Abstract
The observed kinetic order of sulphur sensitization varies with sensitizer near a value of 0.5, in contrast to the first-order formation of sulphide. Several examples are illustrated. The kinetic difference between sulphide formation and sensitization is demonstrated by the complete kinetic separation of the processes in examples in which sensitization continues for as long as lOOmin from sulphide formed within 2min. Sensitization and sulphide speck growth must involve further processes following sulphide formation. A mechanism of nucleation and growth of specks via two-dimensional diffusion of adsorbed sulphide explains the kinetics of sulphur sensitization. This mechanism leads to a characteristic asymmetric speck size distribution in terms of which the photographic characteristics can be explained. The implications of the chemical mechanism of sulphur sensitization on the effect of varying digestion conditions on the number of specks and their size distribution are indicated.
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