Abstract

The application of Raman difference spectroscopy for the determination of the small frequency shifts arising from solvent effects has been demonstrated. Data are presented for benzene-carbon disulfide, benzene-pyridine, and acetone-chloroform mixtures. The majority of the solvent shifts measured are less than 1.0 cm<sup>−1</sup> and these can generally be determined with better than 10% accuracy using a rotating two-compartment liquid cell. The smallest shift measured in this work was 0.06 cm<sup>−1</sup>. While statistical analysis indicates that uncertainties as small as ±0.01 cm<sup>−1</sup> can be obtained in many cases, artifacts may cause apparent shifts up to ±0.03 cm<sup>−1</sup>.

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