Thermodynamics data base

The calculation of vapor and liquid fugacities in multi-component systems has been implemented by a set of computer programs in the form of FORTRAN IV subroutines. These are applicable to systems of up to twenty components, and operate on a thermodynamic data base including parameters for 92 compounds. The set includes subroutines for evaluation of vapor-phase fugacity... 

Benson17 has tried to collect some thermodynamic data based on a number of empirical rules for this class of radicals. He estimated heats of formation for HS02, MeSO 2) PhSO 2 and HOSO 2 as —42, —55, —37 and — 98kcalmor respectively. He also estimated a stabilization energy for the benzenesulfonyl radical of 14 kcal mol"1, which is very similar to that of the benzyl radical. However, recent kinetic studies18 (vide infra) have shown that arenesulfonyls are not appreciably stabilized relative to alkanesulfonyl radicals, in accord with the ESR studies. 

Due to its modularity, the software comes in many parts (shown in Fig. 9). The Chemkin package is composed of four important pieces the Interpreter, the Thermodynamic Data Base, the Linking File, and the Gas-Phase Subroutine Library. The Interpreter is a program that first reads the user s symbolic description of the reaction mechanism. It then extracts thermodynamic information for the species involved from the Thermodynamic Data Base. The user may add to or modify the information in the data base by input to the Interpreter. In addition to printed output, the Interpreter writes a Linking File, which contains all the pertinent information on the elements, species, and reactions in the mechanism. 

Ball, J. W. and D. K. Nordstrom, 1991, User s manual for WATEQ4F, with revised thermodynamic data base and test cases for calculating speciation of major, trace, and redox elements in natural waters. US Geological Survey Open File Report 91-183. 

Burcat [ Thermochemical Data for Combustion Calculations, in Combustion Chemistry. (W. C. Gardiner, Jr., ed.), Chapter 8. John Wiley Sons, New York, 1984] discusses in detail the various sources of thermochemical data and their adaptation for computer usage. Examples of thermochemical data tit to polynomials for use in computer calculations are reported by McBride, B. J Gordon, S., and Reno, M. A., Coefficients for Calculating Thermodynamic and Transport Properties of Individual Species, NASA, NASA Langley, VA, NASA Technical Memorandum 4513, 1993, and by Kee, R. J., Rupley, F. M and Miller, J. A., The Chemkin Thermodynamic Data Base, Sandia National Laboratories, Livermore, CA, Sandia Technical Report SAND87-8215B, 1987. 

Chatteijee N. (1989). An internally consistent thermodynamic data base on minerals Applications to the earth s crust and upper mantle. Ph.D. diss., City University of New York. 

Kee, R. J., P. M. Rupley, and J.A. Miller. 1991. The CHEMKIN thermodynamic data base. Sandia National Laboratories Report, SAND87-8215B. 

Development and application of the Nagra/PSI Chemical Thermodynamic Data Base 01 /01... 

Presently, thermodynamic data bases for environmental chemistry are far from being complete. We believe that many built-in data bases of geochemical codes that include an impressive number of data for aqueous species and solid phases for most elements may easily produce incorrect results if used without criticism. Indeed, one of the main lessons learnt during our update exercise is that completeness and reliability of the data are mutually exclusive. On the other hand, reducing the data base to a small number of best thermodynamic data severely limits its field of applicability. Thus, in order to model specific systems of fundamental relevance for radioactive waste disposal we were forced to make compromises and had to include estimated constants. 

Hummel, W., Berner, U., Curti, E., Pearson, F. J. Thoenen, T. 2002. Nagra/PSl Chemical Thermodynamic Data Base 01/01. Nagra Technical Report NTB 02-16, Nagra, Wettingen, Switzerland. Also published by Universal Publishers/ uPublish.com Parkland, Florida, USA. World Wide Web Address http //www.upublish.com. 

Thoenen, T. Kulik, D. 2003. Nagra/PSI Chemical Thermodynamic Data Base 01/01 for the GEM-Selektor (V.2-PSI) Geochemical Modeling Code Release 28-02-03. PSI Technical Report TM-44-03-04, Paul Scherrer Institut, Villigen, Switzerland. 

We will now consider a practical example of calculating thermochemical properties for the species CH3. Actually a lot is known about the CH3 radical, and we choose it as example in order to compare the calculated results with experimental data. The NIST-JANAF Thermochemical Tables [62] are a standard source for experimental thermochemical data, as well as moments of inertia, vibrational frequencies, and the like. The NIST-JANAF Tables use the same basic approach outlined here to calculate the temperature dependence for their thermodynamic data, based on species vibrational frequencies and moments of inertia. 

