1

Chapter 20
Chemical reaction equilibrium
20.1 A review of basic reaction concepts
Previously we studied the equilibrium behavior of non-reacting systems. Here, we examine
equilibrium when there are reactions present, at both the macroscopic and microscopic
levels. Recall from basic ideas in chemistry that a reversible reaction can be described by
an equilibrium constant K
cq
. onsider for example the reaction,
A + 2B
K
cq
--C
!"#.1$
%n earlier courses on chemistry, you may have seen the equilibrium constant related to the
equilibrium concentrations in moles&molecules per volume of the species involved'
K
cq
=
|C]
|A]|B]
2

!"#."$
where the powers of the concentrations are determined by the stoichiometric coefficients.
(otice that we can consider the case of irreversible reactions as )ust a special subset of
reversible ones, in which the equilibrium constant is very large.
%n this chapter, we will understand the origins of the equilibrium constant in terms
of thermodynamic potentials and microscopic ensembles.
20.2 Chemical reaction equilibrium at the macroscopic level
*irst, let+s understand a reacting system from the point of view of macroscopic
thermodynamic potentials. ,e will ta-e the specific reaction above as an example, and
consider the behavior of a system at constant temperature and pressure. .t constant I and
P, the relevant thermodynamic potential is the /ibbs free energy and at equilibrium, it is at
a minimum.
onsider that we have an initial system of components A, B, and C. %f reactions are
not permitted, and we can independently control the respective amounts of the species, the
/ibbs free energy of the system is given by
0(I, P, N
A
, N
B
, N
C
)
!"#.0$
,hat happens now if we allow the reaction to proceed1 %n this case, the numbers of
molecules of each species can change, sub)ect to a certain conservation rule. 2hat rule says
that the changes in mole numbers are related by the stoichiometric coefficients'
"

JN
A
= JN
C

JN
B
= 2JN
C

!"#.3$
2hese equations say that for every A molecule we get due to the reaction, we have to lose a
C one. 4imilarly, for every C molecule we lose, we also get two B molecules. Here, there is
one macroscopic degree of freedom that can vary due to the reaction. 5ou could thin- of
that as the number of C molecules that react. %f we -now how much C has reacted, we
instantly -now how much A and B have reacted by the considerations above. 6ore
generally, there is one reaction and hence one extent of reaction.
%f the reaction is allowed to proceed from some initial specified composition of the
three components, at equilibrium the /ibbs free energy will be minimi7ed. 2he change in 0
with the amount of the species, at constant I and P is'
J0 = _
J0
JN
A
]
1,P,N
B
,N
C
JN
A
+ _
J0
JN
B
]
1,P,N
A
,N
C
JN
B
+ _
J0
JN
C
]
1,P,N
A
,N
B
JN
C

= p
A
JN
A
+ p
B
JN
B
+ p
C
JN
C

!"#.8$
9ut using the stoichiometric considerations above, we find that'
J0 = (p
A
2p
B
+ p
C
)JN
C

!"#.:$
.t equilibrium the /ibbs free energy is minimi7ed, J0 = u. 2his means that the reaction
reaches equilibrium when the chemical potentials satisfy the condition'
p
A
+ 2p
B
= p
C

!"#.;$
2hus, we find that'
2he thermodynamic quantity that predicts chemical reaction equilibrium is
the chemical potential.
(otice that the condition for chemical potential equality reduces the number of
macroscopic degrees of freedom. %f we specify I, P, N
A
, and N
B
, and we -now that there is a
reaction between A, B, and C, then N
C
is automatically specified by solving the chemical
potential equality above !recall that the chemical potentials are functions of composition$.
%n other words,
*or every reversible reaction in a system, the number of macroscopic
degrees of freedom is reduced by one.
*or the general case, we can introduce a notation for reactions that reads as follows'
v

= u
!"#.<$
where v

is a stoichiometric coefficient and H

is the chemical symbol for component i. 2he

v

+s are defined such that they ta-e on negative values for reactants !the left hand side of
0

the reaction$ and positive for products !the right hand side$. =ur previous example would
be'
A 2B + C = u
!"#.>$
with v
A
= 1, v
B
= 2 , v
C
= 1.
*or one ?instance@ of the reaction from left to rightAfor one chemical eventAthe
change in the number of molecules of each component is v

