CHAP.

8] STATISTICAL THERMODYNAMICS 163

Chapter 8 The conditional probability of finding a chosen system in the ith quantum state, £,, given that the
distribution is ( N u N 2, ...) is
N,
P'(Ni, N 2, ...) = (8.3)
N,

Statistical Thermodynamics where iV, represents the number of systems in the ith quantum state under the given distribution and
N s is the total number of systems. Therefore, considering all distributions, the overall probability of
finding a chosen system in state £, is
E n se m b le s
I N ,n
(8.4)
8.1 INTRODUCTION K in
A canonical ensemble consists of Ns distinguishable systems that are identical in that they have the In (8.4) the summations are extended over all distributions.
same number of molecules ( N ), volume (V), and thermodynamic state. As Ns becomes large, the time
(or observable) average of any mechanical property of a system (such as P or E) becomes equal to EXAMPLE 8.2. Find fl for each of the three acceptable distributions described in Example 8.1. Prepare a table
the instantaneous ensemble average value for the property. Nonmechanical properties (such as T and showing how these distributions are realized for three distinguishable SHOs, A, B, and C.
5) must be calculated using known thermodynamic relationships. The ensemble acts as a single
For (1,1,1, 0, 0 ,...) (8.2a) gives
supersystem having a volume of NSV, a number of molecules equal to NSN, and a total energy of £,.
The number of molecules ( Nt) in each of the allowed energy states in a system is called the distribution 3!
H (l, 1,1,0, 0 ,...) = = 6
and is represented by (N t , N 2, . . .). 1!1!1!0 !0 !. . .
The Boltzmann statistics used in this chapter are obtained as the limiting case of Fermi-Dirac
statistics (systems described by antisymmetric wave functions) and Bose-Einstein statistics (systems Similarly, 0(2, 0, 0,1, 0 ,...) = 3 and fl(0, 3, 0, 0, 0 ,...) = 1. The various assignments of the SHOs are:
described by symmetric wave functions) when it is assumed that there are many more energy states Energy state: 0 1 2 3 4
available than molecules so that there is a very low probability of two molecules being in the same Energy: Ho 3£ 0 5 H0 7 H0 9£„ llE n
energy state. The results of Boltzmann statistics often fail for certain systems at low temperatures. (1,1, 1,0, 0 ,...) : A B C
A C B
EXAMPLE 8.1. Even though the systems in a canonical ensemble have the same macroscopic thermodynamic B A C
state, they are not necessarily in the same microscopic state. Because each system in the ensemble has the same B C A
volume, each system has the same available energy states. However, a given system may be found in any quantum C A B
state consistent with the given values of N, V, and E. Determine the possible distributions among energy states C B A
for systems consisting of three simple harmonic oscillators (SHOs) such that E ,= 9 E 0, given that the quantum- (2,0,0, 1 ,0 ,...): AB C
mechanical solution for energy is AC B
Ev = (v + \)hv (8.1) BC A
(0,3, 0, 0, 0 ,...): ABC
where Ev is the energy of the state corresponding to the integer v, v = 0,1, 2 ,...; h is Planck’s constant; and v is
the frequency of oscillation. Is (1, 0,1,1, 0 ...) an acceptable answer? EXAMPLE 8.3. What is the probability of finding system B in E0 for the acceptable SHO distribution
The energies of the first few states are E0 = \hv, E l =2hv = 7>E0, E2 = jhv = 5E0, etc. The distribution (1,1,1,0, 0 ,...) ? Compare the numerical answer to the actual count of the number of times system B appears in
( 1 ,0 ,1 ,1 ,0 ,...) means that there is one oscillator in state 0, contributing E0 to the total energy; none in state 1; the E0 column of the table prepared in Example 8.2 for this distribution.
one in state 2, contributing 5E0; one in state 3, contributing 7E0; and none above state 3. The total energy would Using (8.3) with = 3 and N 0= 1 gives P0(\, 1,1, 0 ,0 ,...) = 1/3. In Example 8.2, system B appears twice
be 13E0>and so the proposed distribution is not acceptable. The distributions (1 ,1,1 ,0, 0 ,...) , (2, 0, 0 ,1 ,0 ,...) , in the column labeled E0 out of six entries, making the conditional probability of finding B in E0 to be 2/6, or 1/3.
and (0, 3, 0,0, 0 ...) are the only ones that give E, = 9E0.
EXAMPLE 8.4. What is the overall probability of finding system B in E0 for the acceptable SHO distributions
8.2 ENSEMBLE ENERGY STATES AND PROBABILITIES given in Example 8.2? Compare the numerical answer to that predicted by actual count of the number of times
system B appears in the entire E0 column.
The number of ensemble states (ft) corresponding to a given distribution (N u N2, ...) is
Substituting H (l, 1, 1, 0, 0 ,...) = 6, 0 (2 ,0 , 0 ,1 ,0 ,...) = 3, and 0(0, 3, 0, 0, 0 ,...) = 1 into (8.4) gives
ft = (8.2a) „ (l)(6) + (2)(3) + (0)(l)
n Af,i = 0.400
i 3(6 + 3 + 1)
in terms of energy states, or
Among the 10 entries in the E0 column of Example 8.2, system B appears 4 times, giving a probability of 4/10 or
K \ ( n gj)N J 0.400.
________ j
ft = (8.2b)
n Nji EXAMPLE 8.5. In (8.2) the symbol N \ is defined as

in terms of energy levels, where gj is the degeneracy of level j. N \ = N ( N - 1 ) ( N - 2 ) - ■• (2)(1) (8.5)

