Lecture 12
Lecture 12
Lecture 12
Note 12
Chemical-Reaction Equilibria
Lecturer:
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 ...
... d
v1
v2
v3
v4
Reaction coordinate, which characterizes the
extent or degree to which a reaction has taken
place.
(i 1, 2, ..., N )
ni ni 0 vi
yi
n n0 v
ni
ni 0
n ni n0 v
i
dni vi d
(i 1, 2, ..., N )
ni ni 0 vi
(i 1, 2, ..., N )
ni ni 0 vi
yi
n n0 v
i 1 1 1 3 2
i
n0 ni 0 2 1 1 4 8
i
yCH 4
8 2
1
8 2
1
4 3
yH 2
8 2
8 2
yCO
y H 2O
ni ni 0 vi
yi
n n0 v
i 1 1
i
1 1
2 2
n0 ni 0 n0
i
y H 2O
nH 2O
n0
1
n0
2
n0
yO2 2
1
n0
2
1
nO2
2
yH 2
nH 2
1
n0
2
Multireaction
Two or more independent reactions proceed
simultaneously
i,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
yi
ni 0 vi , j j
j
n0 v j j
j
n n0 v j j
j
j i , j
i
summation
n n0
j
i, j
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 1 and 2 .
i
j
1
2
yi
ni 0 vi , j j
j
n0 v j j
CH4
H2O
CO
-1
-1
-1
-2
1
0
CO2
H2
0
1
3
4
yCH 4
2 1 2
5 2 1 2 2
y H 2O
3 1 2 2
5 2 1 2 2
yCO
5 2 1 2 2
yCO2
5 2 1 2 2
yH 2
j
2
2
3 1 4 2
5 2 1 2 2
G t f ( )
Fig 13.1
dni vi d
d (nG ) (nV )dP (nS )dT i i d
i
(nG )
i i i
T ,P
(G t )
at equilibriu
m 0
T ,P
i i (T ) RT ln fi
Gio i (T ) RT ln f i o
fi
i f o
i
f
i Gio RT ln io
fi
vi
K exp
RT
o
f
i
RT
ln
0
i i
o
fi
G o i Gio
o
i
fi
ln o
i fi
vi
i i G
o
i
RT
fi
i iG RT i ln f o
i
o
i
vi
G o
K exp
RT
G o i Gio
M i M
o
Gio
H RT
o
i
d
2
RT
dT
o
i
o
2
RT
i i
H RT
RT
dT
H
d ln K
2
RT
dT
o
i
G
d
dT
RT
Gio H io TS io
summation
o
o
o
S
i i i i i i i i i
G o H o TS o
o
C
P
H o H 0o R
dT
T0
R
o
T C dT
o
o
P
S S 0 R
T0
R T
H 0o G0o
o
S 0
T0
T
o
o
T C
T C dT
T
o
o
P
P
G H
H 0 G0 R
dT RT
T0
T0
T0
R
R T
o
o
0
o
o
T C
T C dT
T
o
o
P
P
G H
H 0 G0 R
dT RT
T
T0
0
T0
R
R T
o
o
0
G o
ln K
RT
K K 0 K1 K 2
G0o
K 0 exp
RT0
H 0o
T0
K1 exp
1
T
RT0
1
K 2 exp
T
T0
o
T C dT
C Po
P
dT
T
0
R
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
G0o
K 0 exp
RT0
o
G0o G298
8378 J mol
H 0o
T0
K1 exp
1
T
RT0
1
K 2 exp
T
C
C dT
dT
T0 R
T0 R T
T
o
P
o
P
C2 H 5OH C2 H 4 H 2O
K0
K1
K2
298.15
29.366
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
vi
fio Po
An ideal solution: i i
i 1
y
i i
y
i
vi
vi
P
o
P
P
o
P
f (composition)
f (P)
y
i i
An ideal gas:
fi i yi P
vi
fi
i P o
f (T)
vi
P
o
P
vi
fi i xi f i
i i xi
f i
o
fi
vi
fi
Gi G o Vi dP RT ln o
P
fi
P
o
i
f i Vi P P o
ln o
fi
RT
P Po
K exp
RT
vi
i i
x
i
Ideal solution
x
ii
V
i i
vi
y
i i P o K
assuming an ideal solution and the equilibrium constant is
known:
v
x
i K
i
y
i