. %f we let the variable indicate

the number of such events, then for a differential change in , the corresponding change in
the amount of each component is'
JN

= v

J
!"#.1#$
2he variable is generally called an extent of reaction. %n this case, the total change in
free energy is'
J0 = _
J0
JN

]
1,P,N
]=i
JN

= J v

!"#.11$
2herefore, with J0 = u, we find that the general expression for reaction equilibrium is
v

= u (20.12)
20.3 Ideal gas reactions
,e have already derived many expressions for the chemical potential of simple
multicomponent systems in previous lectures. *or ideal gas mixtures, for example, we can
write the equilibrium condition using p

= p

0
+ k
B
I lnP

where P

is the partial pressure of

component i'
v

(p

0
+ k
B
I ln P

= u !"#.10$
=r, rearranging'

1
k
B
I
v

= ln_P

v
i

!"#.13$
Bpon exponentiation we find that'
3

_P

v
i

= exp_
_ v

k
B
I
_
!"#.18$
(otice that the right hand side is independent of pressure and composition, since p

0
is only
a function of temperature. 2herefore, we can write this expression as'
_P

v
i

= K
cq
(I) where K
cq
(I) exp_
_ v

k
B
I
_
(20.16)
%n other words, the equilibrium state for a mixture of ideal gases is given by the point at
which the product of the component partial pressures, raised to the stoichiometric
coefficients, equals a temperature-dependent equilibrium constant. %f this had been the
case of a nonideal gas, the mixture fugacity would have replaced the partial pressures.
2his equilibrium constant is often denoted K
P
to indicate that it relates to the gas
partial pressures. %n addition, the quantity _ v

is called the standard change of free

energy of reaction, since it corresponds to the free energy change per reaction instance.
2his quantity is often denoted by the symbol Ag
0
.
Recall that the partial pressure is defined by the expression P

= y

P where y

is the
mole fraction of component i. *or an ideal gas mixture, we can also express the partial
pressure as P

= N

k
B
I I / = |i]k
B
I where |i] denotes the concentration of i in molecules
per volume. ,e can then rewrite the above expression by defining a new equilibrium
constant K
cq
i
'
_|i]
v
i

= K
cq
i
(I) where K
cq
i
(I) exp_
_ v

k
B
I
_ (k
B
I)
-_ v
i i

(20.17)
.gain, since this is an ideal gas, K
cq
i
only depends on the temperature. 4ince K
cq
i
relates
compositions of the components, it is often notated K
C
.
*or the simple example above, we find that the equilibrium conditions reduce to'
P
C
P
A
P
B
2
=
|C]
|A]|B]
2
(k
B
I)
-2
= K
cq
(I)
!"#.1<$
20.4 Ideal solution reactions
Recall that, for an ideal solution, p

= p

-
+ k
B
I ln x

. 4ubstituting this expression into the

equilibrium condition,
v

(p

-
+ k
B
I ln x

= u !"#.1>$
8

=r, after rearranging and exponentiating,
_x

v
i

= exp_
_ v

k
B
I
_ !"#."#$
2he right hand side of this equation is composition-independent, since the quantities p

-

only depend on I and P. However, as discussed in the lectures on ideal solutions, the exact
significance of p

-
can differ depending on whether a component is dilute or nearly pure. %n
either case, we can express the reaction equilibrium as'
_x

v
i

= K
cq
(I, P) where K
cq
(I, P) exp _
_ v

k
B
I
_ (20.21)
,e therefore find that the mole fractions of each component in solution form a
multiplicative term that equals a reaction constant. %f we had used non-ideal solutions, the
expression on the left hand side would involve activity coefficients in addition to mole
fractions.
%f all of the participating components in a reaction are dilute, we can ma-e the
approximation that'
x

=
molecules i
molecules total

=
molecules i
molecules solvent
=
molecules i
Ip
solvent
=
|i]
p
solvent

!"#.""$
where |i] indicates the molarity of i in molecules per volume and p
solvent
is the molar
density of the solvent. 2hus we could rewrite the equilibrium condition using a new
equilibrium constant K
cq
i
'
_|i]
v
i

