Advanced Thermodynamics

Note 12
Chemical-Reaction Equilibria

Lecturer: 郭修伯
 Chemical reaction
• Both the rate and equilibrium conversion of a
chemical reaction depend on the temperature,
pressure, and composition of reactants.
– Although reaction rates are not susceptible to
thermodynamic treatment, equilibrium
conversions are.
– The purpose of this lecture is to determine the
effect of temperature, pressure, and initial
composition on the equilibrium conversions of
chemical reactions.
Reaction coordinate
• A general chemical reaction:
v1 A1  v2 A2  ...  v3 A3  v4 A4  ...
dn1 dn2 dn3 dn4
    ...  d
v1 v2 v3 v4
Reaction coordinate, which characterizes the extent
or degree to which a reaction has taken place.
– A differential change in the number of moles of a
reacting species:
ni 
dni  vi d (i  1, 2, ..., N ) ni 0
dni  vi  d
0
(i  1, 2, ..., N )

ni ni 0  vi
yi   ni  ni 0  vi (i  1, 2, ..., N )
n n0  v n   ni  n0  v
i
For a system in which the following reaction occurs, CH4  H 2O  CO  3H 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 ε.

ni ni 0  vi
yi  
n n0  v

   i  1  1  1  3  2
i

n0   ni 0  2  1  1  4  8
i

2
yCH 4 
8  2
1 
yCO 
8  2
1  4  3
y H 2O  yH 2 
8  2 8  2
Consider a vessel which initially contains only n0 mol of water vapor. If
decomposition occurs according to the reaction,
1
H 2O  H 2  O2
2
find expressions which relate the number of moles and the mole fraction of each
chemical species to the reaction coordinate ε.
ni ni 0  vi
yi  
n n0  v
1 1
   i  1  1  
i 2 2
n0   ni 0  n0
i

n  1 
y H 2O  0  yH 2 
1
1
n0   yO2  2 n0  
1 2
2 n0  
nH 2O  n0   2 nH 2 
1
nO2  
2
 Multireaction
• Two or more independent reactions proceed
simultaneously
– νi,j : the stoichiometric number of species i in reaction j.
– the change of the moles of a species ni: dni   vi , j d j
j

integration
ni  ni 0   vi , j  j
j
ni 0   vi , j  j
total stoichiometric number:
summation
yi 
j  j   i , j
n0   v j  j n  n0   v j  j  
n  n0     vi , j   j
i

j  i 
j j
Consider a system in which the following reactions occur,
CH4  H 2O  CO  3H 2 CH4  2H 2O  CO2  4H 2
if there are present initially 2 mol CH4 and 3 mol H2O, determine expressions for the
yi as functions of ε1 and ε2 .
i CH4 H2O CO CO2 H2
j νj
1 -1 -1 1 0 3 2
2 -1 -2 0 1 4 2
2  1   2
yCH 4 
5  2 1  2 2
ni 0   vi , j  j
3   1  2 2
yi 
j
y H 2O 
n0   v j  j 5  2 1  2 2
j
1
yCO 
5  2 1  2 2
2 3 1  4 2
yCO2  yH 2 
5  2 1  2 2 5  2 1  2 2
 Equilibrium criteria to chemical
reactions
• ε is the single variable that characterizes the
progress of the reaction
– the total Gibbs energy at constant T and P is determined
by ε
– if not in chemical equilibrium, any reaction leads to a
decrease in the total Gibbs energy of the system
• The condition for equilibrium:
– the total Gibbs energy is a minimum G t  f ( )
– Its differential is zero dGt T , P  0
Fig 13.1
 Standard Gibbs energy change
and the equilibrium constant
d (nG)  (nV )dP  (nS )dT   i dni
i

dni  vi d

d (nG)  (nV )dP  (nS )dT   i i d

i

  (nG )    (G t ) 
i i i      
       0
at equilibrium

T ,P  T ,P
The fugacity of a species in solution: i  i (T )  RT ln fˆi
For pure species i in its standard state: Gio  i (T )  RT ln f i o
ˆ
f
i  Gio  RT ln io
vi
 fˆi 
i  f o   K fi
 i   i i 0
i
  G o

K  exp    o ˆ 
f
 RT  i i  i
  G  RT ln i 
o 
fi 
0

G o   i Gio
i

 i i G
vi vi
 fˆi  o
 fˆi 
ln   o   i  iG  RT i ln  f o   0
i o
i
i  fi  RT  i 
   G o 
The equilibrium constant for the reaction, f(T) K  exp  
 RT 
The standard Gibbs energy change of reaction, f(T) G o   i Gio
i

