Chemical Equilibrium

As with all equilibria, the basic equation is: G = 0

Consider a reversible, ideal gas phase reaction:
aA + bB = cC + dD
Let the initial moles be
n A nB
nC nD
(not necessarily stoichiometric)
Change due to reaction is
-an -bn +cn +dn
Then, before reaction, G 0 n A A n B B nC C n D D
After reaction,
G1 (n A an) A (n B bn) B (nC cn) C (n D dn) D

G G1 G 0 ( an) A (bn) B ( cn) C ( dn) D

n( a A b B c C d D )
pi

Defining i = + R T ln o
P
o
i

p
C
P o

G
= [c Co + d oD - a oA - b oB ] + R T ln
n

c pD

o
P

pA a pB b

Po Po

io is the chemical potential of pure i at the reaction

temperature and the standard state pressure of 1 atm
(or 1 bar), which is simply the specific molar Gibbs
Free Energy, gio at these conditions. Hence,
cg dg ag bg G
0
C

0
d

0
A

0
B

Go: the standard free energy change of the reaction

at the given temperature.
Go is similar to the (standard) heat of reaction, Ho,
however,free energies are strongly dependent on
pressure so the fact that the calculation refers to the
standard state of 1 atm (or 1 bar) is vital
At equilibrium, G = 0, then:

0 = G + R T ln

p
C
P o

p D d

o
P
a
b
p B

o
P

p A
P o

 If pressures are measured in atm.(bar)

p
C
P o

G o R T ln

p D d

o
P
a
b
p B

o
P

p A
P o

= R T ln

pCc p dD
a
A

b
B

= R T ln K P

p p

where KP is the equilibrium constant

Go
ln K P = RT
Go is the standard free energy change of the reaction. It
is a function of the reactants and temperature only. It is
not this quantity which is zero at equilibrium, but G, the
actual free energy change

Class Problem 7
a) The gas-phase reaction;
A = B+C
has an equilibrium constant of 2.72 atm at 300 K.
Calculate Go for this reaction at this temperature.
b) For the reaction:

H2 + I2 = 2HI

Go = 1520 kJ/kmol at 298 K .

equilibrium constant?

What is the

c) For the reverse reaction written as: 2HI = H2 + I2

what are its Go and KP

at the same temperature?

Variation of KP with temperature

H
G V

dP

dT

2
T
T T

d
d G 0
H 0

(ln K P )
2
dT
dT RT
RT

Lecture 2, p.13
(Vant Hoff eqn)

Class Problem 9
1) Use the vant Hoff equation to demonstrate that, for an
endothermic reaction, equilibrium shifts to the right for
an increase in temperature (Le Chatelier's Principle).
2) Use the vant Hoff equation to show how, if the
equilibrium constant, K1 is known at T1, the equilibrium
constant, K2 at a new temperature, T2 can be deduced.

Driving Force and Equilibrium

-ln(pc.pd/pa.pb)

For any reaction to occur

spontaneously, G < 0.

pCc p dD

G o + R T ln a b < 0
p p
A B
o
pCc p dD

G
- ln a b >
p p
R T
A B

Take the simple case:

a=b=c=d=1

15
10
5
0
-5
-10
-15

0.2

0.4
0.6
Conversion

0.8

start with an equimolar mixture of A & B, the LHS of the

equation can be expressed as a function of the conversion, x

 For Go/RT = 10, conversion of about 1%,

For larger Go/RT, conversion will be even less;
For values above 20, conversion is less than 0.01%
(reaction is essentially non-existent)
For Go/RT < -20 conversions better than 99.99% are
obtained before equilibrium is reached
(reaction is essentially irreversible)
Go/RT is a measure of the driving force for the
reaction ( large and negative for high conversions).
Reactions with small positive Go/RT will still occur,
but only to low conversions.

