A kinetic study of Ca-containing ions reacting with O, O2, CO2 and H2O: implications for calcium ion chemistry in the upper atmosphere

Physical Chemistry Chemical Physics : PCCP
Sarah BroadleyJohn M C Plane

Abstract

A series of gas-phase reactions involving molecular Ca-containing ions was studied by the pulsed laser ablation of a calcite target to produce Ca+ in a fast flow of He, followed by the addition of reagents downstream and detection of ions by quadrupole mass spectrometry. Most of the reactions that were studied are important for describing the chemistry of meteor-ablated calcium in the earth's upper atmosphere. The following rate coefficients were measured: k(CaO+ + O --> Ca+ + O2) = (4.2 +/- 2.8) x 10(-11) at 197 K and (6.3 +/- 3.0) x 10(-11) at 294 K; k(CaO+ + CO --> Ca+ + CO2, 294 K) = (2.8 +/- 1.5) x 10(-10); k(Ca+.CO2 + O2 --> CaO2+ + CO2, 294 K) = (1.2 +/- 0.5) x10(-10); k(Ca+.CO2 + H2O --> Ca+.H2O + CO2) = (13.0 +/- 4.0) x 10(-10); and k(Ca+.H2O + O2 --> CaO2+ + H2O, 294 K) = (4.0 +/- 2.5) x 10(-10) cm3 molecule(-1) s(-1). The quoted uncertainties are a combination of the 1 sigma standard errors in the kinetic data and the systematic errors in the models used to extract the rate coefficients. Rate coefficients were also obtained for the following recombination (also termed association) reactions in He bath gas: k(Ca+.CO2 + CO2 --> Ca+.(CO2)2, 294 K) = (2.6 +/- 1.0) x 10(-29); k(Ca+.H2O + H2O --> Ca+.(H2O)2) = (1.6 +/- 1.1...Continue Reading

References

Dec 11, 2003·Chemical Reviews·John M C Plane
Nov 20, 2004·The Journal of Chemical Physics·Vitali ZhaunerchykPeter Hlavenka
Mar 10, 2005·Journal of the American Chemical Society·Voislav BlagojevicDiethard K Bohme
Jun 23, 2006·The Journal of Physical Chemistry. a·John M C PlaneArthur Fontijn
Aug 10, 2007·Physical Chemistry Chemical Physics : PCCP·Sarah L BroadleyJohn M C Plane
Apr 7, 2005·Physical Chemistry Chemical Physics : PCCP·A A ViggianoJ Troe

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Citations

Feb 10, 2011·Faraday Discussions·Charlotte L Whalley, John M C Plane
Apr 16, 2020·Physical Chemistry Chemical Physics : PCCP·David L BonesJohn M C Plane
Jun 9, 2012·Chemical Society Reviews·John M C Plane
Jan 27, 2019·Physical Chemistry Chemical Physics : PCCP·Shane M DalyJohn M C Plane
Jan 11, 2012·The Journal of Physical Chemistry. a·John M C Plane, Charlotte L Whalley
Mar 10, 2015·Chemical Reviews·John M C PlaneErin C M Dawkins

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