CHAPTER

13
CHEMICAL-REACTION
EQUILIBRIA

13.1 THE REACTION COORDINATE

The general chemical reaction :

v1 A1 v2 A2 ... v3 A3 v4 A4 ...
where | vi | is a stoichiometric coefficient and Ai stands for a
chemical formula.
For vi :
Positive ( + ) for product

Negative ( - ) for reactants

Example :
CH4 + H2O CO + 3H2
The stoichiometric numbers are :

vCH 4 1

vH 2 O 1

vCO 1

vH 2 3

The stoichiometric number for an inert species is zero.

Since

dn1 dn2 dn3 dn4

... d
v1
v2
v3
v4

 The general relation between a differential change dni in the

number of moles of a reacting species and d is :

dni = vi d

( i = 1 , 2 ,.N)

This variable called the reaction coordinate, characterizes the

extent or degree to which a reaction has taken place.

or

ni

ni0

dni vi d

ni ni0 vi

( i = 1 , 2 ,.N)

 Summation over all species yields :

n ni ni0 vi

or
where

n = n0 + v

n ni
i

n0 ni0
i

v vi
i

Thus the mole fractions yi of the species present are related to by :

ni ni0 vi
yi

n
n0 v

Example 13.2
Consider a vessel which initially contains only no mol of water
vapor. If decomposition occurs according to the reaction,
1
H 2 O H 2 O2
2
find expressions which relate the number of moles and the mole
fraction of each chemical species to the reaction coordinate .

Solution 13.2

1 1
For the given reaction v 1 1
2 2
Application of Eqs. (13.4) and(13.5) yields:

n H 2O n0
y H 2O

n0

1
n0
2

nH 2
yH2

1
n0
2

nO2
y O2

1

2
1

2
1
n0
2

The fractional decomposition of water vapor is:

n0 n H 2O
n0

n0 n0

n0
n0

Thus when no = 1, is identified with the fractional decomposition of

the water vapor.

dni vi , j d j

( i = 1 , 2 ,.N)

After integration :

ni ni0 vi , j j
j

Summing over all species yields :

n ni0 vi , j j n0
i

For the mole fraction:

ni0 vi , j j

yi

n0 v j j
j

v
i

i, j

13.2 APPLICATION OF
EQUILIBRIUM CRITERIA TO
CHEMICAL REACTIONS
At the equilibrium state :
( dGt )T , P = 0
The total Gibbs energy Gt is a minimum
Its differential is zero.

13.3 THE STANDARD GIBBS-ENERGY

CHANGE
AND THE EQUILIBRIUM CONSTANT

The fundamental property relation for single-phase systems,

provides an expression for the total differential of the Gibbs
energy: d nG nV dP S dT dn

i result of a single
If changes in mole numbers ni occur as the
chemical reaction in a closed system , then each dni may be
replaced by the product vi d .

d nG nV dP S dT vi i d

Since nG is a state function , the right sidei of this an exact

differential expression :
t

nG

i vi i
T ,P

T ,P

 For chemical-reaction equilibrium :

v
i

Recall the definition of the fugacity of a species in solution :

i i T RT ln fi
For a pure species i in its standard start at the same temperature :

Gi i T RT ln f i

The difference between these two equations is :

fi

i Gi RT ln
fi

 For the equilibrium state of a chemical reaction :

RT ln f

f 0
v
G

RT
ln
f
i i
i
i
i

v G
i

ln fi f i
i

ln
i

where

vi

fi f i

vi

fi

i vi Gi
RT

K exp
RT

vi

 Alternative expression for K :

G
ln K
RT
Also by definition : G

G
i
i

K is a function of temperature only .

In spite of its dependence on temperature , K is called the
equilibrium constant for the reaction ;

v
G
i i i , represented by G , is called the

standard Gibbs-energy change of reaction ,

13.4 EFFECT OF TEMPERATURE

ON THE EQUILIBRIUM CONSTANT
The dependence of G on T :

Then become:

d G RT
H

dT
RT 2

d ln K H

dT
RT 2
Equation above gives the effect of temperature on equilibrium
constant and hence on the equilibrium conversion.

 When H
negative = exothermic reaction
positive = endothermic reaction
If H is assumed independent of T, then:
K
H 1 1
ln

K
R T T

This approximate equation implies that a plot of ln K vs the

reciprocal of absolute temperature is a straight line. Figure
13.2 in textbook, shows a plot of ln K vs 1/T for a number of
common reactions, illustrates this near linearity.

