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Atkins, Solution, 7th Ed

# Atkins, Solution, 7th Ed

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Atkins, 7th edition solutions manual
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03/18/2014

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19 Statisticalthermodynamics:
the concepts
Solutions to exercises
Discussion questions
E19.1(b)Consider the value of the partition function at the extremes of temperature. The limit ofq asT

approaches zero, is simplyg0, the degeneracy of the ground state. AsT approaches in\ufb01nity, each term in the sum is simply the degeneracy of the energy level. If the number of levels is in\ufb01nite, the partition function is in\ufb01nite as well. In some special cases where we can effectively limit the number of states, the upper limit of the partition function is just the number of states. In general, we see that the molecular partition function gives an indication of the average number of states thermally accessible to a molecule at the temperature of the system.

E19.2(b)The statistical entropy may be de\ufb01ned in terms of the Boltzmann formula,S= k lnW , whereW is the

statistical weight of the most probable con\ufb01guration of the system. The relation between the entropy and the partition function is developed in two stages. In the \ufb01rst stage, we justify Boltzmann\u2019s formula, in the second, we expressW in terms of the partition function. The justi\ufb01cation for Boltzmann\u2019s formula is presented inJusti\ufb01cation 19.6. Without repeating the details of this justi\ufb01cation, we can see that the entropy de\ufb01ned through the formula has the properties we expect of the entropy.W can be thought of as a measure of disorder, hence the greaterW , the greater the entropy; and the logarithmic form is consistent with the additive properties of the entropy. We expect the total disorder of a combined system to be the product of the individual disorders andS= k lnW= k lnW1W2=

kln W1+kln W2=S1+S2.

In the second stage the formula relating entropy and the partition function is derived. This derivation is presented inJusti\ufb01cation 19.7. The expression forW , eqn 19.1, is recast in terms of probabilities, which in turn are expressed in terms of the partition function through eqn 10. The \ufb01nal expression which is eqn 19.34 then follows immediately.

E19.3(b)Since\u03b2 and temperature are inversely related, strictly speaking one can never replace the other. The

concept of temperature is useful in indicating the direction of the spontaneous transfer of energy in the form of heat. It seems natural to us to think of the spontaneous direction for this transfer to be from a body at highT to one at lowT . In terms of\u03b2, the spontaneous direction would be from low to high and this has an unnatural feel.

On the other hand,\u03b2 has a direct connection to the energy level pattern of systems of atoms and molecules. It arises in a natural, purely mathematical, manner from our knowledge of how energy is distributed amongst the particles of our atomic/molecular system. We would not have to invoke the abstract laws of thermodynamics, namely the zeroth and second laws in order to de\ufb01ne our concept of temperature if we used\u03b2 as the property to indicate the natural direction of heat \ufb02ow. We can easily demonstrate that\u03b2 is directly related to the statistical weight W through the relation

\u03b2= (\u2202ln W/\u2202U)N.W, U , andN are all concrete properties of an atomic/molecular system.
E19.4(b)Identical particles can be regarded as distinguishable when they are localized as in a crystal lattice

where we can assign a set of coordinates to each particle. Strictly speaking it is the lattice site that carries the set of coordinates, but as long as the particle is \ufb01xed to the site, it too can be considered distinguishable.