162

164 STATISTICAL THERMODYNAMICS [CHAP. 8 CHAP. 8] STATISTICAL THERMODYNAMICS 165

where 1! = 0! = 1. In many problems N! or In N ! must be evaluated where N is a large number. Using Stirling's I d e a l- G a s P a r titio n F u n c tio n s
approximation,
8.4 INTRODUCTION
In N ! « N l n N - N ( 8. 6 )
Assum e the system u n der consideration consists o f a large num ber ( N ) o f m olecules, each o f which
evaluate In L\. may occupy a num ber o f quantum states. The energy o f the system is
From (8.6), Ej = Ei + e 2 + • • ■+ eN
In L! = L In L —L where e, is the energy o f m olecule 1, e2 is the energy o f m olecule 2, etc. E quation {8.8) becom es
= (6.022 x 1023)(2.303) log(6.022 x 1023) - (6.022 x 1023)
Q = Chq2 - ■ - q N
= (6.022 x 1023)[(2.303)(23.780) - 1] = 323.77 x 1023
in which qa, the molecular partition function for m olecule a , is given by

q a = l e - ' - /kT { 8. 11 )
8.3 MOST PROBABLE DISTRIBUTION The sum m ation in {8.11) is over all the values o f ea th at correspond to the q uantum states o f m olecule
As N s becom es large, N,, the average o f N t, app ro ach es N f , the most probable distribution, which a. Because the m olecules are all the sam e, tj, = q2 — • • • = qN = q and Q = q N. C orrecting for the
indistinguishability o f th e m olecules, we obtain
is given by

( 8. 12)

The contributions to ea for an ideal gas are nuclear, electronic, vibrational, rotatio n al, and
translational (see Secs. 8.5-8.9), giving
w here k is B oltzm ann’s constant ( k = 1.380 662 x 10 23 J K '), and the partition function (Q ) is defined
as trans

R Rnu cR e\ecR v'\b R ro lR t:rans

rans
( 8. 8 )
{8.13)
In this lim iting case, (8.4) becom es
The N ! correction term is traditionally associated with the translational partition function because not
all gases have vibrational and ro tational contributions, and the nuclear and electronic contributions
are negligible for m ost gases. Equation {8.13) does not contain m inor contributions for ro ta tio n a l-
vibrational interactions o r for intram olecular rotation energy levels.

EXAMPLE 8.6. Derive the equation for the ratio of the most probable numbers of systems at two different
energies in the ensemble. Find this ratio for two states such that Eb —Ea= kT. If Eb and £ a represent energy levels
8.5 MOLECULAR TRANSLATIONAL PARTITION FUNCTION
with gb = 3 and ga = 1, repeat the calculations.
Taking a ratio of N ? given by (8.7) for the two energy states gives For an ideal gas w ith A atom s in the m olecule, o f the total o f 3A degrees o f freedom , three are
attributed to translational m otion o f the m olecule as a whole. The quantum -m echanical solution for a
Ng N s e^E«/kT/ Q = e-<«b-cj/kT particle o f m ass m in a cube with side a (see Problem 14.20), gives the energy as
N * ~ N s e~E‘/kT/ Q
(8.14)
If energy levels are used instead of energy states, a factor of gb/g a appears on the right side of the equation [see
(2.11)], giving where the nt are integers an d h is Planck’s constant (h = 6.626 176 x 10 34 J s).

^ l = i h e-(Eb-E.)/kT ( g ]0) EXAMPLE 8.7. The values of e,rans are of the order of 10 42 J apart, and at room temperature a large number
N* ga of states are occupied by the molecules (because AT —4x 10_2‘ J). Using the above expression for etrans, show that

For the two energy states, gb = ga = 1, and (8.10) gives (8.15)

N * / N* = e~(kT)/kT = 0.368 where V is the volume of the cube.

Substituting (8.14) into (8.11) gives
and for the two energy levels, (8.10) gives

N * / N * = (3/1) e~(kT)/kT = 1.104

 166 ST A T IST IC A L T H E R M O D Y N A M I C S [CH AP. 8 : h a p . 8] STATISTICAL THERMODYNAMICS 167

Replacing the summations by integration because of the large number of states occupied gives The number of molecules in a given vibrational state compared to that in the ground state is
given by
: (2vm kT)i/2 —j
*7trans "
exp( dn\ = N v = N 0 e~vx (8.22)
and the number in the ground state compared to the total number present is given by
8 .6 M O L E C U L A R R O T A T IO N A L P A R T IT IO N F U N C T IO N
N0= N ( l - e ~ x) (8.23)
A d ia t o m ic o r lin e a r p o ly a t o m ic m o le c u le h a s t w o r o ta t io n a l d e g r e e s o f fr e e d o m . F o r t h e d ia t o m ic
m o le c u le , t h e s e a re d e s c r ib e d b y th e q u a n t u m -m e c h a n ic a l s o lu t io n fo r th e r ig id r o ta to r ( s e e P r o b le m
1 4 .2 2 ), g iv in g 8.8 MOLECULAR ELECTRONIC PARTITION FUNCTION

