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The tables in this section contain values of the enthalpy and Gibbs energy of formation, entropy, and heat capacity at 298.15 K (25\ue000C). No values are given in these tables for metal alloys or other solid solutions, for fused salts, or for substances of unde\ufb01ned chemical composition.
The values of the thermodynamic properties of the pure substances given in these tables are, for the substances in their standard states, de\ufb01ned 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 of\ue000fH\ue000and\ue000fG\ue000that are given in the tables represent the change in the appropriate thermodynamic quantity when one mole of the substance in its standard state is formed, isothermally at the indicated temperature, from the elements, each in its appropriate standard reference state. The standard reference state at 25\ue000C for each element has been chosen to be the standard state that is thermodynamically stable at 25\ue000C and 1 atm pressure. The standard reference states are indicated in the tables by the fact that the values of\ue000fH\ue000and\ue000fG\ue000are exactly zero.
The values ofS\ue000 represent the virtual or \u201cthermal\u201d entropy of the substance in the standard state at 298.15 K (25\ue000C), omitting contributions from nuclear spins. Isotope mixing effects are also ex- cluded except in the case of the1H9 2H system.
Solutions in water are designated as aqueous, and the concentration of the solution is expressed in terms of the number of moles of solvent associated with 1 mol of the solute. If no concentration is indicated, the solution is assumed to be dilute. The standard state for a solute in aqueous solution is taken as the hypothetical ideal solution of unit molality (indicated as std. state or ss). In this state
American Chemical Society and the American Institute of Physics, 1986 (supplements to JANAF appear inJ. Phys. Chem. Ref. Data); Thermodynamic Research Center,TRC Thermodynamic Tables, Texas A&M University, College Station, Texas; I. Barin and O. Knacke,Thermochemical Properties
Since the elements are in their standard states, the enthalpy change for the reaction is equal to the standard enthalpy of CO2less the standard enthalpies of C and O2, which are zero in each instance. Thus,
Tables of enthalpies, such as Tables 6.1 and 6.3, can be used to determine the enthalpy for any reaction at 1 atm and 298.15 K involving the elements and any of the compounds appearing in the tables.
for the standard enthalpy of formation of the pair of ions H\ue000 and Cl\ue001 in aqueous solution (standard state,m\ue002 1). To obtain the\ue000fH\ue000values for individual ions, the enthalpy of formation of H\ue000(aq) is arbitrarily assigned the value zero at 298.15 K. Thus, from Eq. (6.4):
With similar data from Tables 6.1 and 6.3, the enthalpies of formation of other ions can be deter- mined. Thus, from the\ue000fH\ue000[KCl(aq, std. state, m\ue0021 or aq, ss)] of \ue003419.53 kJ and the foregoing value for\ue000fH\ue000[Cl\ue001(aq, ss)]:\ue000
rium with a liquid reaches 1 atm, the liquid boils and is completely converted to vapor on absorption of the enthalpy of vaporization\ue000Hv at the normal boiling pointTb. A rough empirical relationship between the normal boiling point and the enthalpy of vaporization (Trouton\u2019s rule) is:
which may be used for calculating the enthalpy of vaporization of any compound provided its boiling point at any pressure is known. If an Antoine equation is available (such as Eq. (5.1), page 5.30), differentiation and insertion into the foregoing equation gives:
whereTc andPc are critical constants (Table 6.5). Although critical constants may be unknown, the compressibility factor is very nearly constant for all compounds belonging to the same family, and an estimate can be deduced from a related compound whose critical constants are available.
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