Chapter 13: Chemical Reaction Equilibrium

Extent of a Chemical Reaction (

j
):
Consider the generic chemical reaction:

aA + bB + yY + zZ or v
A
A + v
B
B + v
Y
Y + v
Z
Z

In this particular reaction v
i
is called the stochiometric coefficient of
species i; positive (+) for product species,
negative (-) for reactant species

For each independent chemical reaction, j, the extent (also called degree
of advancement, degree of reaction, or progress variable) is defined by:
d
j
= dn
i,j
/ v
i


For example:
Reaction 1 (j = 1): CH
4
(g) +2H
2
O (g) CO
2
(g) + 4H
2
(g)
Reaction 2 (j = 2): CH
4
(g) + H
2
O (g) CO (g) + 3H
2
(g)
v
CH4,1
= -1; v
CH4,2
= -1; v
H2O,1
= -2; v
H2O,2
= -1
v
CO2,1
= +1; v
CO2,2
= 0; v
CO,2
= +1; v
H2,2
= +3; v
N2,2
= 0
i
o i, i
i
n
n n
i

0

n n
/ dn d
i
o i, i

= =
} }
=
=
=
n n
i io i
+ =
n
n
n
n
] [n
n
n
n
y
o
i io
species # i
1 i
i o
i io
species # i
1 i
i io
i io
species # i
1 i
i
i
i
+
+
=
+
+
=
+
+
= =

=
=
=
=
=
=

=
=
+ =
reaction # j
1 j
j j i, io i
n n

=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
+
+
=
+
+
=
+
+
= =
reactions # j
1 j
j j o
reactions # j
1 j
j j i, io
species # i
1 i
j i,
reactions # j
1 j
j o
reaction # j
1 j
j j i, io
j j i,
reactions # j
1 j
io
species # i
1 i
j j i,
reaction # j
1 j
io
species # i
1 i
i
i
i
n
n
n
n
] [n
n
n
n
y
For a single reaction the subscript j is dropped: d = dn
i
/



For multiple reactions: d
j
= dn
i,j
/
j
2 1
2 1
N2 H2 CO CO2 H2O CH4
CH4
CH4
2 2 5
1
n n n n n n
n
y
+ +

=
+ + + + +
=
2 1
2 1
N2 H2 CO CO2 H2O CH4
H2O
H2O
2 2 5
2 2
n n n n n n
n
y
+ +

=
+ + + + +
=
2 1
2 1
N2 H2 CO CO2 H2O CH4
H2
H2
2 2 5
3 4 0
n n n n n n
n
y
+ +
+ +
=
+ + + + +
=
2 1
1
N2 H2 CO CO2 H2O CH4
CO2
CO2
2 2 5
1
n n n n n n
n
y
+ +
+
=
+ + + + +
=
2 1
2
N2 H2 CO CO2 H2O CH4
CO
CO
2 2 5
0
n n n n n n
n
y
+ +
+
=
+ + + + +
=
2 1 N2 H2 CO CO2 H2O CH4
N2
N2
2 2 5
1
n n n n n n
n
y
+ +
=
+ + + + +
=
For example:
Reaction 1 (j = 1): CH
4
(g) +2H
2
O (g) CO
2
(g) + 4H
2
(g)
Reaction 2 (j = 2): CH
4
(g) + H
2
O (g) CO (g) + 3H
2
(g)
If initially we have the following moles of the given species:
n
CH4,o
= 1; n
H2O,o
= 2; n
CO2,o
= 1; n
N2,o
= 1; n
H2,o
= 0; n
CO,o
=0
Then, in terms of
1
and
2
:
n
CH4
= 1-
1
-
2
; n
H2O
= 2 - 2
1
-
2
; n
CO2
= 1 +
1
; n
CO
= 0 +
2

Chemical Reaction Equilibrium

G
t
(dG
t
)
T,P
= 0 or G
t
is minimum

Constant T and P

( ) ( )
t
T,P
T,P
G
nG
0
c c
(
c
( c
( = =
(
c c
(


( ) ( ) ( ) ( ) ( )
( )
| |
( ) ( ) ( ) ( )
( )
i
i i i i
i i
i i e
i
T,P
o o o o
i i i i i i i i i
i i i
o

o
i i
d nG = nV dP - nS dT + dn = nV dP - nS dT + d
nG
= 0 at = see the previous slide

