r

CHA-PTER

DIATOMIC MOLECULES
In this cha pter subject is trea ted using 'qua
ntu m mec han ical concepts, tho ugh in cha
has alre ady bee n discussed on classical line pter 3 it
s.
7-0. THERMODYNAMIC PROPERTIE
S OF DIATOMIC MO LEC ULE S :
Fot -discussing ther mod yna mic pro pert ies
of diatomic molecules, we sha ll calc ulat
function for all the thre e types of motion e partition
and then eva luat e the ther mod yna mic func
In qua ntu ~ mechanics, to cha ract eris e tions.
the stat es of a dyn ami cal syst em, we hav
eige nva lues and corresponding eige nfu e to specify
ncti ons . Consider a syst em composed of
acting atom s 1, 2, 3 with identical energy thre e noninter-
levels. The single part icle wav e fun ctio
levels are <!>J.,<1>2 , ... q,i;E1 ,E , ... E\. The wave ns and energy
2 function of the syst em is given by
'¥ ijk ~ q>i (l)q> j (2)q>k (3)
·- with
Eijk = Ei (1) + Ej(2) + Ek(3)
where the trip le index ijkdenotes a single stat e of the system. The
can onic al par titio n function is
Z= L
e-<e i+Ej+ Ek)tk T
ijk

= 'Iie- £ilk T'Iie -Ejl kT'I ie-E klkT ,

.•• (1)
i j k
because trip le sum is unr estr icte d and all
the valu es of i mus t be combined wit h valu
es of j etc.,
z = (~e -fil kTJ

=fl'.
Now consider a gas consisting of n molecul
es. Eac h part icle is free to move thro ugh
whole volume and since the inte rcha nge out the
of any two part icle s does not affect the
corresponding stat es mus t be counted distribution, the
indi stin guis hab le, par titio n function becoonce. Therefore for a perf ect gas, as the part icle s are
mes
r Z= -
wh ere / is also term ed as single''particle
n. ... (2)
par titio
n funotion.
Tra nsl atio nal Mo tion : Consider a sing
le diatomic molecule. It will hav e thre
lati ona l deg rees of freedom. To calc ulat e trans·
e the par titio n function z. we con side r
molecules of mass
'
(268)
 1'1'1ic Molecules 269
piato, ..
;;----
enclosed in a rectangular box of edges a, b and c with volume abc. The allowed translational
11'1 gy levels will be
ener
h2 n2
te . = - ---.£+-1..+_z
(n2 n2]
... (3)
i 8m a 2 b2 c2 '
where nx, ny and nz = 1,2,3,4 .. .
Therefore one particle translational wave function is, using equation (1),

z, = * ft = -h2:;kT ]}: exp.( -h2;; ]f exp.(---·h_2n....;;;.;_J

f exp.( Bma 2
... (4)
, • nx=l 8mb kT
ny=l 8mc kT nz=l
At ordinary temperatures and large size of the box (space available for motion is laTge
enough), the quantity
h2
2 << 1.
Bma kT
2
This means that variation in h ~; with nx is small or in other words, the discrete energy
8ma kT ·
levels are closely spaced and we can therefore replace the summation by integration, i.e.,

f exp.(
nx=l
-h
8ma kT
2
:; J= J; exp (
8ma
-h
2
:;
kT
]dnx

(21tmkT)112 a ... (5)

=
h
Therefore the translational partition function becomes
(21tm kT) 312 •
ft = 3
abc
h
2 . .. (6)
= ~(21tmkT)3' .
h3
Using relation (2), partition function for a gas of n diatomic molecules, is
Z =(/it= ~(21tmkT)3n/2 ... (7)
h3nn!
t n!
The t.otal translational energy of n diatomic molecules is
Et = kT 2 a~ (log Z1 )

= kT 2 ~[log{~ 3
aT h nn!
n'2}lj
(21tmkT) 3

t See Gu.p ta, Kumar and Sharma - Quantum Mechunic11.

• Ifwe write
ft • }; IJ ·(t) c- 11,i I It'/'
i i

then for the translational enerlJy h,veb of' u molooul1J 11, (l) • 1beunu•ti thuy urn olu•~lY iptu.~ '1
atatistics, there is no degeneracy
IJi .. 1.
270
Elementary Statistit:aU~ectianits

