 using the Science Citation Index and PUBMED and the keywords listed below. Expert opinion The most effective drug design and development platform comes from an integrated process utilizing all available information from structural, thermodynamic and biological studies. Continuing evolution in our understanding of the energetic basis of molecular interactions and advances in thermodynamic methods for widespread application are essential to realize the goal of thermodynamically-driven drug design. Comprehensive thermodynamic evaluation is vital early in the drug development process to speed drug development towards an optimal energetic interaction profile while retaining good pharmacological properties. Practical thermodynamic approaches, such as enthalpic optimization, thermodynamic optimization plots and the enthalpic efficiency index, have now matured to provide proven utility in design process. Improved throughput in calorimetric methods remains essential for even greater integration of thermodynamics into drug design. PMID:22458502

  9. Orbit accuracy assessment for Seasat

    NASA Technical Reports Server (NTRS)

    Schutz, B. E.; Tapley, B. D.

    1980-01-01

    Laser range measurements are used to determine the orbit of Seasat during the period from July 28, 1978, to Aug. 14, 1978, and the influence of the gravity field, atmospheric drag, and solar radiation pressure on the orbit accuracy is investigated. It is noted that for the orbits of three-day duration, little distinction can be made between the influence of different atmospheric models. It is found that the special Seasat gravity field PGS-S3 is most consistent with the data for three-day orbits, but an unmodeled systematic effect in radiation pressure is noted. For orbits of 18-day duration, little distinction can be made between the results derived from the PGS gravity fields. It is also found that the geomagnetic field is an influential factor in the atmospheric modeling during this time period. Seasat altimeter measurements are used to determine the accuracy of the altimeter measurement time tag and to evaluate the orbital accuracy.

  10. On the thermodynamics of multilevel evolution.

    PubMed

    Tessera, Marc; Hoelzer, Guy A

    2013-09-01

    Biodiversity is hierarchically structured both phylogenetically and functionally. Phylogenetic hierarchy is understood as a product of branching organic evolution as described by Darwin. Ecosystem biologists understand some aspects of functional hierarchy, such as food web architecture, as a product of evolutionary ecology; but functional hierarchy extends to much lower scales of organization than those studied by ecologists. We argue that the more general use of the term "evolution" employed by physicists and applied to non-living systems connects directly to the narrow biological meaning. Physical evolution is best understood as a thermodynamic phenomenon, and this perspective comfortably includes all of biological evolution. We suggest four dynamical factors that build on each other in a hierarchical fashion and set the stage for the Darwinian evolution of biological systems: (1) the entropic erosion of structure; (2) the construction of dissipative systems; (3) the reproduction of growing systems and (4) the historical memory accrued to populations of reproductive agents by the acquisition of hereditary mechanisms. A particular level of evolution can underpin the emergence of higher levels, but evolutionary processes persist at each level in the hierarchy. We also argue that particular evolutionary processes can occur at any level of the hierarchy where they are not obstructed by material constraints. This theoretical framework provides an extensive basis for understanding natural selection as a multilevel process. The extensive literature on thermodynamics in turn provides an important advantage to this perspective on the evolution of higher levels of organization, such as the evolution of altruism that can accompany the emergence of social organization.

  11. Statistical thermodynamics of the isomerization reaction between n-heptane and isoheptane.

    PubMed

    Yu, Tao; Zheng, Jingjing; Truhlar, Donald G

    2012-01-14

    We have employed electronic structure calculations and the recently proposed multi-structural (MS) anharmonicity method to calculate partition functions and thermodynamic quantities, in particular entropy and heat capacity, for n-heptane and isoheptane. We included all structures, of which there are 59 for n-heptane and 37 for isoheptane, and we carried out the calculations both in the local harmonic approximation and by including torsional (T) anharmonicity. In addition, ΔS°, ΔH, and ΔG° for the isomerization reaction between these two species were also calculated. It is found that all calculated thermodynamic quantities based on the MS-T approximation in the temperature range from 298 K to 1500 K agree well with experimental data from the American Petroleum Institute (API) tables or Thermodynamics Research Center (TRC) data series and with values obtained from Benson's empirical parameters fit to experiment. This demonstrates not only the high accuracy of the electronic structure calculations but also that the MS-T method can be used to include both multiple-structure anharmonicity and torsional anharmonicity in the calculation of thermodynamic properties for complex molecules that contain many torsions. It also gives us confidence that we can apply the MS-T statistical thermodynamic method to obtain thermodynamic properties (i) over a broader temperature range than that for which data are available in the API tables, TRC data series, or from empirical estimation and (ii) to the many molecules for which experimental data are not available at any temperature. PMID:22119933

  12. Exploring the thermodynamics of a universal Fermi gas.

    PubMed

    Nascimbène, S; Navon, N; Jiang, K J; Chevy, F; Salomon, C

    2010-02-25

    One of the greatest challenges in modern physics is to understand the behaviour of an ensemble of strongly interacting particles. A class of quantum many-body systems (such as neutron star matter and cold Fermi gases) share the same universal thermodynamic properties when interactions reach the maximum effective value allowed by quantum mechanics, the so-called unitary limit. This makes it possible in principle to simulate some astrophysical phenomena inside the highly controlled environment of an atomic physics laboratory. Previous work on the thermodynamics of a two-component Fermi gas led to thermodynamic quantities averaged over the trap, making comparisons with many-body theories developed for uniform gases difficult. Here we develop a general experimental method that yields the equation of state of a uniform gas, as well as enabling a detailed comparison with existing theories. The precision of our equation of state leads to new physical insights into the unitary gas. For the unpolarized gas, we show that the low-temperature thermodynamics of the strongly interacting normal phase is well described by Fermi liquid theory, and we localize the superfluid transition. For a spin-polarized system, our equation of state at zero temperature has a 2 per cent accuracy and extends work on the phase diagram to a new regime of precision. We show in particular that, despite strong interactions, the normal phase behaves as a mixture of two ideal gases: a Fermi gas of bare majority atoms and a non-interacting gas of dressed quasi-particles, the fermionic polarons.

  13. Thermodynamics of random reaction networks.

    PubMed

    Fischer, Jakob; Kleidon, Axel; Dittrich, Peter

    2015-01-01

    Reaction networks are useful for analyzing reaction systems occurring in chemistry, systems biology, or Earth system science. Despite the importance of thermodynamic disequilibrium for many of those systems, the general thermodynamic properties of reaction networks are poorly understood. To circumvent the problem of sparse thermodynamic data, we generate artificial reaction networks and investigate their non-equilibrium steady state for various boundary fluxes. We generate linear and nonlinear networks using four different complex network models (Erdős-Rényi, Barabási-Albert, Watts-Strogatz, Pan-Sinha) and compare their topological properties with real reaction networks. For similar boundary conditions the steady state flow through the linear networks is about one order of magnitude higher than the flow through comparable nonlinear networks. In all networks, the flow decreases with the distance between the inflow and outflow boundary species, with Watts-Strogatz networks showing a significantly smaller slope compared to the three other network types. The distribution of entropy production of the individual reactions inside the network follows a power law in the intermediate region with an exponent of circa -1.5 for linear and -1.66 for nonlinear networks. An elevated entropy production rate is found in reactions associated with weakly connected species. This effect is stronger in nonlinear networks than in the linear ones. Increasing the flow through the nonlinear networks also increases the number of cycles and leads to a narrower distribution of chemical potentials. We conclude that the relation between distribution of dissipation, network topology and strength of disequilibrium is nontrivial and can be studied systematically by artificial reaction networks.

  14. Thermodynamics of random reaction networks.

    PubMed

    Fischer, Jakob; Kleidon, Axel; Dittrich, Peter

    2015-01-01

    Reaction networks are useful for analyzing reaction systems occurring in chemistry, systems biology, or Earth system science. Despite the importance of thermodynamic disequilibrium for many of those systems, the general thermodynamic properties of reaction networks are poorly understood. To circumvent the problem of sparse thermodynamic data, we generate artificial reaction networks and investigate their non-equilibrium steady state for various boundary fluxes. We generate linear and nonlinear networks using four different complex network models (Erdős-Rényi, Barabási-Albert, Watts-Strogatz, Pan-Sinha) and compare their topological properties with real reaction networks. For similar boundary conditions the steady state flow through the linear networks is about one order of magnitude higher than the flow through comparable nonlinear networks. In all networks, the flow decreases with the distance between the inflow and outflow boundary species, with Watts-Strogatz networks showing a significantly smaller slope compared to the three other network types. The distribution of entropy production of the individual reactions inside the network follows a power law in the intermediate region with an exponent of circa -1.5 for linear and -1.66 for nonlinear networks. An elevated entropy production rate is found in reactions associated with weakly connected species. This effect is stronger in nonlinear networks than in the linear ones. Increasing the flow through the nonlinear networks also increases the number of cycles and leads to a narrower distribution of chemical potentials. We conclude that the relation between distribution of dissipation, network topology and strength of disequilibrium is nontrivial and can be studied systematically by artificial reaction networks. PMID:25723751

  15. Thermodynamic laws in isolated systems.

    PubMed

    Hilbert, Stefan; Hänggi, Peter; Dunkel, Jörn

    2014-12-01

    The recent experimental realization of exotic matter states in isolated quantum systems and the ensuing controversy about the existence of negative absolute temperatures demand a careful analysis of the conceptual foundations underlying microcanonical thermostatistics. Here we provide a detailed comparison of the most commonly considered microcanonical entropy definitions, focusing specifically on whether they satisfy or violate the zeroth, first, and second laws of thermodynamics. Our analysis shows that, for a broad class of systems that includes all standard classical Hamiltonian systems, only the Gibbs volume entropy fulfills all three laws simultaneously. To avoid ambiguities, the discussion is restricted to exact results and analytically tractable examples.

  16. Some problems in relativistic thermodynamics

    SciTech Connect

    Veitsman, E. V.

    2007-11-15

    The relativistic equations of state for ideal and real gases, as well as for various interface regions, have been derived. These dependences help to eliminate some controversies in the relativistic thermodynamics based on the special theory of relativity. It is shown, in particular, that the temperature of system whose velocity tends to the velocity of light in vacuum varies in accordance with the Ott law T = T{sub 0}/{radical}1 - v{sup 2}/c{sup 2}. Relativistic dependences for heat and mass transfer, for Ohm's law, and for a viscous flow of a liquid have also been derived.

  17. Thermodynamics of Lifshitz black holes

    NASA Astrophysics Data System (ADS)

    Devecioǧlu, Deniz Olgu; Sarıoǧlu, Özgür

    2011-06-01

    We apply the recently extended conserved Killing charge definition of Abbott-Deser-Tekin formalism to compute, for the first time, the energies of analytic Lifshitz black holes in higher dimensions. We then calculate the temperature and the entropy of this large family of solutions, and study and discuss the first law of black hole thermodynamics. Along the way we also identify the possible critical points of the relevant quadratic curvature gravity theories. Separately, we also apply the generalized Killing charge definition to compute the energy and the angular momentum of the warped AdS3 black hole solution of the three-dimensional new massive gravity theory.

  18. Thermodynamic Properties of Supported Catalysts

    SciTech Connect

    Gorte, Raymond J.

    2014-03-26

    The goals of this work were to develop Coulometric Titration as a method for characterizing the thermodynamic redox properties of oxides and to apply this technique to the characterization of ceria- and vanadia-based catalysts. The redox properties of ceria and vanadia are a major part of what makes these materials catalytically active but their properties are also dependent on their structure and the presence of other oxides. Quantifying these properties through the measurement of oxidation energetics was the goal of this work.

  19. Statistical thermodynamics of soft surfaces

    NASA Astrophysics Data System (ADS)

    Safran, S. A.

    2002-03-01

    We review the continuum, statistical thermodynamics of surfaces and interfaces in soft matter where both the energy and entropy of the surface are comparable. These systems include complex fluids that are dominated by either surface tension or the interfacial curvature, such as: fluid and solid interfaces, colloidal dispersions, macromolecular solutions, membranes, and other self-assembling aggregates such as micelles, vesicles, and microemulsions. The primary focus is on the theoretical concepts, their universality, and the role of fluctuations and inhomogeneities with connections to relevant experimental systems.

  20. Thermodynamic laws in isolated systems.

    PubMed

    Hilbert, Stefan; Hänggi, Peter; Dunkel, Jörn

    2014-12-01

    The recent experimental realization of exotic matter states in isolated quantum systems and the ensuing controversy about the existence of negative absolute temperatures demand a careful analysis of the conceptual foundations underlying microcanonical thermostatistics. Here we provide a detailed comparison of the most commonly considered microcanonical entropy definitions, focusing specifically on whether they satisfy or violate the zeroth, first, and second laws of thermodynamics. Our analysis shows that, for a broad class of systems that includes all standard classical Hamiltonian systems, only the Gibbs volume entropy fulfills all three laws simultaneously. To avoid ambiguities, the discussion is restricted to exact results and analytically tractable examples. PMID:25615053

  1. Thermodynamic studies on lithium ferrites

    SciTech Connect

    Rakshit, S.K.; Parida, S.C.; Naik, Y.P.; Chaudhary, Ziley Singh; Venugopal, V.

    2011-05-15

    Thermodynamic studies on ternary oxides of Li-Fe-O systems were carried out using differential scanning calorimetry, Knudsen effusion mass spectrometry, and solid-state electrochemical technique based on fluoride electrolyte. Heat capacities of LiFe{sub 5}O{sub 8}(s) and LiFeO{sub 2}(s) were determined in the temperature range 127-861 K using differential scanning calorimetry. Gibbs energies of formation of LiFe{sub 5}O{sub 8}(s) and LiFeO{sub 2}(s) were determined using Knudsen effusion mass spectrometry and solid-state galvanic cell technique. The combined least squares fits can be represented as {Delta}{sub f}G{sub m}{sup o}(LiFe{sub 5}O{sub 8},s,T)/kJ mol{sup -1} ({+-}6)=-2341+0.6764(T/K) (588{<=}T/K{<=}971) {Delta}{sub f}G{sub m}{sup o}(LiFeO{sub 2},s,T)/kJ mol{sup -1} ({+-}3)=-708+0.1656(T/K) (569{<=}T/K{<=}1021) The temperature independent term of the above equations represents {Delta}{sub f}H{sup o}{sub m}(T{sub av}) and temperature dependent term represents negative change in entropy of the respective compounds. Thermodynamic analysis shows that LiFe{sub 5}O{sub 8}(s) is more stable compared to LiFeO{sub 2}(s). -- Graphical abstract: Comparison of {Delta}{sub f}G{sub m}{sup o}(T) of lithium ferrites determined using different techniques. Display Omitted Highlights: {yields} Thermodynamic studies on Li-Fe-O system using DSC, KEQMS and galvanic cell. {yields} Heat capacities of LiFe{sub 5}O{sub 8}(s) and LiFeO{sub 2}(s) were determined using DSC 127-861 K. {yields} {Delta}{sub f}G{sup o}{sub m} of these compounds were determined and compared. {yields} Thermodynamic tables for LiFe{sub 5}O{sub 8}(s) and LiFeO{sub 2}(s) were constructed.

  2. Data Accuracy in Citation Studies.

    ERIC Educational Resources Information Center

    Boyce, Bert R.; Banning, Carolyn Sue

    1979-01-01

    Four hundred eighty-seven citations of the 1976 issues of the Journal of the American Society for Information Science and the Personnel and Guidance Journal were checked for accuracy: total error was 13.6 percent and 10.7 percent, respectively. Error categories included incorrect author name, article/book title, journal title; wrong entry; and…

  3. Improving Speaking Accuracy through Awareness

    ERIC Educational Resources Information Center

    Dormer, Jan Edwards

    2013-01-01

    Increased English learner accuracy can be achieved by leading students through six stages of awareness. The first three awareness stages build up students' motivation to improve, and the second three provide learners with crucial input for change. The final result is "sustained language awareness," resulting in ongoing…

  4. Thermodynamics of Enzyme-Catalyzed Reactions Database

    National Institute of Standards and Technology Data Gateway

    SRD 74 Thermodynamics of Enzyme-Catalyzed Reactions Database (Web, free access)   The Thermodynamics of Enzyme-Catalyzed Reactions Database contains thermodynamic data on enzyme-catalyzed reactions that have been recently published in the Journal of Physical and Chemical Reference Data (JPCRD). For each reaction the following information is provided: the reference for the data, the reaction studied, the name of the enzyme used and its Enzyme Commission number, the method of measurement, the data and an evaluation thereof.

  5. Irreversible thermodynamics of Poisson processes with reaction.

    PubMed

    Méndez, V; Fort, J

    1999-11-01

    A kinetic model is derived to study the successive movements of particles, described by a Poisson process, as well as their generation. The irreversible thermodynamics of this system is also studied from the kinetic model. This makes it possible to evaluate the differences between thermodynamical quantities computed exactly and up to second-order. Such differences determine the range of validity of the second-order approximation to extended irreversible thermodynamics.

  6. Irreversible thermodynamics of Poisson processes with reaction

    NASA Astrophysics Data System (ADS)

    Méndez, Vicenç; Fort, Joaquim

    1999-11-01

    A kinetic model is derived to study the successive movements of particles, described by a Poisson process, as well as their generation. The irreversible thermodynamics of this system is also studied from the kinetic model. This makes it possible to evaluate the differences between thermodynamical quantities computed exactly and up to second-order. Such differences determine the range of validity of the second-order approximation to extended irreversible thermodynamics.

  7. Quantum thermodynamics: a nonequilibrium Green's function approach.

    PubMed

    Esposito, Massimiliano; Ochoa, Maicol A; Galperin, Michael

    2015-02-27

    We establish the foundations of a nonequilibrium theory of quantum thermodynamics for noninteracting open quantum systems strongly coupled to their reservoirs within the framework of the nonequilibrium Green's functions. The energy of the system and its coupling to the reservoirs are controlled by a slow external time-dependent force treated to first order beyond the quasistatic limit. We derive the four basic laws of thermodynamics and characterize reversible transformations. Stochastic thermodynamics is recovered in the weak coupling limit. PMID:25768745

  8. Drawing accuracy measured using polygons

    NASA Astrophysics Data System (ADS)

    Carson, Linda; Millard, Matthew; Quehl, Nadine; Danckert, James

    2013-03-01

    The study of drawing, for its own sake and as a probe into human visual perception, generally depends on ratings by human critics and self-reported expertise of the drawers. To complement those approaches, we have developed a geometric approach to analyzing drawing accuracy, one whose measures are objective, continuous and performance-based. Drawing geometry is represented by polygons formed by landmark points found in the drawing. Drawing accuracy is assessed by comparing the geometric properties of polygons in the drawn image to the equivalent polygon in a ground truth photo. There are four distinct properties of a polygon: its size, its position, its orientation and the proportionality of its shape. We can decompose error into four components and investigate how each contributes to drawing performance. We applied a polygon-based accuracy analysis to a pilot data set of representational drawings and found that an expert drawer outperformed a novice on every dimension of polygon error. The results of the pilot data analysis correspond well with the apparent quality of the drawings, suggesting that the landmark and polygon analysis is a method worthy of further study. Applying this geometric analysis to a within-subjects comparison of accuracy in the positive and negative space suggests there is a trade-off on dimensions of error. The performance-based analysis of geometric deformations will allow the study of drawing accuracy at different levels of organization, in a systematic and quantitative manner. We briefly describe the method and its potential applications to research in drawing education and visual perception.

  9. MAPPING SPATIAL THEMATIC ACCURACY WITH FUZZY SETS

    EPA Science Inventory

    Thematic map accuracy is not spatially homogenous but variable across a landscape. Properly analyzing and representing spatial pattern and degree of thematic map accuracy would provide valuable information for using thematic maps. However, current thematic map accuracy measures (...

  10. Coherence and measurement in quantum thermodynamics

    NASA Astrophysics Data System (ADS)

    Kammerlander, P.; Anders, J.

    2016-02-01

    Thermodynamics is a highly successful macroscopic theory widely used across the natural sciences and for the construction of everyday devices, from car engines to solar cells. With thermodynamics predating quantum theory, research now aims to uncover the thermodynamic laws that govern finite size systems which may in addition host quantum effects. Recent theoretical breakthroughs include the characterisation of the efficiency of quantum thermal engines, the extension of classical non-equilibrium fluctuation theorems to the quantum regime and a new thermodynamic resource theory has led to the discovery of a set of second laws for finite size systems. These results have substantially advanced our understanding of nanoscale thermodynamics, however putting a finger on what is genuinely quantum in quantum thermodynamics has remained a challenge. Here we identify information processing tasks, the so-called projections, that can only be formulated within the framework of quantum mechanics. We show that the physical realisation of such projections can come with a non-trivial thermodynamic work only for quantum states with coherences. This contrasts with information erasure, first investigated by Landauer, for which a thermodynamic work cost applies for classical and quantum erasure alike. Repercussions on quantum work fluctuation relations and thermodynamic single-shot approaches are also discussed.

  11. Classical Solution Thermodynamics: A Retrospective View.

    ERIC Educational Resources Information Center

    Van Ness, H. C.; Abbott, M. M.

