CHM2304(S1)

Data Provided:
Chemistry Ancillary Booklet
THE UNIVERSITY OF SHEFFIELD
DEPARTMENT OF CHEMISTRY
Autumn Semester 2012/2013

2 hours duration

PHYSICAL CHEMISTRY
4 Questions Answer ALL Questions.
Answer each QUESTION in a SEPARATE Answer Book.

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1.

Answer all parts of this question.

(a)

Give a brief description of the difference between a first-order and a second-order

phase transition.
Illustrate your answer diagrammatically.
[5 marks]

(b) The Clapeyron equation for a liquid-vapour boundary is

dp ! vap H
,
=
dT T ! vapV

where the symbols have their usual meaning. Use this equation to estimate the
effect of raising the pressure on the boiling point of a typical liquid. The molar
volume of a perfect gas is 25 dm3 at 1 atm over the required temperature range.
[5 marks]
(c)

The Kelvin equation gives the vapour pressure, p, of a liquid when it is dispersed
as droplets of radius r:
p = p"e 2Vm!

rRT

where p* is the bulk vapour pressure, and the other symbols have their usual
meaning.
Calculate the vapour pressure of a drop of water with radius 25 nm at 25C, given
that the vapour pressure of bulk water at this temperature is 5.623 kPa, and its
density is 994.0 kg m3.
Assume a value of 72.0 mN m1 for the surface tension, .
[5 marks]
(d) The Gibbs energy of one mole of a gas depends on the external pressure according
to the approximate equation
! pf "
Gm ( p f ) = Gm ( pi ) + RT ln #
$,
% pi &

where the symbols have their usual meaning.

(i)

Derive this equation from first principles, stating any approximations made.
[3 marks]

(ii) Calculate the change in chemical potential of a perfect gas when its pressure
is increased isothermally from 1.0 atm to 10.0 atm at 25C.
[2 marks]

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2.

Answer all parts of this question.

(a)

The time-independent Schrdinger equation for a single particle with one degree of
freedom and potential energy function V(x) can be written in general form as

H ! = E!
(i)

What do the symbols and E represent here?

[2 marks]

(ii) Give the detailed mathematical form of the Hamiltonian operator in this onedimensional Schrdinger equation, defining all symbols that you introduce.
[2 marks]
(iii) What conditions must be obeyed by the functions (x) if they are to represent
physically acceptable solutions for this problem?
[4 marks]
(iv) The position operator x and the momentum operator p x do not commute.
What is the physical consequence of this mathematical fact?
[1 mark]
(b) A particular case of the one-dimensional Schrdinger equation applies to the
particle in a box, where a particle is confined to the axis between x = 0 and x = L.
(i)

Describe and sketch the potential function V(x) for this case.
[1 mark]

(ii) State the boundary conditions on the wavefunction for this case.
[1 mark]
(iii) Describe briefly how application of the boundary conditions leads to the
introduction of a quantum number for the particle in a box.
[2 marks]
(iv) Give a formula for the energy levels of the particle-in-a-box system, defining
all symbols that you introduce.
[2 marks]
(v) Give a formula for the wavefunctions of the particle-in-a-box system, defining
all symbols that you introduce.
[2 marks]
(vi) Given that the particle is an electron, and the box is of length 1 nm, calculate
the frequency of radiation needed to raise the system from its ground state to
its first excited state.
[3 marks]
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3.

Answer all parts of this question.

Shown below is the rovibrational infrared absorption spectrum of carbon monoxide,
12 16
C O (overview, top and detail of spectrum, bottom).

0.04
ln (0I / I )

0.03
0.02
0.01
0.00
2050

2100

2150
!~ / cm-1

2200

0.04
ln (0I / I )

0.03
0.02

R(3)

P(4)

R(2)

P(3)
R(1)

P(2)
P(1)

0.01

R(0)

0.00
2125 2130 2135 2140 2145 2150 2155 2160
!~ / cm-1
(a)

Explain the meaning of "R(1)".

[1 mark]

(b) What are the selection rules for electric dipole allowed infrared transitions
concerning the change in rotational quantum number J?
[2 marks]
(c)

Measure the positions of suitable lines, and determine the rotational constant B"
and B' of the ground state and of the excited state, respectively, using the method of
combination differences. Use these values to calculate the bond length of carbon
monoxide in the ground state and in the excited state.
[Note that B =

h
2

8! cI B

and IB = R2]
[10 marks]

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(d) In the vibrationally excited state, the rotational constant B' is expected to be slightly
lower than B" in the ground state. Why?
[2 marks]
(e)

Explain why the CO vibration can be observed by infrared spectroscopy, but the O2
vibration cannot.
[2 marks]

(f)

The stretching vibration of 16O2 occurs at 1556 cm-1 and can be observed by Raman
spectroscopy. For Raman excitation light at = 532 nm, what is the wavelength (in
nm) of the red-shifted Raman scattered light?
[3 marks]

4.

Answer all parts of this question.

(a)

Answer all parts of this question.

A weak acid HA has an dissociation constant of 103 M.
(i)

Define the distribution ratio, D, for the acid and explain the difference
between D and the distribution (or partition) coefficient KD.

(ii) Calculate the percentage of acid left in the aqueous phase at pH 7, if 50 mL of

acid is extracted with 100 mL of dichloromethane (assume KD = 5).
(iii) Explain how the distribution ratio of the acid changes between pH 2 and
pH 7.
[5 marks]
(b) Answer all parts of this question.
(i)

In HPLC, explain what is meant by gradient elution.

How does this differ from isocratic elution?

(ii) Explain why gradient elution is preferable to an isocratic separation.

(iii) Would you increase or decrease the polarity of the mobile phase during
gradient elution when using a C18 stationary phase?
Justify your answer.
[5 marks]

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(c)

A sample containing a pesticide X was analysed using Gas Chromatography (GC).

This sample was treated with an internal standard Q to give a concentration of
Q = 15.0 ppm.
A 1.0 L sample injected into the GC, gives a peak area of 1012 for Q, and a peak
area of 3411 for X.
A 1.0 L standard solution of 30.0 ppm Q with 15.0 ppm of pure X was injected
giving responses of 899 and 2791, respectively.
What is the concentration of X in the sample?
[5 marks]

(d) Answer all parts of this question.

(i)

Give a brief explanation of the basis for separation in ion-exchange

chromatography (IEC).

(ii) Describe the type of mobile phase composition that is needed to achieve
separation in IEC.
(iii) Describe the type of stationary phases that are needed to achieve separation in
IEC.
(iv) Describe two examples of analysis that are suitable for this kind of
chromatographic technique.
[5 marks]

END OF QUESTION PAPER

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