CHEMICAL REACTION

EQUILIBRIA

Dr. Gopinath Halder

Professor & Head
Department of Chemical Engg
[email protected]
+91-94347-88189
REACTION COORDINATE
The progress of a chemical reaction along a pathway can be better
represented by introducing an important factor known as reaction
coordinate. This is an one dimensional coordinate. The reaction
coordinate implies the extent to which a chemical reaction taken
place.
Consider the following chemical reaction:
 P + 3Q 2R
For the above reaction, the stoichiometric numbers are
 VR = 2, VP = -1 and VQ = -3
The reaction can also be represented in the following form
 0 = 2R – P – 3Q

Dr. G. N. Halder- NIT Durgapur

REACTION COORDINATE
 The stoichiometric numbers are given hereunder-
 Products +ve
 Reactants –ve
 Inert 0
 Now, the change in the number of moles of the species present in
the reaction are directly proportional to their respective stoichiometric
numbers.
nP  nQ nR
   --------------------(1)
VP VQ VR

Dr. G. N. Halder- NIT Durgapur

REACTION COORDINATE
It can be stated in another way, for the formation of 1 mole of R, 0.5
mole of P and 1.5 mole of Q are consumed.
In that case, ∆nP = - 0.5, ∆nQ = - 1.5, ∆nR = 1
The equation (1) can be represented in differential form as
dnP d nQ dnR ------------(2)
   .................  d 
VP VQ VR
Here, ε is the reaction coordinate which is defined as the degree to
which a reaction has advanced. Generally, the change in the extent of
reaction is the same for each component but the change in number of
moles dni are different for species ‘i’ and it can be expressed as
 dni --------------------(3)
 d
Vi
Dr. G. N. Halder- NIT Durgapur
 REACTION COORDINATE
Then the equation (3) can be integrated to give
n i 
----------------------------------------(4)

dn i  v i d 
n i0

0

or, n i  n i  v i 0
-----------------------------------------(5)
where, ni = number of moles present after the reaction and
ni = number of moles of the species initially present in the system.
0

Then the total number of moles are given by

n   ni   ni   i  vi  n0  v ----------------------------------------(6)
0
i i i

where,  n i0  n 0 and  v i 0
 v0
i i

Therefore, the mole fraction of component ‘i’ in the reaction mixture given by
ni ni0  vi
yi   ----------------------------------------(7)
0 
nDr. G. N.nHalder-
v 
NIT Durgapur
PROBLEM
The following reaction takes place in a system consisting of 3 mol CH4 ,
1 mol H2O, 1 mol CO and 4 mol H2 initially,
CH4 + H2O → CO + 3H2
Express the composition of the mixture in terms of mole fraction as a
function of extent of reaction.

Dr. G. N. Halder- NIT Durgapur

 SOLUTION:
For the above reaction, total number of moles of various components
initially present, n  n  3  1  1  4  9
0  i
i0

Total stoichiometric numbers, v   vi  1  3  1  1  20

i
Let, ε = extent of reaction
moles of CH4 = 3 – ε
moles of H2O = 1 – ε
moles of CO = 1 + ε
moles of H2 = 4 + 3ε
Total moles of the reaction mixture,
n   ni  n0  v = (3 – ε) + (1 – ε) + (1 + ε) + (4 + 3 ε) = 9 + 2ε
i

Dr. G. N. Halder- NIT Durgapur

 SOLUTION:
Then the mole fractions of different components,
3
yCH 4 
9  2
1 
y H 2O 
9  2

1 
yCO 
9  2
4  3
yH 2 
9  2

Dr. G. N. Halder- NIT Durgapur

MULTIREACTION STOICHIOMETRY:
When two or more independent reaction take place simultaneously, then the
change in number of moles of species ni due to the several reactions is generally
accounted for by introducing a separate reaction coordinate εj.
Then equation (3) can be represented for the multireaction by
dni   vi , j d  j (I = 1, 2,..….., N) ---------------------(8)
j

where, vi,j = stoichiometric number of the species ‘i’ of the reaction ‘j’ and
εj = extent or advancement of the reaction
On integration with the integral limit, n i  n i and εj = 0 the equation (8)
0

gives n i j 

 dni  vi , j  d  j -----(9) or ni  ni   vi, j  j -----------(10)

ni0 0
0
j

where, ni = number of moles present after the reaction and

ni0 = number of moles of the species initially present in the system.
 Multireaction Stoichiometry:
Then the total number of moles of species in the mixture are given by
n   ni0   v i, j j
i i i, j

