PHYSICAL CHEMISTRY 2 WBCH015-05 NAME:

EXAM 25-01-2021, 1600-1800 hours STUDENTNR:

FEEDBACK DOCUMENT
This document contains the exam questions for Physical Chemistry 2 on the date stated above and
provides feedback with pointers to the solutions. Full solutions are not given; you can use the
feedback to train yourself for the exam by working the full solutions out yourself.

Put your NAME and STUDENT NUMBER on each sheet of paper you hand in. Question 1a must
be answered in part on this (the exam) paper. You are required to hand in the exam paper, even if
you do not complete any of the questions.

This exam consists of 4 main questions, subdivided in a total of 16 subquestions on 6 pages. Almost
all subquestions can be answered independently, although you may need to find data and pertinent
information at other (sub)questions.

Write your answers neatly and concisely.

In general, first derive a general appropriate equation or formula for the quantity of interest in terms
of all given variables and constants. Only then start putting in numerical values. Take care to show
that you know how to proceed along each step in manipulating equations. For some questions, a
single master equation may be quite cumbersome, and you may split your answer up into
intermediate results.

The use of non-graphing calculators and the Formula Sheet is allowed. No other written or
electronic material is permitted. Refer to the Formula Sheet if you use information from it. You
must briefly justify the use of a particular formula. Data calculated (or given) earlier may be
used as such in subsequent calculations after brief referral. It may also be advantageous to group
constants in an equation or formula together, give it a separate name or symbol, and determine its
numerical value.

If you are of the opinion there is an error in the question or information provided, please state your
reasoning. During the exam, you cannot ask for clarification of the exam questions.

All answers must be given with the correct units. Unless indicated otherwise, your answer must be
given in the appropriate S.I. units. It is advisable to always do dimensional analysis. In questions
marked by an asterisk (*) it is mandatory to show dimensional analysis explicitly (you get points for
it). The dimensional analysis should be done on the final equation, showing that the formula for the
answer has the desired units.

The maximum number of points for each is indicated. The result on the exam is determined by the
total number of scored points (maximum 100), divided by 10. The final grade for this course is
determined by a weighted average of the result on the exam (75%) and the result of the computer
assignment (25%), rounding to the nearest half integer. The result on the exam must, however, be at
least 4.5 and the computer practical must be handed in. Also, since 5.5 is not an allowed final grade,
all 4.75 ≤ average grades < 5.5 are rounded to final grade 5.

1
(1) N-METHYLACETAMIDE-NAPHTHALENE MIXTURE

Consider a binary mixture of N-methylacetamide (NMA, component 1) and naphthalene (Naph,

component 2) at a fixed temperature of 414.0 K. The total vapor pressures of the mixture and the
mole fractions of NMA in the vapor (y1) and in the liquid (x1) phases were determined for a
number of compositions. Some of the data are reported in Table E1.1. These and more points are
shown in the corresponding phase diagram for this mixture in Figure E1.1.

p (kPa) x1 y1 p (kPa) x1 y1 p (kPa) x1 y1

11.74 0.000 0.000 13.17 0.032 0.135 16.56 0.578 0.500

12.18 0.009 0.045 16.64 0.395 0.434 11.83 0.993 0.973

12.60 0.015 0.083 16.68 0.458 0.458 11.68 1.000 1.000

Table E1.1: Vapor pressure data for a binary N-methylacetamide (1)—naphthalene (2) mixture at
414.0 K.

Figure E1.1: Pressure-composition diagram for NMA-Naph mixture. See text for details.

(a, 4 points)
(i) Draw the co-existence curves in Figure E1.1 and indicate by colors or text which curve belongs
to which data (x1 or y1).
(ii) In Figure E1.1, clearly indicate the regions is which a binary mixture of NMA and Naph is
entirely in the liquid phase, entirely in the vapor phase, and when there is liquid-vapor co-existence.

2
FEEDBACK: See also Lecture 5
The co-existence lines connect the two sets of points. The upper points mark the transition from
liquid (high pressure!) to co-existence; the lower points mark the transition from co-existence to
vapor (low pressure!).

