MOLECULAR PARTITION FUNCTIONS

Introduction
In the last chapter, we have been introduced to the three main ensembles used in
statistical mechanics and some examples of calculations of partition functions were also
given. In chemistry, we are concerned with a collection of molecules. If the molecules are
reasonably far apart as in the case of a dilute gas, we can approximately treat the system
as an ideal gas system and ignore the intermolecular forces. The present chapter deals
with systems in which intermolecular interactions are ignored. The next chapters will
include detailed consideration of intermolecular forces. In ensemble theory, we are
concerned with the ensemble probability density, i.e., the fraction of members of the
ensemble possessing certain characteristics such as a total energy E, volume V, number
of particles N or a given chemical potential and so on. The molecular partition function
enables us to calculate the probability of finding a collection of molecules with a given
energy in a system. The euivalence of the ensemble approach and a molecular approach
may be easily reali!ed if we treat part of the molecular system to be in euilibrium with
the rest of it and consider the probability distribution of molecules in this subsystem
"which is actually uite large compared to systems containing a small number of
molecules of the order of tens or hundreds#. $ince we are dealing with number of
particles of the order of %vogadro number, the ensemble description and the molecular
descriptions are euivalent. The energies of atoms and molecules are uanti!ed. &hile
atoms have only electronic energy levels, molecules have uanti!ed energy levels arising
from electronic, vibrational and rotational motion. % schematic energy level diagram is
shown in 'ig. (.).
&e have already seen that in the canonical ensemble, the probability of a system having
energy E
i
is proportional to the *olt!mann factor and is given in terms of the canonical
partition function by
+"E
i
# =
E , - T E , - T E , - T
i i i
i
e , e e ,


"(.)#
&here is defined by
.
i

e
/ 0 E
i "(.1#
2ere,

. ), -T and e
/ 0 E i
is called the *olt!mann factor. 3ften the *olt!mann constant
is written as -
*
. *ut when there is no ambiguity, we will simply write -.
3nce we -now the probability distribution for energy, we can calculate thermodynamic
properties li-e the energy, entropy, free energies and heat capacities, which are all
average uantities. To calculate +"E
i
#s we need the energy levels of a system. The energy
"4levels4# of a system can be built up from the molecular energy levels. &e will consider
the simpler problem of molecular energy levels which are pictorially shown in the 'ig
(.).

'igure (.) % schematic diagram showing electronic "bold lines#, vibrational and
rotational energy levels. The electronic uantum umbers are shown to the extreme right.
Vibrational uantum numbers are to shown in the extreme left. The rotational uantum
numbers are shown between the vibrational levels.
3.1 Electronic, Vibrtionl, Rottionl nd Trn!ltionl Prtition
Function!
The electronic energy levels are generally very widely separated in energy compared to
the thermal energy -T at room temperature. In each electronic level, there are several
vibrational levels and for each vibrational level, there are several rotational states. This is
a simplified and useful model to start with. The total energy is a sum of all these energies
and is given by
E
total
. E
electronic
5 E
vibrational
5 E
rotational
5 E
translational
5 E
others
"(.(#
The term E
others
includes nuclear spin energy levels and may also be used later to include
the interactions between the first four. %ssuming the first three to be independent and
neglecting the last term, the molecular partition function "ie, a sum over the molecular
energy states# is given by
67
.
5
E
8 "E 5 E 5 E E # , - T E E E
rot trans el ib el rot trans
rot trans el ib
ib
e e e e e

"(.7#
2ere, the summation is over the electronic, vibrational and rotational states can be done
separately since they are assumed to be independent. Therefore,
.
el

vib

rot

trans
"(.9#
The molecular partition function is written as the product of electronic, vibrational,
rotational and partition functions.
The partition function is a sum over states "of course with the *olt!mann factor

multiplying the energy in the exponent# and is a number. :arger the value of , larger the
number of states which are available for the molecular system to occupy. $ince
E
el
; E
vib
; E
rot
; E
trans
, there are far too many translational states available compared to
the rotational, vibrational and electronic states.
el
is very nearly unity,
vib
and
rot
are in
the range of ) to )<< while
trans
can be much in excess of )<
1<
. &e shall calculate the
values of these s and indicate how these s are useful in calculating the euilibrium
constants and also in certain cases, the rate constants.
=sing the standard formulae for the translational, rotational and vibrational energy
levels, we will now calculate the molecular translational, vibrational and rotational
partition functions for diatomic molecules first.
3.1.1 T"e Trn!ltionl Prtition Function, #
tr
.
>onsider a molecule confined to a cubic box. % molecule inside a cubic box of length :
has the translational energy levels given by E
tr
. h
1
"n
x
1
5 n
y
1
5 n
!
1
# , ? m:
1
where n
x
, n
y
and n
!
are the uantum numbers in the three directions "$ee >hapter ) for details#. The
translational partition function is given by
y x !
x y !
E E E E
tr
n n n tr
e e e e


. "(.6#

tr
.
x

!
, "(.@#
&hich is the product of translational partition functions in the three directions. $ince the
levels are very closely spaced, we can replace the sum by an integral
1 1 1
1
1
8 n h , "? m : - T# 8 a n x
* x
x x x 1
) <
*
h
e dn e dn , a
?m: - T


"(.?#
using
1
)
1
<
,
a x
e dx a

we get,

x
. ),1 "

,a#
),1
.
*
? m - T
)
:
1 h

.
*
1 m - T
:
h

. :,A "(.B#
where, A is the de *roglie thermal wavelength given by
*
h
1 m - T
.
Cultipying
x
,
y
and
!
, and using V . volume of the box . :
(
, we have,

tr
. D 1 E m -
*
T , h
1
F
(,1
V . V , A
(
"(.)<##
69
This is usually a very large number ")<
1<
# for volumes of ) cm
(
for a typical small
molecular mass. This means that such a large number of translational states are accessible
or available for occupation by the molecules of a gas.
E$%&le 3.1 >alculate the translational partition function of an I
1
molecule at (<<G.
%ssume V to be ) liter.
Solution' Cass of I
1
is 1 H )1@ H ).66<6 H )<
81@
-g
1Em-
*
T . 1 H (.)7)9 H "1 H )1@ H ).66<6 H )<
81@
-g# H ).(?<@ H )<
81(
I,G H (<< G
. ).<B6B H )<
877
I -g
A . h , "1 E m -
*
T#
),1
. 6.6161 H )<
8(7
I s , ").<B6B H )<
877
I -g#
),1
. 6.(16 H )<
8)1
m

tr
. V , A
(
. )<<< H )<
86
m
(
, "6.(16 H )<
8)1
m #
(
. (.B9 H )<
(<
. This means that (.B9 H
)<
(<
uantum states are thermally accessible to the molecular system
3.1.( T"e Rottionl Prtition Function o) *ito%ic
The rotational energy levels of a diatomic molecule are given by
E
rot
.
*
I "I 5 )# where
*
. h , ? E
1
I c "(.))#
2ere,
*
is the rotational constant expresses in cm
8)
. The rotational energy levels are given
by
1 1
" )# , ?
J
J J h I + , where I is the moment of inertia of the molecule given by r
1
where, is the reduced mass and r, the bond length. 3ften, the energies are also
expressed in terms of the rotational temperature, J
r
or
rot

