CHEMICAL REACTION EQUILIBRIA

THE REACTION COORDINATE

APPLICATION OF EQUILIBRIUM CRITERIA TO CHEMICAL REACTIONS
THE STANDARD GIBBS-ENERGY CHANGE AND THE EQUILIBRIUM CONSTANT
EFFECT OF TEMPERATURE ON THE EQUILIBRIUM CONSTANT
EVALUATION OF EQUILIBRIUM CONSTANTS
RELATION OF EQUILIBRIUM CONSTANTS TO COMPOSITION
EQUILIBRIUM CONVERSIONS FOR SINGLE REACTIONS
THE REACTION COORDINATE
For general chemical reaction

1 A1 + 2 A2 + L 3 A3 + 4 A4 + L (13.1)

where i is stoichiometric coefficient

Ai is chemical formula.
i is stoichiometric number, and it is
positive (+) for product negative (-) for reactant
Example: CH 4 + H 2O CO + 3 H 2
the stoichiometric numbers are
CH4 = -1 H2O = -1 CO = 1 H2 = 3
The stoichiometric number for inert species is zero.
As the reaction in eq. (13.1) progresses, the changes in the
numbers of moles of species present are in direct proportion
to the stoichiometric numbers. E.g. If 0.5 mol CH 4
disappears, 0.5 mol H2O also disappears; simultaneously 0.5
2
mol CO and 1.5 mol H are formed.
 Applied to differential amount of reaction, this principle provides
the equations:
dn2 dn1 dn3 dn1
= = etc.
2 1 3 1
The list continues to include all species. Comparison yields
dn1 dn2 dn3 dn4
= = = = ...
1 2 3 4
All terms being equal, they can be identified collectively by a
single quantity representing an amount of reaction. A definition of
d is given by the equation:
dn1 dn2 dn3 dn4
= = = = ... d (13.2)
1 2 3 4

The general relation connecting the differential change dni with d

is therefore
dni = i d ( i = 1, 2, ..., N ) (13.3)
is called the reaction coordinate (also known as degree of
reaction or extent of reaction), characterizes the extent or degree
to which a reaction has taken place.

3
 Integration of eq. (13.3) from an initial unreacted state
where = 0 and ni = nio to a state reached after an amount
of reaction gives ni dn = d

ni 0 i
i 0

ni = n i 0 + i ( i = 1, 2, ..., N ) (13.4)
or
Summation over all species yields
n = ni = ni 0 + i
i i i

n = n0 +
or
n ni n0 ni 0 i
where i i i

Thus the mole fractions of ithe

ni nyi 0i + species present are related
yi = = (13.5)
to by n n0 +

4
EXAMPLE 13.1
For a system in which the following reaction occurs,

CH 4 + H 2O CO + 3 H 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 .

5
EXAMPLE 13.2
Consider a vessel which initially contains only n0 mol of water
vapor. If decomposition occurs according to the reaction,
H 2O H 2 + 21 O2
find expressions which relate the number of moles and the
mole fraction of each chemical species to the reaction
coordinate .
Solution: = -1 + 1 + 21 = 21
For the reaction,
i = ni 0 + i of eqs.
nApplication
O = n0 -
nH(13.4) nH = yields
and (13.5) nO =
1
2 2 2 2

ni ni 0 + i n - 1

yi = = yH 2 O = 0 1 yH 2 = yO2 = 2
n n0 + n0 + 2 n0 + 21 n0 + 21

n0 - n H2O n0 - ( nof
The fractional decomposition 0 - )
water vapor is
= =
n0 n0 n0

When n0 = 1, is directly related to the fractional 6

Multireaction Stoichiometry
For multireaction, i,j designates the stoichiometric number of
species i in reaction j.
The general relation, eq. (13.3) becomes
dni = i , j d j ( i = 1, 2, ..., N )
j

