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
 Course Learning Outcomes
The student should be able to :
Describe the chemical reaction equilibria and its
importance in chemical engineering.
Derive excess Gibbs energy equation to evaluate
equilibrium constant (K) for a given reaction and
conditions.
Evaluate the equilibrium constant from diagram or excess
Gibbs energy for given reaction and conditions
Apply the equilibrium constant to determine equilibrium
conversion and to calculate reaction mixture equilibrium
compositions.
Calculate the equilibrium conversions for single reactions
 THE REACTION COORDINATE
General chemical reaction:
v1 A1 v2 A2 ... v3 A3 v4 A4 ...
where;
vi stoichiometric coefficien t
Ai chemical formula
vi stoichiometric number
By the sign convention:
Positive (+) for a product Negative (-) for a reactant
 For reaction:
CH4 H2O CO 3H2

the stoichiometric numbers, i are

CH 1
4
H O 1
2
CO 1 H 3
2

As the reaction progresses, the changes in the

numbers of moles of species present are in direct
proportion to the stoichiometric numbers. This
principle provides the equations:
dn2 dn1 dn3 dn1
etc.
2 1 3 1
The list continues to include all species.
dn1 dn2 dn3 dn4
...
1 2 3 4 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, characterizes the extent or

degree to which a reaction has taken place.

5
 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 n
dni i d
i

ni 0 0
or
ni ni 0 i i 1, 2, ..., N (13.4)

Summation over all species yields

n ni ni 0 i
i i i
or n n0
where
n ni n0 ni 0 i
i i i

Thus the mole fractions yi of the species present are related to

by ni ni 0 i
yi (13.5)
n n0 6
Example 13.1
For a system in which the following reaction occurs,
CH4 H2O CO 3H2
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 .
Solution:
For the reaction,
For the given numbers of moles of species initially
present,
i 1 1 1 3 2
i

n0 ni 0 2 1 1 4 8
i
7
Equation (13.5) yields
ni ni 0 i
yi
n n0

2 1
yCH4 y H2O
8 2 8 2
1 4 3
yCO y H2
8 2 8 2

The mole fractions of the species in the reacting mixture

are seen to be functions of the single variable .

8
Example 13.2
Consider a vessel which initially contains only n0 mol of
water vapor. If decomposition occurs according to the
reaction,
H2O H2 21 O2

find expression which relate the number of moles and

the mole fraction of each chemical species to the
reaction coordinate .
Solution:
For the reaction,
1 1 21 1
2

9
 ni ni 0 i (13.4)
ni ni 0 i
yi (13.5)
n n0

Application of eqs. (13.4) and (13.5) yields

nH O n0 nH nO 21
2 2 2

n0 1

y H2O y H2 yO2 2
n0 21 n0 1
2 n0 21
The fractional decomposition of water vapor is
n0 nH O n0 n0
2

n0 n0 n0

Thus, when n0 = 1, is directly related to the

fractional decomposition of the water vapor.

10
 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

ni 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

11
 The definition of a total stoichiometric number i i for
a single reaction has its counterpart here in the definition:
j i , j whence n n0 j j
i j

Combination of this last equation with eq. (13.6) gives the

mole fraction
ni 0 j i , j j
yi i 1, 2, ..., N (13.7)
n0 j j j

12
Example 13.3
Consider a system in which the following reactions occur:
CH4 H2O CO 3H2 1
CH4 2H2O CO2 4H2 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 13
 ni 0 j i , j j
yi i 1, 2, ..., N
n0 j j j
(13.7)

Application of eq. (13.7) gives

2 1 2 1
y CH4 yCO
5 21 2 2 5 21 2 2
3 1 2 2 2
y H2O yCO2
5 21 2 2 5 2 1 2 2
31 4 2
y H2
5 21 2 2

The composition of the system is a function of independent

variables 1 and 2 .

14
 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,

dGt
T ,P
0

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.
 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)

16
 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 i 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 i d .
Eq. (11.2) then becomes
d nG (nV )dP (nS )dT i i d
i

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

is an exact differential expression,
nG
Gt
i i i
T ,P T ,P
 In general, the quantity i
i i represents, the rate of change
of total Gibbs energy of the system with respect to the
reaction coordinate at constant T and P.
Fig. 13.1 shows that this quantity is zero at the equilibrium
state. A criterion of chemical reaction equilibrium is therefore

i
i i 0 (13.8)

Recall the definition of the fugacity of a species in solution:

i i T RT ln fi (11.46)

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

standard state at the same temperature:
Gio i T RT ln fi o
A standard state is a particular state of a species at temperature T and at specified
conditions of pressure, composition and physical condition e.g. gas, liquid or solid.
18
 The difference between these two equations is
fi
i G RT ln o
i
o
(13.9)
fi

Combining eq. (13.8) with eq. (13.9) to eliminate i gives

for the equilibrium state of a chemical reaction:
i i

i
G o
RT

ln f fo 0
i i
or

i
i

i
G RT i i
i
o
ln f fo
i
0
or

i Go
ln fi fi

o
RTi i i

i
where i signifies the product over all species i.