s rol = J ( J + \ ) A y ( 8 .1 6 )
Because the electronic energy states are of the order of 1(T19 J apart, at room temperature most of
0 7T 1 the molecules are in the ground state. The partition function for such a system is
w h e r e J = 0 , 1 , 2 , . . . , e a c h le v e l h a s a d e g e n e r a c y o f 2 J + 1, a n d th e m o m e n t o f in e r tia ( I ) is g iv e n b y
<7ei« = go (8.24)
/ = /xr 2 (8.17)
where g0 is the degeneracy of the ground level.
w h e r e r is t h e d is ta n c e b e tw e e n th e a t o m s in t h e d ia t o m ic m o le c u le a n d th e r e d u c e d m a s s ( / r ) is g iv e n
b y ( 2 . 1 6 ) . T h e v a lu e s o f e rot are o f th e o r d e r o f 1 (T 23 J a p a r t, a n d at r o o m te m p e r a tu r e a la r g e n u m b e r EXAMPLE 8.8. The complete electronic partition function is given by (8.11) as
o f le v e ls a re o c c u p ie d b y th e m o le c u le s .
<lcicc = Z g a e~e" 'kT (8.25)
S u b s t it u t in g th e a b o v e e x p r e s s io n fo r e ro, fo r a d ia t o m ic o r lin e a r p o ly a t o m ic m o l e c u le in t o ( 8 . 1 1 )
a n d in te r g r a tin g o v e r J g iv e s Show that (8.25) becomes (8.24) under the conditions mentioned above.
8 t T2I k T Choosing the reference for zero energy as the ground electronic level, (8.25) gives, upon expansion,
(8.18)
qrol~ h 2a 9eiec = go e~m /k T + g t e - ‘ <'kT + g 2 e ^ kT+ - • •
T h e s y m m e t r y n u m b e r (cr) o f th e m o le c u le r e p r e s e n t s th e n u m b e r o f in d is t in g u is h a b le p o s i t io n s in to [ 1(T19J 1
w h ic h th e m o l e c u le c a n b e p la c e d b y s im p le r ig id r o ta t io n s ; e .g ., c r = 1 fo r a s y m m e tr ic lin e a r m o le c u le s
s u c h a s C O a n d H C N a n d cr = 2 fo r s y m m e tr ic lin e a r m o le c u le s s u c h a s 0 2 a n d C 0 2 . F o r n o n lin e a r
- go + gi eXPL (1.381 x 10-23 J K~')(298 K)J+ '
p o ly a t o m ic m o l e c u le s h a v in g th r e e r o ta t io n a l d e g r e e s o f f r e e d o m ,
= «o + g i(3 x 10“ " ) + - • - = g0

&t t 2( 8 t t 3 IxI yIz ) i , 2 ( k T ) i/2

Orox , 3 ( o . i P )
h cr 8.9 MOLECULAR NUCLEAR PARTITION FUNCTION
w h e r e Ix , I v, a n d I , r e p r e s e n t th e m o m e n ts o f in e r t ia a r o u n d th r e e m u t u a lly p e r p e n d ic u la r a x e s th r o u g h Because the nuclear energy states are spaced very far apart, only a negligible number of atoms in
th e m o l e c u le a n d cr = 2 fo r C 2 H 2 , 3 fo r N H 3 , 4 fo r C 2H 4 , 12 fo r C H 4 , e tc . the molecule are not in the ground state at room temperature. The partition function becomes
*?nuc —gn.O (8.26)
8.7 M O L E C U L A R V IB R A T IO N A L P A R T IT IO N F U N C T IO N where gn-0 is the degeneracy of the nuclear ground state.
T h e r e m a in in g d e g r e e s o f fr e e d o m , 3 A - 5 fo r d ia t o m ic o r lin e a r p o ly a t o m ic m o l e c u le s o r 3 A - 6
fo r n o n lin e a r p o ly a t o m ic m o l e c u le s , a re a tt r ib u te d t o in te r n a l m o t io n w ith in th e m o l e c u le . T h e v ib r a -
t io n a l e n e r g y is d e s c r ib e d b y th e q u a n tu m -m e c h a n ic a l s o l u t io n fo r th e S H O p r o b le m ( s e e P r o b le m 1 4 .5 ): A p p lic a tio n to T h e r m o d y n a m ic s I n v o lv in g I d e a l G a se s
3 A —5 o r 3 A —6
s vib= I (vM )h vt (8.20) 8.10 GENERAL THERMODYNAMIC FUNCTIONS
1=1
In terms of the partition function,
H ere v t a n d a r e th e q u a n tu m n u m b e r a n d fu n d a m e n t a l fr e q u e n c y a s s o c ia t e d w ith t h e ith m o d e o f
v ib r a tio n . T h e v a lu e s o f e vib a re o f th e o r d e r o f 1 0 _2OJ a p a r t, a n d at r o o m t e m p e r a tu r e m o s t o f th e A = -k T \n Q (8.27)
m o le c u le s a re in th e lo w e r sta te s.
I n s e r tin g ( 8 . 2 0 ) in t o ( 8 . 1 1 ) a n d s u m m in g o v e r 0 s y , < o o , 0 s p 2 < o o , . . . , (8.28)
3 A —5 o r 3 A —6 1
S ‘ k T ( 0 T ) v.n + k ' " Q
<7vib= fl 7 (8-21)
P = k T t d ln Q ) (8.29)
\ dV J t m
w h e r e x, is g iv e n in te r m s o f Vj o r v t = v j c b y ( 3 . 6 ) o r ( 3 . 7 ) , i f th e e n e r g y le v e ls a re m e a s u r e d w ith
r e s p e c t to th e z e r o v ib r a t io n a l s ta te o f th e m o le c u le . I f th e e n e r g y le v e ls are m e a s u r e d w ith r e s p e c t to
E = k T 2( d ln (8.30)
t h e h y p o t h e t ic a l m in im u m o f th e p o te n t ia l e n e r g y w e ll, e ~ x,/2 a p p e a r s in t h e n u m e r a to r o f ( 8 . 2 1 ) . \ dT ) V'N