Integration from ni = ni0 and j = 0 to ni and j gives

n i = ni 0 + i, j j ( i = 1, 2, ..., N ) (13.6)
j
Summing over all species yields

n = ni 0 + i , j j = n0 + i , j j

i i j j i
The definition of a total stoichiometric number
a single reaction has its counterpart here in the definition:
(
ii )
for

j i, j thus n = n0 + j j
Combination iof this last equation withj eq. (13.6) gives the
mole fraction
ni 0 + j i , j j
yi = ( i = 1, 2, ..., N ) (13.7)
n0 + j j j 7
EXAMPLE 13.3
Consider a system in which the following reactions occur:

CH 4 + H 2O CO + 3 H 2 ( 1)
CH 4 + 2 H 2O CO2 + 4 H 2 ( 2)
where the numbers (1) and (2) indicate the value of j, the
reaction index. If there are present initially 2 mol CH4 and 3
mol H2O, determine expressions for the yi as functions of 1
and 2.

Solution:
The stoichiometric numbers i,j can be arrayed as follows:
i= CH4 H2O CO CO2 H2
j j
1 -1 -1 1 0 3 2
2 -1 -2 0 1 4 2
8
Application of eq. (13.7) gives
ni 0 + j i , j j
yi = ( i = 1, 2, ..., N )
n0 + j j j

2 - 1 - 2 1
yCH4 = yCO =
5 + 2 1 + 2 2 5 + 2 1 + 2 2
3 - 1 - 2 2 2
yH 2 O = yCO2 =
5 + 2 1 + 2 2 5 + 2 1 + 2 2
3 1 + 4 2
yH 2 =
5 + 2 1 + 2 2

9
APPLICATION OF EQUILIBRIUM
CRITERIA TO CHEMICAL REACTIONS
Total Gibbs energy of a closed system at constant T and P
must decrease during an irreversible process and
equilibrium is reached when Gt attains its minimum value.
At this equilibrium state,
( )
dG t =0
T ,P

If a mixture is not in equilibrium, any reaction at constant T

and P must lead to a decrease in the total Gibbs energy of
the system.

10
 Fig. 13.1 shows the relation of Gt and . The arrows along
the curve indicate the directions of changes in (Gt)T,P. The
reaction coordinate, has its equilibrium value e at the
minimum of the curve.
This figure indicates two
distinctive features of the
equilibrium state for given T
and P,
a) Total Gibbs energy Gt is a
minimum.
b) Its differential is zero.

(For a single chemical

reaction)

11
 THE STANDARD GIBBS-ENERGY CHANGE
AND THE EQUILIBRIUM CONSTANT

Equation (11.2) provides an expression for the total differential of the

Gibbs energy:

d ( nG ) = (nV )dP - (nS )dT + mi dni (11.2)

i

If changes in the mole numbers ni occur as the result of a single

chemical reaction in a closed system, then by eq. (13.3) each dni may
be replaced by the product id. Eq. (11.2) then becomes
d ( nG ) = (nV )dP - (nS )dT + i mi d
i

Because nG is a state function, the right side of this equation is an

exact differential expression,
( nG )
( G t )

i mi =

=


i T ,P




T ,P

i mi
The quantity i represents, in general, the rate of change of total
Gibbs energy of the system with respect to the reaction coordinate at
constant T and P. 12
 Fig. 13.1 shows that this quantity is zero at the equilibrium
state. A criterion of chemical reaction equilibrium is
therefore
i mi = 0
i
(13.8)

Recall the definition

mi = of
Gi (the
T ) +fugacity
f i of a species in solution:
RT ln (11.46)

In addition, eq. (11.31) may be written for pure species i in

its standard state at the same temperature:
Gio = G i ( T ) + RT ln f io

The difference between these two f equations is

mi - Gio = RT ln io (13.9)
fi

13
 Combining eq. (13.8) with eq. (13.9) to eliminate mi gives for
the equilibrium state of a chemical reaction:

i
i

G

o
i + RT ln f f o = 0
i i ( )
or
( )
i
iG + RT ln fi fio
i
o
i
i
=0

( )
i
or ln f f o
= RT
Go
i i i
-
i i
i

where i signifies the product over all species i.

