KESETIMBANGAN

REAKSI KIMIA

Dosen: Bregas S T Sembodo

 Reaksi Kimia
• Laju dan konversi kesetimbangan suatu reaksi
kimia tergantung pada temperatur, tekanan, dan
komposisi reaktan.

• Laju reaksi tidak rentan terhadap perlakuan

termodinamika, konversi kesetimbangan,
sebaliknya, rentan terhadap perlakuan
termodinamika

• Tujuan dari kuliah ini adalah untuk mengetahui

pengaruh suhu, tekanan, dan komposisi awal
pada konversi kesetimbangan reaksi kimia.
Koordinat Reaksi
• Reaksi Kimia secara umum:
v1 A1 + v2 A2 + ... → v3 A3 + v4 A4 + ...
dn1 dn2 dn3 dn4
= = = = ... ≡ dε
v1 v2 v3 v4
Koordinat reaksi, mencirikan tingkat atau derajat
suatu reaksi telah berlangsung
– Perubahan diferensial dalam jumlah mol
suatu spesies yg bereaksi :
ni ε
dni = vi dε (i = 1, 2, ..., N ) ∫ dni = vi ∫ dε (i = 1, 2, ..., N )
ni 0 0

ni ni 0 + viε
yi = = ni = ni 0 + viε (i = 1, 2, ..., N )
n n0 + vε n = ∑ ni = n0 + vε
i
Untuk sistem di mana reaksi berikut terjadi , CH 4 + H 2O → CO + 3H 2
Anggap mula-mula terdapat 2 mol CH4, 1 mol H2O, 1 mol CO and 4 mol H2.
Tentukan yi sebagai fungsi ε.

ni ni 0 + viε
yi = =
n n0 + vε
CH 4 + H 2O → CO + 3H 2
ν = ∑ν i = −1 − 1 + 1 + 3 = 2
i

n0 = ∑ ni 0 = 2 + 1 + 1 + 4 = 8
i

2−ε
yCH 4 =
8 + 2ε
1+ ε
yCO =
8 + 2ε
1− ε 4 + 3ε
y H 2O = yH 2 =
8 + 2ε 8 + 2ε
Suatu vesel awalnya berisi n0 mol uap air, jika dekomposisi terjadi menurut
reaksi 1
H 2O → H 2 + O2
2
tentukan hubungan jumlah mol dan fraksi mol masing-masing spesies kimia
dengan koordinat reaksi ε.
ni ni 0 + viε
yi = =
n n0 + vε
1 1
ν = ∑ν i = −1 + 1 + =
i 2 2
n0 = ∑ ni 0 = n0
i

n −ε 1 ε
y H 2O = 0 ε yH 2 =
1
n0 + ε
1 yO2 = 2 n0 + ε
1 2
2 n0 + ε
nH 2O = n0 − ε 2 nH 2 = ε
1
nO2 = ε
2
 Multi reaksi

• Dua atau lebih reaksi berjalan simultan

– νi,j : koefisien stoikiometrik spesies i dalam reaksi j.
– Perubahan mol spesies ni:
dni = ∑ vi , j dε j
j

integration
ni = ni 0 + ∑ vi , j ε j
j
total koef. stoikiometrik:
ni 0 + ∑ vi , j ε j summation
yi =
j ν j ≡ ∑ν i , j
n0 + ∑ v j ε j n = n0 + ∑ v j ε j  
n = n0 + ∑  ∑ vi , j  ε j
i

