A26191

CALCULATORS MAY BE USED IN THIS EXAMINATION BUT

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WITH THE ABILITY TO STORE TEXT SHOULD HAVE THEIR
MEMORIES DELETED PRIOR TO THE START OF THE
EXAMINATION.
SI UNIT BOOKLET
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MOLYMOD KIT

COLLEGE OF ENGINEERING & PHYSCIAL SICENCES

SCHOOL OF CHEMISTRY
Degree of MSci/BSc with Honours
Chemistry
Chemistry with Industrial Experience
Chemistry with Analytical Science
Chemistry with Bioorganic Chemistry
Chemistry with Business Management
Chemistry with Pharmacology
Chemistry with a Modern Language
Chemistry with Study Abroad
BSc / MSci NatSc Degree
CHM2C1-A/B / 03 21452 & 03 21450
Quantum Mechanics & Atomic Spectroscopy, Non-ideal Thermodynamics & Equilibrium
Electrochemistry
Summer Examinations 2015
Time Allowed: 2 Hours
All FOUR questions should be attempted. You should answer all parts of Section A in
each question, and then choose from either Section B or Section C in each question.
EACH QUESTION MUST BE ANSWERED IN A SEPARATE BOOK AND THE
NUMBER CLEARLY STATED ON THE FRONT OF THE BOOK. All these books
should be assembled with a completed grid (obtainable from an invigilator) and securely
fastened together.
(This examination counts towards your final degree assessment.)
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Section A (COMPULSORY)

1A.

(a)

(i) Calculate the kinetic energy for a proton travelling at 1.2 km s1. Give your
answer in both J and eV.
(3 marks)
(ii) What is the wavelength of the proton?
(3 marks)
(iii) What does the wavelength you calculated tell us about the behaviour of
protons? Briefly explain your answer.
(2 marks)
(iv) Calculate the momentum of the proton. If there is an uncertainty in its
momentum of 0.1 %, then what is the corresponding minimum uncertainty
in its location?
(4 marks)

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Answer Section B or Section C

Section B
EITHER
1B.

Name two sets of experimental evidence that demonstrate the breakdown of classical
mechanics. Describe how these show the failure of classical mechanics and how
quantum mechanics provides an explanation of the experimental observations.
(8 marks)

Section C
OR
1C.

(a)

Explain Borns interpretation of the wavefunction and the importance of the

normalisation factor.
(5 marks)

(b)

The following functions are eigenfunctions of the operator d2/dx2. In each case,
give the corresponding eigenvalue.
(i) eax
(ii) sin kx
(iii) i.cos kx
(3 marks)

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Section A (COMPULSORY)

2A.

(a)

Write the term symbols, including J-levels, arising from the [He]2s22p14p1
configuration of carbon. Which is the lowest energy term and why?
(5 marks)

(b)

For the ground configuration of carbon [He]2s22p2 the ground-term is 3P0. Why
is this not the same ground-term as found for the excited state in (a)?
(2 marks)

(c)

Which transitions are allowed between the ground-term of the [He]2s22p2

configuration and the excited terms of the [He]2s22p14s1 configuration?
(3 marks)

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Answer Section B or Section C

Section B
EITHER

2B.

(a)

What is the physical significance of the Bohr radius, a0?

(2 marks)

(b)

The energy of an electron in a hydrogen atom orbital is found to be

En hcRH

1
n2

where RH is the Rydberg constant, h Plancks constant, c the speed of light and
n is an integer. What does n signify? Use this equation to obtain the Rydberg
formula for the energy of the electronic transition from level n to m in hydrogen
in units of cm1.
(3 marks)
(c)

Using a value of RH = 109,677 cm1, calculate the ionization energy, in J, of a

hydrogen atom from the 2s orbital.
(2 marks)

(d)

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In the hydrogen atom all orbitals within a shell are degenerate. Why is this not
the case for atoms with more than 1 electron?
(3 marks)

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Section C
OR

2C.

(a)

(b)

Why is a beam of silver atoms passing through an inhomogeneous magnetic

field split into two?
(2 marks)
The energy due to spin-orbit coupling for an electron with spin quantum
number, s, orbital angular momentum quantum number, l, and total angular
momentum quantum number, j, is
ESO 12 hcA j j 1 l l 1 ss 1

where A is a constant. Derive the Land interval rule for the energy splitting
between states with the same values of l and s and neighbouring values of j.
(4 marks)
(c)

The ground terms of both Ti (configuration [Ar] 4s23d2) and Ni (configuration

[Ar] 4s23d8) have levels 3F4,3,2. Why is the Ti ground-level 3F2, while for Ni it is
3
F4?
(2 marks)

(d)

The Russell-Saunders coupling scheme uses term symbols of the form

2 S 1

LJ .