In exponential form, this equation becomes

( )
i
f f o =K (13.10)
i i
i

where the definition of K and its logarithm are given by

-DG o
K exp (13.11a)
RT
-DG o
ln K = (13.11b)
RT
14
 Also by definition,
DG o i i Gio (13.12)

Gio, DGo and K are functions of temperature.

K is called the equilibrium constant for the reaction;
iiGio, represented by DGo, is called the standard
Gibbs-energy change of reaction.
The function DGo iiGio in eq. (13.12) is the difference
between the Gibbs energies of the products and reactants
when each is in its standard state as a pure substance at
the standard state pressure, but at the system temperature.
Other standard property changes of reaction are similarly
defined. For general property M:
DM o i M io
i

The relation between the standard heat of reaction and the

standard Gibbs energy change of reaction is
d ( DG o RT )
DH = - RT
o 2
(13.13)
dT
15
EFFECT OF TEMPERATURE ON
THE EQUILIBRIUM CONSTANT
Because the standard state temperature is that of the equilibrium
mixture, the standard property changes of reaction, such as DGo and DHo,
vary with the equilibrium temperature.
The dependence of DGo on T is given by eq. (13.13), which may be
rewritten as
(
d DG o RT ) = -DH o

dT RT 2

In view of eq. (13.11b), this becomes

d ln K DH o
= (13.14)
dT RT 2
If DHo is negative, i.e., if the reaction is exothermic, the equilibrium
constant decreases as the temperature increases. K increases with T for
endothermic reaction.
If DHo is assumed independent of T, integration of eq. (13.14) from T to T
leads to the simple result:
K DH o 1 1 (13.15)
ln ' = - - '
K R T
T
A plot of ln K vs. the reciprocal of absolute temperature is a straight line.16
17
 Effect of temperature on equilibrium constant is based on
the definition of the Gibbs energy at standard state:
Gio = H io - TSio
Multiply by i and summation over all species gives
G = H
i
i
o
i
i
i
o
i -T i Sio
i

As a result of the definition of a standard property change

of reaction, this reduces to (13.16)
DG o = DH o - T DS o

The standard heat of reaction is related to temperature:

T DC p
o

DH = DH 0 + R
o o
dT (4.18)
T0 R

The temperature dependence of the standard entropy

is:o = C o dT
change of reactiondS
i Pi
T
Multiply by i and summation over all species gives
dT
d DS o = DC Po
T
18
 Integration gives
DC Po dT
T
DS = DS + R
o o
0 (13.17)
T0 R T
where DSo and DS0o are the standard entropy changes of
reaction at temperature T and at reference temperature T0.
Eqs. (13.16), (4.18) and (13.17) are combined to yield
T DC T DC
o o
DG = DH 0 + R
o o P
dT - T DS0 - RT
o P
dT
T0 R T0 R
However,
DH 0o - DG0o
DS =o
0
T0
Hence,
T DC T DC
o o
T
DG = DH - ( DH 0 - DG0 ) + R P dT - RT P dT
o o
0
o o

T0 T0 R T0 R

Finally, division by RT yields

DG o DG0 - DH 0 DH 0 1 T DC P o
o o o
T DC
o
P dT

RT T
= + + dT - (13.18)
RT RT0 T0 R T0 R T
19
 The first integral of eq. (13.18) is
DC Po DB 2 2 DC 3 3 t -1
DD
( ) ( )
T
dT = ( D A ) T ( t - 1 ) + T t - 1 + T t - 1 + (4.19)
T0
0 0 0
T0 R 2 3 t

T
where t
T0

OR
DC Po DB 2 DC 3 1 1
( ) ( )
T
dT = ( DA ) ( T - To ) + T - T0
2
+ T - T0
3
- D D -
T0 R 2 3 T To

The second integral of eq. (13.18) is

DC Po dT
T DD
t +1
= DA lnt +
DBT0 + DCT0 + 2 2
2

( t - 1) (13.19)
T0 R T t T0
2

OR
T
DC Po dT T DC 2 DD 1 1
R T
= D A ln
T
+ DB ( T - T0) +
2
( T - T0 )
2
-
2
2
T
-
T 2
T0 0 o
20
 DGo/RT(= - ln K) as given in eq. (13.18) is readily calculated
at any temperature from the standard heat of reaction and
the standard Gibbs energy change of reaction at a reference
temperature (usually 298.15 K).
Factor K may be organized
K = K K Kinto three terms:
0 1 2

