The influence of chemical exchange on the line shape in Raman spectroscopy is investigated. A theory, covering also the „fast case”︁ is derived. The results are compared with the similar but not identical equations valid for the kinetic line broadening in NMR spectroscopy. — The Raman line broadening technique is applicable only to extremely fast reactions with life times of the involved species shorter than about 10 −11 s. — A practical application is given for the protolysis of nitric acid and the formation kinetics of ion pairs of NaNO 3 both in highly concentrated solution. The rate constants obtained are higher than the rate constants for diffusion controlled reactions as calculated with the Smoluchowski‐Debye theory [1]. An explanation is proposed. The p K of nitric acid is reevaluated to be (−0.9 ± 0.3).
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Strehlow et al. (1983) studied this question.
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