c14ChemicalandPhaseEquilibrium.i856 Page 856 7/26/10 11:43:25 PM users-133 /Users/users-133/Desktop/Ramakant_04.05.

09/WB00113_R1:JWCL170/New

856 Chapter 14 Chemical and Phase Equilibrium

This expression can be written alternatively in terms of specific enthalpies and

entropies as

¢G8 5 nC1hC 2 T s C8 2 1 nD1hD 2 T s D8 2 2 nA1hA 2 T s A8 2 2 nB1hB 2 T s 8B2

5 1nC hC 1 nDhD 2 nAhA 2 nBhB2 2 T1nC s C8 1 nD s 8D 2 nAs A8 2 nB s B8 2 (14.29b)

Since the enthalpy of an ideal gas depends on temperature only, the h’s of Eq. 14.29b
are evaluated at temperature T. As indicated by the superscript 8, each of the entro-
pies is evaluated at temperature T and a pressure of 1 atm.
Introducing Eq. 14.29a into Eq. 14.28 and combining the terms involving loga-
rithms into a single expression gives

¢G8 yCnC y nDD p nC 1nD 2nA 2nB

2 5 ln c nA nB a b d (14.30)
RT y A y B pref

Equation 14.30 is simply the form taken by the equation of reaction equilibrium,
Eq. 14.26, for an ideal gas mixture subject to the reaction Eq. 14.24. As illustrated
by subsequent examples, similar expressions can be written for other reactions.
Equation 14.30 can be expressed concisely as

¢G 8
2 5 ln K1T2 (14.31)
RT

where K is the equilibrium constant defined by

y CnC y nDD p nC 1nD 2nA 2nB

equilibrium constant K1T2 5 a b (14.32)
y nAA y nBB pref

Given the values of the stoichiometric coefficients, nA, nB, nC, and nD and the tem-
perature T, the left side of Eq. 14.31 can be evaluated using either of Eqs. 14.29
together with the appropriate property data. The equation can then be solved for the
value of the equilibrium constant K. Accordingly, for selected reactions K can be
evaluated and tabulated against temperature. It is common to tabulate log10K or ln
K versus temperature, however. A tabulation of log10K values over a range of tem-
peratures for several reactions is provided in Table A-27, which is extracted from a
more extensive compilation.
The terms in the numerator and denominator of Eq. 14.32 correspond, respectively,
to the products and reactants of the reaction given by Eq. 14.24 as it proceeds from
left to right as written. For the inverse reaction nCC 1 nDD d S nAA 1 nBB, the equi-
librium constant takes the form
y nAA y nBB p nA 1nB 2nC 2nD
K* 5 a b (14.33)
y nCC y nDD pref
Comparing Eqs. 14.32 and 14.33, it follows that the value of K* is just the reciprocal
of K: K* 5 1/K. Accordingly,

log10 K * 5 2log10 K (14.34)

Hence, Table A-27 can be used both to evaluate K for the reactions listed proceeding
in the direction left to right and to evaluate K* for the inverse reactions proceeding
in the direction right to left.
Example 14.1 illustrates how the log10K values of Table A-27 are determined. Sub-
sequent examples show how the log10K values can be used to evaluate equilibrium
compositions.