Q. 8. PMR of pure chloroform show a one proton singlet at -727.

However on mixing it
with benzene this peak appears at -627. Explain the reason for the upfield shift in the peak
position.
Ans. Firstly the only proton of chloroform is highly deshielded due to presence of three chlorine
atoms attached to carbon, whose electronegativity is much higher than that of hydrogen. So the electron
density around this proton is greatly reduced and the signal appears much downfield at -727. Due to
the strong electron-withdrawing effect of three chhlorine atoms, the H-atom in CHCl3 carries a small
+ve charge. When dissolved in benzene due to the -electron cloud of the benzene which is negatively
charged a complex is formed between benzene and chlorofom. The proton of the chloroform is less
deshielded as some of electron density loss is compensated by the -electrons from the benzene. This
results in shifting of the peak upfield and we observe the peak at -627.
Q. 9. From the dipole moment values of acetonitrile (392 D) and methyl chloride (185 D),
it is expected that methyl protons of acetonitrile should absorb much downfield as compared
methyl protons of methyl chloride. However from the PMR spectra of the two it is found that
methyl protons of acetonitrile absorb at a higher field (-195 D) than those of methyl chloride
(-305). Explain.
Ans. This can be explained on the basis of induced magnetic field. In case of nitrile group the
nature of the -electron cloud of CN is cylindrical. Their circulation under the influence of applied
mangetic field produces induced magnetic field which has the same direction as that of applied magnetic
field. Thus they reinforce and the effective magnetic field felt by CH3 protons of CH3CN increases. As
a result, the CH3 protons get shielded and hence absorb at a higher field (-195).
On the other hand in case of methyl chloride the induced magnetic field is produced due to circulation
of -electrons. The direction of the induced magnetic field and the applied field are just opposite to each
other. This results in lesser value of the effective field felt by methyl protons of methyl chloride or they
are deshielded and that is why they appear downfield i.e. at -305.

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