    1985-01-01

    Examines topics related to classical solution thermodynamics, considering energy, enthalpy, and the Gibbs function. Applicable mathematical equations are introduced and discussed when appropriate. (JN)

  12. Coherence and measurement in quantum thermodynamics.

    PubMed

    Kammerlander, P; Anders, J

    2016-02-26

    Thermodynamics is a highly successful macroscopic theory widely used across the natural sciences and for the construction of everyday devices, from car engines to solar cells. With thermodynamics predating quantum theory, research now aims to uncover the thermodynamic laws that govern finite size systems which may in addition host quantum effects. Recent theoretical breakthroughs include the characterisation of the efficiency of quantum thermal engines, the extension of classical non-equilibrium fluctuation theorems to the quantum regime and a new thermodynamic resource theory has led to the discovery of a set of second laws for finite size systems. These results have substantially advanced our understanding of nanoscale thermodynamics, however putting a finger on what is genuinely quantum in quantum thermodynamics has remained a challenge. Here we identify information processing tasks, the so-called projections, that can only be formulated within the framework of quantum mechanics. We show that the physical realisation of such projections can come with a non-trivial thermodynamic work only for quantum states with coherences. This contrasts with information erasure, first investigated by Landauer, for which a thermodynamic work cost applies for classical and quantum erasure alike. Repercussions on quantum work fluctuation relations and thermodynamic single-shot approaches are also discussed.

  13. Coherence and measurement in quantum thermodynamics.

    PubMed

    Kammerlander, P; Anders, J

    2016-01-01

    Thermodynamics is a highly successful macroscopic theory widely used across the natural sciences and for the construction of everyday devices, from car engines to solar cells. With thermodynamics predating quantum theory, research now aims to uncover the thermodynamic laws that govern finite size systems which may in addition host quantum effects. Recent theoretical breakthroughs include the characterisation of the efficiency of quantum thermal engines, the extension of classical non-equilibrium fluctuation theorems to the quantum regime and a new thermodynamic resource theory has led to the discovery of a set of second laws for finite size systems. These results have substantially advanced our understanding of nanoscale thermodynamics, however putting a finger on what is genuinely quantum in quantum thermodynamics has remained a challenge. Here we identify information processing tasks, the so-called projections, that can only be formulated within the framework of quantum mechanics. We show that the physical realisation of such projections can come with a non-trivial thermodynamic work only for quantum states with coherences. This contrasts with information erasure, first investigated by Landauer, for which a thermodynamic work cost applies for classical and quantum erasure alike. Repercussions on quantum work fluctuation relations and thermodynamic single-shot approaches are also discussed. PMID:26916503

  14. Coherence and measurement in quantum thermodynamics

    PubMed Central

    Kammerlander, P.; Anders, J.

    2016-01-01

    Thermodynamics is a highly successful macroscopic theory widely used across the natural sciences and for the construction of everyday devices, from car engines to solar cells. With thermodynamics predating quantum theory, research now aims to uncover the thermodynamic laws that govern finite size systems which may in addition host quantum effects. Recent theoretical breakthroughs include the characterisation of the efficiency of quantum thermal engines, the extension of classical non-equilibrium fluctuation theorems to the quantum regime and a new thermodynamic resource theory has led to the discovery of a set of second laws for finite size systems. These results have substantially advanced our understanding of nanoscale thermodynamics, however putting a finger on what is genuinely quantum in quantum thermodynamics has remained a challenge. Here we identify information processing tasks, the so-called projections, that can only be formulated within the framework of quantum mechanics. We show that the physical realisation of such projections can come with a non-trivial thermodynamic work only for quantum states with coherences. This contrasts with information erasure, first investigated by Landauer, for which a thermodynamic work cost applies for classical and quantum erasure alike. Repercussions on quantum work fluctuation relations and thermodynamic single-shot approaches are also discussed. PMID:26916503

  15. Stochastic deformation of a thermodynamic symplectic structure.

    PubMed

    Kazinski, P O

    2009-01-01

    A stochastic deformation of a thermodynamic symplectic structure is studied. The stochastic deformation is analogous to the deformation of an algebra of observables such as deformation quantization, but for an imaginary deformation parameter (the Planck constant). Gauge symmetries of thermodynamics and corresponding stochastic mechanics, which describes fluctuations of a thermodynamic system, are revealed and gauge fields are introduced. A physical interpretation to the gauge transformations and gauge fields is given. An application of the formalism to a description of systems with distributed parameters in a local thermodynamic equilibrium is considered.

  16. Stochastic deformation of a thermodynamic symplectic structure

    NASA Astrophysics Data System (ADS)

    Kazinski, P. O.

    2009-01-01

    A stochastic deformation of a thermodynamic symplectic structure is studied. The stochastic deformation is analogous to the deformation of an algebra of observables such as deformation quantization, but for an imaginary deformation parameter (the Planck constant). Gauge symmetries of thermodynamics and corresponding stochastic mechanics, which describes fluctuations of a thermodynamic system, are revealed and gauge fields are introduced. A physical interpretation to the gauge transformations and gauge fields is given. An application of the formalism to a description of systems with distributed parameters in a local thermodynamic equilibrium is considered.

  17. Soft mean spherical approximation for dusty plasma liquids: Level of accuracy and analytic expressions

    SciTech Connect

    Tolias, P.; Ratynskaia, S.; Angelis, U. de

    2015-08-15

    The soft mean spherical approximation is employed for the study of the thermodynamics of dusty plasma liquids, the latter treated as Yukawa one-component plasmas. Within this integral theory method, the only input necessary for the calculation of the reduced excess energy stems from the solution of a single non-linear algebraic equation. Consequently, thermodynamic quantities can be routinely computed without the need to determine the pair correlation function or the structure factor. The level of accuracy of the approach is quantified after an extensive comparison with numerical simulation results. The approach is solved over a million times with input spanning the whole parameter space and reliable analytic expressions are obtained for the basic thermodynamic quantities.

  18. Thermodynamics of reformulated automotive fuels

    SciTech Connect

    Zudkevitch, D.; Murthy, A.K.S.; Gmehling, J.

    1995-06-01

    Two methods for predicting Reid vapor pressure (Rvp) and initial vapor emissions of reformulated gasoline blends that contain one or more oxygenated compounds show excellent agreement with experimental data. In the first method, method A, D-86 distillation data for gasoline blends are used for predicting Rvp from a simulation of the mini dry vapor pressure equivalent (Dvpe) experiment. The other method, method B, relies on analytical information (PIANO analyses) of the base gasoline and uses classical thermodynamics for simulating the same Rvp equivalent (Rvpe) mini experiment. Method B also predicts composition and other properties for the fuel`s initial vapor emission. Method B, although complex, is more useful in that is can predict properties of blends without a D-86 distillation. An important aspect of method B is its capability to predict composition of initial vapor emissions from gasoline blends. Thus, it offers a powerful tool to planners of gasoline blending. Method B uses theoretically sound formulas, rigorous thermodynamic routines and uses data and correlations of physical properties that are in the public domain. Results indicate that predictions made with both methods agree very well with experimental values of Dvpe. Computer simulation methods were programmed and tested.

  19. Thermodynamic indicators for environmental certification.

    PubMed

    Panzieri, Margherita; Porcelli, Marcello; Pulselli, Federico Maria

    2002-09-01

    The Earth is an open thermodynamic system, that remains in a steady state far from the equilibrium, through energy and matter exchanges with the surrounding environment. These natural constraints, which prevent the system from maximizing its entropy, are threatened by human action and our ecosystem needs urgent protection. In this viewpoint the environmental certification was born, according to international standards ISO 14001, ISO 14040, and European Regulation EMAS. These are voluntary adhesions to a program of environmental protection by companies, administrations and organizations which, starting from the respect of the existing environmental laws and regulations, decide to further improve their environmental performance. To obtain and maintain certification of a system is necessary to apply some indicators to evaluate its environmental performance and to demonstrate its progressive improvement. Here we propose to use for this purpose the thermodynamic indicators produced from energy analysis by Odum. The case study is Montalcino city (Italy) and energy indicators are used to evaluate environmental performance of this system where exist different activities, from agricultural productions, to tourism. Results show that energy analysis could become a valid standard monitoring method for environmental certification, especially in consideration of its wide application field.

  20. Thermodynamic properties of triphenylantimony dibenzoate

    NASA Astrophysics Data System (ADS)

    Markin, A. V.; Smirnova, N. N.; Lyakaev, D. V.; Klimova, M. N.; Sharutin, V. V.; Sharutina, O. K.

    2016-10-01

    The temperature dependence of the heat capacity of triphenylantimony dibenzoate Ph3Sb(OC(O)Ph)2 is studied in the range of 6-480 K by means of precision adiabatic vacuum calorimetry and differential scanning calorimetry. The melting of the compound is observed in this temperature range, and its standard thermodynamic characteristics are identified and analyzed. Ph3Sb(OC(O)Ph)2 is obtained in a metastable amorphous state in a calorimeter. The standard thermodynamic functions of Ph3Sb(OC(O)Ph)2 in the crystalline and liquid states are calculated from the obtained experimental data: C p ° ( T), H°( T)- H°(0), S°( T), and G°(T)- H°(0) for the region from T → 0 to 480 K. The standard entropy of formation of the compound in the crystalline state at T = 298.15 K is determined. Multifractal processing of the low-temperature ( T < 50 K) heat capacity of the compound is performed. It is concluded that the structure of the compound has a planar chain topology.

  1. Thermodynamic States in Explosion Fields

    SciTech Connect

    Kuhl, A L

    2009-10-16

    Here we investigate the thermodynamic states occurring in explosion fields from the detonation of condensed explosives in air. In typical applications, the pressure of expanded detonation products gases is modeled by a Jones-Wilkins-Lee (JWL) function: P{sub JWL} = f(v,s{sub CJ}); constants in that function are fit to cylinder test data. This function provides a specification of pressure as a function of specific volume, v, along the expansion isentrope (s = constant = s{sub CJ}) starting at the Chapman-Jouguet (CJ) state. However, the JWL function is not a fundamental equation of thermodynamics, and therefore gives an incomplete specification of states. For example, explosions inherently involve shock reflections from surfaces; this changes the entropy of the products, and in such situations the JWL function provides no information on the products states. In addition, most explosives are not oxygen balanced, so if hot detonation products mix with air, they after-burn, releasing the heat of reaction via a turbulent combustion process. This raises the temperature of explosion products cloud to the adiabatic flame temperature ({approx}3,000K). Again, the JWL function provides no information on the combustion products states.

  2. Phase transition thermodynamics of bisphenols.

    PubMed

    Costa, José C S; Dávalos, Juan Z; Santos, Luís M N B F

    2014-10-16

    Herein we have studied, presented, and analyzed the phase equilibria thermodynamics of a bisphenols (BP-A, BP-E, BP-F, BP-AP, and BP-S) series. In particular, the heat capacities, melting temperatures, and vapor pressures at different temperatures as well as the standard enthalpies, entropies, and Gibbs energies of phase transition (fusion and sublimation) were experimentally determined. Also, we have presented the phase diagrams of each bisphenol derivative and investigated the key parameters related to the thermodynamic stability of the condensed phases. When all the bisphenol derivatives are compared at the same conditions, solids BP-AP and BP-S present lower volatilities (higher Gibbs energy of sublimation) and high melting temperatures due to the higher stability of their solid phases. Solids BP-A and BP-F present similar stabilities, whereas BP-E is more volatile. The introduction of -CH3 groups in BP-F (giving BP-E and BP-A) leads an entropic differentiation in the solid phase, whereas in the isotropic liquids the enthalpic and entropic differentiations are negligible.

  3. Thermodynamic studies on lithium ferrites

    NASA Astrophysics Data System (ADS)

    Rakshit, S. K.; Parida, S. C.; Naik, Y. P.; Chaudhary, Ziley Singh; Venugopal, V.

    2011-05-01

    Thermodynamic studies on ternary oxides of Li-Fe-O systems were carried out using differential scanning calorimetry, Knudsen effusion mass spectrometry, and solid-state electrochemical technique based on fluoride electrolyte. Heat capacities of LiFe 5O 8(s) and LiFeO 2(s) were determined in the temperature range 127-861 K using differential scanning calorimetry. Gibbs energies of formation of LiFe 5O 8(s) and LiFeO 2(s) were determined using Knudsen effusion mass spectrometry and solid-state galvanic cell technique. The combined least squares fits can be represented as Δ fGmo(LiFe 5O 8,s, T)/kJ mol -1 (±6)=-2341+0.6764( T/K) (588≤ T/K≤971) Δ fGmo(LiFeO 2,s, T)/kJ mol -1 (±3)=-708+0.1656( T/K) (569≤ T/K≤1021) The temperature independent term of the above equations represents Δ fHom( Tav) and temperature dependent term represents negative change in entropy of the respective compounds. Thermodynamic analysis shows that LiFe 5O 8(s) is more stable compared to LiFeO 2(s).

  4. Thermodynamic and kinetic investigation of agomelatine polymorph transformation.

    PubMed

    Zhang, Qi; Jiang, Linglei; Mei, Xuefeng

    2016-03-01

    Thermodynamic properties of polymorphic forms I and II of Agomelatine were investigated and the bimorphism was determined to be monotropically related. The phase transition kinetics from metastable form I to thermodynamically stable form II was studied and a quantification method was developed based on X-ray powder diffraction technique. Various solid-state kinetic models were examined and the results were fit to the experimental data. The nucleation kinetic models were found to be the best fit to describe the experimental data across the temperature range. The activation energy of the form transformation was calculated in the range of 116-122 kJ mol(-1), irrespective of which kinetic model selected.

  5. Thermodynamically important contacts in folding of model proteins.

    PubMed

    Scala, A; Dokholyan, N V; Buldyrev, S V; Stanley, H E

    2001-03-01

    We introduce a quantity, the entropic susceptibility, that measures the thermodynamic importance-for the folding transition-of the contacts between amino acids in model proteins. Using this quantity, we find that only one equilibrium run of a computer simulation of a model protein is sufficient to select a subset of contacts that give rise to the peak in the specific heat observed at the folding transition. To illustrate the method, we identify thermodynamically important contacts in a model 46-mer. We show that only about 50% of all contacts present in the protein native state are responsible for the sharp peak in the specific heat at the folding transition temperature, while the remaining 50% of contacts do not affect the specific heat.

  6. Thermodynamic Studies to Support Extraction of Uranium from Seawater

    SciTech Connect

    Rao, Linfeng

    2015-09-01

    This milestone report summarizes the data obtained in FY15 on the major task of quantifying the binding strength of amidoxime-related ligands. Thermodynamic studies of the interaction between U(VI) and amidoxime ligand HLIII were studied to quantify the binding ability of U(VI) with amidoxime-related ligands and help to select grafting/reaction conditions so that higher yield of preferred amidoxime-related ligands is obtained. Besides the thermodynamic task, structural studies on vanadium complexation with amidoxime ligand were conducted to help understand the extremely strong sorption of vanadium on poly(amidoxime) sorbents. Data processing and summarization of the vanadium system are in progress and will be included in the next milestone report.

  7. Thermodynamically driven, syn-selective vinylogous aldol reaction of tetronamides.

    PubMed

    Karak, Milandip; Barbosa, Luiz C A; Acosta, Jaime A M; Sarotti, Ariel M; Boukouvalas, John

    2016-06-01

    A stereoselective vinylogous aldol reaction of N-monosubstituted tetronamides with aldehydes is described. The procedure is simple and scalable, works well with both aromatic and aliphatic aldehydes, and affords mainly the corresponding syn-aldol adducts. In many cases, the latter are obtained essentially free of their anti-isomers (dr > 99 : 1) in high yields (70-90%). Experimental and computational studies suggest that the observed diastereoselectivity arises through anti-syn isomer interconversion, enabled by an iterative retro-aldol/aldol reaction.

  8. High accuracy flexural hinge development

    NASA Astrophysics Data System (ADS)

    Santos, I.; Ortiz de Zárate, I.; Migliorero, G.

    2005-07-01

    This document provides a synthesis of the technical results obtained in the frame of the HAFHA (High Accuracy Flexural Hinge Assembly) development performed by SENER (in charge of design, development, manufacturing and testing at component and mechanism levels) with EADS Astrium as subcontractor (in charge of doing an inventory of candidate applications among existing and emerging projects, establishing the requirements and perform system level testing) under ESA contract. The purpose of this project has been to develop a competitive technology for a flexural pivot, usuable in highly accurate and dynamic pointing/scanning mechanisms. Compared with other solutions (e.g. magnetic or ball bearing technologies) flexural hinges are the appropriate technology for guiding with accuracy a mobile payload over a limited angular ranges around one rotation axes.

  9. A thermodynamic analysis of the system LiAlSiO4-NaAlSiO4-Al2O3-SiO2-H2O based on new heat capacity, thermal expansion, and compressibility data for selected phases

    NASA Astrophysics Data System (ADS)

    Fasshauer, Detlef W.; Chatterjee, Niranjan D.; Cemic, Ladislav

    Heat capacity, thermal expansion, and compressibility data have been obtained for a number of selected phases of the system NaAlSiO4-LiAlSiO4-Al2O3-SiO2-H2O. All Cp measurements have been executed by DSC in the temperature range 133-823K. The data for T>=223K have been fitted to the function Cp(T)=a+cT -2+dT -0.5+fT -3, the fit parameters being The thermal expansion data (up to 525°C) have been fitted to the function V0(T)=V0(T) [1+v1 (T-T0)+v2 (T-T0)2], with T0=298.15K. The room-temperature compressibility data (up to 6 GPa) have been smoothed by the Murnaghan equation of state. The resulting parameters are These data, along with other phase property and reaction reversal data from the literature, have been simultaneously processed by the Bayes method to derive an internally consistent thermodynamic dataset (see Tables 6 and 7) for the NaAlSiO4-LiAlSiO4-Al2O3-SiO2-H2O quinary. Phase diagrams generated from this dataset are compatible with cookeite-, ephesite-, and paragonite-bearing assemblages observed in metabauxites and common metasediments. Phase diagrams obtained from the same database are also in agreement with the cookeite-free, petalite-, spodumene-, eucryptite-, and bikitaite-bearing assemblages known to develop in the subsolidus phase of recrystallization of lithium-bearing pegmatites. It is gratifying to note that the cookeite phase relations predicted earlier by Vidal and Goffé (1991) in the context of the system Li2O-Al2O3-SiO2-H2O agree with our results in a general way.

  10. Thermodynamic scaling of glassy dynamics and dynamic heterogeneities in metallic glass-forming liquid

    NASA Astrophysics Data System (ADS)

    Hu, Yuan-Chao; Shang, Bao-Shuang; Guan, Peng-Fei; Yang, Yong; Bai, Hai-Yang; Wang, Wei-Hua

    2016-09-01

    A ternary metallic glass-forming liquid is found to be not strongly correlating thermodynamically, but its average dynamics, dynamic heterogeneities including the high order dynamic correlation length, and static structure are still well described by thermodynamic scaling with the same scaling exponent γ. This may indicate that the metallic liquid could be treated as a single-parameter liquid. As an intrinsic material constant stemming from the fundamental interatomic interactions, γ is theoretically predicted from the thermodynamic fluctuations of the potential energy and the virial. Although γ is conventionally understood merely from the repulsive part of the inter-particle potentials, the strong correlation between γ and the Grüneisen parameter up to the accuracy of the Dulong-Petit approximation demonstrates the important roles of anharmonicity and attractive force of the interatomic potential in governing glass transition of metallic glassformers. These findings may shed light on how to understand metallic glass formation from the fundamental interatomic interactions.

  11. Thermodynamic scaling of glassy dynamics and dynamic heterogeneities in metallic glass-forming liquid.

    PubMed

    Hu, Yuan-Chao; Shang, Bao-Shuang; Guan, Peng-Fei; Yang, Yong; Bai, Hai-Yang; Wang, Wei-Hua

    2016-09-14

    A ternary metallic glass-forming liquid is found to be not strongly correlating thermodynamically, but its average dynamics, dynamic heterogeneities including the high order dynamic correlation length, and static structure are still well described by thermodynamic scaling with the same scaling exponent γ. This may indicate that the metallic liquid could be treated as a single-parameter liquid. As an intrinsic material constant stemming from the fundamental interatomic interactions, γ is theoretically predicted from the thermodynamic fluctuations of the potential energy and the virial. Although γ is conventionally understood merely from the repulsive part of the inter-particle potentials, the strong correlation between γ and the Grüneisen parameter up to the accuracy of the Dulong-Petit approximation demonstrates the important roles of anharmonicity and attractive force of the interatomic potential in governing glass transition of metallic glassformers. These findings may shed light on how to understand metallic glass formation from the fundamental interatomic interactions. PMID:27634267

  12. Municipal water consumption forecast accuracy

    NASA Astrophysics Data System (ADS)

    Fullerton, Thomas M.; Molina, Angel L.

    2010-06-01

    Municipal water consumption planning is an active area of research because of infrastructure construction and maintenance costs, supply constraints, and water quality assurance. In spite of that, relatively few water forecast accuracy assessments have been completed to date, although some internal documentation may exist as part of the proprietary "grey literature." This study utilizes a data set of previously published municipal consumption forecasts to partially fill that gap in the empirical water economics literature. Previously published municipal water econometric forecasts for three public utilities are examined for predictive accuracy against two random walk benchmarks commonly used in regional analyses. Descriptive metrics used to quantify forecast accuracy include root-mean-square error and Theil inequality statistics. Formal statistical assessments are completed using four-pronged error differential regression F tests. Similar to studies for other metropolitan econometric forecasts in areas with similar demographic and labor market characteristics, model predictive performances for the municipal water aggregates in this effort are mixed for each of the municipalities included in the sample. Given the competitiveness of the benchmarks, analysts should employ care when utilizing econometric forecasts of municipal water consumption for planning purposes, comparing them to recent historical observations and trends to insure reliability. Comparative results using data from other markets, including regions facing differing labor and demographic conditions, would also be helpful.