, which is defined as
1
r 1
?
h
I k

"(.)1#
In the summation for the expression for
rot
, E. "(.)(#, we can do an explicit summation
rot
rot
8 E , , - T
K
K
"1 I 5 )# e
"(.)(#
if only a few terms contribute. The factor "1I5)# for each term accounts for the
degeneracy of a rotational state I. If energy E
I
is degenerate with "1 I 5 )# states
corresponding to it, then, the *olt!mann factor
rot
8 E , , - T
* K
e
has to be multiplied by
"1I5 )# to account for all these states. If the rotational energy levels are lying very close
to one another, we can integrate similar to what we did for
trans
above to get

rot
.
8 * I "I5)# , - T
<
"1I5)# e dI

"(.)7#
the integration can be easily be done by substituting x . I " I5)# and dx . "1I 5 )# dI

rot
. -T ,
*

"(.)9#
'or a homonuclear diatomic molecule, rotating the molecule by )?<
o
brings the molecule
into a configuration which is indistinguishable from the original configuration. This leads
to an overcounting of the accessible states. To correct for this, we divide the partition
function by L, which is called the symmetry number, which is eual to the distinct
number of ways by which a molecule can be brought into identical configurations by
rotations. The rotational partition function becomes,
rot
kT
q
B

"(.)6#
E$%&le 3.( &hat is the rotational partition function of 2
1
at (<<GM
66
Solution' The value of
B
for 2
1
is 6<.?67 cm
8)
. The value of -
*
T in cm
8)
can be obtained
by dividing it by hc, i.e., "-
*
T,hc# . 1<B.@ cm
8)
at (<<G. L . 1 for a homonuclear
molecule. Therefore, ,
rot
q kT B . 1<B.@,"1H6<.?67# . ).@1(. $ince the rotational
freuency of 2
1
is uite large, only the first few rotational states are accessible to at at
(<<G.
3.1.3 T"e Vibrtionl Prtition Function o) *ito%ic
The vibrational energy levels of a diatomic are given by
E
n
. "n 5),1 # h

"(.)@#
where is

the vibrational freuency and n is the vibrational uantum number.

In this case, it is easy to sum the geometric series shown below
n <
)
8 " n 5 # h , - T
1
i b
e

"(.)?#
8 h , "1 - T# 8 h , - T 8 1 h , - T
* * *
e ") 5 e e 5.....#

+
h , 1 -T
e

") 5 x 5 x
1
5 x
(
....# "(.)B#

h , 1 - T
e

D) , ")8 x#F "(.1<#

where x
h , - T
*
e

which is less than ). Threfore,

h , 1 - T
vib h , - T
e

) e

"(.1)#
vib h , - T
)

) e

"(.11#
if the !ero of energy scale is at h ,1-T . %nalogous to J
r
, a vibrational temperature J
v
or
vib

may be defined as hc ,-, where, is the vibrational freuency in cm

8)
.
E$%&le 3.3 >alculate the vibrational partition function of I
1
at (<<G.
Solution' The vibrational freuency of of I
1
is 1)7.9@ cm
8)
. hN,-T . 1)7.9@,1<B.@ .
).<1(1
e
8hN,-T
. <.(9B9
vib

),")8<.(9B9# . ).96). This implies, as before, that very few
vibrational states are accessible.
3.1.+ T"e Electronic Prtition Function
&riting the electronic energy as E
)
, E
1
, E
(
,Owith degeneracies g
)
, g
1
, g
(
,Othe electronic
partition function is given by

el
.
( ) 1
) 1 (
E E E
g e g e g e

+ + "(.1(#
=sually, E
)
PP E
1
or E
(
. Treating E
)
to be the reference value of !ero of energy, we get,

el
. g
)
"(.17#
which is the ground state degeneracy of the system.
E$%&le 3.+ 'ind the electronic partition of 2
1
at (<< G.
Solution The lowest electronic energy level of 2
1
is near 8 (1 eV and the next level is
about 9 eV higher. Ta-ing 8 (1 eV as the !ero "or reference value of energy#,

el
. e
<
5 e
89 eV , -T
5 ...
6@
%t (<< G, T . <.<1eV and
el
. ) 5 e
81<<
5...

).<
&here all terms other than the first are nearly <. This implies that
el
. ). The physical
meaning of this is that only the ground electronic state is generally accessible at room
temperature.
Qepresentative data useful for calculating the electronic, vibrational, and rotational
partition functions is given in Table (.). The electronic degeneracy is represented as g.
The vibrational freuency is written as . The dissociation energy is written as R
<
. It is
uite straight forward to calculate the above partition functions for these molecules.
Table (.) Qepresentative molecular data for a few diatomics.
Colecule g *ond
:ength
"S#
,
cm
8)
vib

,
G
B
,
cm
8)
rot

,G
'orce
consta
nt -
"dynes
,cm#
R
<
"-cal,
mol#
2
1
) <.@7)7 77<< 6((1 6<.B ?@.6 9.@7B )<(.1
R
1
) <.@7)9 ())? 77?@ (<.79 7(.? 9.@@ )<7.6
N
1
) ).<B@ 1(9? ((B( 1.<<) 1.BB 11.B7 119.)
3
1
( ).1<@ )9?< 11@7 ).776 1.<? )).@6 ))?.<
>l
1
) ).B?@ 96< ?<9 <.177 <.(9) (.1 9@.)
>3 ) ).)1? 1)@< ()11 ).B() 1.@? )B.<( 199.?
N3 1 ).)9 )?B< 1@)B ).6B9 1.79 )9.@ )9<.<
2>l ) ).1@9 1B(? 711@ )<.77 )9.<1 7.B )<1.1
2I ) ).6<B 11@< (166 6.76 B.<6 (.< @<.9
Na
1
) (.<B6 )9B 11B <.)97 <.11) <.)@ )@.(
G
1
) (.B@B B1.( )(( <.<96) <.<?) <.)< )).?
E$%&le 3., Express the partition function of a collection of N molecules T in terms of
the molecular partition function .
Solution' %ssuming the N molecules to be independent, the total energy E of molecules
is a sum of individual molecular energies E
s
and
all possible Es i i i
")# "1# "N#

E
i i i
T e . e e ......... e

"(.19#
. ..... .
N
"(.16#
2ere
")#
i

,
"1#
i

O.
"N#
i
are energies of individual molecules and a sum of all E
s
can only
come from summing over all
i

s. Uibbs postulated that

T .
N
, NV "(.1@#
6?
The NV in the denominator is due to the indistinguishability of the tiny molecules "or
other uantum particles in a collection#.
E$%&le 3.- Rerive the Caxwell *olt!mann distribution of molecular speeds.
Solution' If we represent a molecular velocity by v
r
, it has three independent components
v
x
, v
y
and v
!
in the three directions x, y and !. :et us consider monatomic gas of mass m.
The probability ' " x , y , !# that given molecule will have velocity components lying
between x and x 5 dx, y and y 5 d y and ! and ! 5 d! can be written as
' "x, y, !# d! dy d! . f "x# f "y# f"!# dx dy d!.
' is written as a product of three functions f because x, y and ! are independent and since
nature does not distinguish between x, y and ! "unless directional fields li-e gravitational
or electromagnetic are present#, the form of f is the same in the three directions. %gain,
since there is no distinction between positive and negative x, f depends on W x W or x
1
. &e
can rephrase the above euation as
'" # . f " # f " # f" # "(.1?#
The only function that satisfies the above euation is an exponential function since
1 1 1 1 1 1
x y z x y z
e e e e
+ +

and so we conclude that f " # may be written as

f" # . > e
1
b v
x
t

> e
1
b v
x

"(.1B#
&e ta-e only the negative exponent "> and b are positive# because a positive exponent
implies that very large velocities have very high probabilities which is highly unli-ely.
To evaluate >, &e invo-e the physical argument that the velocity has to lie somewhere
between 8

to 5

and that the total probability is ) i.e.,

1
1
8 b v
x
x x x
f "v # d v . > e d v . )



The above integral is a standard integral
1
8 a x
<
e d x

),1
,1
Thus,
1
x
b v
8
> e

d x . > "

, b#
),1
"(.(<#
*ut since we want the right side to be unity, > "

, b#
),1
. ) or > . " b ,

#
),1
and
f " x # . "b , E#
),1

1
8 b v
x
e

'rom a probability distribution such as f " x#, average uantities can be determined. The
averages of x and x
1
are given by
P x ; .