-DG0o
K 0 exp (13.21)
RT
0
DH 0o T0
(13.22)
K 1 exp 1-

0 T
RT
1 TDC Po T DC dT
o
(13.23)
K 2 exp -
T

T0 R
dT +
T0 R
P

T

21
 EVALUATION OF EQUILIBRIUM
CONSTANT
EXAMPLE 13.4
Calculate the equilibrium constant for the vapor phase
hydration of ethylene at 145oC (418.15 K) and at 320oC
(593.15 K) from data given in App. C.

Solution:
The chemical reaction:
C 2 H 4 ( g ) + H 2O ( g ) C 2 H 5OH ( g )

vi A B (x10-3) C (x10-6) D Ho298 Go298

From Table C.1 and C.4: (x105) (J/mol) (J/mol)
C2H5O 1 3.518 20.001 -6.002 - -235100 -168490
H
C2H4 -1 1.424 14.394 -4.392 - 52510 68460
H2O -1 3.470 1.450 - 0.121 -241818 -228572
22
 DA = i Ai = - 1.376
i

DB = i Bi =4.157 10-3
i

DC = i C i = - 1.610 10-6
i

DD = i Di = - 0.121 105
i

DH 298
o
= i H io,298 = -45792 Jmol -1
i

DG298
o
= i Gio,298 = - 8378 Jmol -1
i

For T = 418.15 K, values of integrals in eq. (13.18) are

DC Po
T TDC Po dT
dT = -23.121 eqn. ( 4.19 ) = -0.0692 eqn. ( 13.19 )
T0 R T0 R T
Substitute into eq. (13.18) for a reference temperature of 298.15
K gives:
DG o DG0 - DH 0 DH 0 1 T DC P o
o o o
T DC
o
dT
= + + dT - P (13.18)
RT RT0 RT T T0 R T0 R T
DG418.15
o
-8378 + 45792 -45792 -23.121
= + + + 0.0692 = 1.9356
RT ( 8.314 )( 298.15 ) ( 8.314 )( 418.15 ) 418.15 23
 For T = 593.15 K,
T DC
o

T0 R
P
dT = 22.632

T DC dT
o

T0 R
P

T
= 0.0173

DG593.15
o
-8378 + 45792 -45792 22.632
= + + - 0.0173 = 5.8286
RT ( 8.314 ) ( 298.15 ) ( 8.314 ) ( 593.15 ) 593.15

Finally, by eq. (13.11b)

-DG o
ln K =
RT

At 418.15 K, ln K = -1.9356 and K = 1.443 x 10-1

At 593.15 K, ln K = -5.8286 and K = 2.942 x 10-3

Alternative solution by using eq. (13.21), (13.22) and (13.23).

24
RELATION OF EQUILIBRIUM
CONSTANTS TO COMPOSITION
Gas phase reactions
The standard state for a gas is the ideal gas state of the
pure gas at the standard state pressure Po of 1 bar.
Because the fugacity of ideal gas is equal to its pressure, fio
= Po for each species i. Therefore forf i gas f P o reactions
f io =phase
i
and eq. (13.10) becomes

f
( f )
i
i
i fio =K (13.10) io = K
P
i
(13.25)
i

This eq. relates K to fugacities of the reacting species as
they exist in the real equilibrium mixture. These fugacities
reflect the non-idealities of the equilibrium mixture and
are functions of temperature, pressure and composition.
The fugacity is related to the fugacity coefficient by eq.
(11.52):
f i = fi yi P