Other standard property changes of reaction : M   i M

o
i
o

 Gio    i Gio 
d   i 
RT
H io   RT 2   d 
 RT 
dT  
i  i H i   RT
o 2

dT

H
2

o
d ln K
H   RT
o 2
d Go

RT

RT dT dT
For a chemical species in its standard state:

Gio  H io  TSio
summation

i i i i i i i i i
 G o
  H o
 T  S o
G o  H o  TS o
T C o
H o  H 0o  R  P
dT
T0 R
T C dT
o
S  S0  R 
o o P
T0 R T
H 0o  G0o
S0 
o

T0

T C T C dT
 
o o
T
G  H 
o o
0H 0  G0  R 
o o P
dT RT  P
T0 T0 R T0 R T
 T C T C dT
 
o o
T
G  H 
o o
0 H 0  G0  R 
o o P
dT RT  P
T0 T0 R T0 R T
Readily calculated at any temperature from the standard
 G o
ln K  heat of reaction and the standard Gibbs energy change
RT of reaction at a reference temperature

K  K 0 K1K 2
  G0o 
K 0  exp  
 RT0 
 H 0o  T0  
K1  exp  1   
 RT0  T  
 1 T CPo T C dT 
o
K 2  exp    dT   P

 T 0 R
T T0 R T 
Fig 13.2
Calculation the equilibrium constant for the vapor-phase hydration of ethylene at 145
and at 320 °C from data given in App.c
C2 H 4  H 2O  C2 H 5OH

K  K 0 K1K 2 From Table C.4

  G0o  H 0o  H 298
o
 45792 J mol
K 0  exp  
 RT0 
G0o  G298
o
 8378 J mol
 H 0o  T0  
K1  exp  1    The heat capacity data:
 RT0  T  
  C2 H 5OH   C2 H 4   H 2O
 1 T C o
T C dT 
o
K 2  exp    dT  
P

P

 T 0 R
T T0 R T 

T K0 K1 K2 K
298.15 29.366 1 1 29.366
418.15 29.366 4.985x10-3 0.986 1.443x10-1
593.15 29.366 1.023x10-4 0.9794 2.942x10-3
 • Gas phase reaction:
– Ideal-gas state: f i o  P o
– Standard-state pressure Po of 1 bar
v
 fˆi  fio  P o  fˆi 
v
fˆi  ˆi yi P 

 y ˆ 
i i
 P 
i  f o   K i  P o   K
vi
 o  K
   i
i i
 i    i P 
i


 P 
An ideal solution: ˆi  i  y    o  K
vi
i i
i P 

 P 
ˆi  1  y   o  K
vi
An ideal gas: i
i P 

f (composition) f (P) f (T)

• Liquid phase reaction:
 fˆi 
vi
fˆi   i xi f i   fi  
vi

i  f o   K i   i xi  f o    K
 i    i 
P fi
Gi  G   o Vi dP  RT ln o
i
o
P fi

f i Vi P  P o
ln o 
 
fi RT

 P  Po   V 
  x   K exp   
vi
i i i i
i  RT i 
Except at high pressures

 ix v i
K Ideal solution 
 ii
 x v i
K
i i
Law of mass action
 Equilibrium conversions for single
reactions
• Single reaction in a homogeneous system:
– assuming an ideal gas and the equilibrium constant is
known: 
 P 
i  yi    P o  K
vi

– assuming an ideal solution and the equilibrium constant is

known:

 i K
x vi

– the phase composition at equilibrium can be obtained

The water-gas-shift reaction, CO  H 2O  CO2  H 2 is carried out under the
different sets of conditions described below. Calculate the fraction of steam reacted
in each case. Assume the mixture behave as an ideal gas.
 yH 2 yCO2
 
y 
From Fig 13.2, K = 1
 y 
P vi
 1
 o  K
vi
i
   i  0
i
i P  i yCO yH 2O
i

(a) the reactant consists of 1 mol of H2O vapor and 1 mol of CO, T = 1100 K, P = 1 bar

