Chapter 1

402 Practice Exams

1.1 Prac. Midterm - 1
Relations, Constants, relations of interest.
dl = Tdo 1d\ dH = Tdo +\ d1
d = odT 1d\ dG = odT +\ d1
1 = 8.314[

1olt1
] = 0.082 [
Jo|n
1olt1
] = 0.08314 [
Jbo:
1olt1
]
C
o

(
2
)[

1ol1
] = 30.18 0.0119T + 2.397 10
5
T
2
1.018 10
8
T
3
1. Concept questions. C
r
are molar values of the
heat capacities.
(a) Is the dierential expression,
(2rj)dr + (r
2
j r
2
)dj exact?
(b) Is the isothermal compressibility sign denite?
(c) Starting from the same thermodynamic state
and ending at the same volume does the i)
isothermal or ii) adiabatic expansion have the
lower nal pressure.
(d) Why is C
u
(CH
4
) a function of T and C
u
(Ar)
not?
(e) Estimate values of C
u
(Ar) and C

(Ar).
(f) Estimate the molar heat capacity (197g) of Au
at room T.
(g) Which is larger: i) C
u
(Si(s)) or ii) C
u
(Ge(s))
at the same (modest value of) T.
(h) Estimate the energy required to heat of 1 for-
mula weight of CsI(s) from 300-310 K.
(i) What is j
T
? With the aid of a potential dia-
gram indicate why real gases cool when j
T

0.
(j) Can an endothermic reaction with C

(P)
C

(R) become exothermic with increasing T ?

2. Prove (
J1
J1
)
T
= T(
J\
JT
)

+\.
This derivation parallels that for the internal pres-
sure,
IP (
Ju
Ju
)
T
= T(
J1
JT
)
u
1.
3. A gas obeys the EoS: 1 = 1T +/1,
with / a constant.
(a) Derive an expression for (
Ju
Ju
)
T
and show l(T).
(b) Derive an expression for (
Ju
Ju
)

.
(c) Derive an expression for :(T
2
,
2
) :(T
1
,
1
).
4. Derive an expression for the work done on one mole
of a gas, which is well described by the van der
Waals EoS, which expands from
1
to
2
isother-
mally. The vdW EoS is: (1 +
o
u
2
)( /) = 1T,
where a and b are constants.
5. Consider the reaction:

2
(q) + 3H
2
(q) 2H
3
(q) ;
/
1=1bo:
:rn
(10001) = 123.77 [
|
nolt
].
(a) Write a general expression for /
o
:rn
(3001) in
terms of the the 3 molar heat capacities.
(b) Evaluate this expression for /
o
:rn
(3001) as-
suming C

(N
2
) =3.5R, C

(H
2
) =3.5R and
C

(NH
3
)=4.2 R.
(c) Provide rationalizations for the numerical val-
ues for C

(N
2
) and C

(NH
3
).
6. The compressibility is dened as the negative of the
relative change in volume with change of pressure
under specied conditions.
Show that:
c

c\
=
r
J
rs
.
Hints: Write out the partials on the RHS. Use
Eulers cyclic relation to rewrite the partials in both
the numerator and denominator. Reorganize par-
tials by collecting partials with the same xed vari-
able. Recall that C
r
= T(
JS
JT
)
r
.
1
1.2 Prac. Midterm - 2
dl = Tdo 1d\ dH = Tdo +\ d1
d = odT 1d\ dG = odT +\ d1
1 = 8.314[

1olt1
] = 0.082 [
Jo|n
1olt1
] = 0.08314 [
Jbo:
1olt1
]
1

= exp{

c
rcr
1T
} = 1
o
(
J ln 1
JT
)

=
|
c
ror
1T
2
Clapeyron: (
J1
JT
)
1tj
= (
s
u
)
1tj
GD:
P
I
A
I
dj
I
T1
= 0
1. . Concept questions
(a) Calculate o
nIr
for preparing 1.00 mole of
an ideal solid solution having the composition
X(AgBr(s))=0.728 and X(AgCl(s))=0.272.
(b) How many variables are needed for the com-
plete description of a one component, single
phase thermodynamic system which is in both
gravitational and magnetic elds and can be
subjected to pressure-volume work? (That is,
there are 3 types of allowed work.)
(c) Why is H
sub
= H
ntl|
+H
uo
.
(d) Why is the pressure inside a drop larger than
outside? How does the pressure dierence de-
pend on the radius of the drop?
(e) Ice II is stable at higher pressure than Ice I.
What does this tell you about thermodynamic
state variables for these phases?
(f) Explain why can there be an approximate re-
lationship for all uids that T
b
is reduced by
100
o
C if the pressure is dropped from 760 to
20 torr.?
(g) Arrange the following gases in terms of IN-
CREASING T
1olt
: CH
4
, Kr, H
2
O, He.
2. Prove which of the relations 1
T
= 1 1(
J ln 2
J1
)
T
where 7 is the gross compressibility and
T
is the
isothermal compressiblity, is correct. (Only one of
the signs () is correct, your derivation will show
which.)
3. Methylammonium Chloride exits in a number of
crystalline forms. Some of the thermodynamic
properties for the , and forms are provided below.
(a) Below 20 1 both forms follow the Debye T
3
dependence of the C
.
(b) C
o