25
 Substitute into eq. (13.25) provides an equilibrium expression
displaying the pressure and the composition:
-

( y f )
i P
i i = o K (13.26)
i P

where
and
i i P is the standard state pressure of 1 bar.
o

The yis may be eliminated in favor of the equilibrium value of

the reaction coordinate e. For fixed temperature eq. (13.26)
If P is specify, can be solved.
relates e to fP. can be
i e
evaluated by using eq. (11.63 or 11.64). fi
If the equilibrium mixture is an ideal -
solution, then each
becomes fi , then eq. (13.26) P
i becomes
( y f
i i ) = P o K
(13.27)
i

Each fi for a pure species can be evaluated from a generalized

fi = 1
correlation.
For pressure sufficiently low or temperatures
-
sufficiently high,
the equilibrium mixture behaves P essentially
as an ideal gas.
( )
i

Each y
and eq. (13.26)
i
i =
reduces

K
P o to: (13.28)
26
 Some conclusions based on eq. (13.28) that are true in general:
According to eq. (13.14), the effect of temperature on the
equilibrium constant K is determined by the sign of DHo.

d ln K DH o
= (13.14)
dT RT 2
When DHo is positive, i.e., when the standard reaction is endothermic,
an increase in T results in an increase in K. Eq. (13.28) shows that an
increase in K at constant P results in an increase in i(yi)vi; this
implies a shift of the reaction to the right and an increase in e.
When DHo is negative, i.e., when the standard reaction is exothermic,
an increase in T causes a decrease in K and a decrease in i(yi)vi at
constant P. This implies a shift of reaction to the left and a decrease
in e.
If the total stoichiometric number v (ivi) is negative, eq. (13.28)
shows that an increase in P at constant T causes an increase
in i(yi)vi , implying a shift of the reaction to the right and an
increse in e .
If v is positive, an increase in P at constant T causes a
decrease in i(yi)vi , implying a shift
- of the reaction to the left
P
and a decrease in e(.y ) = K
i
i
i P o

(13.28)
27
Liquid phase reactions
For a reaction occurring in the liquid phase,

( )
i
f f o =K
i i (13.10)
i

Standard state for liquid fio is the fugacity of pure liquid i at

the temperature of the system and at 1 bar.
According to eq. (11.90),
f
f = g x f gi i (11.90)
i i i i
xi f i
The fugacity ratio can be expressed as
f g i xi f i f i
i
= = g x
i i o (13.29)
f io fio f i
Because the fugacities of liquids are weak function of
pressure, the ratio fi/fio is often taken as unity.
For pure liquid i, eq. (11.31) is written for temperature T and
pressure P, and for the same temperature T but for
Gi G i (PTo). + RT ln f i
standard state pressure
Gi o G i ( T ) + RT ln f i o
28
 The difference between these two equations is
f
Gi - Gio = RT ln io
fi
Integration of eq. (6.10) at constant T for the change of
state of pure liquid i from Po to P yields
P
Gi - Gio = o
Vi dP
P
As a result,
fi P
RT ln o = V dP
fi Po i

Because Vi changes little with pressure for liquids (and

solids), integration from Po to P gives
f i Vi ( P - P )
o

ln o = (13.30)
fi RT
With eq. (13.29) and (13.30), eq. (13.10) may be written as

(
P o - P ) ( V )
( x g )
i
i i = K exp
RT

i
i i

(13.31)
i

29
 Except for high pressure, the exponential term is close to
unity and may be omitted. Then,

( xig i )
i
=K (13.32)
i

If the equilibrium mixture is an ideal solution, then gi is

unity and eq. (13.32) becomes
( xi )
i
=K (13.33)
i

30
EQUILIBRIUM CONVERSIONS
FOR SINGLE REACTIONS
EXAMPLE 13.5
A water gas shift reaction,
CO ( g ) + H 2O ( g ) CO2 ( g ) + H 2 ( g )

is carried out under the different sets of conditions

described below. Calculate the fraction of steam reacted in
each case. Assume the mixture behaves as an ideal gas.

31
(a) The reactants consist of 1 mol of H2O vapor and 1 mol of
CO. The
temperature is 1100 K and the pressure is 1 bar.
For the given reaction at 1100 K, 104/T = 9.05, and from
Figure 13.2,ln=
K= = 1 +1 -1-1 = 0
i i 0 and K = 1.

