Chemical Reaction Equilibria

Chapter 13
The Reaction Coordinate
Application of Equilibrium Criteria to Chemical Reactions
The Standard G and the Equilibrium Constant
Effect on Temperature on the Equilibrium Constant
Evaluation of the Equilibrium Constant
Relation of Equilibrium Constant to Composition
Equilibrium Conversion for Single Reactions

Introduction

Transformation of raw materials into products having commercial use and value
is a major industry.
Raw Materials

{crude oil, minerals, etc..}

Products

{Gasoline, NaOH, H2SO4, ammonia, etc..}

This often involves chemical reactions and subsequent separation of the products.
The rate and maximum (or equilibrium) conversion of chemical reaction are of
important concern in its commercial development.

We can often increase reaction rates by the

use of CATALYST, but we can not change
the equilibrium (or ultimate) conversion by
using catalyst.

Degree of reaction

Both of these aspects depend on the T, P, and composition of the reactants.

st
With cataly

th
Wi

ou

Uultimate
conversion

t
lys
a
t
a
tc

Time
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12-2

 Chemical Reaction Course concerns on study of reaction rate and equilibrium,

where the following tasks are often considered:
Design and operation of reaction equipment
Effect of controllable variables upon conversion
Extent of reaction as t
In general:
Reaction Equilibrium is governed by THERMODYNAMICS
while,
Reaction Rate is governed by REACTION KINETICS
Objectives:
Definitions of reaction stoichiometry and criterion of reaction equilibrium.
Dependence of equilibrium constant on temperature and its evaluation.
Development of connection between equilibrium constant and composition.
Calculation of equilibrium conversion for single reactions.

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The Reaction Coordinate

The general chemical reaction can be written as:

1 A1 + 2 A2 + ........ 3 A3 + 4 A4

(I)

where |i| are stoichiometric coefficients and Ai denotes the chemical formulas of
species.
i themselves are stoichiometric numbers
Sign Convention
For products: i is positive (+)

For reactants: i is negative (-)

N.B. The reaction, as written above, does not represent any mechanisms. It
represents only the overall macroscopic picture. It does not tell us what is happening
at the microscopic level.
Example:
H2O = -1
CH4 = -1
CH4 + H2O CO + 3H2
CO = +1
H2 = +3
The stoichiomertric number of an inert species is zero.
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 In all reactions, the change in the number of moles of the species present are related to
each other through the stoichiometric number.
For example, for the reaction CH4 + H2O CO + 3H2, if 0.5 mole CH4
reacts, then 1.5 moles H2 and 0.5 mol CO generated, thats ratio of change in
number of moles to the stoichiometric number of CH4 is the same as that for H2.
Thus, in general for reaction (I), we can write:

dn 2 dn 1
=
2
1

or, in general:

dn 3 dn 1
=
3
1

, etc

dn 1 dn 2 dn 3
=
=
= ......... = d
(II)
1
2
3
where d = the amount of reaction.
It will be observed that the sign of i allows for the fact that:

dni > 0 for the product

& dni < 0 for the reactants
The preceding equation provides the definition for , the Reaction Coordinate; a
quantity characterizes the extent, or degree, to which chemical reaction has taken place.
is also called the Degree of Reaction
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From II, we can write,

dn i = i d

moles

dimensionless

(III)

moles

By convention, = 0 at the initial state (before the reaction occurs). Integration yields:
ni

dn i = i d

ni 0

= f(t)

n i = n i0 + i

ni
= i

Summing over all N species (reactant and products) yields: n =

or,

n = n 0 +

where,

n0 =

ni

&

ni

+ i

The quantity tells us whether there is a net increase or decrease in the total number
of moles in the system.
The mole fraction of species i at any time, or stage of reaction, is by:

n i n i0 + i
yi =
=
n
n 0 +
Chemical Engineering Thermodynamics II

This expression is very useful, since it provides us

with a relationship between species concentration
and the progress of the reaction.
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12-6

Example: Consider the chemical reaction, CH4 + H2O CO + 3H2

Initially there present 2 moles CH4, 1 mole H2O, 1 mole CO and 4 moles H2.
Obtain yi = f().
n0 = n0i = 2 + 1 + 1 + 4 = 8 moles
= i = -1 -1 + 1 + 3 = 2
Application of the equation:

y CH 4

2-
=
8 + 2

y H 2O

yi =

1-
=
8 + 2

n i0 + i
n 0 +

yCO

1+
=
8 + 2

yH 2

4 + 3
=
8 + 2

Definition of a Mole of Reaction

This means that has changed by a unit amount (i.e. 1 mol).
When = 1 mole, the reaction proceeds to such an extent that the change in
mole numbers for each reactant and product species is equal to its stoichiometric
numbers, thats:
ni = i
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Multireaction Stoichiometry
In this case, we allocate a reaction coordinate, j, to each reaction (j = 1, 2, 3, R),
where R = number of separate reactions.
The stoichiometric numbers are now identified as:

i,j

Stoichiometric number of species i in reaction j

ni may change because of the involvement of species i in several reactions.