ni ni 0  vi 1 e 1 e e e
yi   yCO  y H 2O  yCO2  yH 2   e  0.5
n n0  v 2 2 2 2

(b) the same as (a) except that the pressure is 10 bar

Since v = 0, the increase in pressure has no effect:  e  0.5
(c) the same as (a) except that 2 mol of N2 is included in the reactants
Since N2 does not take part in the reaction and serves as a diluent:  e  0.5
(d) the reactants are 2 mol of H2O and 1 mol of CO. other conditions are the same as (a)

ni ni 0  vi 1 e 2  e e e
yi   yCO  y H 2O  yCO2  y H 2   e  0.667
n n0  v 3 3 3 3
The fraction of steam that reacts is then 0.667 / 2 = 0.333
(e) the reactants are 1 mol of H2O and 2 mol of CO. other conditions are the same as (a)

ni ni 0  vi 2  e 1 e e e
yi   yCO  y H 2O  yCO2  y H 2   e  0.667
n n0  v 3 3 3 3
The fraction of steam that reacts is then 0.667
(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 (a)
ni ni 0  vi 1 e 1 e 1 e 
yi   yCO  y H 2O  yCO2  yH 2  e
n n0  v 3 3 3 3
The fraction of steam that reacts is then 0.333
 e  0.333
(g) same as (a) except that the temperature is 1650 K


  From Fig 13.2, K = 0.316 y H 2 yCO2

 iy v i
P
 o  K  0.316
i P     i  0 yCO yH 2O
i

ni ni 0  vi 1 e 1 e e e
yi   yCO  y H 2O  yCO2  yH 2   e  0.36
n n0  v 2 2 2 2

The reaction is exothermic, and conversion decreases with increasing temperature.

Estimate the maximum conversion of ethylene to ethanol by vapor phase hydration at
250°C and 35 bars for an initial steam-to-ethylene ratio of 5.

For a temperature of 250°C, K = 10.02 x 10-3 C2 H 4  H 2O  C2 H 5OH

Assuming the reaction mixture is an ideal solution. ˆi  i    i  1

i


y EtOHEtOH
 y ˆ 
 P   P 
vi
 o  K   o (10.02 10 3 )
i
i i
P  yC2 H 4 C2 H 4 y H 2OH 2O  P 

Tc /K Pc /bar ω Tri Pri B0 B1 φi

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
y EtOHEtOH y EtOH (0.827)  35 
   (10.02 10 3 )
yC2 H 4 C2 H 4 y H 2OH 2O yC2 H 4 (0.977) y H 2O (0.887)  1 

ni ni 0  vi 1 e 5  e e
yi   yC 2 H 4  y H 2O  y EtOH   e  0.233
n n0  v 6  e 6  e 6  e
The equilibrium conversion is a function of temperature, pressure, and the steam-
to-ethylene ratio in the feed:

Fig 13.4
In a laboratory investigation, acetylene is catalytically hydrogenated to ethylene at
1120 °C and 1 bar. If the feed is an equilmolar mixture of acetylene and hydrogen,
what is the composition of the product stream at equilibrium?
C2 H 2  2C  H 2 G o  GIo  GIIo
2C  2H 2  C2 H 4
 G o
C2 H 2  H 2  C2 H 4 ln K 
RT

 RT ln K  RT ln K I  RT ln K II

 
K  K I K II  4 105 2.5 106  1 
 yC2 H 4
 P  Ideal gas
 y   o  K 1
vi
i
i P  yH 2 yC2 H 2

n n v 1 e 1 e e
yi  i  i 0 i yH 2  yC 2 H 2  yC 2 H 4    0.293
n n0  v 2  e 2  e 2  e e

yC2 H 4  0.172 y H 2  yC2 H 2  0.414

 Acetic acid is esterified in the liquid phase with ethanol at 100 °C and atmospheric
pressure to produce ethyl acetate and water according to the reaction:
CH3COOH  C2 H 5OH  CH3COOC 2 H 5  H 2O
If initially there is 1 mol of each of acetic acid and ethanol, estimate the mole
fraction of ethyl acetate in the reacting mixture at equilibrium.
For the reaction at standard state (298 K):