  13. Cost and accuracy of advanced breeding trial designs in apple

    PubMed Central

    Harshman, Julia M; Evans, Kate M; Hardner, Craig M

    2016-01-01

    Trialing advanced candidates in tree fruit crops is expensive due to the long-term nature of the planting and labor-intensive evaluations required to make selection decisions. How closely the trait evaluations approximate the true trait value needs balancing with the cost of the program. Designs of field trials of advanced apple candidates in which reduced number of locations, the number of years and the number of harvests per year were modeled to investigate the effect on the cost and accuracy in an operational breeding program. The aim was to find designs that would allow evaluation of the most additional candidates while sacrificing the least accuracy. Critical percentage difference, response to selection, and correlated response were used to examine changes in accuracy of trait evaluations. For the quality traits evaluated, accuracy and response to selection were not substantially reduced for most trial designs. Risk management influences the decision to change trial design, and some designs had greater risk associated with them. Balancing cost and accuracy with risk yields valuable insight into advanced breeding trial design. The methods outlined in this analysis would be well suited to other horticultural crop breeding programs. PMID:27019717

  14. Quantum Thermodynamics of Photo and Solar Cells

    NASA Astrophysics Data System (ADS)

    Dorfman, Konstantin E.; Chapin, Kimberly R.; Ooi, C. H. Raymond; Svidzinsky, Anatoly A.; Scully, Marlan O.

    2011-12-01

    Quantum coherence can increase the quantum efficiency of various thermodynamic systems. For example, we can enhance the quantum efficiency for a quantum dot photocell, a laser based solar cell and the photo-Carnot quantum heat engine. Our results are fully consistent with the laws of thermodynamics contrary to comments found in the paper of A. P. Kirk, Phys. Rev. Lett. 106, 048703 (2011).

  15. Teaching Differentials in Thermodynamics Using Spatial Visualization

    ERIC Educational Resources Information Center

    Wang, Chih-Yueh; Hou, Ching-Han

    2012-01-01

    The greatest difficulty that is encountered by students in thermodynamics classes is to find relationships between variables and to solve a total differential equation that relates one thermodynamic state variable to two mutually independent state variables. Rules of differentiation, including the total differential and the cyclic rule, are…

  16. A Vector Representation for Thermodynamic Relationships

    ERIC Educational Resources Information Center

    Pogliani, Lionello

    2006-01-01

    The existing vector formalism method for thermodynamic relationship maintains tractability and uses accessible mathematics, which can be seen as a diverting and entertaining step into the mathematical formalism of thermodynamics and as an elementary application of matrix algebra. The method is based on ideas and operations apt to improve the…

  17. Detonation Jet Engine. Part 1--Thermodynamic Cycle

    ERIC Educational Resources Information Center

    Bulat, Pavel V.; Volkov, Konstantin N.

    2016-01-01

    We present the most relevant works on jet engine design that utilize thermodynamic cycle of detonative combustion. The efficiency advantages of thermodynamic detonative combustion cycle over Humphrey combustion cycle at constant volume and Brayton combustion cycle at constant pressure were demonstrated. An ideal Ficket-Jacobs detonation cycle, and…

  18. Understanding Product Optimization: Kinetic versus Thermodynamic Control.

    ERIC Educational Resources Information Center

    Lin, King-Chuen

    1988-01-01

    Discusses the concept of kinetic versus thermodynamic control of reactions. Explains on the undergraduate level (1) the role of kinetic and thermodynamic control in kinetic equations, (2) the influence of concentration and temperature upon the reaction, and (3) the application of factors one and two to synthetic chemistry. (MVL)

  19. Friction Force: From Mechanics to Thermodynamics

    ERIC Educational Resources Information Center

    Ferrari, Christian; Gruber, Christian

    2010-01-01

    We study some mechanical problems in which a friction force is acting on a system. Using the fundamental concepts of state, time evolution and energy conservation, we explain how to extend Newtonian mechanics to thermodynamics. We arrive at the two laws of thermodynamics and then apply them to investigate the time evolution and heat transfer of…

  20. Understanding the Thermodynamics of Biological Order

    ERIC Educational Resources Information Center

    Peterson, Jacob

    2012-01-01

    By growth in size and complexity (i.e., changing from more probable to less probable states), plants and animals appear to defy the second law of thermodynamics. The usual explanation describes the input of nutrient and sunlight energy into open thermodynamic systems. However, energy input alone does not address the ability to organize and create…

  1. Thermodynamic geometry and critical aspects of bifurcations.

    PubMed

    Mihara, A

    2016-07-01

    This work presents an exploratory study of the critical aspects of some well-known bifurcations in the context of thermodynamic geometry. For each bifurcation its normal form is regarded as a geodesic equation of some model analogous to a thermodynamic system. From this hypothesis it is possible to calculate the corresponding metric and curvature and analyze the critical behavior of the bifurcation.

  2. An Experimental Determination of Thermodynamic Values

    ERIC Educational Resources Information Center

    Antony, Erling; Muccianti, Christine; Vogel, Tracy

    2012-01-01

    Measurements have been added to an old demonstration of chemical equilibria allowing the determination of thermodynamic constants. The experiment allows the students an opportunity to merge qualitative observations associated with Le Chatelier's principle and thermodynamic calculations using graphical techniques. (Contains 4 figures.)

  3. Thermodynamic geometry and critical aspects of bifurcations

    NASA Astrophysics Data System (ADS)

    Mihara, A.

    2016-07-01

    This work presents an exploratory study of the critical aspects of some well-known bifurcations in the context of thermodynamic geometry. For each bifurcation its normal form is regarded as a geodesic equation of some model analogous to a thermodynamic system. From this hypothesis it is possible to calculate the corresponding metric and curvature and analyze the critical behavior of the bifurcation.

  4. Thermodynamic properties of liquid metals /A review/.

    NASA Technical Reports Server (NTRS)

    Margrave, J. L.

    1970-01-01

    Summary of the current state of knowledge about the thermodynamic properties of liquid metals, including heats of fusion and heat capacities. A table is presented of consistent thermodynamic data for liquid metals, including estimates for the many high-melting transition metals which have not yet been studied, based on new levitation data and on periodic table correlations.

  5. Advanced working fluids: Thermodynamic properties

    NASA Astrophysics Data System (ADS)

    Lee, Lloyd L.; Gering, Kevin L.

    1990-10-01

    Electrolytes are used as working fluids in gas fired heat pump chiller engine cycles. To find out which molecular parameters of the electrolytes impact on cycle performance, a molecular theory is developed for calculating solution properties, enthalpies, vapor-liquid equilibria, and engine cycle performance. Aqueous and ammoniac single and mixed salt solutions in single and multisolvent systems are investigated. An accurate correlation is developed to evaluate properties for concentrated electrolyte solutions. Sensitivity analysis is used to determine the impact of molecular parameters on the thermodynamic properties and cycle performance. The preferred electrolytes are of 1-1 valence type, small ion size, high molecular weight, and in strongly colligative cosolvent. The operating windows are determined for a number of absorption fluids of industrial importance.

  6. Thermodynamics of freezing and melting.

    PubMed

    Pedersen, Ulf R; Costigliola, Lorenzo; Bailey, Nicholas P; Schrøder, Thomas B; Dyre, Jeppe C

    2016-01-01

    Although the freezing of liquids and melting of crystals are fundamental for many areas of the sciences, even simple properties like the temperature-pressure relation along the melting line cannot be predicted today. Here we present a theory in which properties of the coexisting crystal and liquid phases at a single thermodynamic state point provide the basis for calculating the pressure, density and entropy of fusion as functions of temperature along the melting line, as well as the variation along this line of the reduced crystalline vibrational mean-square displacement (the Lindemann ratio), and the liquid's diffusion constant and viscosity. The framework developed, which applies for the sizable class of systems characterized by hidden scale invariance, is validated by computer simulations of the standard 12-6 Lennard-Jones system. PMID:27530064

  7. Stochastic thermodynamics for active matter

    NASA Astrophysics Data System (ADS)

    Speck, Thomas

    2016-05-01

    The theoretical understanding of active matter, which is driven out of equilibrium by directed motion, is still fragmental and model oriented. Stochastic thermodynamics, on the other hand, is a comprehensive theoretical framework for driven systems that allows to define fluctuating work and heat. We apply these definitions to active matter, assuming that dissipation can be modelled by effective non-conservative forces. We show that, through the work, conjugate extensive and intensive observables can be defined even in non-equilibrium steady states lacking a free energy. As an illustration, we derive the expressions for the pressure and interfacial tension of active Brownian particles. The latter becomes negative despite the observed stable phase separation. We discuss this apparent contradiction, highlighting the role of fluctuations, and we offer a tentative explanation.

  8. Thermodynamics of Photons on Fractals

    SciTech Connect

    Akkermans, Eric; Dunne, Gerald V.; Teplyaev, Alexander

    2010-12-03

    A thermodynamical treatment of a massless scalar field (a photon) confined to a fractal spatial manifold leads to an equation of state relating pressure to internal energy, PV{sub s}=U/d{sub s}, where d{sub s} is the spectral dimension and V{sub s} defines the 'spectral volume'. For regular manifolds, V{sub s} coincides with the usual geometric spatial volume, but on a fractal this is not necessarily the case. This is further evidence that on a fractal, momentum space can have a different dimension than position space. Our analysis also provides a natural definition of the vacuum (Casimir) energy of a fractal. We suggest ways that these unusual properties might be probed experimentally.

  9. Thermodynamics of asymptotically safe theories

    NASA Astrophysics Data System (ADS)

    Rischke, Dirk H.; Sannino, Francesco

    2015-09-01

    We investigate the thermodynamic properties of a novel class of gauge-Yukawa theories that have recently been shown to be completely asymptotically safe, because their short-distance behavior is determined by the presence of an interacting fixed point. Not only do all the coupling constants freeze at a constant and calculable value in the ultraviolet, their values can even be made arbitrarily small for an appropriate choice of the ratio Nc/Nf of fermion colors and flavors in the Veneziano limit. Thus, a perturbative treatment can be justified. We compute the pressure, entropy density, and thermal degrees of freedom of these theories to next-to-next-to-leading order in the coupling constants.

  10. Nonequilibrium thermodynamics of wealth condensation

    NASA Astrophysics Data System (ADS)

    Braun, Dieter

    2006-09-01

    We analyze wealth condensation for a wide class of stochastic economy models on the basis of the economic analog of thermodynamic potentials, termed transfer potentials. The economy model is based on three common transfers modes of wealth: random transfer, profit proportional to wealth and motivation of poor agents to work harder. The economies never reach steady state. Wealth condensation is the result of stochastic tunneling through a metastable transfer potential. In accordance with reality, both wealth and income distribution transiently show Pareto tails for high-income subjects. For metastable transfer potentials, exponential wealth condensation is a robust feature. For example with 10% annual profit 1% of the population owns 50% of the wealth after 50 years. The time to reach such a strong wealth condensation is a hyperbolic function of the annual profit rate.

  11. Thermodynamics of freezing and melting

    PubMed Central

    Pedersen, Ulf R.; Costigliola, Lorenzo; Bailey, Nicholas P.; Schrøder, Thomas B.; Dyre, Jeppe C.

    2016-01-01

    Although the freezing of liquids and melting of crystals are fundamental for many areas of the sciences, even simple properties like the temperature–pressure relation along the melting line cannot be predicted today. Here we present a theory in which properties of the coexisting crystal and liquid phases at a single thermodynamic state point provide the basis for calculating the pressure, density and entropy of fusion as functions of temperature along the melting line, as well as the variation along this line of the reduced crystalline vibrational mean-square displacement (the Lindemann ratio), and the liquid's diffusion constant and viscosity. The framework developed, which applies for the sizable class of systems characterized by hidden scale invariance, is validated by computer simulations of the standard 12-6 Lennard-Jones system. PMID:27530064

  12. Thermodynamics of freezing and melting.

    PubMed

    Pedersen, Ulf R; Costigliola, Lorenzo; Bailey, Nicholas P; Schrøder, Thomas B; Dyre, Jeppe C

    2016-08-17

    Although the freezing of liquids and melting of crystals are fundamental for many areas of the sciences, even simple properties like the temperature-pressure relation along the melting line cannot be predicted today. Here we present a theory in which properties of the coexisting crystal and liquid phases at a single thermodynamic state point provide the basis for calculating the pressure, density and entropy of fusion as functions of temperature along the melting line, as well as the variation along this line of the reduced crystalline vibrational mean-square displacement (the Lindemann ratio), and the liquid's diffusion constant and viscosity. The framework developed, which applies for the sizable class of systems characterized by hidden scale invariance, is validated by computer simulations of the standard 12-6 Lennard-Jones system.

  13. Thermodynamics of freezing and melting

    NASA Astrophysics Data System (ADS)

    Pedersen, Ulf R.; Costigliola, Lorenzo; Bailey, Nicholas P.; Schrøder, Thomas B.; Dyre, Jeppe C.

    2016-08-01

    Although the freezing of liquids and melting of crystals are fundamental for many areas of the sciences, even simple properties like the temperature-pressure relation along the melting line cannot be predicted today. Here we present a theory in which properties of the coexisting crystal and liquid phases at a single thermodynamic state point provide the basis for calculating the pressure, density and entropy of fusion as functions of temperature along the melting line, as well as the variation along this line of the reduced crystalline vibrational mean-square displacement (the Lindemann ratio), and the liquid's diffusion constant and viscosity. The framework developed, which applies for the sizable class of systems characterized by hidden scale invariance, is validated by computer simulations of the standard 12-6 Lennard-Jones system.

  14. Thermodynamics of quantum heat engines

    NASA Astrophysics Data System (ADS)

    Goswami, Himangshu Prabal; Harbola, Upendra

    2013-07-01

    We consider a recently proposed four-level quantum heat engine (QHE) model to analyze the role of quantum coherences in determining the thermodynamic properties of the engine, such as flux, output power, and efficiency. A quantitative analysis of the relative effects of the coherences induced by the two thermal baths is brought out. By taking account of the dissipation in the cavity mode, we define useful work obtained from the QHE and present some analytical results for the optimal values of relative coherences that maximizes flux (hence output power) through the engine. We also analyze the role of quantum effects in inducing population inversion (lasing) between the states coupled to the cavity mode. The universal behavior of the efficiency at maximum power (EMP) is examined. In accordance with earlier theoretical predictions, to leading order, we find that EMP˜ηc/2, where ηc is Carnot efficiency. However, the next higher order coefficient is system dependent and hence nonuniversal.

  15. Thermodynamics of an accelerated expanding universe

    SciTech Connect

    Wang Bin; Gong Yungui; Abdalla, Elcio

    2006-10-15

    We investigate the laws of thermodynamics in an accelerating universe driven by dark energy with a time-dependent equation of state. In the case we consider that the physically relevant part of the Universe is that enveloped by the dynamical apparent horizon, we have shown that both the first law and second law of thermodynamics are satisfied. On the other hand, if the boundary of the Universe is considered to be the cosmological event horizon the thermodynamical description based on the definitions of boundary entropy and temperature breaks down. No parameter redefinition can rescue the thermodynamics laws from such a fate, rendering the cosmological event horizon unphysical from the point of view of the laws of thermodynamics.

  16. Application of thermodynamics to silicate crystalline solutions

    NASA Technical Reports Server (NTRS)

    Saxena, S. K.

    1972-01-01

    A review of thermodynamic relations is presented, describing Guggenheim's regular solution models, the simple mixture, the zeroth approximation, and the quasi-chemical model. The possibilities of retrieving useful thermodynamic quantities from phase equilibrium studies are discussed. Such quantities include the activity-composition relations and the free energy of mixing in crystalline solutions. Theory and results of the study of partitioning of elements in coexisting minerals are briefly reviewed. A thermodynamic study of the intercrystalline and intracrystalline ion exchange relations gives useful information on the thermodynamic behavior of the crystalline solutions involved. Such information is necessary for the solution of most petrogenic problems and for geothermometry. Thermodynamic quantities for tungstates (CaWO4-SrWO4) are calculated.

  17. Thermodynamic Properties of Dimethyl Carbonatea)

    NASA Astrophysics Data System (ADS)

    Zhou, Yong; Wu, Jiangtao; Lemmon, Eric W.

    2011-12-01

    A thermodynamic property formulation for dimethyl carbonate has been developed with the use of available experimental thermodynamic property data. The equation of state was developed with multiproperty fitting methods involving pressure-density-temperature (pρT), heat capacity, vapor pressure, and saturated-liquid density data. The equation of state conforms to the Maxwell criterion for two-phase liquid-vapor equilibrium states, and is valid for temperatures from the triple-point temperature (277.06 ± 0.63) K to 600 K, for pressures up to 60 MPa, and for densities up to 12.12 mol dm-3. The extrapolation behavior of the equation of state at low and high temperatures and pressures is reasonable. The uncertainties (k = 2, indicating a 95% confidence level) of the equation of state in density are 0.05% for saturated-liquid states below 350 K, rising to 0.1% in the single phase between 278 K and 400 K at pressures up to 60 MPa. Due to the lack of reliable data outside this region, the estimated uncertainties increase to 0.5% to 1% in the vapor and critical regions. The uncertainties in vapor pressure are 0.6% from 310 K to 400 K, and increase to 1% at higher temperatures and to 2% at lower temperatures due to a lack of experimental data. The uncertainty in isobaric heat capacity and speed of sound in the liquid phase at saturation or atmospheric pressure is 0.5% from 280 K to 335 K. The uncertainties are higher for all properties in the critical region. Detailed comparisons between experimental and calculated data, and an analysis of the equation, have been performed.

  18. Nanoparticle shape, thermodynamics and kinetics

    NASA Astrophysics Data System (ADS)

    Marks, L. D.; Peng, L.

    2016-02-01

    Nanoparticles can be beautiful, as in stained glass windows, or they can be ugly as in wear and corrosion debris from implants. We estimate that there will be about 70 000 papers in 2015 with nanoparticles as a keyword, but only one in thirteen uses the nanoparticle shape as an additional keyword and research focus, and only one in two hundred has thermodynamics. Methods for synthesizing nanoparticles have exploded over the last decade, but our understanding of how and why they take their forms has not progressed as fast. This topical review attempts to take a critical snapshot of the current understanding, focusing more on methods to predict than a purely synthetic or descriptive approach. We look at models and themes which are largely independent of the exact synthetic method whether it is deposition, gas-phase condensation, solution based or hydrothermal synthesis. Elements are old dating back to the beginning of the 20th century—some of the pioneering models developed then are still relevant today. Others are newer, a merging of older concepts such as kinetic-Wulff constructions with methods to understand minimum energy shapes for particles with twins. Overall we find that while there are still many unknowns, the broad framework of understanding and predicting the structure of nanoparticles via diverse Wulff constructions, either thermodynamic, local minima or kinetic has been exceedingly successful. However, the field is still developing and there remain many unknowns and new avenues for research, a few of these being suggested towards the end of the review.

  19. Sampling Molecular Conformers in Solution with Quantum Mechanical Accuracy at a Nearly Molecular-Mechanics Cost.

    PubMed

    Rosa, Marta; Micciarelli, Marco; Laio, Alessandro; Baroni, Stefano

    2016-09-13

    We introduce a method to evaluate the relative populations of different conformers of molecular species in solution, aiming at quantum mechanical accuracy, while keeping the computational cost at a nearly molecular-mechanics level. This goal is achieved by combining long classical molecular-dynamics simulations to sample the free-energy landscape of the system, advanced clustering techniques to identify the most relevant conformers, and thermodynamic perturbation theory to correct the resulting populations, using quantum-mechanical energies from density functional theory. A quantitative criterion for assessing the accuracy thus achieved is proposed. The resulting methodology is demonstrated in the specific case of cyanin (cyanidin-3-glucoside) in water solution.

