CHEMICAL REACTION

EQUILIBRIA
THE REACTION COORDINATE
APPLICATION OF EQUILIBRIUM CRITERIA TO CHEMICAL REACTIONS
THE STANDARD GIBBS-ENERGY CHANGE AND THE EQUILIBRIUM CONSTANT
EFFECT OF TEMPERATURE ON THE EQUILIBRIUM CONSTANT
EVALUATION OF EQUILIBRIUM CONSTANTS

RELATION OF EQUILIBRIUM CONSTANTS TO COMPOSITION

EQUILIBRIUM CONVERSIONS FOR SINGLE REACTIONS
THE REACTION COORDINATE
For general chemical reaction

1 A1 2 A2 3 A3 4 A4 (13.1)

where i is stoichiometric coefficient

Ai is chemical formula.
i is stoichiometric number, and it is
positive (+) for product negative (-) for reactant
Example: CH 4 H 2O CO 3 H 2
the stoichiometric numbers are
CH 1
4
H O 1
2
CO 1 H 3 2

The stoichiometric number for inert species is zero.

As the reaction in eq. (13.1) progresses, the changes in the numbers of
moles of species present are in direct proportion to the stoichiometric
numbers. E.g. If 0.5 mol CH4 disappears, 0.5 mol H2O also disappears;
simultaneously 0.5 mol CO and 1.5 mol H2 are formed.
2
 Applied to differential amount of reaction, this principle provides the
equations:
dn2 dn1 dn3 dn1
etc.
2 1 3 1
The list continues to include all species. Comparison yields
dn1 dn2 dn3 dn4
...
1 2 3 4
All terms being equal, they can be identified collectively by a single quantity
representing an amount of reaction. A definition of d is given by the
equation:
dn1 dn2 dn3 dn4
... d (13.2)
1 2 3 4

The general relation connecting the differential change dni with d is

therefore
dni i d i 1, 2, ..., N (13.3)
is called the reaction coordinate (also known as degree of reaction or extent
of reaction), characterizes the extent or degree to which a reaction has taken
place.

3
 Integration of eq. (13.3) from an initial unreacted state where = 0 and ni
= nio to a state reached after an amount of reaction gives
ni

ni 0
dni i d
0

or ni ni 0 i i 1, 2, ..., N (13.4)
Summation over all species yields

n ni ni 0 i
i i i

or n n0
where
n ni n0 ni 0 i
i i i

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

ni ni 0 i
yi (13.5)
n n0

4
EXAMPLE 13.1

For a system in which the following reaction occurs,

CH 4 H 2O CO 3 H 2

assume there are present initially 2 mol CH4, 1 mol H2O, 1 mol CO and 4
mol H2. Determine expressions for the mole fractions yi as functions of .

5
EXAMPLE 13.2
Consider a vessel which initially contains only n0 mol of water vapor. If
decomposition occurs according to the reaction,
H2O H2 21 O2
find expressions which relate the number of moles and the mole fraction of
each chemical species to the reaction coordinate .
Solution:
For the reaction, 1 1 21 1
2

Application of eqs. (13.4) and (13.5) yields

ni ni 0 i nH O n0 nH
2 2
nO2 21
ni ni 0 i n 1

yi yH2O 0 1 yH2 yO2 2
n n0 n0 2 n0 21 n0 21
The fractional decomposition of water vapor is
n0 nH2O n0 n0

n0 n0 n0
When n0 = 1, is directly related to the fractional decomposition of the
water vapor.
6
Multireaction Stoichiometry
For multireaction, i,j designates the stoichiometric number of species i in
reaction j.
The general relation, eq. (13.3) becomes
dni i , j d j i 1, 2, ..., N
j

Integration from ni = ni0 and j = 0 to ni and j gives

ni ni 0 i , j j i 1, 2, ..., N (13.6)
j
Summing over all species yields

n ni 0 i , j j n0 i , j j
i i j j i
The definition of a total stoichiometric number i i for a single
reaction has its counterpart here in the definition:
j i , j thus n n0 j j
i j
Combination of this last equation with eq. (13.6) gives the mole fraction
ni 0 j i , j j
yi i 1, 2, ..., N (13.7)
n0 j j j 7
EXAMPLE 13.3
Consider a system in which the following reactions occur:

CH 4 H 2O CO 3 H 2 1
CH 4 2 H 2O CO2 4 H 2 2
where the numbers (1) and (2) indicate the value of j, the reaction index. If
there are present initially 2 mol CH4 and 3 mol H2O, determine expressions
for the yi as functions of 1 and 2.