Because
P the reaction
- mixture is an ideal
1 gas,0 eq.
bar
( ) (
)(
)
-1
( yi ) = applies
i 1 1
( yCO ) yH2O ( 1)
-1
(13.28) o
K yCO2 yH2 =
i P 1 bar
yH2 yCO2
=1 (A)
y y CO H 2O

ni ni 0 + i 1 - e 1 - e e e
yi = By
= eq. (13.5), yCO = yH 2 O = yCO2 = yH 2 =
n n0 + 2 2 2 2

e2
Substitute into eq. (A) = 1gives
or e = 0.5
( 1 - e )
2

noH2O - nH2O 1 - ( 1 - )
Therefore the fraction= of the steam = = 0.5
that reacts is
noH2O 1 32
(b) Same as (a) except that the pressure is 10 bar.
(c) Same as (a) except that 2 mol of N2 is included in the
reactants.
(d) The reactants are 2 mol of H2O and 1 mol of CO. Other
conditions are the same as in (a).
(e) The reactants are 1 mol of H2O and 2 mol of CO. Other
conditions are the same as in (a).
(f) The initial mixture consists of 1 mol of H2O, 1 mol CO
and 1 mol of CO2. Other conditions are the same as in (a).
(g) Same as (a) except that the temperature is 1650 K.

33
EXAMPLE 13.6
Estimate the maximum conversion of ethylene to
ethanol by vapor-phase hydration at 250oC (523.15 K)
and 35 bar for an initial steam to ethylene ratio of 5.
Assume the reaction mixture is an ideal solution.

Solution:
The calculation of K for this reaction is treated in
Example 13.4.
At T = 523.15 K, K = 10.02 x 10-3
For ideal solution, P
-

( y f )

i i
i
= o K (13.27)
i P
i i = 1 - 1 - 1 = -1
Because y f this equation
P
becomes
EtOH EtOH

yC2 H4 fC2 H4 yH2OfH2O

-3
(
= o 10.02 10
P
) ( A)
34
 Fugacity coefficients are evaluated by eq. (11.68).
Pr 0 P
ln f =
Tr
( B + B1 ) or f = exp r ( B 0 + B1 )
Tr

0.422 0.172
B 0 = 0.083 - and B1 = 0.139 -
Tr1.6 Tr4.2

The results are summarized in the following table:

Tc/K Pc/bar i Tri Pri B0 B1 fi
C2H4 282. 50.40 0.087 1.853 0.694 - 0.126 0.977
3 0.074
H2O 647. 220.5 0.345 0.808 0.159 - - 0.887
1 5 0.511 0.281
EtOH 513. 61.48 0.645 1.018 0.569 - - 0.827
Substitute
9 values of fi and P = 35 bar into eqn.
0.327 0.021(A)
gives:
yEtOH ( 0.997 ) ( 0.887 ) 35 10.02 10-3 = 0.367
yC2 H4 yH2O
=
( 0.827 )
1
( ) ( B)

35
By eqn. (13.5),
1 - e 5 - e e
yC2 H 4 = yH 2 O = yEtOH =
6 - e 6 - e 6 - e
Substitute these into eqn. (B) yields:

e ( 6 -e )
= 0.367 or e2 - 6 e + 1.342 = 0
( 5 - e ) ( 1 - e )

The solution for the smaller root is e = 0.233.

Therefore the maximum conversion of ethylene to
ethanolnis - n
oC 2 H 4 C2 H4 1 -( 1 - )
= = = 0.233 = 23.3%
noC2 H4 1

36
EXAMPLE 13.7
In a laboratory investigation, acetylene is catalytically
hydrogenated to ethylene at 1120oC (1393.15 K) and 1 bar.
If the feed is an equimolar mixture of acetylene and
hydrogen, what is the composition of the product stream at
equilibrium?