Usin g.Stirl ing form ula and simp lifym g, we get

3
-
Et =-n kT
2
The tran slati onal entr opy of n diato mic mole cule
s is
E,
st= klog Zt +T
whe re Z =(ft)n
n! t
Rot atio nal mot ion The ener gy leve l of a diato mic mole cule acco
mod el is give n by rdin g to rigid rotator
2
J(J
£ = - -+l)h
- - , J=O , 1, 2, ...
r Bn2I
whe re I is mom ent of iner tia and J is rota tion
al quan tum num ber. The rotat iona l partition
func tion is
= f.r = ~ g 2
-h J(J+l) l8rc2I 1tT
Zr £- re
j=O,l , 2
whe re the dege nera cy facto r gr~ 1. Rota tiona l
leve ls are degenerate. The degeneracy arises due
spac e quan tisat ion of angu lar mom entu m. The to
angu lar mom entu m of the rota ting molecule may
be orie nted in diffe rent direc tions . In quan tum mec hani
cs, ther e are (2J + 1) allowed
orien tatio ns, each corre spon ding to a di.fl'erent
stati onar y state . The state is said to be (2J +
fold dege nera te. Tha t mea ns the term corr espo 1)
ndin g to a give n valu e of J mus t be counted
(2J + 1) time s. Hen ce Cr= (2J + 1) and,

Zr = L (2J + l)e-h 2J(J+ l) l 8x2 I kT.

J
This sum mati on cann ot be chan ged into integ
ratio n but for larg e valu es of I and T, we can
agai n take that spac ing betw een the ener gy leve
ls is sma ll and we can calc ulate the approximate
valu e of zr by integ ratin g the abov e-exp ressi ons
i.e.,
whe n Tis high , zr = J; (2J +l)e -h 2 J(J+I )/Sx2 IkT dJ.
Mos t of the cont ribu tion to this inte gral -will com
e from the larg e valu e of J and unity can be
negl ecte d in the expr essio n (2J + 1) so that

z = Jor- 2 J 2
e-h J(J+ l)l8x 2IkT dJ
r .
whic h is of the stan dard form

io-xe -b.x2
dx=1-
2b.
Th.u s Brl kT
Zr = --- :-- h2
Ther efor e for a gas of n diato mic mole cules , the
rota tion part ition func tion will be
zr =(zr r=( Brl kT) n , .. (8)
h2
The mea n ener gy of the gas will be
 _____ _ _ _ _ _ _ _ _ _ _ _.!!:
.!.
~~::;.o;;.le_c_u_le_s_ _ _ _ _ _ _ 2:7.1
,r

(Er)== kT2 t[l og (zr tJ

2
2 I kT ]
== nk T l.._[1 og 81t h2
ar
== nkT 2 l_[ Iog T]
. ar
== nkT .
ati z •- . . molecules is
1c
The contribution to ent rop y due to rot ona motion of n d1atom
81t 2 /kT nk
S r =n klo g-h2--+ .
·
nal mot·ion of n d"1at om1·c molecul es 1s
utio n to spe cifi c hea
_ t due to rot atio
~I The contrib
(CV )r -n k
nal motion of n diatomic molecules is
The Helmholtz free ene rgy due to rotatio
Frot = Er -TS,;,

; nk T- T[nkl og
8":~T +n k]
2
= - nkT1og B1t IkT
h2
atu re 500 K.. Its
Example : A dia tom ic ga s is
in the rm al equ ilib riu m at tem per
rotational con sta nt is 1
B = 2.0 0 cm -
in the rot ati ona l sta tes
Compute the rel ati ve pop ula tio ns j = 20.
j = 0, j = 10,
and
rigi d rot ato r
ntio ned tha t ene rgy lev els for a diatomic molecule according to
We have me
lllodel are giv en by h2
£ · =j (j+ l)~ wh ere j=0 ,1, 2 ...
1 81t I

=h . - h
2
Further _h . c = hBc,
81t2 I 81t2 Jc .
Wh
Bis term ed as rota tion al con stan t. The n
- ht
ere c is the ve1OCI·t y Of 11g and 10 -16
27 xl0 erg.
Bh c=2 x6. 6xl O- x3x lO =3 .96
· d · - 20 WI·n be
No\1/ energy val ues for the sta tes j = 0, J = IO an l 16 -
Eo =0( 0+l )X3 .96 Xl0 -
=0 16
16 0x3 .96 x10 -
e =lO (lO +I) x3. 96x l0- =11
10 16 16 I I
e = ( 0+I )x3 .96 xlO - = 420 x3. 96x l0-
llo 20t 20
2 giv en by
tational le d Pop ula tion factor for jth ene rgy level is
ve1s are ege ner a e.
Ni =(2 )+1 )ex p.( -ej /kT )
'l'etnp No -16 5 0 - 6 .9 x 10- 14 .
O x O -
era ture is 500 oK so tha t kT = 1.o Bxl
 -~----
I

272 Elementary Statistical Mechanics Diatt

I'
,I
Therefore population ratio for j = 0,
No = (0 + 1) exp.(-0/ kT) =1
No
irhp~ing that all molecules are in ground state. Similarly, we can show that population ratio
~
iJ }=10, Nio
, r ,,