  20. Sampling Molecular Conformers in Solution with Quantum Mechanical Accuracy at a Nearly Molecular-Mechanics Cost.

    PubMed

    Rosa, Marta; Micciarelli, Marco; Laio, Alessandro; Baroni, Stefano

    2016-09-13

    We introduce a method to evaluate the relative populations of different conformers of molecular species in solution, aiming at quantum mechanical accuracy, while keeping the computational cost at a nearly molecular-mechanics level. This goal is achieved by combining long classical molecular-dynamics simulations to sample the free-energy landscape of the system, advanced clustering techniques to identify the most relevant conformers, and thermodynamic perturbation theory to correct the resulting populations, using quantum-mechanical energies from density functional theory. A quantitative criterion for assessing the accuracy thus achieved is proposed. The resulting methodology is demonstrated in the specific case of cyanin (cyanidin-3-glucoside) in water solution. PMID:27494227

  1. Interpersonal Deception: V. Accuracy in Deception Detection.

    ERIC Educational Resources Information Center

    Burgoon, Judee K.; And Others

    1994-01-01

    Investigates the influence of several factors on accuracy in detecting truth and deceit. Found that accuracy was much higher on truth than deception, novices were more accurate than experts, accuracy depended on type of deception and whether suspicion was present or absent, suspicion impaired accuracy for experts, and questions strategy…

  2. Curation accuracy of model organism databases.

    PubMed

    Keseler, Ingrid M; Skrzypek, Marek; Weerasinghe, Deepika; Chen, Albert Y; Fulcher, Carol; Li, Gene-Wei; Lemmer, Kimberly C; Mladinich, Katherine M; Chow, Edmond D; Sherlock, Gavin; Karp, Peter D

    2014-01-01

    Manual extraction of information from the biomedical literature-or biocuration-is the central methodology used to construct many biological databases. For example, the UniProt protein database, the EcoCyc Escherichia coli database and the Candida Genome Database (CGD) are all based on biocuration. Biological databases are used extensively by life science researchers, as online encyclopedias, as aids in the interpretation of new experimental data and as golden standards for the development of new bioinformatics algorithms. Although manual curation has been assumed to be highly accurate, we are aware of only one previous study of biocuration accuracy. We assessed the accuracy of EcoCyc and CGD by manually selecting curated assertions within randomly chosen EcoCyc and CGD gene pages and by then validating that the data found in the referenced publications supported those assertions. A database assertion is considered to be in error if that assertion could not be found in the publication cited for that assertion. We identified 10 errors in the 633 facts that we validated across the two databases, for an overall error rate of 1.58%, and individual error rates of 1.82% for CGD and 1.40% for EcoCyc. These data suggest that manual curation of the experimental literature by Ph.D-level scientists is highly accurate. Database URL: http://ecocyc.org/, http://www.candidagenome.org//

  3. The development of flux-split algorithms for flows with non-equilibrium thermodynamics and chemical reactions

    NASA Technical Reports Server (NTRS)

    Grossman, B.; Cinella, P.

    1988-01-01

    A finite-volume method for the numerical computation of flows with nonequilibrium thermodynamics and chemistry is presented. A thermodynamic model is described which simplifies the coupling between the chemistry and thermodynamics and also results in the retention of the homogeneity property of the Euler equations (including all the species continuity and vibrational energy conservation equations). Flux-splitting procedures are developed for the fully coupled equations involving fluid dynamics, chemical production and thermodynamic relaxation processes. New forms of flux-vector split and flux-difference split algorithms are embodied in a fully coupled, implicit, large-block structure, including all the species conservation and energy production equations. Several numerical examples are presented, including high-temperature shock tube and nozzle flows. The methodology is compared to other existing techniques, including spectral and central-differenced procedures, and favorable comparisons are shown regarding accuracy, shock-capturing and convergence rates.

  4. Redox thermodynamics of lactoperoxidase and eosinophil peroxidase.

    PubMed

    Battistuzzi, Gianantonio; Bellei, Marzia; Vlasits, Jutta; Banerjee, Srijib; Furtmüller, Paul G; Sola, Marco; Obinger, Christian

    2010-02-01

    Eosinophil peroxidase (EPO) and lactoperoxidase (LPO) are important constituents of the innate immune system of mammals. These heme enzymes belong to the peroxidase-cyclooxygenase superfamily and catalyze the oxidation of thiocyanate, bromide and nitrite to hypothiocyanate, hypobromous acid and nitrogen dioxide that are toxic for invading pathogens. In order to gain a better understanding of the observed differences in substrate specificity and oxidation capacity in relation to heme and protein structure, a comprehensive spectro-electrochemical investigation was performed. The reduction potential (E degrees ') of the Fe(III)/Fe(II) couple of EPO and LPO was determined to be -126mV and -176mV, respectively (25 degrees C, pH 7.0). Variable temperature experiments show that EPO and LPO feature different reduction thermodynamics. In particular, reduction of ferric EPO is enthalpically and entropically disfavored, whereas in LPO the entropic term, which selectively stabilizes the oxidized form, prevails on the enthalpic term that favors reduction of Fe(III). The data are discussed with respect to the architecture of the heme cavity and the substrate channel. Comparison with published data for myeloperoxidase demonstrates the effect of heme to protein linkages and heme distortion on the redox chemistry of mammalian peroxidases and in consequence on the enzymatic properties of these physiologically important oxidoreductases.

  5. Thermodynamics and Kinetics of Silicate Vaporization

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan S.; Costa, Gustavo C. C.

    2015-01-01

    Silicates are a common class of materials that are often exposed to high temperatures. The behavior of these materials needs to be understood for applications as high temperature coatings in material science as well as the constituents of lava for geological considerations. The vaporization behavior of these materials is an important aspect of their high temperature behavior and it also provides fundamental thermodynamic data. The application of Knudsen effusion mass spectrometry (KEMS) to silicates is discussed. There are several special considerations for silicates. The first is selection of an appropriate cell material, which is either nearly inert or has well-understood interactions with the silicate. The second consideration is proper measurement of the low vapor pressures. This can be circumvented by using a reducing agent to boost the vapor pressure without changing the solid composition or by working at very high temperatures. The third consideration deals with kinetic barriers to vaporization. The measurement of these barriers, as encompassed in a vaporization coefficient, is discussed. Current measured data of rare earth silicates for high temperature coating applications are discussed. In addition, data on magnesium-iron-silicates (olivine) are presented and discussed.

  6. Molecular simulation of the thermodynamic, structural, and vapor-liquid equilibrium properties of neon.

    PubMed

    Vlasiuk, Maryna; Frascoli, Federico; Sadus, Richard J

    2016-09-14

    The thermodynamic, structural, and vapor-liquid equilibrium properties of neon are comprehensively studied using ab initio, empirical, and semi-classical intermolecular potentials and classical Monte Carlo simulations. Path integral Monte Carlo simulations for isochoric heat capacity and structural properties are also reported for two empirical potentials and one ab initio potential. The isobaric and isochoric heat capacities, thermal expansion coefficient, thermal pressure coefficient, isothermal and adiabatic compressibilities, Joule-Thomson coefficient, and the speed of sound are reported and compared with experimental data for the entire range of liquid densities from the triple point to the critical point. Lustig's thermodynamic approach is formally extended for temperature-dependent intermolecular potentials. Quantum effects are incorporated using the Feynman-Hibbs quantum correction, which results in significant improvement in the accuracy of predicted thermodynamic properties. The new Feynman-Hibbs version of the Hellmann-Bich-Vogel potential predicts the isochoric heat capacity to an accuracy of 1.4% over the entire range of liquid densities. It also predicts other thermodynamic properties more accurately than alternative intermolecular potentials.

  7. Molecular simulation of the thermodynamic, structural, and vapor-liquid equilibrium properties of neon

    NASA Astrophysics Data System (ADS)

    Vlasiuk, Maryna; Frascoli, Federico; Sadus, Richard J.

    2016-09-01

    The thermodynamic, structural, and vapor-liquid equilibrium properties of neon are comprehensively studied using ab initio, empirical, and semi-classical intermolecular potentials and classical Monte Carlo simulations. Path integral Monte Carlo simulations for isochoric heat capacity and structural properties are also reported for two empirical potentials and one ab initio potential. The isobaric and isochoric heat capacities, thermal expansion coefficient, thermal pressure coefficient, isothermal and adiabatic compressibilities, Joule-Thomson coefficient, and the speed of sound are reported and compared with experimental data for the entire range of liquid densities from the triple point to the critical point. Lustig's thermodynamic approach is formally extended for temperature-dependent intermolecular potentials. Quantum effects are incorporated using the Feynman-Hibbs quantum correction, which results in significant improvement in the accuracy of predicted thermodynamic properties. The new Feynman-Hibbs version of the Hellmann-Bich-Vogel potential predicts the isochoric heat capacity to an accuracy of 1.4% over the entire range of liquid densities. It also predicts other thermodynamic properties more accurately than alternative intermolecular potentials.

  8. Molecular simulation of the thermodynamic, structural, and vapor-liquid equilibrium properties of neon.

    PubMed

    Vlasiuk, Maryna; Frascoli, Federico; Sadus, Richard J

    2016-09-14

    The thermodynamic, structural, and vapor-liquid equilibrium properties of neon are comprehensively studied using ab initio, empirical, and semi-classical intermolecular potentials and classical Monte Carlo simulations. Path integral Monte Carlo simulations for isochoric heat capacity and structural properties are also reported for two empirical potentials and one ab initio potential. The isobaric and isochoric heat capacities, thermal expansion coefficient, thermal pressure coefficient, isothermal and adiabatic compressibilities, Joule-Thomson coefficient, and the speed of sound are reported and compared with experimental data for the entire range of liquid densities from the triple point to the critical point. Lustig's thermodynamic approach is formally extended for temperature-dependent intermolecular potentials. Quantum effects are incorporated using the Feynman-Hibbs quantum correction, which results in significant improvement in the accuracy of predicted thermodynamic properties. The new Feynman-Hibbs version of the Hellmann-Bich-Vogel potential predicts the isochoric heat capacity to an accuracy of 1.4% over the entire range of liquid densities. It also predicts other thermodynamic properties more accurately than alternative intermolecular potentials. PMID:27634265

  9. Quantitative code accuracy evaluation of ISP33

    SciTech Connect

    Kalli, H.; Miwrrin, A.; Purhonen, H.

    1995-09-01

    Aiming at quantifying code accuracy, a methodology based on the Fast Fourier Transform has been developed at the University of Pisa, Italy. The paper deals with a short presentation of the methodology and its application to pre-test and post-test calculations submitted to the International Standard Problem ISP33. This was a double-blind natural circulation exercise with a stepwise reduced primary coolant inventory, performed in PACTEL facility in Finland. PACTEL is a 1/305 volumetrically scaled, full-height simulator of the Russian type VVER-440 pressurized water reactor, with horizontal steam generators and loop seals in both cold and hot legs. Fifteen foreign organizations participated in ISP33, with 21 blind calculations and 20 post-test calculations, altogether 10 different thermal hydraulic codes and code versions were used. The results of the application of the methodology to nine selected measured quantities are summarized.

  10. Accuracy of lineaments mapping from space

    NASA Technical Reports Server (NTRS)

    Short, Nicholas M.

    1989-01-01

    The use of Landsat and other space imaging systems for lineaments detection is analyzed in terms of their effectiveness in recognizing and mapping fractures and faults, and the results of several studies providing a quantitative assessment of lineaments mapping accuracies are discussed. The cases under investigation include a Landsat image of the surface overlying a part of the Anadarko Basin of Oklahoma, the Landsat images and selected radar imagery of major lineaments systems distributed over much of Canadian Shield, and space imagery covering a part of the East African Rift in Kenya. It is demonstrated that space imagery can detect a significant portion of a region's fracture pattern, however, significant fractions of faults and fractures recorded on a field-produced geological map are missing from the imagery as it is evident in the Kenya case.

  11. Measuring Diagnoses: ICD Code Accuracy

    PubMed Central

    O'Malley, Kimberly J; Cook, Karon F; Price, Matt D; Wildes, Kimberly Raiford; Hurdle, John F; Ashton, Carol M

    2005-01-01

    Objective To examine potential sources of errors at each step of the described inpatient International Classification of Diseases (ICD) coding process. Data Sources/Study Setting The use of disease codes from the ICD has expanded from classifying morbidity and mortality information for statistical purposes to diverse sets of applications in research, health care policy, and health care finance. By describing a brief history of ICD coding, detailing the process for assigning codes, identifying where errors can be introduced into the process, and reviewing methods for examining code accuracy, we help code users more systematically evaluate code accuracy for their particular applications. Study Design/Methods We summarize the inpatient ICD diagnostic coding process from patient admission to diagnostic code assignment. We examine potential sources of errors at each step and offer code users a tool for systematically evaluating code accuracy. Principle Findings Main error sources along the “patient trajectory” include amount and quality of information at admission, communication among patients and providers, the clinician's knowledge and experience with the illness, and the clinician's attention to detail. Main error sources along the “paper trail” include variance in the electronic and written records, coder training and experience, facility quality-control efforts, and unintentional and intentional coder errors, such as misspecification, unbundling, and upcoding. Conclusions By clearly specifying the code assignment process and heightening their awareness of potential error sources, code users can better evaluate the applicability and limitations of codes for their particular situations. ICD codes can then be used in the most appropriate ways. PMID:16178999

  12. Determining gas-meter accuracy

    SciTech Connect

    Valenti, M.

    1997-03-01

    This article describes how engineers at the Metering Research Facility are helping natural-gas companies improve pipeline efficiency by evaluating and refining the instruments used for measuring and setting prices. Accurate metering of natural gas is more important than ever as deregulation subjects pipeline companies to competition. To help improve that accuracy, the Gas Research Institute (GRI) in Chicago has sponsored the Metering Research Facility (MRF) at the Southwest Research Institute (SWRI) in San Antonio, Tex. The MRF evaluates and improves the performance of orifice, turbine, diaphragm, and ultrasonic meters as well as the gas-sampling methods that pipeline companies use to measure the flow of gas and determine its price.

  13. Thermodynamics of imidacloprid sorption in Croatian soils

    NASA Astrophysics Data System (ADS)

    Milin, Čedomila; Broznic, Dalibor

    2015-04-01

    Neonicotinoids are increasingly replacing the organophosphate and methylcarbamate acetylcholinesterase inhibitors which are losing their effectiveness because of selection for resistant pest populations. Imidacloprid is the most important neonicotinoid with low soil persistence, high insecticidal potency and relatively low mammalian toxicity. In Croatia, imidacloprid is most commonly used in olive growing areas, including Istria and Kvarner islands, as an effective means of olive fruit fly infestation control. Sorption-desorption behavior of imidacloprid in six soils collected from five coastal regions in Croatia at 20, 30 and 40°C was investigated using batch equilibrium technique. Isothermal data were applied to Freundlich, Langmuir and Temkin equation, and the thermodynamic parameters ΔH°, ΔG°, ΔS° were calculated. The sorption isotherm curves were of non-linear and may be classified as L-type suggesting a relatively high sorption capacity for imidacloprid. Our results showed that the KFsor values decreased for all the tested soils as the temperature increases, indicating that the temperature strongly influence the sorption. Values of ΔG° were negative (-4.65 to -2.00 kJ/mol) indicating that at all experimental temperatures the interactions of imidacloprid with soils were spontaneous process. The negative and small ΔH° values (-19.79 to -8.89 kJ/mol) were in the range of weak forces, such as H-bonds, consistent with interactions and par¬titioning of the imidacloprid molecules into soil organic matter. The ΔS° values followed the range of -57.12 to -14.51 J/molK, suggesting that imidacloprid molecules lose entropy during transition from the solution phase to soil surface. It was found that imidacloprid desorption from soil was concentration and temperature dependent, i.e. at lower imidacloprid concentrations and temperature, lower desorption percentage occurred. Desorption studies revealed that hysteretic behavior under different temperature

  14. Thermodynamics of formation of molecular sieves

    NASA Astrophysics Data System (ADS)

    Piccione, Patrick Manuel

    2002-09-01

    Thermodynamic investigations are undertaken to better understand the energetic differences amongst molecular sieve frameworks and the mechanisms and interactions important in molecular sieve self-assembly. The enthalpies relative to quartz at 298.15 K are determined by high-temperature solution calorimetry for a collection of calcined pure-silica molecular sieves with diverse structural features. SiO2 molecular sieves are shown to be only modestly (6.8--14.4 kJ/mol) metastable with respect to quartz. The available thermal energy at typical synthesis conditions is RT = 3.5 kJ/mol. A strong correlation between enthalpy and molar volume is observed. The entropies of four pure-silica molecular sieves with a wide range of molar volumes are determined by heat capacity measurements from 5 to 400 K. The entropies of these structures are almost identical (3.2--4.2 J · K-1mol-1 above quartz). The enthalpy and entropy data are combined to calculate the Gibbs free energies of transition from quartz to eight other silica polymorphs. The molecular sieve Gibbs free energies are only 5.5--12.6 kJ/mol less stable than quartz. Therefore, there are no significant thermodynamic barriers to transformations between silica polymorphs. This result suggests that structure-directing agents (SDAs) in molecular sieves syntheses do not serve to stabilize otherwise very unstable phases. Interaction enthalpies between inorganic frameworks and organic SDAs are measured by HF solution calorimetry for six molecular sieve/SDA pairs. The enthalpies are only moderately exothermic (-1.1 to -5.9 kJ/mol SiO2), as expected if the predominant interactions are silica/hydrocarbon van der Waals contacts. Interaction entropies are estimated for three framework/SDA pairs, and together with the interaction enthalpies allow the calculation of the Gibbs free energies of interaction. The latter values range from -2.0 to -5.4 kJ/mol SiO2. This energy range is comparable to that observed for the SiO2 frameworks

  15. Knowledge discovery by accuracy maximization.

    PubMed

    Cacciatore, Stefano; Luchinat, Claudio; Tenori, Leonardo

    2014-04-01

    Here we describe KODAMA (knowledge discovery by accuracy maximization), an unsupervised and semisupervised learning algorithm that performs feature extraction from noisy and high-dimensional data. Unlike other data mining methods, the peculiarity of KODAMA is that it is driven by an integrated procedure of cross-validation of the results. The discovery of a local manifold's topology is led by a classifier through a Monte Carlo procedure of maximization of cross-validated predictive accuracy. Briefly, our approach differs from previous methods in that it has an integrated procedure of validation of the results. In this way, the method ensures the highest robustness of the obtained solution. This robustness is demonstrated on experimental datasets of gene expression and metabolomics, where KODAMA compares favorably with other existing feature extraction methods. KODAMA is then applied to an astronomical dataset, revealing unexpected features. Interesting and not easily predictable features are also found in the analysis of the State of the Union speeches by American presidents: KODAMA reveals an abrupt linguistic transition sharply separating all post-Reagan from all pre-Reagan speeches. The transition occurs during Reagan's presidency and not from its beginning.

  16. High accuracy time transfer synchronization

    NASA Technical Reports Server (NTRS)

    Wheeler, Paul J.; Koppang, Paul A.; Chalmers, David; Davis, Angela; Kubik, Anthony; Powell, William M.

    1995-01-01

    In July 1994, the U.S. Naval Observatory (USNO) Time Service System Engineering Division conducted a field test to establish a baseline accuracy for two-way satellite time transfer synchronization. Three Hewlett-Packard model 5071 high performance cesium frequency standards were transported from the USNO in Washington, DC to Los Angeles, California in the USNO's mobile earth station. Two-Way Satellite Time Transfer links between the mobile earth station and the USNO were conducted each day of the trip, using the Naval Research Laboratory(NRL) designed spread spectrum modem, built by Allen Osborne Associates(AOA). A Motorola six channel GPS receiver was used to track the location and altitude of the mobile earth station and to provide coordinates for calculating Sagnac corrections for the two-way measurements, and relativistic corrections for the cesium clocks. This paper will discuss the trip, the measurement systems used and the results from the data collected. We will show the accuracy of using two-way satellite time transfer for synchronization and the performance of the three HP 5071 cesium clocks in an operational environment.

  17. Knowledge discovery by accuracy maximization

    PubMed Central

    Cacciatore, Stefano; Luchinat, Claudio; Tenori, Leonardo

    2014-01-01

    Here we describe KODAMA (knowledge discovery by accuracy maximization), an unsupervised and semisupervised learning algorithm that performs feature extraction from noisy and high-dimensional data. Unlike other data mining methods, the peculiarity of KODAMA is that it is driven by an integrated procedure of cross-validation of the results. The discovery of a local manifold’s topology is led by a classifier through a Monte Carlo procedure of maximization of cross-validated predictive accuracy. Briefly, our approach differs from previous methods in that it has an integrated procedure of validation of the results. In this way, the method ensures the highest robustness of the obtained solution. This robustness is demonstrated on experimental datasets of gene expression and metabolomics, where KODAMA compares favorably with other existing feature extraction methods. KODAMA is then applied to an astronomical dataset, revealing unexpected features. Interesting and not easily predictable features are also found in the analysis of the State of the Union speeches by American presidents: KODAMA reveals an abrupt linguistic transition sharply separating all post-Reagan from all pre-Reagan speeches. The transition occurs during Reagan’s presidency and not from its beginning. PMID:24706821

  18. High accuracy time transfer synchronization

    NASA Astrophysics Data System (ADS)

    Wheeler, Paul J.; Koppang, Paul A.; Chalmers, David; Davis, Angela; Kubik, Anthony; Powell, William M.

    1995-05-01

    In July 1994, the U.S. Naval Observatory (USNO) Time Service System Engineering Division conducted a field test to establish a baseline accuracy for two-way satellite time transfer synchronization. Three Hewlett-Packard model 5071 high performance cesium frequency standards were transported from the USNO in Washington, DC to Los Angeles, California in the USNO's mobile earth station. Two-Way Satellite Time Transfer links between the mobile earth station and the USNO were conducted each day of the trip, using the Naval Research Laboratory(NRL) designed spread spectrum modem, built by Allen Osborne Associates(AOA). A Motorola six channel GPS receiver was used to track the location and altitude of the mobile earth station and to provide coordinates for calculating Sagnac corrections for the two-way measurements, and relativistic corrections for the cesium clocks. This paper will discuss the trip, the measurement systems used and the results from the data collected. We will show the accuracy of using two-way satellite time transfer for synchronization and the performance of the three HP 5071 cesium clocks in an operational environment.

  19. High-accuracy EUV reflectometer

    NASA Astrophysics Data System (ADS)

    Hinze, U.; Fokoua, M.; Chichkov, B.