  ---------------------- (11)
 n 0     vi , j  j
j  i 
Now if the stoichiometric number v j   vi , j , then the equation (11) becomes
n  n0   v j  j
i
----------------------------(12)
j

Substituting the value of n of the above equation (12), the mole fraction yi
of species ‘i’ after the reaction can be expressed as
n i0   v i , j  j
ni
yi   j

n n0   v j j -----------------------------(13)
j
PROBLEM
A system initially charged with 3 mol CH4 and 4 mol H2O is
undergoing the following reaction:

CH4 + H2O → CO + 3H2 ------------------------ (A)

CH4 + 2H2O → CO2 + 4H2 ------------------------ (B)

Derive the expression for the mole fractions of the components in terms
of extent of the reactions.

Dr. G. N. Halder- NIT Durgapur

SOLUTION
For the above two reactions, total number of moles of various
components initially present,
n0   ni0  3  4  7
i

For the reaction (A), the total stoichiometric numbers, vA  1  3  1  1  2

For the reaction (B), the total stoichiometric numbers, vB  1  4  1  2  2

Let, εA = extent of reaction (A) and εB = extent of reaction (B)

Dr. G. N. Halder- NIT Durgapur

SOLUTION
Components vi,j ni0 ni  ni0   vi , j j ni
j
yi 
vA vB n
CH4 1 1 3 3 - εA – εB 3 A B
7  2 A  2 B
H2O 1 2 4 4 - εA – 2εB 4   A  2 B
7  2 A  2 B
C0 1 - 0 εA A
7  2 A  2 B
CO2 - 1 0 εB B
7  2 A  2 B
H2 3 4 0 3εA + 4εB 3 A  4 B
7  2 A  2 B

n  n0   v j j  7  2 A  2 B
j

Dr. G. N. Halder- NIT Durgapur

EQUILIBRIUM CRITERION OF A CHEMICAL REACTION
We know that as the process proceeds the total Gibbs free energy of a
closed system in an actual process must decrease at constant temperature
and pressure (during an irreversible process)
 dG T , P  0 ---------------------------- (14)
Accordingly, a chemical reaction must proceed in the direction of
decreasing G. Hence the reaction will ultimately stop and the equilibrium is
reached when Gibbs free energy ‘G’ attains the minimum value.
At the equilibrium state,  dG T , P  0 ---------------------------------- (15)
This is the equilibrium condition or criterion in a chemical reaction. So, the
virtual change occurs in a system at constant temperature and produce no change
in G of the system. We can prove it.
We know, Gibb’s free energy, G = H – TS
EQUILIBRIUM CRITERION OF A CHEMICAL REACTION
Therefore, dG  dH  TdS  SdT
dG  dU  PdV  VdP  TdS  SdT
 dG T , P  dU  PdV  TdS  dQ  TdS  0
It can alternatively be shown as
dG   SdT  VdP   i dni ----------------------(16)
At constant temperature and pressure, the equation reduces to
 dG T , P    i dni  0 ---------------------(17)
For a reaction,
aA  bB  rR  sS
dn A dnB dnR dnS
   ................  d  -------------------- (18)
a b r s
or, dni or, dn  V d
 d i i
Vi
EQUILIBRIUM CRITERION OF A CHEMICAL REACTION
Substituting the value of dni into the equation (17), we have ,
 dG T , P   i dni   i vi d  0
or,  dG T , P   i vi 0 ---------------------------(19)
This is the criterion of equilibrium of a chemical reaction. The change in
free energy with extent of reaction can be graphically represented here
EQUILIBRIUM CRITERION OF A CHEMICAL REACTION
Figure below illustrates the change in Gibbs free energy with extent of reaction
FEASIBILITY OF THE CHEMICAL REACTION
The feasibility of a chemical reaction can be better judged by the change
in Gibbs free energy and from the knowledge of the criterion for chemical

 dG T , P  0
equilibrium i.e.,

Because, the Gibbs free energy of a system reaches a minimum value in

the state of equilibrium.
The equation G    RT ln K P can provide the following important
information’s:

Dr. G. N. Halder- NIT Durgapur

FEASIBILITY OF THE CHEMICAL REACTION
 If G 0 has a negative value, the equilibrium constant has a value
greater than one and the reactants in their standard state spontaneously
react to give the products in their standard state.
 If G 0 is equal to zero, the equilibrium constant value is one and the
reactants in their standard states are in equilibrium with the products in
their standard state.
 If G 0 has a positive value, the equilibrium constant has a value less
than one and it does necessarily mean that the indicated moles of
reactants in their standard states are not covered completely into the
products.