302
INSTRUCTOR\u2019S MANUAL
Numerical exercises
E19.5(b)
ni=Ne\u2212\u03b2\u03b5i
q
whereq=
\ue000
j
e\u2212\u03b2\u03b5j
Thus
n2
n1
=e\u2212\u03b2\u03b52
e\u2212\u03b2\u03b51=e\u2212\u03b2(\u03b52\u2212\u03b51 ) =e\u2212\u03b2\ue000\u03b5 =e\u2212\ue000\u03b5/ kT
Givenn2
n1
=1
2, \ue000\u03b5=300 cm\u22121
k= (1.38066\u00d7 10\u221223 J K\u22121)\u00d7
\ue001
1 cm\u22121
1.9864\u00d7 10\u221223 J
\ue002
=0.69506 cm\u22121 K\u22121
n2
n1
=e\u2212\ue000\u03b5/ kT
ln
\ue003
n2
n1
\ue004
=\u2212\ue000\u03b5/ kT
T=
\u2212\ue000\u03b5
kln(n2/n1)=
\ue000\u03b5
kln(n1/n2)
=
300 cm\u22121
(0.69506 cm\u22121 K\u22121)ln(2)=622.7 K \u2248623 K
E19.6(b)(a)
\ue001= h
\ue003
\u03b2
2\u03c0m
\ue004
1/2
[19.22]=h
\ue003
1
2\u03c0 mkT
\ue004
1/2
=(6.626 \u00d710\u221234 J s)
\u00d7
\ue003
1
(2\u03c0 )\u00d7 (39.95)\u00d7 (1.6605\u00d7 10\u221227 kg)\u00d7 (1.381\u00d7 10\u221223 J K\u22121)\u00d7 T
\ue004
1/2
=276 pm
(T /K)1/2
(b)
q=V
\ue0013[22]=(1.00\u00d7 10\u22126m3)\u00d7 (T /K)3/2
(2.76\u00d7 10\u221210 m)3
=4.76 \u00d71022(T /K)3/2
(i) T=300 K, \ue001=1.59\u00d7 10\u221211m= 15.9 pm, q= 2.47\u00d7 1026
(ii) T=3000 K, \ue001=5.04 pm, q=7.82\u00d7 1027
Question. At what temperature does the thermal wavelength of an argon atom become comparable
to its diameter?
E19.7(b)The translational partition function is
qtr=V
h3(2kT \u03c0 m)3/2
soqXe
qHe=
\ue003
mXe
mHe
\ue004
3/2=
\ue003
131.3 u
4.003 u
\ue0043/2=187.9
STATISTICAL THERMODYNAMICS: THE CONCEPTS
303
E19.8(b)
q=
\ue000
levels
gje\u2212\u03b2\u03b5j= 2+ 3e\u2212\u03b2\u03b51+ 2e\u2212\u03b2\u03b52
\u03b2\u03b5=hc\u02dc
\u03bd
kT=1.4388(\u02dc
\u03bd/cm\u22121)
T/K
Thusq= 2+ 3e\u2212(1.4388\u00d71250/2000)+2e\u2212(1.4388\u00d71300/2000)
=2 +1.2207 +0.7850 =4.006
E19.9(b)
E= U\u2212 U (0)=\u2212Nq
dq
d\u03b2=\u2212Nq
d
d\u03b2(2+ 3e\u2212\u03b2\u03b51+ 2e\u2212\u03b2\u03b52 )
=\u2212Nq
\ue005
\u22123\u03b51e\u2212\u03b2\u03b51 \u22122\u03b52e\u2212\u03b2\u03b52
\ue006
=N hc
q
\ue005
3\u02dc
\u03bd1e\u2212\u03b2hc \u02dc
\u03bd1+2 \u02dc
\u03bd2e\u2212\u03b2hc\u03bd2
\ue006
=
\ue003
NAhc
4.006
\ue004
\u00d7
\ue0073(1250 cm\u22121)\u00d7
\ue005
e\u2212(1.4388\u00d71250/2000)
\ue006
+2(1300 cm\u22121)\u00d7
\ue005
e\u2212(1.4388\u00d71300/2000)
\ue006\ue008
=
\ue003
NAhc
4.006
\ue004
\u00d7(2546 cm\u22121)
=(6.022 \u00d71023mol\u22121)\u00d7 (6.626\u00d7 10\u221234 J s)\u00d7 (2.9979\u00d7 1010cm s\u22121)\u00d7 (2546 cm\u22121)
=7.605 kJ mol\u22121
E19.10(b)In fact there are two upper states, but one upper level. And of course the answer is different if the
question asks when 15 per cent of the molecules are in the upper level, or if it asks when 15 per cent
of the molecules are ineach upper state. The solution below assumes the former.
The relative population ofstates is given by the Boltzmann distribution
n2
n1
=exp\ue003
\u2212\ue000E
kT
\ue004
=exp
\ue003
\u2212hc \u02dc
\u03bd
kT
\ue004
so lnn2
n1
=\u2212hc \u02dc
\u03bd
kT
ThusT=
\u2212hc \u02dc
\u03bd
kln(n2/n1)
Having 15 per cent of the molecules in the upper level means
2n2
n1
=0.15
1\u2212 0.15son2
n1
=0.088
andT=\u2212(6.626 \u00d710\u221234 J s) \u00d7(2.998 \u00d71010 cm s\u22121) \u00d7(360 cm\u22121)
(1.381\u00d7 10\u221223 J K\u22121)\u00d7 (ln 0.088)
=213 K
E19.11(b)The energies of the states relative to the energy of the state withmI= 0 are\u2212\u03b3N\u00af
hB,0,+ \u03b3N\u00af
hB,
where\u03b3N\u00af
h=2.04\u00d7 10\u221227 J T\u22121. With respect to the lowest level they are 0, \u03b3N\u00af
h,2\u03b3N\u00af
h.
The partition function is
q=
\ue000
states
e\u2212Estate /kT
where the energies are measured with respect to the lowest energy. So in this case
q=1 +exp
\ue003
\u2212\u03b3N\u00af
hB
kT
\ue004
+exp
\ue003
\u22122\u03b3N\u00af
hB
kT
\ue004
AsB is increased at any givenT ,q decays fromq= 3 towardq= 1 as shown in Fig. 19.1(a).