The combined effect of temperature and pH on albite dissolution rate under far-from-equilibrium conditions

Two of the most studied aspects of albite dissolution kinetics are the effects of temperature and pH. Previous studies quantified the effect of pH on albite dissolution rate under constant temperature. These studies suggested that the effect of pH on dissolution rate can be attributed to three independent dissolution mechanisms that are dominant in different pH region: acidic - proton-promoted, neutral - water-promoted and alkaline - hydroxide-promoted. Based on experimental results, those studies developed a rate law to predict albite dissolution rate as a function of pH, assuming that the effect of pH is temperature independent. The effect of temperature was attributed either to the temperature dependency of the rate under constant pH or that of the rate law coefficients. Nevertheless no unified rate law that combines both effects was suggested. When applying the effects of temperature and pH assuming they are independent of each other in order to predict the dissolution rate at pH of about 5 and various temperatures, the predicted rate overestimate the rate by 0.5-1 order of magnitude. The current study develops and suggests the use of new rate law that is based on two fast adsorption reactions of protons and hydroxides on two different surface sites. The new rate law considers the effect of surface coverage of protons and hydroxides that is temperature dependent. The new rate law successfully describes the variation of albite dissolution rate (about 8 orders of magnitude) under wide temperature (3.6- 300 degrees C) and pH (1.20-12.40) ranges. Under slightly acidic conditions (pH 5-7) the new rate law predicts a minimum rate zone that was not observed before. In order to confirm whether this minimum rate zone does exist, three SPBE (single-point-batch-experiment) of albite dissolution were conducted at pH 5 and temperatures of 3.6, 25 and 50 degrees C. The SPBE experiments confirm the existence of minimum rate zone predicted by the independent new rate law. The new rate law constrains the expected dissolution rate under far-from-equilibrium conditions and allows extrapolation of rate coefficient under wide range of temperatures and pH with relatively low uncertainty. (C) 2016 Elsevier Ltd. All rights reserved.