Example

Evaluate the lower enthalpy of reaction of benzoic acid (C 6lfsCOOH). The planar diagram
of its structure is shown in Fig 11. 7.

I
CI

c
/
HC

CH

ll

'

0-

c
H

Fig. 11.7 Structure of benzoic acid molecule

Solution
The reaction of benzoic acid with oxygen is
(11.20)
The easiest way to evaluate the enthalpy of reaction is from eqn (11.18):
fl.HR

= (ll.Hr )p

- (ll.Hr )R

The values of Hr were calculated above for CO, and H20, and hence the only unknown
quantity in eqn ( 11.18) is the enthalpy of formation of the benzoic acid:
(11.21)
The acid is in gaseous form before the reaction, see eqn (11.20), and thus AH,,,,,
Substituting values into eqn ( 11.21) gives
(ll.Hr)c6tt 5cooH =
=

0.

L ll.H. - L ll.H(X - Y) - L ll.Hres

7 ll.H.[Cgraphite] + 3 ll.H.[H -H] + ll.H.[0 = O]
-5[H -C]-4[C -C]-3[C= C] -[C= O]
- [C - 0] - [O - H] - [ll.HreshHi> - [ll.HrcsJcooH

(11.22)

Hence
(ll.Hr)c6HsCOOH = 7 x 717.2 + 3 x 435.4 + 498.2 - 5 x 414.5

-4x 347.5-3x615.5-698.l-351.7-428.7-150.4-117.0
(11.23)

= - 230.1 MJ /kmol

The enthalpy of formation of the products is

(!J..Hr )p = 7 (!J..Hr )co2 + 3 (!J..Hr )tt 2o
= 7 x (-381.5) + 3 x (-241.7)
=

(11.24)

-3395.5 MJ/kmol

Thus the enthalpy of reaction of benzoic acid is

(!J..HR)c6 tt 5 cooH = -3395.6 - (-230.1) = 3165.5 MJ/kmol

(11.25)

The tabulated value is 3223.2 MJ/kmol, giving an inaccuracy of about 2%.

11.3

Enthalpy of reaction

The enthalpies of reaction of some commonly encountered fuels are given in Table 11.2.
These have been taken from a number of sources and converted to units consistent with
this text where necessary. There are a number of interesting observations that can be made
from this table:

the enthalpies of reaction of many of the hydrocarbon fuels on a basis of mass are very
similar, at around 44000 kJ/kg;
the stoichiometric air-fuel ratios of many basic hydrocarbon fuels lie in the range
13:1-17:1;
some of the fuels have positive enthalpies of formation;
all of the fuels have negative enthalpies of reaction;
the enthalpies of reaction of the alcohols are less than those of the non-oxygenated
fuels, simply because the oxygen cannot provide any energy of reaction;
the commonly used hydrocarbon fuels are usually mixtures of hydrocarbon compounds.

11.4

Concluding remarks

It has been shown that the energy released by a fuel is contained in it by virtue of its
structure, i.e. the bonds between the atoms. It is possible to assess the enthalpies of
formation or reaction of a wide range of fuels by considering the chemical structure and
the bonds in the compound.
A table of enthalpies of formation and reaction for common fuels has been given.

Up to now this book has concentrated on combustion problems which can be solved by
methods based on equilibrium but which do not require an explicit statement of the fact,
e.g. complete combustion of a hydrocarbon fuel in air can be analysed by assuming that
the products consist only of H20 and C0 2 These methods are not completely correct and a
more rigorous analysis is necessary to obtain greater accuracy.
Consider the combustion of carbon monoxide (CO) with oxygen (0 2 ); up until now the
reaction has been described by the equation
(12.1)
It is implied in this equation that carbon monoxide combines with oxygen to form carbon

dioxide, and as soon as that has happened the reaction ceases. This is not a true description
of what happens in practice. The real process is one of dynamic equilibrium with some of
the carbon dioxide breaking down into carbon monoxide and oxygen (or even more
esoteric components) again, which might then recombine to form carbon dioxide. The
breakdown of the C02 molecule is known as dissociation. To evaluate the amount of
dissociation that occurs (the degree of dissociation) it is necessary to evolve new
techniques.