168 STATISTICAL THERMODYNAMICS [CHAP. 8 ; h a p . 8] STATISTICAL THERMODYNAMICS 169

The following sections describe the calculation of various thermodynamic properties of 1 mol of ideal 8tr2IkT \
R( 1 + ln for a diatomic or linear polyatomic molecule
gas, i.e., N = L. In general, the partition function is pressure-dependent, so we shall assume standard h2a )
pressure conditions (denoted, as usual, by °). Also, see Sec. 3.4 for determining thermal enthalpies and (8.33b)
8 n 2(Sn}IxIvE ) '/2(k T )3/2'
Sec. 3.8 for determining heat capacities for ideal gases. R for a nonlinear polyatomic molecule
h 3a

£°(thermal, vib) ^vib

S°(vib) = + R In
8.11 MOLAR THERMAL ENERGY
The energy content of a mole of ideal gas can be considered to be the sum of the energy contributed 3 A - 5 o r 3 A —6
X;
by the molecular ground states (££) and any additional thermal energy [£°(thermal)] resulting from =R E —ln( 1 —e~x‘) (8.33c)
i= l
the occupation of higher energy levels by the molecules when T> 0. Thus,
S°(elec) = R In g0 (8.33d)
E t = E q + E°( thermal) (8.31)
S°(nuc) = R In gn0 (8.33e)
Note that E°0 = EI°0 = A°0 = G°0 for ideal gases because H°, A°, and G° differ from E° by either R T or
For most chemical reactions, 5°(nuc) is neglected.
ST, which vanish at 0 K.
EXAMPLE 8.10. Calculate S° for H20(g) at 373.12 K and 1.00 bar. The moments of inertia for the molecule are
EXAMPLE 8.9. Derive expressions for £°(thermal) for ideal gases.
s.ch that IxIyI. = 5.765 8 x 10-141 kg3 m6. The ground-state degeneracy for the electronic contribution is 1, and a = 2.
Applying (8.30) and (8.13) to (8.15) gives
Assuming ideality, (1.6) gives
(8.314 m3 Pa KP1 m o r l)[(l bar)/(105 Pa)](373.12 K)
1.00 bar
= 3.102 x 10~2 m3 m o f 1
±nd the mass of one molecule is m = (0.018 01 kg mol ')/ L = 2.991 x 10 26 kg.
Using (8.33) and the results of Problem 3.2 gives
'5 [(2 t t )(2.991 x 10~26)(1,380 7 x 10~23)(373.12)]3/2(3.102 x 10~2)]
S°(trans) = (8.314)
= R T 2[ 0 + l(l/T )] = lR T 2 " (6.626 x 10~34)3(6.022 1023) x J
E°( thermal, trans) = Efrans( T) - E°rans(0) = 149.57 J K “ ‘ m o r '
=j RT - jR ( 0) = jRT (8.32a) S°( t) = (8 3 1 4 )l-+ l ^ ^ t 877^ 5-765 8 x 10 i 41) ]'/2[(1-380 7 x 10~23)(3 73.12)]3/2
U° [2 (6.626 x l 0 “34)3(2)
Likewise, applying (8.30) and (8.13) to (8.18) or (8.19), (8.21), (8.24), and (8.26) gives
= 46.51 J K ' mol 1
RT for a diatomic or linear polyatomic molecule 14.101
E°(thermal, rot) (8.32b) S°(vib) = (8.314) - ln( 1 - e - 4 101) + - ln( 1 - e -6 149) + - ln( 1 - e - '4 483)
\ RT for a nonlinear polyatomic molecule '.-1
3 A —5 o r 3 A —6 RTXj = 0.13 J K '1m oP 1
£°(thermal, vib) I (8.32c)
ex‘ - 1
S°(elec) = R In 1 = 0 J K“ ' m oP 1
£°(thermal, elec) = 0 (8.32d)
S°(nuc) = 0 J K.^1 m oP 1
E°(thermal, nuc) = 0 (8.32e)
The total of the contributions is S°= 196.21 J K-1 m o P 1.

8.12 MOLAR ENTROPY

%.\3 FREE ENERGY FU N C T IO N
Applying (8.28) and (8.13) to (8.15), (8.18) or (8.19), (8.21), (8.24), and (8.26) gives
The free energy is related to the partition functions by
, £°(thermal, trans) <7.rans , „
]
N
5 (trans) = -----------—----------- b R In —— + R / ° o o o \N
(8.34a)
T L \ ^ ro tT vib^elec^n u c/

]
(2 nm kT)3/2V°^ N
(8.33a) or ( si°r ot ^rt°v ib rt° rt° (8.34b)
h3L ^ e le c ^ n u c /

y ( r o . ) - E ,(,h e r; aL r0tL « l n f e ! Equation (8.34b) is the free energy function defined in Sec. 6.5 (where H q = Eg) and can be used to
calculate ArG°r along with (6.19) and (6.20a).
 170 STATISTICAL THERMODYNAMICS [CHAP. 8 CHAP. 8] STATISTICAL THERMODYNAMICS 171

EXAMPLE 8.11. Predict K for the isotopic exchange reaction The right-hand sides o f ( 8.35)-(8.37), as well as th at o f (3.25) exclusive o f the electronic term , have
35Cl2(g) + 37Cl2(g) ; = ± 2 35C137Cl(g) been tab u lated as functions o f 0 D/T .

