Advanced NMR Spectroscopy Spin Physics Problem Sheet

1) The first commercially available spectrometer operated at a proton frequency of 60

MHz. The largest spectrometer operational, in the CNRS lab in Lyon, operates at a proton
frequency of 1000 MHz (1 GHz).

What magnetic field strengths do these resonant frequencies correspond to?

What is the energy splitting between the two spin levels of a proton in these two
spectrometers?

What are the relative population differences of the two spin levels in the two
spectrometers at 300 K?

H = 42.576 MHz T
1


2) In an experiment to determine the optimum pulse length for an experiment, a positive
signal for pulse widths of 5 and 10 s was observed; as the pulse was lengthened
further the intensity decreased going through a null at 20.5 s and then turning
negative.

Explain what is happening in this experiment and use the data to determine the RF
field strength in Hz and the length of a 90 pulse.

A further null in the signal was seen at 41.0 s; to what do you attribute this?

3) Consider the spin echo sequence where the phase of the 90 pulse is held along the x
axis but the phase of the 180 pulse is changed:

90 (x) delay 180 () delay

The axis about which the pulse is applied is given in brackets after the flip angle.
Explain in what way the outcome is different depending on whether the phase of the
pulse is chosen to be x, y, x or y.

Assume that the spins precess an angle during the delays.

4) Sketch the multiplet of atom A in the spin system AM2X, where JAM>JAX.

5) What
13
C spectrum would you expect for deuterated chloroform?

6) A very studious and dutiful research student measured the 1 bond H-C coupling
constants of ethane, ethene and ethyne, obtaining the results 125 Hx, 157 Hz and 250 Hz
respectively. In light of the mechanism of scalar coupling, explain these results.

Why might two bond coupling constants be negative?

Does it matter?



7) Consider the spin echo sequence where the phase of the 90 pulse is held along the x
axis but the phase of the 180 pulse is changed:

90 (x) delay 180 () delay

Use a product operator approach to calculate the magnetisation at the end of the
second delay for a single uncoupled spin, with the phase of the pulse is chosen to be
x, y, x or y.

Repeat using a pair of weakly coupled spins.

8) Two groups of protons, interconverted by a conformational change of a fluxional
molecule, have chemical shifts 4.0 and 5.3 ppm. In a 60 MHz spectrometer, the peaks
coalesce at 280 K but on a 300 MHz spectrometer, the sample needs to be heated to 300
K.

From this observation, calculate the activation energy of the conformational change.

9) The Bloch equation for the evolution of magnetisation along the z axis is given by:

()

[() () ]z
()

After a 90 pulse has been applied to a sample, the magnetisation lies in the xy plane. In
the absence of any other pulses, use the equation above to calculate the evolution of the
z-magnetisation as a function of time and sketch this behaviour.

Two spins are present in the sample, spin A has T1 = 5 s and spin X has T1 = 1 s.
Calculate the value of Mz(A)/Mz(X) after a delay of 2.5 s after the application of a 90
pulse.