G +RTln f / f = 0 G + RTln f / f = 0
-G

= ln f / f
RT
c
c
( c
=
(
c

(
H
(

i
1 n

i
o
i
f(T,P,y ,..y
o
f(T)
)
only
=
-G
K Exp
RT

f
f
| |
H
|
|
|
\
|

|
\ .
.
Standard or Reference State Properties
Are defined for each species at an arbitrary pressure, P
0
, but at the system
temperature, T.
Standard state need not be the same for all species taking part in a reaction
For a particular species the standard state chosen for must be the same as
that for
For a gaseous species, G
i
o
is usually taken as that of an ideal gas at P
0
= 1
bar and the system T. Hence f
i
o
= 1 bar
For a liquid species, G
i
o
is usually taken as that of a pure liquid at at P
0
= 1
bar and the system T. Hence f
i
o
= f
i
(T,1 bar)

o
i
G
o
i
f
The Chemical Reaction Equilibrium Problem
Given:
Known initial mole numbers (n
io
) of chemical
species are reacted at T and P, through known
chemical reaction(s) occurring in a homogeneous
phase of gas or liquid, until equilibrium is attained
at T and P.

Required:
a) At equilibrium, what is the composition (e.g.,
mole fraction) of each chemical species in the
reaction mixture?
b) How do these compositions change if the
reaction T and/or P are changed

Procedure
Identify the independent, balanced, chemical reactions involved (J) and write
down these reactions (see example 13-11 for the case when only species prevailing
at equilibrium are kno
-
( ) O
1 2 J
o
P
T
rxn i
o
T
wn)
Compute the equilibrium constant for each reaction, K , K , ..K , at the given
T from Gibbs free change for each reaction at T G and C values
eq 13-18 when H =f(T) or
o
-
A
o o
T 298
T
rxn i
i
1 2 N
eq 13-15 when H = H f(T)
-G
That is: K Exp i = 1,.., J
RT
Express mole fractions of each species in terms of the reaction extents, , ,..,
R
o
( A A =

| |
| |
|
|

| |
\ .
\ .
-
-
,
i
1 2 J j
o
i
elate each equilibrium constant to species mole fractions expressed in terms of
f
reactions extents, , ,.., , i.e., K
f
The results are J algebraic equation
i j
i
v
(
| |
( =
|
(
\ .

-
[
j
s in J reactions extents (each independent
reaction has its own extent, ). Solve for these extents and find the corresponding
mole fractions of each species
Convert mole fractions
c
- into other concentration units, like partial pressure, molarities,...
Thermodynamic Equilibrium Constant, K
The equilibrium constant of a reaction, j, like:
aA + bB yY + zZ, is given by


Where a
A
, a
B
, a
Y
, and a
Z
are the activities of species
A, B, Y, and Z, respectively, in the equilibrium
reaction mixture at its T, P, and composition
.

Activity is a function of T, P and composition of the
equilibrium reaction mixture.



( )
,
i,j
i i
y z

o y z a b
Y Z
j i Y Z A B
a b
A B
a a

K f /f a a a a a
a a
i j
v

= [ = [ = =
i
i
o
i

f
a =
f
Thermodynamic Equilibrium Constant, K (Continued)
aA + bB yY + zZ
Real Cases: a
i
= y
i
P
i
(T,P,y
1
,y
2
,,y
N
)/P
o







total pressure
mole fraction of species i
in the reaction mixture
fugacity coefficient of species
i in the reaction mixture
reference pressure (1 bar)
Z Y Z Y
A A
z y a b
z y z y
T,j
a b a b
B B o
y y
P
K
y y P


+
( (
(
=
( (
(
( (


The equilibrium constant of reaction j at T
Thermodynamic Equilibrium Constant, K (Continued)
Ideal Cases: a
i
= y
i
P/P
o







total pressure
mole fraction of species i
in the reaction mixture
Z Y
A
z y a b
z y
T,j
a b
B o
y y
P
K
y y P
+
(
(
=
(
(
(


reference pressure (1 bar)
Thermodynamic Equilibrium Constant (Continued), K

Liquid reactions in real solutions:
a
i
= f
i
/f
i
o
= x
i
f
i

i
(T,P,x
1
,x
2
,,x
N
)/f
i
o








Liquid reactions in ideal solutions: set all s to 1
mole fraction of species i
in the liquid mixture
activity coefficient of species
i in the liquid mixture
( )
( )
Z Y Z Y
A A
o
z y z y
T,j i i
a b a b
i
B B
P-P
x x
K exp V
x x RT
| |
( (
|
=
( (
|
( (

\ .

