International Journal of Hydrogen Energy, Vol.37, No.1, 335-344, 2012
Influence of temperature and alkalinity on the hydrolysis rate of borohydride ions in aqueous solution
The paper studies the influence of temperature (50-100 degrees C) and alkalinity (C-OH(-)=2.33-9.53 M) of aqueous solutions on the hydrolysis (self-destruction) kinetics of borohydride ions BH4-. Characteristic peculiarities of the kinetic curve have been established and formulae to approximate the temperature-concentration dependence of the hydrolysis rate are proposed. An increase in temperature leads to an increase in the rate constant k of borohydride hydrolysis, and the temperature dependence of k satisfactorily obeys Arrhenius' equation. The influence of solution alkalinity on the borohydride hydrolysis rate was explored. Within the temperature range studied, the k = f(C-OH(-)) curve consists of two fragments, each with the prevalence of one of two different mechanisms (paths) of borohydride hydrolysis. In highly-alkaline aqueous solutions, non-catalytic hydrolysis mainly occurs, whose rate is determined by temperature, being pH-independent. At lower alkalinity, the hydrolysis rate sharply increases due to catalysis by H+ ions. A power dependence of k on the H+ concentration has been found; the point where the mechanisms are switched is determined by temperature. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
Keywords:Borohydride;Hydrogen storage;Hydrolysis reaction;Rate constant;Activation energy;Homogeneous catalysis