Solution:
The stoichiometric numbers i,j can be arrayed as follows:

i= CH4 H2O CO CO2 H2

j j
1 -1 -1 1 0 3 2
2 -1 -2 0 1 4 2
8
Application of eq. (13.7) gives
ni 0 j i , j j
yi i 1, 2, ..., N
n0 j j j

2 1 2 1
yCH4 yCO
5 2 1 2 2 5 2 1 2 2
3 1 2 2 2
yH 2 O yCO2
5 2 1 2 2 5 2 1 2 2
3 1 4 2
yH 2
5 2 1 2 2

9
APPLICATION OF EQUILIBRIUM
CRITERIA TO CHEMICAL REACTIONS
Total Gibbs energy of a closed system at constant T and P must decrease
during an irreversible process and equilibrium is reached when Gt attains
its minimum value. At this equilibrium state,

dG
t
T ,P
0

If a mixture is not in equilibrium, any reaction at constant T and P must

lead to a decrease in the total Gibbs energy of the system.

10
 Fig. 13.1 shows the relation of Gt and . The arrows along the curve
indicate the directions of changes in (Gt)T,P. The reaction coordinate, has
its equilibrium value e at the minimum of the curve.

This figure indicates two distinctive

features of the equilibrium state for
given T and P,
a) Total Gibbs energy Gt is a minimum.
b) Its differential is zero.

(For a single chemical reaction)

11
 THE STANDARD GIBBS-ENERGY
CHANGE AND THE EQUILIBRIUM
CONSTANT
Equation (11.2) provides an expression for the total differential of the Gibbs
energy:

d nG (nV )dP (nS )dT i dni (11.2)

i

If changes in the mole numbers ni occur as the result of a single chemical reaction
in a closed system, then by eq. (13.3) each dni may be replaced by the product
id. Eq. (11.2) then becomes
d nG (nV )dP (nS )dT i i d
i

Because nG is a state function, the right side of this equation is an exact

differential expression,

nG Gt
i i i
T ,P T ,P
The quantity i i represents, in general, the rate of change of total Gibbs
energy of the system
i with respect to the reaction coordinate at constant T and P.
12
 Fig. 13.1 shows that this quantity is zero at the equilibrium state. A
criterion of chemical reaction equilibrium is therefore

i
i i 0 (13.8)

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

T RT ln f
i i i (11.46)

In addition, eq. (11.31) may be written for pure species i in its standard
state at the same temperature:

Gio i T RT ln fio

The difference between these two equations is

f
i G RT ln io
o
i
(13.9)
fi

13
 Combining eq. (13.8) with eq. (13.9) to eliminate i gives for the equilibrium
state of a chemical reaction:

i
i
G o RT ln f f o 0
i i i
or

i
iG RT ln fi fio
i
o
i
i
0

i
or
ln f f o
RT
Go
i i i
i i
i

where i signifies the product over all species i.

In exponential form, this equation becomes

i
f f o K (13.10)
i i
i

where the definition of K and its logarithm are given by

G o
K exp (13.11a)
RT
G o
ln K (13.11b)
RT
14
 Also by definition,
G o i i Gio (13.12)

Gio, Go and K are functions of temperature.