j  i 
j j
Consider a system in which the following reactions occur,
CH 4 + H 2O → CO + 3H 2 CH 4 + 2 H 2O → CO2 + 4 H 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 − ε1 − ε 2
yCH 4 =
5 + 2ε1 + 2ε 2
ni 0 + ∑ vi , j ε j
3 − ε1 − 2ε 2
yi =
j
y H 2O =
n0 + ∑ v j ε j 5 + 2ε1 + 2ε 2
j
ε1
yCO =
5 + 2ε1 + 2ε 2
ε2 3ε1 + 4ε 2
yCO2 = yH 2 =
5 + 2ε1 + 2ε 2 5 + 2ε1 + 2ε 2
 Aplikasi Kriteria Kesetimbangan pada
Reaksi Kimia
• ε: variabel tunggal yg menunjukkan perkem-
bangan reaksi
– Energi Gibbs total pada T dan P konstan ditentukan
oleh ε
– Jika tidak dalam kesetimbangan, reaksi apapun akan
mengalami penurunan Energi Gibbs total sistemnya
• Kondisi saat Kesetimbangan tercapai:
– Energi Gibbs total adalah minimum G t = f (ε ) min
– Differensial/ turunan pada titik itu sama dengan NOL
(dG )
t
T ,P =0
Fig 13.1
 Perubahan Energi Gibbs Standar
dan Konstanta Kesetimbangan
d ( nG ) = ( nV ) dP − ( nS ) dT + ∑ µ i dni
i

dni = vi dε

d ( nG ) = ( nV ) dP − ( nS ) dT + ∑ν i µ i dε
i

 ∂ ( nG )   ∂ (G t ) 
∑i i i  ∂ε   ∂ε 
ν µ = =   → = 0
at equilibriu m

T ,P  T ,P
The fugacity of a species in solution: µ i = Γi (T ) + RT ln fˆi
For pure species i in its standard state: Gio = Γi (T ) + RT ln f i o
ˆ
f
µ i − Gio = RT ln io
vi
 fˆi 
∏i  f o  = K fi
 i  ∑ν µ i i =0
i
 − ∆G o

K ≡ exp   o ˆ 
f
 RT  ∑i i  i
ν  G + RT ln i 
o 
fi 
=0

∆G o ≡ ∑ν i Gio
i

ˆf  i − ∑ ν i Gio
v v
  ˆ 
i
f
ln ∏  i 
= i
∑i i i
ν G o
+ RT ∑i  f o  = 0
 ln i 

i  f i o  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 ≡ ∑ν i Gio
i

Other standard property changes of reaction : ∆M o ≡ ∑ν i M io

i

 Gio   ∑ν i Gio 
d 
RT   i 
H i = − RT
o 2  d
RT 
 
dT  
∑i i i
ν H o
= − RT 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 − TS io
summation

∑i i i ∑i i i ∑i i i
ν G o
= ν H o
− T ν S o
∆G o = ∆H o − T ∆ S o
T ∆C Po
∆H = ∆H + R ∫
o o
0 dT
T0 R
T ∆C dT
o
∆S o = ∆S 0o + R ∫ P
T0 R T
∆H 0o − ∆G0o
∆S 0 =
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
 (
∆G o ∆H 0o ∆G0o − ∆H 0o 1 ) T ∆C Po T ∆C dT
o

RT
=
RT
+
RT0
+
T ∫T0 R
dT − ∫
T0
P
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 K1 K 2
 − ∆G0o 
K 0 ≡ exp 
 RT0 
 ∆H 0o  T0  
K1 ≡ exp 1 −  
 RT0  T  
 1 T ∆C Po T ∆C dT 
o
K 2 ≡ exp −
 T
∫T0 R
dT + ∫
T0
P
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 K1 K 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 ∆Co
T ∆C dT 
o
K 2 ≡ exp −
 T
∫T0 R
P
dT + ∫
T0
P
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
 • Reaksi fase Gas:
– Keadaan Gas Ideal: i f o
= P o

– Standard-state pressure Po of 1 bar

v
fi o = P o
v
fˆi = φˆi yi P −ν

∏ (y φˆ )
 fˆi   fˆi 
i i
 P 
∏i  f o  = K ∏i  P o  = K
vi
= o  K
ν ≡ ∑ν i
i i
 i    i P 
i

−ν
 P 
An ideal solution: φˆi = φi ∏ (y φ ) = o  K
vi
i i
i P 
−ν
 P 
φi = 1 ∏ (y ) = o  K
vi
An ideal gas: i
i P 

