Q.1.

(a) Calculate the percentage difference in the fundamental vibration wavenumber of

and
on the assumption that their force constants are the same.
(b) Given that the spacing of lines in the microwave spectrum of
is constant at 1.033
calculate the moment of inertia and bond length of the molecule. [Given, m
m
]

,
and

Q.2. (a) The wavenumber of the fundamental vibrational transition of

is 323.2 cm-1.
Calculate the force constant of the bond.
[Given, m
]
(b) Consider the vibrational mode that corresponds to the boat-like bending of a benzene ring. Is it
(i) Infrared active? (ii) Raman active?
Q.3. (a) Calculate the value of Bohr magneton N for a proton in the corresponding Tesla units and

Gauss units respectively. Given: charge of an e = 1.602 x 10-19 C; mass of proton = 1.6727 x 10-27
kg.
(b) For a given nucleus 31X (I = ) at a field strength of 2.5 T, find the NMR frequency. Given that
the nuclear g factor (gN) for 31X is 2.261 and the nuclear magneton N is 5.051 x 10-27 JT-1.
(c) The frequency separation between protons in benzene and TMS (the internal standard) is 510.5
Hz. At a magnetic flux density of 1.65 T, What is the chemical shift () of the benzene protons? (gN
for 1H is 5.585).
(d) An NMR machine operates at 400 MHz for 1H NMR. At what frequency this machine will
operate for 13C NMR. (gN for 1H is 5.585 and for 13C = 1.405).
Q.4. (a) What can be the value of for a nucleus in an NMR spectrometer operating at 200 MHz, if
it has a resonance frequency of 500 MHz.
(b) What is the shift in the resonating frequency (in Hz) for a proton with = 4 with respect to TMS,
when the operating frequency of the NMR instrument is 500 MHz.
(c) The chemical shift for the benzene proton is 7.2686 ppm on an NMR operating at 70.234 MHz.
What will be the difference in Hz for these protons if it operates at 200 MHz?
(d) What is the ratio of the no. of proton spins in the lower state to the no. of proton spins in the
higher state in a magnetic field of 1.4 T at atemperature of 25 C? Boltzmann const = 1.38 x 10 -23
JK-1. Interpret the result with respect to the working of NMR instruments.
Q.5. (a) How many signals would be observed in the 1H NMR spectrum of ethyl acetate? (b) Which
signal will be the most downfield and why? (c) Which signal will correspond to the most shielded
protons? (d) Sketch the NMR spectrum clearly showing the splitting of each signal.
Q.6. n-propyl benzene shows four distinct sets of signals in its NMR spectrum. (a) Identify the four sets
of protons in its structure giving rise to the four signals. (b) Arrange the signals in order of decreasing
values. (c) What is the multiplicity of different proton peaks in 1HNMR of n-propyl benzene through
spin-spin coupling? (d) Show how many sets of protons should theoretically appear for the benzene ring.
(e) A student was asked to take the 1HNMR of a compound having molecular formula C3H7Br. The NMR
showed absorption peaks at : 1.7 (doublet) and 3.0 (septet). Find out the structural formula of the

compound. Indicate the multiplicity for each set of protons in its structure. Also indicate how many
signals should appear in its 13C NMR spectrum. Another student was asked to take the IR spectrum of the
same compound and she reported that the IR spectrum shows a strong band at around 1720 cm -1. Verify
her report in one or two sentences.
END