K is called the equilibrium constant for the reaction; iiGio,
represented by Go, is called the standard Gibbs-energy change of
reaction.
The function Go iiGio in eq. (13.12) is the difference between the
Gibbs energies of the products and reactants when each is in its standard
state as a pure substance at the standard state pressure, but at the system
temperature.
Other standard property changes of reaction are similarly defined. For
general property M:
M o i Mio
i

The relation between the standard heat of reaction and the standard Gibbs
energy change of reaction is

H o RT 2
d G o
RT
(13.13)
dT
15
EFFECT OF TEMPERATURE ON THE
EQUILIBRIUM CONSTANT
Because the standard state temperature is that of the equilibrium mixture, the
standard property changes of reaction, such as Go and Ho, vary with the
equilibrium temperature.
The dependence of Go on T is given by eq. (13.13), which may be rewritten as

d G o RT H o

dT RT 2
In view of eq. (13.11b), this becomes

d ln K H o (13.14)

dT RT 2
If Ho is negative, i.e., if the reaction is exothermic, the equilibrium constant
decreases as the temperature increases. K increases with T for endothermic
reaction.
If Ho is assumed independent of T, integration of eq. (13.14) from T to T leads
to the simple result:
K H o 1 1 (13.15)
ln ' '
K R T T
A plot of ln K vs. the reciprocal of absolute temperature is a straight line. 16
17
 Effect of temperature on equilibrium constant is based on the definition of
the Gibbs energy at standard state:
Gio H io TSio
Multiply by i and summation over all species gives
i i i i i i

i
G o
H o

i
T S o

As a result of the definition of a standard property change of reaction, this

reduces to
G o H o T S o (13.16)

The standard heat of reaction is related to temperature:

T C po
H H 0 R
o o
dT (4.18)
T0R
The temperature dependence of the standard entropy change of reaction
is: dT
dSio C Poi
T
Multiply by i and summation over all species gives
dT
dS o C Po
T
18
 Integration gives
C Po dTT
S S R
o o
0
(13.17)
T0 R T
where So and S0o are the standard entropy changes of reaction at
temperature T and at reference temperature T0.
Eqs. (13.16), (4.18) and (13.17) are combined to yield
C P o T T C
o
G H R
o o
0 dT T S0 RT
o P
dT
T0 R T0 R
However,
H0o G0o
S o
0
T0
Hence,
T C T C
o o
T
G H
o o
0
T0
o

H0 G0 R
o
T0 R
P

dT RT
T0 R
P
dT

Finally, division by RT yields

G o G0 H 0 H0 1
o o o
T C P o T C
o
P dT
RT

RT0

RT T T0 R dT T0 R T (13.18)
19
 The first integral of eq. (13.18) is
C Po B 2 2 C 3 3 D 1

T
T0 R dT A T 1 T 1 T 1 (4.19)
T0
0 0 0
2 3

T
where
T0

OR
C Po B 2 C 3 1 1

T
T0 R dT A T To T T0
2
T T0
3
D
2 3 T To

The second integral of eq. (13.18) is

C Po dT
T D 1
T0 R T 1
2
A ln BT CT 2 2 (13.19)

0

0
T0 2

OR
T
C Po dT T C 2 D 1 1
T R T A ln
T
B T T0
2
T T
0
2

2
2
T


T 2
0 0 o
20
 Go/RT(= - ln K) as given in eq. (13.18) is readily calculated at any
temperature from the standard heat of reaction and the standard Gibbs
energy change of reaction at a reference temperature (usually 298.15 K).
Factor K may be organized into three terms:
K K0 K1 K 2

G0o
K 0 exp (13.21)
RT0

H0o T0 (13.22)
K1 exp 1 T
RT0
1 T C Po T C dT
o
(13.23)
K2 exp dT P

T T0 R T0 R T

21
 EVALUATION OF EQUILIBRIUM
CONSTANT
EXAMPLE 13.4
Calculate the equilibrium constant for the vapor phase hydration of
ethylene at 145oC (418.15 K) and at 320oC (593.15 K) from data given in
App. C.