Z Y
A
z y a b
z y
a b
B o
y y
P
y y P
+
(
(
(
(
(

= =
(
(

K
RT
G
exp
o
T
Z Y Z Y
A A
z y a b
z y z y
a b a b
B B o
y y
P
y y P


+
( (
(
( (
(
( (

















(
(

(
(

b
B
a
y z
b
B
a
y z


x x
x x
A
Y Z
A
Y Z
(
(

b
B
a
y z
x x
x x
A
Y Z
real gas mixture
gas mixture assumed ideal solution
ideal gas mixture
Real liquid mixtures
f(T) only. Why?
f(T, P , composition (extents))
Z Y Z Y
A A
z y a b
z y z y
a b a b
B B o

y y
P

y y P


+
( (
(
( (
(
( (

ideal liquid mixtures
aA + bB yY + zZ

Note that:

For an exothermic reaction, i.e., is negative, then as T goes
up, K goes down

For an endothermic reaction, i.e., is positive, then as T goes
up, K goes up too.

ln(K) goes linearly with (1/T) with a slop of =

Typical variation of ln(K) with (1/T) for some reactions are shown in
the coming slide (can be used to get K also)
(

=
To
1
T
1
R
H
lnK lnK
o
j To,
j To, j T,
o
H
R
H
o
j 298,

o
H
what? tells Linearity
T at slope R H
R
H
d(1/T)
dlnK
o
T
o
T
= =
(

=
=

298
1
T
1
R
H
lnK lnK
Appendix) : (Table G
R 298.15
1
lnK
) T of t independen is H (i.e., H H If
o
j 298,
j 298, j T,
o
i f,298, j i, j 298,
o
j T,
o
j 298,
o
j T,
} }
A

A
+ +
A A
=
A
=
=
T
To
T
To
dT
RT
C
dT
R
C
T
1
RT
H
RT
H G
RT
G
lnK -
) T on depends H (i.e., f(T) H If
0
j P,
0
j P,
0
T
o
0
T
0
T
0
j T,
j T,
o
j T,
o
j T,
j o, j o, j o,
Consider the gas phase reaction: aA + bB yY + zZ
Assume further that the reaction mixture is an ideal gas.
Therefore, at equilibrium:




At a given T, K is constant (why?). So, if (y+z-a-b) is > 0 and P
increases, the amount must decrease.
But if (y+z-a-b) is < 0 and P increases, the amount
must increase.

Z Y
A
z y a b
z y
a b
B o
y y
P
y y P
+
(
(
(
(
(

= =
(
(

K
RT
G
exp
o
T
Z Y A
z y a b
B
(y y )/(y y )
Z Y A
z y a b
B
(y y )/(y y )
Effect of Pressure on Equilibrium Composition
Gas Reactions
Example 2:
Consider the chemical reaction:
2H
2
O(g) + C
2
H
6
(g)

= 2CO(g) + 5H
2
(g)

Find H
o
298
. Is the reaction exothermic or endothermic at
298 K?

Calculate the equilibrium constant (K) at 25
o
C

Assuming H
o
to be temperature independent, find K at 750 K

If a reactor is initially charged with 4 moles H
2
O, 1 mole C
2
H
6
,
1 mole N
2
what are the mole fractions and the mole numbers of
of all species if the reaction reaches equilibrium at 750 K
and 1 bars (assume ideal gas mixtures).


Example 2 (Continued)
Solution:
From Appendix C, obtain the following data:
Species
f
H
o
298
(Jmol
-1
)
f
G
o
298
(Jmol
-1
)
C
2
H
6
(g)

-83,820 -31,855
H
2
O(g) -241,818 -228,572
CO(g) -110,525 -137,160
H
2
(g) 0 0
(1)
H
o
298
= 5(0) + 2(-110,525) -1(-83,820) -2(-241,818)
= 346,406 Jmol
-1

Since H
o
298
is positive, the reaction is endothermic
(2)
G
o
298
= 5(0) + 2(-137,160) -1(-31,855) -2(-228,572)
= 214,679 Jmol
-1
Example 2 (Continued)
Since G
o
298
is positive, then the reaction as written in not spontaneous,
i.e., for its occurrence work must be done on the reaction system.
K
298
= exp(-G
o
298
/RT) = exp[-214,679/(8.314*298)] = 2.33810
-38

extremely low K at 298 K means that almost no products will form
(3)
To find K
750
, and because H
o
is constant;



lnK
750
= ln(2.33810
-38
) (346,406/8.314)*(750
-1
-298
-1
) = -2.3861
K
750
= exp(-2.3861) = 0.092
(4) Now relate K
750
to mole fractions through reaction extent

