title: Electron transfer and ligand addition to atomic mercury cations in the gas phase: kinetic and equilibrium studies at 295 k.
abstract: Results are reported for experimental measurements of the room-temperature chemical reactions between ground-state Hg*+ ions and 16 important environmental and biological gases: SF6, CO, CO2, N2O, D2O, CH4, CH3F, O2, CH3Cl, OCS, CS2, NH3, C6F6, NO2, NO*, and C6H6. The inductively coupled plasma/selected-ion flow tube tandem mass spectrometer used for these measurements has provided both rate and equilibrium constants. Efficient electron transfer (>19%) is observed with CS2, NH3, C6F6, NO2, NO*, and C6H6, molecular addition occurs with D2O, CH4, CH3F, CH3Cl, and OCS, and SF6, CO, CO2, N2O, and O2 showed no measurable reactivity with Hg*+. Theory is used to explore the stabilities and structures of both the observed and unobserved molecular adducts of Hg*+, and reasonable agreement is obtained with experimental observations, given the uncertainties of the theory and experiments. A correlation is reported between the Hg*+ and proton affinities of the ligands investigated. Solvation of Hg*+ with formic acid was observed to increase the rate of electron transfer from NO* by more than 20%.
authors.affiliation: Department of Chemistry, Centre for Research in Mass Spectrometry and Centre for Research in Earth and Space Science, York University, Toronto, Ontario, Canada M3J 1P3.
authors.forename: Xiang
authors.initials: X
authors.lastname: Zhao
authors.forename: Eric
authors.initials: E
authors.lastname: Flaim
authors.forename: Lise
authors.initials: L
authors.lastname: Huynh
authors.forename: Michael J Y
authors.initials: MJ
authors.lastname: Jarvis
authors.forename: Ping
authors.initials: P
authors.lastname: Cheng
authors.forename: Vitali V
authors.initials: VV
authors.lastname: Lavrov
authors.forename: Voislav
authors.initials: V
authors.lastname: Blagojevic
authors.forename: Gregory K
authors.initials: GK
authors.lastname: Koyanagi
authors.forename: Diethard K
authors.initials: DK
authors.lastname: Bohme