Dr. G. N. Halder- NIT Durgapur

FEASIBILITY OF THE CHEMICAL REACTION
Therefore, the condition for the feasibility of a reaction can be represented
as
 ∆G < 0, then K > 1, the reaction is spontaneous and feasible

 ∆G = 0, then K = 1, the system attained a state of equilibrium

 ∆G > 0 the reaction proceeds spontaneously in the reverse direction

Dr. G. N. Halder- NIT Durgapur

RELATION BETWEEN EQUILIBRIUM CONSTANT AND
STANDARD GIBBS FREE ENERGY CHANGE
Consider the following reaction
aA  bB  rR  sS
From the knowledge of criterion of equilibrium for a chemically reacting
system,
 r  R  s S    a  A  b B   0
or,  v   0
i i ---------------------------------------------(34)
i

We also know that the chemical potential of a component ‘i' is defined

as  
 i  RT ln f  G i -----------------------------------------(35)
i
where, = fugacity of component ‘i'

Dr. G. N. Halder- NIT Durgapur

RELATION BETWEEN EQUILIBRIUM CONSTANT AND
STANDARD GIBBS FREE ENERGY CHANGE
At standard state, the chemical potential of the component ‘i' is given
by 0 0 
i  RT ln fi  G i

Where, G = constant depends only on the temperature and

i


fi = standard state fugacity of component ‘i'

0 0  0
f
i    RT ln f  RT ln f    RT ln i
i i i i 0

fi

 i  RT ln ai  -------------------------------- (36)
f
 i

where, ai = 0

fi = activity coefficient of species ‘i’

RELATION BETWEEN EQUILIBRIUM CONSTANT AND
STANDARD GIBBS FREE ENERGY CHANGE
Substituting the value of μi in equation (36), we get
Eq. 16 is an useful v 
i
i i 0

relation between
  
Gibb’s free energy Or,  i  i
v   RT ln ai 0

change and 
equilibrium Or,  v   RT  v ln a
i i i i 0
constant by which

the equilibrium  G   RT  vi ln ai   RT  ln ai vi
constant can be Or,
Or,  G   RT ln  ai v    RT ln K

determined at the i

given ΔG0 & 

 G
temperature Or, K  e RT ------------------ (16)
PROBLEM
Calculate the standard Gibbs free energy change and the equilibrium constant at
1 bar and 298 K for the ammonia synthesis reaction
N2 (g) + 3H2 (g) → 2NH3 (g)
Given that the standard free energies of formation at 298 K for NH3 are -
16.750 kJ/mol
SOLUTION
For the reaction, the standard Gibbs free energy change at 298 K can be
estimated as
G298  2G f 298  NH 3  g    G f 298  N 2  g    3G f 298  H 2  g  
0 0 0 0

or, = 2 x (-16.750 kJ/mol) – 0 – 0 = -33.5 kJ

Using the relation between standard Gibbs free energy change and
equilibrium constant, we get
G  RT ln K
G 0 33500
or, ln K   
RT 8.314  298 =-13.521

13.521
or, K e  1.342  10 6
 DO IT NOW
 Calculate the equilibrium constant KP at 25 0C for the
water-gas reaction
 CO (g) +H2O (g) → CO2 (g) + H2 (g)
 Given that
G 0f ,CO  32.8kcal

G 0f , H 2O  54.64kcal

G 0f ,CO2  94.26kcal

Ans: K  e  1.06  10
11.517 5

EFFECT OF TEMPERATURE ON EQUILIBRIUM CONSTANT:
VAN’T HOFF EQUATION:
The influence of temperature on equilibrium constant of a
chemical reaction at given enthalpy change can be better
explained by Van’t Hoff’s equation. This is also known as Vant
Hoff’s isochore.
We know that dG  SdT  VdP
Or,  G    S -----------------------(38)
 
