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The depolarized Rayleigh spectra of aqueous solutions of pyridine have been studied using a high‐finesse Fabry–Perot interferometer as a function of temperature and concentration. The Rayleigh relaxation times are found to have a complex concentration and viscosity dependence. The classical Stokes–Einstein–Debye equation for molecular reorientation breaks down in this system. The Rayleigh relaxation time of pyridine molecules is not determined by the macroscopic shear viscosity of the solution. The specific interaction due to the formation of hydrogen bonds between pyridine and water molecules plays a very important role in affecting the relaxation time. At a fixed temperature the plot of πray/η versus pyridine concentration shows two maxima at low and high pyridine concentrations. The low concentration maximum is due to the incorporation of pyridine molecules in the water network structure and the high concentration maximum is associated with the formation of individual pyridine–water complexes. The activation energy for the reorientation of pyridine molecules depends on the pyridine concentration. At low pyridine concentration the activation energy corresponds well to the N⋅⋅⋅H–O hydrogen bonding energy. Above 70% volume the activation energy decreases with increasing pyridine concentration, and above this concentration range the reorientational relaxation time becomes less structure controlled.

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Journal of Chemical Physics

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Chemistry Commons