Thermodynamic tables

Knacke, O. (1973) Thermochemical Properties of Inorganic Substances. Springer-Verlag, Heidelberg, 922 p. 

Earner, H.E. Scheuerman, R.V. (1978) Handbook of Thermochemical Data for Compounds and Aqueous Species. John Wiley Sons, New York. 

(1998) NIST-JANAF Thermochemical Tables, 4th. ed. Part. I (Al-Co) and Part II (Cr-Zr), Journal of Physical and Chemical Reference Data, Monograph No. 9, Joint Publication of the American Chemical Society (ACS), the American Institute of Physics (AIP) and the National Institute of Standards and Technology (NIST), Springer, New York. 

Hulgren, R. Desai, P.D. HAWKINS, D.T. Gleiser, M. Kelley, K.K. (1973) Selected Values of the Thermodynamics Properties of the Elements University of California, Berkeley/American Society for Metals. 

Pankratz, L.B. (1982) Thermodynamic Properties of Elements and Oxides. U.S. Bureau of Mines Bulletin No. 672, U.S. Government Printing Office, Washington D.C.. 

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Example of NHV calculation for toluene based on thermodynamic data from Thermodynamic Tables - Hydrocarbons" edited by TRC (Thermodynamic Research Center, The Texas A M University System College Station, Texas, USA). 

References D. D. Wagman, et ah, The NBS Tables of Chemical Thermodynamic Properties, in J. Phys. Chem. Ref. Data, 11 2,1982 M. W. Chase, et ah, JANAF Thermochemical Tables, 3rd ed., American Chemical Society and the American Institute of Physics, 1986 (supplements to JANAF appear in J. Phys. Chem. Ref. Data) Thermodynamic Research Center, TRC Thermodynamic Tables, Texas A M University, College Station, Texas I. Barin and O. Knacke, Thermochemical Properties of Inorganic Substances, Springer-Verlag, Berlin, 1973 J. B. Pedley, R. D. Naylor, and S. P. Kirby, Thermochemical Data of Organic Compounds, 2nd ed.. Chapman and Hall, London, 1986 V. Majer and V. Svoboda, Enthalpies of Vaporization of Organic Compounds, International Union of Pure and Applied Chemistry, Chemical Data Series No. 32, Blackwell, Oxford, 1985. 

TRCTHERMO database, TRC Thermodynamics Tables Hydrocarbons and Non-Hydrocarbons, Thermodynamics Research Center, Texas A M University System, College Station, Tex., July 1993. 

K. Raznjevic, Handbook of Thermodynamic Tables and Charts, McGraw-HiU Book Co., New York, 1976, p. 247a. 

Ambrose, D., National Physical Lahotatoty Repotts Chem. 92, 98, and 107, Teddington, Middlesex, United Kingdom, 1978, 1979, and 1980. Angus, S., B. Armstrong, and K. M. de Reuck, Carhon Dioxide, International Thermodynamic Tables of the Fluid State, Vol. 3. lUPAC, Pergamon Press, Elmsford, NY, 1976. 

Heat Capacity, C° Heat capacity is defined as the amount of energy required to change the temperature of a unit mass or mole one degree typical units are J/kg-K or J/kmol-K. There are many sources of ideal gas heat capacities in the hterature e.g., Daubert et al.,"" Daubert and Danner,JANAF thermochemical tables,TRC thermodynamic tables,and Stull et al. If C" values are not in the preceding sources, there are several estimation techniques that require only the molecular structure. The methods of Thinh et al. and Benson et al. " are the most accurate but are also somewhat complicated to use. The equation of Harrison and Seaton " for C" between 300 and 1500 K is almost as accurate and easy to use ... 

Ideal gas absolute entropies of many compounds may be found in Daubert et al.,"" Daubert and Danner," JANAF Thermochemical Tables,TRC Thermodynamic Tables,and Stull et al. ° Otherwise, the estimation method of Benson et al. " is reasonably accurate, with average errors of 1-2 J/mol K. Elemental standard-state absolute entropies may be found in Cox et al." Values from this source for some common elements are listed in Table 2-389. ASjoqs may also be calculated from Eq. (2-52) if values for AHjoqs and AGJoqs are known. 

The work done by an expanding fluid is defined as the difference in internal energy between the fluid s initial and final states. Most thermodynamic tables and graphs do not presentbut only h, p, v, T (the absolute temperature), and s (the specific entropy). Therefore, u must be calculated with the following equation ... 

To use a thermodynamic graph, locate the fluid s initial state on the graph. (For a saturated fluid, this point lies either on the saturated liquid or on the saturated vapor curve, at a pressure py) Read the enthalpy hy volume v, and entropy from the graph. If thermodynamic tables are used, interpolate these values from the tables. Calculate the specific internal energy in the initial state , with Eq. (6.3.23). 

