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

Wai Kit Tang; Christian van der Linde; Chi-Kit Siu; Martin K. Beyer

doi:10.1021/acs.jpca.6b09715

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

Wai Kit Tang, Christian van der Linde, Chi-Kit Siu^*, Martin K. Beyer^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

7 Citations (Scopus)

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.

Original language	English
Pages (from-to)	192-197
Journal	The Journal of Physical Chemistry A
Volume	121
Issue number	1
Online published	13 Dec 2016
DOIs	https://doi.org/10.1021/acs.jpca.6b09715
Publication status	Published - 12 Jan 2017

Funding

M.K.B. acknowledges startup funds from the University of Innsbruck. C.K.S. thanks City University of Hong Kong (CityU) for financial support (Project No. 7004401). W.K.T. acknowledges Chow Yei Ching School of Graduate Studies, CityU, for his postgraduate studentship and scholarship.

Research Keywords

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

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

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.",

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

author = "Tang, {Wai Kit} and {van der Linde}, Christian and Chi-Kit Siu and Beyer, {Martin K.}",

year = "2017",

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doi = "10.1021/acs.jpca.6b09715",

language = "English",

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journal = "The Journal of Physical Chemistry A",

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TY - JOUR

T1 - Hydration Leads to Efficient Reactions of the Carbonate Radical Anion with Hydrogen Chloride in the Gas Phase

AU - Tang, Wai Kit

AU - van der Linde, Christian

AU - Siu, Chi-Kit

AU - Beyer, Martin K.

PY - 2017/1/12

Y1 - 2017/1/12

N2 - 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.

AB - 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.

KW - MOLECULAR NEGATIVE-IONS

KW - PHOTODISSOCIATION SPECTROSCOPY

KW - CLUSTER IONS

KW - NITRIC-ACID

KW - DYNAMICS

KW - MODEL

KW - CO3

KW - THERMOCHEMISTRY

KW - PHOTODETACHMENT

KW - CHEMISTRY

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U2 - 10.1021/acs.jpca.6b09715

DO - 10.1021/acs.jpca.6b09715

M3 - RGC 21 - Publication in refereed journal

SN - 1089-5639

VL - 121

SP - 192

EP - 197

JO - The Journal of Physical Chemistry A

JF - The Journal of Physical Chemistry A

IS - 1

ER -

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

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