CHM2304(S1)

Data Provided:
Chemistry Ancillary Booklet
THE UNIVERSITY OF SHEFFIELD
DEPARTMENT OF CHEMISTRY
Autumn Semester 2013/2014

2 hours duration

PHYSICAL CHEMISTRY
4 Questions Answer ALL Questions
You MUST answer each QUESTION in a SEPARATE Answer Booklet

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1.

Answer all parts of this question.

The Clapeyron equation, shown below, gives the rate of change of pressure with
temperature for a first-order phase transition, in terms of entropy and volume changes.

(a)

Provide a simple derivation of this equation.

[6 marks]

(b) The Clausius-Clapeyron equation for the variation of vapour pressure with
temperature can be written as

d ln p vapH

=
dT RT 2
where the symbols have their usual meaning. Derive this equation from the
Clapeyron equation, stating any approximations that you make.

[6 marks]
(c)

The vapour pressure of ethene as a function of temperature is given by the

expression

log( p /Pa) =

843.13
+1.75 xlog(T /K) 8.375 x10 3 (T /K) + 5.3240
T /K

Calculate the enthalpy of vaporisation of ethene at its normal boiling point

(169.3 K)

[6 marks]
(d) State Troutons rule. Does your answer to part (c) agree with this rule? If not, why
not?
[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)

Give the detailed mathematical form of the Hamiltonian operator in this onedimensional Schrdinger equation, defining all symbols that you introduce.

[2 marks]

(ii) What conditions must be obeyed by the functions (x) if they are to represent
physically acceptable solutions for this problem?
[4 marks]
(iii) What does it mean to say that two wavefunctions are orthogonal?
[1 mark]
(iv) What does it mean to say that two wavefunctions are orthonormal?
[1 mark]
(v) What does it mean to say that two wavefunctions are degenerate?
[1 mark]
(b) A particular case of the one-dimensional Schrdinger equation applies to the
particle on a ring, where a particle is confined to a circular path defined by an
angle .
(i)

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

(ii) State the boundary condition on the wavefunction, and explain why this leads
to the introduction of a quantum number for the particle on a ring.
[2 marks]
(iii) Give a formula for the energy levels of the particle on a ring, defining all
symbols that you introduce. Illustrate the formula with an energy level
diagram, showing any degeneracies that may be present.
[4 marks]
(iv) What is the analogue of the usual Heisenberg Uncertainty Principle for the
case of the particle on a ring?
[1 mark]
(v) Given that the particle is a proton, and the circle is of radius 0.1 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.

(a)
(i)

Define the terms molecularity and order of a chemical reaction.

[2 marks]

(ii) Describe the concept of the pre-equilibrium and of the rate-limiting step.
[2 marks]
(b) Consider a process, which has the following experimental rate law:
v = kr[CH3CO]3/2
Assume that the mechanism consists of the following elementary steps:
CH3CHO
CH3 + CH3CHO
CH3CO
CH3 + CH3
(i)

CH3 +CHO
CH4 + CH3CO
CH3 + CO
C2H6

What is the role of CH3 and CH3CO?

[1 mark]

(ii) Assign names to each elementary step in this reaction.

[1 mark]
(iii) What is the stoichiometric equation for this reaction?
[2 marks]
(iv) Define the steady-state approximation.
[2 marks]
(v) Write down a rate equation for each of the intermediates in this reaction,
CH3 and CH3CO.
[2 marks]
(vi) Apply steady-state approximation to the intermediates from (v).
[2 marks]
(vii) Derive the equation for the concentration of the CH3 radical.
[2 marks]
(viii) Use the equation for the concentration of CH3 radical to derive the reaction
rate law with respect to CH4.
[2 marks]
(ix) Does the rate law you derived under (viii) correspond to the experimental rate
law? Justify your answer.
CHM2304(S1)

[2 marks]
CONTINUED

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4.

Answer all parts of the following question.

(a)
(i)

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

(ii) Calculate the percentage of base B left in the aqueous phase at pH 10, when
100 mL of a solution of base B in water is extracted with 50 mL of
dichloromethane (assume KD = 5 and Ka = 10-9 M).
(iii) Will base B be more soluble or less soluble in the dichloromethane phase at
pH 2? Explain your reasoning.
[5 marks]
(b)
(i)

Explain the thermodynamic basis of a chromatographic separation.

(ii) Define the height equivalent to a theoretical plate (HETP). Explain how this
parameter is used for the selection of a chromatographic column, assuming
that the columns have the same number of theoretical plates.
(iii) In ion-exchange chromatography, how would you increase the ionic strength
of the mobile phase during elution?
[5 marks]
(c) An HPLC analysis was conducted for caffeine on a sports drink. A 10.1 ppm
methanol internal standard was introduced, both into the unknown sample and into a
solution of 304 ppm caffeine standard. The absorbances for methanol and for
caffeine are summarised in the table below. Calculate the concentration of caffeine
in the sports drink.

methanol internal standard

caffeine

(arbitrary units)

(arbitrary units)

unknown sample

23141

52777

304 ppm caffeine standard

28441

77313
[6 marks]

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(d)
(i)

Briefly explain the basis of separation in gas chromatography (GC).

(ii) State the type of stationary phase you would choose to separate a mixture of
hydrocarbons with a wide range of molecular weights.
(iii) How would you elute high molecular weight hydrocarbons showing peaks
with high retention times in GC?
[4 marks]
END OF QUESTION PAPER

CHM2304(S1)