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

 −ν
 P 
∏ (y ) = o  K
vi
i
i P 

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

∆ ∆

εe ∆

εe
• Liquid phase reaction:

v
ˆf  i fˆi = γ i xi f i 
vi
 fi  
∏i  i 
o 
fi 
=K ∏i  γ i xi  f o   = K
   i 
P fi
Gi − G = ∫ o Vi dP = RT ln
i
o
P fio

f i Vi P − P o
ln o =
( )
fi RT
(
 P − Po ) (ν V )
∏ (γ x ) = K exp  ∑
vi
i i 
i i
i  RT i 
Except at high pressures
(
∏ ix )v i
=K Ideal solution (
∏ ii
γ 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: −ν
 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.
−ν y H 2 yCO2
∏ (y )
  From Fig 13.2, K = 1
∏ (y )
P vi
= =1
= o  K
vi
i
ν ≡ ∑ν i = 0
i
i P  i yCO y H 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 + viε 1− εe 1− εe εe εe
yi = = yCO = y H 2O = yCO2 = yH 2 = ε e = 0.5
n n0 + vε 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: ε 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: ε 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 + viε 1− εe 2 − εe εe εe
yi = = yCO = y H 2O = yCO2 = y H 2 = ε e = 0.667
n n0 + vε 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 + viε 2 − εe 1− εe εe εe
yi = = yCO = y H 2O = yCO2 = y H 2 = ε e = 0.667
n n0 + vε 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 + viε 1− εe 1− εe 1+ εe ε
yi = = yCO = y H 2O = yCO2 = yH 2 = e
n n0 + vε 3 3 3 3
The fraction of steam that reacts is then 0.333
ε e = 0.333
(g) same as (a) except that the temperature is 1650 K

−ν
  From Fig 13.2, K = 0.316 y H 2 yCO2
(
∏ iy )v i
P
= o  K = 0.316
i P  ν ≡ ∑ν i = 0 yCO y H 2O
i

ni ni 0 + viε 1− εe 1− εe εe εe
yi = = yCO = y H 2O = yCO2 = yH 2 = ε e = 0.36
n n0 + vε 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. φˆi = φi ν ≡ ∑ν i = −1

i

−ν
y EtOH φ EtOH
∏( )  P   P 
y φˆ
vi
= o  K =  o (10.02 × 10 −3 )
i
i i
P  yC2 H 4 φC2 H 4 y H 2Oφ 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 φ EtOH y EtOH (0.827)  35 
= =  (10.02 × 10 −3 )
yC2 H 4 φC2 H 4 y H 2Oφ H 2O yC2 H 4 (0.977 ) y H 2O (0.887)  1 

ni ni 0 + viε 1− εe 5 − εe εe
yi = = yC 2 H 4 = y H 2O = y EtOH = ε e = 0.233
n n0 + vε 6 − εe 6 − εe 6 − εe
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 + 2 H 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 )
−ν yC 2 H 4
 P  Ideal gas
∏ (y ) = o  K =1
vi

i
i
P  y H 2 yC 2 H 2

ni ni 0 + viε 1− εe 1− εe εe
yi = = yH 2 = yC 2 H 2 = yC2 H 4 = ε = 0.293
n n0 + vε 2 − εe 2 − εe 2 − εe 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:
CH 3COOH + C2 H 5OH → CH 3COOC 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 K 373 = 4.8586
Assuming ideal solution:

(
∏ ix )v i
=K
xEtAc xH 2O
=K
i x AcH xEtOH

ni ni 0 + viε 1− εe εe
xi = = x AcH = xEtOH = xEtAc = xH 2O = ε e = 0.6879
n n0 + vε 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
εe
Energy balance: ∆H 298
o
ε e + ∆H Po = ∆H = 0 T= o
+ 298.15
CP
H