The general equation analogous to Eq. (III) for single reactions is:

dn i =

i , j d j

(i = 1, 2, .N; j = 1, 2, . , R)

Integration yields; n i = n i0 + ( i , j j )
j

Summing over all species: n =

Similarly, v j =

i , j

Mole fraction,

n
yi = i
n

ni = n 0 + ( i , j j ) = n 0 + ( i , j j )
i j
j i
n = n 0 + ( j j )
j

n i0 +
=

Chemical Engineering Thermodynamics II

( i , j j )

n0 +

j j

(i = 1, 2, . , N)

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12-8

Example:

Consider the following reactions,

CH4 + H2O CO + 3H2
CH4 + 2H2O CO2 + 4H2

(1)
(2)

j=1
j=2

There are present 2 mol CH4 and 3 mol H2O. Obtain expressions for yi = f(1, 2).
Construct the following table for i,j:
i=
j

CH4

H2O

CO

1
2

-1
-1

-1
-2

1
0

CO2

H2

0
1

3
4

j
1 = 2
2 = 2

n = n 0 + ( j j ) = 5 + 21 + 22
j

y CH 4

2 - 1 - 2
=
5 + 2 1 + 2 2
y CO 2

y H 2O

3 - 1 - 2 2
=
5 + 2 1 + 2 2

2
=
5 + 2 1 + 2 2

Chemical Engineering Thermodynamics II

yH2
ChE 342

y CO

1
=
5 + 2 1 + 2 2

3 1 + 4 2
=
5 + 2 1 + 2 2
12-9

Application of Equilibrium Criterion to Chemical Reactions

As noted previously, in a closed system at equilibrium (constant T &P):
(dGt)T,P = 0
Recalling that Gt decreases during an irreversible process (eg. Mixing process,
chemical rxn, etc)
If a mixture is not in equilibrium, any reaction that occurs at constant T and P must
lead to a decrease in the total energy of the system
is the single variable that characterizes
the progress of the reaction.
Recall that is related to the
composition of the system
Criterion for equilibrium:
1. (dGt)T,P = 0
2. Gt() is minimim
N.B. Equilibrium expression can also be
used for OPEN SYSTEM at constant T & P.
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The Standard Gibbs Energy Change and the Equilibrium Constant

Recall the fundamental property relation for single-phase system:

d ( nG ) = ( nV ) dP - ( nS ) dT + i dn i
i

If changes in ni occur as a result of single reaction in a closed system, then:

dn i = i d
d ( nG ) = ( nV ) dP - ( nS ) dT + i i d
i
( nG )
At equilibrium state, according to the
[
]T , P = i i = 0.0

previous figure.
The criterion for chemical reaction equilibrium can be expressed as:

i i

= 0 .0

Since i = G i

(A)
Recall that i = i (T ) + RT ln f i
Write this equation for pure species in its standard state at the same temperature
G io = i (T ) + RT ln f i o
(B)
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See section 4.3 (p. 133) for the definition of standard state:
Gases: pure species in ideal gas state at 1 bar (or 1 atm)
Liquids or solids: actual pure liquid or solid at 1 bar (or 1 atm)
Subtracting (B) from (A):

i _ G io = RT ln f i / f i o= RT ln a i

where a i is the activity of species i in solution.

ai

N.B.
the activity coefficient ( i = f i / x i f i )

o
Now, i = G i + RT ln a i & i i = 0 . 0

[ i G i0 + i RT
or

ln

( a i ) vi

or

ln a i ] = 0

=-

i G i0

[ i G i0 ] +

i
ln( a i )

RT

=0

where product over all species

RT

( a i ) vi = Exp[- i G i0 / RT ] = K

Goi = f(T) only, independent of pressure;

- RT ln K =

i G io

Chemical Engineering Thermodynamics II

= G o

K = the equilibrium constant = f(T) only

where G o the Standard Gibbs
Energy Change of Reaction.

