ASSIGNMENT 1

(a) Estimate the de Broglie wavelength of electrons that have been

accelerated from rest through a potential difference of 40 kV. [4]
(b) Deduce the Plank’s constant given that the following kinetic energies
were observed when electrons were photo-ejected by radiation of
wavelengths indicated in the table below.

ƛ/nm 320 330 345 360 385

Ek/eV 1.17 1.05 0.885 0.735 0.511
[6]

(c) Given that Einstein’s constant volume molar heat capacity for
monoatomic solids is given by
θE 2

( )
2
θE e 2T
f= ( )
T θ
E
C v, m=3 Rf where e T −1 ,
(a) define ƟE [1]

(b) show that at high temperatures

C v, m=3 R and
C v , m →0 at
very low temperatures
[7]
(d) Describe how the Raleigh-Jeans equation brings about the uv-
catastrophe and how Plank’s relation resolved this.
8 π kT
ρ=
Hint 1; Raleigh-Jeans relation λ4

8π hc
ρ= hc

Hint 2; Plank’s relation

5
λ e ( λ kT
−1 ) where ΔE=ρΔλ
[7]

1
2
a) Given that the Shrodinger equation is given by
dψ 2m
=− ( E−V )ψ ikx
dx 2 ℏ e
, and has a general solution, , draw
synergies with the de Broglie.
[10]
b) The wavefunction of an electron in its lowest energy state in the ion He +

−2r
ao
is proportional to e . Calculate the relative probabilities of finding the
electron inside a region of 1 pm 3 which is small even in the atomic scale
located at
(i) The nucleus.
(ii) A distance ao from the nucleus.
Comment on the values. [5]
c) Normalize the equation in (b).
∞
n!
∫ x n e−ax dx= an+1
HINT ; 0 [10]

ASSIGNMENT 2
1 nπx
(a) Find the normalization factor in the following, ψ II =A sin [7]
L
(b) Lithium has a workfunction of 2.90 eV. Determine the electron escape
velocity of radiation of 4.77 x 1015 s-1 is absorbed. [3]
(c) Deduce the de Broglie wavelength of a 100 kg automobile travelling at
100 km h-1 and an electron travelling at 1 % the speed of light. [4]
(d) Comment on the values obtained in (d). [3]
(e) β Carotenes are highly conjugated polyenes found in many vegetables.
They can be oxidized and used to synthesize pigments that play
important roles in the chemistry of mammalian vision. The parent
compound, β carotene, has a maximum absorption of light that occurs at

2
 480 nm. If this transition corresponds to an n = 10 to n = 11 transition of
an electron in a particle in a box system, what is the approximate length
of the molecular “box”? [8]

2
a) Suppose that in an industrial batch process, a substance A
produces the desired compound I which goes to decay to a
worthless product C, each step of the reaction being first order.
Determine the stage at which the concentration of I will be at its
maximum. [6]
b) The variation in partial pressure of azomethane with time was
followed at 600 K with the results given in the following table.
Confirm that the decomposition is first order in azomethane and
establish the rate constant k at this temperature. [8]
CH3N2CH3 (g) CH3CH3 (g) + N2 (g)
t/s 0 1000 2000 3000 4000
p/Pa 10.9 7.63 5.32 3.71 2.59

c) The rate of the second order decomposition of acetyldehyde was

measured over the temperature range 700 K – 1000 K and the rate
constants are reported below. Deduce the activation energy Ea and
the pre-exponential factor A [11]

T/K 700 730 760 790 810 840 910 1000

k/(dm3 mol-1 s-1) 0.011 0.035 0.105 0.343 0.789 2.17 20.0 145

3
3

(a) (i) Define the acronym ‘laser’. [1]

(i) With reference to lasers, describe and explain the meaning of the
following terms: low divergence, coherent, monochromatic, very
short pulses and high intensities. [4]
(ii) With the help of relevant diagrams distinguish between a three
level and four level laser. [2]
(b) Illustrate and explain the following processes:

(i) Intersystem crossing.

(ii) Two photon absorption.

(iii) Excited state absorption.

(iv) Phosphorescence.

(v) Internal conversion. [8]

(c) Which of the following function are Eigen functions of their first
derivative
(i) eikx,
(ii) cos kx,
(iii) k,
(iv) e-ax' Giving the eigen values where appropriate. [10]