(b, 4 points)
(i) What is an azeotrope?
(ii)) Does the NMA—Naph mixture have an azeotrope at 414.0 K, and if so, what data (boiling
pressure and overall composition) characterize the azeotrope?

FEEDBACK: Yes, there is an azeotrope and the data for it are in Table E1.1.—see Atkins,

(c, 8 points)
Calculate the amount (in mol) of NMA (component 1) in the liquid phase that is at equilibrium with
the vapor phase at a pressure of 13.17 kPa and at an overall mole fraction of Naph (component 2)
that is 0.90, if the total amount of material is 5.20 mol. Read any composition data you require to
make your calculation from Table E1.1 if pertinent data can be found in Table E1.1 or from Figure
E1.1 if pertinent data are not available in Table E1.1 (do not spend time on performing any
calculations or approximations of the data you require).

FEEDBACK: Examples of detailed calculations can be found in Lecture 5, and in TP-PD-9, 10.
Use the lever rule correctly to determine the amounts of material in the liquid and vapor phases, and
from the composition of the liquid phase determine the amount of ethanol in the liquid phase.
The lever rule gives the RATIO between total amount of material in the liquid (l) and vapor (g),
phases. The amount of material in the liquid phase is:

nl = 1.77 mol

The amount of NMA (component 1) in the liquid phase is:

n1l = 0.057 mol

The data in Table E1.1 can be used to calculate the partial pressures of mixtures of NMA and Naph
at liquid-vapor equilibrium as a function of the mole fraction of NMA.

(d, 4 points)
Calculate the partial pressure of NMA in a liquid-vapor equilibrium at 414.0 K and at a total
pressure of 12.18 kPa, using the data given in Table E1.1. State any assumption(s) that you need to
make.

FEEDBACK: Example calculations can be found in Lecture 4 and in TP-PD-8 and are based on
application of Dalton’s law, which assumes that the total pressure exerted by a mixture of gasses
comes about proportionally by the pressure exerted by each gas, which in turn is a consequence of
the perfect gas law which assumes there are no interactions between the molecules.
p NMA = 548 Pa
3
(e, 6 points)
(i) From the data in Table E1.1, calculate Henry’s Law constant for Naph in NMA.

Henry’s Law constant for NMA in Naph is 60.9 kPa.

(ii) Interpret Henry’s law constants for NMA in Naph and Henry’s Law constant for Naph in NMA
in terms of their mutual interactions. In your answer, give qualitative but if possible, also
quantitative information about the interactions relative to that of the pure components and about the
relative disturbances of component 1 in component 2 versus component 2 in component 1.

FEEDBACK: For example calculations, see Lecture 4 and TP-PD-8. These sources also discuss the
interpretation of Henry’s Law constants.

(i) KH, Naph in NMA = 45.7 kPa

(ii) Compare Henry’s Law constants to the vapor pressure of the pure substances. The absolute
differences are not that informative; you must consider ratios.

4
(2) GRAHAM’S METHOD FOR DETERMINING VAPOR PRESSURE

The vapor pressure of solids and liquids can be measured using the so-called effusion oven. In this
method, an initially closed vessel is loaded with an amount of solid or liquid in such a way that a
solid-vapor or liquid-vapor equilibrium is established, i.e. the amount of solid or liquid is such that
there is enough space for vapor but not so much that all solid/liquid sublimes/evaporates. The vessel
is kept at a constant, known temperature, and placed in a balance or on scales in order to monitor its
weight. The measurement starts when a small hole is punched in the vessel that allows the vapor to
escape. The weight (or mass) of the vessel and its contents is then monitored over time. During part
of the experiment a constant rate of mass change is observed, and the rate of this mass change is
used to determine the vapor pressure. This analysis is based on the so-called collision flux.

(a, 8 points)
(i) Show that the rate of change of mass of the vessel plus contents vM = dM/dt during the time that
it is constant, and with an area of the hole in the vessel A0, is given by Eq. (E2.1).
(ii) Do any assumptions need to be made to arrive at Eq. (2.1)? If so, which one(s)?

dM m1/2 pA0
=− (E2.1)
( 2π kBT )
1/2
dt

FEEDBACK: Lecture 14 and TP-TD-11.