Equilibria in non-ideal gas mixtures

If the gases are non-ideal, the partial pressures are
replaced by fugacities:

Kf =

f c f d
C D
fo fo

f a f b
A

B
fo fo

f C
= a
f

Go
ln K f = RT

f D
b
f
B

 Since fi i p i then, Kf = KpK

c

C D
K = a b

For ideal mixtures at high
use the Lewisi pressure,
i
Randall Rule for which
i is found from figures, this gives K,
Kf can be calculated from KP and K,

Practical Calculation
0
G 298
(ni G 0f ) products (ni G 0f ) reac tan ts

At any other temperature, apply the definition of G:

G = H - TS
(16)
0

S
At T = 298 K, 298 is determined from known values
0
0
of H 298
and G298
:
0
S 298

0
0
H 298
- G 298
=
298
T

H = H +

C P0 d T

C P0
dT
T

0
T

298
T

S T0 = S

0
298

298

Worked Example
Ethanol decomposes in the vapour phase over a suitable
catalyst:
C2H5OH = C2H4 + H2O
a) Calculate the equilibrium constant, KP at low pressure
(ideal gas) and 650 K.
b) What is the equilibrium conversion of pure ethanol feed
at 2 atm and 650 K?
c) Repeat the above calculations for 200 atm and 650 K.

 cPo is given by: cPo = a + bT + cT2 + dT3

Units

MJ kmol-1
H 0f

C2H5OH
C2H4
H2O

-235.0
+52.34
-242.0

kJ kmol-1K-1

G 0f

-168.4
+68.16
-228.8

9.014
3.806
32.24

103 b

105 c

109 d

214.1 -8.390 1.373

156.6 -8.348 17.55
1.924 1.055 -3.596

(i) For the reaction, we can calculate:

0
H 298
= 52.34 - 242.0 + 235.0 = 45.34 MJ kmol-1

0
G298
= 68.16 - 228.8 + 168.4 = 7.76 MJ kmol-1

C p0 = 27.032 - 55.58x10-3T + 1.097x10-5T2 +

12.58x10-9T3 kJ kmol-1 K-1

650
298

c0P dT = 27.032(650 - 298) - 55.58x 10-3 (6502 - 2982) / 2

+ 1.097x 10-5 (6503 - 2983) / 3 + 12.58x 10-9 (6504 - 2984) / 4

= 1686.6 kJ kmol-1 = 1.69 MJ kmol-1

0
H 650

= 45.34 + 1.69 = 47.03 MJ kmol-1

(ii) S 0 = ( H 0 - G 0 )/298 = 0.1261 MJ kmol-1 K-1

298
298
298
cP
650
dT = 27.032 ln
- 55.58x 10-3 (650 - 298)

T
298
+ 1.097x 10-5 (6502 - 2982) / 2 + 12.58x 10-9 (6503 - 2983) / 3
650
298

= 4.390 kJ kmol-1K-1 = 0.0044 MJ kmol-1K-1

0
S 650
= 0.1261 + 0.0044= 0.1305 MJ kmol-1K-1
0
G650
= 47.03 650x0.1305 = -37.80 MJ kmol-1

(iii) For an ideal gas, -G0 = RT ln KP

KP

p H 2 O pC 2 H 4
pC 2 H 5 OH

37.8 x 1000
= exp
= 1090 atm
8.3144 x 650

b) Consider 1 kmol ethanol feed, giving at equilibrium x

kmol ethene, x kmol water and (1 - x) kmol ethanol.
Writing pi = yiP = (ni/ni)P gives:
x
x
2
2
2
2
x
1+ x
1+ x =
=
= 1090
KP
2
1- x
1- x
2
1+ x
1090
whence x =
= 99.91 % conversion
1092

c) Calculate Tr and Pr at 650K/200 atm:

Compound

Tc/K

Pc/bar

Tr

Pr

C2H5OH
H2O
C2H4

513.9
647.3
282.4

61.4
221.2
50.4

1.265
1.004
2.302

3.300
0.916
4.020

Using the Lewis & Randall Rule i

i :

0.69 x 0.96

= 1.07
C 2 H 5 OH = 0.62; H 2 O = 0.69; C 2 H 4 = 0.96; K =
0.62
1090
K
f
KP =
=
= 1018 atm
1.07
K

x
x
200
200
2
2
00
x
1
+
x
1
+
x
=
= 1090
KP =
2
1- x
1- x
200
1+ x
1018
whence x =
= 91.43 % conversion
1218
NOTE that the Lewis and Randall Rule is not likely to
be very accurate for this highly polar system, but
there is no simple alternative that is any better.