12.1

Gibbs energy

The concept of Gibbs energy, G, was introduced in Chapter 1. The change in the specific
Gibbs energy, g, for a system of fixed composition was defined in terms of other
properties as
dg = v dp - s dT

(12.2)

It was also shown that for a closed system at constant temperature and pressure,
performing only mechanical work, to be in equilibrium,
dG)p,T = 0

(12.3)

Equations (12.2) and (12.3) are based on the assumption that G =mg= mg( p, T), and
this is quite acceptable for a single component system, or one of fixed composition. If the
system has more than one component, and these components can react to form other

compounds, e.g. if the system contained carbon monoxide, oxygen and carbon dioxide as
defined in eqn (12.1), then it is necessary to define the Gibbs energy as
G=mg=mg(p, T,m;) where m; is the mass of component i, and m=I m;. The
significance of changes of composition on the value of the Gibbs energy of a mixture will
now be investigated.
If

(12.4)

G=mg=mg(p, T,m;)

and if it is assumed that G is a continuous function with respect top, and T and the masses
of constituents comprising the mixture, then the change of G with changes in the
independent variables is

oG)
oG)
dG = ( -oG) dp + ( -oG) dT + ( dm 1 + ( dm
op T,m
oT p,m
Om1 p,T,m;.1
Omn p,T,m;-. n

(12.Sa)

where dm 1 dmn are changes in mass of the various constituents. A similar equation can
be written in terms of amount of substance n, and is

(oG)

(oG)

dG= dp+ (oG)

dT+ dn 1+ (oG)
dn
Op T,n
OT p,n
On1 p,T,n;, 1
Onn p,T,n;'" n

(12.Sb)

For the initial part of the development of these equations the mass-based relationship (eqn
(12.5a)) will be used because the arguments are slightly easier to understand. The term

oG)
dm
( Om1 p,T,m;.
I
1

represents the 'quantity' of Gibbs energy introduced by the transfer of mass dm 1 of

constituent 1 to the system. (This can be more readily understood by considering the
change in internal energy, dU, when the term (0U/om 1 )p,T,m;, 1 dm 1 has a more readily
appreciated significance.)
The significance of the terms on the right of eqn (12.Sa) is as follows:
1.

2.

3.

The first term denotes the change of Gibbs energy due to a change in pressure,
the temperature, total mass and composition of the system remaining constant.
This is equivalent to the term derived when considering a system of constant
composition, and is V dp.
The second term denotes the change of Gibbs energy due to a change in
temperature, the pressure and total mass of the system remaining constant. This
is equivalent to -S dT derived previously.
The third term shows the change of Gibbs energy due to a change in the mass (or
amount of substance if written in terms of n) of constituent m1, the pressure,
temperature and masses of other constituents remaining constant. It is convenient
to define this as
(12.6)

4.

The fourth term is a general term of the form of term (3) in eqn ( 12.6).

Hence, in terms of masses

n

dG

(12.7a)

Vdp -SdT+ L;dm;

i~

while in terms of amount of substance

n

(12.7b)

dG = Vdp - SdT + Lm;dn;

i= I

12.2

Chemical potential,

The term is called the chemical potential and is defined as

(:~1.T.m;,

The significance of will now be examined. First, it can be considered in terms of the
other derived properties.
By definition
dG = d(H - TS)= dH - T dS - S dT

(12.8)

dH = dG + T dS + S dT
= V dp - S dT +I; dm; + T dS + S dT
= V dp + T dS +I; dm;

(12.9)

