Evaluation of basis sets and theoretical methods for estimating rate constants of mercury oxidation reactions involving chlorine

Jennifer Wilcox, David C J Marsden, Paul Blowers

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

The occurrence of elemental mercury in flue gases from coal combustion is a problem of current environmental concern. Oxidized mercury species can be effectively removed from the flue gases by chemical scrubbers. However, the detailed mechanism by which oxidation occurs remains unclear. Theoretical rate constants are calculated for mercury oxidation by atomic chlorine. The potential energy surface is determined using standard quantum chemical methods with relativistic effects included via the use of an effective core potential (ECP). Experimental thermodynamic and kinetic data are employed to assess the accuracy of these calculations. Results show that the QCISD method with the 1992 basis set of Stevens et al. gives good agreement with experiment, suggesting that this combination may be useful for other mercury-chlorine chemical systems.

Original languageEnglish (US)
Pages (from-to)391-400
Number of pages10
JournalFuel Processing Technology
Volume85
Issue number5
DOIs
StatePublished - Apr 15 2004

Fingerprint

Chlorine
Mercury
Rate constants
Flue gases
Oxidation
Potential energy surfaces
Scrubbers
Coal combustion
Thermodynamics
Kinetics
Experiments

Keywords

  • Chlorine
  • Effective core potential
  • Mercury oxidation

ASJC Scopus subject areas

  • Organic Chemistry
  • Energy Engineering and Power Technology
  • Fuel Technology

Cite this

Evaluation of basis sets and theoretical methods for estimating rate constants of mercury oxidation reactions involving chlorine. / Wilcox, Jennifer; Marsden, David C J; Blowers, Paul.

In: Fuel Processing Technology, Vol. 85, No. 5, 15.04.2004, p. 391-400.

Research output: Contribution to journalArticle

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