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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.
CHM2304(S1)
CONTINUED
CHM2304(S1)
1.
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 &
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]
CHM2304(S1)
CONTINUED
CHM2304(S1)
2.
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)
(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]
CHM2304(S1)
CONTINUED
CHM2304(S1)
3.
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)
(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]
CHM2304(S1)
CONTINUED
CHM2304(S1)
(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.
Define the distribution ratio, D, for the acid and explain the difference
between D and the distribution (or partition) coefficient KD.
CHM2304(S1)
CONTINUED
CHM2304(S1)
(c)
(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]
CHM2304(S1)
CONTINUED