"b , E#
),1
x
1
8 b v
x
e
d x . < "(.()#
P x
1
; .

x
1
"b , E#
),1

1
8 b v
x
e
d x .),1b "(.(1#
The averages have been denoted by P ; . &e have also used another standard integral,
1
1 a x
<
x e

dx . ),7 "E,a
(
#
),1
"(.((#
The integral for P x ; is !ero because the value of the integrand for positive x is eual
and opposite to its value at / x. Thus the area on the left of x . < is eual and opposite in
sign to the area on the right. This is a special case of a general result that the integral of
6B
the product of an even function and an odd function of x is !ero over a symmetric interval
around !ero.
To evaluate b, we ta-e the help of the -inetic theory of gases. Ro loo- up the details.
The pressure of a gas is given in terms of the mean suare velocity "speed# as
p . ),( "N, V# m Pv
1
;
&here N, V . "number of molecules of the gas , volume# . the density of the gas. *ut N
. nN
%
where n . number of moles and N
%
, the %vogadro numberX and since pV . nQT,
we have
pV . ),( Nm P v
1
; . ),( n N
%
m P v
1
; . nQT "(.(7#
P v
1
; . ( QT , mN
%
. ( -
*
T , m "(.(9#
&here -
*
. Q , N
%
is the *olt!mann constant, ).(?<6 H )<
81(
I , G. $ince
Pv
1
; . ( -
*
T , m, we have Pv
x
1
; . -
*
T, m and substituting, we get b . m , 1 -
*
T.
Euations for f and ' now become
f"v
x
# . "m , 1 -
*
T #
),1

8 m v , 1 - T
*
1
x
e
"(.(6#
'"v
x
, v
y
, v
!
# . "m , 1 -
*
T#
( , 1

*
1 1 1
m "v 5 v 5 v #,1- T
x y !
e

"(.(@#
This is the Caxwell 8 *olt!mann distribution of molecular speeds. '"v
x
, v
y
, v
!
# dv
x
dv
y
dv
!
gives the probability of finding an arbitrary molecule with a velocity "v
x
, v
y
, v
!
# in the
volume element dv
x
dv
y
dv
!
. % more appealing interpretation of the same is that it is the
fraction "of the total molecules# of molecules having velocities "v
x
, v
y
, v
!
#. %nalogous to
the radial probability distribution in coordinate space, we can now estimate the
probability of finding a particle in a spherical shell of volume
1
7 v dv . This probability
in such a spherical shell of radius v and thic-ness dv is given by

1
7 v dv "m , 1 -
*
T#
( , 1

*
1 1 1
m "v 5 v 5 v #,1- T
x y !
e

"(.(?#
3.( T"er%od.n%ic Function!
&e will be restricting ourselves to the canonical ensemble here. >onsider a collection of
N molecules. The probability of finding a molecule with energy E
i
is eual to the fraction
of the molecules with energy E
i
.
In the collection of N molecules, how many molecules "n
i
# have the energy E
i
M.This has
to be N exp
80 Ei
, T. This is because the fraction of molecules n
i
,N having the energy E
i
is
e
80 Ei
, T which is the same as the probability of finding a molecule with energy E
i
in the
collection. The average energy is obtaining by multiplying E
i
with its probability and
summing over all i . ie,
8 E 8 E 8 E
i i i
i i
i
i i
) )
E E + E , T . 8 e . 8 e
T T
e

< >

.
) T ln T
.
T



"(.(B#
@<
Retailed connection between partition functions and thermodynamic functions has been
derived in >hapter 1, $ection 1.7.1, The relations between T and pressure and entropy are
given by Ens. "1.)6?# and "1.)@)# respectively. The pressure p can also be obtained as
the ensemble average of "8YE,YV#
T
. "8 d w,dV#
T
giving,
) ) ln
i
E
i i
i
i i
E E e Q Q
p P
V V Q Q V V

"(.7<#
The entropy is given by
ln " # S k Q E +
"(.7)#
The notation change is that Z is written as T here and
E
is written as
E
.
:et us recall the four fundamental thermodynamic relations.
dE TdS pdV
"(.71#

dH TdS Vdp +
"(.7(#
dA SdT pdV
"(.77#
dG SdT Vdp +
"(.79#
2ere, E is the internal energy, 2 . E 5 pV, the enthalpy, % . E /T$, the 2elmholt! free
energy and U . 2 / T$, the Uibbs free energy. :et us now replace PE; by simply E or
more correctly by E / E"<#, where E"<# is the reference value of E at T . <. This is
necessary because, the absolute value of E is not measurable and only differences can be
measured. The same idea holds for 2, % as well as U. Therefore, we rewrite the euation
for energy as
E / E"<# . 8 "Y ln T , Y0#
V
"(.76#
'rom the euation for enthalpy, 2 . E 5 pV, we get,
"<# " ln # " ln #
V
H H Q kTV Q V

+
"(.7@#
$ince p . 8 "Y%,YV#
T
, we get from "(. #,
"<# ln A A kT Q
"(.7?#
%nd finally we have for U
"<# ln " ln # G G kT Q kTV Q V

+
"(.7B#
'or an ideal gas, pV . nQT where, n . number of moles of the gas and Q . N
%
- . the gas
constant and N
%
is the %vogadro number. $ubstituting this and T .
N
,NV in the above
euation, we get,
"<# ln ln V G G kT q kT ! "T + +
Noting that N . nN
%
and using $tirling[s approximation,
"<# ln " ln # G G !"T q kT ! "T + +
"<# ln ln ln ln
#
A
A
q q
G G ! "T q ! "T ! ! "T ! "T

+
"(.9<#
&here,
m
. , n, the molar partition function in units of mol
8)
. The function
DU"T# /U"<#F , T is referred to as the Uaiuue function.
E$%&le 3.- The euipartition principle states that each uadratic degree of freedom
contributes \ -T to the energy at high temperature. Verify this assertion for the
rotational, translational and vibrational motions of a diatomic molecule.
@)
Solution
>onsider the molecular partition functions. The rotational energy is given by
) ) ) )
rot rot
rot
q
B kT
q B





"(.9)#
The classical expression for the rotational energy is ( )
1 1
)
1 x y
I +
, where I is the moment
of inertia and ]
x
and ]
y
are the angular velocities in the x and y directions. The rotation
along the molecular axis "the ! axis here# has no meaning in uantum mechanics because
the rotations along the molecular axis lead to configurations which are indistinguishable
from the original configuration. The two degrees of freedom have thus given a value of
-T. The translational contribution gives,
(
(
) ( ( (
1 1
tr tr
tr
q V
kT
q V

"(.91#
Thus, the three translational degrees of freedom in three dimensions satisfy the
euipartition theorem. Turning to the vibrational contribution, we get,
( )
( )
1
) )
)
)
)
h$ h$
vib
vib
h$
h$
vib vib
q h$ e e
h$ kT i% h$
q q e
e

<<

"(.9(#
The classical expression for the vibrational energy is \ -x
1
5 \ v
x
1
. %t high
temperature the euipartition theorem is valid but at low temperature, only a few
vibrational states are occupied and the euipartition principle is not valid.
E$%&le 3./ >alculate the vibrational heat capacity for diatomic and s-etch its
temperature dependence.
Solution The vibrational energy is given by the above expression and the heat capacity at
constant volume, >
V
, is given by YE,YT.
&e have, Y ,YT . "Y0,YT# "Y ,Y0# . "8),-T
1
# "Y ,Y0# . "8- 0
1
# "Y ,Y0# "(.97#
Therefore, >
V
. "8- 0
1
# "Y ^
vib
,Y0# .
( ) { }
( )
1
1
1
1
) " # " #
)
)
V
V
T V
h$ h$ h$
h$
T
e
e h$ e h$ e
T
k h$ k
e
e