=11.28 and for 20

=20, NN =3.71. Heln
N 0
j
o
i
Vibrational Moti'on : A diatomic molecule has only one degree of freedom corresponding to
the vibrational motion of the nuclei along the axis joining them. Vibrational energy of a diatomic
molecule, as harmonic oscillator approximation, is
'I Ev =(v +1 / 2)hv, v =0, 1, 2
\l
so that the vibrational partition function can be written as
l1 ~ - (v+'!..)hv/kT
Ev=fv=£.Je 2 relat
I'
v=O
I' = e-hv/2kT L00

e-v.(hvlkT)
v=O
I =e-hv/2kT[l+e-hvlkT +e-2hvlkT + ...]
I
I
= e-hv/2kT [ 1 ]
( I
1-e-hvlkT
e-hv/2kT
or Zv = l _ e-hv I kT .
·I
I Therefore for a gas of n diatomic molecules, the partition function will be
= (zvt = e-nhv (1-e-hvl RTrn ... (9)
Zv
At high temperatures the numerator can be set approximately equal to unity and the ThJ
denominator becomes
[1-(1-hv/ kT + ... )] = kT,
hv Fro,
so that the partition function reduces to
1 kT The SE
Zu=---=-,
· hvlkT hv
which_ is s~me as obtained in equation (12) .of art. 3.6 classically. ·
Vibrational Energy: For the vibrational energy of a gas of n diatomic molecules we write
d .
Ev = kT 2 -[log zn]
dT e v

= nkT 2 ~[log
dt
z ]
e v so tha

= nkT2 -d ·[ log _e-hvl2kT

_ __ ] Ne
dt el-e-hv/kT

=nkT 2 ~[-~-Iog· (l-e-hvlkT)]

dT 2kT e
 ·o:.:.::lec_u_,e_s_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _.:2~7=-3
-, ""llil.C~M~
o,at011:.., .
~

- 2 [ hv e-hvtkT hv ]
-nkT - - + - - - - - - +
2kT2 1-e-hvlkT"kT2 ...
1 nhv
= - n hv + --=------- ... (10)
2 ehvlkT -1
·uel~holtz free energy:
Fv = -n ,iTlogzv

= -nkT[- hv -log(l- e-hvt kT)]

2kT ·
1
= -n hv + nkTlog(l-e-hvlkT) ... (11)
2 I

Contribution to Entropy : The vibrational contribution to entropy can be ~alculated by the

relation
8 - =-(aFv)
v · ar
= _ _i_[..!.n hv + nkTlog(l-e-hvlkT)]
ar2
= k
n [-l og (l- e-hvlkT) + ehvlkT
hvlkT]-1 ... (12)
\ Contribution to specific heat at constant volume : The specific heat at constant volume
in terms of partition function is expressed as
a2
Cv = nT i)T 2 (kT_logz). ...(13)
The vibrational contribution will be
a2
(Cv\ib = nkT aT 2 (Tlogzv).
From relatiop (12), we find that
a hv / kT log(l-e-hvlkT)
aT (Tloge Zv) = ehvlkT -1
The second differel}tiation will be_
a2
-(Tlog zv>=-a[hvlkT
h tkT log(l-e -hvlkT]
)
aT2 e aT e V -1
(hv)2 ehvlkT
= k2T3 - (ehvlkT -l)2
nh 2v2 ehv t kT
so that (Cv\ib = kT2 (ehvtkT -l)2 · ... (l 4)
Now we write about total partition function of assembly of n diatomic molecules. It is
Z = ZtZr?v .
(ftt (81t I kT)n. e-n hvl2kT (1-e-hvlkTrn
2
=
n! h2
(Using eqs_. 7, 8, 9)
r
1
!27~4!,__ _ _ _ _ _ _ _
__ _ _ _ _ _ _ _ _ _ _ Elementary Statist
_ _ _....:..~;:,;:,:,::::::!!
ica!e~l Mc~h~an .
~,<:!
Discussion of the thermod
ynamic pr op ert ies of po
this book. lya tom ic molecules is
beyond the scope of
7•1. NUCLEAR SPIN EFFE
CTS IN DIATOMIC MOL
We have already dis ECULES :
cussed th e thermody1;1a
shall introduce the effect mic. pr op er tie s of di ato
of nuclear sp in which ~i c molecules. Now we
already shown to be, for will ch an ge th e ro tat io
a single diatomic molecule na l pa rti tio n function
, as
Zr = L
(2J + l)e -h~ J(J +l) /Sn 2Ik T
J
(a) Partition function for
he te ro nu cle ar di at om
. In a heteronuclear dia ic m ol ec ul es :
tom ic molecule, th e two ato
atom will have a spin va ms wi ll be of dif fer en t
lue of sa y i un its (in un kin ds . Since every
to (2i + 1) for every value its of h/21t), th er e wi ll be sp
of i. Therefore if th e two in degeneracy equal
i', the spin degeneracy fac ato ms of a dia tom ic mo
tor of th e diatomic molec lecule ha ve spins i and
function will be ule wi ll be (2i +1) (2 i' +
1) so th at th e partition