The enthalpy change of the products at T

∆H Po = C Po (T − 298.15) = ∑ ni C Pio (T − 298.15)
H H
i
Assuming ideal gas:
ν ≡ ∑ν i = 0.5
−ν 0 .5
 P  i  ε e  3.857 − 0.5ε e 
∏ (y ) = o  K    =K
vi

 1 − ε e  0.6 − 0.5ε e 
i
i P 
K = K 0 K1 K 2
 − ∆G0o 
K 0 ≡ exp 
 RT0 

 ∆H 0o  T0  
K1 ≡ exp 1 −  
 RT0  T 
 1 T ∆C Po T ∆C dT 
o
K 2 ≡ exp −
 T
∫T0 R
dT + ∫
T0
P
R T 


+ IDCPS − (IDCPH )
11894 .4 1
ln K = −11.3054 +
T T

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

1− εe
ySO2 = = 0.0062
3.857 − 0.5 × ε 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 ) → C 2 H 5OH ( g )

Assuming ideal gas :
v
 fˆi 
i
fˆEtOH P o
= 1 bar
∏i  P o  = K K=
ˆf ˆf
P o
K 473.15 K = 0.031
  C2 H 4 H 2O T = 473.15 K
 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 ˆ v fˆ v
f ˆ l fˆ l
f
i i C2 H 4 H 2O C2 H 4 H 2O

For vapor phase: fˆi v = yiφˆi P

For liquid phase: fˆi l = xi γ i f i l

x EtOH γ EtOH f EtOH

l
K=
( )(
o

)
P
yC2 H 4 φˆC2 H 4 P xH 2Oγ H 2O f Hl 2O

f i l ~ f i sat = φisat Pi sat

Ideal solution (vapor): φi = φˆi
xEtOH γ EtOH φ EtOH
sat sat
PEtOH
K= o

( )(
yC2 H 4 φC2 H 4 P xH 2Oγ H 2Oφ Hsat2O PHsat2O
P
)
 xEtOH γ EtOH φ EtOH
sat sat
PEtOH
K=
( )( )
o
P
yC2 H 4 φC2 H 4 P x H 2Oγ H 2Oφ Hsat2O PHsat2O
Known values:
φ sat
φ sat
P, T, H 2O , EtOH , φC H , PHsatO , PEtOH
2 4 2
sat

0.0493 xEtOH γ EtOH

K=
( )(
yC 2 H 4 x H 2 O γ H 2 O )
yC 2 H 4 = 1 − y EtOH − y H 2O
xiγ iφisat Pi sat
yi =
φi P
x EtOH γ EtOH φ EtOH
sat sat
PEtOH xH 2Oγ H 2Oφ Hsat2O PHsat2O
yC 2 H 4 = 1− −
φ EtOH P φ H 2O P

yC 2 H 4 = 1 − 0.907 xEtOH γ EtOH − 0.493 xH 2Oγ H 2O

xH 2O = 1 − xEtOH − xC 2 H 4
volatile
 0.0493 xEtOH γ EtOH
K=
( )( )
yC 2 H 4 x H 2 O γ H 2 O

yC2 H 4 = 1 − 0.907 xEtOH γ EtOH − 0.493 xH 2Oγ H 2O

xH 2O = 1 − xEtOH Values of γ EtOH, γ H 2O are determined experimentally

Assume xEtOH xH2O yC2H4 K

check K 473.15 K = 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:
• For reacting systems F = 2 −π + N
– 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] :
– With special constraints s: F = 2 −π + N − r
F = 2 −π + 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 − π + N − r = 2 − 2 + 2 − 0 = 2
With azeotrope (x1=y1, one constraint): F = 2 − π + 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 − π + N − r = 2 − 3 + 3 −1 = 1
(c) Single reaction: NH 4Cl( s ) → NH 3 ( g ) + HCl ( g )
Three chemical species and two phases: NH 4Cl( s ) NH 3 ( g ) + HCl( g )
One constraint: gas phase is equimolar
F = 2 − π + N − r − s = 2 − 2 + 3 −1−1 = 1
(d) 5 species, a single gas phase, and no special constraints: F = 2 − π + 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
CH 4 + O2 → 2 H 2 + CO2
C + 2 H 2 → CH 4