+


' ;

"(.99#
'or large T, the molar >
V
becomes N
%
- . Q and for small T, >
V
goes to !ero as shown in
the s-etch below. The vibrational temperature
V

is defined as
V

.
h$
, -. 'or 2
1
, it
has a value of 6(1( G and for I
1
it is (<B G.
@1
'igure (.( Vibrational heat capacity of a diatomic as a function of
V

,T .
3.3 Rottionl nd Vibrtionl Prtition Function! o) Pol.to%ic
Molecule!
'or a polyatomic molecule containing n atoms, the total number of coordinate degrees of
freedom is (n. 3ut of these, three degrees of freedom are ta-en up for the translational
motion of the molecule as a whole. The translational partition function is given by the
same formula as E. "(.1<# with the mass now given by the total mass of the molecule,
_m
i
where m
i
is the mass of a constituent atom. &e have to consider the three rotational
degrees of freedom and the (n / 6 vibrational degrees. 'or a linear molecule, the
rotational motional motion along the molecular axis is uantum mechanically not
meaningful as the rotated configuration is indistinguishable from the original
configuration. Therefore, for a linear molecule, there are two rotational degrees of
freedom and (n / 9 vibrational degrees of freedom.
To investigate the rotational motion, we need to fix the center of mass of the molecule
and calculate the three principal moments of inertia I
%
, I
*
and I
>
of the ellipsoid of
inertia. The center of mass is defined as the point for which the following identities hold.
<
i i i i i i
i i i
# x # y # z

"(.96#
The inertia products are defined by
( )
1 1
X
xx i i i xy i i i
i i
I # y z I # x y +

"(.9@#
The other components I
yy
, I
x!
,.. are defined analogously. To find the direction cosines
" #
i i i

of the three principle moments of inertia, we need to solve the following matrix
euations.
" # <
xx xy xz
I I I
"(.9?#
" # <
xy yy yz
I I I +
"(.9B#
" # <
xz yz zz
I I I +
"(.6<#
If the off diagonal terms I
xy
are !ero in the above euations then the x, y, ! axis will be
the principal axis. The energy of a rotor with the three moments of inertia I
%
, I
*
and I
>
is
given by
@(
1 1 1
1 1 1
) ) )
1 1 1
1 1 1
& A B
A A B B & &
A B &
' ' '
I I I
I I I
+ + + +
"(.6)#
2ere,
,
A B

and
&

are the three angular speeds and :

%
, :
*
and :
>
are the three
angular momenta. 'or a symmetric top molecule such as ammonia, or chloromethane,
two components of the moments of inertia are eual, i.e., I
*
. I
>
. The rotational energy
levels of such a molecule are specified by two uantum numbers I and G. The total
angular momentum is determined by I and the component of this angular momentum
along the uniue molecular axis is determined by G. The energy levels are given by
1
, 1 1
" )# " # X ,
? ?
J (
B A
h h
B J J A B ( B A
$I $I

+ +
in cm
8)
"(.61#
&here, I ta-es on values <,),1,O.and G . 8 I, 8 I 5 ), 8 I 5 1,O<, ), 1,OI. The rotational
partition function is given by
I
1
rot
I < G I
8 *I"I5)# , - T "%8 *#G , - T
)
"1 I 5 )# e e

"(.6(#
This can be converted to an integral as in "(.)7# and the result is
), 1
1 1 ), 1
1 1
? ?
B A
rot
I kT I kT
q
h h

_ _

, ,
"(.67#
'or asymmetric tops, the expressions for rotational energies are more complex and the
conversions to integrations are not easy. 3ne can actually calculate the sum of terms
using a computer. %n intuitive answer can be obtained by integrating over the angular
momenta '
A
, '
B
and '
&
as
" , # , ), 1 ), 1 ), 1
"1 # "1 # "1 #
H p q kT
A & & A B &
e d' d' d' I k T I k T I k T

"(.69#
%nd then multiplying by a factor of ? E
1
,L h
(
we get the rotational partition function. The
factor of ?E
1
accounts for the angular integration. 'or any axis chosen in a molecule, a
complete rotation contributes a factor of 1E. Integration over all possible orientations of
this axis contribute another factor of 7E. The symmetry number L corrects for
overcounting of rotational configurations and the factor of h
(
is for the conversion from
the classical phase space to the uantum mechanical phase space. The final result is
), 1 ), 1 ), 1
1 1 1 ), 1
1 1 1
? ? ?
& A B
rot
I kT I kT I kT
q
h h h

_ _ _

, , ,
"(.66#
&e can explicitly obtain the classical rotational partition function of an asymmetric top.
by writing the classical expression for the rotational energy in terms of the Euler angles.
The orientation of a rigid rotor can be specified by there Euler angles `, a and b with the
ranges of angles < to E, < to 1E and < to 1E respectively. The rotational 2amiltonian for
the -inetic energy can be written in terms of the angles and their conKugate momenta
, p p

and
p

as
1
1
sin cos
" cos #
1 sin sin
A
H p p p
I

' ;

@7

1
1
1
cos sin )
" cos #
1 cos cos 1
B &
p p p p
I I

+ + +
' ;

"(.6@#
The rotational partition function is given by
1 1
" , # ,
(
< < <
)
H p q kT
rot
q e dp dp dp d d d
h

"(.6?#
The integrations can be simplified by rewriting H)p*q+ , kT as
1
1 1
1 1
) sin cos ) ) sin cos
, " cos #
1 sin cos
sin
A A B B A
A B
H kT p p p
I kT I I I I
I I

_ _

+ +
' ;
_
, ,

+


,
1
1
1 1 1
) ) )
" cos #
1 sin 1 sin cos
A B &
A B
p p p
k T I I (TI
I I

+ +
' ;
_

+


,
"(.6B#
=sing the following integral,
1 1
" #
,
a x b a x
e dx e dx a

+



"(.@<#
Integration over p
-
gives using the above expression,,
), 1
1 1
), 1
sin cos
"1 #
A B
kT
I I

_
+

,
"(.@)#
Integration over p
.
gives the factor,
), 1
1 1
), 1
sin cos
"1 # sin
A B
A B
k T I I
I I


_
+

,
"(.@1#
This cancels partly the second suare root in the earlier expression. Integration over p
/
gives the factor
), 1
"1 #
&
k T I "(.@(#
Integration over `, a and b gives a factor of ? E
1
.
1 1
< < <
sin 1X 1 X 1 d d d



"(.@7#
>ombining all the integrals, we finally get,
), 1 ), 1 ), 1
1 1 1 ), 1
1 1 1
? ? ?
& A B
rot
I kT I kT I kT
q
h h h

_ _ _

, , ,
"(.@9#
2ere, we have reintroduced the symmetry number L as before. %nd with
@9
1 1 1
1 1 1
, ,
? ? ?
A B &
A B &
h h h
I kT I kT I kT

"(.@6#

The partition function simplifies to
1
)
ln ln
1
rot
A B &
q

"(.@@#

%nd the molar thermodynamic function can be readily calculated as
1
1
( )
ln ln X ln
1 1 1
A B & rot
rot rot rot
V A B &
A "T
A "T q S "
T


_ _
+


,
,
"(.@?#
%nd
,
( (
X
1 1
rot V rot
E "T & " "(.@B#
Improvements over the classical approximation for the rotational partition function have
been obtained and one of the improved version is
q
rot
1
<
1
1 1 1
)
B6
& A B
rot
A B & A B B & A &
I I I h
q
kT I I I I I I I I I
1 _
+ + +
1
1 , ]

