Chemistry 304 - Final Exam Solutions - 2016

PART I: TRUE OR FALSE (20 marks total)

Indicate whether each of the following statements is true or false and on the line underneath write
one sentence to justify your choice. There will be no penalties for incorrect answers. Each correct
answer with accompanying explanation is worth 2.5 marks.

1. The volume of a fixed amount of pure gas is doubled using an adiabatic process. The
change in entropy of the gas is greater when the process is done irreversibly than when
done reversibly.
1) True 2) False

For a reversible, adiabatic process, dqrev = 0 so dS = 0 while for an irreversible, adiabatic process,
dS > 0. The latter is true because dSuniverse > 0 for an irreversible process, and dSuniverse = dS
for an adiabatic process since dSsurr = 0. This is not inconsistent with the fact entropy is a state
function, and hence is independent of path, provided the system starts and ends at the same
states. For an adiabatic process, the final state of the system depends upon whether the process
was done reversibly, so in this case, the reversible and irreversible processes carry the system to
different final states (meaning one cannot argue dS = 0 because entropy is a state function). This is
subtle but emphasizes the key idea that state function arguments require one to carefully examine
the initial and final states involved in processes.

2. Pulling apart the ends of an ideal (freely jointed) chain causes the chain’s entropy to
decrease.
1) True 2) False

An ideal chain prefers to be in a random coil as this provides the greatest number of conformations
(the degeneracy of this state is the greatest). Pulling apart the ends of a chain stretches it into a
more linear configuration which has less conformations, hence less entropy.

3. A reversible process obeying dU = T dS does not change the energies of the microstates
of a system.
1) True 2) False

For a reversible process, T dS = dqrev so dU = T dS = dqrev . This means the process involves only
heat exchange, no work nor changes in composition. Since microstate energies depend upon N and
V , and these are fixed, the energies will be as well. Alternatively, a process involving purely heat
exchange will only change the distribution among the microstates, not the microstates themselves.

4. A sealed container holding a pure substance in equilibrium at 300 K is observed to

contain only a gas. The pressure in the system must be equal to the vapour pressure
of the substance at that temperature.
1) True 2) False

The pressure must be less than the vapour pressure. To be at the vapour pressure, the container
needs some amount of liquid to establish the liquid-vapour equilibrium.
5. At constant temperature and pressure, dissolving a substance in a pure liquid lowers
the liquid’s chemical potential.
1) True 2) False

There are several ways one could argue this. The fact dissolution occurs shows that chemical
potentials were lowered. One has to be a bit careful with this argument though because the system
has two components, both the liquid and solute, and it is the combination of them that determines
the chemical potential for the system. Attributing the lower chemical potential of the system to
the behaviour of one of the components alone can lead to incorrect conclusions. A better argument
uses µi = µ0i + RT ln γi xi . For a pure liquid, γi = 1 and xi = 1 so µi = µ0i . When something
is dissolved in the pure liquid, xi < 1 so ln γi xi < 0 and µi < µ0i . In other words, the chemical
potential is less than what it was in the pure state.

6. The chemical potential of a supercooled pure liquid is greater than the chemical po-
tential of the solid at the same temperature and pressure.
1) True 2) False

A supercooled liquid is a state where a substance is in liquid form below its freezing point. This
means the substance is not in its preferred thermodynamic state which by definition has the lowest
chemical potential. Thus, a supercooled liquid must have a greater chemical potential than the
solid. That is why a supercooled liquid rapidly freezes when it is perturbed (by adding a small
amount of crystal or vibrations, for example). It is a metastable state.

7. For a large enough number of particles, the fluctuation in particle energies becomes
very small so that most particles have an energy close to the average.
1) True 2) False

It is true that the fluctuations in the total energy of a system become relatively smaller as N in-
creases, so most microstates have energies close to the average. However, this is not true for parti-
cle energies, which always have broad distributions independent of the number of particles present.
See for example the Maxwell-Boltzmann distribution, or the distribution of vibrational/rotational
states at a given temperature. Most particles do not have energies close to the average.

