L. Strong, C. L. Brummel, P. Lindower
Feb 1, 1987
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0
Influential Citations
10
Citations
Journal
Journal of Solution Chemistry
Abstract
Precision conductance measurements as a function of concentration and temperature between 0 and 100°C have been made for 2,3-, 2,5-, 3,4-, and 3,5-difluorobenzoic acids and pentafluorobenzoic acid in water. Standard state changes in enthalpy, entropy, and heat capacity as a function of temperature are reported for the ionization of these acids. Comparisons are made with other fluorobenzoic acids that have been reported earlier and with the corresponding methylbenzoic acids. The differences between the ionization of a fluorobenzoic acid and its counterpart methylbenzoic acid is almost entirely a difference in the entropies of ionization with only a small difference in the enthalpies of ionization. Each fluorine substituted in the meta or para position increases the entropy of ionization while substitution in the ortho position decreases the entropy. This is in contrast to the effect of methyl substitution where substitution in any position decreases the entropy of ionization. Walden products for the various anions follow the pattern found for the methylbenzoate anions with a sharp increase from 0 to about 30°C and with ortho substituted anions less mobile than those without ortho substitutents.