4-32 THERMODYNAMICS

For species present as gases in the actual reactive system, the standard and Eq. (4-342) becomes
state is the pure ideal gas at pressure P. For liquids and solids, it is 
P j

usually the state of pure real liquid or solid at P. The standard-state (yi ˆ i) Kj
i, j
(all j) (4-344)
pressure P is fixed at 100 kPa. Note that the standard states may rep- i P
resent different physical states for different species; any or all of the where j i i,j and P is the standard-state pressure of 100 kPa,
species may be gases, liquids, or solids. expressed in the same units used for P. The yi may be eliminated in
The most commonly used standard property changes of reaction favor of equilibrium values of the reaction coordinates j. Then, for
are fixed temperature Eqs. (4-344) relate the j to P. In principle, specifi-
cation of the pressure allows solution for the j. However, the problem
Gj i, jGi i, j i (4-338) may be complicated by the dependence of the ˆ i on composition, that
i i

is, on the j. If the equilibrium mixture is assumed an ideal solution,

Hj i, j Hi (4-339) then each ˆ i becomes i, the fugacity coefficient of pure species i at
i the mixture T and P. This quantity does not depend on composition
and may be determined from experimental data, from a generalized
CP i, j CP (4-340)
i
i
i correlation, or from an equation of state.
An important special case of Eq. (4-344) is obtained for gas-phase
The standard Gibbs-energy change of reaction Gj is used in the cal- reactions when the phase can be assumed an ideal gas. In this event
culation of equilibrium compositions. The standard heat of reaction ˆ i 1, and
Hj is used in the calculation of the heat effects of chemical reaction, P j
and the standard heat-capacity change of reaction is used for extra- (yi)i, j Kj (all j) (4-345)

polating Hj and Gj with T. Numerical values for Hj and Gj are i P

computed from tabulated formation data, and CP isi determined In the general case the evaluation of the ˆ i requires an iterative
from empirical expressions for the T dependence of the CP i (see, e.g., process. An initial step is to set the ˆ i equal to unity and to solve
Eq. [4-142]). the problem by Eq. (4-345). This provides a set of yi values, allowing
Equilibrium Constants For practical application, Eq. (4-336) evaluation of the ˆ i by, for example, Eq. (4-196), (4-200), or (4-231).
must be reformulated. The initial step is elimination of the i in favor of Equation (4-344) can then be solved for a new set of yi values, and the
fugacities. Equation (4-74) for species i in its standard state is sub- process continues to convergence.
tracted from Eq. (4-77) for species i in the equilibrium mixture, giving For liquid-phase reactions, Eq. (4-342) is modified by introduction
i f̂ i /xi fi, where xi is the liquid-phase mole
of the activity coefficient,
i Gi RT ln âi (4-341) fraction. The activity is then
where, by definition, âi fˆi /fi and is called an activity. Substitution of fi
f̂ i
this equation into Eq. (4-341) yields, upon rearrangement, âi i i x
fi fi

[i, j(Gi RT ln âi)] 0 Both fi and fi represent fugacity of pure liquid i at temperature T, but
i at pressures P and P, respectively. Except in the critical region, pres-
i i is
i,j

or (i, jGi) RT ln âi 0
sure has little effect on the properties of liquids, and the ratio f /f
i i
often taken as unity. When this is not acceptable, this ratio is evaluated
by the equation
(i,jGi) f 1 P V (P P)

i, j
i ln Vi dP

i i
or ln âi
fi RT P

RT RT
i
When the ratio fi /fi is taken as unity, âi i xi, and Eq. (4-342)
The right-hand side of this equation is a function of temperature only becomes
for given reactions and given standard states. Convenience suggests
setting it equal to ln Kj; whence (i xi)i,j Kj (all j) (4-346)
i

âi i, j
Kj (all j) (4-342) Here the difficulty is to determine the i , which depend on the xi . This
i
problem has not been solved for the general case. Two courses are
 open: the first is experiment; the second, assumption of solution ide-
Gj
where Kj exp (4-343) ality. In the latter case, i 1, and Eq. (4-346) reduces to
RT

Quantity Kj is the chemical-reaction equilibrium constant for reaction (xi)i,j Kj (all j) (4-347)

j, and Gj is the corresponding standard Gibbs-energy change of
reaction (see Eq. [4-338]). Although called a “constant,” Kj is a func-
tion of T, but only of T.
The activities in Eq. (4-342) provide the connection between the
equilibrium states of interest and the standard states of the con-
stituent species, for which data are presumed available. The standard
states are always at the equilibrium temperature. Although the stan-
dard state need not be the same for all species, for a particular species
it must be the state represented by both Gi and the fi upon which the
activity âi is based.
 i
The application of Eq. (4-342) requires explicit introduction of
composition variables. For gas-phase reactions this is accomplished the law of mass action. The significant feature of Eqs. (4-345) and
through the fugacity coefficient: (4-347), the simplest expressions for gas- and liquid-phase reaction
equilibrium, is that the temperature-, pressure-, and composition-
âi fˆi/fi yi ˆ iP/fi dependent terms are distinct and separate.
However, the standard state for gases is the ideal gas state at the stan- Example 2: Single-Reaction Equilibrium Consider the equilib-
dard-state pressure, for which fi P. Therefore rium state at 1,000 K and atmospheric pressure for the reaction
yˆP CO H2O CO2 H2
âi i i
P Let the feed stream contain 3 mol CO, 1 mol H2O, and 2 mol CO2 for every
mole of H2 present. This initial constitution forms the basis for calculation, and
for this single reaction, Eq. (4-334) becomes ni ni i. Whence
0
nCO 3 nH2O
1 nCO2 2
nH2 1
ni 7
i

Each mole fraction is therefore given by yi ni/7.