Hence

Considering each of the terms in eqn (12.9), these can be interpreted as the capacity to
do work brought about by a change in a particular property. The first term is the increase
in capacity to do work that is achieved by an isentropic pressure rise (cf. the work done in
a feed pump of a Rankine cycle), and the second term is the increased capacity to do work
that occurs as a result of reversible heat transfer. The third term is also an increase in the
capacity of the system to do work, but this time it is brought about by the addition of a
particular component to a mixture. For example, if oxygen is added to a mixture of carbon
monoxide, carbon dioxide, water and nitrogen (the products of combustion of a
hydrocarbon fuel) then the mixture could further react to convert more of the carbon
monoxide to carbon dioxide, and more work output could be obtained. Thus ; is the
increase in the capacity of a system to do work when unit mass (or, in the case of m; unit
amount of substance) of component i is added to the system.; can be considered to be a
'chemical pressure' because it is the driving force in bringing about reactions.
Assuming that H is a continuous function,

(aH)

dH = ap

(aH)
as

dp + S,m

(aH)
am1

dS + - p,m

S,p,m;.

(aH)

dm 1 + + - amn

dm
S,p,m;.,,

n
(12.10)

By comparison of eqns (12.9) and (12.10)

j = ( : : tp,m; I

(12.11)

Similarly it can be shown that

(12.12)

The following characteristics of chemical potential may be noted:

(i)

the chemical potential, , is a function of properties and hence is itself a

thermodynamic property;
(ii) the numerical value of is not dependent on the property from which it is
derived (all the properties have the dimensions of energy and, hence, by the
conservation of energy this is reasonable);
(iii) the numerical value of is independent of the size of the system and is hence
r.n intensive property, e.g.
(12.13)
Since is an intensive property it may be compared with the other intensive
properties p and T etc. By the two-property rule this means that
p=p(, T)

(12.14)

and similarly
=(p, T)

(12.15)

It can be shown that the chemical potential for a pure phase is equal in magnitude to the
specific Gibbs energy at any given temperature and pressure, i.e.
=g

(12.16)

[Note: Although = g, it is different from g inasmuch as it is an intensive property

whereas g is a specific property. Suppose there is a system of mass m, then the total
Gibbs energy is G =mg whereas the chemical potential of the whole system is still {cf.
p or T}.]

12.3

Stoichiometry

Consider the reaction

(12.17)
Equation (12.17) shows the stoichiometric proportions of the reactants and products. It
shows that 1 mol CO and !mol 0 2 could combine to form 1 mol C0 2 If the reaction
proceeded to completion, no CO or 0 2 would be left at the final condition.
This is the stoichiometric equation of the reaction and the amounts of substance in the
equation give the stoichiometric coefficients.

The general equation for a chemical reaction is

vaA+ vbB<=>vcC+vdD

(12.18)

where vis a stoichiometric coefficient, and A, B, C and Dare the substances involved in
the reaction. Applying eqn (12.18) to the CO+! 0 2 reaction gives
Vco

= -1

(12.19)

Vai=-1/2
Vcai= 1

It is conventional in chemistry to assign negative values to the stoichiometric

coefficients on the left-hand side of the equation (nominally, the reactants) and positive
signs to those on the right-hand side (nominally, the products).

12.3.1

MIXTURES

Mixtures are not necessarily stoichiometric and the following terms were introduced in
Chapter 10 to describe the proportions of a mixture:
(i)
(ii)
(iii)

If reactants occur in proportion to the stoichiometric coefficients then the

mixture is said to be chemically correct or stoichiometric.
If the reactants have a greater proportion of fuel than the correct mixture then it
is said to be rich.
If the reactants have a lesser proportion of fuel than the correct mixture then it
is said to be weak.

e.g. chemically correct mixture is CO+! 0 2 => C0 2

Rich mixture (excess of fuel)

1
(1 + n)CO + - 0 2 => C0 2 + nCO
2

(12.20)

Weak mixture (excess of oxidant)

co+(~ +n)0

=>C0 2 +n0 2

(12.21)

NB. Equations (12.20) and (12.21) have been written neglecting dissociation.