 T  P
Then we can obtain at standard state,
 
    
  G 
     vi Gi  
   
 vi H i  T vi S i  
 T  
 T  P  T  
 P    P

where, S = Standard enthalpy change of the reaction
EFFECT OF TEMPERATURE ON EQUILIBRIUM CONSTANT:
VAN’T HOFF EQUATION:
Hence,
 

  G     
    

 T  i i   
 v H  T  v S i
 T     P  T    P
i

 P
 
 0   v i S i   S

     
Now, 
   G / T   
 
---------------(40)
     1   G    G  S G


T 

T  T 
 P
T2  
 P T T2

  
Since, G   H T S put the value of  G into the equation (40)
VAN’T HOFF EQUATION:
We get,     G / T  

  
  -----(41)
T S G 
 
  
      S  G
  H


T 

T T2  T 2
  2
 P   T
We know that 
G
  R ln K -----------------(42)
T
Therefore,   
 
 -------------------(43)
  G / T 
  ln K 
  
  
 T   T 
 
 P

Comparing equation (41) with (43), we get


  ln K   H ---------(45)
  2
 T  T
Continued…

If the reaction is exothermic one, then  H <0 and the equilibrium
constant K decreases with
increase in temperature. While for an
endothermic reaction,  H >0 and equilibrium constant K increases with
increasing temperature for an endothermic reaction.
Van’t Hoffs’ equation predicts the effect of temperature on the equilibrium
constant.

If  H is assumed to be constant in the temperature range T1 to T2, the
Van’t Hoff’s equation can be integrated to obtain

K 2  H  1 1 --------------------------------------------(12-46)

ln    
K1 R  T1 T2 
where, K1 = equilibrium constant at absolute temperature T1 and
K2 = equilibrium constant at absolute temperature T2
Continued…
Now, if the lnK is plotted against 1/T, then the nature of the graph will
be straight line as shown in the fig.
The standard heat of reaction can appreciably vary with temperature. Here, it
can be expressed by molal heat capacities in terms temperature.
Continued…
From Kirchhoff’s equation, we get
  H 
 CP  CPPr oducts  CPRe ac tan ts
------------------------(47)
T
We know that the standard heat of reaction at temperature T is given by
T
H T  H T   CP dT
0 0 ----------------------(48)
0
T0

where, CP     T   T 2
Thus, the equation becomes
 2  3 ----------------(49)
H T0  H T00   T  T  T  ....
2 3
The Van’t Hoff’s equation will then be written as
 2  3
H T00   T  T  T  ....
  ln K  H
0
2 3
 
T

 T  RT 2
RT 2
Continued…
The above equation can be rearranged as
  ln K   H 0
   T ---------------- (50)
   
T0

 T  RT
2
RT 2 R 3R
On integration,
H T00 ln T  T  T 2 -------------------(51)
ln K      I
RT R 2R 6R
where, I = Integration Constant of the isochore

Put the value of lnK in the equation G  RT ln K to evaluate the Gibbs free
energy change and it can be determined by the following way,
  T 2
 T 3
---------------------(52)
G  H T0   T ln T 
0 0
  IRT
2 6
Integration constant ‘I’ can easily be determined.
PROBLEM
Estimate the standard Gibbs free energy and the equilibrium constant at
1000 K for the reaction
CO (g) +H2O (g) → CO2 (g) + H2 (g)
Given that the standard heat of reaction, H 298 and standard Gibbs free energy
0

of the reaction, G f ,298 for the formation of products, are -41,450 J/mol and -
0

28.888 J/mol respectively. The specific heat data in kJ are given below as
function of temperature.
Components α β x 103
CO2 (g) 45.369 8.688
H2 (g) 27.012 3.509
CO (g) 28.068 4.631
H2O (g) 28.850 12.055
SOLUTION
Given, H 298
0
= -41,450 J/mol and G 0f ,298 = -28,888 J/mol
Now,
  45.369  27.012  28.068  28.850  15.463
   8.688  3.509  4.631  12.055  103  4.489  103
To obtain the standard heat of reaction at the desired temperature, we
can use the following equation
 2  3
H   H    T 
0
T
0
T0 T  T  ....
2 3
Since, the values of coefficient γ are not given, then it can safely be
neglected. So the above equation becomes
 2
H T  H T0   T 
0 0
T
2
SOLUTION
Substituting these values in the following equation to get
4.489  10
5