 The rigorous development of the effect of temperature on

the equilibrium constant is based on the definition of the
Gibbs energy , written for a chemical species in its standard
state:
Gi = Hi -TSi
Multiplication by vi and summation over all species gives:

v
G

v
H

T
v
S
i i i i i i
i

 As a result of the definition of standard property change of

reaction, this reduces to:
G=H - TS
Where the standard heat of reaction and standard entropy
change is related to temperature:

C
P
H H 0 R
dT
T0
R
T

P dT
S S0 R
T0
R T
T

 However
whence

G
0
0
S 0
T0

G G0 H 0 H 0o 1

RT
RT0
RT T
and

G
ln K
RT

T C dT
C P
P
dT

T0 R
T0 R T
T

 The preceding equation may be reorganized so as to factor

K into three terms , each representing a basic contribution
to its value :
K = K0 K1 K2
K0 represents the equilibrium constant at reference
temperature T0 :
G
K 0

RT0

H 0
T0
K 1 exp
1
T
RT0

 1
K 2 exp
T

T C dT
C P
P
dT

T0 R
T0 R T
T

with heat capacities given :

1
K 2 exp A ln

2
2
2

1
1 1
1 D 1
2 1 2

2 BT0 6 CT0
2
2

2
T

13.5 EVALUATION OF EQUILIBRIUM

CONSTANTS
Example 13.4
Calculate the equilibrium constant for the vapor-phase
hydration of ethylene at 145 and at 320C from data given in
App. C.
Solution 13.4
First determine values for A, B, C, and D for the
reaction:
C2H4 (g) + H2O (g) C2H5OH (g)

The meaning of is indicated by: A = (C2H5 OH) - (C2H4) (H2O). Thus, from the heat-capacity data of Table C. 1:
A = 3.518 - 1.424 - 3.470 = - 1.376
B = (20.001 - 14.394 - 1.450) x 10-3 = 4.157 x l0-3
C = (-6.002 + 4.392 - 0.000) x 10-6 = -1.610 x 10-6
D = (-0.000 - 0.000 - 0.121) x 105 = -0.121 x 105

Values of H298 and G298 at 298.15 K for the hydration reaction are
found from the heat-of-formation and Gibbs-energy-of-formation data
from Table C.4:
H298 = -235,100 - 52,510 - (-241,818) = -45,792 J mol-1
G298 = -168,490 - 68,460 - (-228,572) -8,378 J mol-1
For T = 145 + 273.15 = 418.15 K, values of the integrals in Eq. (13.18)
are:
IDCPH(298.15,418.15;-1.376,4.157E-3,-1.610E-6,-0.121 E+5) = -23.121
IDCPS(298.15,418.15;-1.376,4.157E-3,-1.610E-6,-0.121 E+5) = -0.06924

Substitution of values into Eq. (13.18) for a reference temperature of

298.15 gives:

G418
8,378 45,792
45,792
23.121

0.06924 1.9356
8.314 298.15 8.314 418.15 418.15
RT

For T = 320 + 273.15 = 593.15 K,

IDCPH(298.15,593.15;-1.376,4.157E-3,-1.610E-6,-0.121 E+5) =
22.632
IDCPS(298.15,593.15;-1.376,4.157E-3,-1.610E-6,-0.121 E+5) =
0.01731
Whence,

G593
8,378 45,792
45,792
22.632

0.01731 5.8286
8.314 298.15 8.314 593.15 593.15
RT

Finally,
@418.15K: ln K = -1.9356 and K = 1.443 x 10-1
@593.15K: ln K = -5.8286 and K = 2.942x 10-3
Application of Eqs. (13.21), (13.22), and (13.24) provides an
alternative solution to this example. By Eq. (13.21),

8,378

H
45,792
0
K 0 exp
29.366

18.473
8.314 298.15
8.314 298.15
RT0

Moreover,
With these values, the following results are readily obtained:
T/ K

K0

K1

K2

298.15

29.366

29.366

418.15

1.4025

29.366

4.985x10-3

0.9860

1.443x10-1

593.15

1.9894

29.366

1.023x10-4

0.9794

2.942x10-3

Clearly, the influence of K1, is far greater than that of K2. This
is a typical result, and accounts for the fact that the lines on
Fig. 13.2 are nearly linear.

13.6 REELATION OF EQUILIBRIUM

CONSTANTS TO COMPOSITION
The standard state for gas is the ideal gas-state of the pure
gas at the standard-state pressure P of 1 bar.
Since for ideal gas : fi = P
Thus :

fi

fi

fi

and

fi
i P

vi

where the constant K is a function of temperature only .

For a fixed temperature the composition at equilibrium must

change with pressure in such a way that
f P v K remains constant .