(i) The derivation uses the collision flux (on the Formula Sheet) and the fact that each molecule
carries its own mass along with it.
(ii) Equilibrium between solid and vapor within the chamber must be established, and also
equilibrium between gases in the air of the laboratory and inside the chamber must be established.

(b *, 5 points)
Show by calculation that the vapor pressure of naphthalene at 434.0 K is 22.7 kPa, as measured by
Graham’s method based on a constant mass rate change of −5.39 10-3 kg·s-1 when the area of the
hole punched in the vessel was 100.0 mm2. The molecular mass of naphthalene is 128.17 amu.
Make sure you explicitly show the way the units of your answer are arrived at.

FEEDBACK:
Rewrite Eq. (E2.1) to solve for the pressure and plug in the numbers given.

(c, 7 points)
Use the vapor pressures of naphthalene at 414.0 K (11.7 kPa from Table E1.1) and at 434.0 K (22.7
kPa from Question 2(b)) to show that a good estimate of the enthalpy of vaporization at 424.0 K is
49.4 kJ/mol. If you know the formula for the estimation by heart, you may use it without further
derivation or justification. Otherwise, you will first have to derive the expression.

FEEDBACK: Lecture 3 and TP-PD-7.

The enthalpy of phase transitions involving a vapor can be estimated from just the vapor pressures
and the temperatures by using the Clausius-Clapeyron equation in integrated form. The Clausius-
Clapeyron equation can be remembered with the aid of the Van ’t Hoff equation that is on the
Formula Sheet because it is very similar in structure.

5
(3) STATISTICAL TREATMENT OF TRANSLATION

Statistical thermodynamics predicts the thermodynamics of molecules by considering the

distribution of the molecules over available molecular states. Here, we focus on the translational
contribution to the energy and entropy of naphthalene in the vapor and in the liquid state. This
molecule has a molecular mass of 128.17 amu.

Translational energies of the quantum levels n in one dimension in a box of length L are given by
Eq. (E3.1):
n2h2
En = , n = 1,2, 3,... (E3.1)
8mL2

(a, 7 points)
(i) Show that the translational contribution to the canonical partition function for motion in one
dimension is given by Eq. (E3.2).
(ii) What assumption(s) and/or approximation(s) need to be made to arrive at this result?
1/2
⎛ 2π mkBT ⎞
qtr, 1D =⎜ L (E3.2)
⎝ h 2 ⎟⎠

FEEDBACK: The full derivation can be found in Lecture 8.

(b, 6 points)
Starting from the expression U = ∑ pi Ei, show that, in general, the internal energy can be calculated
from the partition function as given in Eq. (E3.3), where β is (kB T)-1. HINT: what is pi?
d ln q
U=− (E3.3)
dβ

FEEDBACK: Lecture 6, slide 15. Make sure your notation is correct and you do not skip any steps!
If it helps you, you can first write down the derivation in the opposite direction (i.e., start from
d ln q 1 dq
− =− = etc . . ) on your scrap paper and then write it down neatly so that it is
dβ q dβ
starting from U = ∑ pi Ei as asked.

(c, 5 points)
Show by using the one-dimensional translational partition function that the translational energy
does not depend on the size of a system.

FEEDBACK: See also Lecture 8 and TP-ST-8.

Simply use Eq. (E3.3) and Eq. (E3.2), making use of the rules for manipulating logarithms; you
should conclude that the average translational energy depends only on temperature and therefore
not on volume.

6
(d, 10 points)
(i) Use the enthalpy of vaporization of 49.4 kJ/mol calculated in Question 2(c) to calculate the
entropy of vaporization for naphthalene at 424 K.
(ii) Calculate the difference in the translational entropy of naphthalene between the liquid and and
the vapor states at 424 K from the partition functions. You may assume that the vapor is a perfect
gas. It is given that the vapor pressure of naphthalene at 424 K is 16.5 kPa, and the volume per
molecule naphthalene in the liquid is 2.31 10-28 m3.
(iii) Compare the values of the entropy of vaporization as calculated from the experiment and from
the translational partition functions for liquid and vapor. Are there other contributions to the entropy
of vaporization and what may be their relevance to the vapor-liquid equilibrium?

FEEDBACK: See also TP-ST-10.