-41,450 J/mol = HT + 15.463 x 298  2  298

0 2
0

H T0 = -46.056 kJ
0

We know, G 0f ,298 = -28,888 J/mol

Putting the value of standard Gibbs free energy into the equation to get the
value of integration constant ‘I’ at 298 K,
 T 2 -------------------(52)
 G   H T0    T ln T 
0 0
 IRT
2
4.489  103
 298
2
or, -28,888 = -46056 - 15.463 x 298 ln298 + -IR x 298
2
or, IR = 133.67
SOLUTION
Now, substitute T = 1000 K and the value of IR in equation (52), we get
 3
1000 
2
4.489 10
G  46056  15.463  1000  ln1000 
0
 133.67  1000
2
= -284.296 kJ
The equilibrium constant K1000 can be determined as
G 0 2842
ln K     0.3418
RT 8.314  1000
or, K1000  e0.3418  1.4
Therefore, the standard Gibbs free energy and equilibrium constant are
284.296 kJ and 1.4 respectively.
HOMOGENEOUS GAS-PHASE RxN EQUILIBRIUM
Homogeneous reaction is defined as the reaction in which the reacting
substances and the products are required to be in the single phase. In order to
describe the equilibrium in homogeneous reaction a standard state is
necessary to be specified and chosen for the species associated with the
chemical reactions.
For a gas, the standard state is the ideal gas state of the pure gas at the
standard state of 1 bar or atmosphere. That is, P 0  1 .
Now for a homogeneous gas phase reaction, if the reaction is assumed to
behave like an ideal gas, then the fugacity of the gas is equal to its
pressure, i.e.,
fi  P  1
0 0
HOMOGENEOUS GAS-PHASE RxN EQUILIBRIUM
Then the activity of the species ‘i' is given by

fi  
ai  0  fi   i yi P
fi [ as ]fi 0  1 --------------(57)

where,  i = fugacity coefficient = a dimensionless ratio and for an ideal gas,
the partial pressure is given by,
pi  yi P
where, P = Total pressure and p = partial pressure
Substituting the value of ai in the expression of equilibrium constant
applicable to all chemical reactions and it is given by
v
  
i
v --------------(58)

 
i

K a  ai     i yi P      i Pi 
vi

   
 
HOMOGENEOUS GAS-PHASE RxN EQUILIBRIUM
The equation (58) can be re-arranged as
 

v
   -------------(59)
i

K a     i Pi      ivi    Pi vi 
   
Now, if the equilibrium mixture is assumed to behave ideally, then

i  i

 vi 
Therefore, K a    i  Pi vi    ivi   Pi vi   K  K P  K  K y P ----------(60)
vi

 

where, K y   yivi = equilibrium constant in terms of mole fractions

Since at sufficiently low pressure and high temperature, the gas mixture

behaves like an ideal gas, then  i  1 and consequently, K  1

HOMOGENEOUS GAS-PHASE RxN EQUILIBRIUM
Ka  K P  K y P
v
Thus, the equation (60) becomes, i

Consider the following chemical reaction

aA  bB  rR  sS
Then the three equilibrium constants can be represented as
r s
a R aS
K a  ai  a b
vi

a A aB
pRr pSs
K P  pi  a b
vi

p A pB
r s
y R yS
K y  yi  a b
vi

y A yB
PROBLEM
Ammonia synthesis reaction is represented by
N 2  g   3H 2  g   2 NH 3  g 

Initially, 1 mole of nitrogen and 5 moles of hydrogen gas are fed into the
reactor. The process is maintained at 800 K and 250 bar. Estimate the molar
composition of the gases at equilibrium assuming that the reaction mixture
behaves like an ideal gas. Given, equilibrium constant, K = 1.106 x 10-5
SOLUTION
The reaction involved is
N 2  g   3H 2  g   2 NH 3  g 
Let, ε = degree of conversion of nitrogen into ammonia at equilibrium
Component N2 (g) H2 (g) NH3 (g)
Moles in feed 1 5 0
Moles at equilibrium 1- e 5-3 e 2 e

