CHM 373

Solutions to UPC Chapter #2

July 3, 2013

1. The system does work by lifting a 1lb weight 1ft using an internal battery with a power output of 1W
(which produces both work and heat).

a)
W = F × D = −mgd = −(0.454kg)(9.8m/s2 )(0.305m)

W = −1.36J

The sign is negative in this case because we define work being done by the system on the surroundings as
negative.

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b) E = ∆U = Q + W ; We solved for the work exchanged (W) in part a (W = -1.36J)
E = 1J/s × 2s = −2J

−2J = Q + (−1.36J)

Q = −0.64J

Again, the sign is negative because heat is dissipated from the system to the surroundings.

c) ∆U = Q + W = (−0.64J)(−1.36J)

∆U = −2J

Again, sign is negative because system loses energy to the surroundings (in the form of both work and heat
exchanges).

d) We would expect the temperature to increase if the system were not connected to the heat sink. The heat
capacity of any material tells you how much heat it would take to raise its temperature by one degree. So,
it makes sense that any material would have a positive heat capacity, and so we expect the temperature of
the system to increase if it were not able to exchange heat with the surrounding isothermal bath.

2. a) ∆S = nR ln VV12 (a positive value) for both cases, which may be obtained by integrating dS = δQT (which
is only valid for reversible processes). Since entropy is a state function, is the same for both the reversible
and irreversible process (as long as they both have the same end points). In other words, only the initial
and final states of the system determine the change in the entropy of the system, regardless of what path is
taken (either reversible or irreversible).

b) For the irreversible process, ∆SSurr = 0 because there is no change at all in the state of the surroundings.
For the reversible process, dSSurr = δQ
T (because δQSurr = −δQsys = δQ) and so, ∆SSurr = −nR ln V1 ).
V2

c) For the irreversible process, ∆SU niv = ∆S + ∆SSurr = nR ln VV21 (Notice that this spontaneous process
results in a positive ∆SU niv ).

For the reversible (equilibrium) process, ∆SU niv = ∆S + ∆SSurr = nR ln VV12 − nR ln VV21 = 0 (Notice that
there is no entropy change for this reversible process).

3. a) Boltzmann’s expression of entropy is S = kB ln Ω , where in this case Ω represents the number of

translational quantum states available to the system (see Eq. 2.9). The entropy change for a single gas atom
(i.e. in terms of kB ) following isothermal expansion from state 1 to state 2 is
Ω2
∆S = kB ln Ω2 − kB ln Ω1 = kB ln .
Ω1
If the number of translational states are proportional to V, then we can write Ω = aV , where a is a constant
of proportionality that is dependent on temperature (but not volume). Substituting this expression for Ω
yields a formula relating the entropy change to the change in volume,
aV2 V2
∆S = kB ln = kB ln .
aV1 V1

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b) Assuming the entropy change of the ith atom is additive,
N
X V2
Si = N kB ln
i=1
V1
If N is equal to avagodro’s number, N = Na , then R = Na kB , giving
V2
∆S = R ln
V1
where ∆S is in molar units.

4. a) Converting density to Molar concentration using the molecular weight of 44.01 g/mol for CO2 gives.

g cm3 1000mL 1mol

0.001773 × × × = 0.0403M
cm3 mL 1L 44.01g

The number density is

3
6.02 × 1023 molecules

g 100cm 1mol molecules
0.001773 × × × = 2.43 × 1025
cm3 1m 44.01g mol m3

b) Using the ideal gas law we derive the molar concentration,[c], of CO2

P V = nRT

P n
= = [c]
RT V

0.1MPa 106 Pa Pa N/m2 mol

M= J
× = 40.09mol · = 40.09mol · = 40.09 3
8.314 K·mol × 300K 1MPa J N·m m
3
1000cm3

mol 1m
M = 40.09 3 × × = 0.0401M
m 100cm 1L
The corresponding number density is then

mol 6.02 × 1023 molecules molecules

40.09 3
× = 2.41 × 1025 .
m mol m3
The ideal gas law only slightly deviates from the experimental values at ∼ 1 atm (0.1 MPa).

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5. a)

b) Both processes are isothermal (T = const), so ∆U = 0.

