Dissolution kinetics of granular calcium carbonate in concentrated aqueous sodium dichromate solution at pH 6.0-7.0 and 110-130 degrees C

An understanding of the factors controlling calcite dissolution is important for modeling geochemical cycles and impacts of greenhouse gases on climate, diagenesis of sediments, and sedimentary rocks. It also has practical significance in the investigation of behavior of carbonates in petroleum and natural gas reservoirs and in the preservation of buildings and monuments constructed from limestone and marble. A large number of papers have been published on dissolution kinetics of calcium carbonate in aqueous solutions. But few involved the near-equilibrium region, especially at elevated temperatures and in concentrated solutions. In this paper, the dissolution kinetics of calcium carbonate in concentrated aqueous sodium dichromate solutions at pH 6.0-7.0 and 110-130 degrees C were studied in a 2-L autoclave. The results indicate that the dissolution reaction is mix-controlled, with surface reaction as the prevailing factor. The concentration of calcium ions in solution hardly affects the dissolution rate, but carbon dioxide in the vapor phase inhibits the dissolution reaction. The dissolution rate can be expressed by R = k(1)a(2)(H+) + k(2), and the apparent activation energy is 55-84 kJ mol(-1).