Mole fraction 1-e  5-3e  2 e

2 3   e  2 3   e  2 3   e 

Total moles at equilibrium 1- e + 5 - 3 e + 2 e = 6 - 2 e = 2 (3- e )

SOLUTION
Now, the sum of the stoichiometric coefficients = vi  2  3  1  2
Operating pressure, P = 250 bar
We know that  
2
2 e
 
  e  4 e  3   e  
2
2 3   
K y   yi 
vi

i  1- e     5-3 e   1- e  5-3 e 3
  
 2  3   
e  2  3   
e 

Since, the equilibrium constant, K = 1.106 x 10-5

  4  3     2 
1.1067 105  K y (250) 2   
e  2

e
 (250)
    
3
 1- e 5-3 e 
 e = 0.4337
SOLUTION
Hence, the degree of conversion at equilibrium = 0.4337
Therefore, the molar composition of the gases are given by
1 e
yN2   0.1103
2 3   e 

5  3 e
yH 2   0.7207
2 3   e 

2 e
yNH3   0.1690
and 2 3   e 
ASSIGNMENT

The oxidation of sulfur reaction is given by

1
SO2  g   O2  g   SO3  g 
2
A mixture of sulfur dioxide and oxygen is fed to the reactor in the mole
ratio 5:4. The process is maintained at 750 K and 1 bar. Estimate the molar
composition of the reactor effluent gases at equilibrium assuming that the
reaction mixture behaves like an ideal gas. Given, equilibrium constant,
K = 74
EFFECT OF PRESSURE ON CHEMICAL EQUILIBRIUM
The pressure of the reaction mixture affects the equilibrium composition
in a gas phase reaction, but it has no effect on equilibrium constant. This
can be substantiated by the following way:
Consider the chemical reaction,
aA  bB  rR  sS
The equilibrium constant is given by
yRr ySs v vi v v ---------------------(53)
K  K a  a b P   yi P  K y P
y A yB
where,
v  vPr oducts  vRe ac tan ts  vR  vS  v A  vB
EFFECT OF PRESSURE ON CHEMICAL EQUILIBRIUM
The influence of pressure on equilibrium of chemical reaction greatly
depends on the sign of ∆v or the difference between the number of
moles of the products and the number of moles of the reactants in the
stoichiometric reaction.
If v  ve , then an increase in pressure at a specified temperature
increases the number of moles of the reactants and decreases the number
of moles of the products as well as reduces the degree of conversion at
equilibrium. On the contrary, if v  ve , there will be an opposite effect
i.e., an increase in pressure increases the degree of conversion and when
v  0 , there is no change in mole number, then P v  1 as a result, K  K y
, the pressure will have no effect on degree of conversion at equilibrium.
To illustrate, the ammonia synthesis reaction can be represented as,
,
EFFECT OF PRESSURE ON CHEMICAL EQUILIBRIUM
To illustrate, the ammonia synthesis reaction can be represented as,
N 2  g   3H 2  g   2 NH 3  g  v  2  3  1  2
Since v  ve , then an increase in pressure at specified temperature,
decreases the number of moles of the reactants and increases the number
of moles of the products as well as increases the degree of conversion at
equilibrium.
Hence, the formation of ammonia will be favored by the increase in
pressure, because the system will respond in such a way that tends to
minimize the effect of the increase in pressure.
EFFECT OF PRESSURE ON CHEMICAL EQUILIBRIUM
Hence, it can be concluded that, in the gas-phase reaction,
When v  0 , a rise in pressure will have an unfavorable effect and the
equilibrium of the reaction will be shifted to the right by a decrease in
pressure.
When v  0 , it will be advantageous to raise the pressure and the
equilibrium of the reaction will be shifted towards the formation of
products.

Hence, the equilibrium constant is independent of pressure

HETEROGENEOUS REACTION EQUILIBRIA :
Heterogeneous reaction requires at least two phases to proceed. The phases
involved are known heterogeneous phases.