    2007-03-01

    Developers and users of EUV-optics need precise tools for the characterization of their products. Often a measurement accuracy of 0.1% or better is desired to detect and study slow-acting aging effect or degradation by organic contaminants. To achieve a measurement accuracy of 0.1% an EUV-source is required which provides an excellent long-time stability, namely power stability, spatial stability and spectral stability. Naturally, it should be free of debris. An EUV-source particularly suitable for this task is an advanced electron-based EUV-tube. This EUV source provides an output of up to 300 μW at 13.5 nm. Reflectometers benefit from the excellent long-time stability of this tool. We design and set up different reflectometers using EUV-tubes for the precise characterisation of EUV-optics, such as debris samples, filters, multilayer mirrors, grazing incidence optics, collectors and masks. Reflectivity measurements from grazing incidence to near normal incidence as well as transmission studies were realised at a precision of down to 0.1%. The reflectometers are computer-controlled and allow varying and scanning all important parameters online. The concepts of a sample reflectometer is discussed and results are presented. The devices can be purchased from the Laser Zentrum Hannover e.V.

  20. Relating single-molecule measurements to thermodynamics.

    PubMed

    Keller, David; Swigon, David; Bustamante, Carlos

    2003-02-01

    Measurements made on large ensembles of molecules are routinely interpreted using thermodynamics, but the normal rules of thermodynamics may not apply to measurements made on single molecules. Using a polymer stretching experiment as an example, it is shown that in the limit of a single, short molecule the outcome of experimental measurements may depend on which variables are held fixed and which are allowed to fluctuate. Thus an experiment in which the end-to-end distance of the polymer molecule is fixed and the tension fluctuates yields a different result than an experiment where the force is fixed and the end-to-end distance fluctuates. It is further shown that this difference is due to asymmetry in the distribution of end-to-end distances for a single molecule, and that the difference vanishes in the appropriate thermodynamic limit; that is, as the polymer molecule becomes long compared to its persistence length. Despite these differences, much of the thermodynamic formalism still applies on the single-molecule level if the thermodynamic free energies are replaced with appropriate potentials of mean force. The primary remaining differences are consequences of the fact that unlike the free energies, the potentials of mean force are not in general homogeneous functions of their variables. The basic thermodynamic concepts of an intensive or extensive quantity, and the thermodynamic relationships that follow from them, are therefore less useful for interpreting single-molecule experiments.

  1. Thermodynamics of cosmological matter creation.

    PubMed

    Prigogine, I; Geheniau, J; Gunzig, E; Nardone, P

    1988-10-01

    A type of cosmological history that includes large-scale entropy production is proposed. These cosmologies are based on reinterpretation of the matter-energy stress tensor in Einstein's equations. This modifies the usual adiabatic energy conservation laws, thereby including irreversible matter creation. This creation corresponds to an irreversible energy flow from the gravitational field to the created matter constituents. This point of view results from consideration of the thermodynamics of open systems in the framework of cosmology. It is shown that the second law of thermodynamics requires that space-time transforms into matter, while the inverse transformation is forbidden. It appears that the usual initial singularity associated with the big bang is structurally unstable with respect to irreversible matter creation. The corresponding cosmological history therefore starts from an instability of the vacuum rather than from a singularity. This is exemplified in the framework of a simple phenomenological model that leads to a three-stage cosmology: the first drives the cosmological system from the initial instability to a de Sitter regime, and the last connects with the usual matter-radiation Robertson-Walker universe. Matter as well as entropy creation occurs during the first two stages, while the third involves the traditional cosmological evolution. A remarkable fact is that the de Sitter stage appears to be an attractor independent of the initial fluctuation. This is also the case for all the physical predictions involving the present Robertson-Walker universe. Most results obtained previously, in the framework of quantum field theory, can now be obtained on a macroscopic basis. It is shown that this description leads quite naturally to the introduction of primeval black holes as the intermediate stage between the Minkowski vacuum and the present matter-radiation universe. The instability at the origin of the universe is the result of fluctuations of the

  2. Thermodynamics of cosmological matter creation.

    PubMed

    Prigogine, I; Geheniau, J; Gunzig, E; Nardone, P

    1988-10-01

    A type of cosmological history that includes large-scale entropy production is proposed. These cosmologies are based on reinterpretation of the matter-energy stress tensor in Einstein's equations. This modifies the usual adiabatic energy conservation laws, thereby including irreversible matter creation. This creation corresponds to an irreversible energy flow from the gravitational field to the created matter constituents. This point of view results from consideration of the thermodynamics of open systems in the framework of cosmology. It is shown that the second law of thermodynamics requires that space-time transforms into matter, while the inverse transformation is forbidden. It appears that the usual initial singularity associated with the big bang is structurally unstable with respect to irreversible matter creation. The corresponding cosmological history therefore starts from an instability of the vacuum rather than from a singularity. This is exemplified in the framework of a simple phenomenological model that leads to a three-stage cosmology: the first drives the cosmological system from the initial instability to a de Sitter regime, and the last connects with the usual matter-radiation Robertson-Walker universe. Matter as well as entropy creation occurs during the first two stages, while the third involves the traditional cosmological evolution. A remarkable fact is that the de Sitter stage appears to be an attractor independent of the initial fluctuation. This is also the case for all the physical predictions involving the present Robertson-Walker universe. Most results obtained previously, in the framework of quantum field theory, can now be obtained on a macroscopic basis. It is shown that this description leads quite naturally to the introduction of primeval black holes as the intermediate stage between the Minkowski vacuum and the present matter-radiation universe. The instability at the origin of the universe is the result of fluctuations of the

  3. Thermodynamic universality of quantum Carnot engines.

    PubMed

    Gardas, Bartłomiej; Deffner, Sebastian

    2015-10-01

    The Carnot statement of the second law of thermodynamics poses an upper limit on the efficiency of all heat engines. Recently, it has been studied whether generic quantum features such as coherence and quantum entanglement could allow for quantum devices with efficiencies larger than the Carnot efficiency. The present study shows that this is not permitted by the laws of thermodynamics-independent of the model. We will show that rather the definition of heat has to be modified to account for the thermodynamic cost of maintaining non-Gibbsian equilibrium states. Our theoretical findings are illustrated for two experimentally relevant examples.

  4. Thermodynamic universality of quantum Carnot engines.

    PubMed

    Gardas, Bartłomiej; Deffner, Sebastian

    2015-10-01

    The Carnot statement of the second law of thermodynamics poses an upper limit on the efficiency of all heat engines. Recently, it has been studied whether generic quantum features such as coherence and quantum entanglement could allow for quantum devices with efficiencies larger than the Carnot efficiency. The present study shows that this is not permitted by the laws of thermodynamics-independent of the model. We will show that rather the definition of heat has to be modified to account for the thermodynamic cost of maintaining non-Gibbsian equilibrium states. Our theoretical findings are illustrated for two experimentally relevant examples. PMID:26565187

  5. Black holes: Combinatorics and the thermodynamic limit

    NASA Astrophysics Data System (ADS)

    Barbero G., J. Fernando

    2012-07-01

    The purpose of this contribution is to review the combinatorial methods used in loop quantum gravity to compute the entropy of black holes and discuss some applications of the formalism, in particular to the study of the thermodynamic limit. The main reason to look at this issue is the fact that the entropy must be a smooth function if one wants to remain within the confines of standard thermodynamics. Also, in precision studies of the entropy, it is important to check wether subdominant corrections for the statistical and the thermodynamical entropy coincide.

  6. Considerations on non equilibrium thermodynamics of interactions

    NASA Astrophysics Data System (ADS)

    Lucia, Umberto

    2016-04-01

    Nature can be considered the "first" engineer! For scientists and engineers, dynamics and evolution of complex systems are not easy to predict. A fundamental approach to study complex system is thermodynamics. But, the result is the origin of too many schools of thermodynamics with a consequent difficulty in communication between thermodynamicists and other scientists and, also, among themselves. The solution is to obtain a unified approach based on the fundamentals of physics. Here we suggest a possible unification of the schools of thermodynamics starting from two fundamental concepts of physics, interaction and flows.

  7. Thermodynamic universality of quantum Carnot engines

    SciTech Connect

    Gardas, Bartłomiej; Deffner, Sebastian

    2015-10-12

    The Carnot statement of the second law of thermodynamics poses an upper limit on the efficiency of all heat engines. Recently, it has been studied whether generic quantum features such as coherence and quantum entanglement could allow for quantum devices with efficiencies larger than the Carnot efficiency. The present study shows that this is not permitted by the laws of thermodynamic —independent of the model. We will show that rather the definition of heat has to be modified to account for the thermodynamic cost of maintaining non-Gibbsian equilibrium states. As a result, our theoretical findings are illustrated for two experimentally relevant examples.

  8. Thermodynamic universality of quantum Carnot engines

    DOE PAGES

    Gardas, Bartłomiej; Deffner, Sebastian

    2015-10-12

    The Carnot statement of the second law of thermodynamics poses an upper limit on the efficiency of all heat engines. Recently, it has been studied whether generic quantum features such as coherence and quantum entanglement could allow for quantum devices with efficiencies larger than the Carnot efficiency. The present study shows that this is not permitted by the laws of thermodynamic —independent of the model. We will show that rather the definition of heat has to be modified to account for the thermodynamic cost of maintaining non-Gibbsian equilibrium states. As a result, our theoretical findings are illustrated for two experimentallymore » relevant examples.« less

  9. Thermodynamical stability of the Bardeen black hole

    SciTech Connect

    Bretón, Nora; Perez Bergliaffa, Santiago E.

    2014-01-14

    We analyze the stability of the regular magnetic Bardeen black hole both thermodynamically and dynamically. For the thermodynamical analysis we consider a microcanonical ensemble and apply the turning point method. This method allows to decide a change in stability (or instability) of a system, requiring only the assumption of smoothness of the area functional. The dynamical stability is asserted using criteria based on the signs of the Lagrangian and its derivatives. It turns out from our analysis that the Bardeen black hole is both thermodynamically and dynamically stable.

  10. Simplified curve fits for the thermodynamic properties of equilibrium air

    NASA Technical Reports Server (NTRS)

    Srinivasan, S.; Tannehill, J. C.; Weilmuenster, K. J.

    1986-01-01

    New improved curve fits for the thermodynamic properties of equilibrium air were developed. The curve fits are for p = p(e,rho), a = a(e,rho), T = T(e,rho), s = s(e,rho), T = T(p,rho), h = h(p,rho), rho = rho(p,s), e = e(p,s) and a = a(p,s). These curve fits can be readily incorporated into new or existing Computational Fluid Dynamics (CFD) codes if real-gas effects are desired. The curve fits were constructed using Grabau-type transition functions to model the thermodynamic surfaces in a piecewise manner. The accuracies and continuity of these curve fits are substantially improved over those of previous curve fits appearing in NASA CR-2470. These improvements were due to the incorporation of a small number of additional terms in the approximating polynomials and careful choices of the transition functions. The ranges of validity of the new curve fits are temperatures up to 25,000 K and densities from 10 to the minus 7th to 100 amagats (rho/rho sub 0).

  11. [Navigation in implantology: Accuracy assessment regarding the literature].

    PubMed

    Barrak, Ibrahim Ádám; Varga, Endre; Piffko, József

    2016-06-01

    Our objective was to assess the literature regarding the accuracy of the different static guided systems. After applying electronic literature search we found 661 articles. After reviewing 139 articles, the authors chose 52 articles for full-text evaluation. 24 studies involved accuracy measurements. Fourteen of our selected references were clinical and ten of them were in vitro (modell or cadaver). Variance-analysis (Tukey's post-hoc test; p < 0.05) was conducted to summarize the selected publications. Regarding 2819 results the average mean error at the entry point was 0.98 mm. At the level of the apex the average deviation was 1.29 mm while the mean of the angular deviation was 3,96 degrees. Significant difference could be observed between the two methods of implant placement (partially and fully guided sequence) in terms of deviation at the entry point, apex and angular deviation. Different levels of quality and quantity of evidence were available for assessing the accuracy of the different computer-assisted implant placement. The rapidly evolving field of digital dentistry and the new developments will further improve the accuracy of guided implant placement. In the interest of being able to draw dependable conclusions and for the further evaluation of the parameters used for accuracy measurements, randomized, controlled single or multi-centered clinical trials are necessary. PMID:27544966

  12. [Navigation in implantology: Accuracy assessment regarding the literature].

    PubMed

    Barrak, Ibrahim Ádám; Varga, Endre; Piffko, József

    2016-06-01

    Our objective was to assess the literature regarding the accuracy of the different static guided systems. After applying electronic literature search we found 661 articles. After reviewing 139 articles, the authors chose 52 articles for full-text evaluation. 24 studies involved accuracy measurements. Fourteen of our selected references were clinical and ten of them were in vitro (modell or cadaver). Variance-analysis (Tukey's post-hoc test; p < 0.05) was conducted to summarize the selected publications. Regarding 2819 results the average mean error at the entry point was 0.98 mm. At the level of the apex the average deviation was 1.29 mm while the mean of the angular deviation was 3,96 degrees. Significant difference could be observed between the two methods of implant placement (partially and fully guided sequence) in terms of deviation at the entry point, apex and angular deviation. Different levels of quality and quantity of evidence were available for assessing the accuracy of the different computer-assisted implant placement. The rapidly evolving field of digital dentistry and the new developments will further improve the accuracy of guided implant placement. In the interest of being able to draw dependable conclusions and for the further evaluation of the parameters used for accuracy measurements, randomized, controlled single or multi-centered clinical trials are necessary.

  13. Selection of Electronic Resources.

    ERIC Educational Resources Information Center

    Weathers, Barbara

    1998-01-01

    Discusses the impact of electronic resources on collection development; selection of CD-ROMs, (platform, speed, video and sound, networking capability, installation and maintenance); selection of laser disks; and Internet evaluation (accuracy of content, authority, objectivity, currency, technical characteristics). Lists Web sites for evaluating…

  14. THERMODYNAMIC TABLES FOR NUCLEAR WASTE ISOLATION, V.1: AQUEOUSSOLUTIONS DATABASE

    SciTech Connect

    Phillips, S.L.; Hale, F.V.; Silvester, L.F.

    1988-05-01

    Tables of consistent thermodynamic property values for nuclear waste isolation are given. The tables include critically assessed values for Gibbs energy of formation. enthalpy of formation, entropy and heat capacity for minerals; solids; aqueous ions; ion pairs and complex ions of selected actinide and fission decay products at 25{sup o}C and zero ionic strength. These intrinsic data are used to calculate equilibrium constants and standard potentials which are compared with typical experimental measurements and other work. Recommendations for additional research are given.

  15. Pulse oximetry: accuracy of methods of interpreting graphic summaries.

    PubMed

    Lafontaine, V M; Ducharme, F M; Brouillette, R T

    1996-02-01

    Although pulse oximetry has been used to determine the frequency and extent of hemoglobin desaturation during sleep, movement artifact can result in overestimation of desaturation unless valid desaturations can be identified accurately. Therefore, we determined the accuracy of pulmonologists' and technicians' interpretations of graphic displays of desaturation events, derived an objective method for interpreting such events, and validated the method on an independent data set. Eighty-seven randomly selected desaturation events were classified as valid (58) or artifactual (29) based on cardiorespiratory recordings (gold standard) that included pulse waveform and respiratory inductive plethysmography signals. Using oximetry recordings (test method), nine pediatric pulmonologists and three respiratory technicians ("readers") averaged 50 +/- 11% (SD) accuracy for event classification. A single variable, the pulse amplitude modulation range (PAMR) prior to desaturation, performed better in discriminating valid from artifactual events with 76% accuracy (P < 0.05). Following a seminar on oximetry and the use of the PAMR method, the readers' accuracy increased to 73 +/- 2%. In an independent set of 73 apparent desaturation events (74% valid, 26% artifactual), the PAMR method of assessing oximetry graphs yielded 82% accuracy; transcutaneous oxygen tension records confirmed a drop in oxygenation during 49 of 54 (89%) valid desaturation events. In conclusion, the most accurate method (91%) of assessing desaturation events requires recording of the pulse and respiratory waveforms. However, a practical, easy-to-use method of interpreting pulse oximetry recordings achieved 76-82% accuracy, which constitutes a significant improvement from previous subjective interpretations.

  16. Bayesian second law of thermodynamics

    NASA Astrophysics Data System (ADS)

    Bartolotta, Anthony; Carroll, Sean M.; Leichenauer, Stefan; Pollack, Jason

    2016-08-01

    We derive a generalization of the second law of thermodynamics that uses Bayesian updates to explicitly incorporate the effects of a measurement of a system at some point in its evolution. By allowing an experimenter's knowledge to be updated by the measurement process, this formulation resolves a tension between the fact that the entropy of a statistical system can sometimes fluctuate downward and the information-theoretic idea that knowledge of a stochastically evolving system degrades over time. The Bayesian second law can be written as Δ H (ρm,ρ ) + F |m≥0 , where Δ H (ρm,ρ ) is the change in the cross entropy between the original phase-space probability distribution ρ and the measurement-updated distribution ρm and F |m is the expectation value of a generalized heat flow out of the system. We also derive refined versions of the second law that bound the entropy increase from below by a non-negative number, as well as Bayesian versions of integral fluctuation theorems. We demonstrate the formalism using simple analytical and numerical examples.

  17. Bayesian second law of thermodynamics.

    PubMed

    Bartolotta, Anthony; Carroll, Sean M; Leichenauer, Stefan; Pollack, Jason

    2016-08-01

    We derive a generalization of the second law of thermodynamics that uses Bayesian updates to explicitly incorporate the effects of a measurement of a system at some point in its evolution. By allowing an experimenter's knowledge to be updated by the measurement process, this formulation resolves a tension between the fact that the entropy of a statistical system can sometimes fluctuate downward and the information-theoretic idea that knowledge of a stochastically evolving system degrades over time. The Bayesian second law can be written as ΔH(ρ_{m},ρ)+〈Q〉_{F|m}≥0, where ΔH(ρ_{m},ρ) is the change in the cross entropy between the original phase-space probability distribution ρ and the measurement-updated distribution ρ_{m} and 〈Q〉_{F|m} is the expectation value of a generalized heat flow out of the system. We also derive refined versions of the second law that bound the entropy increase from below by a non-negative number, as well as Bayesian versions of integral fluctuation theorems. We demonstrate the formalism using simple analytical and numerical examples. PMID:27627241

  18. Thermodynamics of catalytic nanoparticle morphology

    NASA Astrophysics Data System (ADS)

    Zwolak, Michael; Sharma, Renu; Lin, Pin Ann

    Metallic nanoparticles are an important class of industrial catalysts. The variability of their properties and the environment in which they act, from their chemical nature & surface modification to their dispersion and support, allows their performance to be optimized for many chemical processes useful in, e.g., energy applications and other areas. Their large surface area to volume ratio, as well as varying sizes and faceting, in particular, makes them an efficient source for catalytically active sites. These characteristics of nanoparticles - i.e., their morphology - can often display intriguing behavior as a catalytic process progresses. We develop a thermodynamic model of nanoparticle morphology, one that captures the competition of surface energy with other interactions, to predict structural changes during catalytic processes. Comparing the model to environmental transmission electron microscope images of nickel nanoparticles during carbon nanotube (and other product) growth demonstrates that nickel deformation in response to the nanotube growth is due to a favorable interaction with carbon. Moreover, this deformation is halted due to insufficient volume of the particles. We will discuss the factors that influence morphology and also how the model can be used to extract interaction strengths from experimental observations.

  19. Thermodynamics of confined gallium clusters

    NASA Astrophysics Data System (ADS)

    Chandrachud, Prachi

    2015-11-01

    We report the results of ab initio molecular dynamics simulations of Ga13 and Ga17 clusters confined inside carbon nanotubes with different diameters. The cluster-tube interaction is simulated by the Lennard-Jones (LJ) potential. We discuss the geometries, the nature of the bonding and the thermodynamics under confinement. The geometries as well as the isomer spectra of both the clusters are significantly affected. The degree of confinement decides the dimensionality of the clusters. We observe that a number of low-energy isomers appear under moderate confinement while some isomers seen in the free space disappear. Our finite-temperature simulations bring out interesting aspects, namely that the heat capacity curve is flat, even though the ground state is symmetric. Such a flat nature indicates that the phase change is continuous. This effect is due to the restricted phase space available to the system. These observations are supported by the mean square displacement of individual atoms, which are significantly smaller than in free space. The nature of the bonding is found to be approximately jellium-like. Finally we note the relevance of the work to the problem of single file diffusion for the case of the highest confinement.

  20. Thermodynamics of antibody-antigen interaction revealed by mutation analysis of antibody variable regions.

    PubMed

    Akiba, Hiroki; Tsumoto, Kouhei

    2015-07-01

    Antibodies (immunoglobulins) bind specific molecules (i.e. antigens) with high affinity and specificity. In order to understand their mechanisms of recognition, interaction analysis based on thermodynamic and kinetic parameters, as well as structure determination is crucial. In this review, we focus on mutational analysis which gives information about the role of each amino acid residue in antibody-antigen interaction. Taking anti-hen egg lysozyme antibodies and several anti-small molecule antibodies, the energetic contribution of hot-spot and non-hot-spot residues is discussed in terms of thermodynamics. Here, thermodynamics of the contribution from aromatic, charged and hydrogen bond-forming amino acids are discussed, and their different characteristics have been elucidated. The information gives fundamental understanding of the antibody-antigen interaction. Furthermore, the consequences of antibody engineering are analysed from thermodynamic viewpoints: humanization to reduce immunogenicity and rational design to improve affinity. Amino acid residues outside hot-spots in the interface play important roles in these cases, and thus thermodynamic and kinetic parameters give much information about the antigen recognition. Thermodynamic analysis of mutant antibodies thus should lead to advanced strategies to design and select antibodies with high affinity.