12.4

Dissociation

The basis of dissociation is the atomic model that all mixtures of gases are in a state of
dynamic equilibrium. Molecules of the compounds are being created whilst existing ones
are breaking down into simpler compounds or elements (dissociating). In the equilibrium
situation the rates of creation and destruction of molecules of any compounds are equal.
This means that macroscopic measuring techniques do not sense the changes but give the
impression that the system is in a state of 'static' equilibrium. The effect of this is that the

reactions can no longer be said to be unidirectional but must be shown as

1
(12.22)
CO+ - 0 2 <::::>C0 2
2
On a molecular basis the above reaction can go either way. It is now necessary to
consider a technique which will define the net direction of change for a collection of
molecules. First, consider the general equation for the CO + ! 0 2 reaction, neglecting
particularly esoteric and rare compounds:
1
CO+ - 0 2 <=>aC0 2 + bCO + d0 2 +eC+f0
2

(12.23)

where the carbon (C) and atomic oxygen (0) are formed by the breakdown of the
reactants. Experience shows that in the ranges normally encountered in practice, the C and
0 atoms have a negligible effect. This allows the general reaction to be simplified to
1
CO + - 0 2 <=> aC0 2 + bCO + d0 2
2

(12.24)

It is possible to write this equation in a slightly different form by considering the amount
of C0 2 that has dissociated. This can be defined as a= (1 - a), and the equation for the
dissociation of C0 2 is

(12.25)
2
2
By considering the stoichiometric equation (eqn (12.22)) and the dissociation equation
(eqn (12.25)) a general equation may be constructed in terms of a:
aC0 2 <=>aCO + - 0

CO+ 1/20 2 ~ Ca0 2

aC0 2<::::>aCO + - 0

(12.26)

Adding eqns (12.26) gives

1
a
CO+ - 0 2 ~ (1 - a)C0 2 + aCO + - 0 2
(12.27)
2
2
In eqn (12.27), a is known as the degree of dissociation. This equation shows the effect
of dissociation on a chemically correct mixture. Before discussing methods of evaluating
a, the effect of dissociation on non-stoichiometric mixtures will be shown, first using the
carbon monoxide reaction, and then a general hydrocarbon fuel.

12.4.l

WEAK MIXTURE WITH DISSOCIATION

Equation without dissociation:

Co+(~ +n)o2 ~C02 +n0 2

(12.28)

Dissociation of C0 2 :
(12.29)

Adding eqns (12.28) and (12.29) gives

co+(~+n)02=>0-a)C02+aco+(; +n)o
12.4.2

(12.30)

RICH MIXTURE WITH DISSOCIATION

Equation without dissociation:

1

(12.31)

(1 + n)CO + - 0 2 => C0 2 + nCO

2
Dissociation of C0 2 :

Total reaction:
1

(1 + n)CO + - 0 2 => (1 + a)C0 2 + (n + a)CO + - 0 2

12.4.3

(12.32)

GENERAL HYDROCARBON REACTION WITH DISSOCIATION

A general hydrocarbon fuel can be defined as CxHy and this will react with the
stoichiometric quantity of air as shown in the following equation:
CxHy +

(x + ~)(0 2 + 3.76N2) => xC0 + ~ H 20 + 3.76(x + ~)N 2

2

(12.33)

The dissociation of the C0 2 and H20 can be added into this equation as (eqn (12.29))

and
(12.34)
which gives a general equation with dissociation
CxHy +

(x + ~)(02 + 3.76N2)
y

=>x(l - a 1)C0 2 + - (1- a 2)H 20 +xa 1CO + - a 2H 2

+(

~ a + ~ a 2)0 2 + 3.76(x + ~)N 2

1

(12.35)

If the fuel was benzene (C 6f\) then eqn (12.35) would become

C 6Hn + 7.5(0 2 + 3.76N 2 )