Heterogeneous reaction equilibrium can broadly be categorized into two

classes. These are,
1. Solid-gas reaction equilibrium and
2. Liquid-gas reaction equilibrium
SOLID-GAS REACTION EQUILIBRIUM:
The standard state for the solid-phase reactions may be the pure solid at 1
bar and reaction temperature. While considering a heterogeneous equilibrium,
the equilibrium constant involves only the activity or partial pressures of the
gaseous constituents and does not include any terms for the concentration of
either solids or liquids. The equilibrium constant is thus independent of the
amount of pure solid or liquid phase.
At moderate pressure, the activity of the solid components is considered to
be unity. 
fi
Activity of the solid is given by i f10 a  ---------------------------(1)

where, f i = fugacity of the species ‘i' at the actual temperature and pressure
fi 0 = fugacity of pure liquid in the standard state
SOLID-GAS REACTION EQUILIBRIUM:
For example, consider the dissociation of calcium carbonate
CaCO3  s   CaO  s   CO2  g 
The equilibrium constant, Ka is given by
a CaO a CO2 ----------------------(2)
Ka 
a CaCO3

Since, the activities of solid components, CaO and CaCO3 may be taken
as unity, i.e., aCaO  aCaCO  13

Hence, the equation (2) reduces to

K a  aCO 2 ----------------------- (3)
Comparing equation (3) with equation (1), we get


K a 
f CO2 ------------------------------(4)
a CO2 0
f CO 2
SOLID-GAS REACTION EQUILIBRIUM:
The standard state for gases is referred to as ideal-gas state and at that
0
state fCO 1.
2 
Hence, we can get, K a  aCO  f CO
2 2
----------------- (5)
Since, CO2 is assumed to behave like an ideal gas, then fugacity is

exactly equal to idealized partial pressure, p i.e., f CO  p CO
2 2

Then K P  pCO2 -------------------(6)

The equation (6) can be expressed as

G 0 [ As G 0   RT ln K ] ------------ (7)
K P  pCO2  e RT
Hence the dissociation pressure of calcium carbonate would be constant. This
pressure exerted by gaseous CO2 depends on temperature only.
SOLID-GAS REACTION EQUILIBRIUM:
For another instance, hydrogen from reduction of steam
3Fe  4 H 2O  Fe3O4  4 H 2
2 4
aFe3O4  a4
 aH2   PH2 
Ka   
 aH O   PH O 
H2
3
aFe  aH4 2O  2   2 
4
Hence,  PH 2  , P P
KP    H2 H 2O
 H 2O 
P

Thus the ratio of PH 2 is constant. It does necessarily imply that an increase

PH 2O
in steam pressure yields a higher amount of hydrogen.
PROBLEM
The following thermal decomposition occurs at 400 K
A s  B  s  C  g 
The standard Gibb’s free energy of the reaction,
G 0  85, 000  213.73T  6.71T ln T  0.00028T 2
Determine the decomposition pressure at 400 K and 700 K. Also determine the
decomposition temperature at 1 bar.
SOLUTION
At 400 K, the standard Gibb’s free energy change of the reaction is given
by
G400  85, 000  213.73  400  6.71  400 ln 400  0.00028  400 
0 2

= 15544.20 J
Similarly, at 700 K,
G  85, 000  213.73  700  6.71  700 ln 700  0.00028  700 
0 2
700

= 33978.20 J
G 0 15544.20
 
At 400 K, the equilibrium constant is evaluated as K  e RT = 8.314400
e
= 0.0093 bar
G 0 33978.20
At 700 K, the equilibrium constant   = 343.09 bar
K  e RT  e 8.314400
SOLUTION
Now, the equilibrium constant for solid-gas reaction is given by
aB aC 
K  aC  f C  PC
aA
G 0