2
Zr = (2i + 1)(2i' + 1) S7t Ik T
,
h2 ... (1)
. 2
ms tea d of 8n Ik T
h2
(b) Pa
hydrogen): rtition function for ho m on uc lea r di at
om ic m ol ec ul es : (O
rth o- an d para-
H2 molecule is a homonu
clear molecule (consisting
of tw o pr oto ns ). Th e pr
. . f h ot on spin, i, is ~
m uruts O - The spins of th t
2n · e wo pr oto ns m · 2
an tip ara lle l (H). When H 2 molecule ma y be eit
th e s ins a he r pa ra lle l (ii ) or
zero wh en the spms . P 11
are an tip ara lle l. re pa ra el, th e re su lta nt sp
in va lu e s wi ll be un .
Also for each value of re , , ity while
su lta nt s . ,
field Therefore th e • h
. (
spins are parallel re
, is a 2s +1) folpm d de
, s, t er e ar e (2s + 1) po
ssi ble or ien tat io ns in a .
(s = l) th d .
ge ne rac y co rre sp on di ng ma gneti c
degeneracy factor is equa to ea ch va lu e of s. He
l to· el Tehgen:racy fac tor nce when
· • ere1ore is 3, wh ile for an tip ar
all el sp in s (s = O) the
St ati sti ca l weight of mo
St ati sti ca l weight of lecul t
ar s ate, qf hy dr og en wi
When th mo1ecu1ar sta te of h d th pa ra lle l sp in 3
Y .
ro ge n wi th an tip ar all el =-
e spectrum of or din ary mo sp in 1
to possess odd value of lecul . .
th e r t t· ar
t h ey should correspond o a ion qu hy dr og en 1s stu di ed th e
to pa ra lle ls . an tum nu , in ten se lin es ar e observe
d
co rre sp on d to an tip ara lle mb er .(J = 1, 3, 5 ... ). Si
. l s . ( - pi n nu cle ar ar nc e th e lin es ar e intense,
antisymmetric, . pin s - 0) Th ra ng em en t (s = 1) wh
. wh ile tho se 'th . . e ro ati on t . ,
ile th e we ak lines should
ant1symmetr1.c levels wi ev en v 1 lev els wi th od d va lu es of J ar e considere d as
ca n be considered a ue
sta te an d symmetric lev
els to par t
s of i (J = 0, 2, 4) as symm
etric. There1o c
to be as so cia ted re
as ate. wi th s = 1 wh ich co rre sp
on d to ort ho
E.,!!!iat~om::.:i:;.c.;,,;,M,;,.o_le_c_ul_es_ _ _ _ _ _ _ _ _ _ _ _ _~_ _ _ _ _ _ _ _ _ _ __,!~
275

Therefore for fl 2 molecule :

States Spin Resultant Spin
i.---
Spin states
Spins are parallel Resultant Spin =1
Ortho Hz Triplet (since 2s + 1 =3)
..
Para Hz Spins are anti-parallel Resultant Spin =O Singlet (since 2s + 1 =1)
- Now, m general, if the spm of each nucleus 1s i, the resultant - spin of the diatomic molecule
will be either 2i for parallel arrangement or zero for antiparallel. Hence the set of resultant spin
values can be expressed as
2i, 2i-1,2i-2, ... 3, 2, 1, 0. ... (2)
Of these, 1st, 3rd, 5th, etc. are considered to correspond a set of antisymmetric levels, while
2nd, 4th, 6th, etc. correspond to the symmetrical levels. In general, the resultant nuclear spin
= =
may be written as s (2i - n) where n is integer (n ~ 2i). Since n 0, 2, 4, would give 1st, 3rd, 5th
terms etc. in relation (2), these values of s should then correspond to antisymmetric and he~ce
ortho r.tates, while n = 1, 3, 5, etc. give 2nd, 4th, 6th terms, they would correspond to symmetric
and hence para states. The degeneracy factor is (2r + 1) = [2 (2i- n) + 1]. We can now write
L 2(2i-n)+l
St. weight of ortho state __n_=o-'-,---'2,_4_ _ __
St. weight of para state - L 2(2i- n)+ 1
n=l , 3, 6
(4i + 1) + (4i - 3) + (4i - 7) + ...
=
(4i -1) + (4i - 5) + ...
(i + 1)(2i +1) ... (3)
= i(2i + 1)