8. The translational and rotational contributions to the entropy become independent of

the size of a molecule, provided the classical limit is valid.
1) True 2) False

Translational and rotational contributions to the entropy depend upon particle mass and moment
of inertia; two properties that depend upon the size of a molecule. This is true whether the system
is treated classically or quantally.
 PART II: SHORT ANSWER (18 marks total)

[5] 1. A researcher is looking for a relatively direct way to study molecular interactions
using thermodynamics. Which thermodynamic quantity would you recommend they
use? In your response, explain how this quantity gives information about molecu-
lar interactions in a relatively direct way, and indicate how it could be determined
experimentally.

There are many possible answers to this question, some better than others. While all thermody-
namic quantities for real systems depend upon interactions, the question asks to identify quantities
whose values can be linked to interactions fairly directly. For example, determining (∂U/∂V )T is
such a quantity. It is zero in a non-interacting system and non-zero only when interactions are
present. So, the values of this quantity are directly related in some way to interactions. Quantities
like U , S or heat capacity are poor answers to this question because even in non-interacting sys-
tems, they have significant values. This means the interacting and non-interacting contributions
need to be separated, and this may not be so easy to do in practice. In other words, there is no
relatively direct way to get solely the contributions due to interactions alone.

[5] 2. Briefly define the term “entropic force”. Describe one example of an entropic force.

An entropic force arises when the thermodynamic potential for a system is the entropy. In other
words, the system is driven solely by the tendency to maximize its entropy. Several examples of
entropic forces were introduced in CHEM 304, such as the force to stretch an ideal chain, the
entropy of mixing (which is also the driving force for osmosis and membrane potentials), and the
spontaneous flow of heat from hot to cold.
[5] 3. a) Using reasoning based upon the chemical potential, explain why the melting point
of pure substances typically increases when the pressure is increased. You may use
equations and/or diagrams in your answer, if you wish.

µ
The melting point of a pure substance occurs at the tem- P1
perature, say T1 , where the chemical potentials of the liq- P2
uid and solid phases are equal (at a certain pressure, say
P1 ). When pressure is increased, chemical potentials in-
crease qualitatively like Vm P . Now, for typical substances, solid
Vm (liquid) > Vm (solid) so the chemical potential for the
liquid increases more than that for the solid for a given
pressure increase. So, at a higher pressure, say P2 , the solid liquid
will become the preferred state if the temperature remains
at T1 . This means the melting point at P2 must be at a
higher temperature, that is T2 > T1 . This is shown graphi-
T1 T2
cally in the plot to the right. T

[3] 3. b) If the unfolding transition for a protein is modelled as a melting process, then the
trend above predicts the folded state should be favoured under higher pressure. Ex-
perimentally though, many proteins denature under increased pressure. How can this
behaviour be reasoned? Do you think the denatured state under high pressure is a
random coil?

In principle, this question raises many interesting concepts because the system in this case is not
simply the protein but also includes water, ions and possibly other components. Arguments about
the system should consider contributions and interaction effects from all these components. These
are very interesting to consider but a sophisticated response along these lines was not required.
The purpose of this question is to test the ability to create rational arguments based upon specific
effects to explain a physical process, in this case the denaturing of proteins under high pressure.
One possible response is given below.
Typically, the folded state of a protein is more compact than the unfolded state, that is
Vm (unf olded) > Vm (f olded). In this sense, the unfolding transition looks like a melting pro-
cess which should obey the trends above with the unfolded state playing the part of the liquid,
and the folded state the solid. Experimentally, the opposite trend is seen which means from a
thermodynamic point of view, Vm (solid) > Vm (liquid). This is like the case with water, where the
solid state is less compact than the liquid state near the freezing point. So, this implies that under
high pressure, the system moves to a less compact state, which then denatures the protein. This
does not necessarily imply the state is a random coil though because the higher pressure may still
favour more ordered structures.
 PART III (15 marks total)

A heat engine uses an ideal, heteronuclear, di- P

atomic gas with Θrot = 2 K and Θvib = 1000 K in Step 2
(T2= 500K) (T3= 1500K)
the four step thermodynamic cycle pictured in P2
the graph to the right. The temperatures are
labelled at the beginning and end of each step.
The efficiency is given by

Step 3
Step 1
|w|
η= ,
qin
P1
where w is the total work done in the cycle, and (T1= 100K) Step 4 (T4= 300K)
qin is the total heat transferred into the cycle.
V1 V2 V
[12] a) Calculate the efficiency.