or, K  PC  1  e RT

G 0
or, 
RT
 ln1  0or, G0  0
Substituting the value of G 0 in the above equation of T, we have
0  85, 000  213.73T  6.71T ln T  0.00028T 2
Solving for T, we get
T = 1020 K
Therefore, the decomposition temperature is 1020 K.
LIQUID-GAS REACTION EQUILIBRIUM
Consider the following reaction occurring between a gas and a liquid
aA  g   bB  l   rR  aq 
The equilibrium in the above reaction can be treated by the following
methodology-
The reaction may be assumed to occur in the gas phase only. The
mass transfer takes place between gas and liquid phases to maintain the
phase equilibrium. In order to evaluate the equilibrium constant of the
reaction, the conventional standard state for the gases is used and it is
ideal gas state at 1 bar and reaction temperature. The two equations based
on standard state for the gases and the mass transfer between gas and
liquid phases are coupled to get the desired result.
LIQUID-GAS REACTION EQUILIBRIUM
The reaction may be assumed to take place in the liquid phase
only to evaluate the equilibrium constant on the basis of conventional
standard state for the liquids and couple the resulting expression with the
phase equilibrium relation.
In this methodology, consider the mixed states shown in the reaction
occurring and use ideal gas state as the conventional standard state for gas
A, pure liquid state for liquid B, and hypothetical 1-molal aqueous state
for aqueous solution C to evaluate the equilibrium constant by the
following expression-
aRr mRr
K a b 
a A aB    a
 f A    B xB 
b

 
FUEL CELL
It is our common experience that the burning of fuel provides thermal energy.
As a consequence, the work potential of the fuel is lost to a greater
extent. Fuel cell plays an important role in saving this energy.

A fuel cell is an electrochemical energy conversion device in which the

chemical energy of a fuel such as methane, hydrogen etc is converted
directly into electrical energy by their oxidation in suitable anode. A fuel
cell comprises of an anode and a cathode separated by an electrolyte and
connected to each other through an electrical load in the external circuit.
The fuel on the anode side and the oxidant (usually O2 of air) on the
cathode side react in the presence of an electrolyte. At the cathode
oxygen is dissolved to form OH- ions.
FUEL CELL
A fuel cell functions like a battery or electrolytic cell. But there is a
difference between fuel cell and battery. In fuel cell, the reactants are
not stored, but they must be fed continuously and products flow out. But
the battery is useful only until the reactants initially put into it have
been consumed, i.e., the reactant are stored in the battery.
The operation of a hydrogen-oxygen fuel cell is shown in the Fig.12.5,
where H2 and O2 react to form water. Its operation is as follows:
The electron flow in the external circuit from anode to cathode. Oxygen
enters the cathode side and hydrogen enters the anode side. At the ion-
exchange membrane surface the hydrogen is ionized according to the
reaction.
2H2 → 4H+ + 4e-
FUEL CELL
FUEL CELL
The electrons flow through the external circuit and the hydrogen ions flow
through the membrane to the cathode, where the following reaction takes
place:
4H+ + 4e- + O2 → 2H2O
Thus electricity flows through the electrical load due to potential
difference between cathode and anode and work is produced. Also heat
transfer takes place between the fuel cell and the environment.
Some other fuels used for cells shown in the table 4T-2, are CH4 (g),
C3H8(g), C8H18 (l), C16H34 (l), CH8OH (l), NH8 (g), C (s). In case of
CH4 (g) as a fuel, the reaction at the anode, cathode and overall are-
Anode: CH4 + 2H2O → CO2 + 8H+ + 8e-
Cathode: 2O2 + 8e- + 8H+ → 2H2O + 2H2O
Overall: CH4 + 2O2 → CO2 + 2H2O
FUEL CELL
In the fuel cell, electrons must be free from impurities and should be
porous. The polarization due to adsorption and poisoning of the electrodes
reduce the cell performance. The concentration of the electrolyte and
temperature have the great influence on the e.m.f. of cells.
Fuel Cell Electrode Electrolyte Reaction at anode

H2 …………..O2 Pt/Ni NaOH ½ H2 + H2O → H3O+ +e-

CH4 …….…..O2 Pt/Pt H2SO4 CH4 + 2H2O → 8H+ + CO2 +8e-

N2H4 ………..O2 Ni/C KOH N2H4 → N2 + 4H+ +4e-

CO…………..O2 Cu/Ag KOH CO + H2O → CO2 + 2H+ + 2e-

ADVANTAGES OF FUEL CELL
• produces power at low cost at considerable periods
• requires easy maintenance
• have harmless bye-products
• is flexible in application
• compact, light weight and no major moving parts.
APPLICATION AREA OF FUEL CELL
The fuel cells are used
 as auxiliary power sources in remote locations such as spacecraft,
submarines, remote weather stations, large parks, in certain military
application
 to replace gasoline and diesel-powered generators and automobile
engines
 to convert household sewage and other waste to less noxious
products.