. (3) that for H.2 molecules ' since i = .!_, ratio of ortho form to -para
We ob serve fram equat 10n 2

form is 3: 1.
The rotation partition function can then be written as
""' -h 2J(J+l)t8rr2IkT
1
:I
I
z = degeneracy factor of ortho form £.J (2J + 1) e
r J=l, 3, 6

""' -h2 J(J+l)t8rr2IkT

+ degeneracy factor of para form £.J (2J + l)e
J=O, 2, 4
2
""' ( J l) -h2J(J+l)/8n IkT
=(i+1)(2i+l) £.J 2 + e
ortho J =l, 3, 6

. 1) ""' (2J+l) ih2J(J+I)l81t2lkT .. . (4)

+i(2i + £.J
para J=O , 2, 4

. h 2 / 81t2 Ik T 1or
The quantity e t of the diatomic molecules (with. the exception of H 2 and
mos
D2) is found to be quite small at all temperatures and hence we can write
2 l 81t 2 1kT
~ -J(J+l)h2l81t IkT =
£.J (2J + l)e 2 h2
J=O
In b all values of J, odd or even, are included in equal number. If we
Sep a ove summation,
arate them, then
276 Elementary Statistical Mechanics

L (2J + l) 2 2
e-J(J+1)1 t 1s1t IkT =
"""
i.J (2J + 1) e-J(J +l)h
2
I sn2 IkT
J=l, 3, 5 J=2,4, 6
2
81t IkT
1
= ... (5)
h2
2
Substit uting equation (5) in equation (4), we get
1 81t2 IkT
Zr = [(i + 1) (2i + l)+ i(2i + l)]
2- h2

. 41t 2 IkT
= (2i + 1)2 ... (6)
h2
Ortho and Para Hydro gen: Applying equations (4) to a H2 molecule, we write
(i + 1) (2i + 1) """
£..J (2J + 1) e-EJlkT
Ortho H 2 J-1,a,s
Para H 2 i (2i + 1) L
(2J + 1) e-EJ lkT
J=O, 2,4
hz
where EJ = --.J( J + 1).
2
81t 1
Since for hydrogen i = ~,
2
Ortho H 2 [ 3e-E1 ikT + 7e-E3ikT +lle-E5 ikT + ... ]
3
Para H 2 · [1+5e-EzikT +9e-ql kT + ... ]
from which one can compute the ratio of ortho to para
hydrogen at a particu lar temper ature T, by insertin g
the rotatio nal energy of various levels as determ ined
from the spectru m of molecular hydrogen. t100
Equilibrium proportion of ortho and para-hy drogen
as a function of temper ature is shown in the fig. 1. At
,I1/o 15 ortho-
(1:1
low temper ature, sine~ all the molecules are in the <ii 50
a.
lowest J = 0 state, hydrogen consists exclusively almost 0
of paraform, while at high temper ature they are in the €25
0
proportion 3 : 1 as is evident from above theoret ical
discussion. 0 100

7•2. SPECIFIC HEAT OF SOLIDS : Fig.1

An ideal solid may be considered as consisting of a space lattice of indepe
ndent atoms
vibrati ng about their mean positions. The atoms are, however, assume d
to be non-interacting
with each other and their vibration is considered strictly harmonic. At ordina
ry temperatures,
the contribution of electronic heat capacity to the heat capacit y of solids
ignored. is small and .can be

7.2-1. DULONG AND PETIT -LAW:

We consider a monoaiumic crystal containing n atoms. Regard ed as a giant 1

molecule'. the
crystal has three degrees of freedom of transla tion and three degrees of
freedom of rotational
motion . There are three 3n - 6 """ 3n degrees of vibrati onal freedom. A classic
al harmonic vibrator
 ----====::::::::~ ~~~ ,~s -~ .-• .

► \
\
\

'\. '

rn:::;:ic~M:;.;o;;..le_c_u_le_s_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _~.__ ------