When thermodynamic tables are used, read the enthalpy hf, volume Vj, and entropy Sf of the saturated liquid at ambient pressure, po, interpolating if necessary. In the same way, read these values (hg, Vg, Sg) for the saturated vapor state at ambient pressure. Then use the following equation to calculate the specific internal energy... 

We are free to choose either K or Kc to report the equilibrium constant of a reaction. However, it is important to remember that calculations of an equilibrium constant from thermodynamic tables of data (standard Gibbs free energies of formation, for instance) and Eq. 8 give K, not Kc. In some cases, we need to know Kc after we have calculated K from thermodynamic data, and so we need to be able to convert between these two constants. 

This calculation shows that reaction energies and reaction enthalpies are usually about the same, even when reactions Involve gases. For this reason, chemists often use A 5 reaction nd A reaction interchangeably. Because many everyday processes occur at constant pressure, thermodynamic tables usually give values for enthalpy changes. Nevertheless, bear In mind that these are different thermodynamic quantities. For processes with modest AE values and significant volume changes, A " and A H can differ substantially. 

The third law of thermodynamics establishes a starting point for entropies. At 0 K, any pure perfect crystal is completely constrained and has S = 0 J / K. At any higher temperature, the substance has a positive entropy that depends on the conditions. The molar entropies of many pure substances have been measured at standard thermodynamic conditions, P ° = 1 bar. The same thermodynamic tables that list standard enthalpies of formation usually also list standard molar entropies, designated S °, fbr T — 298 K. Table 14-2 lists representative values of S to give you an idea of the magnitudes of absolute entropies. Appendix D contains a more extensive list. 

Given the equation 3CE — 203, we definitely cannot say that O2 reacts with itself to form 03. This equation is the overall reaction, and does not give any information about the mechanism of the reaction, i.e. the order in which bonds are broken and formed to create the products from the reactant. It is only telling us that for every 3 moles of O2 that react, 2 moles of 03 are formed. There is no information in the equation as to how that happens. However, using thermodynamic tables and Hess s Law, we find that AHnn = +286 kJ and AArxn = -137.4 J/mol K, so AGrxn is positive at all temperatures and the reaction must be nonspontaneous at all temperatures. 

Thermodynamic tables, 24 658 Thermodynamic temperature, 15 749 measurements, 24 436 Thermodynamic thermometers, types of, 24 435t... 

Modem computational programs [4] and thermodynamic tables [5] now make it possible to explicitly calculate metal-oxygen flame temperatures, thereby opening up a unique aspect of combustion thermodynamics that could be important in the consideration of metal as fuels and as reactants in combustion synthesis. 

Raznjevic, Kuzman, HANDBOOK OF THERMODYNAMIC TABLES AND CHARTS. Hemisphere Publishing Corporation, New York, NY (1976). 

MATHEMATICAL PREPARATION FOR THERMODYNAMICS TABLE 2.2. Si-Derived Units... 

The International Union of Puie and AppUed Chemistry now recommends a standard pressure of 0.1 MPa (1 bar) in place of the previously accepted standard of 101.325 kPa (1 atm). The difference in thermodynamic quantities is not significant for condensed phases, and differences in A// values are not significant even for gases, but the user of thermodynamic tables will have to note carefully the standard state chosen for any compilation of data. See Ref. 1, pp. 2—23 lUPAC Division of Physical Chemistry, Commission on Symbols, Terminology and Units, Manual of symbols and terminology for physico-chemical quantities and units, M. L. McGlashan, M. A. Paul, and D. N. Whiffen, eds., Pure andApp. Chem 51, 1 (1979), and Appendix IV, Pure and Applied Chem. 54, 1239 (1982). 

The thermodynamic tables of Robie et al. (1978) use the Haas-Fisher polynomial (eq. 3.53.1). Helgeson et al. (1978) use the Maier-Kelley expansion, changing sign at the third term ... 

The NIST-JANAF Thermodynamics Tables are available online from the National Institute of Standards www.nist.gov/srd/monogr.htm. 

It is possible to calculate a heat of reaction for a high-energy system by assuming what the reaction products will be and then using available thermodynamic tables of heats o/formation. "Heat of formation" is the heat associated with the formation of a chemical compound from its constituent elements. For example, for the reaction... 

Interestingly, the standard entropies (and in turn heat capacities) of both phases were found to be rather similar [69,70]. Considering the difference in standard entropy between F2(gas) and the mixture 02(gas) + H2(gas) taken in their standard states (which can be extracted from general thermodynamic tables), the difference between the entropy terms of the Gibbs function relative to HA and FA, around room temperature, is about 6.5 times lower than the difference between enthalpy terms (close to 125 kJ/mol as estimated from Tacker and Stormer [69]). This indicates that FA higher stability is mostly due to the lower enthalpy of formation of FA (more exothermic than for HA), and that it is not greatly affected by entropic factors. Jemal et al. [71] have studied some of the thermodynamic properties of FA and HA with varying cationic substitutions, and these authors linked the lower enthalpy of formation of FA compared to HA to the decrease in lattice volume in FA. 

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