19
 In exponential form, this equation becomes

i
fi fi o K (13.10)
i

where the definition of K and its logarithm are given by

G o (13.11a)
K exp
RT
G o (13.11b)
ln K
RT
Also by definition,
Go i iGio (13.12)

Go and K are functions of temperature.

20
 K is called the equilibrium constant for the reaction;
ii Gio, represented by Go, is called the standard
Gibbs-energy change of reaction.
The function Go 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:
M o i Mio
i

21
 For example, the relation between the standard heat of
reaction and the standard Gibbs energy change of reaction is
developed from Eq. (6.39) written for species i in its standard
state: o
d (Gi / RT )
H RT
i
o 2

dT

Then, multiplication of both sides of this equation by vi and

summation over all species gives
d (i vi Gio / RT )
i i
v
i
H o
RT 2

dT
Therefore, using Eq.4.14 and Eq. 13.12, relation written as
Eq.(4.14)
H RT
o 2
d
G o
RT (13.13)
H vi H
o
i
o
dT
i
 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 Go and Ho, vary with the equilibrium
temperature.
The dependence of Go on T is given by eq. (13.13),

d Go RT H o

dT RT 2
In view of eq. (13.11b), this becomes
d ln K H o (13.14)

dT RT 2
If Ho is negative, i.e., if the reaction is exothermic, the
equilibrium constant decreases as the temperature increases.
K increases with T for endothermic reaction.
23
 If Ho is assumed independent of T, integration of eq. (13.14)
from T to T leads to the simple result:
K H o 1 1 (13.15)
ln ' T T '
K R

A plot of ln K vs. (1/T) the reciprocal of absolute temperature

is a straight line.

24
A plot of ln K vs. (1/T) for a number of common reactions

25
 The rigorous development of the effect of temperature on
equilibrium constant is based on the definition of the Gibbs
energy at standard state:
Gio Hio TSio
Multiply by i and summation over all species gives
i i i i i i

i
G o

i
H o
T S o

As a result of the definition of a standard property change of

reaction, this reduces to
Go H o T So (13.16)
The standard heat of reaction is related to temperature:
T Cpo
H o H0o R dT (4.18)
T0 R

26
 The temperature dependence of the standard entropy
change of reaction is:
dT
dSio CPoi
T
Multiply by i and summation over all species gives
dT
d S o CPo
T
Integration gives
TCPo dT
S S R
o o
0 (13.17)
T0 R T
where So and S0o are the standard entropy changes of
reaction at temperature T and at reference temperature T0.

27
 Eqs. (13.16), (4.18) and (13.17) are combined to yield
CP o
T T C
o
G H R
o o
0 dT T S0 RT
o P
dT
T0 R T0 R
However,
H o
G o
S0o 0 0

T0
Hence,
T C T C
o o
Go H0o
T
T0

H0o G0o R
T0 R
P
dT RT
T0 R
P
dT

Finally, division by RT yields

G0o H 0o H0
o
G o
1 CP o
T T C
o
P dT
RT

RT0

RT T
T0 R dT T0 R T
(13.18)

28
 The first integral of eq. (13.18) is
CPo B 2 2 C 3 3 D 1

T
T0 R dT A T0 1
2
T0 1
3
T0 1
T0
(4.19)
The second integral is
CPo dT D 1
T0 R T A ln BT0 CT0 2T0 2 1 (13.19)
T
2

where
T

T0

29
 Go/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 into three terms:
K K0K1K2 (13.20)

G0o (13.21)
K 0 exp
RT 0

H0o T0
K1 exp 1 (13.22)
RT0 T
1 T CPo T C dT
o
K 2 exp dT P
(13.23)
T T0 R T0 R T

30
 Temperature dependence of the heat capacity (eq. 4.4):
CP
A BT CT 2 DT 2
R
The expression for K2 becomes:

2 2 2
1 1
1 1 1 2 1 D 1
K 2 exp A ln 2 BT CT 2



0
6
0
2 T0
2
2


(13.24)