Work is done in Steps 2 and 4, which are isobaric, so w = P ∆V . Using the ideal gas law then gives

w2 = −P2 (V2 − V1 ) = −nR(T3 − T2 ) = −1000nR

w4 = −P1 (V1 − V2 ) = −nR(T1 − T4 ) = 200nR
w = w1 + w2 = −800nR

Heat enters the cycle in Steps 1 and 3. For Step 1, w1 = 0 because the process is isochoric, and
using the First Law gives q1 = ∆U1 . For Step 2, the First Law gives q2 = ∆U2 − w2 . Overall,
qin = q1 + q2 = ∆U1 + ∆U2 − w2 . One then needs to find values of ∆U for various Steps.
Since molecular parameters are given, and the system is ideal (that is, non-interacting) we can
use the formulae derived in class to calculate ∆U . Since U is a state function, we can calculate
∆U = ∆U1 + ∆U2 directly between state (P1 , V1 , T1 ) and (P2 , V2 , T3 ). Since Θrot is much less than
the temperatures in the engine, we can use classical expressions for the translational and rotational
contributions (the latter of which is for a linear molecule since we are dealing with a diatomic) but
need to use exact expressions for the vibrational contribution (a single normal mode in this case),
giving
 
3 1 1
∆U = nR(T3 − T1 ) + nR(T3 − T1 ) + nRΘvib −
2 eΘvib /T3 − 1 eΘvib /T1 − 1
 
5 1 1
= nR(1500 − 100) + 1000nR 2/3 − 10
2 e −1 e −1
= 3500nR + 1055.1nR = 4555.1nR ,
qin = ∆U − w2 = 4555.1nR − (−1000nR) = 5555.1nR

Putting all the pieces together then gives

|w| 800nR
η= = = 0.144 .
qin 5555.1nR

Note: calculating the changes in internal energy separately for each Step gives ∆U1 = 1156.5nR
and ∆U2 = 3398.6nR.
 [3] b) If the engine were to operate between hot and cold baths maintained at 1500 K and
100 K, respectively, would its efficiency be greater than, less than, or equal to a Carnot
engine operating between the same two baths? Please justify your response.

The hot and cold baths given in this question have temperatures which would allow the heat engine
to operate by allowing it to reach its maximum and minimum cycle temperatures. However, the
heat exchanges in each Step would occur across a finite temperature difference. In other words,
the hot bath is always hotter and the cold bath always colder than the engine fluid throughout the
cycle. This means these Steps are necessarily irreversible, so the engine could never be operated
reversibly under these conditions. Since the efficiency of any irreversible engine is always less than
a Carnot engine operating between the same two baths, the efficiency in part a) should also be
less. In fact, the efficiency of the Carnot engine would be 1 − Tc /Th = 1 − 1/15 = 0.93 in this case,
which is substantially greater than the efficiency calculated in part a).

PART IV (14 marks total)

The experimental values of CV,m in J K−1 mol−1 at T =

298 K for gaseous Ne, O2 , O3 , CS2 , Cl2 , and C2 H6 , are
Species CV,m / J K−1 mol−1
listed below in random order.
Ne 12.47

44.22, 37.36, 12.47, 25.61, 20.97, 30.39 CS2 37.36

O3 30.39
[12] a) Complete the table to the right by writing the values
in the appropriate cells. Note: you do not need to show O2 20.97
your work for this part. Only the values in the table will be
graded.
C 2 H6 44.22
[2] b) For which of these gases is the value of CV,m expected
to vary the least with temperature? Please justify Cl2 25.61
your response.

