The reactions of positive and negative halogen ions with Cl2 and Br2

Article abstract of DOI:10.1063/1.464473

A selected ion flow tube study has been carried out at 300 K of the reactions of some atomic and molecular positive and negative halogen ions with Cl2 and Br2 from which the rate coefficients k and ion product distributions have been determined.For the energetic F⁺ ion reactions, dissociative charge transfer is the dominant process, while for the Cl⁺ ions, only nondissociative charge transfer occurs.For the less energetic Br⁺ and I⁺ reactions, dihalogen molecular ions are important products.All these positive ion reactions proceed quite efficiently, i.e., the k are appreciable fractions of k_c, their respective collisional rate coefficients, except for the reactions of Cl2 with the lower energy ions of the spin-orbit triplet of I⁺, i.e., I⁺(³P_1,0), for which k ca. 0.07k_c, this being due to the endothermicities of the reactions.The molecular ion Cl2⁺ undergoes rapid nondissociative charge transfer with Br2, a process which is, of course, endothermic for the reaction of Br2⁺ with Cl2 and so no reaction is observed.The less-energetic atomic negative ion reactions proceed-via atom exchange-in which the atomic negative ion of the reactant molecular species and a dihalogen molecule are produced.For those reactions that are exothermic, the k are, within error, equal to (2/3)k_c, implying that they proceed via complexes which separate statistically back to reactants (1/3) and forward to products (2/3).Both the Br^- + Cl2 and Cl^- + Br2 reactions are somewhat less efficient (i.e., k <2/3k_c), a result of the slight endothermicities of the reactions.Of the molecular negative ion reactions, electron transfer is the major process in the Cl2^- reaction with Br2, whereas the reaction of Br2^- with Cl2 proceeds relatively slowly producing the triatomic ion BrCl2^-.

Full text of DOI:10.1063/1.464473

The reactions of positive and negative halogen ions with Cl2 and Br2
P. Španěl, M. Tichý, and D. Smith
Citation: The Journal of Chemical Physics 98, 8660 (1993); doi: 10.1063/1.464473
View online: http://dx.doi.org/10.1063/1.464473
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/98/11?ver=pdfcov
Published by the AIP Publishing
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.49.23.145 On: Thu, 18 Dec 2014 02:45:35

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.49.23.145 On: Thu, 18 Dec 2014 02:45:35

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.49.23.145 On: Thu, 18 Dec 2014 02:45:35

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.49.23.145 On: Thu, 18 Dec 2014 02:45:35

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.49.23.145 On: Thu, 18 Dec 2014 02:45:35

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.49.23.145 On: Thu, 18 Dec 2014 02:45:35

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.49.23.145 On: Thu, 18 Dec 2014 02:45:35