31
 EVALUATION OF EQUILIBRIUM
CONSTANTS
Values of Go for many formation reactions are tabulated in
standard references.
The reported values of Gof are not measured experimentally,
but are calculated by Eq. 13.16.
Go H o T So
Values of Gof298 and Hof298 for a limited number of chemical
compounds are listed in Table C.4 of App. C. These for a
temperature of 298.15K.
Values of Go for other reactions are calculated from
formation-reaction values.
In more extensive compilations of data, values of Gof and
Hof are given for a wide range of temperature. When data is
lacking, methods of estimation are available.
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:
First determine the values for A, B, C and D for the
reaction
C2H4 g H2O g C2H5OH g

= (C2H5OH) (C2H4) (H2O)

From Table C.1:
A = 3.518 1.424 3.470 = -1.376
B = (20.001 14.394 1.450) x 10-3 = 4.157 x 10-3
C = (-6.002 +4.392 0) x 10-6 = -1.610 x 10-6
D = (-0 0 0.121) x 105 = -0.121 x 105
33
 Values of Ho298 and Go298 at 25oC (298.15 K) for the
hydration reaction are found from Table C.4:
H298
o
235100 52510 241818 45792 Jmol-1

G298
o
168490 68460 228572 8378 Jmol-1
For T = 418.15 K, values of integrals in eq. (13.18) are
T CPo
T0 R dT 23.121
T C dT
o

T0 R P T 0.0692
Substitute into eq. (13.18) for a reference temperature of
298.15 K gives:
G418
o
8378 45792 45792 23.121
0.0692 1.9356
RT 8.314 298.15 8.314 418.15 418.15

34
 For T = 593.15 K,
T CPo
T0 R dT 22.632
T C dT
o

T0 R P T 0.0173
G593
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)

G 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 (13.24).

35
 RELATION OF EQUILIBRIUM CONSTANTS TO COMPOSITION
EQUILIBRIUM CONVERSIONS FOR SINGLE REACTIONS
 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 for gas phase reactions fi fi o fi P o
and eq. (13.10) becomes

fi
i
(13.10) (13.25)
f fi o
i
K i P o K
i
i

This eq. relates K to fugacities of the reacting species as they
exist in the real equilibrium mixture.

2
 The fugacity is related to the fugacity coefficient by eq. (11.52):

fi i y i P

Substitute into eq. (13.25) provides an equilibrium expression

displaying the pressure and the composition:

P
y
i
i i o K (13.26)
i P
If the equilibrium mixture is an ideal solution, then each i
becomes i , then eq. (13.26) becomes

P
y
i
i i o K (13.27)
i P

3
 For pressure sufficiently low or temperatures sufficiently high,
the equilibrium mixture behaves essentially as an ideal gas.
Each i 1 and eq. (13.26) reduces to:

P
i y i P o K
i (13.28)

General conclusions of Eq. (13.28),

According to Eq. (13.14), the effect of T on the K is determined by the sign of Ho.
When Ho is positive, the standard reaction is endothermic, an
(13.14) increase in T results in increase in K. Eq. (13.28) shows that an
increase in K at constant P results in increase i(yi)vi . So, the
d ln K H o
2
reaction shift to the right and increase in e.
dT RT
When Ho is negative, the standard reaction is exothermic, an
increase in T results in decrease in K and decrease in i(yi)vi at
constant P. So, the reaction shift to the left and decrease in e.
If the total stoichiometric number v ( ivi) is negative, Eq. (13.28) shows that
increase in P at constant T causes an increase in i(yi)vi, so the reaction shift to
the right and increase in e. 4
If v is positive, an increase in P at constant T causes a decrease in i(yi)vi , a shift
on reaction to the left and decrease in e.
Liquid phase reactions
For a reaction occurring in the liquid phase,

i
fi fi o K (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), defines activity coefficient
fi i xi fi
The fugacity ratio can be expressed as
fi i xi fi fi
o
o i xi o (13.29)
fi fi fi

5
 For pure liquid i, eq. (11.31) is written for temperature T and
pressure P, and for the same temperature T but for standard
state pressure Po.
Gi i T RT ln fi
Gi o i T RT ln fi o

The difference between these two equations is

fi
Gi G RT ln o
i
o

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 G
o
i Vi dP
Po
As a result,
f P
RT ln io
fi
Po
Vi dP

