Spectroscopic analysis reveals two distinct dynamic regimes in liquid acetonitrile mixtures, indicating altered rotational diffusion near an azeotropic composition.
The effect of both temperature and dilution on the orientational relaxation rate of acetonitrile has been considered. The half bandwidths obtained by Raman scattering and infrared absorption techniques were corrected considering the effective temperature of the scattering volume in the Raman, and the thermostatic temperature in the IR experiments. This procedure, adopted for the first time in studies of dynamical processes, has shown the presence of two different dynamic regimes in the CH3CN/CCl4 solutions, due to the low-boiling azeotropic mixture. The results obtained have been discussed within the framework of the rotational diffusion theory. Experimental values of the molecular and hydrodynamic volumes of acetonitrile were compared with the respective theoretical values.
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Morresi et al. (2000) studied this question.
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