 G o H o d ln K
ln K  
H 298
o
 3640 J RT  G298
o
4650 RT 2 dT
ln K    1.8759
G298
o
 4650 J RT 8.314  298.15 K373  4.8586
Assuming ideal solution:


 ix v i
K
xEtAc xH 2O
K
i x AcH xEtOH

ni ni 0  vi 1 e e
xi   x AcH  xEtOH  xEtAc  xH 2O   e  0.6879
n n0  v 2 2

xEtAc  0.6879 / 2  0.344

The gas phase oxidation of SO2 to SO3 is carried out at a pressure of 1 bar with 20%
excess air in an adiabatic reactor. Assuming that the reactants enter at 25°C and that
equilibrium is attained at the exit, determine the composition and temperature of the
product stream from the reactor
1 H 298
o
 98890 J
SO2  O2  SO3 For the reaction at standard state (298 K):
2 G298
o
 70866 J
Assuming 1 mol of SO2 entering the reactor,
O2: 0.5 x (1.2) = 0.6 mol entering
N2: 0.6 x (79/12) = 2.257 mol entering
In the product stream: SO2: 1 - εe SO3: εe
total moles: 3.857-0.5εe
O2: 0.6 - 0.5εe N2: 2.257

 H 298
o
e
Energy balance: H 298 e  H P  H  0
o o T o
 298.15
CP
H

The enthalpy change of the products at T

H Po  C Po (T  298.15)   ni CPio (T  298.15)
H H
i
Assuming ideal gas:
   i  0.5
 0.5
 P  i   e  3.857  0.5 e 

 iy v i
 o  K    K
i P   1   e  0.6  0.5 e 
K  K 0 K1K 2
  G0o 
K 0  exp  
 RT0 

 H 0o  T0  
K1  exp  1   
 RT0  T 
 1 T CPo T C dT 
o
K 2  exp    dT   P

 T 0 R
T T0 R T 

 IDCPS  IDCPH 
11894.4 1
ln K  11.3054 
T T

Assume T ln K e T Converges at T = 855.7 K, εe = 0.77

1 e
ySO2   0.0062
3.857  0.5   e
...
 • Reactions in heterogeneous systems
– a criterion of vapor/liquid equilibrium, must be satisfied
along with the equation of chemical-reaction
equilibrium
Estimate the compositions of the liquid and vapor phases when ethylene reacts with
water to form ethanol at 200°C and 34.5 bar, conditions which assure the presence of
both liquid and vapor phases. The reaction vessel is maintained at 34.5 bar by
connection to a source of ethylene at this pressure. Assume no other reactions.
According to phase rule (see later): F = 2 (say, P, T)
the material balance equations do not enter into the solution of this problem.

Regarding the reaction occurring in the vapor phase: C2 H 2 ( g )  H 2O( g )  C2 H 5OH ( g )

Assuming ideal gas :
 fˆi 
v i
fˆEtOH P o
 1 bar
i  P o   K K
ˆf ˆf
P o
K 473.15K  0.031
  C 2 H 4 H 2O T  473.15K
 fˆEtOH Phase equilibrium: fˆEtOH
v ˆl
f
K P o
K  P o
 EtOH
P o
fˆC2 H 4 fˆH 2O ˆf v  fˆ l fˆCv2H4 fˆHv2O fˆCl2H4 fˆHl 2O
i i

For vapor phase: fˆi v  yiˆi P

For liquid phase: fˆi l  xi i f i l

xEtOH EtOH f EtOH

l
K
 
o


P
yC2 H 4 ˆC2 H 4 P xH 2O H 2O f Hl 2O

f i l ~ f i sat  isat Pi sat

Ideal solution (vapor): i  ˆi
xEtOH EtOHEtOH
sat sat
PEtOH
K o

 
yC2 H 4 C2 H 4 P xH 2O H 2OHsat2O PHsat2O
P

 xEtOH EtOHEtOH
sat sat
PEtOH
K o

 
yC2 H 4 C2 H 4 P xH 2O H 2OHsat2O PHsat2O
P

Known values:
 sat
 sat
P, T, H 2O , EtOH , C H , PHsatO , PEtOH
2 4 2
sat

0.0493xEtOH EtOH
K
 
yC2 H 4 xH 2O H 2O 
yC2 H 4  1  y EtOH  y H 2O
xi iisat Pi sat
yi 
i P
xEtOH EtOHEtOH
sat sat
PEtOH xH 2O H 2OH 2O PH 2O
sat sat

