THE UNIVERSITY OF THE WEST INDIES

Semester l □x□ Supplemental/Summer School □

Semester II

Examinations of December □x /April/May □ /July □ 2015

Originating Campus: Cave Hill □ Mona □x St. Augustine □

Mode: On Campus □ x By Distance □

Course Code and Title: CHEM2310 – PHYSICAL CHEMISTRY A

Date: Time:

Duration: 2 Hours. Paper No: 1

Materials required:

Answer booklet: Normal □ Special □

x Not required □
Calculator: Programmable □ Non Programmable □
(where applicable)

Multiple Choice answer sheets: numerical □ alphabetical □ 1-20 □ 1-100

□
Auxiliary/Other material(s) – Please specify:

Candidates are permitted to bring the following items to their desks:

Instructions to Candidates: This paper has 5 pages & 6 questions.

Candidates are reminded that the examiners shall take into account the proper use of the English
Language in determining the mark for each response.

ANSWER ANY FOUR QUESTIONS

The use of non-programmable calculators is permitted

The bracketed numbers down the right hand side of the paper are an indication of the
normal marks for parts of questions. An excellent answer may well glean one or
two extra marks (but may not cause the total for the question to exceed 25).

Begin each question on a new page

 Page 2

1. When ammonium chloride is heated the vapour pressure at 427oC is 4560

mmHg. At 459oC the vapour pressure has risen to 8360 mmHg.
What is
(i) the equilibrium constant for the dissociation reaction

NH4Cl(s) NH3(g) + HCl(g) (5)

(ii) the standard Gibbs energy, (6)

(iii) the enthalpy, (8)
(iv) the standard entropy, (6)
all evaluated at 427oC?

Assume the vapour to behave as a perfect gas mixture.

Van ’t Hoff’s isobar is
d ln K  H
=− r
d (1 / T ) R
(1 bar = 750 mmHg)

2. (a) Some liquid ethanol (CH3CH2OH) is placed inside a 10 dm3 sealed container.
At 292 K, the vapour density is found to be 0.101 g dm-3.
At 308 K, the vapour density above the liquid is 0.240 g dm-3.
(i) Assuming that the vapour behaves as an ideal gas, calculate the vapour
pressure at 292 K and at 308 K. (6)

(ii) Using the Clausius-Clapeyron equation,

d ln p  vap H
=− ,
d (1 / T ) R

compute  vap H for ethanol, assuming it to be independent of temperature.

(7)
o
(b) When chloroform is added to acetone at 25 C the molar volume of the mixture
varies with composition as follows:

x 0 0.19 0.39 0.56 0.79 0.89 1.00

V /cm3 mol-1 74.0 75.3 76.5 77.6 79.1 79.8 80.7

where x is the mol fraction of chloroform.

From a plot of these data, determine the partial molar volumes of the two
components at x = 0.5. (12)
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3. (a) At 90oC the vapour pressure of toluene is 400 mmHg, and that of o-xylene is
150 mmHg. A mixture of the two liquids is approximately ideal.

(i) What is the composition of a liquid mixture that will boil at 90oC when the
pressure is 380 mmHg? (6)

(ii) What is the composition of the vapour produced? (6)

.
(b) (i) The potential of the cell Ag | AgBr(s) | AgI(aq) | Ag is +0.73 V at 25 ºC,
Calculate the solubility product of AgBr and its solubility. (7)

(ii) Calculate the equilibrium constant for the following reaction at 25oC:
Fe(s) + 2Fe3+(aq) 3Fe2+(aq),
using the given standard potential data.

[Eº (Fe3+/Fe2+) = +0.77 V, Eº (Fe2+/Fe) = –0.44 V] (6)

4. (a) (i) For the reaction

C6H5N(CH3)2 + CH3I C6H5N+(CH3)3I-

Derive an expression involving the standard enthalpy of activation

(  H  ) and standard entropy of activation (  S  ) given in
k T
Eyring’s formula: k r =  B K  (assume κ = 1).
h
State the meaning of all the symbols in the above formula. (8)

(ii) A plot of ln(kr/T) vs. 1/T for the above reaction yields a gradient of
–6,250 K and an intercept of –2.5.
Calculate the values of  H  and  S  . (5)

(b) Carbon dating of artefacts of dead organic material using 14C is an

important tool in archaeology as it allows the determination of the age of
the material. The half-life for the radioactive decay of 14C is 5,700 years.
The amount of it remaining in a sample is measured in units of
“counts per minute per gram carbon” (c.p.m.g-1).
A sample of charcoal taken from an archaeological dig was analysed
and was found to have a count of 5 c.p.m.g-1. A fresh sample of the
same type of wood has a count of 15 c.p.m.g-1.
Calculate the approximate age of the charcoal sample. (12)
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5. (a) Consider the reaction

NO2(g) + CO2 → NO(g) + CO2(g)

The experimentally determined rate equation is r = k[NO2(g)]2.

(i) Show that the rate expression is consistent with the following
mechanism:
k1
2NO2(g) N2O4(g) fast
k-1
N2O4(g) k2 NO(g) + NO (g) slow
3

NO3(g) + CO(g) k3 NO2(g) + CO2(g) fast (8)

(ii) Express the empirical rate constant in terms of the individual rate
constants of the different steps. (5)

(b) (i) Use the following data to determine the order of a bimolecular
reaction between species A and B with respect to these reactants:

[A] / 10-4 M [B] / 10-5 M Initial rate / M s-1

2.0 3.0 5.25 x 10-4

4.0 6.0 4.20 x 10-3
8.0 6.0 1.68 x 10-2
(8)
(ii) Calculate the rate constant for the reaction. (4)
 Page 5

6. (a) Consider the cell,

Zn(s) | ZnCl2 (0.0050 mol kg–1) | Hg2Cl2(s) | Hg(l)
for which the cell reaction is:
Hg2Cl2(s) + Zn(s) → 2Hg(l) + 2Cl–(aq) + Zn2+(aq).

[Eº (Zn2+, Zn) = –0.763 V, Eº (Hg2Cl2, Hg) = +0.268 V]

(i) Write the anode and cathode reactions. (4)

(ii) Determine the standard cell potential. (2)
(iii) Write the Nernst equation for the cell . (4)
(iv) Determine the activity of Zn2+(aq) and Cl–(aq).
[Making use of the Debye–Huckel limiting law,
log γ± = – A | zA zB | I1/2; A = 0.509 mol-1/2 kg1/2] (7)
(v) Calculate the cell potential (5)
(vi) Determine ∆rGº. (3)

END OF QUESTION PAPER