  1. Cochrane diagnostic test accuracy reviews.

    PubMed

    Leeflang, Mariska M G; Deeks, Jonathan J; Takwoingi, Yemisi; Macaskill, Petra

    2013-10-07

    In 1996, shortly after the founding of The Cochrane Collaboration, leading figures in test evaluation research established a Methods Group to focus on the relatively new and rapidly evolving methods for the systematic review of studies of diagnostic tests. Seven years later, the Collaboration decided it was time to develop a publication format and methodology for Diagnostic Test Accuracy (DTA) reviews, as well as the software needed to implement these reviews in The Cochrane Library. A meeting hosted by the German Cochrane Centre in 2004 brought together key methodologists in the area, many of whom became closely involved in the subsequent development of the methodological framework for DTA reviews. DTA reviews first appeared in The Cochrane Library in 2008 and are now an integral part of the work of the Collaboration.

  2. Increasing Accuracy in Environmental Measurements

    NASA Astrophysics Data System (ADS)

    Jacksier, Tracey; Fernandes, Adelino; Matthew, Matt; Lehmann, Horst

    2016-04-01

    Human activity is increasing the concentrations of green house gases (GHG) in the atmosphere which results in temperature increases. High precision is a key requirement of atmospheric measurements to study the global carbon cycle and its effect on climate change. Natural air containing stable isotopes are used in GHG monitoring to calibrate analytical equipment. This presentation will examine the natural air and isotopic mixture preparation process, for both molecular and isotopic concentrations, for a range of components and delta values. The role of precisely characterized source material will be presented. Analysis of individual cylinders within multiple batches will be presented to demonstrate the ability to dynamically fill multiple cylinders containing identical compositions without isotopic fractionation. Additional emphasis will focus on the ability to adjust isotope ratios to more closely bracket sample types without the reliance on combusting naturally occurring materials, thereby improving analytical accuracy.

  3. Accuracy of Pressure Sensitive Paint

    NASA Technical Reports Server (NTRS)

    Liu, Tianshu; Guille, M.; Sullivan, J. P.

    2001-01-01

    Uncertainty in pressure sensitive paint (PSP) measurement is investigated from a standpoint of system modeling. A functional relation between the imaging system output and luminescent emission from PSP is obtained based on studies of radiative energy transports in PSP and photodetector response to luminescence. This relation provides insights into physical origins of various elemental error sources and allows estimate of the total PSP measurement uncertainty contributed by the elemental errors. The elemental errors and their sensitivity coefficients in the error propagation equation are evaluated. Useful formulas are given for the minimum pressure uncertainty that PSP can possibly achieve and the upper bounds of the elemental errors to meet required pressure accuracy. An instructive example of a Joukowsky airfoil in subsonic flows is given to illustrate uncertainty estimates in PSP measurements.

  4. Thermodynamic Modeling and Experimental Study of the Fe-Cr-Zr System

    SciTech Connect

    Yang, Ying; Tan, Lizhen; Bei, Hongbin; Busby, Jeremy T

    2013-01-01

    Wide applications of zircaloys, stainless steels and their interactions in nuclear reactors require the knowledge on phase stability and thermodynamic property of the Fe-Cr-Zr system. This knowledge is also important to develop new Zr-contained Fe-Cr ferritic steels. This work aims at developing thermodynamic models for describing phase stability and thermodynamic property of the Fe-Cr-Zr system using the Calphad approach coupled with experimental study. Thermodynamic descriptions of the Fe-Cr and Cr-Zr systems were either directly adopted or slightly modified from literature. The Fe-Zr system has been remodeled to accommodate recent ab-initio calculation of formation enthalpies of various Fe-Zr compounds. Reliable ternary experimental data and thermodynamic models were mainly available in the Zr-rich region. Therefore, selected ternary alloys located in the vicinity of the eutectic valley of (Fe,Cr,Zr) and (Fe,Cr)2Zr laves phase in the Fe-rich region have been experimentally investigated in this study. Microstructure has been examined by using scanning electron microscope, energy-dispersive Xray spectroscopy and X-ray diffraction. These experimental results, along with the literature data were then used to develop thermodynamic models for phases in the Fe-Cr-Zr system. Calculated phase equilibria and thermodynamic properties of the ternary system yield satisfactory agreements with available experimental data, which gives the confidence to use these models as building blocks for developing a Zr, Fe and Cr contained multicomponent thermodynamic database for broader applications in nuclear reactors.

  5. Evolution of the Second Law of Thermodynamics

    ERIC Educational Resources Information Center

    Raman, V. V.

    1970-01-01

    Presents the history surrounding the evolution of the second law of thermodynamics. Discusses Sadi Carnot's contributions, but also refers to those by Clapeyron, Thomson, Joule, Clausius, and Boltzman among others. (RR)

  6. Stochastic approach to equilibrium and nonequilibrium thermodynamics

    NASA Astrophysics Data System (ADS)

    Tomé, Tânia; de Oliveira, Mário J.

    2015-04-01

    We develop the stochastic approach to thermodynamics based on stochastic dynamics, which can be discrete (master equation) and continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second the definition of entropy production rate, which is non-negative and vanishes in thermodynamic equilibrium. Based on these assumptions, we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasiequilibrium processes; the convexity of the equilibrium surface; the monotonic time behavior of thermodynamic potentials, including entropy; the bilinear form of the entropy production rate; the Onsager coefficients and reciprocal relations; and the nonequilibrium steady states of chemical reactions.

  7. Thermodynamics of Nonequilibrium Systems with Feedback Control

    NASA Astrophysics Data System (ADS)

    Sagawa, Takahiro

    2015-03-01

    In modern nonequilibrium physics, ``Maxwell's demon'' has attracted renewed attentions in both terms of theory and experiment. The demon plays a key role to unify thermodynamics and information theory, which can extract the useful work from a heat bath by using the obtained information via feedback control. In this talk, I will talk about the recent development of thermodynamics of information. In particular, I will focus on the generalizations of the second law of thermodynamics and the Jarzynski equality in the presence of feedback control, where information contents and thermodynamic quantities are treated on an equal footing. I will also discuss recent experimental results that realized Maxwell's demon by colloidal particles and single electrons.

  8. Limits to catalysis in quantum thermodynamics

    NASA Astrophysics Data System (ADS)

    Ng, N. H. Y.; Mančinska, L.; Cirstoiu, C.; Eisert, J.; Wehner, S.

    2015-08-01

    Quantum thermodynamics is a research field that aims at fleshing out the ultimate limits of thermodynamic processes in the deep quantum regime. A complete picture of thermodynamical processes naturally allows for auxiliary systems dubbed ‘catalysts’, i.e., any physical systems facilitating state transformations while remaining essentially intact in their state, like an auxiliary system, a clock, or an actual catalyst. In this work, we present a comprehensive analysis of the power and limitation of such thermal catalysis. Specifically, we provide a family of optimal catalysts that can be returned with minimal trace distance error after facilitating a state transformation process. To incorporate the genuine physical role of a catalyst, we identify very significant restrictions on arbitrary state transformations under dimension or mean energy bounds, using methods of convex relaxations. We discuss the implication of these findings on possible thermodynamic state transformations in the quantum regime.

  9. Thermodynamic Cycles--One More Time.

    ERIC Educational Resources Information Center

    Nolan, Michael J.

    1995-01-01

    Discusses interesting aspects of the Carnot cycle and other thermodynamic cycles that are generally not dealt with in elementary physics texts. Presents examples that challenge the student to think about the extraction of net work from a cycle. (JRH)

  10. On the thermodynamic properties of vanadium

    SciTech Connect

    Daans, J.M.; Carbotte, J.P.; Ashraf, M.; Baquero, R.

    1984-04-01

    The thermodynamic properties of superconducting vanadium are calculated from the tunneling-derived microscopic parameters for this metal. Consideration is given to the possible role of spin fluctuations and to anisotropy. A comparison with experiment is included.

  11. Stochastic approach to equilibrium and nonequilibrium thermodynamics.

    PubMed

    Tomé, Tânia; de Oliveira, Mário J

    2015-04-01

    We develop the stochastic approach to thermodynamics based on stochastic dynamics, which can be discrete (master equation) and continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second the definition of entropy production rate, which is non-negative and vanishes in thermodynamic equilibrium. Based on these assumptions, we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasiequilibrium processes; the convexity of the equilibrium surface; the monotonic time behavior of thermodynamic potentials, including entropy; the bilinear form of the entropy production rate; the Onsager coefficients and reciprocal relations; and the nonequilibrium steady states of chemical reactions. PMID:25974471

  12. Quantum thermodynamics of general quantum processes.

    PubMed

    Binder, Felix; Vinjanampathy, Sai; Modi, Kavan; Goold, John

    2015-03-01

    Accurately describing work extraction from a quantum system is a central objective for the extension of thermodynamics to individual quantum systems. The concepts of work and heat are surprisingly subtle when generalizations are made to arbitrary quantum states. We formulate an operational thermodynamics suitable for application to an open quantum system undergoing quantum evolution under a general quantum process by which we mean a completely positive and trace-preserving map. We derive an operational first law of thermodynamics for such processes and show consistency with the second law. We show that heat, from the first law, is positive when the input state of the map majorizes the output state. Moreover, the change in entropy is also positive for the same majorization condition. This makes a strong connection between the two operational laws of thermodynamics. PMID:25871066

  13. Stochastic approach to equilibrium and nonequilibrium thermodynamics.

    PubMed

    Tomé, Tânia; de Oliveira, Mário J

    2015-04-01

    We develop the stochastic approach to thermodynamics based on stochastic dynamics, which can be discrete (master equation) and continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second the definition of entropy production rate, which is non-negative and vanishes in thermodynamic equilibrium. Based on these assumptions, we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasiequilibrium processes; the convexity of the equilibrium surface; the monotonic time behavior of thermodynamic potentials, including entropy; the bilinear form of the entropy production rate; the Onsager coefficients and reciprocal relations; and the nonequilibrium steady states of chemical reactions.

  14. Extrinsic and intrinsic curvatures in thermodynamic geometry

    NASA Astrophysics Data System (ADS)

    Hosseini Mansoori, Seyed Ali; Mirza, Behrouz; Sharifian, Elham

    2016-08-01

    We investigate the intrinsic and extrinsic curvatures of a certain hypersurface in thermodynamic geometry of a physical system and show that they contain useful thermodynamic information. For an anti-Reissner-Nordström-(A)de Sitter black hole (Phantom), the extrinsic curvature of a constant Q hypersurface has the same sign as the heat capacity around the phase transition points. The intrinsic curvature of the hypersurface can also be divergent at the critical points but has no information about the sign of the heat capacity. Our study explains the consistent relationship holding between the thermodynamic geometry of the KN-AdS black holes and those of the RN (J-zero hypersurface) and Kerr black holes (Q-zero hypersurface) ones [1]. This approach can easily be generalized to an arbitrary thermodynamic system.

  15. Thermodynamic benchmark study using Biacore technology.

    PubMed

    Navratilova, Iva; Papalia, Giuseppe A; Rich, Rebecca L; Bedinger, Daniel; Brophy, Susan; Condon, Brad; Deng, Ta; Emerick, Anne W; Guan, Hann-Wen; Hayden, Tanya; Heutmekers, Thomas; Hoorelbeke, Bart; McCroskey, Mark C; Murphy, Mary M; Nakagawa, Terry; Parmeggiani, Fabio; Qin, Xiaochun; Rebe, Sabina; Tomasevic, Nenad; Tsang, Tiffany; Waddell, M Brett; Zhang, Fred Feiyu; Leavitt, Stephanie; Myszka, David G

    2007-05-01

    A total of 22 individuals participated in this benchmark study to characterize the thermodynamics of small-molecule inhibitor-enzyme interactions using Biacore instruments. Participants were provided with reagents (the enzyme carbonic anhydrase II, which was immobilized onto the sensor surface, and four sulfonamide-based inhibitors) and were instructed to collect response data from 6 to 36 degrees C. van't Hoff enthalpies and entropies were calculated from the temperature dependence of the binding constants. The equilibrium dissociation and thermodynamic constants determined from the Biacore analysis matched the values determined using isothermal titration calorimetry. These results demonstrate that immobilization of the enzyme onto the sensor surface did not alter the thermodynamics of these interactions. This benchmark study also provides insights into the opportunities and challenges in carrying out thermodynamic studies using optical biosensors.

  16. Thermodynamic power stations at low temperatures

    NASA Astrophysics Data System (ADS)

    Malherbe, J.; Ployart, R.; Alleau, T.; Bandelier, P.; Lauro, F.

    The development of low-temperature thermodynamic power stations using solar energy is considered, with special attention given to the choice of the thermodynamic cycle (Rankine), working fluids (frigorific halogen compounds), and heat exchangers. Thermomechanical conversion machines, such as ac motors and rotating volumetric motors are discussed. A system is recommended for the use of solar energy for irrigation and pumping in remote areas. Other applications include the production of cold of fresh water from brackish waters, and energy recovery from hot springs.

  17. Thermodynamic restrictions on mechanosynthesis of strontium titanate

    SciTech Connect

    Monteiro, J.F.; Ferreira, A.A.L.; Antunes, I.; Fagg, D.P.; Frade, J.R.

    2012-01-15

    Chemical potential phase stability diagrams were calculated from relevant thermodynamic properties and used to predict the thermodynamic driving force under prospective conditions of room temperature mechanosynthesis. One analysed the dependence of chemical potential diagrams on temperature and partial pressure of evolving gases such as oxygen or carbon dioxide, as expected on using strontium peroxide or strontium carbonate as precursor reactants for the alkali earth component. Thermodynamic calculations were also obtained for changes in titania precursor reactants, including thermodynamic predictions for reactivity of strontium carbonate with amorphous titania. Experimental evidence showed that strontium titanate can be obtained by mechanosynthesis of strontium carbonate+anatase mixtures, due to previous amorphization under high energy milling. Ability to perform mechanosynthesis with less energetic milling depends on the suitable choice of alternative precursor reactants, which meet the thermodynamic requirements without previous amorphization; this was demonstrated by mechanosynthesis from anatase+strontium peroxide mixtures. - Graphical abstract: X-Ray diffractograms of the starting TiO{sub 2} (anatase)+SrCO{sub 3} mixture and after mechanical activation at 650 rpm, for 1, 2, and 7 h. Different symbols are used to identify reflections ascribed to anatase (diamonds), SrCO{sub 3} (squares) and SrTiO{sub 3} (triangles). Highlights: Black-Right-Pointing-Pointer Prediction of thermodynamic driving force for room temperature mechanosynthesis. Black-Right-Pointing-Pointer Dependence of chemical potential diagrams on temperature and partial pressure. Black-Right-Pointing-Pointer Thermodynamic calculations for changes in titania precursor. Black-Right-Pointing-Pointer Experimental support for thermodynamic predictions.

  18. Hadron thermodynamics in relativistic nuclear collisions

    NASA Technical Reports Server (NTRS)

    Ammiraju, P.

    1985-01-01

    Various phenomenological models based on statistical thermodynamical considerations were used to fit the experimental data at high P sub T to a two temperature distribution. Whether this implies that the two temperatures belong to two different reaction mechanisms, or consequences of Lorentz-contraction factor, or related in a fundamental way to the intrinsic thermodynamics of Space-Time can only be revealed by further theoretical and experimental investigations of high P sub T phenomena in extremely energetic hadron-hadron collisions.

  19. Thermodynamic analysis of total energy gas turbines

    NASA Astrophysics Data System (ADS)

    Stecco, S. S.

    For a thermodynamic analysis of gas turbine power plants (GTPP) with exhaust gases recovery, a simple recovery cogeneration plant and a steam-gas combined cogeneration plant are analyzed according to the First and Second Laws of Thermodynamics. Attention is given to the convenience of different GTPP solutions for different ratios of heat to electricity production; methods of analysis of bottoming Rankine cycle power plants with respect to various fluids; and fuel savings.

  20. Thermodynamic power of non-Markovianity

    PubMed Central

    Bylicka, Bogna; Tukiainen, Mikko; Chruściński, Dariusz; Piilo, Jyrki; Maniscalco, Sabrina

    2016-01-01

    The natural framework to discuss thermodynamics at the quantum level is the theory of open quantum systems. Memory effects arising from strong system-environment correlations may lead to information back-flow, that is non-Markovian behaviour. The relation between non-Markovianity and quantum thermodynamics has been until now largely unexplored. Here we show by means of Landauer’s principle that memory effects control the amount of work extraction by erasure in presence of realistic environments. PMID:27323947

  1. Thermodynamic performance of a laser cryocooler.

    PubMed

    Wu, Feng; Chen, Lingen; Wu, Shuang; Sun, Fengrui

    2007-05-28

    The quantum dynamic action of a laser cooling system is analyzed by means of a simplified luminescence center model with ground state and excited state in this paper. The thermodynamic performance of a laser cryocooler is described by solving quantum master equation. The cooling load and the coefficient of performance of the cooler are obtained by using finite time thermodynamics. Some features of the system under the weak coupling and under the intense coupling conditions are discussed.

  2. Research into the origins of engineering thermodynamics

    SciTech Connect

    Bejan, A.

    1988-09-01

    This paper draws attention to a series of misconceptions and misstatements regarding the origin and meaning of some of the most basic concepts of engineering thermodynamics. The six examples exhibited in the paper relate to the concepts of reversibility, entropy, mechanical equivalent of the calorie, the first law of thermodynamics for open systems, enthalpy and the Diesel cycle. A complete list of the pioneering references concludes the paper.

  3. Thermodynamics of rock forming crystalline solutions

    NASA Technical Reports Server (NTRS)

    Saxena, S. K.

    1971-01-01

    Analysis of phase diagrams and cation distributions within crystalline solutions as means of obtaining thermodynamic data on rock forming crystalline solutions is discussed along with some aspects of partitioning of elements in coexisting phases. Crystalline solutions, components in a silicate mineral, and chemical potentials of these components were defined. Examples were given for calculating thermodynamic mixing functions in the CaW04-SrW04, olivine-chloride solution, and orthopyroxene systems.

  4. Complex competitive systems and competitive thermodynamics.

    PubMed

    Klimenko, A Y

    2013-01-13

    This publication reviews the framework of abstract competition, which is aimed at studying complex systems with competition in their generic form. Although the concept of abstract competition has been derived from a specific field--modelling of mixing in turbulent reacting flows--this concept is, generally, not attached to a specific phenomenon or application. Two classes of competition rules, transitive and intransitive, need to be distinguished. Transitive competitions are shown to be consistent (at least qualitatively) with thermodynamic principles, which allows for introduction of special competitive thermodynamics. Competitive systems can thus be characterized by thermodynamic quantities (such as competitive entropy and competitive potential), which determine that the predominant direction of evolution of the system is directed towards higher competitiveness. There is, however, an important difference: while conventional thermodynamics is constrained by its zeroth law and is fundamentally transitive, the transitivity of competitive thermodynamics depends on the transitivity of the competition rules. The analogy with conventional thermodynamics weakens as competitive systems become more intransitive, while strongly intransitive competitions can display types of behaviour associated with complexity: competitive cooperation and leaping cycles. Results of simulations demonstrating complex behaviour in abstract competitions are presented in the electronic supplementary material.

  5. Thermodynamics for separation-process technology

    SciTech Connect

    Prausnitz, J.M.

    1995-10-01

    When contemplating or designing a separation process, every chemical engineer at once recognizes the thermodynamic boundary conditions that must be satisfied: when a mixture is continuously processed to yield at least partially purified products, energy and mass must be conserved and work must be done. In his daily tasks, a chemical engineer uses thermodynamic concepts as tacit, almost subconscious, knowledge. Thus, qualitative thermodynamics significantly informs process conception at its most fundamental level. However, quantitative design requires detailed knowledge of thermodynamic relations and physical chemistry. Most process engineers, concerned with flow sheets and economics, cannot easily command that detailed knowledge and therefore it is advantageous for them to maintain close contact with those specialists who do. Quantitative chemical thermodynamics provides an opportunity to evaluate possible separation processes not only because it may give support to the process engineer`s bold imagination but also because, when coupled with molecular models, it can significantly reduce the experimental effort required to determine an optimum choice of process alternatives. Six examples are presented to indicate the application of thermodynamics for conventional and possible future separation processes.

  6. Thermodynamic characterization of networks using graph polynomials

    NASA Astrophysics Data System (ADS)

    Ye, Cheng; Comin, César H.; Peron, Thomas K. DM.; Silva, Filipi N.; Rodrigues, Francisco A.; Costa, Luciano da F.; Torsello, Andrea; Hancock, Edwin R.