= K
cq
i
(I, P) where K
cq
i
(I, P) exp_
_ v

k
B
I
_ p
solvent
_ v
i i
(20.23)
*or dilute solutions, the solvent molar density does not change appreciably with the
concentrations of the dilute components, and hence we can approximate that K
cq
i
is
concentration-independent.
*or the simple example above, we find that
x
C
x
A
x
B
2
=
|C]
|A]|B]
2
p
solvent
2
= K
cq
(I)
!"#."3$
20. !emperature and pressure dependence of K
eq

onsider the temperature-derivative of the logarithm of the ideal gas equilibrium constant'
:

J lnK
P
JI
=
J
JI
_
_ v

k
B
I
_
!"#."8$
Bsing the thermodynamic identity b = I
2
J(p I / )JI'
J ln K
P
JI
=
1
k
B
I
2
v

!"#.":$
,e can define a standard change of enthalpy of reaction such that'
J ln K
P
JI
=
Ab
0
k
B
I
2
where Ab
0
v

!"#.";$
(otice that Ab
0
depends on the ideal gas enthalpies, since for an ideal gas b = b
0
. .nother
way of writing this equation is the following'
J ln K
P
J(1 I / )
=
Ab
0
k
B
where Ab
0
v

(20.28)
2his equation gives the vant Hoff relation. %t shows that a plot of the logarithm of the
equilibrium constant versus the inverse temperature has a slope given by the negative
enthalpy of reaction. 4uch a plot is called a van+t Hoff plot. ,hen these -inds of plots are
linear, they show that Ab
0
is independent of temperature. %n such cases, one can integrate
this equation to obtain the dependence of the equilibrium constant with temperature'
K
P
exp_
Ab
0
k
B
I
_
!"#.">$
omparing the equilibrium constant at two temperatures,
K
P
(I
1
)
K
P
(I
2
)
= exp _
Ab
0
k
B
_
1
I
1

1
I
2
]_
!"#.0#$
%f this had been an ideal solution, rather than an ideal gas mixture, we would have obtained
a similar relationship'
J lnK
cq
J(1 I / )
=
Ab
-
k
B
where Ab
-
v

(20.31)
(ote that here, the b
-
+s give the molar enthalpies for the pure components. %n addition to a
temperature-dependence, the ideal solution equilibrium constant also has a pressure
dependence. ,e can find a similar relationship by ta-ing the pressure derivative of ln K
cq
'
J ln K
cq
JP
=
J
JP
_
_ v

k
B
I
_
!"#.0"$
Bsing Jp JP / = : for a pure system, where : is the molar volume, we find that'
;

J lnK
cq
JP
=
A:
-
k
B
I
where A:
-
v

(20.33)
Here, A:
-
is the difference in molar volumes of the pure phase components, for one
instance of the reaction.
20." Chemical reaction equilibrium at the microscopic level
,e now ta-e a molecular-based perspective of chemical reaction equilibrium. *or
simplicity, we will examine the case at constant temperature and volume. 2hat is, we will
examine equilibrium in the canonical ensemble. .t constant temperature and volume, a
nearly identical derivation to that which we examined for the /ibbs free energy above
shows that the macroscopic condition for chemical reaction equilibrium corresponds to the
same chemical potential condition'
v

= u

!"#.03$
Here, we will ma-e a connection to microscopic properties. ,e will specifically examine
the case of independent olec!les. Recall that an ideal gas mixture corresponds to a
system of independent molecules, where there are no potential energies.
*or the example multicomponent system above we can write the partition function
for a set of independent molecules as'
(I, I, N
A
, N
B
, N
C
) =
q
A
N
A
q
B
N
B
q
C
N
C
N
A
! N
B
! N
C
!