The value of CV,m for Ne is expected to vary the least with temperature because this gas has no
vibrations, and it is the vibrational contributions (being not in the classical limit) that produce the
bulk of the temperature dependence in the heat capacity.
 PART V (16 marks total)

The two lowest energy conformers of a substituted cyclohexane are chair forms.
The lowest energy one, labelled ‘A’, has the substituent in the equatorial position.
The other conformer, labelled ‘B’, has the substituent in the axial position, and is
 = 3.85 kJ mol−1 higher in energy. For the purposes of this question, treat these con-
formers as a two-level system, composed of identical but distinguishable particles, with
conformer A having an energy of zero.
[3] a) What fraction of particles are conformer B at 0 ◦ C?

This is a two-level system with a ground state energy of 0 and an excited state energy of , so the
particle partition function is q = 1 + e−β . The probability for conformer B is the same as the
probability for being in the excited state, namely

e−β e−β
pB = = = 0.155 ,
q 1 + e−β

after having substituted

 3850 J mol−1
β = = = 1.695 .
RT 8.3145 J mol−1 K−1 × 273.15 K

Note: the value of  supplied is a molar quantity. One can either calculate the per particle energy
as 3850 J mol−1 /NA = 6.393 × 10−21 J, and then use this in /kT , or recognize that NA k = R and
use the molar quantity directly as /RT , as shown above.

[4] b) Treating the system as ideal, the equilibrium constant for the two conformers is K =
xB /xA , where xA and xB are the mole fractions of conformer A and B, respectively.
Find an expression for K in terms of temperature and . Calculate the limiting values
of K for i) very small, and ii) very large temperatures.

The mole fractions of A and B are the same as the probabilities for finding a particle in conformers
A and B, that is
xB pB e−β /q
K= = = = e−β ,
xA pA 1/q
which can be expressed as either e−/kT if  is a per particle energy, as or e−/RT if  is the molar
energy.

For very small temperatures, T → 0 and the expression for K gives K = 0, that is, the system is
completely in conformer A. For very large temperatures, T → ∞ and the expression for K gives
K = 1, that is, the system is a 50:50 mixture of conformers A and B.
[3] c) In the graph to the right is plot-
ted the contribution of the conformer heat capacity
0.7 entropy
states to the heat capacity, Cv,m /R,

Sm / R
and entropy, Sm /R. On the same 0.6 K
graph, sketch K as a function of tem-
0.5
perature from −150 ◦ C to 500 ◦ C in a
semi-quantitative way (for example,

CV,m / R,
0.4
draw a curve through 3-4 calculated
0.3
points).
0.2
[6] d) Rationalize the shapes of the three
0.1

K,
curves in the graph, being sure to
include a description of the state of 0
-100 0 100 200 300 400 500
the system at the microscopic level
in your response. Temperature / C

For low temperatures, we expect most particles to be in the ground state, that is have conformer A.
In this case, K will be very small as will S, because there are not many microstates being populated
(there is only one in the limit of zero temperature). The heat capacity is also expected to be small
because fluctuations are smaller when less microstates are populated.
As temperature increases, the excited state begins to be significantly populated, and K, S, and
CV,m grow as a result. This behaviour is seen in the graph for temperatures below 0 ◦ C.
At high temperatures, when kT is larger than the energy gap between the conformers, the system
approaches the high temperature limit with equal populations in the ground and excited states,
that is in each conformer. In this limit, K = 1, and Sm /R approaches the value ln 2 = 0.693. The
heat capacity also decays to zero because the system has effectively absorbed all the energy it can
once it has reached the maximum entropy state. In the graph, the curves are close to, but have
not yet reached, the high temperature limit, even at T = 500 ◦ C. However, one can see that the
curves are approaching these limiting values.
 PART VI (17 marks total)

Trichloromethane (labelled ‘t’) and 1,2-epoxybutane (labelled ‘e’) form a non-ideal

solution. When nt = 3.53 mol and ne = 6.47 mol are mixed together at T = 298 K, the
vapour in equilibrium with the solution has a total pressure of 18.75 kPa and a mole
fraction yt = 0.285. Under these conditions, it is determined that γt = 0.5756 and
γe = 0.8855.
[2] a) Which component in the solution would you expect to behave more ideally? Do the
values of the activity coefficients support this? Please justify your response.