6
 Because Vi changes little with pressure for liquids (and solids),
integration from Po to P gives
fi
ln o

Vi P P o (13.30)
fi RT
With eq. (13.29) and (13.30), eq. (13.10) may be written as
Po P V
x
i
i i K exp i i
(13.31)
i RT i

Except for high pressure, the exponential term is close to unity and
may be omitted. Then,
xi i K
i
(13.32)
i

If the equilibrium mixture is an ideal solution, then i is unity and

eq. (13.32) becomes

x
i
i K (13.33)
i

7
 EQUILIBRIUM CONVERSIONS FOR
SINGLE REACTIONS
Suppose a single reaction occurs in a homogeneous system
and suppose the equilibrium constant is known.
The calculation of the phase composition at equilibrium is
straightforward if the phase is assumed an ideal gas or an
ideal solution.
When assumption of ideality is not reasonable, the gas phase
reactions can be solved through application of equation of
state.
At equilibrium, there can be no tendency for change to occur,
either by mass transfer between phases or by chemical
reaction.
Example 13.5

A water gas shift reaction,

CO g H2O g CO2 g H2 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.

9
Solution:
(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 = 0 and K = 1. For this reaction,
i i 1 1 1 1 0
Because the reaction mixture is an ideal gas, eq. (13.28) applies
y H2 yCO2
K 1 (A)
yCO y H2O
By eq. (13.5),
1 e 1 e e e
yCO y H2O yCO2 y H2
2 2 2 2
Substitute into eq. (A) gives
e2
1 or e 0.5
1 e
2

Therefore the fraction of the steam that reacts is 0.5 10

(b) The reactants consist of 1 mol of H2O vapor and 1 mol of CO.
The temperature is 1100 K and the pressure is 10 bar.
Because = 0, the increase in pressure has no effect on the ideal
gas reaction, and e = 0.5.

(c) The reactants consist of 1 mol of H2O vapor and 1 mol of CO

and 2 mol of N2 is included in the reactants. The temperature
is 1100 K and the pressure is 1 bar.
N2 does not take part in the reaction and serves only as a diluent. It
does increase the initial number of moles no from 2 to 4, and the
mole fractions are all reduced by factor of 2. However, Eq. (A) is
unchanged and reduced to the same expression as before.
Therefore e = 0.5.

11
(d) The reactants are 2 mol of H2O and 1 mol of CO.
The temperature is 1100 K and the pressure is 1 bar.
In this case the mole fractions at equilibrium are
1 e 2 e e e
yCO y H2O yCO2 y H2
3 3 3 3
Eq. (A) becomes
e2
1 or e 0.667
1 e 2 e
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.

The temperature is 1100 K and the pressure is 1 bar.
The expressions for yCO and yH2O are interchanged, but this
leaves the equilibrium equation the same as in (d).
Therefore e = 0.667, and the fraction of steam reacts is 0.667.

12
(f) The initial mixture consists of 1 mol of H2O, 1 mol CO and 1
mol of CO2. The temperature is 1100 K and the pressure is 1 bar.
In this case eq. (A) becomes
e 1 e
1 or e 0.333
1 e
2

The fraction of steam reacted is 0.333.

(g) The reactants consist of 1 mol of H2O vapor and 1 mol of CO.
The temperature is 1650 K and the pressure is 1 bar.
At 1650 K, 104/T = 6.06, and from Fig. 13.2, ln K = -1.15 or K = 0.316.
Therefore eq. (A) becomes
e2
0.316 or e 0.36
1 e
2

The reaction is exothermic, and conversion decreases with

increasing temperature.
13
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:
C2H2 2C H2 I
2C 2H2 C2H4 II
The sum of reactions (I) and (II) is the hydrogenation reaction:
C2H2 H2 C2H4

14
 G GI GII
o o
Also, o

By eq. (13.11b),
RT ln K RT ln KI RT ln KII or K KI KII
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 KI 12.9 KI 4.0 105
ln KII 12.9 KII 2.5 106
Therefore, K = KIKII = 1.0
At this temperature and pressure of 1 bar, assume ideal
gases. By eq. (13.28),
y C2H4
1
y H2 y C2H2

15
On the basis of one mole initially of each reactant, eq. (13.5)
gives
1 e e
y H yC H and yC H
2
2 e
2 2
2 e 2 4

Therefore,
e 2 e
1
1 e
2

The smaller root of this quadratic expression is e = 0.293.

