Abstract

In the determination of energy differences of conformers in the fluid states by infrared spectroscopy it is nearly always assumed that the ratio of the molar absorptivities at the band maxima of two separate absorption bands is independent of temperature. This assumption has been tested by fitting the data obtained from <i>n</i>-butyl bromide to a mathematical model which can be iterated to convergence on a value of the energy difference between the trans and gauche isomers. The data utilized are the C-Br stretching modes of the two conformers at about 655 and 567 cm<sup>−1,</sup> respectively. It is shown that the assumption of temperature independence of the ratios of the molar absorptivities at the peak maxima is a good one, although both values are individually temperature dependent.

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