Solution:
The chemical reaction:
C2 H4 g H2O g C2 H5OH g

vi TableAC.1 and
From B (x10
C.4: )
-3 C (x10-6) D (x105) Ho298 Go298
(J/mol) (J/mol)
C2H5OH 1 3.518 20.001 -6.002 - -235100 -168490
C2H4 -1 1.424 14.394 -4.392 - 52510 68460
H2 O -1 3.470 1.450 - 0.121 -241818 -228572

22
 A i Ai - 1.376
i

B i Bi 4.157 10-3
i

C i C i 1.610 10-6
i

D i Di - 0.121 105
i

H298
o
i Hio,298 45792 Jmol-1
i

G298
o
i Gio,298 8378 Jmol-1
i

For T = 418.15 K, values of integrals in eq. (13.18) are

T C Po T C Po dT
T0 R dT 23.121 eqn. 4.19 T0 R T 0.0692 eqn. 13.19

Substitute into eq. (13.18) for a reference temperature of 298.15 K gives:

G0o H 0o
o
G o
H0 1 T C P o T C
o
P dT
RT

RT0

RT T T0 R dT T0 R T (13.18)

G418.15
o
8378 45792 45792 23.121
0.0692 1.9356
RT 8.314298.15 8.314 418.15 418.15 23
 For T = 593.15 K,
T C Po
T0 R dT 22.632
T C dT
o

T0 R T 0.0173
P

G593.15
o
8378 45792 45792 22.632
0.0173 5.8286
RT 8.314298.15 8.314 593.15 593.15

Finally, by eq. (13.11b)

G o
ln K
RT
At 418.15 K, ln K = -1.9356 and K = 1.443 x 10-1
At 593.15 K, ln K = -5.8286 and K = 2.942 x 10-3

Alternative solution by using eq. (13.21), (13.22) and (13.23).

24
RELATION OF EQUILIBRIUM
CONSTANTS TO COMPOSITION
Gas phase reactions
The standard state for a gas is the ideal gas state of the pure gas at the
standard state pressure Po of 1 bar.
Because the fugacity of ideal gas is equal to its pressure, fio = Po for each
species i. Therefore for gas phase reactions fi fio fi P o and eq.
(13.10) becomes

f
f
i
i
i fio K (13.10) i P io K (13.25)
i

This eq. relates K to fugacities of the reacting species as they exist in the
real equilibrium mixture. These fugacities reflect the non-idealities of the
equilibrium mixture and are functions of temperature, pressure and
composition.
The fugacity is related to the fugacity coefficient by eq. (11.52):
f y P
i i i

25
 Substitute into eq. (13.25) provides an equilibrium expression displaying the
pressure and the composition:

y
i P
i i o K (13.26)
i P

where i i and Po is the standard state pressure of 1 bar.

The yis may be eliminated in favor of the equilibrium value of the reaction
coordinate e. For fixed temperature eq. (13.26) relates e to P. If P is specify, e
can be solved. i can be evaluated by using eq. (11.63 or 11.64).
If the equilibrium mixture is an ideal solution, then each i becomes i , then
eq. (13.26) becomes

P

i i i P o K
i
y (13.27)

Each i for a pure species can be evaluated from a generalized correlation.

For pressure sufficiently low or temperatures sufficiently high, the equilibrium
mixture behaves essentially as an ideal gas. Each i 1 and eq. (13.26)
reduces to:

P
y
i
i o K (13.28)
i P
26
 Some conclusions based on eq. (13.28) that are true in general:
According to eq. (13.14), the effect of temperature on the equilibrium
constant K is determined by the sign of Ho.

d ln K H o (13.14)

dT RT 2
When Ho is positive, i.e., when the standard reaction is endothermic, an
increase in T results in an increase in K. Eq. (13.28) shows that an increase in
K at constant P results in an increase in i(yi)vi; this implies a shift of the
reaction to the right and an increase in e.
When Ho is negative, i.e., when the standard reaction is exothermic, an
increase in T causes a decrease in K and a decrease in i(yi)vi at constant P.
This implies a shift of reaction to the left and a decrease in e.
If the total stoichiometric number v (ivi) is negative, eq. (13.28) shows
that an increase in P at constant T causes an increase in i(yi)vi ,
implying a shift of the reaction to the right and an increse in e .
If v is positive, an increase in P at constant T causes a decrease in
i(yi)vi , implying a shift of the reaction to the left and a decrease in e .