(12.01) = 0.85 [

1olt1
],
C
~

(19.51) = 5.97 [

1olt1
]
(c)
R
220.4
12.0
c
{

T
dT = 93.41[

1olt1
],
R
220.4
19.5
c

T
dT = 99.92[

1olt1
].
From the above information calculate
(a) The entropy of the , and phases at 12.0 and
19.5 K, respectively.
(b) The entropy of each phase at the equilibrium
transition temperature of 220.4 1.
(c) The enthalpy of the equilibrium transforma-
tion , .
4. A 1 liter vessel is sealed with a mixture of Ar(g) and
N
2
(g) under 1 bar at 300K. It takes 5.9 J to heat
the gas mixture 10
o
. Estimate how much of each
gas is present. (Clearly state your assumptions.)
5. Consider the transition between two forms of solid
tin, Sn(s,gray) Sn(s,white). The two phases are
in equilibrium at 1 bar and 18
o
C. The densities for
gray and white tin are 5750 and 7280 kg m
3
, re-
spectively, and S
1tj
= 8.8 (J/ K mol). Estimate
the temperature at which the two phases are in equi-
librium at 200 bar. Is the Clapeyron slope +ve or
-ve?
6. Prove the activity coecient form of the GD equa-
tion:
P
I
A
I
d ln
I
T1
= 0.
7. Example problem in the text 9.12 pg 217. (Derive
the equations you use stating from denitions. State
all assumptions.)
2
1.3 Practice Final
dl = Tdo 1d\ dH = Tdo +\ d1
d = odT 1d\ dG = odT +\ d1
1 = 8.314[

1olt1
] = 0.082 [
Jo|n
1olt1
] = 0.08314 [
Jbo:
1olt1
]
1. 1

= exp{

c
rcr
1T
} = 1
o
2. (
J ln 1
JT
)

=
|
c
ror
1T
2
(
J1
JT
)
1tj
cJ
= (
s
u
)
1tj
GD:
P
I
A
I
dj
I
T1
= 0 =
P
I
A
I
d ln
I
= 1
1
T|:Q

|:
cl
= [\ (
2tn1
T
T
|
2
)
3/2
]
:o|
cl
= (
211
T
T
|
2
)
1
c

uIb
=
t
{!:2
[1t
{!:
]
R

c
r
2
dr =

r
2
c
or
2
dr =
1
2

c
3/2
1. Concept questions
(a) Can an exothermic reaction with C

(P)
C

(R) become endothermic with decreasing T

?
(b) Why are the activity coecients from the
Debye-H uckel theory always less than 1?
(c) What is the equal-partition theorem?
(d) Why is the equal-partition theorem inherently
classical?
(e) For which degrees of freedom is a classical ap-
proximation good, reasonable, poor, bad?
(f) Do vibrational DOFs contribute to the pres-
sure? Why?
(g) What does Boltzmanns o = /
1
|:\ formula
tell you about the 3
:J
law entropy at T = 0 K?
(h) What is <
3
r
and why?
(i) Why does the MB speed distribution go to zero
at both high and low values of
s
?
(j) What is the energy zero of the electronic par-
tition function? Why is this zero chosen?
(k) What is assumed when one write
=
|:

:o|

uIb

tlt

nuc
?
(l) In the evaluation of
uIb
=
t
{!:2
[1t
{!:
]
, where
does the numerator come from?
(m) What did Einsteins model for the heat capac-
ity of crystals get correct and what did it fail
to reproduce?
(n) What is Ficks rst Law?
2. The absolute entropy of C|
2
(q) at T = 298 K and
P=1 bar is o
o
298
=223.1 [J/K*mol] and the heat ca-
pacity (of C|
2
(q)) at constant pressure is well de-
scribed by, c

[J,1 :o|] = (a+/ T +c T

2
) with
a = 31.28, / = 10.14 10
3
, c = 40.4 10
7
. The
units of a, /, and c have been suppressed for clarity.
(a) Calculate :
o
1500
(C|
2
(q)).
(b) Calculate :
1500
(C|
2
(q)) at 0.5 bar. You can as-
sume that C|
2
(q) is ideal at this temperature.
3. Calculate the partition function, the average energy,
heat capacity and what 1 equals for an ideal gas
conned to move in 2 dimensions.
4. Calculate the mean angular momentum for a di-
atomic molecule with moment of inertia 1 at tem-
perature T. Assume the high-temperature (clas-
sical) limit is valid.
5. Consider a system of N spacial locations, each with
two energy levels - (or 0, -; as you wish). Calcu-
late the partition function and U(T), plot the lat-
ter. How would you calculate C(T)? What should
the function C(T) looks like (i.e. what are the low
and high T limits)?
3