assuming that any differences in the translational, vibrational, electronic, and nuclear contributions are negligible
and that the rotational contributions differ only with respect to a.
For the reaction, applying (6.20a) to (8.34b) gives Solved Problems
A(G°r
rT--JE D J lY iW T , . . . 0 ^ 1 I
J. Iclnj^^ J ( 9rol9vib9elec9 nuc) J J
EN SEM B LES
fftrans \ / o o o o \ 8.1. The quantum -m echanical solution for a particle in a one-dim ensional box is
jy J Wrot^vib^elec^nuc/
"] }
—11 —^l n [ ( ^ ^ £H) (9 ro .^ ib 9 elcc 9 n u c)N j
37-37 J
j
w here E n is the energy o f the state corresponding to the integer n, n = 1 , 2 , 3 , . . . ; h is Planck’s
( ^ r a n s / ^ ) 2 N (< ?e ib < ? :ie c < ? n u c)2 N (< ?°ot .3 5 -3 7 )2 N
= —/c In jn ] co nstant; m is the mass o f the particle; and a is the length o f the box. ( a ) W hat are the energies
( tfrans/N) (9vib9e1ec9nuc) (<?rol,35-35) (<?rol, 37-3?) o f the first four states expressed in term s o f £ , ? ( b ) W hat are the possible d istributions o f three
(9°oi.35-37)2 particles such th at E, = 81E, ? Is (0, 0, 0, 0 ,0 ,0 , 0, 0 , 1 , 0 , . . . ) an acceptable answ er? (c) Find 0
= - N k In -
( 9rot.35-35)(9rot. 37-37) for each o f the acceptable distributions, (d ) W hat is the probability o f finding particle A in £ ,
Now, by (8.18) and the assumption regarding the rotational contributions, q°M is proportional to l/a . Hence, for the distribution (1 ,0 , 0 ,1 , 0 , 0 , 0 , 1 , 0 , . . . ) ? ( e ) W hat is the overall probability o f finding
particle A in £ , for the acceptable d istributions?
h(G°T ~ E%) (°r35-35)(£r37-37)
-------t ------ = - N k In —----- r r — (a) E i, E2 = 4 E ,, £ 3 = 9 E ,, E4= 1 6 £,
T ( 035 -37)
(b ) The distributions
= - N k In = - Nk In 4 = - R In 4
( 1, 0 , 0 , 1, 0 , 0 , 0 , 1, 0 , . . . ) , (0, 0 , 0 , 2 , 0 , 0 , 1, 0 , 0 , . . . ) , ( 0, 0 , 1, 0 , 0 , 2 , 0 , 0 , 0 , . . . )

Because the bond energies of the molecules are assumed to be the same, AEJ = 0 and (6.19) gives have £, = 81 £ ,. The energy of (0, 0, 0, 0,0, 0, 0, 0,1, 0 ,...) is £, = 92£ , = 81 £ ,, but because only one
particle is present it does not satisfy the requirements.
ArG 0= - R T l n 4
(c) Applying (8.2a) to the distributions gives
and then (7.1b) gives K = e,n4 = 4.
_________ 3J________
n ( l,0 , 0 ,1 ,0 ,0 ,0 ,1 ,0 ,...) = - = 6
1!0!0 !1!0!0!0!1!0 !•
M o n a to m ic C r y s ta ls _________ 3!_________
n ( o , o, o, 2 , o, o , i , o , o , . . . ) = =3
0!0 !0 !2 !0 !0 !1!0!0 !•• •
8.14 PARTITION FUNCTIONS AND MOLAR HEAT CAPACITIES
_________ 3J_________
The atoms in a crystal are localized at definite lattice points rather than being able to move freely n ( o , o , i , o , o, 2 , o, o , o , . . . ) = =3
0 !0 !1 !0 !0 !2 !0 !0 !0 !-••
as in a gas. Einstein assumed the vibrational motion of the atoms located at these lattice points to be
given by the solution to the SHO problem; the corresponding partition function for each of the three (d) Using (8.3) with N, = 3 and iV, = 1 gives
directions is then given by a term similar to those found in (8.21). The expressions for Cv as derived P ,(l, 0 ,0 ,1 ,0 ,0 , 0, 1, 0 ,...) = j
from the Einstein and Debye theories were presented in Sec. 3.9.
(e ) Equation (8.4) gives
(l)(6) + (0)(3) + (0)(3) ,
8.15 OTHER THERMODYNAMIC PROPERTIES (3)(6 + 3 + 3)

In terms of the Debye theory for solids,

8.2. The energy difference betw een the ground state an d first vibrational state for 0 2 is 3.139 1 x 10-20 J.
E °-E °0 / T \ 3 f 0o/T x 'd x
3R T “3\0o/ Jo ex - l
(8.35) C om pare the ratios o f m olecules in these states at 750 K (a typical atm ospheric nighttim e
tem perature at 400 km ) and 2 000 K (a typical daytim e tem perature).
Using (8.10) with gf = 1 gives
(8.36)
N% T_______ 3.139 l x 10~2OJ
= 0.048 2
N* ~ £XPL (1.380 7 x 10“23 J K~l)(750 K)
(8.37)
3 « =3( « J L [ e- - r * Jln<1- c “> ] * at night and, similarly, N ^ / N* =0.320 9 during the day, an increase by a factor of about 6.7.

