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Advanced Thermodynamics

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 ...

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:
dni vi d

(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 )

For a system in which the following reaction occurs, CH 4 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 .

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

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 .

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

total stoichiometric number:

n n0 v j j
j

j i , j
i

summation

n n0
j

i, 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 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

Equilibrium criteria to chemical


reactions
is the single variable that characterizes the
progress of the reaction
the total Gibbs energy at constant T and P is determined
by
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
Its differential is zero dG t T , P 0

G t f ( )

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 )
i i i

T ,P

(G t )

at equilibriu
m 0
T ,P

The fugacity of a species in solution:

i i (T ) RT ln fi

For pure species i in its standard state:

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

The equilibrium constant for the reaction, f(T)

G o i Gio

The standard Gibbs energy change of reaction, f(T)

M i M
o

Other standard property changes of reaction :

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

For a chemical species in its standard state:

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

Readily calculated at any temperature from the


standard heat of reaction and the standard Gibbs energy
change of reaction at a reference temperature

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

From Table C.4


o
H 0o H 298
45792 J mol

G0o

K 0 exp
RT0

o
G0o G298
8378 J mol

H 0o
T0
K1 exp
1


T
RT0

1
K 2 exp
T

The heat capacity data:

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

Gas phase reaction:


Ideal-gas state: f i o P o
Standard-state pressure Po of 1 bar
fi
i f o
i

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

Liquid phase reaction:


fi
i f o
i

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

Law of mass action

Ideal solution

x
ii

V

i i

Except at high pressures

Equilibrium conversions for single


reactions
Single reaction in a homogeneous system:
assuming an ideal gas and the equilibrium constant is
known:

vi

y
i i P o K
assuming an ideal solution and the equilibrium constant is
known:
v

x
i K
i

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.

y
i

vi

P
o
P

From Fig 13.2, K = 1


i 0

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

(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)

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

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)

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

The fraction of steam that reacts is then 0.667


(f) the initial mixture consists of 1 mol of H 2O, 1 mol of CO and 1 mol of CO2 . other
conditions are the same as (a)

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

The fraction of steam that reacts is then 0.333

(g) same as (a) except that the temperature is 1650 K

y
i

yi

vi

P
o
P

ni ni 0 vi

n n0 v

From Fig 13.2, K = 0.316 y H 2 yCO2


i 0

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

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

Estimate the maximum conversion of ethylene to ethanol by vapor phase hydration at


250C and 35 bars for an initial steam-to-ethylene ratio of 5.
For a temperature of 250C, K = 10.02 x 10 -3

C2 H 4 H 2O C2 H 5OH

Assuming the reaction mixture is an ideal solution. i i

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

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
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

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 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

Assuming ideal solution:


v

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

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 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

The enthalpy change of the products at T


H Po C Po

(T 298.15) ni C Pio
i

(T 298.15)

Assuming ideal gas:


v

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

Converges at T = 855.7 K, e = 0.77


y SO2

1 e
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 200C 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 :

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

For vapor phase: fi v yii P


l
l
For liquid phase: fi xi i f i

l
xEtOH EtOH f EtOH
o
K
P
yC2 H 4 C2 H 4 P xH 2O H 2O f Hl 2O

f i l ~ f i sat isat Pi sat


Ideal solution (vapor): i i
sat
sat
xEtOH EtOH EtOH
PEtOH
o
K
P
yC2 H 4 C2 H 4 P xH 2O H 2OHsat2O PHsat2O

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

0.0493 xEtOH EtOH


yC 2 H 4 x H 2 O H 2 O

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

yC2 H 4 1 0.907 xEtOH EtOH 0.493 xH 2O H 2O


xH 2O 1 xEtOH xC2 H 4
volatile

0.0493 xEtOH EtOH


yC 2 H 4 x H 2 O H 2 O

yC2 H 4 1 0.907 xEtOH EtOH 0.493 xH 2O H 2O


xH 2O 1 xEtOH

Assume xEtOH

Values of EtOH, H 2O are determined experimentally

xH2O

yC2H4

check K 473.15 K 0.031


Converged at:
EtOH
H2O
C2H4

xi
0.06
0.94
0.00
=1

yi
0.180
0.464
0.356
=1

Phase rule and Duhems theorem for


reacting systems
For non-reacting systems
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)

Phase-equilibrium equations: (-1) N


r independent chemical reactions at equilibrium within the
system: r equations
F = [2+(N-1) ] - [(-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 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

(c) Single reaction: NH 4Cl( s ) NH 3( g ) HCl( g )


Three chemical species and two phases: NH 4Cl( s )
One constraint: gas phase is equimolar

F 2 N r s 2 2 3 1 1 1

CaO( s )

CO2 ( g )

NH 3 ( g ) HCl( g )

(d) 5 species, a single gas phase, and no special constraints: F 2 N r s


???

The formation reactions:

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

For reacting system:

A variable is introduced for each independent reaction: j


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
v
each reaction:
fi
f o K j
i, j

gas phase reaction

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

If these reactions reach equilibrium, what is the product composition?

yC 2 H 4 yC 2 H 6

Assuming ideal gas:

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

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

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,

N2 = (0.79)(2.38) = 1.88 mol

The formation reactions for the compounds are:

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

Carbon is a pure solid phase:

fC
f C (@ 20 bar )

1
o
o
fC
f C (@ 1 bar )

Assuming ideal gases for the remaining species:

KI

y
i

vi , j

P
o
P

Kj

With a basis of 1 mol of C feed:

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

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.

Lagranges undetermined multiplier


method
The material balance on each element k :

n a

i ik

Ak

multiply the Lagrange multipliers

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

F (and Gt) minimum value?

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

gas phase reaction


pure ideal gas

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

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 Gf at 1000 K of each
species are given.

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 )

For the 5 species:

nCH 4
19720
C 4H 0
ln
ni RT RT
RT
i

CH4 :

5 equations

...
For the 3 elements:
C:

nCH 4 nCO nCO2 2

H:

4nCH 4 2nH 2O 2nH 2 14

O:

nH 2O nCO 2nCO2 3

n
i

nCH 4 nH 2O nCO nCO2 nH 2

3 equations

1 equations

Solve
simultaneously