Hydration Leads to Efficient Reactions of the Carbonate Radical Anion with Hydrogen Chloride in the Gas Phase

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Detail(s)

Original languageEnglish
Pages (from-to)192-197
Journal / PublicationJournal of Physical Chemistry A
Volume121
Issue number1
Online published13 Dec 2016
Publication statusPublished - 12 Jan 2017

Abstract

The carbonate radical anion CO3•− is a key intermediate in tropospheric anion chemistry. Despite its radical character, only a small number of reactions have been reported in the literature. Here we investigate the gas-phase reactions of CO3•− and CO3•−(H2O) with HCl under ultrahigh vacuum conditions. Bare CO3•− forms OHCl•− with a rate constant of 4.2 x 10-12 cm3 s-1, which corresponds to an efficiency of only 0.4%. Hydration accelerates the reaction, and ligand exchange of H2O against HCl proceeds with a rate of 2.7 X 10-10 cm3 s-1. Quantum chemical calculations reveal that OHCl•− is best described as an OH hydrogen bonded to Cl-, while the ligand exchange product is Cl-(HCO3). Under tropospheric conditions, where CO3•−(H2O) is the dominant species, Cl-(HCO3) is efficiently formed. These reactions must be included in models of tropospheric anion chemistry.

Research Area(s)

  • MOLECULAR NEGATIVE-IONS, PHOTODISSOCIATION SPECTROSCOPY, CLUSTER IONS, NITRIC-ACID, DYNAMICS, MODEL, CO3, THERMOCHEMISTRY, PHOTODETACHMENT, CHEMISTRY

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