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12-12

Note: For a specific species the standard state represented by G o must be the same
i
o
state represented by fi upon which the activity coefficient a i is specified
Case of Gases
The standard state is the ideal gas state of pure species at a pressure of 1 bar.
fio = 1 bar for each species in has phase reaction

f i
ai = o = f i
fi

Example:

K =

+ for product, - for reactant

v
(f i ) i

must be measured in bar

A + 2B + 3C D + 4 E
v
(f i ) i

-1
(f A )

-2

-3

=
( f B) ( f C) ( f D) ( f E)4
K =

4
(
f
)
(
f
)
or
D
E
K =
2
3
( f A ) ( f B) ( f C)
Case of liquids and solids
The usual standard state is pure liquid or pure solid at 1 bar and T of the system.

for this state, fio is not generally equal to 1 bar, thus

f i
ai =

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f io
12-13

Other Standard Property Change of Reaction

For the general property, M, we can write
Mo = i Mio
For example:

Ho = i Hio
CPo = i CPio

f(T) only

Relationship between Hio and Gio

Previously, we have derived:

H
= -T
RT

( G / RT )
]P
T

Therefore, in the standard state for species i:

H io

= - RT

d ( G io / RT )
= f(T)
dT

Why we removed
the partial derivative?

Summing over all species:

i H io = - RT 2
Chemical Engineering Thermodynamics II

d i G io
[
]
dT
RT
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12-14

H
But,

= - RT

d G o
[
]
dT RT

ln K = - G o / RT

Relationship between Ho and Go

d ln K
dT

H o
=
RT 2

Highly important
relation

Note: If Ho is negative (exothermic reactions) K as T

Special case:

Assuming Ho is independent of T,

H o 1 1
ln( K / K 1 ) = [ - ]
R T T1

A plot of lnK vs. 1/T should

be a straight line

See the next slide for plot of K versus 1/T for several reactions.

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Important Remarks:
This figure allows determination of K
at any temperature.
If K1 is known at T1 K can be
determined at any temperature for a
given Ho.
Slope of the lines are ve or +ve;
-ve for endothermic reactions
+ve for exothermic reactions

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Determination of Go
K can be determined from the previous figure at a given temperature for certain
reactions if Ho is constant ( f(T))
Another alternative method, when Ho = f(T), for determination of K is by using:

G o
= f(T)
ln K = RT

If an estimate of Go is available K can be determined

Go can be calculated by using the general relation:
(A)
G o = H o - TS o
Recalling (from Chapter 4 and 5):

H o

C
= H 0o + R P dT
T0 R

Recall that
Go = f(T)
Go = iGio
Ho = iHio
So = iSio
CPo/R = iGPio/R
T

or:

C
P dT
o
o
S = S0 + R
T
T0 R

Where H0o and S0o is the standard enthalpy and entropy changes at a reference
temperature T0, respectively.
Substituting in (A) gives:
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12-17

C
G o = H 0o + R P dT - T S 0o - RT
T0 R

C Po dT
R T
T0

According to (A):

o
o

G
0
0
S 0o =
T0
whence:
T
C Po
T
o
o
G = H 0 + R
dT - ( H 0o - G 0o ) - RT
T0
T0 R

Division by RT:

G o H 0o G 0o - H 0o 1
=
+
+
RT
RT
RT 0
T

C Po dT
R T
T0

T
C Po
C Po dT
R dT - R T
T0
T0
T

CPio/R = f(T) presented in Tables C.1-C.3 (pp. 657/658)

Go and Ho values are tabulated for many formation reactions at standard conditions
Gof298 and Gof298 (G0o and H0o) for a number of chemical compounds are listed
in Table C.4 (pp. 569/660)
Go/RT can be determined after determining the two integrals in the above
equations
Hence, K can be determined
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Example: calculate the equilibrium constant for the vapor-phase hydration of ethylene
at 145 & 320oC from data given in Appendix C
C2H4(g) + H2O(g) C2H5OH(g)

Data:

Species
C2H4(g)
H2O(g)
C2H5OH(g)