    2015-09-01

    In this paper, we present a method for characterizing the evolution of time-varying complex networks by adopting a thermodynamic representation of network structure computed from a polynomial (or algebraic) characterization of graph structure. Commencing from a representation of graph structure based on a characteristic polynomial computed from the normalized Laplacian matrix, we show how the polynomial is linked to the Boltzmann partition function of a network. This allows us to compute a number of thermodynamic quantities for the network, including the average energy and entropy. Assuming that the system does not change volume, we can also compute the temperature, defined as the rate of change of entropy with energy. All three thermodynamic variables can be approximated using low-order Taylor series that can be computed using the traces of powers of the Laplacian matrix, avoiding explicit computation of the normalized Laplacian spectrum. These polynomial approximations allow a smoothed representation of the evolution of networks to be constructed in the thermodynamic space spanned by entropy, energy, and temperature. We show how these thermodynamic variables can be computed in terms of simple network characteristics, e.g., the total number of nodes and node degree statistics for nodes connected by edges. We apply the resulting thermodynamic characterization to real-world time-varying networks representing complex systems in the financial and biological domains. The study demonstrates that the method provides an efficient tool for detecting abrupt changes and characterizing different stages in network evolution.

  7. Thermodynamic properties of water solvating biomolecular surfaces

    NASA Astrophysics Data System (ADS)

    Heyden, Matthias

    Changes in the potential energy and entropy of water molecules hydrating biomolecular interfaces play a significant role for biomolecular solubility and association. Free energy perturbation and thermodynamic integration methods allow calculations of free energy differences between two states from simulations. However, these methods are computationally demanding and do not provide insights into individual thermodynamic contributions, i.e. changes in the solvent energy or entropy. Here, we employ methods to spatially resolve distributions of hydration water thermodynamic properties in the vicinity of biomolecular surfaces. This allows direct insights into thermodynamic signatures of the hydration of hydrophobic and hydrophilic solvent accessible sites of proteins and small molecules and comparisons to ideal model surfaces. We correlate dynamic properties of hydration water molecules, i.e. translational and rotational mobility, to their thermodynamics. The latter can be used as a guide to extract thermodynamic information from experimental measurements of site-resolved water dynamics. Further, we study energy-entropy compensations of water at different hydration sites of biomolecular surfaces. This work is supported by the Cluster of Excellence RESOLV (EXC 1069) funded by the Deutsche Forschungsgemeinschaft.

  8. STATTHERM: a statistical thermodynamics program for calculating thermochemical information

    SciTech Connect

    Marinov, N.M.

    1997-03-01

    A statistical thermodynamics program is presented which computes the thermochemical properties of a polyatomic molecule using statistical thermodynamic formulas. Thermodynamic data for substances involving C, H,O,N, and Cl elements are fitted into NASA polynomial form for use in combustion research or research where thermodynamical information is important.

  9. Thermodynamic and transport properties of gaseous tetrafluoromethane in chemical equilibrium

    NASA Technical Reports Server (NTRS)

    Hunt, J. L.; Boney, L. R.

    1973-01-01

    Equations and in computer code are presented for the thermodynamic and transport properties of gaseous, undissociated tetrafluoromethane (CF4) in chemical equilibrium. The computer code calculates the thermodynamic and transport properties of CF4 when given any two of five thermodynamic variables (entropy, temperature, volume, pressure, and enthalpy). Equilibrium thermodynamic and transport property data are tabulated and pressure-enthalpy diagrams are presented.

  10. Cloud thermodynamic phase detection with polarimetrically sensitive passive sky radiometers

    NASA Astrophysics Data System (ADS)

    Knobelspiesse, K.; van Diedenhoven, B.; Marshak, A.; Dunagan, S.; Holben, B.; Slutsker, I.

    2014-12-01

    The primary goal of this project has been to investigate if ground-based visible and near-infrared passive radiometers that have polarization sensitivity can determine the thermodynamic phase of overlying clouds, i.e. if they are comprised of liquid droplets or ice particles. While this knowledge is important by itself for our understanding of the global climate, it can also help improve cloud property retrieval algorithms that use total (unpolarized) radiance to determine Cloud Optical Depth (COD). This is a potentially unexploited capability of some instruments in the NASA Aerosol Robotic Network (AERONET), which, if practical, could expand the products of that global instrument network at minimal additional cost. We performed simulations that found, for zenith observations, cloud thermodynamic phase is often expressed in the sign of the Q component of the Stokes polarization vector. We chose our reference frame as the plane containing solar and observation vectors, so the sign of Q indicates the polarization direction, parallel (positive) or perpendicular (negative) to that plane. Since the quantity of polarization is inversely proportional to COD, optically thin clouds are most likely to create a signal greater than instrument noise. Besides COD and instrument accuracy, other important factors for the determination of cloud thermodynamic phase are the solar and observation geometry (scattering angles between 40 and 60° are best), and the properties of ice particles (pristine particles may have halos or other features that make them difficult to distinguish from water droplets at specific scattering angles, while extreme ice crystal aspect ratios polarize more than compact particles). We tested the conclusions of our simulations using data from polarimetrically sensitive versions of the Cimel 318 sun photometer/radiometer that comprise AERONET. Most algorithms that exploit Cimel polarized observations use the Degree of Linear Polarization (DoLP), not the

  11. Food Label Accuracy of Common Snack Foods

    PubMed Central

    Jumpertz, Reiner; Venti, Colleen A; Le, Duc Son; Michaels, Jennifer; Parrington, Shannon; Krakoff, Jonathan; Votruba, Susanne

    2012-01-01

    Nutrition labels have raised awareness of the energetic value of foods, and represent for many a pivotal guideline to regulate food intake. However, recent data have created doubts on label accuracy. Therefore we tested label accuracy for energy and macronutrient content of prepackaged energy-dense snack food products. We measured “true” caloric content of 24 popular snack food products in the U.S. and determined macronutrient content in 10 selected items. Bomb calorimetry and food factors were used to estimate energy content. Macronutrient content was determined according to Official Methods of Analysis. Calorimetric measurements were performed in our metabolic laboratory between April 20th and May 18th and macronutrient content was measured between September 28th and October 7th of 2010. Serving size, by weight, exceeded label statements by 1.2% [median] (25th percentile −1.4, 75th percentile 4.3, p=0.10). When differences in serving size were accounted for, metabolizable calories were 6.8 kcal (0.5, 23.5, p=0.0003) or 4.3% (0.2, 13.7, p=0.001) higher than the label statement. In a small convenience sample of the tested snack foods, carbohydrate content exceeded label statements by 7.7% (0.8, 16.7, p=0.01); however fat and protein content were not significantly different from label statements (−12.8% [−38.6, 9.6], p=0.23; 6.1% [−6.1, 17.5], p=0.32). Carbohydrate content explained 40% and serving size an additional 55% of the excess calories. Among a convenience sample of energy-dense snack foods, caloric content is higher than stated on the nutrition labels, but overall well within FDA limits. This discrepancy may be explained by inaccurate carbohydrate content and serving size. PMID:23505182

  12. The thermodynamic properties of radium

    NASA Astrophysics Data System (ADS)

    Langmuir, Donald; Riese, Arthur C.

    1985-07-01

    The enthalpy, Gibbs free energy, and entropies of aqueous radium species and radium solids have been evaluated from empirical data, or estimated when necessary for 25°C and 1 bar. Estimates were based on such approaches as extrapolation of the thermodynamic properties of Ca, Sr, and Ba complexes and solids plotted against cationic radii and charge to radius functions, and the use of the Fuoss or electrostatic mathematical models of ion pair formation (Langmuir, 1979). Resultant log K (assoc) and ΔH0 (assoc) (kcal/mol) values are: for RaOH + 0.5 and 1.1; RaCl + -0.10 and 0.50; RaCO 03 2.5 and 1.07; and RaSO 04 2.75 and 1.3. Log Ksp and ΔH0 (dissoc) (kcal/mol) values for RaCO 3(c) and RaSO 4(c) are -8.3 and -2.8, and -10.26 and -9.4, respectively. Trace Ra solid solution in salts of Pb and of the lighter alkaline earths, has been appraised based on published distribution coefficient ( D) data, where D ˜- ( mM2+)( NRaX)/( mRa2+)( NMX) ( m and N are the aqueous molality and mole fraction of Ra and cation M in salt X, respectively. The empirical solid solution data have been used to derive both enthalpies and Gibbs free energies of solid solution of trace Ra in sulfate and carbonate minerals up to 100°C. Results show that in every case D values decrease with increasing temperature. Among the sulfate and carbonate minerals, D values decrease for the following minerals in the order: anhydrite > celestite > anglesite > barite > aragonite > strontianite > witherite > cerussite.

  13. Nuclear chiral dynamics and thermodynamics

    NASA Astrophysics Data System (ADS)

    Holt, Jeremy W.; Kaiser, Norbert; Weise, Wolfram

    2013-11-01

    This presentation reviews an approach to nuclear many-body systems based on the spontaneously broken chiral symmetry of low-energy QCD. In the low-energy limit, for energies and momenta small compared to a characteristic symmetry breaking scale of order 1 GeV, QCD is realized as an effective field theory of Goldstone bosons (pions) coupled to heavy fermionic sources (nucleons). Nuclear forces at long and intermediate distance scales result from a systematic hierarchy of one- and two-pion exchange processes in combination with Pauli blocking effects in the nuclear medium. Short distance dynamics, not resolved at the wavelengths corresponding to typical nuclear Fermi momenta, are introduced as contact interactions between nucleons. Apart from a set of low-energy constants associated with these contact terms, the parameters of this theory are entirely determined by pion properties and low-energy pion-nucleon scattering observables. This framework (in-medium chiral perturbation theory) can provide a realistic description of both isospin-symmetric nuclear matter and neutron matter, with emphasis on the isospin-dependence determined by the underlying chiral NN interaction. The importance of three-body forces is emphasized, and the role of explicit Δ(1232)-isobar degrees of freedom is investigated in detail. Nuclear chiral thermodynamics is developed and a calculation of the nuclear phase diagram is performed. This includes a successful description of the first-order phase transition from a nuclear Fermi liquid to an interacting Fermi gas and the coexistence of these phases below a critical temperature Tc. Density functional methods for finite nuclei based on this approach are also discussed. Effective interactions, their density dependence and connections to Landau Fermi liquid theory are outlined. Finally, the density and temperature dependences of the chiral (quark) condensate are investigated.

  14. High accuracy broadband infrared spectropolarimetry

    NASA Astrophysics Data System (ADS)

    Krishnaswamy, Venkataramanan

    Mueller matrix spectroscopy or Spectropolarimetry combines conventional spectroscopy with polarimetry, providing more information than can be gleaned from spectroscopy alone. Experimental studies on infrared polarization properties of materials covering a broad spectral range have been scarce due to the lack of available instrumentation. This dissertation aims to fill the gap by the design, development, calibration and testing of a broadband Fourier Transform Infra-Red (FT-IR) spectropolarimeter. The instrument operates over the 3-12 mum waveband and offers better overall accuracy compared to the previous generation instruments. Accurate calibration of a broadband spectropolarimeter is a non-trivial task due to the inherent complexity of the measurement process. An improved calibration technique is proposed for the spectropolarimeter and numerical simulations are conducted to study the effectiveness of the proposed technique. Insights into the geometrical structure of the polarimetric measurement matrix is provided to aid further research towards global optimization of Mueller matrix polarimeters. A high performance infrared wire-grid polarizer is characterized using the spectropolarimeter. Mueller matrix spectrum measurements on Penicillin and pine pollen are also presented.

  15. ACCURACY OF CO2 SENSORS

    SciTech Connect

    Fisk, William J.; Faulkner, David; Sullivan, Douglas P.

    2008-10-01

    Are the carbon dioxide (CO2) sensors in your demand controlled ventilation systems sufficiently accurate? The data from these sensors are used to automatically modulate minimum rates of outdoor air ventilation. The goal is to keep ventilation rates at or above design requirements while adjusting the ventilation rate with changes in occupancy in order to save energy. Studies of energy savings from demand controlled ventilation and of the relationship of indoor CO2 concentrations with health and work performance provide a strong rationale for use of indoor CO2 data to control minimum ventilation rates1-7. However, this strategy will only be effective if, in practice, the CO2 sensors have a reasonable accuracy. The objective of this study was; therefore, to determine if CO2 sensor performance, in practice, is generally acceptable or problematic. This article provides a summary of study methods and findings ? additional details are available in a paper in the proceedings of the ASHRAE IAQ?2007 Conference8.

  16. Astrophysics with Microarcsecond Accuracy Astrometry

    NASA Technical Reports Server (NTRS)

    Unwin, Stephen C.

    2008-01-01

    Space-based astrometry promises to provide a powerful new tool for astrophysics. At a precision level of a few microarcsonds, a wide range of phenomena are opened up for study. In this paper we discuss the capabilities of the SIM Lite mission, the first space-based long-baseline optical interferometer, which will deliver parallaxes to 4 microarcsec. A companion paper in this volume will cover the development and operation of this instrument. At the level that SIM Lite will reach, better than 1 microarcsec in a single measurement, planets as small as one Earth can be detected around many dozen of the nearest stars. Not only can planet masses be definitely measured, but also the full orbital parameters determined, allowing study of system stability in multiple planet systems. This capability to survey our nearby stellar neighbors for terrestrial planets will be a unique contribution to our understanding of the local universe. SIM Lite will be able to tackle a wide range of interesting problems in stellar and Galactic astrophysics. By tracing the motions of stars in dwarf spheroidal galaxies orbiting our Milky Way, SIM Lite will probe the shape of the galactic potential history of the formation of the galaxy, and the nature of dark matter. Because it is flexibly scheduled, the instrument can dwell on faint targets, maintaining its full accuracy on objects as faint as V=19. This paper is a brief survey of the diverse problems in modern astrophysics that SIM Lite will be able to address.

  17. Quality--a radiology imperative: interpretation accuracy and pertinence.

    PubMed

    Lee, Joseph K T

    2007-03-01

    Physicians as a group have neither consistently defined nor systematically measured the quality of medical practice. To referring clinicians and patients, a good radiologist is one who is accessible, recommends appropriate imaging studies, and provides timely consultation and reports with high interpretation accuracy. For determining the interpretation accuracy of cases with pathologic or surgical proof, the author proposes tracking data on positive predictive value, disease detection rates, and abnormal interpretation rates for individual radiologists. For imaging studies with no pathologic proof or adequate clinical follow-up, the author proposes measuring the concordance and discordance of the interpretations within a peer group. The monitoring of interpretation accuracy can be achieved through periodic imaging, pathologic correlation, regular peer review of randomly selected cases, or subscription to the ACR's RADPEER system. Challenges facing the implementation of an effective peer-review system include physician time, subjectivity in assessing discordant interpretations, lengthy and equivocal interpretations, and the potential misassignment of false-positive interpretations.

  18. Total Variation Diminishing (TVD) schemes of uniform accuracy

    NASA Technical Reports Server (NTRS)

    Hartwich, PETER-M.; Hsu, Chung-Hao; Liu, C. H.

    1988-01-01

    Explicit second-order accurate finite-difference schemes for the approximation of hyperbolic conservation laws are presented. These schemes are nonlinear even for the constant coefficient case. They are based on first-order upwind schemes. Their accuracy is enhanced by locally replacing the first-order one-sided differences with either second-order one-sided differences or central differences or a blend thereof. The appropriate local difference stencils are selected such that they give TVD schemes of uniform second-order accuracy in the scalar, or linear systems, case. Like conventional TVD schemes, the new schemes avoid a Gibbs phenomenon at discontinuities of the solution, but they do not switch back to first-order accuracy, in the sense of truncation error, at extrema of the solution. The performance of the new schemes is demonstrated in several numerical tests.

  19. Thermodynamic Activity Measurements with Knudsen Cell Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Copland, Evan H.; Jacobson, Nathan S.

    2001-01-01

    Coupling the Knudsen effusion method with mass spectrometry has proven to be one of the most useful experimental techniques for studying the equilibrium between condensed phases and complex vapors. The Knudsen effusion method involves placing a condensed sample in a Knudsen cell, a small "enclosure", that is uniformly heated and held until equilibrium is attained between the condensed and vapor phases. The vapor is continuously sampled by effusion through a small orifice in the cell. A molecular beam is formed from the effusing vapor and directed into a mass spectrometer for identification and pressure measurement of the species in the vapor phase. Knudsen cell mass spectrometry (KCMS) has been used for nearly fifty years now and continues to be a leading technique for obtaining thermodynamic data. Indeed, much of the well-established vapor specie data in the JANAF tables has been obtained from this technique. This is due to the extreme versatility of the technique. All classes of materials can be studied and all constituents of the vapor phase can be measured over a wide range of pressures (approximately 10(exp -4) to 10(exp -11) bar) and temperatures (500-2800 K). The ability to selectively measure different vapor species makes KCMS a very powerful tool for the measurement of component activities in metallic and ceramic solutions. Today several groups are applying KCMS to measure thermodynamic functions in multicomponent metallic and ceramic systems. Thermodynamic functions, especially component activities, are extremely important in the development of CALPHAD (Calculation of Phase Diagrams) type thermodynamic descriptions. These descriptions, in turn, are useful for modeling materials processing and predicting reactions such as oxide formation and fiber/matrix interactions. The leading experimental methods for measuring activities are the Galvanic cell or electro-motive force (EMF) technique and the KCMS technique. Each has specific advantages, depending on

  20. Ground Truth Sampling and LANDSAT Accuracy Assessment

    NASA Technical Reports Server (NTRS)

    Robinson, J. W.; Gunther, F. J.; Campbell, W. J.

    1982-01-01

    It is noted that the key factor in any accuracy assessment of remote sensing data is the method used for determining the ground truth, independent of the remote sensing data itself. The sampling and accuracy procedures developed for nuclear power plant siting study are described. The purpose of the sampling procedure was to provide data for developing supervised classifications for two study sites and for assessing the accuracy of that and the other procedures used. The purpose of the accuracy assessment was to allow the comparison of the cost and accuracy of various classification procedures as applied to various data types.

  1. Optimality and thermodynamics determine the evolution of transcriptional regulatory networks†

    PubMed Central

    Yarmush, Martin L.

    2014-01-01

    Transcriptional motifs are small regulatory interaction patterns that regulate biological functions in highly-interacting cellular networks. Recently, attempts have been made to explain the significance of transcriptional motifs through dynamic function. However, fundamental questions remain unanswered. Why are certain transcriptional motifs with similar dynamic function abundant while others occur rarely? What are the criteria for topological generalization of these motifs into complex networks? Here, we present a novel paradigm that combines non-equilibrium thermodynamics with multiobjective-optimality for network analysis. We found that energetic cost, defined herein as specific dissipation energy, is minimal at the optimal environmental conditions and it correlates inversely with the abundance of the network motifs obtained experimentally for E. coli and S. cerevisiae. This yields evidence that dissipative energetics is the underlying criteria used during evolution for motif selection and that biological systems during transcription tend towards evolutionary selection of subgraphs which produces minimum specific heat dissipation under optimal conditions, thereby explaining the abundance/rare occurrence of some motifs. We show that although certain motifs had similar dynamical functionality, they had significantly different energetic cost, thus explaining the abundance/rare occurrence of these motifs. The presented insights may establish global thermodynamic analysis as a backbone in designing and understanding complex networks systems, such as metabolic and protein interaction networks. PMID:22076617

  2. Maximum entropy principle for stationary states underpinned by stochastic thermodynamics

    NASA Astrophysics Data System (ADS)

    Ford, Ian J.

    2015-11-01

    The selection of an equilibrium state by maximizing the entropy of a system, subject to certain constraints, is often powerfully motivated as an exercise in logical inference, a procedure where conclusions are reached on the basis of incomplete information. But such a framework can be more compelling if it is underpinned by dynamical arguments, and we show how this can be provided by stochastic thermodynamics, where an explicit link is made between the production of entropy and the stochastic dynamics of a system coupled to an environment. The separation of entropy production into three components allows us to select a stationary state by maximizing the change, averaged over all realizations of the motion, in the principal relaxational or nonadiabatic component, equivalent to requiring that this contribution to the entropy production should become time independent for all realizations. We show that this recovers the usual equilibrium probability density function (pdf) for a conservative system in an isothermal environment, as well as the stationary nonequilibrium pdf for a particle confined to a potential under nonisothermal conditions, and a particle subject to a constant nonconservative force under isothermal conditions. The two remaining components of entropy production account for a recently discussed thermodynamic anomaly between over- and underdamped treatments of the dynamics in the nonisothermal stationary state.

  3. Maximum entropy principle for stationary states underpinned by stochastic thermodynamics.

    PubMed

    Ford, Ian J

    2015-11-01

    The selection of an equilibrium state by maximizing the entropy of a system, subject to certain constraints, is often powerfully motivated as an exercise in logical inference, a procedure where conclusions are reached on the basis of incomplete information. But such a framework can be more compelling if it is underpinned by dynamical arguments, and we show how this can be provided by stochastic thermodynamics, where an explicit link is made between the production of entropy and the stochastic dynamics of a system coupled to an environment. The separation of entropy production into three components allows us to select a stationary state by maximizing the change, averaged over all realizations of the motion, in the principal relaxational or nonadiabatic component, equivalent to requiring that this contribution to the entropy production should become time independent for all realizations. We show that this recovers the usual equilibrium probability density function (pdf) for a conservative system in an isothermal environment, as well as the stationary nonequilibrium pdf for a particle confined to a potential under nonisothermal conditions, and a particle subject to a constant nonconservative force under isothermal conditions. The two remaining components of entropy production account for a recently discussed thermodynamic anomaly between over- and underdamped treatments of the dynamics in the nonisothermal stationary state.

  4. Thermodynamic and related properties of parahydrogen from the triple point to 300 K at pressures to 1000 bar

    NASA Technical Reports Server (NTRS)

    Weber, L. A.

