CM4011 – Advanced Analytical Chemistry

Topic 5 – EPR Spectroscopy

Question 1

(a) With reference to Pascal's triangle (which you need to know how to draw), what are the
numbers and relative intensities of the lines expected for the EPR spectra of following molecules.
Assume that no minor isotopes are detected.

O
H3C O
(i) (ii) (iii)
O CH3
O
1:5:10:10:5:1 1:4:6:4:1 1:6:15:20:15:6:1

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(b) A paramagnetic molecule contains two equivalent nitrogen nuclei. Draw the EPR pattern and
relative intensities that would be expected to result from the nuclear hyperfine coupling to the two
nitrogen atoms.

Pattern should be (2nI + 1) lines = (2 × 2 × 1 + 1) = 5 lines.

Intensity will be 1:2:3:2:1

(c) Calculate the maximum number of lines that would be expected in the EPR spectra of the
following radical anions. Assume that no minor isotopes are detected.

N (2 × 2 × 1 + 1) × (2 × 4 × ½ + 1) × (2 × 4 × ½
+ 1)
(i)
=5 × 5 × 5 = 125

O
(2 × 2 × ½ + 1) × (2 × 2 × ½ + 1) × (2 × 2 × ½
+ 1)
(ii) = 3 × 3 × 3 = 27

NC CN
(2 × 4 × 1 + 1) × (2 × 4 × ½ + 1) × (2 × 4 × ½
(iii) + 1)
= 9 × 5 × 5 = 225
NC CN

(2 × 1 × 1 + 1) × (2 × 2 × ½ + 1) × (2 × 2 × ½
+ 1) × (2 × 3 × ½ + 1)
(iv) F3C NO2 = 3 × 3 × 3 × 4 = 108

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Question 2

(a) The methyl radical (•CH3) has 3 geometrically equivalent protons. Draw the statistical
combination of all possible spin states that give rise to an EPR spectrum of four lines with the
intensity ratio 1:3:3:1. Use up (↑) and down (↓) arrows to represent the spin states.

(a)

All alligned Two with One with All alligned

(b)

(b) A paramagnetic molecule contains four equivalent nitrogen nuclei. What is the EPR pattern and
relative intensities that would be expected to result from the nuclear hyperfine coupling to the four
nitrogen atoms?

1 4 10 16 19 16 10 4 1

1 3 6 7 6 3 1

1 2 3 2 1

1 1 1

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(c) A paramagnetic molecule contains 2 equivalent nitrogen nuclei (aN = 3.0 G) and 3 equivalent
hydrogen nuclei (aH = 0.2 G). Draw the EPR pattern and relative intensities that would be expected
to result from the nuclei hyperfine coupling to all the nitrogen and hydrogen atoms. Draw a second
diagram showing how the spectrum would appear if the linewidth (Hpp) was 1.0 G.

3468 3472 3476 3480 3484 3488 3492

(d) With reference to Pascal's triangle, what are the numbers and relative intensities of the lines
expected for the EPR spectra of following molecules? Assume that no minor isotopes are detected.

H3C O

O CH3
1:6:15:20:15:6:1
O

O 1: 4:6:4:1

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(e) Predict the maximum number of lines that will appear in the EPR spectra of the following
molecules. Assume that there is no overlap of the lines and only calculate for those isotopes whose
natural abundance is ≥ 99%. [(2nI) +1]

F3C NO2
[(2 × 1 × 1) +1] × [(2 × 2 × ½) +1] × [(2 × 2 × ½) +1] ×
[(2 × 3 × ½) +1] = 108

S S +

S S [(2 × 4 × ½) +1] × [(2 × 4 × ½) +1] = 25

[(2 × 6 × ½) +1] × [(2 × 3 × ½) +1] × [(2 × 1 × 1) +1] = 84

S +
HN NH

[(2 × 2 × 1) +1] × [(2 × 2 × ½) +1] × [(2 × 2 × ½) +1] ×

NC CN

NC CN
3 × 3 × 3 × 3 × 2 × 2 × 2 × 2 × 2 × 2 × 2 × 2 = 20736

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Question 3

(a) Explain the purpose of spin traps and spin labels and how they function.

Spin traps use the principal that an unstable (reactive) free radical reacts with a diamagnetic
molecule (the spin trap) to form a relatively long-lived free radical. The vast majority of spin traps
form radical adducts through the addition of the radical to the trap to form a nitroxide (NO•) radical.
There are two major classes of traps: nitrones and nitroso compounds.

If the compound of interest does not have an unpaired electron, it will not display an EPR spectrum.
Instead, a radical compound (spin label) can be attached (by reaction) to the molecule of interest.
The EPR spectrum of the spin label should change reflecting the new environment that the radical is
in.

(b) Describe the methods that can be used to produce paramagnetic compounds for EPR spectro-
scopic analysis.

Photochemical
Electrochemical
Chemical
-Irradiation