Module Code

CHE00009C

BSc and MBIOCHEM Degree Examinations 2018-9

Department:
Chemistry

Title of Exam:
Foundation Chemistry for Biochemistry II

Time Allowed:
ONE hour and THIRTY minutes

Allocation of Marks:
All questions carry equal marks
Allocation of marks is indicated in the right hand margin

Instructions for Candidates:

Answer ALL questions
Answer all parts of a question unless choice is indicated
Answer each question in a new booklet
Only the first question answered in each booklet will be marked

Materials Supplied:
One Blue Booklet Per Question
Chemistry Databook
Calculator

Do not write on this booklet before the exam begins

Do not turn over this page until instructed to do so by an invigilator

Page 1 of 7
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Page 2 of 7
Question 1 – answer each question in a new booklet

(a) N2O5 is thought to decompose via the elementary reaction 1, given below.

k1
N 2O5  NO 2  NO3 (1)

(i) Write down an equation for the rate of change of the concentration of N2O5. (1)

(ii) Use your answer from part (a)(i) to derive the integrated rate law shown below. (3)

[N 2 O5 ]t  [N 2 O 5 ]0 e  k1t

(iii) In an experiment at 298K the concentration of N2O5 drops from (2)

2.5×1010 molecules cm–3 to 1.0×1010 molecules cm–3 in 20 s. Using these data,
calculate the rate constant at this temperature.

(iv) Write down the Arrhenius equation and, given that reaction (1) has an (2)
activation energy of 103 kJ mol–1, use your answer from part (a)(iii) to calculate
the pre-exponential factor in the equation.

(b) Ozone (O3) can decompose at elevated temperatures to give O2 as shown in reaction 2
below.
k2
2O3  3O2 (2)

A proposed mechanism for this reaction involves elementary reactions (3) and (4)
below.

k3

O3  
 O2  O (3)
k3

k4
O  O3  2O2 (4)

(i) Derive an expression for the overall rate of change of the concentration of (3)
oxygen atoms, [O], from the proposed mechanism given above. Hence, using
the steady state approximation, derive an expression for [O] for this
mechanism.

(ii) Use your expression for the steady state concentration of oxygen atoms from (4)
part (b)(i) to derive an expression for the overall rate of reaction (2) in terms of
the rate constants, k3, k–3 and k4, and the concentrations of the reactant, [O3],
and product, [O2]. Hence, describe how [O3] will be changing early in the
reaction when [O] is very low.

Page 3 of 7
Question 2 – answer each question in a new booklet

(a) (i) Briefly describe the types of electronic transition that can give rise to (3)
absorption bands in the UV/vis spectra of transition metal chlorides.

(ii) Explain why ScCl3 and ZnCl2 are colourless. (3)

(b) Sketch the structure of the complex [FeI4]2− considering that the effective magnetic (6)
moment of the complex is 4.9 μB. Use the spin-only equation (1) and crystal field
theory to explain your answer.

eff  n(n  2) (1)

(c) With the aid of an orbital overlap diagram, explain why the structure of (3)
[Cu(H2O)6]2+ deviates from perfect octahedral geometry. Hence outline how the
distortion stabilises the complex.

Page 4 of 7
Question 3 – answer each question in a new booklet

(a) The reaction of sodium bromide with compound 1 in propanone (acetone) gives one
major substitution product, compound 2 (80% yield) and a mixture of elimination
products, compound 3a (18% yield, E-isomer) and 3b (2% yield).

Compounds 3a and 3b can be further reacted to give a diol, 4, and alcohol, 5,

respectively.

H NaBr
Cl 2 (80%) + 3a (18%) + 3b (2%)
propanone
1
i. RCO3H

ii. H3O+ Reagents?

4

OH
5

(i) Use the Cahn-Ingold-Prelog (CIP) priority rules to assign a stereochemical (2)
descriptor to compound 1 and give its full systematic name.

(ii) Draw the structure of compound 2 and, using CIP rules, assign its stereochemical (2)
descriptor.

(iii) Give a curly arrow mechanism to explain the formation of compound 2 from (3)
compound 1 and briefly comment on the stereochemical outcome including the
role of solvent.

(iv) Draw the structures of compounds 3a and 3b showing stereochemistry where (2)
appropriate.

(v) Give suitable reagents for the conversion of 3b to 5. (1)

(vi) Deduce the structure of compound 4. (1)

Note: stereochemistry is not required.

(vii) Give a curly arrow mechanism for the formation of 4 from 3a. (4)

Turn over/

Page 5 of 7
Question 4 – answer each question in a new booklet

(a) Showing the participating atomic orbitals and indicating the phases of the atomic and (4)
molecular orbitals, draw sketches to show how a pz orbital forms a  bonding orbital in
combination with:
 another pz orbital
 an s orbital

(b) (i) The orbital energies of the valence atomic orbitals in Cl and F are given in the
table below:

Atom Orbital Orbital energy / eV

Cl 3s –25

3p –14

F 2s –40

2p –19

Sketch a fully labelled molecular orbital energy level diagram for ClF, assuming (4)
that the core electrons do not participate in the bonding and that sp mixing is
absent. Populate the molecular orbitals with the appropriate numbers of
electrons.

(ii) Write an expression for the highest occupied molecular orbital of ClF in terms (3)
of the participating atomic orbitals. Define any terms you have used and, giving
your reasons, state the relative magnitudes of the orbital coefficients.

(iii) Write the electronic configuration of the first excited state of ClF. If unpaired (2)
electrons are present in this configuration, clearly indicate the spins of these
electrons in the lowest energy arrangement.

(c) Use arguments based on bond order to predict whether ClF or ClF+ will display the (2)
greater bond dissociation energy.

Page 6 of 7
Question 5 – answer each question in a new booklet

(a) According to Trouton’s rule, vapH / Tb  85 J K–1 mol–1 for most liquids.

(i) Explaining your reasons, give two examples of liquids, other than benzene (3)
(C6H6), that can be expected to follow Trouton’s rule, and two examples of
liquids that are likely to show significant deviations from this rule.

(ii) Use Trouton’s rule to estimate the enthalpy of vaporization of benzene at its (2)
boiling point, 80.1 °C at 1 atm.

(b) The Clausius-Clapeyron equation, 1 below, describes the temperature dependence of

the vapour pressure of a liquid.

d (ln p )  vap H
 (1)
dT RT 2

(i) Briefly explain the assumptions under which equation 1 can be integrated to (2)
give equation 2.

 vap H 1
ln p    constant (2)
R T

(ii) Using equation 2, show that the vapour pressures, p1 and p2, at two (3)
temperatures, T1 and T2, respectively, are linked by equation 3.

p2  vap H 1 1
ln     (3)
p1 R  T1 T2 

(iii) Using equation 3 and the value you calculated in part (a)(ii), estimate the (5)
vapour pressure of benzene at 25.0 °C in bar.

Note: R = 8.314 J K–1 mol–1; 1 atm = 1.013 bar

END OF EXAMINATION

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