The vibrational spectra of benzene derivatives—I: Nitrobenzene, the benzoate ion, alkali metal benzoates and salicylates

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Abstract

Infra-red and Raman spectra have been recorded for nitrobenzene and a complete vibrational assignment is given. The infra-red spectra of the alkali metal benzoates have been recorded and, together with the Raman spectra data, a substantially complete assignment is given for the benzoate ion. The infra-red spectra of the alkali metal salicylates, salicylic acid and o-nitrophenol have been measured, correlated and partial assignments made. Examination of the difference Δν between the symmetric (νs,) and antisymmetric (νas)CO2 stretching frequencies in the two series of salts shows that, whereas for the benzoates Δν increases steadily from lithium to caesium, for the salicylates, with the exception of the lithium salt, it is either constant or decreases slightly ; νas is 20–30 cm−1 higher in the salicylates than in the corresponding benzoates; νs, is lower in lithium salicylate than in lithium benzoate, but in rubidium and caesium salicylate νs is higher than in the corresponding benzoate. No simple linear relationship is found between Δν and the polarizability of the free ions or the electronegativities of the alkali metals.

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