"(.?<#
where
<
rot
q is the classical approximation.
:et us now consider the vibratinal partition function. &e have already considered the
:agrangian : for the N oscillators in E. ").7(#. &e saw there that there were cross terms
involving x, y and ! components of different atoms. This ma-es the solution of the
problem difficult. 2owever, it is possible to ta-e appropriate linear combinations of the
coordinates so that the cross terms are eliminated and the classical 2amiltonian as well as
the operator corresponding to it contains no cross terms and in terms of the new
coordinates, the 2amiltonian can be written as,
1 1
1
1
) )
1 1
% %
i
i
i i
i
k
H

h
"(.?)#
2ere, the degrees of freedom % is (n 8 9 for a linear molecule and (n 8 6 for a nonlinear
molecule. 2ere, -
i
is the force constant and
i
is the reduced mass for that particular
vibrational mode which is referred to as a normal mode. The E. "(.?)# represents %
linearly independent harmonic oscillators and the total energy for such a system is
)
1
)
" #
%
vib i i
i
! h

"(.?1#
The vibrational freuencies are given by
)
1
i
i
i
k

"(.?(#
The vibrational partition function is given by the product of f vibrational functions for
each freuency.
@6
,
,
, 1
,
)
") #
vib i
vib i
T
%
vib T
i
e
q
e

,
,
,
vib 0 i
h k
"(.?7#
&here, the
, vib 0

is called the characteristic vibrational temperature. The molar energies

and the heat capacities are given by
,
,
,
, ,
,
)
1 )
vib i
vib i
T
%
vib i vib i
vib T
i
e
E k
e

1

+ 1

1
]

"(.?9#
,
,
1
,
,
, ,
1
) ") #
vib i
vib i
T
%
vib i
V vib T
i
e
& k
T e

"(.?6#
'igure (.( The three vibrational modes of water, the symmetric stretch "(696.@, 9)6<#,
the asymmetric stretch "(@99.?, 9(6<# and the bending mode ")9B7.?,11B<# are shown.
The vibrational freuencies in cm
8)
and the characteristic temperature in G for each mode
are shown in parenthesis.
E$%&le 3.- The three characteristic rotational temperatures for N3
1
are )).9 G, <.617 G
and <.9B< G and the three vibrational temperatures in Gelvin are )B<<, )B?< and 1((<.
calculate the rotational and vibrational partition functions at (<<G.
$olutionc The rotational temperature is given by
1
1
?
A
A
h
I k

The rotational partition
function becomes,
), 1 ), 1 ), 1
), 1
rot
A B &
T T T
q

_ _ _

, , ,
( ) ( ) ( )
), 1
), 1 ), 1 ), 1
(<<,)).9 (<<, <.617 (<<, <.9B<
rot
q

. ").@@1 , 1# H 9.)<? H 1).B@ H 11.99 . 1171.7

The vibrational partition is calculated by ta-ing the !ero point energies as the reference
points with respect to which the other energies are measured.
,
, ,
, 1
, , )B<<, (<< )B?<, (<< 1((<, (<<
) )
) ) ) )
) ) ) ") # ") #
vib i
vib i vib i
T
% %
vib T T
i i
e
q
e e e e e

. ).<<)? H ).<<)7 H ).<<<7 . ).<<(9
The implication is that while several rotational state sare accessible at room temperature,
very few vibrational states "other than the ground vibrational state# are accessible
@@
3.+ Ort"o nd Pr 0.dro1en!
The molecules of hydrogen can exist in two forms depending on the spins on the two
hydrogen nuclei. If both the nuclear spins are parallel, the molecule is called ortho and if
the spins are antiparallel, it is referred to as para "In disubstituted ben!ene, para refers to
the two groups at two opposite ends, while in ortho, they are adKacent or dparallele to
each other#. The spin on the hydrogen nucleus has a magnitude of \ f. The presence of
nuclear spins leads to very interesting conseuences for the populations of the rotational
states and on a macroscopic scale, has conseuences on measured entropies and heat
capacities as well.
The total partition function of 2
1
can be written as

tot
.
elec

vib

rot

trans

nucl
"(.?@#
where, the subscripts refer to the respective motions.
%fter dhalfe a rotation, the nuclei are superimposed on each other. $ince a proton is a spin
half nucleus, the total wavefunction must be antisymmetic with respect to the exchange
of the particles. i.e.,
"), 1# "1,)#
"(.??#
The translational motion refers to the motion of the molecular center of mass and has no
influence on the symmetry of the nuclear wavefunction. Vibrational motion depends on
the magnitude of the internuclear distance and has no effect on the particle exchange. The
electronic motion also has no effect on the symmetry properties of the nuclear
wavefunction. Therefore, the product of the nuclear spin and rotational wavefunctions
must be antisymmetric with respect to the particle exchange.
'or the nuclear spin functions, there are four combinations. 3ne combination is a singlet
,
")# "1# "1# ")#
!1 2

"(.?B#
%nd the other three combinations are the three states of a triplet.
,
")# "1#
")# "1# "1# ")#
")# "1#
!1 t

+ "(.B<#
The rotational wavefunctions " b
r
# are given in terms of the associated :egendre
polynomials
W W
" #
#
3
P x where x . cos ` .
W W
"cos #
i # #
r 3
e P

"(.B)#
( )
W W 1
W W, 1
W W 1
W W
" # ) " )#
" # ) X " #
1 V
# 3 3
#
# 3
3 3 # 3 3
d P x d x
P x x P x
dx 3 dx

"(.B1#
&hen the nuclei are interchanged, ` becomes E 8 ` and a is changed to a 5 E. The
polynomials change as

W W W W W W
" # " )# " #X " # " )# " #
3 # 3 # #
3 3 3 3
P x P x P x P x

"(.B(#
@?
The exponential function changes as
" # W W
" )#
i # i # i # # i #
e e e e
+
"(.B7#
Therefore, the rotational wavefunction changes as
W W W W
" , # " )# " )# " , # " )# " , #
3 # # 3
r r r

+ "(.B9#
r

symmetrical for even K, and antisymmetrical for odd K "(.B6#
>ombining the nuclear spin and the rotational parts, we see that, the product
r

!1

must be antisymmetrical "with respect to the exchange of nuclei#for half integral nuclear
spins and symmetrical for integral spins. To accomplish this, the singlet nuclear states
"para# must be combined with the even rotational functions and the triplet nuclear states
must be combined with the odd rotational states. The rotational partition functions for
ortho and para hydrogens are, thus,
" )# ,
, ,
),(,9..
( "1 )#
"
0 0 T
ortho !1 t r odd
0
q q q 0 e
+

"(.B@#
%nd
" )# ,
, ,
<,1,7..
) "1 )#
"
0 0 T
para !1 2 r eve!
0
q q q 0 e
+

"(.B?#
&here J
Q
is the rotational temperature defined by E. "(.)1#.
The total partition function consisting both ortho and para hydrogens is given by
" )# , " )# ,
,
<.1.7.. ),(,9..
) "1 )# ( "1 )#
" "
0 0 T 0 0 T
rot !1
0 0
q 0 e 0 e
+ +

+ + +

"(.BB#
The ratio of ortho to para hydrogens at thermal euilibrium is given by
" )# ,
),1,(..
" )# ,
<.1.7..
( "1 )#
"1 )#
"
"
0 0 T
0
o
0 0 T
p
0
0 e