~6(1-

a 1 )C0 2 + 3(1- a 2 )H20 + 6a 1CO + 3a 2H2 + (3a 1 +l.5a 2 )0 2 +28.2N 2

(12.36)

If the mixture were not stoichiometric then eqn (12.33) would be modified to take
account of the air-fuel ratio, and eqns (12.35) and (12.36) would also be modified. These
equations are returned to in the later examples. In eqn (12.36) the combination of nitrogen
and oxygen has been neglected. In many combustion processes the oxygen and nitrogen
join together at high temperatures to form compounds of these elements: one of these
compounds is nitric oxide (NO), and the equations can be extended to include this
reaction. This will also be introduced later.

12.4.4

GENERAL OBSERVATION

As a result of dissociation there is always some oxidant in the products; hence dissociation
always reduces the effect of the desired reaction, e.g. if the reaction is exothermic then
dissociation reduces the energy released (see Fig 12.1).
Reactants
Products
(with dissociation)

Products
(with compl ete combustion)

TP fo r dissociation
T ~ for complete
combustion

T,

Temperature, T

Fig. 12.1 Effect of dissociation on combustion

Having introduced the concept of dissociation it is necessary to evolve a method that

allows the value of the degree of dissociation, a, to be calculated. This method will be
developed in the following sections.

12.5

Calculation of chemical equilibrium and the law of mass action

General relationships will be derived, and the particular case of the CO + ~ 0 2 reaction will
be shown in brackets { }.
It was previously shown that for a system at constant pressure and temperature to be in
an equilibrium state it must have a minimum value of Gibbs energy i.e. dG)p.T = 0.

But, by definition, for a system at constant pressure and temperature

(12.37)

dG)p.T = 1 dm 1+ 2 dm 2 + n dmn

where m 1, m 2 m" are the masses (or amounts) of the possible constituents of the
mixture.
Only four constituents will be considered during this discussion, two reactants and two
products, but the theory can be extended to any number of constituents. The equilibrium
equation for the complete reaction is

(12.38)
At some intermediate stage in the reaction the state may be represented as
v aA + v bB ---. ( 1 - e) v aA + ( 1 - e) vbB + eve C + ev dD

je.g.

CO+~ 0 2--+(1 - e)CO + (1 - e)~ 0

+ eC021

(12.39)

where stoichiometric coefficients equal to unity are implicit.

e is known as the fraction of reaction and is an instantaneous value during the reaction
as opposed to a, the degree of dissociation, which is a final equilibrium value. The use of
e allows the changes in Gibbs energy to be considered as the reaction progresses.
For the purposes of evaluating the dissociation phenomena it is possible to consider the
reaction occurring at constant temperature and pressure (equal to values obtained by other
means or calculated by an implicit iterative technique). The Gibbs energy of the system
may be described by the following equation:
G = (1 - e) Vaa + (1 - e) lvbb + Evcc + Vddl

I G = (1 - e) co+ -2 (1 - ) o 2 +co 2 }

(12.40)

To find the equilibrium condition while maintaining pressure and temperature constant,
this function has to be minimised with respect to ,i.e. it is necessary to locate when

~~L ~o
Now
dG = V dp - S dT +I; dm;

(12.41)

dG)p.T = l dm1 + 2 dm2 + n dmn

(12.42)

and

From here on, the mass form of the equation (eqn 12.Sa) will be replaced by the mole
form of the equation (eqn 12.Sb), because this is more appropriate for chemical reactions.