1
H 2 + O2 → H 2O
2 Eliminating O2
1
CO + O2 → CO2 CO2 + H 2 → CO + H 2O Eliminating O2
2
CH 4 + 2 H 2O → 4 H 2 + CO2
CH 4 + O2 → 2 H 2 + CO2

r=2
F = 2 − π + 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)π + π ] − [(π − 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)π + π ] − [(π − 1) N + N ] + 1 − 1 = 2
 Multireaction equilibria
• A separate equilibrium constant is evaluated for each
reaction:
vi , j
 fˆi 
∏i  f o  = Kj
 i 

– gas phase reaction vi , j

 fˆi 
∏i  P o  = Kj
 

Ideal gas
−ν 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 H 10 → C2 H 4 + C2 H 6 C4 H 10 → C3 H 6 + CH 4
If these reactions reach equilibrium, what is the product composition?
−1
Assuming ideal gas: yC2 H 4 yC2 H 6  P
=  o  KI
−ν j yC4 H10 P 
 P 
∏ (y ) = o 
vi , j
i Kj −1
P  yC3 H 6 yCH 4  P
=  o  K II
i

yC4 H10 P 

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

1 − ε I − ε II εI ε II
yC4 H10 = yC2 H 4 = yC2 H 6 = yC3 H 6 = yCH 4 =
1 + ε I + ε II 1 + ε I + ε II 1 + ε I + ε II

ε I = 0.1068 ε 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 y H 2 P 
−ν j 1
 P  y  P  2

∏ (y ) = o  K II = CO  o 
vi , j
i Kj
i P  yO2  P 
yCO2
K III =
yO2
With a basis of 1 mol of C feed:

−εI ε II ε III
yH 2 = yCO = yCO2 =
(
3.38 + ε II − ε I
) (
3.38 + ε II − ε I
) (
3.38 + ε II − ε I
)
2 2 2
1+ ε I 1 (1 − ε I − ε II ) − ε III
1.88
y H 2O = yN2 =
(
3.38 + ε II − ε I
) yO2 = 2 (
3.38 + ε II − ε I
( ) )
2 2 3.38 + ε II − ε 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
– (G t )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

 
λk  ∑ ni aik − Ak  = 0
 i 
summed over k
 
∑ λk  ∑ ni aik − Ak  = 0
k  i 

 
F = G t + ∑ λk  ∑ ni aik − Ak 
k  i 
  
F = G t + ∑ λk  ∑ ni aik − Ak 
k  i 
F (and Gt) minimum value?

 ∂F   ∂G t 
  =   + ∑ λk aik = 0 (i = 1,2,..., N )
 ∂ni T , P ,n j  ∂ni T , P , n j k

µ i + ∑ λk aik = 0 (i = 1,2,..., N )
k

 fˆi  gas phase reaction  fˆi 

µ i = G + RT ln o 
i
o
µ i = G + RT ln o 
i
o

 f i  pure ideal gas P 

 yiφˆi P 
µ i = ∆G + RT ln o 
o
fi
 P 
 yiφˆi P 
∆G + RT ln o  + ∑ λk 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 ∆G°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

 yiφˆi P 
∆G + RT ln  o  + ∑ λk aik = 0
o
fi (i = 1,2,..., N )
 P  k
P
Ideal gas: φˆi = 1 =1
Po

∆G ofi  ni 
+ ln   + ∑ λk aik = 0 (i = 1,2,..., N )
RT  ∑ ni  k RT
 i 
∆G ofi  ni  λk
+ ln   +∑ aik = 0 (i = 1,2,..., N )
 ∑i ni  k RT
RT  

For the 5 species:

19720  nCH 4  λC 4λH

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