Dislocations and the thermal reactivity of calcite

Abstract

A study has been made of the effect of dislocation movement on the kinetics of thermal decomposition of freshly cleaved calcite crystals. It is shown for the first time that the thermal history of the crystal has a marked effect on its reactivity and two patterns of behaviour have been identified; that in the temperature range up to ca . 700 K in which the kinetics of decomposition are sensitively dependent upon the nature and extent of the crystal’s previous history, and the range above 700 K in which annealing is rapid and reproducible kinetics are obtained for all crystals studied. This effect has not been observed in previous studies of calcite. It is suggested that this is because the experiments were carried out in the temperature range where movement of dislocations is so rapid that the surface structure is virtually constant during the measurements. Tentative correlations are made between the various stages of the observed rates of decomposition and the known dislocation systems in the crystal. The influence of applied stress was studied but because of limitations in the method of stressing the crystal, the amount of plastic deformation was small and its effect on reactivity was not marked. Qualitative consideration is given to the role of dislocations in the reactivity of solids and it is concluded that the elastic energy associated with the strain fields around or at the core of the dislocation cannot be used to promote chemical reactivity but that it is the change in the stereochemical environment of molecules in the dislocated region of the crystal which is important. ‘ . . . a curious illustration of the influence of mechanical forces over chemical affinity. . . ’ M. Faraday (1834)