...--
piato_ =2~7
\
7~
\
s a mean kinetic energy of (l / 2) kT and a mean potenti al energy of
(1/2) kT; the total
:ration al ener~ is therefore 3nkT and the !9-°lar heat capacit y at constan
t, volume Cv is
predicted to be
d
dt (3nkT) = 3nk = 3R,
and is constan t. But we fin~ that at low 1;.emperatures the heat capacit \
y d~reas es a_nd
approaches z~ro as T_➔ O._ This s~ows t~e depend ence of heat capacit y
on temper ature which
oontr adicts
~
this law. Emste m explam ed this variati on
· \ ,
\
-
t•2-2- EINSTEIN THEO RY OF SPECIFIC HEAT OF SOLIDS :
According to Einste in model, each atom in the crystal may- regard ed
00 as three-d imensi onal
oscillator of freque ncy v, indepe ndent of the vibrati on of other atoms
a\d ·thus having three
degrees of freedom. In the_ disc~ss ion of thermo dynam ic proper ties .
of "diatomic molecu les,
regarding the latter as one dimens ional harmo nic oscillat or, we have derive
dthe 'mean energy of
a system of n diatom ic molecu les, given by
\
- 1 nhv
E = 2 nhv + ehv t kT - l
Since here we are dealing with three dimens ional harmo nic oscillat or, the
.
' '"- '
'
.
partiti on functio n
will be
Zv = e-3hv/2 kT[l-e- hvlkTr 3
and for a crystal of n atoms, the partiti on functio n will be

Z = (zvt
= e-3nhv/2kT (l- e-hvlkT f3n.
Putting this value of Zin the expres sion

E = kT 2 a(log Z)
ar '
we can arrive at E=~nh v+3nh v(ehvt kT -1)- 1 ,
... (1)
2
Proceeding exactly in the same. way as in the article on diatom ic molecu
les eq. (10) art 7 .0.
Putting Eo ~ ~nhv we write
2 ,

E -Eo = 3nhv (ehvl kT -1r 1

and therefore specifi c heat

Cy = (-JaE
aT ~ = 3nk
. (h.)2
V
kT
__hvlkT -::-
e-:-::::---
(ehvlkT -1)2. ... (2)
 . ------t(TiUKn
, . . ...--
-w~, J Y f'V"'I ...,i . \ . II

Elementary Statistical Mechanics

278

This expression can be written as

Cv = 3RL,,~;;~)~ )'] ... (3)

9 _ hvE
where E - k '

where vEis called Einstein frequency for a solid and 9E is called Einstein's temperature. We now
discuss the following cases :
(i) At high temperatures : hv /kT approaches very small values so that we may put .
2
(ehvlkT hv +_!_( hv ) +... -l]
-l)2 =[l+ kT 2! kT

Eq. (2), for specific heat, then becomes

C aR[1+~+ ... ]( hv )2

I -
v (;;)' kT

= 3R [ 1 + : ; +... ]
· hv
= 3R as T
i.e., - ➔ O ➔ oo
kT
which agrees with experimental results, and Dulong and Petit's law.
(ii) At very low Temperatures : At very low temperatures hv I kT will be sufficiently high
so as to neglect 1 in comparison to ehvlkT. Therefore eq. (2), becomes

ehvlkT
Cv =3Rx---x ~
( h )2
(ehvlkT)2 kT
2
= 3R (hv I kT)
... (4)
ehv I kT
I

= 3R (hv I kT) 2

[i+ :; + :,(:; r r + :,(:; +.'. . J

= 3R

[(:~r +(!;) +:, +:,(:;)+... ]

➔O asT ➔ O
 mic~M:;.o,;.;.le_c_ul_e_s_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _,_..;;;;..;.;:~:..._-----..;.;:--....,,.;;;............- - ~ ~
~-- 279
fbe atomic heat, it means, tends to zero as the t .
(4) with hv = k0 w . emperature tends to absolute zero.
froIIl eq. , e can write

r
E E,

Cv = 3R(°; .-•EIT

ich predicts that specific heat is proportional to e-6EtT 1or c T Th . h t

wh . << 0E. us atomic ea
· ,
ases with decrease in temperature but the E'm~ t ems . .
decre function falls off more rapidly than it
should.
· Though the Einstein's th eor~ ~s in ~ood agreement with the experiment but in case of some
elements e.g., copper a nd alumi~mm, it is observed that the atomic heat at low temperature
decreases more slowly th an predicted by this theory. The result is that for silver at 14K the
value calculated fro_m th is theory is 28 times lower than the experimental value. This theory
suffers from a .serious d~aw~ack because of the assumption that atoms in the solid are
independent osc~lators whic~ is not ~uite valid but, on the contrary, they are bound with each
other under the mflu~nce of ~he elastic force. Therefore the atoms would behave, collectively, as
system of coupled oscillators. The concept was due to Debye who gave the following theory.