P
y
i
i o K (13.28)
i P 27
Liquid phase reactions
For a reaction occurring in the liquid phase,

i
f f o K
i i (13.10)
i

Standard state for liquid fio is the fugacity of pure liquid i at the
temperature of the system and at 1 bar.
According to eq. (11.90),
f
f x f i i (11.90)
i i i i
xi fi
The fugacity ratio can be expressed as
f i xi f i fi
i
x
i i o (13.29)
fio fio f
i
Because the fugacities of liquids are weak function of pressure, the ratio
fi/fio is often taken as unity.
For pure liquid i, eq. (11.31) is written for temperature T and pressure P,
and for the same temperature T but for standard state pressure Po.
Gi i T RT ln f i
Gi o i T RT ln f i o
28
 The difference between these two equations is
fi
Gi Gio RT ln
fio
Integration of eq. (6.10) at constant T for the change of state of pure liquid
i from Po to P yields
P
Gi G o Vi dP
o
i P
As a result,
fi P
RT ln
fi o
P o
Vi dP

Because Vi changes little with pressure for liquids (and solids), integration
from Po to P gives
f i Vi P P
o

ln o (13.30)
fi RT
With eq. (13.29) and (13.30), eq. (13.10) may be written as

Po P V
x
i
i i K exp i i (13.31)
i RT i

29
 Except for high pressure, the exponential term is close to unity and may be
omitted. Then,

xi i
i
K (13.32)
i

If the equilibrium mixture is an ideal solution, then i is unity and eq.

(13.32) becomes
xi
i
K (13.33)
i

30
EQUILIBRIUM CONVERSIONS FOR
SINGLE REACTIONS
EXAMPLE 13.5
A 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.

31
(a) The reactants consist of 1 mol of H2O vapor and 1 mol of CO.The
temperature is 1100 K and the pressure is 1 bar.
For the given reaction at 1100 K, 104/T = 9.05, and from Figure
13.2, ln K = 0 and K = 1.
i i 1 1 1 1 0
Because the reaction mixture is an ideal gas, eq. (13.28) applies
0
P 1bar
y y y
1 1 1
y
i
yCO 1
1
i o K
i P H 2O CO2 H2
1bar
yH2 yCO2
1 (A)
yCO yH2O
By eq. (13.5),
ni ni 0 i 1 e 1 e e e
yi yCO yH2O yCO2 yH2
n n0 2 2 2 2

Substitute into eq. (A) gives

e2
1 or e 0.5
1 e
2

Therefore the fraction of the steam that reacts is

noH2O nH2O 1 1
0.5
noH2O 1 32
(b) Same as (a) except that the pressure is 10 bar.
(c) 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 CO and 1 mol
of CO2. Other conditions are the same as in (a).
(g) Same as (a) except that the temperature is 1650 K.

33
EXAMPLE 13.6
Estimate the maximum conversion of ethylene to ethanol by vapor-
phase hydration at 250oC (523.15 K) and 35 bar for an initial steam
to ethylene ratio of 5. Assume the reaction mixture is an ideal
solution.

Solution:
The calculation of K for this reaction is treated in Example 13.4.
At T = 523.15 K, K = 10.02 x 10-3
For ideal solution,

P
y
i
i i o K (13.27)
i P
Because i i 1 1 1 1 this equation becomes
yEtOH EtOH P

o 10.02 103
yC2 H4 C2 H4 yH2OH2O P
A
34
 Fugacity coefficients are evaluated by eq. (11.68).

P Pr 0 1

Tr

ln r B0 B1 or exp
T

B B
r

0.422 0.172
B0 0.083 and B1 0.139
Tr1.6 Tr4.2

The results are summarized in the following table:

Tc/K Pc/bar i Tri Pri B0 B1 i
C2H4 282.3 50.40 0.087 1.853 0.694 -0.074 0.126 0.977
H2O 647.1 220.55 0.345 0.808 0.159 -0.511 -0.281 0.887
EtOH 513.9 61.48 0.645 1.018 0.569 -0.327 -0.021 0.827

Substitute values of i and P = 35 bar into eqn. (A) gives:

yEtOH 0.997 0.887 35 10.02 103 0.367
yC2 H4 yH2O

0.827 1
B

35
By eqn. (13.5),
1 e 5 e e
yC2 H4 yH2O yEtOH
6 e 6 e 6 e
Substitute these into eqn. (B) yields:
e 6 e
0.367 or e2 6 e 1.342 0
5 e 1 e

The solution for the smaller root is e = 0.233. Therefore the

maximum conversion of ethylene to ethanol is
noC2 H4 nC2 H4 1 1
0.233 23.3%
noC2 H4 1

36
EXAMPLE 13.7
In a laboratory investigation, acetylene is catalytically hydrogenated to
ethylene at 1120oC (1393.15 K) and 1 bar. If the feed is an equimolar
mixture of acetylene and hydrogen, what is the composition of the product
stream at equilibrium?

