Electron transfer and ligand addition to atomic mercury cations in the gas phase: kinetic and equilibrium studies at 295 k.
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%.
Zhao
Xiang
X
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.
Flaim
Eric
E
Huynh
Lise
L
Jarvis
Michael J Y
MJ
Cheng
Ping
P
Lavrov
Vitali V
VV
Blagojevic
Voislav
V
Koyanagi
Gregory K
GK
Bohme
Diethard K
DK