= _
q
A
c
N
A
]
N
A
_
q
B
c
N
B
]
N
B
_
q
C
c
N
C
]
N
C

!"#.08$
Here, the partition functions q

(I, I) are the single-molecule partition functions for each

species. 2he factorial terms in the denominator account for the fact that the particles are
indistinguishable, which is the general case for most matter according to quantum
mechanics. 2he second line invo-es 4tirling+s approximation.
%n general, therefore, we can write the partition function as'
(I, I, {N

]) = _
q

N
i
N

= __
q

c
N

]
N
i

!"#.0:$
*inding the chemical potentials in terms of partition functions,
<

p

= _
JA
JN

]
1,v,N
]=i

= k
B
I
J ln
JN

= k
B
I ln_
q

]
!"#.0;$
4ubstituting this expression into the chemical potential condition at reaction equilibrium,
we find that'
k
B
I v

ln_
q

= u !"#.0<$
=r, after simplifying and exponentiating,
_N

v
i

= _q

v
i

!"#.0>$
,e divide through by [ I
v
i

on both sides to get the molar concentrations. *inally, we find

that'
__
N

I
]
v
i

= _[
q

v
i

!"#.3#$
=r, rewriting using concentrations !molecules per volume$ and an equilibrium constant'
_|i]
v
i

= K
cq
where K
cq
_[
q

v
i

(20."1)
2his derivation says that we can write the equilibrium constant for independent molecules
as a product of single-molecule partition functions for each species. *or the example above,
we would have'
|C]
|A]|B]
2
= K
cq
where K
cq
=
q
C
q
A
q
B
2
I
2

!"#.3"$
%n general, the single molecule partition functions are dependent on both temperature and
volume. *or the case of an ideal gas, q

= IA

(I)
3
where A is the thermal de 9roglie
wavelength. 2herefore, for an ideal gas reaction, we find'
K
cq
= _A

(I)
-3v
i

!"#.30$
and hence K
cq
depends only on the temperature, as we have seen before. (ote that the A+s
differ for different species due to different masses of each particle.
>

20.# $luctuations
2he considerations above used the macroscopic condition for reaction equilibrium, based
on the chemical potentials, to express the equilibrium constant in terms of partition
functions. 2he use of the macroscopic condition, which depended on a minimi7ation of the
free energy, neglects fluctuations. .t a microscopic level, we -now that the numbers of
A, B, and C molecules in our example can fluctuate around an average equilibrium value,
due to the rule of equal a priori probabilities. .s we have seen many times before,
however, the magnitude of these fluctuations is typically too small to notice at a
macroscopic scale.
Cet+s consider a simpler reaction example for the proceeding'
A
K
cq
--B
!"#.33$
%f we start with a fixed total number of molecules N = N
A
+ N
B
and allow the system to
reach equilibrium through the reaction above, N will remain unchanged but N
A
and N
B
will
experience fluctuations around an equilibrium value. ,e can write the canonical partition
function for this system as
(I, I, N) = (I, I, N
A
, N
B
)
all N
A
,N
B
such
that N
A
+N
B
=N

=
q
A
N
A
q
B
N
B
N
A
! N
B
!
N
A
,N
B

=
1
N!

N!
N
A
! N
B
!
q
A
N
A
q
B
N
B
N
A
,N
B

=
(q
A
+ q
B
)
N
N!

!"#.38$
2he sum in this expression !abbreviated ?N
A
, N
B
@in the second line$ correspond to all
possible variations of N
A
and N
B
given the constraint of the total number of molecules. 2he
last line simply comes from the binomial expansion.
2he probability that the system will have a particular value of N
A
is then'
(N
A
) =
(I, I, N
A
, N
B
)
(I, I, N)

!"#.3:$
where implicitly N
B
= N N
A
. 2he average number of A molecules is therefore'
(N
A
) = (N
A
)N
A
N
A
,N
B

!"#.3;$
1#

Bsing the expression for (N
A
), it can be shown that this average can also be extracted
using'
(N
A
) = q
A
_
J ln(I, I, N)
Jq
A
_
q
B
,N
!"#.3<$
.nd hence'
(N
A
) = N
q
A
q
A
+ q
B

!"#.3>$
. similar expression exists for B, in which the subscripts are swapped. 2his expression
clearly satisfies the macroscopic equilibrium condition for this case, (N
A
) (N
B
) / = q
A
q
B
.
Proceeding through higher order moments of the particle number, it can be shown
that'
o
N
A
2
= o
N
B
2
= (N
A
2
) (N
A
)
2

=
(N
A
)(N
B
)
N

!"#.8#$
.nd thus magnitude of the fluctuations in N
A
goes as N
1 2 /
. ompared to the average value
of N
A
, which goes as N, the fluctuations vanish in the macroscopic limit.