Ho298
-1 52510
-1 -241818
+1 -235100

Go298
68460
-228572
-168490

Ai
Bi 103 Ci 105
1.424 14.394 - 4.392
3.47
1.45
----3.518 20.001 - 6.002

where Cpi/R = Ai + Bi T + Ci T2

i H io, 298 = (-1)(52510) + (-1)(-241818)+(1)(-235100) = - 45792 J/mol

o
G 298
= i G io, 298 = (-1)(52510) + (-1)(-241818)+(1)(-235100) = - 45792 J/mol
C Po / R = i ( C Po ,i / R ) = i Ai + ( i Bi )T + ( i Bi )T 2

o
H 298
=

= [(-1)(1.424) + (-1)(3.47) + (1)(3.518)] + [(-1)(14.39) + (-1)(1.45) + (1)(20.0)]10-3T

+ [(-1)(-4.392) + (-1)(0.0) + (1)(-6.002)] 10-5T2
= -1.376 + 4.157 10-3T - 1.61 10-6T2

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@ T = 145oC = 418 K:
G o
- 45792
- 8378 + 45792
1
=
+
+
RT
(8 . 314 )( 418 )
(8 . 314 )( 298 )
418

418

[ -1.376 + 4.157 10 -3 - 1.61 10 -6 T 2 ] dT

298

418

[ -1.376 + 4.157 10 -3 - 1.61 10 -6 T 2 ]

298

G o
@T=
= 418 K:
= 1 .936
RT
o
G
K = exp(-1.936) = 0.1443
ln K =
RT

dT
T

145oC

Similarly @ T = 320oC = 593 K

Chemical Engineering Thermodynamics II

K = 0.00294

ChE 342

K with T
Exothermic rxn

12-20

Relationship between Equilibrium Constant and

Composition
Gas-Phase Reactions

For the gas phase reactions: a = f i = f

i
i
o

f
i
i
K = i ( fi )
But

( where fio = Po = 1 bar)

K = f(T) only

& f i = f (T , P , y i )
Reflects nonideality of the equilibrium mixture
This means that for a given T, the composition at eqm must change

with P in such away that ( fi ) i remains constant

Now,

f i = i y i P K = i ( i y i P ) i

Separate P term, K = i ( i y i ) i [ P ]

Or,

K P - = i ( i y i ) i

where = i

Relates K to e for a given T and P

(recalling that yi can be related to e)

Complicated problem because: i = f (T , P , y i ) iterative solution is needed

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12-21

Special cases:
For equilibrium mixture as an ideal solution
-
whence, K P = i ( i y i )

i = i

For sufficiently low pressure, equilibrium mixture behaves as an ideal gas

i = 1
whence,

K P = i ( y i )

T, P, and composition-dependent terms are

distinct are separate, thus solution for any one of
e, T or P given the other two is straightforward

Conclusion remarks
- Dependence of T can be seen through K:
If Ho +ve, ENDO rxn, K with T (yi)i for a fixed P e
rxn shifts to the right
If Ho -ve, EXO rxn,
K with T (yi)i for a fixed P e
rxn shifts to the left
- If (i) -ve, P @ constant T (yi)i rxn shifts to the right, e
If (i) +ve, P @ constant T (yi)i rxn shifts to the left, e
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Example: Consider the water-gas shift reaction

CO(g) + H2O(g) CO2(g) + H2(g)
Assuming ideal gas mixture, what is the fraction of the steam reacted in each of the
following cases: (Hint: fraction of steam converted = (ni0 nie)/ni0 = -ie/ni0)
(a) n0,H2O = 1, n0, CO = 1 mol, T = 1100 K, P = 1 bar

n0 = 2 mol

& = 0.0

From Fig. 13.2: @ 1/T = 1/(1100 K) = 9.09 10-4 for the above rxn lnK = 0 or K = 1.0

=1

K (1) = i ( y i ) = 1

y CO y H 2

=1
y CO y H 2 O

1-
y H 2 = e , y H 2O =
2
2

0 + e e
1-
= ,
y CO =
,
2+0
2
2
2

e
Substituting:
= 1 e = 0.5 fraction of steam reacts = 0.5
2
4 (1 - e ) / 4
y CO 2 =

(b) n0,H2O = n0, CO = 1 mol, T = 1100 K, P = 10 bar

Since = 0 P has no effect; e = 0.5

(c) n0,H2O = n0, CO = 1 mol, n0,N2 = 2 mol, T = 1100 K, P = 1 bar

As an inert N2 = 0
Chemical Engineering Thermodynamics II

Does not affect the calculations, e remains the same.

