Chem (3/5)501

Introduction to Thermodynamics,
Kinetics, and Statistical Mechanics

3 Credits

Fall Semester 2010

Homework Problem Set Number 7Solutions

1. McQuarrie and Simon, 7-1. Paraphrase: Derive Eqs. 7.7 and 7.8 for the
temperature and pressure dependence of the entropy.
We know from the First Law that

dU = q + w
= qrev + wrev
= TdS PdV
where the equality of the first and second lines derives from U
being a state function, and the final line comes from the

definition of reversible dS and reversible work.

We could expand dS from the equation above to explore its
temperature and pressure dependence, but the dV term
introduces a variation that were not interested in. Thus, it
would be nice to get rid of it by considering some other state
function. If we consider the enthalpy, we have

dH = dU + d ( PV ) = dU + VdP + PdV
= TdS PdV + VdP + PdV
= TdS + VdP
Now we have an expression that involves dP (which well be
considering for entropy), so we may proceed as

dH = TdS + VdP
S
S
= T dT + T dP + VdP
T P
P T
S

S
= T dT + T + V dP
T P
P T

If we consider the general derivative of enthalpy with respect to

T and P, we have

H
H
dH = dT +
dP
T P
P T
Relating the terms in dT and dP, respectively, in the above two
equations, gives

S
H
S
H
T =
= CP (T ) and T + V =

T P T P
P T
P T
which, upon rearrangement, gives the desired results:

S
S
CP (T )
1 H
and = V
=
T
T P
P T T P T

2. McQuarrie and Simon, 7-4, 7-5, and 7-6. Paraphrase: Given a molar heat

capacity
at constant volume (units of R, T in K) for ethylene of 16.4105
6085.929/T+822826/T2, what is the change in entropy when one mole of
ethylene is heated from 300 to 600 K? What if the heating takes place at
constant pressure instead of constant volume (assuming ethylene is ideal)?
What is the relationship between the two as a function of the initial and final
temperatures?

Recalling

S
CV (T )
=

T
T V
and noting that we are working at constant volume, we can
rearrange and integrate to get

6085.929 822826
16.4105

2
T
600
T
S = R 300
dT
T
60016.4105 6085.929 822826
= R 300

+
dT
2
3
T
T
T

600
600

600
1
822826 1

= R 16.4105ln (T )
+ 6085.929

300
2 T 2
T 300
300

= 4.66R

As for constant pressure, we just derived above the expression

relating entropy change to CP, and recall that for an ideal gas,
where energy and enthalpy depend only on temperature, we
may derive

dH d (U + PV ) d (U + RT )
=
=
dT
dT
dT
dU
=
+ R CP = CV + R
dT
Since above we have CV in units of R, that suggests that we need
only change the first term in the heat capacity expression to

17.4105 instead of 16.4105 and we can integrate for the entropy

change and constant pressure (the result is 5.353R).
As for the general relationship, noting that the difference
between the two integrals may be expressed as
T

SP SV = T f
i
= R

CP CV
dT
T

Tf
Ti

T f
dT
= R ln
T
Ti

thus, the two values we derived should differ from one another
by ln2 (in units of R), and, of course, they do (0.693).

3. McQuarrie and Simon, 7-12. Paraphrase: Why is the molar entropy of

vaporization so much more positive than the molar entropy of fusion?
A productive way to think about this question is to consider the
possible contributions to entropy for a pure substance:
electronic, vibrational, rotational, and translational. The larger
the partition function, the larger the entropy. So, the closer
together energy levels are, the larger the entropy. We dont
expect the levels of electronic states to change much liquid to
gas, nor vibrations, since we arent making or breaking bonds in
individual molecules. But, in a gas, molecules can freely rotate,
while in a liquid, the contact with surrounding molecules
suppresses such free rotation (leading to new kinds of
vibrations, called librations that typically have higher
frequencies than rotations). Finally, and most importantly, at
constant pressure the gas occupies a vastly larger volume
compared to the liquid (the vaporization process involves this
change) than does the liquid compared to the solid (the fusion
process involves this change), so the translational levels

available to the gas are substantially denser and there is much

greater entropy.
4. McQuarrie and Simon, 7-27. Paraphrase: Starting from the dependence
of molar entropy on the ensemble partition function Q, derive the
dependence on the molecular partition function q for an ideal gas.
As always, the ideal gas approximation lets us ignore
intermolecular interactions between our indistinguishable gas
molecules, so that we know that

Q( N ,V ,T ) =

q (V ,T )

N!

So, starting from

ln Q
S = kB ln Q + kBT

T N ,V

and noting N = NA for the molar case, we can substitute


N A
q (V ,T )

ln

N A
N
!
A

q (V ,T )

+ k BT
S = kB ln
N
!
T

N =N ,V
A
N ln q ln ( N !)
A

= R ln q k B ln ( N A!) + k BT A

T
T

ln q
= R ln q k B N A ln ( N A ) N A + RT
0
T V

ln q
= R ln q R ln ( N A ) R + RT

T V
qe
ln q
= R ln
+ RT

T V
N A

where weve made use of the properties of the logarithm and

Stirlings approximation to simplify things along the way.
Q.E.D.