172 STATISTICAL THERMODYNAMICS [CHAP. 8 CHAP. 8] STATISTICAL THERMODYNAMICS 173

ID E A L -G A S P A R T IT IO N F U N C T IO N S The other contributions to S298 using x = 7.64 and g0 = 3 are calculated from (8.33) as
8.3. Calculate £trans(l, 1,2) for an oxygen molecule in a cubic container of side a = 1.00 m.
The molecular mass is given by 5°(vib) = (8.314) j
—ln(l - e~TM) = 3.5 x 10"2 J K "1mol-1

32.00 x l0 ~ 3 kg m oP 1 S°(elec) = (8.314) In 3 = 9.134 J K "1 mol"1

= 5.314 xlO "26 kg
6.022 x 1023 mol-1
S°(nuc) = 0
Equation (8.14) gives
Summing these contributions gives S298 = 205.010 J K "1 mol"1
(6.626 x IQ-34 J s ) 2
<W,s = (12+ 1 2+ 22);
8.7. Calculate ACG°T at 298 K and 500. K for the burning of CH4(g) to form gaseous water given
K "1mol"1) = —175.9 and -191.0 for 0 2(g), -152.4 and -170.4 for CH4(g),
8.4. Calculate erM(J = 2) for an oxygen molecule given r = 0.120 74 nm. -182.2 and -199.4 for C 0 2(g), and -155.4 and -172.7 for H20(g), at 298 K and 500. K,
respectively.
Using (2.16) gives
(16.00X 10"3/L )(1 6 .0 0 x 10"3/L ) Using (6.20a) with A E l = -804.17 kj (see Problem 4.11),
m =;(16.00 x 10“3/ L) + (16.00 x 10"3/ L) = 1.328 xlO "26 kg
Ac C |98 = - 804.17 +(298.15)[(2)(—155.4)+ ( 1 ) ( - 182.2)
and (8.17) gives
- ( 2 ) ( - 175.9) - (1)(-152.4)](10"3) = - 800.8 kJ
I = (1.328 x 10~26 kg)(1.207 4 x 10"10 m)2 = 1.936 x 10"46 kg m2
which upon substitution into (8.16) gives AcG|oo = - 804.17 + (500.)[(2)(- 172.7) + ( 1 ) ( - 199.4)

- ( 2 ) ( - 191.0) —(!)(—170.4)](10“3) = -800.4 kJ

^ = (2X2 -1) !6:626X 1° ~ ^ S )2 2- = 1.723 x 10" 22 J
rM ’ 8 t t 2(1.936 x 10-46kg m2)

8.8 . The relation between G and the thermodynamic partition function is

8.5. Calculate evib for an oxygen molecule if v = 0 and v = 1 580.246 cm"1.
G = - N k T ( d In Q / d N ) v_T
Here there is a single vibrational mode with t>, = v and v, = cv. Thus (8.20) gives
(a) Derive (8.34a). (b) Find a general expression for (G°T-E°0) / T for ideal diatomic gases,
eVib = (0 + j)(6.626 2 x 10"34 J s)(2.997 9 x 10l° cm s_1)(l 580.246 cm"1)
(c) Evaluate (G°T—E°0) / T for 1 mol of 0 2 at 298 K given that g0 = 3, x = 7.64, <r = 2, / =
= 1.569 6 x 10"20 J. 1.937 x 10"46 kg m2, and M = 32.00 g mol"'.

A P P L IC A T IO N T O T H E R M O D Y N A M IC S IN V O L V IN G ID E A L G A S E S (a) The logarithm of (8.13) is

. .
8 6 The expressions for the translational and rotational contributions in (8.33) can be simplified to In Q = N ( In <jtrans + ln <jrot + ln <?vib+ ln <feicC+ ln <?„„<:)-In N \

5°(trans)/(J K " 1 mol"1) = (12.471 62) In M + (20.786 0) In T - (9.685 21) (8.38a) and taking the derivative gives

(8.314 41) ln [(/x 104 7 )r/< r] —(22.377 8 6 ) /d in Q\ , , /d in N \ \

y J —In ^trans"bIn ^rot + In ^vjb+ In ^e]ec + In ^nuc ^ j
5°(rot)/(J K _ 1 m ol"') = • 229.591 0 +(12.471 62) In T - (8.314 41) In cr (8.38b)
+ (4.157 21) \n(IxIyI2 x 10114) where
where M is the molar mass in g mol"1, I is in kg m2, and the first form of (8.38b) is valid for a linear / din N !\ d (N ln N - N )
molecule and the second form is valid for a nonlinear molecule. Calculate S 298 for 1 mol of 0 2 using = ln N
\ d N ) V T~ dN
the data in Problems 8.3-8.5.
upon using (8.6) for In N \. Therefore,
Substituting M = 32.00 g mol 1 and I = 1.937 x 10 46 kg m2 into (8.38) gives
G = - N k T (In <jtrans + ln <jrot + ln <jvib + ln qe,ec+ ln qnuc- In N )
S°(trans) = (12.471 62) ln(32.00) + (20.786 0) ln(298.15)-9.685 21
= 151.968 J K " 1 mol"1 Evaluating G at 0 K. gives Gb = E°0 = 0, so

S°(rot) = (8.314 41) ln[(19.37)(298.15)/(2)] - (22.377 86) G°t -E°0 = - NkT[\n(q°ranJ N ) + \n <tf01+ ln <tfib+ ln <7°iec + ln q°nuc]
= 43.873 J K " 1mol"1 which is another form of (8.34a).
174 STATISTICAL THERMODYNAMICS [CHAP. 8 CHAP. 8] STATISTICAL THERMODYNAMICS 175

(b) For 1 mol of an ideal diatomic gas, The system is diagrammed in Fig. 8-1. Using (8.34b) for the reaction gives

G°t -E°0 (G°t -E°0 G°t - E \ G °t ~ E g

A(G°7
It - e d r , ,nr / ^ a „ s\ N. „ 0 . . j i
Y 1 ^ \ JV / ^ rot^ v*b^ e,ec^ nuc^ J J