Solution:
The required reaction is obtained by addition of the two
formation reactions written as follows:
C 2 H 2 2C + H 2 ( I)
2C + 2 H 2 C 2 H 4 ( II )

The sum of reactions

C 2 H 2 +(I)
H 2and
C(II) is the hydrogenation
2H4
reaction:
o o
DG o = DGI + DGII
- RT ln K = - RT ln K I - RT ln K II or K = K I K II
37
Also,
Data for both reactions (I) and (II) are given by Fig. 13.2. For
1120oC (1393.15 K), 104/T = 7.18, the following values are
read from the graph:
ln K I = 12.9 K I = 4.0 105
ln K II = -12.9 K II = 2.5 10-6

Therefore, K = KIKII = 1.0

At this temperature and pressure of 1 bar, assume ideal
gases.
P
-
yC2 H4
By eq. (13.28),
( yi ) = o K

i
i

P yH2 yC2 H2
=1

1 - e e
y
On the basis= yCof = and y
2 H 2one mole initially of each=
2 -reactant, eq.
H2
2 - e
C2 H 4
e
(13.5) gives
e ( 2 - e )
=1
( 1 - e )
2

Therefore,

38
 The equilibrium composition of the product gas is then
1 - 0.293 0.293
yH2 = yC2 H2 = = 0.414 and yC2 H4 = = 0.172
2 - 0.293 2 - 0.293

39
EXAMPLE 13.8
Acetic acid is esterified in the liquid phase with ethanol at
100oC (373.15 K) and atmospheric pressure to produce
ethyl acetate and water according to the reaction:
CH 3COOH ( l ) + C 2 H 5OH ( l ) CH 3COOC 2 H 5 ( l ) + H 2O ( l )

If initially there is one mole each of acetic acid and ethanol,

estimate the mole fraction of ethyl acetate in the reacting
mixture at equilibrium.

Solution:
DHo298 (J) DGo298 (J)
CH3COOC2H5 -480 000 -332 000
H2O -285 830 -237 130
CH3COOH -484 500 -389 900
C2H5OH -277 690 -174 780
40
 By eq. (13.11b),
DH 298
o
= i i H io
= ( 1 ) ( -480000 ) + ( 1 ) ( -285830 ) + ( -1 ) ( -484500 ) + ( -1 ) ( -277690 ) = -3640 J
DG298
o
= i i Gio
= ( 1 ) ( -332200 ) + ( 1 ) ( -237130 ) + ( -1 ) ( -389900 ) + ( -1 ) ( -174780 ) = -4650 J

For small temperature change from 298.15 K to 373.15 K, eq.

(13.15) is adequate for estimation of K. Therefore,

-DG298
o
4650
ln K 298 = = = 1.8759 or K 298 = 6.5266
RT ( 8.314 )( 298.15 )

K 373 -DH 298

o
1 1
or ln = -
K 298 R
373.15 298.15
and
K 373 3640 1 1
ln = - = -0.2951
6.5266 8.314
373.15 298.15

K 373 = ( 6.5266 ) ( 0.7444 ) = 4.8586

41
For the given reaction, eq. (13.5), with x replacing y, yields
1 - e
x AcH = x EtOH = x EtAc = x H 2O = e
2 2
Because the pressure is low, eq. (13.32) is applicable. In the
absence of data for activity coefficients, assume the
reacting species form an ideal solution. In this case eq.
(13.33) i is employed, giving
( xi ) = K (13.33) K = x EtAc x H2O
i
x AcH x EtOH
2

4.8586 = e
1 - e

Solution yields
e = 0.6879 and x EtAc = 0.6879/2 = 0.344

42
REFERENCES
Smith, J.M., Van Ness, H.C., and Abbott, M.M. 2005.
Introduction to Chemical Engineering
Thermodynamics. Seventh Edition. Mc Graw-Hill.
http://www.chem1.com/acad/webtext/thermeq/TE4.html
http://www.chem1.com/acad/webtext/thermeq/TE5.html

43
PREPARED BY:
MDM. NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
norasmah@salam.uitm.edu.my
03-55436333/019-2368303