Metal ion-molecule kinetics at combustion temperatures: The reaction of Ca+ with O2

Cosic, Biljana; Ermoline, Alexandre; Fontijn, Arthur; Marshall, Paul

doi:10.1016/j.proci.2006.07.047

Cited by 2 publications

(2 citation statements)

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“…This stretched ion package is treated as a quasi-continuous ion beam and can be sampled 30 times by the TOF analyzer operated at a repelling frequency of 33 kHz. In current experiments, the appearance of oxidation ions (e.g., WO + in Figure ) are further deferred because the ion molecule reactions occur several hundred microseconds after the laser plasma …”

Section: Resultsmentioning

confidence: 98%

“…In current experiments, the appearance of oxidation ions (e.g., WO + in Figure 2) are further deferred because the ion molecule reactions occur several hundred microseconds after the laser plasma. 39 In the experiment, the Nd:YAG laser was operated at the maximum repetition rate of 10 Hz, leaving 100 ms for ion detection per laser pulse. The temporal ion distribution indicates that only the first millisecond after the laser pulse is useful for sampling ion signals in the repelling region.…”

Section: Resultsmentioning

confidence: 99%

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Applicability of Standardless Semiquantitative Analysis of Solids by High-Irradiance Laser Ionization Orthogonal Time-of-Fight Mass Spectrometry

Huang

et al. 2009

Anal. Chem.

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A compact high-irradiance laser ionization time-of-flight mass spectrometry system has been developed for the multielemental analysis of solids. Helium was introduced into the ion source as a buffer gas to cool high kinetic energy ions and suppress the interference of multicharged ions. A special pulse train repelling mode was used to achieve explicit spectra. Two quantitative methods are described for the laser ionization mass spectrometry in this paper. The first of these is the routine calibration curve quantitation, in which various matrix-matched standards are required; the second method, which is based on the uniform correlation between the signal and elemental concentration of different samples, is more convenient and covers a typical dynamic range of 6 orders. All the investigations and results indicate satisfactory performance of the newly developed instrument and its applicability for simultaneous multielemental analysis of solid samples.

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Applicability of Standardless Semiquantitative Analysis of Solids by High-Irradiance Laser Ionization Orthogonal Time-of-Fight Mass Spectrometry

Huang

et al. 2009

Anal. Chem.

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A kinetic study of the reactions of Ca+ ions with O3, O2, N2, CO2 and H2O

Broadley

Vondrak

Plane

2007

Phys. Chem. Chem. Phys.

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The reactions between Ca(+)(4(2)S(1/2)) and O(3), O(2), N(2), CO(2) and H(2)O were studied using two techniques: the pulsed laser photo-dissociation at 193 nm of an organo-calcium vapour, followed by time-resolved laser-induced fluorescence spectroscopy of Ca(+) at 393.37 nm (Ca(+)(4(2)P(3/2)-4(2)S(1/2))); and the pulsed laser ablation at 532 nm of a calcite target in a fast flow tube, followed by mass spectrometric detection of Ca(+). The rate coefficient for the reaction with O(3) is essentially independent of temperature, k(189-312 K) = (3.9 +/- 1.2) x 10(-10) cm(3) molecule(-1) s(-1), and is about 35% of the Langevin capture frequency. One reason for this is that there is a lack of correlation between the reactant and product potential energy surfaces for near coplanar collisions. The recombination reactions of Ca(+) with O(2), CO(2) and H(2)O were found to be in the fall-off region over the experimental pressure range (1-80 Torr). The data were fitted by RRKM theory combined with quantum calculations on CaO(2)(+), Ca(+).CO(2) and Ca(+).H(2)O, yielding the following results with He as third body when extrapolated from 10(-3)-10(3) Torr and a temperature range of 100-1500 K. For Ca(+) + O(2): log(10)(k(rec,0)/cm(6) molecule(-2) s(-1)) = -26.16 - 1.113log(10)T- 0.056log(10)(2)T, k(rec,infinity) = 1.4 x 10(-10) cm(3) molecule(-1) s(-1), F(c) = 0.56. For Ca(+) + CO(2): log(10)(k(rec,0)/ cm(6) molecule(-2) s(-1)) = -27.94 + 2.204log(10)T- 1.124log(10)(2)T, k(rec,infinity) = 3.5 x 10(-11) cm(3) molecule(-1) s(-1), F(c) = 0.60. For Ca(+) + H(2)O: log(10)(k(rec,0)/ cm(6) molecule(-2) s(-1)) = -23.88 - 1.823log(10)T- 0.063log(10)(2)T, k(rec,infinity) = 7.3 x 10(-11)exp(830 J mol(-1)/RT) cm(3) molecule(-1) s(-1), F(c) = 0.50 (F(c) is the broadening factor). A classical trajectory analysis of the Ca(+) + CO(2) reaction is then used to investigate the small high pressure limiting rate coefficient, which is significantly below the Langevin capture frequency. Finally, the implications of these results for calcium chemistry in the mesosphere are discussed.

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Metal ion-molecule kinetics at combustion temperatures: The reaction of Ca+ with O2

Cited by 2 publications

References 36 publications

Applicability of Standardless Semiquantitative Analysis of Solids by High-Irradiance Laser Ionization Orthogonal Time-of-Fight Mass Spectrometry

Applicability of Standardless Semiquantitative Analysis of Solids by High-Irradiance Laser Ionization Orthogonal Time-of-Fight Mass Spectrometry

A kinetic study of the reactions of Ca+ ions with O3, O2, N2, CO2 and H2O

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