(i) During vaporization, liquid and vapor are at equilibrium: ΔvapG = 0 (Lectures 2 and 3). This
allows calculation of Δvap S from Δvap H.

Δvap S = 116 J ⋅ mol−1 ⋅ K−1

(ii) An expression for the entropy in terms of the partition function can be derived in several ways.
The result is:
U
S= + kB ln q
T

Entropy differences therefore involve differences in internal energies and ratios of partition
functions (differences in logarithms of partition functions). In this case, the difference in energies is
zero (because in both cases, we are looking only at the translational internal energies which do not
depend on the volume). The translational partition functions do depend on volume, and the perfect
gas equation may be used for the volume of the vapor.

ΔSvap,tr = 60 J ⋅ K−1 ⋅ mol−1

(iii) The translational entropy of vaporization is about half of the experimental entropy. Other
contributions are rotation, vibration, and electronic—the interaction does not play a role in the
entropy for the process because that merely shifts all the levels and does not affect the number of
available levels within the liquid compared to within the vapor.
The most likely candidate for the extra entropy difference is the rotational contribution.
Naphthalene is a flat molecule that is likely to pack in more restricted fashion in the liquid, whereas
it is completely free to rotate in the vapor. One could also say that part of the rotational freedom is
effectively transformed into a vibrational freedom (librations), increasing the spacing between the
levels in the liquid.

7
(4) GAS-PHASE EQUILIBRIUM OF THE ELEMENTS AND AMMONIA

The dissociation equilibrium of ammonia to form the elements in the gas phase may be written as
given in Eq. (E4.1).
1 3
NH 3 ! N2 + H2 (E4.1)
2 2
At chemical equilibrium at a temperature of 298.15 K and a total pressure of 2.00 bar = 200 kPa,
the partial pressures of NH3, N2, and H2, were found to be 191.1 kPa, 2.2 kPa, and 6.7 kPa,
respectively.

(a, 5 points)
Show by calculation that the standard Gibbs free energy of formation of ammonia at 298.15 K and
in the gas phase is −16.4 kJ per mol ammonia formed. State any assumptions that need to be made
in this calculation.

FEEDBACK: Lecture 11.

Under the assumption that the partial pressures can be used instead of activities, i.e. using the
perfect gas law, the equilibrium constant can be calculated from the partial pressures. Do not forget
to use STANDARD PRESSURE (not total pressure)! The relation between the equilibrium constant
and the standard Gibbs energy of reaction (Formula Sheet) can then be used.

The equilibrium constant Kp for the reaction as given in Eq. (E4.1) is 4.37×10-3 at 318.15 K.

(b, 6 points)
(i) Calculate the standard enthalpy of reaction for the dissociation of ammonia to the elements at
308.15 K.
(ii) Do you need to make any assumption(s) in this calculation?

FEEDBACK: Lecture 11.

Use the van ‘t Hoff relation (see Formula Sheet). Integration leads to the reaction enthalpy
difference in terms of the difference between the ln Kp values at two different temperatures. The
assumption that is made in this calculation is that the enthalpy of reaction does not depend on
temperature.

Δr H 0 = + 46.4 kJ ⋅ mol−1 reactions

(c, 5 points)
Is the equilibrium composition sensitive to the total pressure? If yes, does the amount of product for
the reaction as written in Eq. (E4.1) increase or decrease as the total pressure is decreased at
constant temperature? Briefly justify your answer(s). (No points for guessing.)

FEEDBACK: Use the principle of Le Chatelier and van ’t Hoff. See also Lecture 11.

8
(d, 10 points)
Calculate the partial pressures of NH3, N2, and H2 in an equilibrium mixture of NH3, N2, and H2 at
318.15 K and at a total pressure of 1.00 bar.
NOTE that this may take some time, but that you can gain points already if you clearly explain what
needs to be done without actually getting the final answer.

FEEDBACK: Follow the chain of calculations discussed in Lecture 11. The keys are the use of the
extent of reaction and application of Dalton’s law.

4Kp p 0
xeq = = . . . = 0.058
(4Kp p0 + )
33/2 p

ntot = 2.116 mol; pNH3 = 0.890; pN2 = 0.027; pH2 = 3pN2 = 0.082 bar