7•2-3. DEBYE THEORY OF SPECIFIC HEAT OF SOLIDS :

On Debye lines, a monatomic crystal containing n atoms must be considered as a system of
3n coupled harmonic oscillators. The frequency of oscillation of each . oscillator is considered no
more equal but, instead, there is a frequency distribution and the lowest frequency is taken as
zero. If the temperature is not too high, amplitudes of vibration of individual atoms in a solid are
relatively small. Further, the collective modes of vibration involving groups of atoms are the
possible sound waves which can propagate through solids. The energy of sound waves inside a
solid medium can be considered to be quantized in the form of phonons. This is similar as the
energy of electromagnetic radiation is quantized in the fo;rm of photons. The phonons have
integral angular momentum. There is no restriction on the number of phonons in a given mode.
a
So the assembly of phonons in solid may be treated as a boson gas. Since we can not have free
phonons in empty space without crystal lattice, phonon is not considered as a true particle.
We must, now, obtain energy from eq. (1) art. 7•2-2 by averaging over all p~ible 3n
vibrational frequencies.
-E 3nhv i -_ Lm
E - 1 Lm ---=-- hv i
---=-=--- ... (1)
. ivi I kT - l '
- 0 -
3n i=O ehvi I kT - l
i=O

where vi is the frequency of oscillation of ith normal mode of oscillation of the crystal.
The number of modes of vibration dN, with frequencies in one direction, lying in the range
v and v+dv, is given by ·

dN = 41tV v: dv, [See chapter 6]

C
tlte
:here_ c is velocity of elastic waves in the solid. T~ere are_ two. kinds of w~ves_ in a rigid
_atenal; the transverse waves with a velocity Ce and with two directions of polarisation for any
gi'ven direction of propagation and also longitudinal waves with a velocity c1• To each
longitudinal vibration, there correspond two transverse vibrations. Therefore
 .
Elementary Statistical Mechan1cs
280

2
-
dN = 41tV(_!_+~J v dv. ••.(2)
cf c; / .,-:
'
In all, ther e are 3n - 6 = 3n diffe rent no~ al mod es in a crys tal with n atom s. Therefore

3n= J;m dN ,

giving
1 c2)
(~+ 3 --
9n
41tVv 3m ·
l t

Putt ing this valu e in equa tion (2), we get

dN=
9 2
n:
dv.
vm
...(3)

v is max imu m allow ed freq uenc y rela ted to the wav elen gth of the same order of
whe re m
ed to
is calle d char acte risti c freq uenc y and is relat
mag nitu de as the inte rato mic dista nce. This
the so calle d Debye tem pera ture Tv as
_ hvm ... (4)
Tv - - -
k
tion (1), we get
Rep lacin g the sum mat ion by inte grat ion in equa
E - Eo = ~ hv = rvm hv dN
~ ehvi lkT - 1 Jo e hv l kT -1

9nh rvm v3 dv ... (5)

= 7m Jo ehvlk T -1

on usin g equa tioh (3).

The n specific hea t is give n by

(aE) 9nh 2
Io
Vm v 4 ehvlk T dv
Cv = aT l' = kT.v ! (ehv lkT -1)2

= 3nk ( kT J
3 4 ... (6)
rhvm lkT x eadx
hvm Jo (ea -1)2

hv d hvm
whe re x = kT an xm = kT .
l db 1•nfinity.
At ver y low tem per atur es, k:;
hv Tv
=T becomes very larg e and can be rep ace Y

Equ atio n (5) on subs titut ing

xkT
V=--
h
p I.

oiatornic Molecules
~ 281

kT
nd dv= -dx
11 h '
E-Eo = 9nh Jhvmlk T (kT I h)4x3
becomes v3 o x . dx.
m e -1
At very low tempe rature , as T ➔ 0, we have hv m I kT ➔ ~ -so that
E _:_ Eo = 9nh f"° (kT I h)4 x3dx ..
v! 0
(ex -1)

<r(k:n~:J 2
=9nk T -kT J- 1t
4
31t
4
nkT T 3
( hvm 15 5 · Tf>
31t 4 nk T 4
--5- .TiJ . ... (7)
The specific heat at const ant volume can be obtained from

Cv =(aE Jv
ar ,
= 121t .n k ·(I__J
4 3

5 Tv
3
4
= ·2·47t nk ( Tv
T J ... (8)

. From equation (8) we fi.nd that Cv oc T 3 . ·This-is the famou

s Debye T 3 law for the specific
heat of a solid at low tempe rature s.
Debye theory fails at extremely high tempe rature s.
Criticism of -D e bye's Theo ry : Although the Debye ~ppro
ximation met a great success but
accurate measurements show deviations from theoreti~al predic
tions in low temp eratu re range.
According to Debye, the T 3 law should hold in the tempe
rature region T $ 0.1 Tv. But
Blackman's paper showed that it is not always true and T 3 law
holds for temp eratu re region
T 5 TD I 50, i.e., at considerably lower tempe rature than predic
ted by Debye. ·
th Th~s inspite of the great success of Debye's theory, one finds
it difficult to agree. with its
eoretical foundations . It suffers from the following defects:
(i) Debye treate d the vibra tions of a solid as if it were a contin
.uous medium whereas a solid is
a co~~ction of discrete ions held togeth er by the forces of cohesion.:

t~: ~s
c (u) In Debye's theory, solid is treate d as isotropic body while
brought togeth er by press ure. No account of crystalline struct
solids are .composed of definite
ure has been -taken in this
 Elementary Statistical Me h .
282 - · _c ~n1cs

