Abstract
Ultraviolet absorption spectra of benzoic acid in n-heptane were measured at 25°C and up to 640 MPa. The reaction volume for the cyclic dimerization of benzoic acid was estimated as 0.4 ±0.9 cm 3 mol −1 from the pressure dependence of the dimerization constant. This is much more positive than those for noncylic hydrogen-bond formations which are from −3 to −6 cm 3 mol −1. It is ascribed to a compensation between a reduction in the volume accompanying the hydrogen-bond formation and an increase accompanying the cyclization. These two contributions to the reaction volume are estimated quantitatively.
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