5. McQuarrie and Simon, 7-29. Paraphrase: For a monatomic ideal gas,

derive the general dependence of S on temperature and volume.
For a monatomic ideal gas, we have (eq. 7-23)

2mk BT 3/ 2
q (V ,T ) =
VgGS
2
h

where gGS is the degeneracy of the electronic ground state. Since

we will always need the logarithm of q, we may as well expand
that now

3 2mkB 3
ln q = ln
+ ln (T ) + ln (V ) + ln ( gGS )
2 h 2 2
3
= C + ln (T ) + ln (V )
2
where C is a constant independent of T and V.

If we insert this into the expression we derived above for the

molar entropy of an ideal gas, we have

qe
ln q
S = R ln
+
RT

T V
N A

3
C + ln (T ) + ln (V )
e

2
3

= R C + ln (T ) + ln (V ) + R ln
+ RT
2
T

N A
e 3
3
= RC + R ln (T ) + R ln (V ) + R ln
+ R
2
N A 2
3
= B + R ln (T ) + R ln (V )
2

where B is a new constant. So, the difference in molar entropies

for two temperatures would be

3
3
S (T2 ) S (T1 ) = B + R ln (T2 ) + R ln (V2 ) B + R ln (T1 ) + R ln (V1 )
2
2
T2
V2
3
= R ln + R ln
2
T1
V1
T2
V2
= CV ln + R ln
T1
V1

where the final substitution of CV for (3/2)R is valid for a

monatomic ideal gas.

6. McQuarrie and Simon, 7-40 (and explain each answer, of course).

Paraphrase: Look at some pairs of molecules and decide which substance, a
gas, would have the higher entropy at a given T and V.
In the various pairs of molecules, one would expect greater
entropy, as always, based on a larger partition function (because
entropy increases with increase in Q). And the partition
function increases with denser energy levels. In some cases,
intuition about disorder may be stronger than intuition about
energy levels, but, lets start from there.
So, comparing CO to CO2, the latter has greater mass (denser
translational levels), a greater moment of inertia (denser
rotational levels), and at high enough temperatures more
vibrations to play a role. So, CO2 has the greater entropy.
Comparing propane to cyclopropane, there is a small mass
difference (favoring propane, so higher entropy for propane),
and perhaps a small moment of inertia difference. In this case,
intuition suggests that tying the ends of propane together into
cyclopropane ought to somehow decrease disorder and,
indeed, this is born out in the vibrations: the torsions of the
methyl groups in propane about their bond to the central atom

have very, very low frequencies (internal rotors, these are

called), but no such torsions are present in cyclopropane
(although a new CC stretch at much higher frequency replaces
some CH stretches, which were also high frequency). Putting
all of these together leads to the conclusion that propane has
the higher entropy.
Lastly, n-pentane vs. neopentane. Now we have true isomers, so
there will be no translational difference. Rotational is not easy
to see, given three different moments of inertia that need to be
considered. Again, we sort of need to connect our intuition
about crowdedness in the molecule with vibrations. The steric
congestion in neopentane leads to higher vibrational
frequencies and less entropy.

7. McQuarrie and Simon, 7-42 (and explain your ordering, of course).

Paraphrase: Order some reactions in order of increasing entropy of reaction.
The trick here is to recognize that under ordinary conditions,
gases have vastly greater entropy than solids or liquids, in
essence because of the much larger volume available to them
(which, more technically, affects their partition functions in a
way that increases their entropy). So, all we really need to do is
to decide what is the net change in the number of moles of gases
on going from reactants to products. The greater the value, the
greater the entropy change.
The reactions are (with change in moles of gas listed):

(a ) S(s ) + O2( g) SO2( g) ( g) = 0

(b) H2( g) + O2( g) H2O2(l) ( g) = 2
(c) CO( g) + 3H2( g) CH4( g) + H2O( l) ( g) = 3
(d) C(s ) + H2O( g) CO( g) + H2( g) ( g) = 1

so the correct order will be (c) < (b) < (a) < (d), the latter being
the important water-gas shift reaction, which is highly
endothermic and is only driven to the right by high
temperatures that take advantage of the large positive entropy
of reaction.

8. The following expressions for entropy (or entropy changes) are valid only
under certain conditions. What are those conditions?

(a )
(b)
(c)
(d)

H
T
S (0 K ) = 0

S =

C
dS = P dT
T
q
dS =
T

Lets start at the end. The Second Law states that dS is always
greater than or equal to q/T. The equality in (d) holds for a
reversible process.
For a constant pressure process, the change in heat is equal to
dH, which is equal to CPdT. Again, the equality will hold for a
reversible process; otherwise, dS would be greater than the
quantity indicated in (c).

As for the first equation (a), by its construction, it must be the

case that T is a constant, so we have an isothermal process. In
addition, q = H for a constant pressure process, so the
equation will be valid for a reversible (because of the equality),
isothermal, isobaric process. If that sounds hard to arrange, it
isnt actually that uncommon. Recall that all phase transitions
(melting, vaporizing, subliming, etc.) take place at constant
temperature and pressure.
Finally, from the Third Law, entropy at 0 K is zero for a perfect
crystal (which has a degeneracy of 1), leading to (b). Only a
(hypothetical) perfect crystal has this property.