0 e
+

"(.)<<#
%t high temperature, the two summations become eual and therefore, the high
temperature limit of
o p

is (. %t low temperature, the ratio becomes,

1 ,
9 ,
(" ( ......#
<,
)") 9 ....#
"
"
T
o
T
p
e
e


+

+ +
as
< T
"(.)<)#
% good experimental verification of the above analysis is a comparison between the
calculated rotational heat capacities at constant volume ">
V
#
rot, nu
"calculated from
E T < > , where PE; .
,
ln
rot !1
q
#. The heat capacities are shown as a function of
temperature in 'ig. (.7.
@B
'igure (.7 The heat capacities of o8 and p8 hydrogens as a function of temperature. The
curve mar-ed Exp depicts the experimental data, the curve e represents the data for an
euilibrated mixture of o8 and p8 at a given temperature and the curves o8 and p8
represent the heat capacities of pure o8 and pure p8 hydrogens.
The curve mar-ed Exp gives the experimental data, the curve e represents the data for
an euilibrated mixture of o8 and p8 at a given temperature. The curves o8 and p8
represent the heat capacities of pure o8 and pure p8 hydrogens calculated from the o8 and
p8 partition functions given by Es. "(.B@# and "(.B?# respectively. Initially it was a
pu!!le as to why the experimental data differs from the calculated values. In fact, the
experimental data seemed to agree very well with the following euation.
( ) ( ) ( )
, , ,
( )
" # " #
7 7
V V V
rot !1 rot !1 rot !1
& & ortho & para + "(.)<1#
The reason for this is that, when 2
1
is cooled down from a higher temperature, the ortho
para ratio continues to remain <.@9 , <.19 "the high temperature value# because the ortho
para interconversion rate is very very small and we do not reach the euilibrium
composition unless a catalyst such as activated charcoal is added to the gas mixture. E.
"(.)<1# corresponds to a dfro!en high temperature mixturee of ortho para hydrogens. In
the presence of the catalyst, the experiments also give the curve labeled as e in the
graph. This in indeed a very nice case where the experiments support not only the
methods of statistical thermodynamics but also of the antisymmetry principle for bosons
and fermions. If we consider the case of
)6
1
4 , where the nuclear spins are !ero, the
rotational wavefunction has to be symmetric as only symmetric wavefunctions are
permitted for bosons. Thus, only even rotational states contribute to the partition
function.
?<
" )# ,
)6
, 1
<,1,7..
" # "1 )#
"
0 0 T
rot !1
0
q 4 0 e
+

"(.)<(#
C"e%icl E#uilibri
>onsider a reaction which may be represented as
a % 5 b * g c > 5 d R 5 e E "(.)<7#
The euilibrium constant
eq
(
for the reaction is given by
ln
o
eq
G "T (
"(.)<9#
&here the superscript
o
represents the standard state, i.e., the state at ) bar pressure at
each temperature. The free energy of a species is given by e. "(.(B# as
"<# ln
#
A
q
G G ! "T

"(.)<6#
%nd the molar free energy in the standard state for a species I is given by
,
, ,
"<# ln
o
J # o o
J # J #
A
q
G G ! "T

"(.)<@#
The standard free energy change for this reaction is given by
, , , , ,
, , , , ,
"<# "<# "<# "<# "<#
ln ln ln ln ln
o o o o o o o
rea$tio! r & # 5 # E # A # B #
o o o o o
& # 5 # E # A # B #
A A A A A
G G $G d G eG aG bG
q q q q q
$ "T d "T e "T a "T b "T

+ +
+ +

"(.)<?#
*ut since U"<# is the same as E"<#,
( ) ( )
< < , , , , ,
"<# "<# "<# "<# "<#
o o o o o o o
& # 5 # E # A # B #
r r
G E $G d G eG aG bG + +
"(.)<B#
%nd the euilibrium constant is given by
( )
( ) ( ) ( )
( ) ( )
, , ,
<
, ,
ln ln
$ e
o o o
& # A 5 # A E # A
o
a b
r o o
A # A B # A
q q d q
"T ( E "T
q q

"(.))<#
( ) ( ) ( )
( ) ( )
( ) <
, , , ,
, ,
o
r
$ e
o o o
E "T & # A 5 # A E # A
a b
o o
A # A B # A
q q d q
( e
q q

' ;


"(.)))#
It is instructive to analyse G of E. "((.)))# in terms of molecular energy levels and their
populations. >onsider the energy levels for the following euilibrium,
A

B "(.))1#
The energy levels of systems containing only %, only * and both % and * are
schematically shown in 'ig. (.9.
?)
'igure (.9 "a# Energy levels of individual molecules %, * and the individual populations
of these levels, "b# Energy levels of the combined system % and * and the relative
populations of the combined levels at euilibrium "schematic#.
If the molecules of % and * are -ept in separate containers, each container will be in a
state of euilibrium with the populations of % and * given by their separate *olt!mann
distributions. This is shown in 'ig (.9"a#. The partition functions of the systems % and *
are given by
%
and
*
. 'ig (.9"b# shows the combined system and the population of the
levels of the combined system. The population of the i th level of the combined system is
given by
i
E
i i
e
! P
q

"(.))(#
&here is the partition function of the combined system and E
i
is the energy of the i
th
level of the combined system. In the combined system, the total population of %
molecules at euilibrium is given by summing n
i
for % molecules. $imilarly, for *. &e
thus have,
" #
i A
E
A i A
A33 3eve32 o% A 3eve32 o% A

! e q
q q


"(.))7#
< <
" # D" # F ,
i B i B
E E E E "T
B i B
A33 3eve32 o% B 3eve32 o% B 3eve32 o% B

! e e q e
q q q
+

"(.))9#
?1
The prime in e "((.)6# indicates that the levels "E
i
#h
*
are now measured from the lowest
level of the combined states of % and *, which is "E
<
#
%
. Expressing Eh
i
in terms of E
i
, we
have,
( ) ( ) ( ) ( ) ( )
< < < i i i
B B B A B
E E E E E E + +
"(.))6#
The euilibrium constant is now given by
K = NB/ NA = (q B / qA)
<
, E "T
e

"(.))@#
'or a more general reaction % 5 *
I
> 5 R, the euilibrium constant is given by
( = 6 q
&
q
5
, q
A
q
B
7 e "(.))?#

&here, 8E
9
= )E
9
+
&
: )E
9
+
5
; )E
9
+
A
; )E
9
+
B
"(.))B#
3., Acti2ted Co%&le$ t"eor.
In many reactions, mixing the reactants does not lead to products instantaneously. % short
lived high energy configuration of molecules, referred to as the activated complex is
formed which may lead to products or the reactants depending on the specific motions in
the activated complex. %lthough the terms transition state and activated complex are
often used synonymously, the transition state does not have a chemically significant life
time. >onsider the reaction
A : B < &

< P "(.)1<#
The potential energy diagram for this reaction is given in 'ig (.6. In E. "(.)1<#, >

is
the activated complex which forms the products + with a unimolecular rate constant -
.
'igure (.6. +otential energy of reaction as a function of the reaction coordinate. The
energy levels of the shallow activated complex >
i
are shown in the inset to the right.
The ordinate is the potential energy "+E# and the absissa is the reaction coordinate. %t a
specific configuration of the reactants, the potential energy is maximum, the slope is !ero
and the +E falls to lower values in both the forward and the reverse direction. %ll the
structures in the vicinity of this transition state or configuration may be considered as the
4activated complex4, which is very reactive. % motion along the 4forward4 direction will
?(
lead to the products. The activated complex theory or the transition state theory provides
a way to calculate the rate constant for the reaction. The assumptions involved in the
transition state theory arec
)# The electronic motion "which can only be described only uantum mechanically# may
be separated from the motion of the nuclei and a classical description of the nuclear
motion is used to evaluate the rate constant. 1# The energy distribution of the reactants is
described by the euilibrium *olt!mann distribution throughout the reaction.
(# The activated complex which has crossed the transition state can not return to the
reactant configuration. In the transition state, motion along the reaction coordinate may
be separated from all other motions. 7# The activated complex is also distributed
according to the *olt!mann distribution. The rate of the reaction can thus be expressed
as
d 6& 7 , dt = k 6& 7 "(.)1)#
The concentration of & is expressed in terms of the concentrations of % and * through
the proportionality constant ( "which is not an euilibrium constant#.
6& 7 = ( 6A7 6B7 "(.)11#
substituting E. "(.)11# into E. "(.)1)#, we have,
d 6& 7 dt = k
=
6A7 6B7 >here k
=
= k ( . "(.)1(#
&e now will determine the values of the constants k and ( ? It should be obvious that
the process represented in E. "(.)11# is not a regular euilibrium process because, as the
products are formed, 6A7 and 6B7 are decreasing with time and 6& 7 is not increasing
with time since the collisions responsible for the formation of & are themselves
decreasing in freuency as the reaction evolves. The activated complex can exhibit
several motions such as translations, rotations and vibrations, since it has a finite life
time. The motion leading to the product is assumed to be a specific vibration with a
freuency N. This vibrational motion along the reaction coordinate is euated to the
constant k ? The transition state is in a shallow well with a vibrational freuency much
smaller than that of the reactants and the products. The energy levels of the shallow
activated complex & are shown to the right in 'ig. (.6.
k @ A "(.)17#
3ur next tas- is the determination of the concentration of & . :et us express the
euilibrium constant for the reaction A : B < & in terms of the partial pressures of %,
B and & "p
A
* p
B
and p
&
, written simply as p
&
#.
( = 6& 7 , 6 A7 6 B7 = 6 p
&
,
p
7 , 6 ) p
A
,
p
+ ) p
B
,
p
+ 7 "(.)19#
&here
p
is the standard pressure of ) bar. These partial pressure can be expressed in
terms of molar concentrations of %, * and > as follows.
6A7 = !
A
, V B V = ! "T , pB p
A
= x
A
p = !
A
p , ! "(.)16#
?7