Solution:
The required reaction is obtained by addition of the two formation
reactions written as follows:

C 2 H 2 2C H 2 I
2C 2 H 2 C 2 H 4 II
The sum of reactions (I) and (II) is the hydrogenation reaction:
C2 H2 H2 C2 H 4

o o
Also, G GI GII
o

By eq. (13.11b), RT ln K RT ln K I RT ln K II or K K I K II 37
Data for both reactions (I) and (II) are given by Fig. 13.2. For 1120oC
(1393.15 K), 104/T = 7.18, the following values are read from the graph:
ln K I 12.9 K I 4.0 105
ln K II 12.9 K II 2.5 106

Therefore, K = KIKII = 1.0

At this temperature and pressure of 1 bar, assume ideal gases.
By eq. (13.28),

P

yC2 H4
y
i
i o K 1
i P yH2 yC2 H2

On the basis of one mole initially of each reactant, eq. (13.5) gives
1 e e
yH2 yC2 H2 and yC2 H4
2 e 2 e
Therefore,
e 2 e
1
1 e
2

The smaller root of this quadratic expression is e = 0.293.

38
 The equilibrium composition of the product gas is then
1 0.293 0.293
yH2 yC2 H2 0.414 and yC2 H4 0.172
2 0.293 2 0.293

39
EXAMPLE 13.8
Acetic acid is esterified in the liquid phase with ethanol at 100oC (373.15
K) and atmospheric pressure to produce ethyl acetate and water according
to the reaction:
CH3COOH l C2 H5OH l CH3COOC2 H5 l H2O l

If initially there is one mole each of acetic acid and ethanol, estimate the
mole fraction of ethyl acetate in the reacting mixture at equilibrium.

Solution:

Ho298 (J) Go298 (J)

CH3COOC2H5 -480 000 -332 000
H2O -285 830 -237 130
CH3COOH -484 500 -389 900
C2H5OH -277 690 -174 780
40
 By eq. (13.11b),
H 298
o
i i H io
1 480000 1 285830 1 484500 1 277690 3640 J
G298
o
i i Gio
1 332200 1 237130 1 389900 1 174780 4650 J

For small temperature change from 298.15 K to 373.15 K, eq. (13.15) is

adequate for estimation of K. Therefore,
G298
o
4650
ln K298 1.8759 or K298 6.5266
RT 8.314 298.15

K 373 H298
o
1 1
or ln
K298 R 373.15 298.15

and K 373 3640 1 1

ln 0.2951
6.5266 8.314 373.15 298.15

K373 6.52660.7444 4.8586

41
For the given reaction, eq. (13.5), with x replacing y, yields
1 e
x AcH x EtOH x EtAc x H2O e
2 2
Because the pressure is low, eq. (13.32) is applicable. In the absence of data
for activity coefficients, assume the reacting species form an ideal solution.
In this case eq. (13.33) is employed, giving

xi x EtAc x H2O
i
K (13.33) K
i
x AcH x EtOH
2

4.8586 e
1 e
Solution yields
e 0.6879 and x EtAc 0.6879/2 0.344

42
REFERENCES
Smith, J.M.,Van Ness, H.C., and Abbott, M.M. 2005. Introduction to
Chemical Engineering Thermodynamics. Seventh Edition. Mc Graw-Hill.
http://www.chem1.com/acad/webtext/thermeq/TE4.html
http://www.chem1.com/acad/webtext/thermeq/TE5.html

43
PREPARED BY:
MDM. NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
norasmah@salam.uitm.edu.my
03-55436333/019-2368303