CCHE 4273

FIRST PUBLIC EXAMINATION

Preliminary Examination in Chemistry

SUBJECT 3 : PHYSICAL CHEMISTRY

LONG VACATION 2013

Monday, 9th September 2013, 9.30 a.m. - noon

Time allowed 2 12 hours

Candidates should attempt ALL questions in section A and TWO questions in section B.

Use SEPARATE booklets for your answers to Section A and Section B.

The numbers in square brackets indicate the approximate weight given to each part of the
question.

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

1
 Fundamental Constants
Speed of light in a vacuum c 2.998 × 108 m s−1
Planck constant h 6.626 × 10−34 J s
~ = h/2π 1.055 × 10−34 J s
Boltzmann constant kB 1.381 × 10−23 J K−1
Gas constant R 8.314 J K−1 mol−1
Faraday constant F 9.649 × 104 C mol−1
Elementary charge e 1.602 × 10−19 C
Electron mass me 9.109 × 10−31 kg
Proton mass mp 1.673 × 10−27 kg
Neutron mass mn 1.675 × 10−27 kg
Electric constant ǫ0 8.854 × 10−12 F m−1
Avogadro constant NA 6.022 × 1023 mol−1
Atomic mass unit u 1.661 × 10−27 kg
Gravitational constant G 6.674 × 10−11 N m2 kg−2
Gravitational acceleration g 9.807 m s−2

Other conventions
p−◦ = 1 bar = 1 × 105 Pa
1 atm = 101.3 kPa = 760 Torr
0 ◦C = 273.15 K

CCHE 4273

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 SECTION A
Attempt ALL six questions

1. (a) The half-life for the first order decomposition of N2 O5 is 2.05 × 104 s. Calculate
how long it will take for a sample of N2 O5 to decay to 60% of its initial value. [3]

(b) Show that the ratio of the half-life to the one-quarter life, t 1 /t 1 , for a reaction
2 4
that is nth order (n > 1) in reactant A, is independent of concentration.
Note that the one-quarter life is defined as the time at which the concentration is
1
4
of the initial concentration. [4]

2. (a) Use the principle of classical equipartition to estimate the molar heat capacity
at constant volume for Cl2 (g) and H2 O(g) at room temperature. Vibrational
contributions to CV,m may be neglected at room temperature. [4]

(b) Account for the fact that, at much higher temperatures, CV,m for H2 O exceeds
that for Cl2 by ∼ 25 R. [3]

(c) Neglecting vibrational contributions, estimate the change in molar internal energy
for the dissociation of Cl2 upon increasing the temperature from 298 K to 350 K
at constant volume. [3]

3. (a) For an electron with a spherically symmmetric, hydrogenic wavefunction, Ψ(r),

the radial distribution function is 4πr2 |Ψ(r)|2 . What is the precise interpretation
of the radial distribution function? [2]
In units where the Bohr radius a0 ≡ 1, the normalized 1s wavefunction for a
hydrogenic atom with nuclear charge Z is
 3  12
Z
Ψ(r) = exp (−Zr) .
π
(b) Calculate the most probable radius at which the electron will be found, and
comment on your result in physical terms. [4]

(c) Calculate the average electron-nuclear separation, hri, and comment on your
answer in comparison to that for part (b).

m!
rm exp(−cr) dr =
R∞
Note that 0 cm+1
: m ≥ 0 and c > 0. [4]

CCHE 4273 TURN OVER

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 4. The Maxwell-Boltzmann distribution of molecular speeds, c, in a gas at temperature
T may be written as

mc2
 m 3/2  
f (c) dc = exp − 4πc2 dc .
2πkT 2kT

(a) Explain the physical significance of the individual terms in the distribution func-
tion. [4]

(b) Given that the kinetic energy of a particle of mass m is E = 21 mc2 , transform the
above distribution of speeds to a distribution of kinetic energies, f (E)dE. [2]

(c) For a fixed temperature, sketch the distribution f (E), and derive an expression
for the most probable energy. [4]

5. The energy levels of a quantum harmonic oscillator, E(v), are given by

E(v) = (v + 12 ) hν

where v is the vibrational quantum number and ν is the vibrational frequency of the
oscillator.

(a) Compare the behaviour of a quantum harmonic oscillator with that of a classical
harmonic oscillator. [3]

(b) A 5 g mass suspended on a rubber band has a vibrational frequency ν = 7.5 s−1 .
Calculate the force constant of the band, and the zero point energy. [The effects
of gravity should be ignored.] [2]

(c) The maximum displacement of the band from its equilibrium length is
0.725 cm. Calculate the total vibrational energy, and estimate the vibrational
quantum number corresponding to this energy. [3]

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 6. Consider the following reaction:

Sn(s) + Sn4+ (aq) ⇋ 2 Sn2+ (aq).