6A7 = !
A
p , !"T = x
A
p , " T = p
A
, "T or p
A
= "T 6A7 "(.)1@#
In E. "(.)16#, V . total volume, p . total pressure, ! . total number of moles, !
A
.
number of moles of A, x
A
. !
A
, !, the mole fraction, " is the gas constant and T absolute
temperature $ubstituting each partial pressure in terms of the mole fractions, we have
( = "T 6& 7 ,
p
, 6)"T 6A7 ,
p
+ )"T 6B7 ,
p
+7 "(.)1?#
= 6& 7
p
, 6A7 6B7 "T "(.)1B#
or & = 6A7 6B7 "T ,
p
( "(.)(<#
>omparing this euation with E. "(.)11#, we have
or ( = ( "T ,
p
"(.)()#
In E. "(.)11#, ( was merely a proportionality constant and now it has been related to
the euilibrium constant for the formation of the activated complex
$pecific vibration of the activated complex along the reaction coordinate leads to
product formation. &hen we have a reaction such as A : B

& , the euilibrium
constant given in terms of partition functions by "see E. (.)))#.
( = )A q
&
, qA qB+
<
E
e



"(.)(1#
&here 8E
9
= )E
9
+
&
; )E
9
+
A
; )E
9
+
B
. 2ere
A
is the %vogadro number. In the above
euation, we have suppressed the standard state and molarity labels
o
and m of E.
"(.)))#. Qeturning to E. "(.)1(#, k
=
= k ( , the unimolecular rate constant k is
ta-en as proportional to the vibrational freuency along the reaction coordinate k = A .
The partition functions for this vibrational motion of the transition state is
) q
V
+
&
= C, )C;
,
B
h k T
e

+ "(.)((#
=sually this freuency is uite small because the transition state falls apart into products
with this freuency. Very high freuencies of the transition state are improbable and they
would lead, not to the usual products but to rather highly disintegrated products.
Expanding the denominator, e
;hA,k
B
T
C;

hA,k
B
T,
) q
V
+
&
= kBT , h A "(.)(7#
&riting
>

in terms of the vibrational modes "

v
#
>

D which is approximated as -
*
T , h
NF and all the other remaining modes D
&
q
F, we have for
>

,
q
&

= )k
B
T , h A+
&
q


( 3.135)
>ombining Es. "(.)1(#, "(.)()# and "(.)(1#, we have,
k
=
= k ( = A ) "T ,
p
+ ( = (A k BT , h A+6) A
&
q
, q A qB+
<
E
e



"T ,
p
+ "(.)(6#
?9
= kB T , h
(
"(.)(@#
&here
(
is the second, suare brac-eted expression in E. "(.)(6# which is a-in to an
euilibrium constant with the vibrational mode of & removed. There are often factors
not included in E. "(.)(@# and they are included through a transmission coefficient j and
the rate constant in the transition state theory becomes,
k
=
= D ) k
B
T , h +
(
"(.)(?#
&e want to express
(
in terms of molecular partition functions. :et us obtain a formula
for simple species of % and * where % and * are atoms. The partition function of atoms
is simply the translational partition function "as rotations and vibrations are absent#. The
translational partition function of %, using the molar volume, becomes
( )
(, 1
<
,
1
tr A A B #
q # k T V

"(.)(B#
< (
,
,
tr A # A
q V
, where
( )
), 1
, 1
A A B
h # k T

"(.)7<#
&here V
9
#
is the standard molar volume, given by "T ,
p
? 'or the activated complex,
the partition function is the product of translational, vibrational and rotational partition
functions, because in our present model, %* is a diatomic. 2owever, we have already
considered the vibrational partition function in E. "(.)(9# and we need to consider
&
q

now which includes only rotation and translation.
This is given by
1 < (
"1 , #
B #
& &
q I k T V

h
"(.)7)#
The first term in the brac-ets is the rotational partition function of the activated complex.
The moment of inertia I is given by r
1
where r is the 4bond length4 of the activated
complex and . "m
%
m
*
# , " m
%
5 m
*
# is the reduced mass. $ubstituting the values of
%
,

*
and
>
in euations "(.)(6# and "(.)(?#, we get
k
=
= D )k
B
T , h+)"T ,
p
+
A

( ( ( <
,
A B #
&
V

) = I k
B
T , h
=
+
<
E
e



"(.)71#
>anceling "T ,
p
and V
9
#
" which are eual # and substituting the values of
A
,
B
and
&
, we get
k
=
= A )E kBT ,FG+
C, =
)D F r
=
+
<
E
e



"(.)7(#
If we identify the reaction cross section as j E r
1
, this euation is identical to the euation
derived using a simple collision theory. It is indeed remar-able that two very different
approaches give the same resultV Roes it mean that this result is more 4correct4 than the
result that is usually obtained from a single theory M &hile it would be tempting to say
yes, what this means is that we have captured some of the essential features relevant in
the dynamics of chemical reactions in both approaches. 'urther improvements will come
when we consider the cross sections of each of the states of the reacting species and also
when we remove the reuirement that &

is not in euilibrium with A and B. In the next

section, we relate -
1
to the activation parameters for the reaction
?6
%ctivation +arameters
In the %rrhenius theory, the only activation parameter that was introduced was the
activation energy. In the transition state theory developed in this chapter, we have related
the concentration of the activated complex to the reactant concentrations through an
euilibrium constant (. Treating "
p
, QT#
(
of Es. "(.)1B# and "(.)(6# as an
euilibrium constant "although one vibrational mode is removed from >

#, we can
define the Uibbs free energy of activation kU as
8G

. 8 "T 3! )
(
p
, "T+ "(.)77#
the rate constant -
1
becomes
k2 = D k
B
T ,h )"T ,
p
) e
, G "T
e

"(.)79#
The free energy of activation can be divided into enthalpy and entropy terms "analogous
to G = 8H H TS # through
8G

= 8H

; T 8S

"(.)76#
'or the time being let us either ta-e D . ) or include it in the entropy term. The rate
constant then becomes
, ,
1
S " H "T
k Be e


with * . )k
B
T , h+) " T ,
p
+ "(.)7@#
The activation energy of the %rrhenius euation k
=
. A e8
Ea,QT
,
a
E
is defined through
a
E
. Q T
1
" d ln -
1
, dT#. "(.)7?#
$ubstituting -
1
into this, we get
1
a
E H "T

+ "(.)7B#
$ubstituting this in E. "(.)7@#, we get
k2 = e
- 2
B
, S "
e

e
; E
a
, "T
"(.)9<#

and the %rrhenius factor A becomes
A = e
- 2

, S "
e

"(.)9)#
=sually, when % and * form a complex "%*#
l
, more ordering is created and entropy is
reduced. k$
l
is thus negative. This is based on a collision complex model for the
reaction. In addition to this decrease, there is a further orientational or steric decrease due
to the preference of only certain configurations for the activated complex "as in the case
of a reaction between molecules such as >
1
2
7
and 2
1
#. The steric factor P of collision
theory may be associated with
,
2teri$
S "
e

, i.e.,
P .
,
2teri$
S "
e

, "(.)91#
where,
$o33i2io!a3 2teri$
S S S

+

"(.)9(#
$imilar to activation enthalpies and entropy, activation volume can also be defined
through
( )
G p

. V

"(.)97#
'or reactions in solution, these kV values are small, but for gas phase reactions, they
may be approximated by the ideal gas values
?@
P V

= !