(

=
To
1
T
1
R
H
lnK lnK
o
To
To T
Z Y
A
z y a b
z y
T
a b
B o
y y
P
K
y y P
+
(
(
=
(
(
(

Example 2 (Continued)
with P
o
= 1bar, P = 1 bars, y+z-a-b = 5+2-1-2 = 4, and
n
H2
= 0 + 5 x
H2
= 5/(6+4 )
n
CO
= 0 + 2 x
CO
= 2/(6+4 )
n
C2H6
= 1 - x
C2H6
= (1 ) /(6+4 )
n
H2O
= 4 - 2 x
C2H6
= (4 - 2) /(6+4 )
n
N2
= 1 x
N2
= 1 /(6+4 )
0.092 = 12500
7
/[(1- )(4-2 )
2

(6+4 )
4
] [1/1]
4


7.36 10
-6
-
7
/[(1- )(4-2 )
2

(6+4 )
4
] [1/1]
4
=0
Solution (using Goal-Seek in Excel) gives: = 1.0
Substituting for = 1 to get:
n
H2
= 0 + 5 = 5 x
H2
= 5/(6+4 ) = 0.5
n
CO
= 0 + 2= 2 x
CO
= 2/(6+4 ) = 0.2
n
C2H6
= 1 =0 x
C2H6
= (1 ) /(6+4 ) = 0
n
H2O
= 4 - 2 = 2 x
C2H6
= (4 - 2) /(6+4 ) = 0.2
n
N2
= 1 x
N2
= 1 /(6+4 ) = 0.1
x
i
= = 1.00

Example 3
Based on thermodynamic considerations only, which is better to
carry out the previous reaction in example 2 at lower or higher
pressures? What about temperature?

Since y + z a b = 4, which is > 1, then increasing pressure
will shift the reaction to the left (lower products) and vise versa.

As to Temperature, since the reaction is endothermic,
decreasing T will decrease K, hence, the reaction will shift to
the left by lowering T.

Example 13.6
Consider producing ethanol (C
2
H
5
OH) by the direct hydration
of ethylene (C
2
H
4
) phase at 250
o
C (523 K) and 35 bar (vapor
phase reaction) for an initial steam-to-ethylene ratio of 5

(1) Find the equilibrium constant for the above reaction at the
specified temperature of 250
o
C.

(2) Estimate the maximum conversion of ethylene to ethanol
assuming the reaction mixture as a real gas mixture

(3) Repeat part (2) assuming the reaction mixture to be an ideal gas

Solution:
(1) Following the same procedure used in example 2 before, you
can show that for the reaction: C
2
H(g) + H
2
O(g) = C
2
H
5
OH(g)
K
523
= 10.0210
-3
(verify this answer)


Example (Continued)
Po = 1bar, P = 35 bars, = 1-1-1 = -1, and
n
C2H4
= 1 - y
C2H4
= (1 ) /(6 - )
n
H2O
= 5 - y
H2O
= (5 - ) /(6 - )
n
C2H5OH
= y
C2H5OH
= 1 /(6 - )
Lets assume the gas as an ideal solution. In this case



Therefore, we need to compute fugacity coefficients for all
species. Let us the generalized correlation based on virial EoS,
i.e.

C2H5OH
H2O
1
1
1
C2H5OH
1 1 1 1
H2O C2H4 C2H4 o
y P
K
y y P

(
( (
=
(
( (
(

( )
4.2
r
1 1.6
r
o
1 o
r
r
i
0.172/T 0.139 B and 0.422/T 0.083 B
: with B B
T
P
exp
= =
(

+ =
Example (Continued)


T
c
/K P
c
/bar
i
T
ri
P
ri
B
o
B
1

i
C
2
H
4
282.3 50.40 0.087 1.853 0.694 -0.074 +0.126 0.977
H
2
O
647.1 220.55 0.345 0.808 0.159 -0.511 -0.281 0.887
C
2
H
5
OH
513.9 61.48 0.645 1.018 0.569 -0.327 0.021 0.827
Example (Continued)
Substituting for K,
i
, P, Po, the x
i
,s in terms of in the K-
expression below



and solving for yields: = 0.233
Now go back and solve for all mole fractions

C2H5OH
H2O
1
1
1
C2H5OH
1 1 1 1
H2O C2H4 C2H4 o
y P
K
y y P

(
( (
=
(
( (
(

Problem 13.29