Path A:

   
1 1 P2
WA = −P2 ∆V = −P2 (V2 − V1 ) = −P2 nRT − = nRT −1
P2 P1 P1
(note: the ideal gas law was used to substitute the expression nRT /P for volume)

 
P2
QA = ∆U − WA = nRT 1−
P1
Path B:

Z V2 Z V2
1 V1 P2
WB = − P dV = −nRT dV = nRT ln = nRT ln
V1 V1 V V2 P1
P1
Q = −WB = nRT ln
P2
6. Path A:
   
P2 J 0.1MPa
WA = nRT − 1 = 1mol × 8.314 × 300K × −1
P1 K · mol 1MPa

WA = −2.2 × 103 J
Path B:

P2 J 0.1MPa
WB = nRT ln = 1mol × 8.314 × 300K × ln
P1 K · mol 1MPa

WB = −5.74 × 103 J

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Work is done on the surroundings by the system, so the signs are negative. More work is done by the path
B since the process is reversible.

7. For an isothermal process, the change in internal energy is ∆U = 0 . If work is done in the process, the first
law requires that Q = −W . In other words, the heat added to the system must be exactly equal to the work
done by the system, and when W < 0 then Q > 0. The latter heat exchange represents a transfer of energy
from the surrounding (constant temperature bath) to the system. If the system were thermally insulated,
then it would cool as it performed work adiabatically. But when the system is in contact with a constant
temperature bath then heat is drawn by the system from the bath in order to prevent the system from cooling.

8. a) The initial volume of one mole of monatomic is calculated using the ideal gas law from P1 and T1
J
nRT1 8.314 K·mol × 300K
V1 = = = 2.5 × 103 m3
P1 1Pa
UPC equation 2.20 can be used to find the final volume V2
 −3/2  −3/2
T2 200K
V2 = V1 = (2.5 × 103 m3 ) = 4.6 × 103 m3
T1 300K
b) Using the ideal gas law

J
1mol × 8.314 K·mol × 200K
P2 = = 0.36Pa
4.6 × 103 m3
c) With UPC equation 2.19

3 3 J
W = nR∆T = × 1mol × 8.314 (200K − 300K) = −1.25 × 103 J
2 2 K · mol

9. Since entropy is a state function, ∆S is path independent. For any isothermal ideal gas process, ∆S is
equivalent to the expression calculated for a reversible path,
V2
∆S = nR ln
V1
a) Irreversible path:

∆Suniv = ∆S + ∆Ssurr > 0

V2 Qsurr
∆Suniv = nR ln +
V1 Tsurr
The term Qsurr /Tsurr corresponds to the entropy change of the surroundings. If we assume that the sur-
roundings is simply a heat bath, then any heat added to it will produce an entropy change of Qsurr /Tsurr .

The heat added to the surroundings is equivalent to the heat removed from the system, but with an opposite
sign.
Qsurr −Qirr
=
Tsurr Tsurr

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From the problem 5a we know that the Qirr = nRT 1 − P 2
P1 so ∆Ssurr = −nR 1 − P2
P1 = nR P2
P1 −1
h i
and therefore ∆Suniv = nR ln VV21 + P2
P1 − 1 (recalling P2 /P1 is less than 1).

Also, recall that in an irreversible isothermal expansion less work is performed (because less weight is lifted)
so less heat is absorbed by the system than in an irreversible expansion and therefore
Qrev Qirr Qrev Qirr
> and ∆Suniv = − >0
T T T T
thus confirming the Clausius inequality, which predicts that an irreversible process will produce an increase
in the entropy of the universe.

b) Reversible path:

In the reversible process, the entropy change of the surroundings is exactly equal and opposite to the entropy
change of the system, and so there is no change in the entropy of the universe
Qsys Qsurr Qrev Qrev
∆Suniv = + = − =0
Tsys Tsurr T T
c) There is no heat or work exchange with the surroundings in a free expansion, so ∆Ssurr = 0. This gives
V2
∆Suniv = ∆S = nR ln
V1
The change in entropy will be greater for the free expansion. This makes sense since in a free expansion
the only entropy change that occurs is that within the system, and so the entropy change of the universe is
simply equal to the entropy change of the system.