Chemical Engineering 301

Lecture Notes
Chapters 13. Chemical-Reaction Equilibria
General Chemical-Reaction Equilibrium Relations
Writing a general chemical reaction as

Ai 0

we define the "reaction coordinate" (sometimes called "extent of reaction") by the

following:
dn1 dn2
dn

i d
1
2
i

ni
i

ni nio i
n no
yi

nio i
no

i
yi yi

The condition for equilibrium at fixed T and P is that the Gibbs free energy (G)
must be a minimum.
This condition leads to (see text, pp. 472-5):
N

i 1

Now, just like for phase equilibria work, we want to replace the chemical
potentials with fugacities:

i
io
i

io

f
i
fio

RT ln

i
RT ln a

Gio
Gio

RT ln
0

RT ln K

f
i
fio

Gio

RT

ln

f
i

fio

Calculation of Standard Gibbs Energy Change of Reaction

Use "Standard Gibbs Energy Changes of Formation" to calculate this function at
298 K (see Append. C for values):
o
G298
i G of 298i

To use this to calculate the equilibrium constant, it must be corrected from 298 K
to the actual temperature of the system at equilibrium:

d G o / RT

H o
dT
RT 2
T
o
G298
G o
H o

dT
RT
R ( 298) 298 RT 2

o
C p
H o
H298

dT
R
R
R
298
o

C po
R

A BT CT 2 DT 2
A

Ai

etc.

The latter equation is for ideal gas heat capacities. If this can be used, then the
integrals can be done analytically (see pp.578-9).
For liquid-phase reactions, one must either know how the heat of reaction varies
with temperature, or some simplifying assumption must be made.
If it is assumed that the heat of reaction is independent of temperature (valid if the
temperature is not too far from 298 K, and often a good approximation at any
processing Ts),

RT ln

o
o
G298
H 298
G o
1
1

RT
R (298)
R T 298

ln

o
H 298
K

K 298
R

1
1

T 298

Discuss Fig. 13.2, p. 477. The curves for each reaction are nearly straight lines,
over rather large temperature ranges. K decreases with T for exothermic reactions.
Relations of K to Composition
Gas-phase reactions
The standard state is the pure gas at 1 bar pressure:
f i o 1 bar
K

fi Pyi i
K P yi

K P K y K

Discuss Example 13.5, p. 486. Use this as a group exercize, with each
group taking a different part.

Liquid-phase reactions
The standard state is the pure liquid at 1 bar pressure:
f
K io
fi

f x
i io i
fi

V P 1
fi
exp i
1
o
fi
RT

K K x K

Discuss Example 13.8, p. 491.

Dilute components in water -- aqueous solutions (see p. 485).
The standard state is the hypothetical ideal (Henry's law) 1 molal solution
of the solute in water at 1 bar.

fi k i mi
f o k (1)
i

fi
mi
f o
i

Solids.
The standard state is the pure solid at 1 bar. Neglecting the small effect of
pressure on the solid-phase fugacity

fi
1
f io
Heterogeneous systems
Both phase equilibrium and chemical reaction equilibrium relations must be
satisfied.
The fugacities must be evaluated in concert with the standard states chosen
in the calculation of the standard Gibbs free energy change of reaction.
Discuss Example 13.10, p. 495, assuming ethanol and water participate in
the reaction in the gas phase, and then where these are liquids in the
reaction. Ethylene is assumed to be negligibly soluble in the liquid phase.
In the first case, Eqn. E is obtained for K, whereas, in the second approach,
the equation for K becomes,
K

Py

x EtOH EtOH
C2 H4

C2 H4 x H2 O

H2 O

Note that the effect of pressure on liquid fugacities has been neglected.
The Phase Rule
The phase-rule variables are T, P, and the mole-fraction compositions in all
phases present at equilibrium.
The degrees of freedom (F) is the number of phase-rule variables that must
be fixed to solve for the rest.

F N 2 r s

r = number of independent chemical reactions (see p. 591 for

the method to determine r)
s = number of equations expressing special constraints (eg., x=y
for an azeotrope).
Duhem's Theorem
For any closed system formed initially from given masses (or number of moles) of
a set of chemical species, the equilibrium state (both intensive and extensive) is
determined by specification of any two independent variables (usually T and P for
reacting systems).
Proof:
Number of Variables = 2 + (N-1)r
The first term represents T and P, the second the mole fractions in all phases, the
third the total moles in each phase, and the fourth the extent of reaction for each
reaction.
Number of Equations = (N + N + r
The first term represents the phase-equilibrium relations, the second the material
balances for each component, and the third the chemical reaction equilibrium
relations.
F = No. Var. - No. Eqns. = 2