The equilibrium composition of the product gas is then

1 0.293 0.293
y H2 yC2H2 0.414 and yC2H4 0.172
2 0.293 2 0.293

16
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:
CH3COOH l C2H5OH l CH3COOC2H5 l H2O 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:
Ho298 (J) Go298 (J)
CH3COOC2H5 -480 000 -332 200
H2O -285 830 -237 130
CH3COOH -484 500 -389 900
C2H5OH -277 690 -174 780
17
H298
o
I i Hio
1 480000 1 285830 1 484500 1 277690 3640 J
G298
o
I iGio
1 332200 1 237130 1 389900 1 174780 4650 J
By eq. (13.11b),
G298
o
4650
ln K 298 1.8759 or K 298 6.5266
RT 8.314 298.15
For small temperature change from 298.15 K to 373.15 K, eq.(13.15)
is adequate for estimation of K. Therefore,
K373 H298
o
1 1

R 373.15 298.15
ln
K 298
or
K373 3640 1 1
ln 0.2951
6.5266 8.314 373.15 298.15
and
K373 6.5266 0.7444 4.8586 18
For the given reaction, eq. (13.5), with x replacing y, yields
1 e e
x AcH xEtOH xEtAc xH2O
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) is
employed, giving
xEtAc xH2O
K
x AcH xEtOH
2
e
4.8586
1 e
Solution yields
e 0.6879 and xEtAc 0.6879 / 2 0.344

19
 Example 13.9
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 (298.15K) and that equilibrium is
attained at the exit, determine the composition and
temperature of the product stream from the reactor.
Solution:
The reaction is
SO2 + O2 SO3
for which, H298 = - 98 890 Jmol-1 G298 = -70 866 Jmol-1
On the basis of one mole of SO2 entering the reactor,
Moles O2 entering = (0.5)(1.2) = 0.6
Moles N2 entering = (0.6)(79/21) = 2.257
Application of eq. (13.4) yields the amounts of the species in
the product stream:
Moles SO2 = 1 e
Moles O2 = 0.6 0.5e
Moles SO3 = e
Moles N2 = 2.257
Total moles = 3.857 0.5e
The energy balance and equilibrium equation required to solve
for e and temperature.
H298e + HP = H = 0 Eq. (A)
The enthalpy change of the products as they are heated from
298.15K to T is
HP = CP H (T 298.15) Eq. (B)

where CPH is defined as the total heat capacity of the product

Co P H n i Co P H
stream:
i
Eq. (A) and (B) combine to yield

H298e + CP H (T 298.15) = 0
Solution for T gives,

H 298
o
e
T 298.15 Eq. (C)
C P H
o

At the conditions of T and P of the equilibrium state, the

equilibrium constant becomes
0.5
e 3.857 0.5 e
K Eq. (D)
1 e 0.6 0.5 e
Because lnK = G/RT, Eq. (13.18) can be written as
G0o H 0o H 0o 1 T CPo T C dT
o
ln K dT P
RT0 RT T T0 R T0 R T

Data from Table C.1 provide CPH /R values:

SO2 : (298.15,T; 5.699,0.801E-3,0.0,-1.015E+5)
O2 : (298.15,T; 3.639,0.506E-3,0.0,-0.227E+5)
SO3: (298.15,T; 8.060,1.056E-3,0.0,-2.028E+5)
O2 : (298.15,T; 3.280,0.593E-3,0.0,0.040E+5)
Data for first and second integral of CPH /R
T C Po

T0 R
dT IDCPH (298.15, T ;0.5415,0.002 E 30.0,0.8995E 5)

T C Po dT

T0 R T
IDCPS (298.15, T ;0.5415,0.002 E 30.0,0.8995E 5)
Substitution of numerical values yields:
11894.4 1
ln K 11.3054 ( IDCPH ) IDCPS Eq. (E)
T T
An iteration scheme for solution of these equation for e and T
that converges fairly rapidly is as follows:
1. Assume a starting values for T.
2. Evaluate IDCPH and IDCPS at this value of T.
3. Solve Eq. (E) for K and Eq. (D) for e by trial.
4. Evaluate and solve Eq. (C) for T.
5. Find a new value of T as the arithmetic mean of the
value just calculated and the initial value.
6. Return step 2.
This scheme converges on the values e = 0.77 and T = 855.7 K.
For the product,
1 0.77 0.23
y SO2 0.0662
3.857 (0.5)(0.77) 3.472
0.6 (0.5)(0.77) 0.215
yO2 0.0619
3.472 3.472
0.77
y SO3 0.2218
3.472
2.257
yN2 0.6501
3.472