vi
P
o
P
vi
y H 2 yCO2
yCO y H 2O
(a) the reactant consists of 1 mol of H2O vapor and 1 mol of CO, T = 1100 K, P = 1 bar
yi
ni ni 0 vi
n n0 v
yCO
1 e
1 e
y H 2O
yCO2 e y H 2 e e 0.5
2
2
2
2
(d) the reactants are 2 mol of H2O and 1 mol of CO. other conditions are the same as (a)
yi
ni ni 0 vi
n n0 v
yCO
1 e
2 e
e
e
y H 2O
yCO2
y H 2 e 0.667
3
3
3
3
yi
ni ni 0 vi
n n0 v
yCO
2 e
1 e
e
e
y H 2O
yCO2
y H 2 e 0.667
3
3
3
3
ni ni 0 vi
yi
n n0 v
yCO
1 e
1 e
1 e
y H 2O
yCO2
yH 2 e
3
3
3
3
e 0.333
y
i
yi
vi
P
o
P
ni ni 0 vi
n n0 v
yCO y H 2O
0.316
yCO
1 e
1 e
y H 2O
yCO2 e y H 2 e e 0.36
2
2
2
2
C2 H 4 H 2O C2 H 5OH
yii
vi
P
o
P
Tc /K
C2H4 282.3
H2O 647.1
EtOH 513.9
i 1
i
y EtOH EtOH
P
o (10.02 10 3 )
yC2 H 4 C2 H 4 y H 2OH 2O P
Pc /bar
Tri
Pri
B0
B1
i
50.40 0.087 1.853 0.694 -0.074 0.126 0.977
220.55 0.345 0.808 0.159 -0.511 -0.281 0.887
61.48 0.645 1.018 0.569 -0.327 -0.021 0.827
y EtOH EtOH
y EtOH (0.827)
35
3
(10.02 10 )
yC2 H 4 C2 H 4 y H 2OH 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
n n0 v
6 e
6 e
6 e
e 0.233
The equilibrium conversion is a function of temperature, pressure, and the steamto-ethylene ratio in the feed:
Fig 13.4
C2 H 2 2C H 2
2C 2 H 2 C2 H 4
C2 H 2 H 2 C2 H 4
G o GIo GIIo
G o
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
y
i
yi
vi
P
o
P
ni ni 0 vi
n n0 v
yH 2
Ideal gas
yC 2 H 4
y H 2 yC 2 H 2
1 e
1 e
yC 2 H 2
2 e
2 e
yC 2 H 4
e
e 0.293
2 e
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 3COOC2 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):
o
H 298
3640 J
G o
ln K
RT
o
G298
4650
ln K
1.8759
RT
8.314 298.15
o
G298
4650 J
H o d ln K
RT 2
dT
K 373 4.8586
x
i
xi
ni ni 0 vi
n n0 v
xEtAc xH 2O
x AcH xEtOH
x AcH xEtOH
K
1 e
xEtAc xH 2O
e 0.6879
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 25C and that
equilibrium is attained at the exit, determine the composition and temperature of the
product stream from the reactor
o
H 298
98890 J
1
SO2 O2 SO3 For the reaction at standard state (298 K):
o
2
G298
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
SO3: e
In the product stream: SO2: 1 - e
total moles: 3.857-0.5e
O2: 0.6 - 0.5e
N2: 2.257
o
o
Energy balance: H 298 e H P H 0
o
H 298
e
T
298.15
o
CP
H
(T 298.15) ni C Pio
i
(T 298.15)
y
i
P
o
P
i 0.5
e 3.857 0.5 e
1 e 0.6 0.5 e
K K 0 K1 K 2
0.5
G0o
K 0 exp
RT
0
H 0o
T
K1 exp
1 0
T
RT0
1
K 2 exp
T
T0
o
T C dT
C Po
P
dT
T
0
R
R T
11894 .4
1
ln K 11.3054
IDCPS IDCPH
T
T
Assume T
ln K
1 e
0.0062
3.857 0.5 e
...