It is possible to relate the amount of substance of each constituent in terms of E, namely

na=(l-t:)va+A
nb=(l-t:)vb+B
nc= EVc+C
nd= EVd+D

(12.43)

where A, B, C and D allow for the excess amount of substance in non-stoichiometric

mixtures. Hence
dna=-vadE

(12.44)

and applying similar techniques

dna
dnb
dnc
dnd
--=--=-=-=de

(12.45)

This is known as the equation of constraint because it states that the changes of amount
of substance (or mass) must be related to the stoichiometric equation (i.e. changes are
constrained by the stoichiometry). Hence
(12.46)
giving

oG)
OE

-vaa - vbb + vcc + vdd

=0

for equilibrium

(12.47)

i.e. at equilibrium
(12.48)
Since = g it is possible to describe in a similar way to g, namely
= 0 + r:xr In Pr

(12.49)

o= o+ (T)

(12.50)

where

and is called the standard chemical potential, and is the value of at temperature T and
the datum pressure, Po
The value of pressure to be used in eqn (12.49) is the ratio of the partial pressure of the
individual constituent to the datum pressure.
Substituting for in the equilibrium equation, eqn (12.48)
v a(~+ fflT In p,J + v b(g + r:xT In p,b) = v cC~ + r:xT In Pr)+ v j~ + r:xr In Pr)
(12.51)

which can be rearranged to give

(va~+ vbg- vc~- vd~) +r:xT(va In Pra +vb In Prb - vc ln Pre - vd ln Pr) =0

(12.52)

Hence

(12.53)

The left-hand side of eqn (12.53) is the difference in the standard chemical potentials at the
reference pressure p 0 of 1 bar or 1 atmosphere. This is defined as
(12.54)
Hence
(12.55)
g1vmg
(12.56)
Kp, is called the equilibrium constant, and is a dimensionless value. Sometimes the
equilibrium constant is defined as

(12.57)
i.e.
or

(12.58)

KP has the dimensions of pressure to the power of the sum of the stoichiometric
coefficients, i.e. pl.v. The non-dimensional equilibrium constant is defined as
!iGo
lnK = _ _T
r,

9\T

(12.59)

Now !iG~ is a function of T alone (having been defined at a standard pressure, p 0 ),

therefore Kp, = f(T). Equation (12.56) shows that the numerical value of Kp, is related to
the datum pressure used to define 0 If the amounts of substance of reactants and products

are the same then the value of KP is not affected by the datum pressure (because
v a + vb - v c - v d = 0). However, if the amounts of substance of products and reactants are
not equal, as is the case for the CO + ~ 0 2 ____, C0 2 reaction, then the value of KP will be
dependent on the units of pressure. Hence, the value of equilibrium constant, KP' is the
same for the water gas reaction (CO+ H2 0-C0 2 + H 2 ) in both SI and Imperial units
because KP is dimensionless in this case.
12.5.1

KP DEFINED IN TERMS OF MOLE FRACTION

The definition of partial pressure is

(12.60)

Pa =XaP

Hence, replacing the terms for partial pressure in eqn (12.57) by the definition in eqn
(12.60) gives

9tTln Pcv,
~

p/d I= 9tT[1nj Xcv, x/dlp (v,.+vJ-va-vh)l

Pa Pb

Xa

Xb

(12.61)

which results in the following expression for KP in terms of mole fraction:

(12.62)
The above expressions are known as the law of mass action.

12.6

Variation of Gibbs energy with composition

Equations (12.57) and (12.62) show that the equilibrium composition of a mixture is
defined by the equilibrium constant, which can be defined in terms of the partial pressures
or mole fractions of the constituents of the mixture; the equilibrium constant was evaluated
by equating the change of Gibbs energy at constant pressure and temperature to zero, i.e.
dG)p,T = 0. It is instructive to examine how the Gibbs energy of a mixture varies with
composition at constant temperature and pressure. Assume that two components of a
mixture, A and B, can combine chemically to produce compound C. This is a slightly
simplified form of eqns (12.38) and (12.39). If the chemical equation is
A+ B

2C

(12.63)

then at some point in the reaction, defined by the fraction of reaction,

composition is

E,

the chemical

(1- E)A + (1- E)B+2EC

(12.64)

and the Gibbs energy is

G= (1- E)a+ (1- E)b+2Ec

(12.65)

