Thermodynamic property, standard states

The database contains thermochemical property data at standard state conditions for over 15 000 inorganic substances and small organic molecules having up to two carbon atoms. NISTTHERMO corresponds to the Tables of Chemical Thermodynamic Properties. Standard state properties at 298.15 K and 1 bar stored are enthalpy of formation, Gibbs energy of formation for the elements, enthalpy, heat capacity at constant pressure, and entropy. 

The standard-state fugacity of any component must be evaluated at the same temperature as that of the solution, regardless of whether the symmetric or unsymmetric convention is used for activity-coefficient normalization. But what about the pressure At low pressures, the effect of pressure on the thermodynamic properties of condensed phases is negligible and under such con-... 

The values of the thermodynamic properties of the pure substances given in these tables are, for the substances in their standard states, defined as follows For a pure solid or liquid, the standard state is the substance in the condensed phase under a pressure of 1 atm (101 325 Pa). For a gas, the standard state is the hypothetical ideal gas at unit fugacity, in which state the enthalpy is that of the real gas at the same temperature and at zero pressure. 

The values given in the following table for the heats and free energies of formation of inorganic compounds are derived from a) Bichowsky and Rossini, Thermochemistry of the Chemical Substances, Reinhold, New York, 1936 (h) Latimer, Oxidation States of the Elements and Their Potentials in Aqueous Solution, Prentice-Hall, New York, 1938 (c) the tables of the American Petroleum Institute Research Project 44 at the National Bureau of Standards and (d) the tables of Selected Values of Chemical Thermodynamic Properties of the National Bureau of Standards. The reader is referred to the preceding books and tables for additional details as to methods of calculation, standard states, and so on. 

Compiled from Daubert, T. E., R. R Danner, H. M. Sibiil, and C. C. Stebbins, DIPPR Data Compilation of Pure Compound Properties, Project 801 Sponsor Release, July, 1993, Design Institute for Physical Property Data, AlChE, New York, NY and from Thermodynamics Research Center, Selected Values of Properties of Hydrocarbons and Related Compounds, Thermodynamics Research Center Hydrocarbon Project, Texas A M University, College Station, Texas (extant 1994). The compounds are considered to be formed from the elements in their standard states at 298.15 K and 101,325 P. These include C (graphite) and S (rhombic). Enthalpy of combustion is the net value for the compound in its standard state at 298.15K and 101,325 Pa. 

For liquid mixtures at low pressures, it is not important to specify with care the pressure of the standard state because at low pressures the thermodynamic properties of liquids, pure or mixed, are not sensitive to the pressure. However, at high pressures, liquid-phase properties are strong functions of pressure, and we cannot be careless about the pressure dependence of either the activity coefficient or the standard-state fugacity. 

In Chapter 10. we will calculate the thermodynamic properties of gases from the molecular parameters, and these calculations, which provide the standard state values, are most easily done for the ideal gas. 

A number of other thermodynamic properties of adamantane and diamantane in different phases are reported by Kabo et al. [5]. They include (1) standard molar thermodynamic functions for adamantane in the ideal gas state as calculated by statistical thermodynamics methods and (2) temperature dependence of the heat capacities of adamantane in the condensed state between 340 and 600 K as measured by a scanning calorimeter and reported here in Fig. 8. According to this figure, liquid adamantane converts to a solid plastic with simple cubic crystal structure upon freezing. After further cooling it moves into another solid state, an fee crystalline phase. 

The thermodynamic standard state of a substance is its most stable state under standard pressure (1 atm) and at some specific temperature (usually 25°C). Thermodynamic refers to the observation, measurement and prediction of energy changes that accompany physical changes or chemical reaction. Standard refers to the set conditions of 1 atm pressure and 25°C. The state of a substance is its phase gas, liquid or solid. Substance is any kind of matter all specimens of which have the same chemical composition and physical properties. 

The standard state (and thus any standard thermodynamic property) of a pure solid refers to the pure substance in the solid phase under the pressure p of 1 bar (0.1 MPa). The standard state of a pure liquid refers to the pure substance in the liquid phase at p = 1 bar. When the substance is a pure gas, its standard state is that of an ideal gas at p = 1 bar (or, which is equivalent, that of a real gas at P = o). 

However, since the standard state of carbon is the condensed state, carbon graphite, the only partial pressure it exerts is its vapor pressure (pw), a known thermodynamic property that is also a function of temperature. Thus, the preceding formation expression is written as... 

As the Gibbs function is a thermodynamic property, values of AG do not depend on the intermediate chemical reactions that have been used to transform a set of reactants, under specified conditions, to a series of products. Thus, one can add known values of a Gibbs function to obtain values for reactions for which direct data are not available. The most convenient values to use are the functions for the formation of a compound in its standard state from the elements in their standard states, as given in Tables 7.2... 

We can summarize our conclusions about the thermodynamic properties of the solute in the hypothetical 1-molal standard state as follows. Such a solute is characterized by values of the thermodynamic functions that are represented by p2. 77m2. and 5m2- Frequently a real solution at some molality m2(j) also exists (Fig. 16.4) for which p.2 = that is, for which the activity has a value of 1. The real solution for which // i2 is equal to H 2 is the one at infinite dilution. Furthermore, 5 n,2 has a value equal to 5 2 for some real solution only at a molahty m2(k) that is neither zero nor m2( j). Thus, three different real concentrations of the solute exist for which the thermodynamic qualities p,2, //mi. and S a respectively, have the same values as in the hypothetical standard state. 

The examples in section 3.1.2 of calculations using stability constants involve concentrations of M, L, and ML . Rigorously, a stability constant, as any thermodynamic equilibrium constant should be defined in terms of standard state conditions (see section 2.4). When the system has the properties of the standard state conditions, the concentrations of the different species are equal to their activities. However, the standard state conditions relate to the ideal states described in Chapter 2, which can almost never be realized experimentally for solutions of electrolytes, particularly with water as the solvent. For any conditions other than those of the standard state, the activities and concentrations are related by the activity coefficients as described in Chapter 2, and especially... 

Table 5.36 Thermodynamic properties of pure pyroxene components in their various structural forms according to Saxena (1989) (1), Berman (1988) (2), and Holland and Powell (1990) (3) database. = standard state entropy of pure component at 7) = 298.15 K and Py = bar (J/mole) Hjp p = enthalpy of formation from elements at same standard state conditions. Isobaric heat capacity function Cp is... 

The left-hand-side of the equation is defined as the Gibbs energy relative to a standard element reference state (SER) where is the enthalpy of the element or substance in its defined reference state at 298.IS K, a, b, c and dn are coefficients and n represents a set of integers, typically taking the values of 2, 3 and -1. From Eq. (S.3), further thermodynamic properties can be obtained as discussed in Chapter 6. 

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. 

USNBS 1982. United States National Bureau of Standards tables of molar thermodynamic properties. J. Phys. Chem Ref. Data, 11 (Supp. 2). World Wide Web Addresses http //www.ualberta.ca/ jplambec/che/data/p00404.htm and http // www.ucdsb.on.ca/tiss/stretton/cheml/data3.htm. 

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