(iii) Debye assumed that the sound velocity is conSt ant for all wavelengths. Actually th
--
velocity of elastic vibrations depends upon the wavelength ~hen the wa~e~ength of vibration i:
comparable with atomic distances; the shorter waves travel with less velocities.
(iv) Debye's theory completely neglects the interatomic interactions and the electronic
contribution to specific heat.
Keesom has shown that Debye's theory almost breaks ~own in the li~uid ~elium temperature
region for many metals: At about 0. 74K, -the observed. specific ~ea_t for silv~r is fo~nd to be much
larger than that predicted, by Debye th~ory. He attributed this mcrease m specific heat to the
influence of free electrons (electronic contribution).
· . (v) In some cases it is observed that the _specific heat of solid increases with the decrease in
temperature near absolute zero. The magnetic studies on neodynium ethyl sulphate over the
temperature range 0.95K to 2.15!£.-provide a good example of this. The specific heat at constant
magnetisation Cm, is found to obey the relation
b
cm =-2'
T
where b is a constant at a particular temperature.
(vi) It has been observed that Debye temperature, Tn, though assumed to be a constant for a
give~ substance, shows variation with temperature. For silver, below 6K, its falls off rapidly and
continuously from 215 to 160. Similar variation has been observed in case of LiF also.
Ex. 1. For a mole of Argon at N. T.P. calculate :
(a) the translational partition function.
(b) the kinetic energy of the gas molecule.
(c) molar heat capacity at constant pressure assuming the ideal behaviour.
(a) The translational partition function is given by (eq. 6 art 7.0)
312
ft= ..!::._(21tmkT)a12 =RT. (21tmkT)
ha P
. ha .
~ Argohn is a monatomic gas, it will have only translational partition function and energy. To
find '" we ave
M 40
m = mass of one molecule · ---- = 6.64x10-23
6.02x10 23
N
k = Boltzmann constant =l.38x1Q- 16 erg/K.
t = at ooc = 273K
h =Planck's constant =6.6x10-27 erg. sec.
p = _fressure = 1 atm.
R = gas constant = * 82.05 c.c atm. deg- 1 . mole- 1
Therefore,

* This value of R is to be used only when . .

Other values of gas constant are pressure is m atmosphere and other quantities are in C.G.S.

R =8.314x107 erg deg-1 mole-l;R =1.987 Cal. deg-1 inole-1

r __
lc,.!!M::;O::,:lec _ _ _ _ _ _ _ _ _ _ _ _ _ _ _.;.,__ _ _ _ _ _ _ _ _
u,_es ~!.
~ 283

/, 82.05X273X( 2 3 14
t = x · Xl.38x10-16 X273x6.64x1 0 23 )312
lx(6.6x10-27 )3
= 82.05x273x(6 .28.x'l.38x27 3x0.664)3/2 21 26
( 6.6) 3 xl0 = 48.5lxl0
(b) J{inetic energy, which will be translational only, is given by I I

3 3
Et= 2 RT = xl.987x273 = 813.67 cal/mole
2
(c) The molar heat capacity at constant pressure
5 5
Cp =Cv +R = 2 R = xl.987 =4.967 cal/deg/mole
2
Ex. 2. Find ro_tational partition function, kinetic energy of gas molecules, and rotati~nal ~~t
moment of inertia is
capac ity for40 chlorine2 gas at 27°C. Assume the molecule to be rigid. Given
J14.5Xl0- gm. cm .
(a) Rotational partition function is given by (eq. 8 art 7.0)
2
8
zr = IkT '
1t
nh2 (n == 2 for homonuclear diatomic niolecule)

Here, J = 114.5xl0-4° gm. cm 2 , T =273 + 27 =300K,

R = 1.987 cal. deg- 1mole- 1, h = 6.6x10-27 erg. sec.,
..k = 1.38x10-16 erg/K
Therefore,
8x(3.14)2 ><114.5x10-40 xl.38x10-16 x300 = 4.29x102
Zr = 2x(6.6xl0-27 ) 2

(b) Rotational kinetic energy is given by

. E r = RT = 1. 987 x 300 = 596.1 cal/mole
(c) Rotational heat capacity is
Cr =R =1.987 cal/deg/mole .
□□□