The effect of pressure on the kinetics of γ-anhydrite crystallization investigated by diamond anvil cell

Abstract

The crystallization kinetics of γ-anhydrite was investigated in the temperature and pressure ranges of 373–473K and 1094–1903MPa using a hydrothermal diamond anvil cell (HDAC) and Raman spectroscopy. A calcium sulfate solution was formed by dissolving gypsum in water at high pressure, and γ-anhydrite crystallized due to the increasing temperature. The relationship among the reaction rate, k, the temperature, T, and the pressure, P was established as k=−1.75×10−3+1.83×10−6P+3.57×10−7T, with an R2 value of 0.943, of which the applicable range is 373K≤T≤473K and 1196MPa≤P≤1903MPa. An elevation of T or P will accelerate the crystallization rate of γ-anhydrite. The time exponent n obtained between 0.96 and 1.29 indicates that the process of crystallization should be controlled by instant nucleation on the grain boundary and diffusion controlled growth. In the process of crystallization, the volume is reduced because of the decrease of pressure, and the volume change ΔV is equal to −6.05×10−6m3/mol. The calculated activation energy Ea is 10.7kJ/mol, and the pre-exponential factor A is 2.27×10−2s−1.