    1975-01-01

    Compressibility measurements and thermodynamic properties data for parahydrogen were extended to higher temperatures and pressures. Results of an experimental program are presented in the form of new pressure, volume and temperature data in the temperature range 23 to 300 K at pressures up to 800 bar. Also given are tables of thermodynamic properties on isobars to 1000 bar including density, internal energy, enthalpy, entropy, specific heats at constant volume and constant pressure, velocity of sound, and surface derivatives. The accuracy of the data is discussed and comparisons are made with previous data.

  5. Factors affecting the accuracy of chest compression depth estimation

    PubMed Central

    Kang, Jung Hee; Cha, Won Chul; Chae, Minjung Kathy; Park, Hang A; Hwang, Sung Yeon; Jin, Sang Chan; Lee, Tae Rim; Shin, Tae Gun; Sim, Min Seob; Jo, Ik Joon; Song, Keun Jeong; Rhee, Joong Eui; Jeong, Yeon Kwon

    2014-01-01

    Objective We aimed to estimate the accuracy of visual estimation of chest compression depth and identify potential factors affecting accuracy. Methods This simulation study used a basic life support mannequin, the Ambu man. We recorded chest compression with 7 different depths from 1 to 7 cm. Each video clip was recorded for a cycle of compression. Three different viewpoints were used to record the video. After filming, 25 clips were randomly selected. Health care providers in an emergency department were asked to estimate the depth of compressions while watching the selected video clips. Examiner determinants such as experience and cardiopulmonary resuscitation training and environment determinants such as the location of the camera (examiner) were collected and analyzed. An estimated depth was considered correct if it was consistent with the one recorded. A multivariate analysis predicting the accuracy of compression depth estimation was performed. Results Overall, 103 subjects were enrolled in the study; 42 (40.8%) were physicians, 56 (54.4%) nurses, and 5 (4.8%) emergency medical technicians. The mean accuracy was 0.89 (standard deviation, 0.76). Among examiner determinants, only subjects’ occupation and clinical experience showed significant association with outcome (P=0.03 and P=0.08, respectively). All environmental determinants showed significant association with the outcome (all P<0.001). Multivariate analysis showed that accuracy rate was significantly associated with occupation, camera position, and compression depth. Conclusions The accuracy rate of chest compression depth estimation was 0.89 and was significantly related with examiner’s occupation, camera view position, and compression depth.

  6. Evaluating marginal likelihood with thermodynamic integration method and comparison with several other numerical methods

    DOE PAGES

    Liu, Peigui; Elshall, Ahmed S.; Ye, Ming; Beerli, Peter; Zeng, Xiankui; Lu, Dan; Tao, Yuezan

    2016-02-05

    Evaluating marginal likelihood is the most critical and computationally expensive task, when conducting Bayesian model averaging to quantify parametric and model uncertainties. The evaluation is commonly done by using Laplace approximations to evaluate semianalytical expressions of the marginal likelihood or by using Monte Carlo (MC) methods to evaluate arithmetic or harmonic mean of a joint likelihood function. This study introduces a new MC method, i.e., thermodynamic integration, which has not been attempted in environmental modeling. Instead of using samples only from prior parameter space (as in arithmetic mean evaluation) or posterior parameter space (as in harmonic mean evaluation), the thermodynamicmore » integration method uses samples generated gradually from the prior to posterior parameter space. This is done through a path sampling that conducts Markov chain Monte Carlo simulation with different power coefficient values applied to the joint likelihood function. The thermodynamic integration method is evaluated using three analytical functions by comparing the method with two variants of the Laplace approximation method and three MC methods, including the nested sampling method that is recently introduced into environmental modeling. The thermodynamic integration method outperforms the other methods in terms of their accuracy, convergence, and consistency. The thermodynamic integration method is also applied to a synthetic case of groundwater modeling with four alternative models. The application shows that model probabilities obtained using the thermodynamic integration method improves predictive performance of Bayesian model averaging. As a result, the thermodynamic integration method is mathematically rigorous, and its MC implementation is computationally general for a wide range of environmental problems.« less

  7. Lunar Reconnaissance Orbiter Orbit Determination Accuracy Analysis

    NASA Technical Reports Server (NTRS)

    Slojkowski, Steven E.

    2014-01-01

    LRO definitive and predictive accuracy requirements were easily met in the nominal mission orbit, using the LP150Q lunar gravity model. center dot Accuracy of the LP150Q model is poorer in the extended mission elliptical orbit. center dot Later lunar gravity models, in particular GSFC-GRAIL-270, improve OD accuracy in the extended mission. center dot Implementation of a constrained plane when the orbit is within 45 degrees of the Earth-Moon line improves cross-track accuracy. center dot Prediction accuracy is still challenged during full-Sun periods due to coarse spacecraft area modeling - Implementation of a multi-plate area model with definitive attitude input can eliminate prediction violations. - The FDF is evaluating using analytic and predicted attitude modeling to improve full-Sun prediction accuracy. center dot Comparison of FDF ephemeris file to high-precision ephemeris files provides gross confirmation that overlap compares properly assess orbit accuracy.

  8. Nonequilibrium Thermodynamics in Biological Systems

    NASA Astrophysics Data System (ADS)

    Aoki, I.

    2005-12-01

    1. Respiration Oxygen-uptake by respiration in organisms decomposes macromolecules such as carbohydrate, protein and lipid and liberates chemical energy of high quality, which is then used to chemical reactions and motions of matter in organisms to support lively order in structure and function in organisms. Finally, this chemical energy becomes heat energy of low quality and is discarded to the outside (dissipation function). Accompanying this heat energy, entropy production which inevitably occurs by irreversibility also is discarded to the outside. Dissipation function and entropy production are estimated from data of respiration. 2. Human body From the observed data of respiration (oxygen absorption), the entropy production in human body can be estimated. Entropy production from 0 to 75 years old human has been obtained, and extrapolated to fertilized egg (beginning of human life) and to 120 years old (maximum period of human life). Entropy production show characteristic behavior in human life span : early rapid increase in short growing phase and later slow decrease in long aging phase. It is proposed that this tendency is ubiquitous and constitutes a Principle of Organization in complex biotic systems. 3. Ecological communities From the data of respiration of eighteen aquatic communities, specific (i.e. per biomass) entropy productions are obtained. They show two phase character with respect to trophic diversity : early increase and later decrease with the increase of trophic diversity. The trophic diversity in these aquatic ecosystems is shown to be positively correlated with the degree of eutrophication, and the degree of eutrophication is an "arrow of time" in the hierarchy of aquatic ecosystems. Hence specific entropy production has the two phase: early increase and later decrease with time. 4. Entropy principle for living systems The Second Law of Thermodynamics has been expressed as follows. 1) In isolated systems, entropy increases with time and

  9. Accuracy of TCP performance models

    NASA Astrophysics Data System (ADS)

    Schwefel, Hans Peter; Jobmann, Manfred; Hoellisch, Daniel; Heyman, Daniel P.

    2001-07-01

    Despite the fact that most of todays' Internet traffic is transmitted via the TCP protocol, the performance behavior of networks with TCP traffic is still not well understood. Recent research activities have lead to a number of performance models for TCP traffic, but the degree of accuracy of these models in realistic scenarios is still questionable. This paper provides a comparison of the results (in terms of average throughput per connection) of three different `analytic' TCP models: I. the throughput formula in [Padhye et al. 98], II. the modified Engset model of [Heyman et al. 97], and III. the analytic TCP queueing model of [Schwefel 01] that is a packet based extension of (II). Results for all three models are computed for a scenario of N identical TCP sources that transmit data in individual TCP connections of stochastically varying size. The results for the average throughput per connection in the analytic models are compared with simulations of detailed TCP behavior. All of the analytic models are expected to show deficiencies in certain scenarios, since they neglect highly influential parameters of the actual real simulation model: The approach of Model (I) and (II) only indirectly considers queueing in bottleneck routers, and in certain scenarios those models are not able to adequately describe the impact of buffer-space, neither qualitatively nor quantitatively. Furthermore, (II) is insensitive to the actual distribution of the connection sizes. As a consequence, their prediction would also be insensitive of so-called long-range dependent properties in the traffic that are caused by heavy-tailed connection size distributions. The simulation results show that such properties cannot be neglected for certain network topologies: LRD properties can even have counter-intuitive impact on the average goodput, namely the goodput can be higher for small buffer-sizes.

  10. Machine tool accuracy characterization workshops. Final report, May 5, 1992--November 5 1993

    SciTech Connect

    1995-01-06

    The ability to assess the accuracy of machine tools is required by both tool builders and users. Builders must have this ability in order to predict the accuracy capability of a machine tool for different part geometry`s, to provide verifiable accuracy information for sales purposes, and to locate error sources for maintenance, troubleshooting, and design enhancement. Users require the same ability in order to make intelligent choices in selecting or procuring machine tools, to predict component manufacturing accuracy, and to perform maintenance and troubleshooting. In both instances, the ability to fully evaluate the accuracy capabilities of a machine tool and the source of its limitations is essential for using the tool to its maximum accuracy and productivity potential. This project was designed to transfer expertise in modern machine tool accuracy testing methods from LLNL to US industry, and to educate users on the use and application of emerging standards for machine tool performance testing.

  11. Thermodynamic prediction of hydrogen production from mixed-acid fermentations.

    PubMed

    Forrest, Andrea K; Wales, Melinda E; Holtzapple, Mark T

    2011-10-01

    The MixAlco™ process biologically converts biomass to carboxylate salts that may be chemically converted to a wide variety of chemicals and fuels. The process utilizes lignocellulosic biomass as feedstock (e.g., municipal solid waste, sewage sludge, and agricultural residues), creating an economic basis for sustainable biofuels. This study provides a thermodynamic analysis of hydrogen yield from mixed-acid fermentations from two feedstocks: paper and bagasse. During batch fermentations, hydrogen production, acid production, and sugar digestion were analyzed to determine the energy selectivity of each system. To predict hydrogen production during continuous operation, this energy selectivity was then applied to countercurrent fermentations of the same systems. The analysis successfully predicted hydrogen production from the paper fermentation to within 11% and the bagasse fermentation to within 21% of the actual production. The analysis was able to faithfully represent hydrogen production and represents a step forward in understanding and predicting hydrogen production from mixed-acid fermentations. PMID:21875794

  12. Method and apparatus for adapting steady flow with cyclic thermodynamics

    DOEpatents

    Swift, Gregory W.; Reid, Robert S.; Ward, William C.

    2000-01-01

    Energy transfer apparatus has a resonator for supporting standing acoustic waves at a selected frequency with a steady flow process fluid thermodynamic medium and a solid medium having heat capacity. The fluid medium and the solid medium are disposed within the resonator for thermal contact therebetween and for relative motion therebetween. The relative motion is produced by a first means for producing a steady velocity component and second means for producing an oscillating velocity component at the selected frequency and concomitant wavelength of the standing acoustic wave. The oscillating velocity and associated oscillating pressure component provide energy transfer between the steady flow process fluid and the solid medium as the steady flow process fluid moves through the resonator.

  13. Accuracy of GIPSY PPP from a denser network

    NASA Astrophysics Data System (ADS)

    Gokhan Hayal, Adem; Ugur Sanli, Dogan

    2015-04-01

    Researchers need to know about the accuracy of GPS for the planning of their field survey and hence to obtain reliable positions as well as deformation rates. Geophysical applications such as monitoring of development of a fault creep or of crustal motion for global sea level rise studies necessitate the use of continuous GPS whereas applications such as determining co-seismic displacements where permanent GPS sites are sparsely scattered require the employment of episodic campaigns. Recently, real time applications of GPS in relation to the early prediction of earthquakes and tsunamis are in concern. Studying the static positioning accuracy of GPS has been of interest to researchers for more than a decade now. Various software packages and modeling strategies have been tested so far. Relative positioning accuracy was compared with PPP accuracy. For relative positioning, observing session duration and network geometry of reference stations appear to be the dominant factors on GPS accuracy whereas observing session duration seems to be the only factor influencing the PPP accuracy. We believe that latest developments concerning the accuracy of static GPS from well-established software will form a basis for the quality of GPS field works mentioned above especially for real time applications which are referred to more frequently nowadays. To assess the GPS accuracy, conventionally some 10 to 30 regionally or globally scattered networks of GPS stations are used. In this study, we enlarge the size of GPS network up to 70 globally scattered IGS stations to observe the changes on our previous accuracy modeling which employed only 13 stations. We use the latest version 6.3 of GIPSY/OASIS II software and download the data from SOPAC archives. Noting the effect of the ionosphere on our previous accuracy modeling, here we selected the GPS days through which the k-index values are lower than 4. This enabled us to extend the interval of observing session duration used for the

  14. Thermodynamic constraints on kinetic proofreading in biosynthetic pathways.

    PubMed Central

    Ehrenberg, M; Blomberg, C

    1980-01-01

    We develop a quantitative theory of kinetic proofreading with an arbitrary number of checking steps after the hydrolysis of a nucleoside triphosphate. In particular, we investigate the relationship between the minimum dissipation of free energy required for a given error frequency in such systems. Several conclusions can be drawn from the present treatment: first, the ultimate accuracy of error correcting selective pathways is set by the displacement from equilibrium of the nucleoside triphosphates. Second, it is advantageous to achieve a desired accuracy at a small energy dissipation with several checking steps rather than a single one. This could explain antinomies in the amino acylation reaction as well as in mRNA translation, where small structural differences lead to large differences in flow rates between right and wrong substrates. Third, all checking steps should contribute equally to the accuracy, which implies a specific and symmetrical set of rate constants for the checking events on the enzyme. PMID:7260292

  15. Impact of Atmospheric Infrared Sounder (AIRS) Thermodynamic Profiles on Regional Weather Forecasting

    NASA Technical Reports Server (NTRS)

    Chou, Shih-Hung; Zavodsky, Bradley T.; Jedlovee, Gary J.

    2010-01-01

    In data sparse regions, remotely-sensed observations can be used to improve analyses and lead to better forecasts. One such source comes from the Atmospheric Infrared Sounder (AIRS), which together with the Advanced Microwave Sounding Unit (AMSU), provides temperature and moisture profiles with accuracy comparable to that of radiosondes. The purpose of this paper is to describe a procedure to assimilate AIRS thermodynamic profile data into a regional configuration of the Advanced Research Weather Research and Forecasting (WRF-ARW) model using its three-dimension variational (3DVAR) analysis component (WRF-Var). Quality indicators are used to select only the highest quality temperature and moisture profiles for assimilation in both clear and partly cloudy regions. Separate error characteristics for land and water profiles are also used in the assimilation process. Assimilation results indicate that AIRS profiles produce an analysis closer to in situ observations than the background field. Forecasts from a 37-day case study period in the winter of 2007 show that AIRS profile data can lead to improvements in 6-h cumulative precipitation forecasts due to instability added in the forecast soundings by the AIRS profiles. Additionally, in a convective heavy rainfall event from February 2007, assimilation of AIRS profiles produces a more unstable boundary layer resulting in enhanced updrafts in the model. These updrafts produce a squall line and precipitation totals that more closely reflect ground-based observations than a no AIRS control forecast. The location of available high-quality AIRS profiles ahead of approaching storm systems is found to be of paramount importance to the amount of impact the observations will have on the resulting forecasts.

  16. Assessing the accuracy of Landsat Thematic Mapper classification using double sampling

    USGS Publications Warehouse

    Kalkhan, M.A.; Reich, R.M.; Stohlgren, T.J.

    1998-01-01

    Double sampling was used to provide a cost efficient estimate of the accuracy of a Landsat Thematic Mapper (TM) classification map of a scene located in the Rocky Moutnain National Park, Colorado. In the first phase, 200 sample points were randomly selected to assess the accuracy between Landsat TM data and aerial photography. The overall accuracy and Kappa statistic were 49.5% and 32.5%, respectively. In the second phase, 25 sample points identified in the first phase were selected using stratified random sampling and located in the field. This information was used to correct for misclassification errors associated with the first phase samples. The overall accuracy and Kappa statistic increased to 59.6% and 45.6%, respectively.Double sampling was used to provide a cost efficient estimate of the accuracy of a Landsat Thematic Mapper (TM) classification map of a scene located in the Rocky Mountain National Park, Colorado. In the first phase, 200 sample points were randomly selected to assess the accuracy between Landsat TM data and aerial photography. The overall accuracy and Kappa statistic were 49.5 per cent and 32.5 per cent, respectively. In the second phase, 25 sample points identified in the first phase were selected using stratified random sampling and located in the field. This information was used to correct for misclassification errors associated with the first phase samples. The overall accuracy and Kappa statistic increased to 59.6 per cent and 45.6 per cent, respectively.

  17. Thermodynamics of the variable modified Chaplygin gas

    NASA Astrophysics Data System (ADS)

    Panigrahi, D.; Chatterjee, S.

    2016-05-01

    A cosmological model with a new variant of Chaplygin gas obeying an equation of state(EoS), P = Aρ ‑ B/ρα where B= B0an is investigated in the context of its thermodynamical behaviour. Here B0 and n are constants and a is the scale factor. We show that the equation of state of this `Variable Modified Chaplygin gas' (VMCG) can describe the current accelerated expansion of the universe. Following standard thermodynamical criteria we mainly discuss the classical thermodynamical stability of the model and find that the new parameter, n introduced in VMCG plays a crucial role in determining the stability considerations and should always be negative. We further observe that although the earlier model of Lu explains many of the current observational findings of different probes it fails the desirable tests of thermodynamical stability. We also note that for 0n < our model points to a phantom type of expansion which, however, is found to be compatible with current SNe Ia observations and CMB anisotropy measurements. Further the third law of thermodynamics is obeyed in our case. Our model is very general in the sense that many of earlier works in this field may be obtained as a special case of our solution. An interesting point to note is that the model also apparently suggests a smooth transition from the big bang to the big rip in its whole evaluation process.

  18. Thermodynamics Insights for the Redshift Drift

    NASA Astrophysics Data System (ADS)

    Zhang, Ming-Jian; Liu, Wen-Biao

    2015-01-01

    The secular redshift drift is a potential measurement to directly probe the cosmic expansion. Previous study on the redshift drift mainly focused on the model-dependent simulation. Apparently, the physical insights on the redshift drift are very necessary. So in this paper, it is investigated using thermodynamics on the apparent, Hubble and event horizons. Thermodynamics could analytically present the model-independent upper bounds of redshift drift. For specific assumption on the cosmological parameters, we find that the thermodynamics bounds are nearly one order of magnitude larger than the expectation in standard ΛCDM model. We then examine ten observed redshift drift from Green Bank Telescope at redshift 0.09 < z < 0.69, and find that these observational results are inconsistent with the thermodynamics. The size of the errorbars on these measurements is about three orders of magnitude larger than the effect of thermodynamical bounds for the redshift drift. Obviously, we have not yet hit any instrumental systematics at the shift level of 1m s-1 yr-1.

  19. A thermodynamic formulation of root water uptake

    NASA Astrophysics Data System (ADS)

    Hildebrandt, Anke; Kleidon, Axel; Bechmann, Marcel

    2016-08-01

    By extracting bound water from the soil and lifting it to the canopy, root systems of vegetation perform work. Here we describe how root water uptake can be evaluated thermodynamically and demonstrate that this evaluation provides additional insights into the factors that impede root water uptake. We derive an expression that relates the energy export at the base of the root system to a sum of terms that reflect all fluxes and storage changes along the flow path in thermodynamic terms. We illustrate this thermodynamic formulation using an idealized setup of scenarios with a simple model. In these scenarios, we demonstrate why heterogeneity in soil water distribution and rooting properties affect the impediment of water flow even though the mean soil water content and rooting properties are the same across the scenarios. The effects of heterogeneity can clearly be identified in the thermodynamics of the system in terms of differences in dissipative losses and hydraulic energy, resulting in an earlier start of water limitation in the drying cycle. We conclude that this thermodynamic evaluation of root water uptake conveniently provides insights into the impediments of different processes along the entire flow path, which goes beyond resistances and also accounts for the role of heterogeneity in soil water distribution.

  20. The second laws of quantum thermodynamics.

    PubMed

    Brandão, Fernando; Horodecki, Michał; Ng, Nelly; Oppenheim, Jonathan; Wehner, Stephanie

    2015-03-17

    The second law of thermodynamics places constraints on state transformations. It applies to systems composed of many particles, however, we are seeing that one can formulate laws of thermodynamics when only a small number of particles are interacting with a heat bath. Is there a second law of thermodynamics in this regime? Here, we find that for processes which are approximately cyclic, the second law for microscopic systems takes on a different form compared to the macroscopic scale, imposing not just one constraint on state transformations, but an entire family of constraints. We find a family of free energies which generalize the traditional one, and show that they can never increase. The ordinary second law relates to one of these, with the remainder imposing additional constraints on thermodynamic transitions. We find three regimes which determine which family of second laws govern state transitions, depending on how cyclic the process is. In one regime one can cause an apparent violation of the usual second law, through a process of embezzling work from a large system which remains arbitrarily close to its original state. These second laws are relevant for small systems, and also apply to individual macroscopic systems interacting via long-range interactions. By making precise the definition of thermal operations, the laws of thermodynamics are unified in this framework, with the first law defining the class of operations, the zeroth law emerging as an equivalence relation between thermal states, and the remaining laws being monotonicity of our generalized free energies. PMID:25675476