Experiment S2: Electronic Spectroscopy

Results and Discussion

Firstly a correction value was calculated for I2. The true values of the two yellow
sodium D-lines was 5896 and 5890 respectively. 3 readings of the observed
lines were recorded in table 1, their averages were taken and the mean
correction for the spectrometer was calculated:
The mean corresponding to the true value 5896 is calculated as:
(5908.8+5907.2+5907.7)/3 = 5907.9
The correction value for the first band was calculated as true observation:
5896 5907.9 = -11.9
The mean correction was calculated by taking the average correction values of
both lines.
(-11.9) + (-14.4)/2 = -13.5
The values obtained were inserted into table 1.
Table 1: Readings of the two yellow sodium D-lines and the mean correction
value for the spectrometer.
True:

5896

True:

Readi
ng
Line 2

5890

Readi
ng
Line 1

5908.
8

5905

5907.
2

5905

5907.
7

5903.
2

Mean of
observations

5907.
9

5904.
4

Correction
(TrueObservation)

-11.9

-14.4

Mean
Correction

-13.15

The 2 sets of experimental values obtained for the absorption bands of iodine are
tabulated into table 2. The mean of the 2 sets were calculated for reliability, the
corrected values were obtained by adding the mean correction value to the
obtained set of means as shown in column 4 of table 2 with the following as an
example:
5493.2 13.15 = 5480.1
n denotes the first excited energy level where the 5480 corresponds to the
25th energy level of I2 with each successive reading being one energy level higher
so the second reading of 5455.7 corresponds to the 26 th energy level.
The readings were converted from angstroms () to wavenumbers v (cm-1) in the
following way:
(1/5480.1) * 1x10-8 = 18248.01 cm-1
The obtained values were inserted into column 6 of table 2.
The difference in energy were calculated by the difference between the
wavenumbers using equation [1]1.
n (cm-1) = n+1 - n = v ' 2(n + 1)x v

[1]

Where v corresponds to the vibrational frequency of I 2 in the upper excited

electronic state and x is the corresponding anharmonicity constant.
So using the first 2 readings as an example calculation
n+1 - n = 18329.62 - 18248.01 = 81.61
The obtained values were inserted into column 8 of table 2 and paired off with
the n + 1 values of column 7.
All the data obtained from these calculations were entered into table 2.

Table 2: Values for the emission spectra of I 2

1st
reading
/
5493.4

2nd
reading
/
5493.0

Mean
/

Correct
ed /

n'

v /cm-1

n' +1

5493.2

5480.1

25

26

5468.8

5468.8

5468.8

5455.7

26

5446.9

5444.8

5445.9

5432.7

27

5421.5

5422.7

5422.1

5409.0

28

5399.5

5399.7

5399.6

5386.5

29

5379.4

5379.8

5379.6

5366.5

30

5359.8

5360.0

5359.9

5346.8

31

5339.5

5340.0

5339.8

5326.6

32

5320.0

5320.4

5320.2

5307.1

33

5301.6

5301.2

5301.4

5288.3

34

5283.9

5285.8

5284.9

5271.7

35

5267.7

5268.9

5268.3

5255.2

36

5252.3

5251.2

5251.8

5238.6

37

5235.8

5237.7

5236.8

5223.6

38

5221.0

5224.2

5222.6

5209.5

39

5208.0

5207.4

5207.7

5194.6

40

5194.5

5194.0

5194.3

5181.1

41

5180.7

5180.2

5180.5

5167.3

42

5168.5

5168.0

5168.3

5155.1

43

18248.
01
18329.
62
18407.
05
18487.
88
18565.
10
18634.
29
18702.
95
18773.
70
18842.
86
18909.
85
18969.
21
19028.
95
19089.
07
19143.
89
19195.
88
19250.
95
19300.
92
19352.
47
19398.

en'+1-en'
-1
/ cm

27

81.61

28

77.43

29

80.82

30

77.23

31

69.19

32

68.66

33

70.75

34

69.16

35

66.99

36

59.37

37

59.74

38

60.12

39

54.82

40

52.00

41

55.06

42

49.97

43

51.55

44

45.80

5156.8

5156.8

5156.8

5143.7

44

27
19441.
45

45

43.18

A6. The graph of n against n+1 is shown in Figure 1.

n against n'+1
100.00
80.00

f(x) = - 2.07x + 135.13

R = 0.96

60.00
en'+1-en' / cm-1

40.00
20.00
0.00
25

30

35
n'+1

Figure 1: graph to show n against n+1

The equation of the curve is y = -2.0663x + 135.13

40

45

The intercept at v = 135.13 when we set x = 0.

