A kinetic investigation of high-temperature mercury oxidation by chlorine.
First-stage mercury oxidation reactions typical of coal combustion flue gases were investigated. The present study is a determination of the kinetic and thermodynamic parameters of the bimolecular reactions, Hg + Cl(2) <--> HgCl + Cl, Hg + HCl <--> HgCl + H, and Hg + HOCl <--> HgCl + OH, at the B3LYP/RCEP60 VDZ level of theory over a temperature range of 298.15 to 2000 K at atmospheric pressure. Conventional transition state theory was used to predict the forward and reverse rate constants for each reaction and ab initio based equilibrium constant expressions were calculated as a function of temperature. Reasonable agreement was achieved between the calculated equilibrium constants and the available experimental values.
Wilcox
Jennifer
J
Department of Energy Resources Engineering, Stanford University, 367 Panama Street, Stanford, California 94305, USA. wilcoxj@stanford.edu
D002713:Chlorine / Q000737:chemistry*; D003198:Computer Simulation; D006358:Hot Temperature; D007700:Kinetics; D008628:Mercury / Q000737:chemistry*; D008956:Models, Chemical; D010084:Oxidation-Reduction; D013816:Thermodynamics
D002713:Chlorine; D008628:Mercury