"T "(.)99#
E$%&le 3.13
'or the G 5 *r
1
gG*r 5 *r reaction at (<< G, find the thermodynamic activation
parameters kU

, k2

and k$

of the transition state theory. The %rrhenius
parameters for the above reaction are given to be % . ).< m )<
)1
C
8)
s
8)
and
E
a
. < -I,mol.
Solution' k$

. Q ln n h %
p
, N
%
e
1
-
1
*
T
1
o
2ere h . 6.69 m )<
8(7
Is,
p
. ) bar . )<
9
I,m
(
, N
%
. 6.<1 m )<
1(
mol
8)
-
*
. ).(? m )<
81(
I, G, % . )<
)1
C
8)
s
8)
. )<
)1
mol
8)
dm
5(
s
8)
$ubstitute all these values and show that
h %
p
, N
%
e
1
-
1
*
T
1
. @.?)1 m )<
8))
"%,C
8)
s
8)
# , "T,G#
1
$ubstituting the above value in the euation for k$

, we have
k$

. Q ln n @.?)1 H )<
8))
H )<
)1
H (<<
1
o . 8 9? IG
8)
mol
8)
k2

. E
a
8 1 QT . < / 1H ?.()7 m (<< I , mol . 81.9 -I , mol
kU

. k2

8 Tk$

. 81.9 8 (<< H "89?# , )<
8(
-I , mol . )9 -I , mol
Su%%r.
The populations or the occupation numbers of different levels that are available for
molecules are expressed in terms of partition functions which measure the number of
available states with each state weighted by the *olt!mann factor, e
8 E , -T
. $ince the total
molecular energy can be written as a sum over electronic vibrational, rotational and
translation energies, the total partition function was expressed as the product of
electronic, rotational, vibrational and translational partition functions. $eparate
expressions were obtained for these partition functions their estimates were given. The
partition function for a collection of molecules and the average energy of a system was
obtained in terms of partition functions. The relation of partition functions to
thermodynamic functions and euilibrium constants was outlined. The ratio of ortho and
para hydrogens in a 2
1
mixture, their heat capacities was derived in terms of their
partition functions and the interesting connection with experiment was shown. The use of
partition functions in chemical -inetics and their use in estimating activation parameters
of chemical reactions has been illustrated.
Re)erence!
%t-ins, +. &. Phy2i$a3 &he#i2try, @
th
ed, 3xford =niversity +ress, 1<<6.
CcTuarrie, R.%. and $imon, Phy2i$a3 &he#i2try* A Io3e$13ar Approa$h, 1<<(
2ill, T. :. A! I!trod1$tio! to Stati2ti$a3 Ther#ody!a#i$2* Rover +ublications, )B?6.
Cayer, I. E. and Cayer, C. U. Stati2ti$a3 Ie$ha!i$2, 1
nd
ed, Iohn &iley and $ons, )B@@.
Ravidson, N. Stati2ti$a3 Ie$ha!i$2, CcUraw82ill *oo- company, )B61.
CcTuarrie, R.%. Stati2ti$a3 Ie$ha!i$2, Viva *oo-s +vt. :td., 1<<(
Proble%!
??
)# If the nucleus has a spin of s
n
, then its spin degeneracy g
n
, . 1 s
n
5 ). The diatomic
molecule formed from such a nucleus will have g
n
1
spin functions which have to be
combined to form symmetric and antisymmetric functions. >arry out an analysis similar
to that of 2
1
for R
1
where the deuterium nucleus has a spin of ).
1# Rerive the thermodynamic functions from the polyatomic rotational partition function.
(# >arry out the integration for the rotational partition function of the symmetric top.
7# >alculate the total partition function and the thermodynamic functions of water at
)<<<G. The three moments of inertia of water are ).<1, ).B) and 1.B1 in )<
8 7@
-g m
1
. The
symmetry number is 1. The vibrational data in given in 'ig. (.9. %ssume a non8
degenerate electronic ground state.
9# Verify that the symmetry numbers for methane, ben!ene and $'
6
are )1, )1 and 17
respectively.
6# The ground state of Na is a doublet "two states with the same energy#. %ssuming this
to be the !ero of energy and assuming that the next energy level to be 1 eV higher than
the ground state, calculate
el
.
@# The bond length r
e
of 3
1
is ).1 S. The moment of inertia I is m r
e
1
, 1 where m of 3 is
)6 H ).66 H)<
81@
-g . >alculate * and the rotational partition function of 3
1
at (<< G.
?# The vibrational freuency N of I>l is (?7 cm
8)
. &hat is its vibrational partition
function at (<< GM &hat is the fraction of molecules in the ground state "n . <# and the
first excited state n . )M
B# >alulate the translational partition function of N
1
at (<< G. 'or volume, use the molar
volume at (<< G.
)<# %n isotope exchange reaction between isotopes of bromine is
@B @B ?) ?) @B ?)
1 Br Br Br Br Br Br +

. The fundamental vibrational freuency of
@B ?)
Br Br

(1(.(( cm
8)
. %ll the molecules can be assumed to have the same bond length and have a
singlet ground electronic state. >alculate the euilibrium constant at (<<G and )<<<G.
))# 'or the reaction I
1
p 1I, calculate the euilibrium constant at )<<<G. The relevant
data are as follows. The ground electronic state of I is
1
(, 1
P whose degeneracy is 7. The
rotational and vibrational freuencies of I
1
are <.<(@( cm
8)
and 1)7.(6 cm
8)
respectively.
The dissociation energy of I
1
is ).9711 eV.
)1# The representative molecular data for a few molecules is given in table (.). =sing the
relevant data, calculate the euilibrium constant for the reaction 2
1
5 >l
1
I
2>l at
)<<<G. &hat is the value of the euilibrium constant as T g qM
?B
)(# E. "(.9<# is related to the Uiauue function. Estimate the total molar Uiauue
function for molecules that behave as harmonic oscillators8rigid rotors.
)7# The energy of a molecule in the rigid rotor / harmonic oscillator approximation is
E
vib, rot
is "n 5),1# hN 5
B
I "I5)# Qeal molecules deviate from this behaviour due to the
existence of anharmonicity "anharmonicity constant x
e
#, centrifugal distortion
"centrifugal distortion constant
5
# and the interaction between vibration and rotation "r
is the coupling constant between the vibrational and rotational modes#. The expression
for the energy when these affects are included is
1 1 1
) ) )
1 1 1 ,
" # " )# " # " )# " # " )#
vib rot e
E ! h BJ J x ! h 5J J ! J J + + + + + + + +
2ere, the third term is due to anharmonicity, the fourth term is due to centrifugal
distortion and the last term is due to the interaction between vibration and rotation.
>alculate the
vib, rot
which includes the effects of these distortions.
B<