The fugacity is related to the fugacity coefficient :

fi i y i P

Substitution of this equation :

y
i i

vi

P

P

where
v i vi and P is the standard state pressure if 1 bar ,
expressed in the same units used for P .

 For ideal solution :

v

ii

P

P

i for a pure species can be evaluated from a generalized

correlation once the equilibrium T and P are specified .
For pressure sufficiently low or temperature sufficiently high,
the equilibrium behaves essentially as an ideal gas
v

y
i
i

P

P

For reaction occurring in liquid phase :

fi
i f
i

Since

vi

fi i xi f i

The fugacity ratio expresses :

fi
fi i xi f i

i xi

fi
fi
fi
the fugacities of liquids are weak function of pressure .

For reaction that take place in high pressure

xi i

vi

P P
K exp
RT

v V

For low pressure :

i i

If the equilibrium mixture is an ideal solution , then i is unity :

v

x
i

This simple relation is known as the law of mass action. Since

liquids often form nonideal solutions, equation above can be
expected in many instances to yield poor result .

For species at low concentration in aqueous solution,

Henrys law can be use :

fi k i mi
where ki is a constant which dependent on temperature and
mi is molality .

13.7 EQUILIBRIUM
CONVERSIONS FOR SINGLE
REACTIONS
Example 13.5
The water-gas-shift reaction, CO(g) + H2O(g) CO2(g) + H2(g)
is carried out under the different sets of conditions described below.
Calculate the fraction of steam reacted in each case. Assume the
mixture behaves as an ideal gas.
(a)The reactants consist of 1 mol of H2O vapor and 1 mol of CO. The
temperature is 1,100 K and the pressure is 1 bar.
(b)Same as (a) except that the pressure is 10 bar.
(b)Same as (a) except that 2 mol of N2 is included in the reactants.

(d)The reactants are 2 mol of H2O and 1 mol of CO. Other

conditions are the same as in (a).
(e)The reactants are 1 mol of H2O and 2 mol of CO. Other
conditions are the same as in (a).
(f) The initial mixture consists of 1 mol of H2O, 1 mol of CO,
and 1 mol of CO2. Other conditions are the same as in (a).
(g) Same as (a) except that the temperature is 1,650 K.

Solution 13.5
(a)
For the given reaction at 1,100 K, 104/T = 9.05, and
Fig. 13.2 provides the value. ln K0 or K = 1. For this reaction
v vi 1 1 1 1 0. Since the reaction mixture is an ideal
i

gas, Eq. (13.28) applies, and here becomes:

y H 2 y CO2
K 1
y CO y H 2O
By Eq. (13.5):

y CO

1 e

y H 2O

1 e

y CO2

yH2

Substitution of these values into Eq. (A) gives:

e2
1
2
or
e = 0.5
1 e
Therefore the fraction of the steam that reacts is 0.5.
(b) Since v = 0 , the increase in pressure has no effect on the
ideal-gas reaction, and e is still 0.5.
(c) The N2 does not take part in the reaction, and serves only as a
diluent. It does increase the initial number of moles no from 2 to 4,
and the mole fractions are all reduced by a factor of 2. However,
Eq. (A) is unchanged and reduces to the same expression as
before. Therefore, e is again 0.5.

(d) In this case the mole fractions at equilibrium are:

y CO

1 e

y H 2O

2 e

y CO2

yH2

and Eq. (A) becomes:

e2
1
1 e 2 e

or

e = 0.667

The fraction of steam that reacts is then 0.667/2 = 0.333

(e)Here the expressions for yCO and yH2O are interchanged , but this
leaves the equilibrium equation the same as in (d). Therefore e =
0.667, and the fraction of steam that reacts is 0.667.
(f) In this case Eq. (A) becomes:

e 1 e

1 e

or

e = 0.333

The fraction of steam reacted is 0.333.

(g) At 1,650 K, 104/T = 6.06, and from Fig. 13.2, in K = -1.15

or K = 0.316.
Therefore Eq. (A) becomes:
e2
0.316
1 e

or

e = 0.36

The reaction is exothermic, and conversion decreases with increasing

temperature.

13.8 PHASE RULE AND DUHEMS

THEOREM FOR REACTING
SYSTEM
This is phase rule for reacting systems.
F = 2 + N r
where is number of phases , N number of chemical species
and r is number of independent chemical reactions at
equilibrium within the system .

13.9 MULTIREACTION EQUILIBRIA

fi
i f
i

vi , j

Kj

where j is the reaction index.

For gas phase reaction :
fi
i P

vi , j

Kj

For the equilibrium mixture is an ideal-gas,

v

y
i
i

i, j

P

P

v j

Kj