ChE 342

12-23

(d) n0,H2O = 2, n0, CO = 1 mol, T = 1100 K, P = 1 bar

n0 = 3 mol

y CO 2

e
= ,
3

y CO

1-
=
,
3

yH2

e
= ,
3

y H 2O

1-
=
3

e2
Substituting:
= 1 e = 0.667 fraction of steam reacts = 0.667/2 = 0.33
( 2 - e )(1 - e )
(e) n0,H2O = 1, n0, CO = 2 mol, T = 1100 K, P = 1 bar

n0 = 3 mol

y CO 2

e
= ,
2

y CO

e
2-
=
, yH2 = ,
3
3

y H 2O

1-
=
3

e2
Substituting:
= 1 e = 0.667 fraction of steam reacts = 0.667
( 2 - e )(1 - e )

(f) n0,H2O = 2, n0, CO = 1 mol, n0, CO2 = 1 mol, T = 1100 K, P = 1 bar

e
1-
1-
+

1
e
y H 2 = , y H 2O =
n0 = 3 mol
,
y CO 2 =
, y CO =
3
3
3
3
e (1 + e )
Substituting:
= 1 e = 0.0.33 fraction of steam reacts = 0.33

(1 - e ) 2

(g) n0,H2O = 1, n0, CO = 1 mol, T = 1650 K, P = 1 bar

From Fig. 13.2: @ 1/T = 1/(1650 K) lnK = -1.15 or K = 0.316

e2

2 = 0 . 316
(1 - e )

Chemical Engineering Thermodynamics II

e = 0.36
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12-24


Liquid-Phase Reactions
fi

For the liquid phase reactions: a i = o

fi

Then K remains as K = ( ai ) vi
For liquid:

f i = i x i f i

where fio 0

ai

Determination of fi/fio:

fi
fi
= o = i x i o
fi
fi

@ T and P: G i = i (T ) + RT ln f i

o
o
@ T and Po: G i = i (T ) + RT ln f i

Subtracting: G i - G io = RT ln f i / f i o
But:
dG i = Vi dP - S i dT
o
Integration at constant T from Po to P: G i - G i =
Substitute (B) in (A): RT ln

fi
o =
fi

Vi dP

(A)
P

Vi dP

(B)

Po

fi
For liquids Vi is weak function of P upon integration RT ln o = V i ( P - P o )
fi
fi
o
or
o = exp[ V i ( P - P ) / RT ]
fi
Chemical Engineering Thermodynamics II

Po

ChE 342

12-25

a i = i x i exp[ Vi ( P - P o ) / RT ]
and K = [ i x i exp{ Vi ( P - P o ) / RT }] i
Vi ( P - P o )
= ( i x i ) i [ e RT ]i
Vi i ( P - P o )
i
= ( i x i ) e RT

o
(
)
V
P
P
i
i
iVi ]
K = [ ( i x i ) ] exp[
RT
i

Special cases
At low P: exp[{Vi(P-Po)/RT}{iVi}] 1.0

K = ( i x i ) i
i

For the case of ideal solution:

K = ( x i ) i
i

(or when P Po)

Requires determination i, but i = f(xi)

xi can be found in this case iteratively.
i = 1.0
Law of Mass Action

xi = f(e)
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Example: Esterification of acetic acid in the liquid phase at 100oC and 1 atm:
CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)
Species i

Hof298 (J)

Gof298 (J)

CH3COOH(l), i=1
C2H5OH(l), i=2
CH3COOC2H5(l), i=3
H2O(l), i=4

-1
-1
+1
+1

-484,500
-277690
-480,000
-285,830

-389,900
-174,780
-332,200
-273,129

n0,acetic acid = n0,C2H5OH = 1 mol

Estimate the mole fraction of ethyl acetate (x3) at equilibrium. Assuming ideal solution and
that Ho does not change significantly with from 25oC to 100oC.

K = ( x i ) i
i

First, determine K:

i H io, 298
= i G io, 298

o
H 298
=
o
G 298

= 484,500 + 277,690 480,00 285,830 = - 3640 J

= 389,990 + 174,780 -332,200 273,129 = - 4650 J

lnK = -Go/RT
Chemical Engineering Thermodynamics II

K298 = exp[-4650/(8.314)(298)]
ChE 342

K298 = 6.527
12-27

For constant Ho, apply the following,

H o 1 1
ln( K / K 1 ) = [ - ]
R T T1

ln( K 373 / 6 .527 ) = -

1
3640 1
]
[
8 . 314 373 298

K373 = 4.859
Now:

x 4 x3
K =
x1 x 2

K = 4.859,

n0 = 2, = 0

1 - e
1 - e
n0 i + i e
x
=
,
x1 =
,
2
xi =
2
2
n0
e2 / 4

= 4 . 859 e = 0.6879
2
(1 - e ) / 4

x3 =

e
,
2

x4 =

e
,
2

x3 = 0.344
(see other examples in the textbook)

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12-28