\ g °t - e 0° } J -fc ln ^ ^ ) ( ^ tf ib r f u .r f u c ) '''] }
+
l T J elec [ T J
= - N k :\ l n ( 4 = * )
= _ R ln ^ = _ R |n ( W RT V 9elec,A/
where
V T A ra n s L h3L From (8.8),
= 30.473 J KP1 mol '- 1 .5 R In M -2 .5 R In T (8.39a) <?elec,B= (3) e~0,kT = 3
8 t r2IkT
R In qyM= - R In —- 5----
m . - h2d 9ciec.A-(l)e + ( l ) e x p [ - (1 3 8 0 7 x l 0 - 23)(298) ] + ( l ) exp [ - (1 3807xi0-23)(298)]
= 2.929
= 30.728 J K "1 m oP ' + R l n - - R ln (/x 1047) (8.39b)
at 298 K. Recognizing that N = L and AF£ = (2 x 10"22 J)(L), we have from ( 7.1b):

/ G r~ £ g \ ( 2 x l0 " 22)(6.022:x 1023)1 / 3 \

R l n ( l - e_x) (8.39c) K = exp^- ------- - ------ =0.976
\ T / vib (8.314)(298);) J \ 2.929/
Repeating the calculations at 1 000 K gives <Jeiec,B= 3, <?eiec,A = 2.978, and K = 1.010. Note that at lower
(9 izK ) ,_KIn g0 (8.39d) temperatures the equilibrium lies on the side of the reactants, and at higher temperatures the situation is
V T / elec
reversed.

m - K In g„,0 (8.39e)
T
upon substitution of {8.15), {8.18), {8.21), {8.24), and {8.26), respectively, A E £ = 2 X 10-22 J
(c) Equations {8.39) give -------------V
Ea = 1 X 10-2 2 J
' J ____
30.473 —(1.5)(8.314) In 32.00 —(2.5)(8.314) In 298.15
(\ ^ * ) / tra n s - ■

Fig. 8-1
= —131.17J K_1 mol-1

( G t - E o\ = 30 j 28 + (8.314) ln(2/298.15) —(8.314) ln(19.37)

V T /ro t
MONATOMIC CRYSTALS

= -35.52 J KP1 m oL 1 8.10. F ind E ° - E ° 0, A ° - E l , and S° for alum inum at 298 K.

For &D/ T = 1.43 (see Problem 3.10), the right-hand sides of (8.35), (8.36), and (8.37) have the values
( G r-E o ^ = (g 314) ln(! _ e-7.64) = _ 4.o x 10“3 J KP1 m o l'1 0.563 7, 0.461 9, and 1.025 5, respectively. Therefore,
E°-E°0 = (3X8.314 x 10“3)(298)(0.563 7) = 4.190 kJ mol"1
/ G°, - E f°,\ = _ ( 8 314) ln 3 = - 9 . 13 J KP1 m oP 1 A°-E°0 = (3)(8.314 x 10"3)(298)(0.461 9) = 3.433 kJ mol"1
\ T / elec
S° = (3X8.314X1.025 5) = 25.58 J K 1 mol"1

(^ ) -
\ * / nuc

Summing these gives for {G°T - E°0) / T at 298 K the value - 175.82 J KP1m o l 1. Supplementary Problems

ENSEMBLES
8.9. C o nsider the chem ical reaction A . B, where the m olecules o f A have three equally spaced 8.11. Evaluate 11! (a) by using Stirling’s approximation, (8.6); (b) by using the improved approximation
energy states (sim ilar to electronic states) 1 x 1CT22 J apart, an d those o f B have a triply degenerate
level th at is 2 x 10-22 J above the ground state o f A. W hat is K for this reaction at 25 °C and In N ! = N In N - N + \ In 2irN
1 000 K ? and (c) by actual calculation. Arts, (a) 4.77 x 106, (b) 3.96 x 107, (c) 39 916 800

176 STATISTICAL THERMODYNAMICS [CHAP. 8 CHAP. 8] STATISTICAL THERMODYNAMICS 177

8 .1 2 . Find the overall probability of finding system A in E, for the acceptable distributions given in Example 8.1. ground level of A and a doubly degenerate level 1 x 10 22 J above its own ground level. Calculate K at
Ans. 1 1 (1 ,1 ,1 ,0 ,0 ,...) = 6, ft(2, 0 ,0 ,1 ,0 ,...) = 3, ft(0, 3,0, 0, 0 ,...) = 1; P, = 0.300 10 K. and 1 000 K.
Ans. QA = 1 003, Q b = 3.969, K = 0.450; Q°A = 2.834, Q°B= 4.986, /C = 1.722
8.13. Consider a system of energy states where £„ = n E ,. Find the possible distributions of three particles such
that E, = 10E,. Determine ft for each distribution. Find the overall probability of finding a chosen system 8.24. Predict K for the isotopic exchange reaction
in E ,.
,60 2(g) + ,80(g) 160 l80(g) + 160(g)
Ans. (2, 0 ,0 ,0 ,0 , 0 ,0 ,1 ,0 ,0 ,...) , (1,1,0, 0, 0, 0,1 ,0, 0 ,0 ,...), (1 ,0 ,1 ,0 ,0 ,1 ,0 , 0 ,0 ,0 ,...) ,
(0, 2, 0 ,0 ,0 ,1 ,0 , 0, 0, 0 ,...) , (1,0, 0 ,1 ,1 ,0 , 0, 0, 0, 0 ,...) , (0 ,1 ,1 ,0 ,1 ,0 ,0 ,0 , 0 ,0 ,...) , making assumptions similar to those in Example 8.11. What is the driving force of this reaction?
(0 ,1 ,0 ,2 ,0 ,0 , 0,0, 0 ,0 ,...), (0, 0, 2,1,0, 0, 0,0, 0 ,0 ,...); ft = 3, 6, 6,3, 6, 6, 3, 3; 0.222 Ans. 2, entropy increase

