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Electron attachment to halomethanes at high temperature: , , , and attachment rate constants up to 1100 K
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10.1063/1.3212598
/content/aip/journal/jcp/131/8/10.1063/1.3212598
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/8/10.1063/1.3212598

Figures

Image of FIG. 1.
FIG. 1.

Data obtained with the HT-FALP apparatus for at 495 K in a He/Ar buffer gas vs reaction time . The diffusion data were obtained in the absence of the . The solid curves are solutions of rate equations using . represents molecular cations produced in reaction with (and some ). The reaction rate was taken to be , and the electron recombination rate constant was estimated at at 495 K.

Image of FIG. 2.
FIG. 2.

Comparison of the present data (AFRL) with those of Boston College (BC, Ref. 16), Birmingham University (B’ham, Ref. 11), and Oak Ridge National Laboratory (ORNL, Ref. 14, extrapolated to thermal energy in the present work). Off scale are Rennes data (Ref. 16) at temperatures of .

Image of FIG. 3.
FIG. 3.

Temperature dependence of halomethane electron attachment rate constants. Solid circles are the present (AFRL) data. The other data showing temperature dependences are those of Birmingham University (Ref. 11), except for (at 300, 400, and 500 K) which are from ORNL (Ref. 14). The points shown only at 300 K are all ORNL data (Ref. 20). The datum is likely in error (see text).

Image of FIG. 4.
FIG. 4.

Correlation of 300 K electron attachment rate constants (yielding ion product) with reaction exothermicity (a negative value implying endothermicity). The lines are drawn to guide the eyes for molecules containing no F atoms (right) and molecules with no H atoms (left). The closed circles are data plotted vs energetics from G3 calculations (Table I). The open points are the same data plotted vs energetics deduced from BDEs minus EA(Cl).

Tables

Generic image for table
Table I.

Calculated G3 total energies, adiabatic EAs, and C–Cl BDEs at 0 K for , , , , and dissociation fragments relevant to the energetics of attachment reactions. is included as relevant to comments in the text on endothermic electron attachment to .

Generic image for table
Table II.

Electron attachment rate constants for , , and obtained at temperatures . Data for were given in Ref. 1. The present experimental uncertainty is ±25% except for cases where significant correction for electron-ion recombination was made: If , then the estimated uncertainty is ±35%.

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/content/aip/journal/jcp/131/8/10.1063/1.3212598
2009-08-31
2014-04-17
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Electron attachment to halomethanes at high temperature: CH2Cl2, CF2Cl2, CH3Cl, and CF3Cl attachment rate constants up to 1100 K
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/8/10.1063/1.3212598
10.1063/1.3212598
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