The component in the greatest amount is expected to behave most ideally. Thus, 1,2-epoxybutane
is expected to behave most ideally, and this is supported by its activity coefficient, γe , which has a
value closer to 1 (the ideal limit) than that for trichloromethane.
Note that non-interacting systems are by definition in the ideal limit. However, the non-interacting
formalism can also be used to rationalize behaviour in interacting systems through the mean-
field approximation. So, interacting systems, like liquids, can still behave “ideally” provided their
interactions don’t change significantly as a result of being mixed. So, “ideal” in this case is not
equated with “no interactions” but rather “no changing interactions”. This is why the component in
greatest amount is expected to behave most ideally because its interaction environment is expected
to be changed the least (compared with its pure state) owing to its dominance in the solution. This
also explains why the particular interactions present for each of these molecules is not important
because these interactions also exist in the pure liquid. It is the change in such interactions upon
mixing that is important, that is how one component interacts with the other.

[6] b) Calculate what the pressure, in kPa, would be above the solution if it were ideal.

In order to find the ideal pressure we need to know the vapour pressures, Pt∗ and Pe∗ , of the
components. However, these values were not supplied, so instead must be calculated. In general,
ai = γi xi = Pi /Pi∗ . Here, activity coefficients and mole fractions in the solution and vapour are
provided so,
Pt yt P 0.285 × 18.75 kPa
Pt∗ = = = = 26.30 kPa ,
γt xt γt xt 0.5756 × 0.353
Pe (1 − yt )P 0.715 × 18.75 kPa
Pe∗ = = = = 23.40 kPa ,
γe xe γe xe 0.8855 × 0.647
in which the mole fractions in the solution were determined as n = nt + ne = 10 mol, and xt =
nt /n = 0.353, xe = ne /n = 0.647. The ideal pressure is then be obtained using Raoult’s Law, that
is
P = xt Pt∗ + xe Pe∗ = 0.353 × 26.30 kPa + 0.647 × 23.40 kPa = 24.42 kPa .
[3] c) Calculate the change in Gibbs’
P free energy, in kJ, resulting from the mixing process.
Recall that ∆Gmix = nRT xi ln ai .

Using the values supplied and n = 10 mol gives

∆Gmix = nRT [xt ln at + xe ln ae ]

= nRT [xt ln(γt xt ) + xe ln(γe xe )]
= 10 mol × 8.3145 J K−1 mol−1 × 298 K
× [0.353 × ln(0.5756 × 0.353) + 0.647 × ln(0.8855 × 0.647)]
= −22.868 kJ .

[4] d) Calculate what the change in part c) would be if the solution were ideal. Determine
the excess Gibbs’ free energy of mixing, in kJ.

The ideal value is obtained using γt = γe = 1 in the general formula, that is

∆Gideal
mix = nRT [xt ln(xt ) + xe ln(xe )]
= 10 mol × 8.3145 J K−1 mol−1 × 298 K[0.353 × ln(0.353) + 0.647 × ln(0.647)]
= −16.087 kJ .

The excess value is then the difference between the actual and ideal values, that is

∆Gexcess
mix = ∆Gmix − ∆Gideal
mix = −22.868 kJ − (−16.087 kJ) = −6.781 kJ .

[2] e) Given the data and calculations above, what conclusions, if any, can be made concern-
ing the interactions between the components in the solution?

A negative value of ∆Gexcess

mix implies the solution is more favourable than would be implied from
ideal mixing alone. In other words, the interactions in the solution are more favourable than they
are in the pure liquids. This can be analyzed a bit more as follows (remembering that the mixing
occurs at constant temperature and pressure):

∆Gmix = ∆Hmix − T ∆Smix , and

∆Gideal
mix = ideal
−T ∆Smix , so that
excess
∆Gmix = ∆Gmix − ∆Gideal
mix
ideal
= ∆Hmix − T (∆Smix − ∆Smix ).

So, ∆Gexcess
mix < 0 implies ∆Hmix < 0 and/or ∆Smix > ∆Smix ideal
, that is either the components
interact favourably with each other thus lowering their enthalpy, or the gain in entropy from the
mixing is greater than that arising simply from ideal effects (that is, the greater volume occupied by
the components). This could happen, for example, if constraining hydrogen-bonding interactions
in the pure liquids are disrupted in the solution.