This can be written, by substituting for from eqns (12.49) and (12.50), as
G = (1 - E)~ + ffiT ln Pr"+ (1 - E)~ +ffiT ln p,h + 2E(~ + ffiT ln Pr)
= ((1 - E)~ + (1 - E)~

+ 2E~] + ffiT[(l - E)ln Pra + (1 - E)ln Prb + 2E 1n

p,J
(12.66)

The partial pressures are defined by eqn (12.60) as p; = X; p, and the mole fractions of the
constituents are
1-e

Xa

1-e

= - - ; Xb = - - ; Xe=
2

2e
-

= t:

(12.67)

Substituting these terms in eqn (12.66) gives

0

G = [(l - e)a + (1- e)b + 2ec]

+91T[(l - <)In( I
0

= [(1 - e)a

'k

+ (I - e)ln( I ;

')p,

+ 2elnep,]

0
+ (1 - e)b0 + 2ec]
+ C1>
.;l\T[(I - e) + (1 - e) + 2e] lnp,

+91T[(l - e)ln(

I~')+ (I - e) 1n( I~')+ 2elne]

(12.68)

Equation (12.68) can be rearranged to show the variation of the Gibbs energy of the
mixture as the reaction progresses from the reactants A and B to the products C by
subtracting 2~ from the left-hand side, giving
0

G - 2c

e) + e lne

(1 - e)[a + b - 2cl
o + 25RTlnp, + 25RT [ (1 - e)ln ( -1 - 2

(12.69)
Equation (12.69) consists of three terms; the second one simply shows the effect of
pressure and will be neglected in the following discussion. The first term is the difference
between the standard chemical potentials of the separate components (~ + g) before any
reaction has occurred, and the standard chemical potential of the mixture (2~) after the
reaction is complete. Since the standard chemical potentials are constant throughout this
isothermal process, this term varies linearly with the fraction of reaction, e. The third term
defines the change in chemical potential due to mixing, and is a function of the way in
which the entropy of the mixture (not the specific entropy) varies as the reaction
progresses. The manner in which the first and third terms might vary is shown in Fig 12.2,
and the sum of the terms is also shown. It can be seen that for this example the equilibrium
composition is at e = 0.78. This figure illustrates that the Gibbs energy of the mixture
initially reduces as the composition of the mixture goes from A+ B to C. The standard
chemical potential of compound C is less than the sum of the standard chemical potentials
of A and B, and hence the reaction will tend to go in the direction shown in eqn (12.63). If
the standard chemical potentials were the only parameters of importance in the reaction
then the reactants A and B would be completely transformed to the product, C. However,
as the reaction progresses, the term based on the mole fractions varies non-monotonically,
as shown by the line labelled

29lr[o - l 1n(

~')+<In J.

and this affects the composition of the mixture, which obeys the law of mass action. If the
two terms are added together then the variation of G - 2~ with e is obtained. It can be

seen that the larger the difference between the standard chemical potentials (i.e. the steeper
the slope of the line PQ) then the larger is the fraction of reaction to achieve an
equilibrium composition. This is to be expected because the driving force for the reaction
has been increased. Some examples of dissociation are given later, and these can be more
readily understood if this section is borne in mind.

Standard Gibbs Energy

of mixing of A and B

-1

Minimum
Gibbs Energy
of mixture

-2

o.so

0.00

1.00

Fraction of reaction
Fig. 12.2 Variation of the Gibbs energy of a mixture

12.7
12.7.1

Examples of significance of KP
EXAMPLE 1

Consider the reaction in eqn (12.1),

1
CO + - 0 2 => C0 2
2

Vco =

-1,

Kp , =

PrC0 2
~
Prco vPro 2

'Y0i =

-1/2,

'Yc0i =

Hence
(12.70)

Thus, if KPr is known, the ratio of the partial pressures in the equilibrium state is known.