The gradient m = -2x v which implies -2.0663 = -2*x*135.13
-2.0663/(-2*135.13) = x
7.64x10-3 = x
The ground state value of v = 214 cm-1 is higher than v =135.13 cm-1 as v
has its electrons promoted from a bonding orbital to an anti-bonding orbital. This
weakens the I2 bond so less energy is required to vibrate the molecule causing v
to be lower in energy than v .
A9.
To calculate the energy level of convergence n c.
We know that n converges to 0 as the diatomic molecule approaches closer to
dissociation. This is given by the following equation:
nc=0= v 2 (nc +1)x v
=> nc = 1/2x -1

[2]

[3]

Using equation [3] we can calculate the energy level of convergence

nc = 1/2(7.64x10-3) -1 = 64.45
Since energy levels must be integers rounding this number to the next whole
integer we get a value of 65.
With the following equation we are able to calculate the dissociation energy D e.
n (cm-1) = (nc +1/2) v x v (nc+1/2)2 = De/hc

[4]

Substituting the values obtained previously into equation [4] yields the following
results.
((65+1/2)* 135.13)-((7.64x10-3)*135.13(65+1/2)2)=De/hc
De/hc =4421.79 cm-1
A10
The zero state point vibrational energy occurs when n=0 using equation [4] we
can calculate the energy required.
0 = (1/2*135.13) ((7.64x10-3)*135.13*(0+1/2)2)
0 = 67.31 cm-1
The dissociation energy (D0) was found by subtracting De- 0. This shows us the
real minimum as so far we have assumed the minimum point has an energy of 0
but this is not the case.

D0/hc = 4421.79 cm-1 - 67.31 cm-1 = 4354.48 cm-1

A11
To convert to kJ mol-1 we first multiply through by hc and then by avogadros
constant.
De=4421.79*6.626x10-34*2.998x1010
De=8.784x10-20J
Now multiply by avogadros constant to get J mol -1.
De= 8.784x10-20J*6.022x1023
De52897.25 J mol-1
De=52.9 kJ mol-1
Now to calculate D0
D0/hc =4354.48 cm-1
D0 = 4354.48*6.626x10-34*2.998x1010*6.022x1023=52090.69 J mol-1
D0 = 52.09 kJ mol-1
A12
To calculate the dissociation energy *from the ground state n=0 we first find
the energy of dissociation from n=25 by substituting values into equation [4]
25= ((25+1/2)*135.13) ((7.64x10-3)*135.13*(25+1/2)2)
25 = 2774.5 cm-1
We know from previously that the energy level of convergence is n= 65 so
subtracting the two energies and adding on the first obtained reading from table
2 column 6 we get the total dissociation energy * from the ground state.
65- 25= 4421.79 - 2774.50 = 1647.29 cm-1
*= 1647.29 + 18248.01=19895.3 cm-1
Converting this to kJ mol-1 by multiplying by hc and Avogadros constant.
19895.3*6.626x10-34*2.998x1010*6.022x1023*1/1000= 238.00kJ mol-1
A13
The dissociation energy D0 for the ground state molecule of I2 is calculated by :
D0 = E*-Eex
D0 = 238.00-90.93 kJ mol-1 = 147.07 kJ mol-1

The literature value is 149.0 kJ mol -1.

The % difference between the experimental and literature is equal to (149.0147.07)/149.0 * 100 =1.3%
The error in the dissociation energy of I 2 molecules in ground state was
calculated using the using data from the lab manual, with the errors in values of
x and nc having errors <2% which corresponds to 1.6x10 -4 and 1. The errors
associated with v and De are 5.6 cm-1 and 2.1 kJmol-1
The difference in percentage of 1.3%

Part B