IDEAL-GAS PARTITION FUNCTIONS 8.25. Calculate (a) //"(thermal) for Cl2(g), F2(g), and ClF(g) at 298 K and 1 000. K, given that g0= 1, 1, and 1;
f/(c m - I ) = 561.1, 923.1, and 784.39; r/(nm ) = 0.198 6, 0.1409, and 0.162813; cr = 2, 2, and 1; and
8.14. Calculate etrans(l, 1.1) for an oxygen molecule in a cubic container that has a = 1.00 m, and determine
N f ,.2/ N f , , at 25 °C (see Problem 8.3). M /( g mol-1) = 70.906, 38.00, and 54.451 4, for Cl2(g), F2(g), and ClF(g), respectively. Using the values of
//"(thermal) and the fact that A o f ClF(g) is -54.48 kj mol-1, (b) calculate A,E°0 and Af/Z'ooo. (c)
Ans. 3 .10x l0"42J, e"7 53x10-22=1 Calculate S° for the gases at 298 K and 1 000. K. and AfS° at 298 K and 1 000. K.. ( d ) Using the values of
AfH° and AfS°, calculate AfG° at both temperatures, (e) Given [(C°r - E°0) / T ] / ( i K-1 mol-1) = - 187.8 and
8.15. Calculate for / = 4 for an oxygen molecule, and determine N f ^ / N f =2 at 25 °C (see Problem 8.4). -231.8 for Cl2(g), - 173.0 and -210.9 for F2(g), and - 187.8 and -226.3 for ClF(g), at 298 K and 1 000. K,
respectively, calculate AfG° at both temperatures.
Ans. 5.745 x 10"22 J, f \e "°-0977= 1.632
Ans. (a) //"(therm al)/(kJ mol-1) = 9.151, 8.801, and 8.890 at 298 K and 34.501, 33.085, and 33.590 at
8.16. Calculate the number of molecules in the first three vibrational states for 1 mol of 0 2 molecules at 25 °C. 1 000. K.
See Problem 8.5 for pertinent data. (b) AE°0 = -54.39 kJ, A,H\000 = -54.60 kj mol-1
(c) S"/(J K-1 mol-1) = 222.83 and 266.18 for Cl2(g), 202.53 and 243.76 for F,(g), and 217.71 and
Ans. x = 7.630, N 0 = 0.999 5IE, iV, = 4 .9 x 10“4L, JV2 = 2.4x 10“7L 259.77 for ClF(g), at 298 K and 1 000. K, respectively; AfS°/(J K-1 mol-1) = 5.03 and 4.80 at 298 K
and 1 000. K, respectively
8.17. Given that the first excited electronic level of 0 2 is 15.72 x 10“20 J above the ground level, calculate N */ N* (d ) AfG°/(kJ mol-1) = -5 5 .9 8 and -59.40 at 298 K and 1 000. K., respectively
at 298 K. and 1 500 K. The degeneracies are g0 = 3 and g, = 2. (e) AfG°/(kJ mol-1) = -55.96 and -59.34 at 298 K and 1 000. K, respectively
Ans. § e_38 2 = 1.6 x 10~17; 3.3 xlO "4
MONATOMIC CRYSTALS
8.18. Derive (8.22) and (8.23), beginning with (8.10). 8.26. If the value of the right-hand side of (8.35) is 0.580 6 and 0.858 0 for tungsten at 298 K. and 1 000 K,
respectively, calculate A U° for heating 1.00 mol from 25 °C to 1 000 K.

8.19. Derive (8.18) beginning with (8.11) and (8.16). (Hint: Use the technique shown in Example 8.7 to evaluate Ans. E(thermal) = 4.315 kK mol-1 at 298 K and 21.400 kJ mol-1 at 1 000 K, AE°(thermal) = A t/° =
the summation.) 17.085 kJ

APPLICATION TO THERMODYNAMICS INVOLVING IDEAL GASES

8.20. Calculate S |98 for 1 mol of CO(g) using r = 0.11281 nm, P = 2 169.52 cm-1, and g0 = 1.
Ans. 197.53 J K "1mol-1

8.21. Evaluate (G°T - E l) / T for 1 mol of N2(g) at 1 000. K, given that g0= l , P = 2 357.55 cm"1, <7= 2, r =
0.108 758 nm, and M = 28.013 4 g mol"1.
Ans. I = 27.5 x 10"47 kg m2, x = 3.392; (G°r - E%)/ T = —203.50 J K "1 mol"1

8.22. Calculate ArG°ooo for

N2(g) + 2 0 2(g) ^ = ± 2N 02(g)

given ArG 298 = 102.62 kJ and [(G°r - £ S ) / r ] / ( J K "1 mol"1) = -162.3 and -197.8 for N2(g), -175.9 and
-212.0 for 0 2(g), and -205.7 and -251.9 for N 0 2(g), at 298 K and 1 000. K, respectively.
Ans. [A(Gp - E°0)/ T ]/(J K."1) = 102.7 at 298 K and 118.0 at 1 000. K, AE q = 72.00 kJ, ArG?00o = 190.0 kJ

8.23. Consider the equilibrium between system A having three singly degenerate levels spaced 8 x 10“22 J apart
(similar to electronic levels) and system B having a triply degenerate ground level 3x 10"22 J above the