Answers Tutorial 3 SCES 2250
Answer Tutorial 3
1.For HF, m1 = 1 g mol-1 and m2 = 19 g mol-1 so =
For H35Cl, m1 = 1 g mol-1 and m2 = 35 g mol-1 so =
For H37Cl, m1 = 1 g mol-1 and m2 = 37 g mol-1 so =
For H79Br, m1 = 1 g mol-1 and m2 = 37 g mol-1 so =
For H81Br, m1 = 1 g mol-1 and m2 = 37 g mol-1 so =
For H127I, m1 = 1 g mol-1 and m2 = 127 g mol-1 so =
2. (a) HBr and (c) CO
3.
(a) Solving for k,
E hv
1
h
hc
c
k 4
k
and
4 2 2.998 108
516.3 Nm 1
34.969 1.66110
2991100 1.008
35.977
2
27
Answers Tutorial 3 SCES 2250
DCl
HCl
HCl
DCl
3(b) The vibrational frequency for DCl is lower by a substantial
amount
m H mCl
m H mCl
m D mCl
m D mCl
1.008
2.0140 34.969
2.0140
1.008 34.969
0.9798 0.5276
0.719
2886
(1 2 xe )
4.
2 2886 (1 3xe )
5668
1 2 x e
5772 17316 xe 5668 11336 xe
xe 0.0174 cm 1
2886
e
2990 cm 1
(1 2 0.0174 )
Force constant, k 4 2 c 2 e
k 4 3.14 3 1010 cms 1
2
516 Nm
2990cm 1.6 10
2
1 2
27
35 g 2 mol 2
36 gmol 1 6.023 1023 mol 1 103
kg
Answers Tutorial 3 SCES 2250
1.6 10 27 kg
5. (a) The R-branch is converging, while the P-branch is diverging. This is brought about by
The rotational constant of the upper state being slightly smaller than the ground state,
and hence the bond is longer in the excited state than it is in the ground state.
This doesnt make any sense in the harmonic oscillator limit, because the average bond length
for a harmonic oscillator remains the same irrespective of vibrational frequency (the potential
is symmetric so the average remains at the equilibrium position). A normal harmonic
oscillator, e.g. characterised by a Morse potential, is shallower for the
5(a) extended molecule than the compressed molecule, so it makes sense that the average
bond length is longer for higher vibrational states.
(b)
The P(11) and R(9) transitions are shown in the energy level diagram. Notice that if
you subtract these two transitions, the difference in energy corresponds to the difference
in energy of the J=11 and J=9 states in the lower (v=0) vibrational state. As usual, F(J)
= BJ(J+1). So,
R(9) P(11) = F(11) F(9),
2179.761 2099.096 = 1112B - 910B
80.665 cm 1 = 42 B
B = 1.921 cm 1.
(c)
The P(9) and R(9) transitions are shown in the energy level diagram at right. Notice that
if you subtract these two transitions, the difference in energy corresponds to the
difference in energy of the J=10 and J=8 states in the upper (v=1) vibrational state.
Therefore,
R(9) P(9) = F(10) F(8),
2179.761 2107.413 = 1011B - 89B
72.348 cm 1 = 38 B
B = 1.904 cm 1.
Answers Tutorial 3 SCES 2250
6.
Answers Tutorial 3 SCES 2250
7.
Answers Tutorial 3 SCES 2250
8. (i) Low reduced mass of bonds involving H.
(ii) Force constant increases with strength / stiffness of bond: k
(iii)
C-O
<k
C=O
<k
CO
iv)
The reduced mass of HX becomes increasingly close to 1 g mol-1 as the mass of X
increases. For a molecule AB where the mass of A is much smaller than the mass of B,
the reduced mass tends towards the smaller mass:
9.
.
10. Acetylene is a symmetrical linear molecule. It has seven normal modes of vibration, two
of which are double degenerate. These normal modes may be represented as follows:
Answers Tutorial 3 SCES 2250
v 4 ,
11.
12.
Answers Tutorial 3 SCES 2250
1
1
G (0) e 0 e xe 0
2
2
1
4
1 cm =1.239 10 eV
13. (a) Fundamental transition, v =0 v=1
G (1) G (1) G (0)
1
1
1
1
1 e 1 e cm -1 0 e 0 e
2
2
2
2
9
1
1
3
e e e e cm -1
4
2
4
2
e 2 e cm -1
2169 26 cm -1 2143 cm -1
Hot band transition, v =1 v =2
cm -1
Answers Tutorial 3 SCES 2250
G (1) G ( 2) G (1)
1
1
2 e 2 e cm -1
2
2
1
1
1 e 1 e
2
2
cm -1
25
3
9
5
e e e e cm -1
4
2
4
2
e 4 e cm -1
2169 52cm -1 2117 cm -1
(b)(i) T = 300 K
G
N1
=exp kT
N0
1
exp
34
10
2143cm 6.626 10 m kgs 3.0 10 cms
23 2
2 1
1.38 10 m kgs K 300 K
3.4 10
At room temperature, only about 0.003% of the molecule will be in the v =1 level.
So absorption from this level can safely be neglected. The spectrum shows the strong
fundamental (2143 cm-1) transition.
b(ii) T = 1000 K.
G
N1
=e xp kT
N0
1
e xp
34
10
2143 cm 6.626 10 m kgs 3.010 cms
23 2
2 1
1.38 10 m kgs K 1000 K
0.046
At 1000K, around 5 % of the molecule will be in the v =1 level so absorption from
this level may be observed.
In additional to the peaks in of fundamental, a small hot band has appeared at 2117
cm-1 with an intensity which is about 5% of the fundamental.
14.
Answers Tutorial 3 SCES 2250
15.