fi
P o
vi
o
f
P
1 bar
o
EtOH
K
P
f
f
T 473.15K
C 2 H 4 H 2O
K 473.15 K 0.031
v
l
fEtOH
Phase equilibrium:
fEtOH
f
o
o
o
EtOH
K
P
K
P
fC2 H 4 fH 2O
fCv2H4 fHv2O
fCl2H 4 fHl 2O
fi v fi l
l
xEtOH EtOH f EtOH
o
K
P
yC2 H 4 C2 H 4 P xH 2O H 2O f Hl 2O
sat
sat
xEtOH EtOH EtOH
PEtOH
o
K
P
yC2 H 4 C2 H 4 P xH 2O H 2OHsat2O PHsat2O
Known values:sat
sat
P, T, H 2O , EtOH ,
sat
C2 H 4 , PHsatO , PEtOH
2
yC2 H 4 1 y EtOH y H 2O
xi iisat Pi sat
yi
i P
yC 2 H 4
sat
sat
xH 2O H 2OHsat2O PHsat2O
xEtOH EtOH EtOH
PEtOH
1
EtOH P
H 2O P
Assume xEtOH
xH2O
yC2H4
xi
0.06
0.94
0.00
=1
yi
0.180
0.464
0.356
=1
F 2 N
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 CaCO 3 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 )
F 2 N r 2 3 3 1 1
F 2 N r s 2 2 3 1 1 1
CaO( s )
CO2 ( g )
NH 3 ( g ) HCl( g )
1
C O2 CO
2
C O2 CO2
1
H 2 O2 H 2O
2
C 2 H 2 CH 4
Eliminating C
1
CO O2 CO2
2
1
H 2 O2 H 2O
2
Eliminating O2
1
CO O2 CO2
CO2 H 2 CO H 2O
2
CH 4 O2 2 H 2 CO2
r=2
F 2 N r s 2 1 5 2 0 4
Eliminating C
CH 4 O2 2 H 2 CO2
Eliminating O2
CH 4 2 H 2O 4 H 2 CO2
Duhems 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
F [2 ( N 1) ] [( 1) N N ] 1 1 2
Multireaction equilibria
A separate equilibrium constant is evaluated for
v
each reaction:
fi
f o K j
i, j
fi
i P o
vi , j
Kj
Ideal gas
v
y
i
i
i, j
P
o
P
Kj
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
yC 2 H 4 yC 2 H 6
vi , j
P
o
P
Kj
yC4 H10
yC3 H 6 yCH 4
yC4 H10
P
o
P
P
o
P
KI
1
K II
yC4 H10
1 I II
1 I II
yC 2 H 4 yC 2 H 6
I
1 I II
yC3 H 6 yCH 4
II
1 I II
I 0.1068 II 0.8914 yC4 H10 0.001 yC2 H 4 yC2 H 6 0.0534 yC3 H 6 yCH 4 0.4461
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,
1
H 2 O2 H 2O
2
1
C O2 CO
2
C O2 CO2
T (K)
1000
1100
1200
1300
1400
1500
H2O
-192424
-187000
-181380
-175720
-170020
-164310
G o
ln K
RT
Gf J/mol
CO
-200240
-209110
-217830
-226530
-235130
-243740
K = ...
CO2
-395790
-395960
-396020
-396080
-396130
-396160
fC
f C (@ 20 bar )
1
o
o
fC
f C (@ 1 bar )
KI
y
i
vi , j
P
o
P
Kj
3.38
I
II I
yO2 y H 2
P
o
P
y P
K II CO o
yO2 P
K III
yH 2
y H 2O
yCO
2
yCO2
yO2
II
I
3.38 II
yCO2
2
III
I
3.38 II
1 1
I
II
III
2
yO2
3.38
3.38 II I
2
2
2
Three equations and three unknowns can be solved.
y H 2O
1 I
I
3.38 II
yN2
1.88
II I
n a
i ik
Ak
n
a
A
i i ik k 0
summed over k
n
a
i ik
k 0
i
k
k
F G k
t
n a
i ik
Ak
F G t k
k
ni aik Ak
ni
T , P ,n j
G t
ni
i k aik 0
T , P ,n j
k aik 0
(i 1,2,..., N )
(i 1,2,..., N )
fi
i G RT ln o
fi
o
i
fi
i G RT ln o
P
yii P
i G RT ln
o
P
o
fi
yii P
k aik 0
G RT ln
o
k
P
o
fi
(i 1,2,..., N )
o
i
species
CH4
H2O
CO
CO2
H2
Element k
C
O
H
Ak = no. of atomic masses of k in the system
2
3
14
aik = no. of atoms of k per molecule of i
1
0
4
0
1
2
1
1
0
1
2
0
0
0
2
yii P
k aik 0
G RT ln
o
k
P
o
fi
Ideal gas: i 1
G ofi
RT
P
1
o
P
k aik 0
ni
k RT
i
ln
ni
(i 1,2,..., N )
(i 1,2,..., N )
G ofi
RT
k aik 0
ni
k RT
i
ln
ni
(i 1,2,..., N )
nCH 4
19720
C 4H 0
ln
ni RT RT
RT
i
CH4 :
5 equations
...
For the 3 elements:
C:
H:
O:
nH 2O nCO 2nCO2 3
n
i
3 equations
1 equations
Solve
simultaneously