A general formulation of the problem of solid-liquid phase equilibrium in quaternary systems was presented and required the evaluation of two thermodynamic quantities, By and Ty. Four methods for calculating Gy from experimental data were suggested. With these methods, reliable values of Gy for most compound semiconductors could be determined. The term Ty involves the deviation of the liquid solution from ideal behavior relative to that in the solid. This term is less important than the individual activity coefficients because of a partial cancellation of the composition and temperature dependence of the individual activity coefficients. The thermodynamic data base available for liquid mixtures is far more extensive than that for solid solutions. Future work aimed at measurement of solid-mixture properties would be helpful in identifying miscibility limits and their relation to LPE as a problem of constrained equilibrium. 

Solubility estimates made by the techniques discussed above are reported in the last column of Table H. In addition to the limited number of such measurements, the results do not compare favorably in all cases with the theoretical values listed. This fact is hardly surprising considering the recognized limitations in the thermodynamic data base and difficulties encountered in interpreting results of solubility experiments. Furthermore, the theoretical estimates are based on the assumption that the thermodynamically most stable solid for a radionuclide controls its solubility. The effects of metastability are not included and, in this sense, theoretical solubility estimates are not conservative. A series of sorption-type experiments designed to yield solubility estimates for a number of the radionuclides included in this paper is in progress, and the results will be reported at a later date. 

As a new addition, a CD with a tabulation of the current enthalpies of formation and free energies of formation of the compounds occurring in this publication is included with the book for the first time. This tabulation is a compilation of data from the very comprehensive thermodynamic data base published and continually updated by the Fraunhofer Institute for Chemical Technology (ICT). 

These programs are able to model the geological systems soil/rock-aqueous solution systems that is the concentration and distribution of the thermodynamically stable species can be determined based on the total concentrations of the components and the parameters just mentioned. In addition, the programs can also be used to estimate thermodynamic equilibrium constants and/or surface parameters from the concentrations of the species determined through experiments. Thermodynamic equilibrium constants can be found in tables (Pourbaix 1966) or databases (e.g., Common Thermodynamic Database Project, CHESS, MINTEQ, Visual MINTEQ, NEA Thermodynamical Data Base Project (TDB), JESS, Thermo-Calc Databases). Some programs (e.g., NETPATH, PHREEQC) also consider the flowing parameters. 

J.W. Ball and D.K. Nordstrom, Users Manual for WATEQ 4F, with Revised Thermodynamic Data Base and Test Cases for Calculating Speciation of Major, Trace and Redox Elements in Natural Waters, US Geological Survey Open File Report, Menlo Park, CA, 1991, 91. 

Despite the incomplete state of a thermodynamic data base and limited mechanistic insight, several attempts to model alkali vapor transport in reactive atmospheres have been made. The increased sophistication of modeling efforts in recent years is demonstrated by the following examples ... 

Using our experimental activity data for Na20 in glass, we have modeled the effect of a typical combustion gas mixture on alkali vaporization ( ). For this purpose we have acquired, and adapted to our computers, a code known as SOLGASMIX (7 ) which is unique in its ability to deal with non-ideal solution multicomponent heterogeneous equilibria. Previous attempts to model this type of problem have been limited to ideal solution assumptions ( ). As is demonstrated in Table III, if solution non-ideality is neglected, drastic errors result in the prediction of alkali vapor transport processes. Table III and Figure 21 summarize the predicted alkali species partial pressures. The thermodynamic data base was constructed mainly from the JANAF (36) compilation. Additional details of this study will be presented elsewhere. 

WATEQ2 consists of a main program and 12 subroutines and is patterned similarly to WATEQF ( ). WATEQ2 (the main program) uses input data to set the bounds of all major arrays and calls most of the other procedures. INTABLE reads the thermodynamic data base and prints the thermodynamic data and other pertinent information, such as analytical expressions for effect of temperature on selected equilibrium constants. PREP reads the analytical data, converts concentrations to the required units, calculates temperature-dependent coefficients for the Debye-HKckel equation, and tests for charge balance of the input data. SET initializes values of individual species for the iterative mass action-mass balance calculations, and calculates the equilibrium constants as a function of the input temperature. MAJ EL calculates the activity coefficients and, on the first iteration only, does a partial speciation of the major anions, and performs mass action-mass balance calculations on Li, Cs, Rb, Ba, Sr and the major cations. TR EL performs these calculations on the minor cations, Mn, Cu, Zn, Cd, Pb, Ni, Ag, and As. SUMS performs the anion mass... 

The computerized aqueous chemical model of Truesdell and Jones (, 3), WATEQ, has been greatly revised and expanded to include consideration of ion association and solubility equilibria for several trace metals, Ag, As, Cd, Cu, Mn, Ni, Pb and Zn, solubility equilibria for various metastable and(or) sparingly soluble equilibrium solids, calculation of propagated standard deviation, calculation of redox potential from various couples, polysulfides, and a mass balance section for sulfide solutes. Revisions include expansion and revision of the redox, sulfate, iron, boron, and fluoride solute sections, changes in the possible operations with Fe (II, III, and II + HI), and updating the model s thermodynamic data base using critically evaluated values (81, 50, 58) and new compilations (51, 26 R. M. Siebert and... 

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