(a) Write down the Nernst equation for this reaction. [2]

(b) If metallic tin is in equilibrium with a solution of Sn2+ (aq) in which the activity
of Sn2+ is 0.25, calculate the activity of Sn4+ at equilibrium at 298 K. [3]

You will require the following standard reduction potentials:

Sn2+ (aq) + 2e− → Sn(s) E −◦ = −0.1375 V

Sn4+ (aq) + 2e− → Sn2+ (aq) E −◦ = +0.1510 V

CCHE 4273 TURN OVER

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 SECTION B
Attempt any TWO questions

7. (a) Starting from the thermodynamic definition of Cp,m , the molar heat capacity at
constant pressure of a single species, derive Kirchoff’s equation
 
∂∆r H −◦
= ∆r Cp,m
∂T p

where ∆r H −◦ is the standard enthalpy change for a chemical reaction. Include in

your answer a clear definition of ∆r Cp,m . [6]

(b) Show that the corresponding standard entropy change satisfies

 
∂∆r S −◦ ∆r Cp,m
= .
∂T p T

[3]

The data below give the standard enthalpies of formation, absolute molar en-
tropies and molar heat capacities, at T = 298 K, for reactants and products of
the gas phase reaction

2 HNO2 ⇋ H2 O + NO + NO2 .

∆Hf,m
−◦
/ kJ mol−1 Sm
−
◦
/ J K mol−1 Cp,m / J K mol−1
HNO2 −79.5 254.1 45.6
H2 O −241.8 188.8 33.6
NO 90.2 210.8 29.8
NO2 33.2 240.1 37.2

You may assume the heat capacities of all species to be constant over the tem-
perature range considered.

(c) Calculate the standard enthalpy change for the reaction at T = 400 K. [6]

(d) Calculate the equilibrium constant, Kp , at T = 400 K. [8]

(e) As T is increased above 400 K, does Kp increase further, or decrease? Justify

your answer. [2]

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 8. (a) State the de Broglie relation between the wavelength of a quantum particle and
its linear momentum. [1]

A quantum particle of mass M is confined to a ring of radius r. The classical

expression for the energy of the particle is |Jz |2 /2I where |Jz | is the magnitude of
its angular momentum and I is the moment of inertia.

(b) Write down an expression for the moment of inertia, I. [1]

(c) Using the de Broglie relation, derive an expression for the energy levels of the
quantum particle. Specify the allowed values that the associated quantum number
(m) can take. [5]
1 ˆ2
(d) The Hamiltonian is given by Ĥ = where Jˆz = −i~ dφ
J ,
2I z
d
is the angular momen-
tum operator. Show that Ψ(φ) = N exp(imφ) is an eigenfunction of both Jˆz and
Ĥ, and determine the corresponding eigenvalues. N is a constant, and φ is the
azimuthal angle. [6]

(e) The quantum states of a particle on a ring are doubly degenerate. Explain what
is meant by this statement, and why it is not always true. [3]

(f) Explain the physical significance of the fact that degenerate states of given energy
do not correspond to the same angular momentum. [4]

(g) Determine the normalization constant, N , and hence |Ψ(φ)|2 . Comment on your
result for |Ψ(φ)|2 . [5]

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 9. (a) Describe briefly the experimental evidence which indicates that unimolecular
decompositions occur by multiple elementary steps. [4]

(b) Within the Lindemann mechanism, the reagent A may be activated by collisions
with either another reagent molecule, or with a non-reactant molecule M such as
a buffer gas. The rates of activation need not be the same for these two processes,
and in this case the mechanism is:

k1
A+M ⇄ A∗ + M
k−1
k2
A+A ⇄ A∗ + A
k−2
k
3
A∗ −
→ P

(i) Write down expressions for d[P]/dt and d[A∗ ]/dt. [3]

(ii) Use the steady state approximation on your expression for d[A*]/dt to show that
the rate of product formation for the mechanism is:

d[P] k3 [A] (k1 [M] + k2 [A])

= [5]
dt k−1 [M] + k−2 [A] + k3

(iii) In the limit where [M] = 0 show that the rate law reduces to d[P]/dt = k uni [A]
where k uni depends upon [A]. [2]

(c) In the unimolecular isomerization of pure cyclobutane to butene, the following

values for k uni as a function of cyclobutane concentration, [A], were measured at
350 K:

[A]/ 10−3 moles dm−3 4.9 9.4 17.4 34.0

k uni /s−1 9.6 10.3 10.52 10.64

Assuming that the Lindemann mechanism accurately describes the reaction,

determine k 2 and the ratio k −2 /k 3 . [8]

(d) Calculate the half-life for the unimolecular decomposition at a cyclobutane con-
centration of 34 × 10−3 moles dm−3 and a temperature of 350 K. [3]

CCHE 4273

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 10. The van der Waals equation of state is:
RT a
p = − 2
Vm − b Vm
where V m is the molar volume and a, b are constants. The compression factor, z, for
a gas is defined as z = pVm /RT .

(a) Discuss the physical significance of the coefficients a and b. [3]

(b) State the value of z for an ideal gas. Show that if Vm ≫ b, the compression factor
for a van der Waals gas can be approximated as:
 
 a  1
z = 1+ b− .
RT Vm
[4]

(c) Given that    

∂z 1 ∂z
≃
∂p T RT ∂[1/Vm ] T
for Vm ≫ b, show that
 
∂z 1  a 
≃ b− .
∂p T RT RT
[2]

(d) The temperature at which  

∂z
= 0
∂p T
is known as the Boyle temperature. Given that a = 1.345 dm6 bar mol−2 and
b = 0.032 dm3 mol−1 , estimate the Boyle temperature for argon. [4]

(e) For values of z close to 1,

 
∂z
z(p) ≃ 1 + p.
∂p T

Sketch z(p) for conditions such that the temperature is (i) above and (ii) below,
the Boyle temperature. Give a physical interpretation of the behaviour that you
sketch. [6]

(f) One mole of argon undergoes an isothermal reversible expansion from an initial
volume of 2 dm3 to a final volume of 85 dm3 at 310 K. Calculate the work done
in this process using the van der Waals equation of state. [6]

CCHE 4273 LAST PAGE