Class Problem 10

G 0f

for nitric oxide gas, NO is given as +86.7 MJ

kmol-1. What are the chances of finding a catalyst
which would permit its manufacture from air at
ambient temperature?
Given that H for this compound is +90.4 MJ kmol-1,
what conditions would improve the yield?

Accuracy of estimation of KP

G
f
Values of H and
from
different sources shows
deviation from the ones determined earlier
0

G
f
Although calculated values for
range from 7.43
to 8.13 MJ kmol-1 (only 700 kJ kmol-1 < 10%),
KP values ranged from 0.0498 to 0.0376 (25%
variation).
0
f

Source

H 0f
G

0
f

R&S

Daubert

Kyle

Sandler*

CRC*

C2H5OH -235.0
52.34
C2H4
-242.0
H2O

-234.43
52.28
-241.82

-235.0
52.32
-242.0

-218.53# -235.31
52.28
52.28
-241.84
-241.83

-219.79
52.28
-241.83

C2H5OH -168.4
68.16
C2H4
-228.8
H2O

-167.90
68.12
-228.59

-168.4
68.17
-228.7

-168.32
68.12
-228.59

-168.32
68.12
-228.59

-168.62
68.12
-228.61

Perry*

Reactions involving Solids

Consider as an example the decomposition of Calcium
Carbonate:
CaCO3(s) = CaO(s) + CO2(g)
The two solids do not form solid solutions, and hence
they exist as separate, pure components, in separate
solid phases.

For a pure component: P = v
T
As molar volumes for solids are very small (high
density), is almost independent of pressure:
0
CaCO 3 = Value at 1 atm . = CaCO3

 Similarly for the CaO. Eq (3) for this system (Po = 1):
G/n = Go + RT ln(pCO2) (18)
since all the other terms in pi vanish (Eq (2)).
At equilibrium,
G =0
0

(19)

G
= ln pCO 2 , eqm
RT

Since Go = f(T) alone, there is a fixed equilibrium

partial pressure of CO2 for a given temperature.
If the pCO p,COthe, eqm
reaction will go to the left, and the
quicklime will absorb CO2:
if the pCO p,COthe, eqm
reaction will go to the right, and the
limestone will decompose.
2

 In reactions involving more than one gas plus one or

more solids, the KP term contains all the gases but
none of the solids.
ZnO(s) + H2S(g) = ZnS(s) + H2O(g)

p H 2O
G0

= ln
p
RT
H 2S
This reaction is used in industry to remove traces of
the catalyst poison H2S from a gas stream before
passing it to a catalytic reactor.

 The behaviour of salt hydrates is a good example of

gas-solid equilibrium:
salt(s) + H2O(g) = hydrate(s)
As there is only one gas (water vapour), there will be
a fixed equilibrium vapour pressure at a given
temperature in the presence of a mixture of a salt plus
its hydrate.
Such mixtures are used in the laboratory to give
precisely controlled humidities in desiccators.

 Ambient humidity in the UK in summer is typically 70% to

80% RH at 20oC, which gives an actual pH2O of around
0.017 atm.
Any hydrate whose equilibrium pressure is greater than this
will lose water: the salt is said to be efflorescent (eg
Na2CO3.10H2O).
Conversely, for a salt whose equilibrium pressure is less
than this, the anhydrous salt will gain water: the salt is said
to by hygroscopic. (eg CuSO4).
Certain very soluble salts can form saturated solutions
where the mole fraction of water is so small that the vapour
pressure of water above the solution is less than ambient.
Such salts are said to be deliquescent, and the solid left in
contact with ambient air will form a solution (eg NaOH, or
CaCl2.6H2O).