yC2 H 4  1 
EtOH P  H 2O P

yC2 H 4  1  0.907 xEtOH EtOH  0.493xH 2O H 2O

xH 2O  1  xEtOH  xC2 H 4
volatile
 0.0493xEtOH EtOH
K
  
yC2 H 4 xH 2O H 2O

yC2 H 4  1  0.907 xEtOH EtOH  0.493xH 2O H 2O

xH 2O  1  xEtOH Values of  EtOH,  H 2O are determined experimentally

Assume xEtOH xH2O yC2H4 K

check K 473.15K  0.031

Converged at:
xi yi
EtOH 0.06 0.180
H2O 0.94 0.464
C2H4 0.00 0.356
Σ =1 Σ =1
Phase rule and Duhem’s theorem for
reacting systems
• For non-reacting systems
– π phases and N chemical species: F  2    N
• For reacting systems
– Phase rule variables in each phase: temperature,
pressure and N-1 mole fraction. Total number of these
variable: 2 + (N-1) π
– Phase-equilibrium equations: (π-1) N
– r independent chemical reactions at equilibrium within
the system: r equations
– F = [2+(N-1) π ] - [(π-1) N] – [r] : F  2    N  r
– With special constraints s: F  2    N  r  s
Determine the number of degree of freedom F for each of the following systems:
(a) A system of two miscible non-reacting species which exists as an azeotrope in
vapor/liquid equilibrium.
(b) A system prepared by partially decomposing CaCO3 into an evacuated space.
(c) A system prepared by partially decomposing NH4Cl into an evacuated space.
(d) A system consisting of the gases CO, CO2, H2, H2O, and CH4 in chemical
equilibrium
(a) Two non-reacting species in two phases
With no azeotrope: F  2    N  r  2  2  2  0  2
With azeotrope (x1=y1, one constraint): F  2    N  r  s  1

(b) Single reaction: CaCO3( s )  CaO( s )  CO2 ( g )

Three chemical species and three phases: CaCO3( s ) CaO( s ) CO2( g )
F  2    N  r  2  3  3 1  1
(c) Single reaction: NH 4Cl( s )  NH3( g )  HCl( g )
Three chemical species and two phases: NH 4Cl( s ) NH3( g )  HCl( g )
One constraint: gas phase is equimolar
F  2    N  r  s  2  2  3 1 1  1
(d) 5 species, a single gas phase, and no special constraints: F  2    N  r  s

The formation reactions: ???

1
C  O2  CO
2 Eliminating C
C  O2  CO2 1
CO  O2  CO2
1 2
H 2  O2  H 2O Eliminating C
2
CH4  O2  2H 2  CO2
C  2H 2  CH4

1
H 2  O2  H 2O
2 Eliminating O2
1
CO  O2  CO2 CO2  H 2  CO  H 2O Eliminating O2
2
CH4  2H 2O  4H 2  CO2
CH4  O2  2H 2  CO2

r=2
F  2    N  r  s  2 1  5  2  0  4
 Duhem’s theorem
• For non-reacting system :
– For any closed system formed initially from given masses
of particular chemical species, the equilibrium state is
completely determined by specification of any two
independent variables.
– F  [2  ( N  1)   ]  [(  1) N  N ]  2
• For reacting system:
– A variable is introduced for each independent reaction: εj
– A equilibrium relation can be written for each independent
reaction
– F  [2  ( N  1)   ]  [(  1) N  N ]  1  1  2
 Multireaction equilibria
• A separate equilibrium constant is evaluated for
each reaction:  fˆi 
v i, j

  f o

  Kj
i  i 

v
 fˆi 
i, j

– gas phase reaction i  P o   K j

 

Ideal gas
 j
 P 

 iy v i, j
 o  Kj
i P 
A feed stock of pure-n-butane is cracked at 750K and 1.2 bar to produce olefins. Only
two reactions have favorable equilibrium conversions at these conditions:
C4 H10  C2 H 4  C2 H 6 C4 H10  C3 H 6  CH 4
If these reactions reach equilibrium, what is the product composition?
1
Assuming ideal gas: yC 2 H 4 yC 2 H 6  P 
  o  KI
 j yC4 H10 P 
 P 
 y   o 
vi , j
i Kj 1
P  yC3 H 6 yCH 4  P 
  o  K II
i

yC 4 H 1 0 P 

With a basis of 1 mol of n-butane feed:

1   I   II I  II
yC4 H10  yC2 H 4  yC2 H 6  yC3 H 6  yCH 4 
1   I   II 1   I   II 1   I   II

 I  0.1068  II  0.8914 yC H  0.001 yC H  yC H  0.0534 yC H  yCH  0.4461

4 10 2 4 2 6 3 6 4
A bed of coal in a coal gasifier is fed with steam and air, and produce a gas stream
containing H2, CO, O2, H2O, CO2, and N2. If the feed to the gasifier consists of 1
mol of steam and 2.38 mol of air, calculate the equilibrium composition of the gas
stream at P = 20 bar for temperature 1000, 1100, 1200, 1300, 1400, and 1500 K.
The feed stream:
1 mol C, O2 = (0.21)(2.38) = 0.5 mol, N2 = (0.79)(2.38) = 1.88 mol

The formation reactions for the compounds are:

1 Δ Gºf J/mol
H 2  O2  H 2O
2 T (K) H2O CO CO2
1 1000 -192424 -200240 -395790
C  O2  CO 1100 -187000 -209110 -395960
2
1200 -181380 -217830 -396020
C  O2  CO2 1300 -175720 -226530 -396080
1400 -170020 -235130 -396130
1500 -164310 -243740 -396160

 G o
ln K 
RT
K = ...
 fˆC f C (@ 20 bar )
Carbon is a pure solid phase: o
 o
1
fC f C (@ 1 bar )

Assuming ideal gases for the remaining species:

1
y H 2O  P  2
KI   o
yO2 yH 2 P 
 j 1
 P  y  P  2

 y   o  K II  CO  o 
vi , j
Kj
yO2  P 
i
i P 
yCO2
K III 
yO2
With a basis of 1 mol of C feed:

I  II  III
yH 2  yCO  yCO2 

3.38   II   I
 
3.38   II   I
 
3.38   II   I

2 2 2
1  I 1 1   I   II    III
1.88
y H 2O  yN2 

3.38   II   I
 yO2  2 
3.38   II   I
  
2 2 3.38   II   I
2
Three equations and three unknowns … can be solved.
 Non- stoichiometric method
• Alternative method to solve chemical reaction
equilibrium problems
– base on the fact that the total Gibbs energy of the
system has it minimum value
– the basis for a general scheme of computer solution
– Gt T ,P  g n1, n2 , n3 , ...nN 
– Find the set {ni} which minimizes Gt for specified T
and P, subject to the constraints of the material balances.
Lagrange’s undetermined multiplier
method
• The material balance on each element k :
n a
i
i ik  Ak

multiply the Lagrange multipliers

 
k   ni aik  Ak   0
 i 
summed over k
 
 k   ni aik  Ak   0
k  i 

 
F  G   k   ni aik  Ak 
t

k  i 
  
F  G t   k   ni aik  Ak 
k  i 
F (and Gt) minimum value?

 F   G t 
       k aik  0 (i  1,2,..., N )
 ni T , P ,n j  ni T , P ,n j k

i   k aik  0 (i  1,2,..., N )
k

 fˆi  gas phase reaction  fˆi 

i  G  RT ln  o 
i
o
i  G  RT ln  o 
i
o

 f i  pure ideal gas P 

 yiˆi P 
i  G  RT ln  o 
o
fi
 P 
 yiˆi P 
G  RT ln  o    k aik  0
o
fi (i  1,2,..., N )
 P  k
Calculate the equilibrium compositions at 1000 K and 1 bar of a gas-phase system
containing the species CH4, H2O, CO, CO2, and H2. In the initial unreacted state,
there are present 2 mol of CH4 and 3 mol of H2O. Values of ΔG°f at 1000 K of each
species are given.
Element k
C O H
Ak = no. of atomic masses of k in the system
2 3 14
species aik = no. of atoms of k per molecule of i
CH4 1 0 4
H2O 0 1 2
CO 1 1 0
CO2 1 2 0
H2 0 0 2

 yiˆi P 
G  RT ln  o    k aik  0
o
fi (i  1,2,..., N )
 P  k
Ideal gas: ˆi  1
P
o
1
P

G ofi  ni 
 ln     k aik  0 (i  1,2,..., N )
RT   ni  k RT
 i 
G ofi  ni 
 ln     k aik  0 (i  1,2,..., N )
RT   ni  k RT
 i 
For the 5 species:

19720  nCH 4  C 4H

CH4 :  ln    0
 i ni  RT RT
RT  
5 equations
...

For the 3 elements:

C: nCH 4  nCO  nCO2  2 Solve

simultaneously
H: 4nCH 4  2nH 2O  2nH 2  14 3 equations

O: nH 2O  nCO  2nCO2  3

n i i  nCH 4  nH 2O  nCO  nCO2  nH 2 1 equations