Why is this scheme not appropriate for heavy atoms such as lead? What
scheme should be used instead?
(2 marks)

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Section A (COMPULSORY)

3A.

(a)

What conditions need to be fulfilled for compounds A and B to form an ideal

solution upon mixing?
(2 marks)

(b)

The data below were recorded when mixing liquids A and B at 27 C:

xA

0.998

0.996

0.994

0.992

PB / kPa

12.15

22.92

34.40

47.28

(i) Define xA and PB.

(2 marks)
(ii) Justify why Henrys law can be applied to B.
(1 mark)
(iii) What is the Henrys constant for component B?
(3 marks)
(iv) What would you expect to happen to the vapour pressure of B as the
proportion of B keeps increasing?
(2 marks)

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Answer Section B or Section C

Section B
EITHER

3B.

A system consists of 2.6 mol of CO2(gas) initially at 12 C and 9 atm and confined to
a cylinder of cross section 80 cm2.
The sample is allowed to expand adiabatically against an external pressure of 1.5 atm
until the piston has moved outwards by 20 cm. Assume CO2 is a perfect gas with
Cv,m = 28.8 J K1 mol1.
Calculate Q, W, U, T and S given that the change of entropy with volume in a
reversible isothermal process is;
V f
S nR ln
Vi

and the change of entropy with temperature in a reversible isochoric process is:
Tf
S nC v,m ln
Ti

(10 marks)

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Section C
OR
3C.

(a)

A polar organic molecule possesses a permanent dipole.

Calculate the dipole moment in Debye where q = 0.24e and l = 0.34 nm.
1 D = 3.3 1030 C m
(3 marks)
(b)

Dipoles are involved in various intermolecular forces: ion-dipole interactions,

dipole-dipole interactions and dipole-induced dipole interactions.
(i) Which interaction is the strongest amongst the three interactions given
above.
(1 mark)
(ii) Among H2O, H2Se, H2Te, and H2S, which molecule has the strongest
dispersion forces. Justify.
(2 marks)
(iii) Among H2O, H2Se, H2Te, and H2S, which molecule will form the strongest
interaction with ammonia. Justify.
(2 marks)

(c)

Explain why small alkanes are slightly soluble in water, despite being
hydrophobic molecules.
(2 marks)

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Section A (COMPULSORY)

4A.

(a)

(i) Explain why reference potentials are an important part of electrochemistry

and describe how they are defined.
(ii) What are the essential characteristics of a reference electrode? Briefly
describe the construction of the Standard Hydrogen Electrode, explaining
which materials are used and how the required characteristics of a reference
electrode are achieved.
(10 marks)

Answer Section B or Section C

Section B
EITHER
4B.

(b)

(i) Two electrodes of area A are placed in an electrolyte solution a distance of l

apart. A voltage V is applied and a current I flows. Derive an equation to
show how the conductivity of the electrolyte may be obtained from the
values of V, I, A and l. What are its units?
(ii) The table below gives limiting molar conductivities for some common
anions. Define the term limiting molar conductivity and explain the trend
observed.
Ion
OH
F
Cl
Br

/ 1 cm2 mol1
199
55
76
78
(10 marks)

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OR

4C.

(c)

(i) The Debye-Hckel Limiting Law:

log10 j Az j

is used to estimate activity coefficients of ions in solution. Use the DebyeHckel Limiting Law to predict the mean activity coefficient of solutions of
MgSO4 at 25 C at each of the following molalities: 1 mmol kg1,
0.1 mol kg1 and 1 mol kg1. The value of A at this temperature is
0.509 mol1/2 kg1/2.
(4 marks)
(ii) The measured values of activity coefficients of some solutions are given in
the table below. Rationalise the observations, explaining in detail what you
would expect and any discrepancies between these values and those you
predicted in (i).
molality (mol kg1)
0.001
0.1
1

BeSO4
0.807
0.150
0.053

MgSO4
0.809
0.150
0.0485

ZnSO4
0.809
0.150
0.0435
(6 marks)

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