Temperature dependence of the rate constants and branching ratios for the reactions of Cl- (D2O)1-3 with CH3Br and thermal dissociation rates for Cl-(CH3Br)

John V. Seeley; Robert A. Morris; A. A. Viggiano; Haobin Wang; William L. Hase

doi:10.1021/ja960872u

Temperature dependence of the rate constants and branching ratios for the reactions of Cl^- (D₂O)_1-3 with CH₃Br and thermal dissociation rates for Cl^-(CH₃Br)

John V. Seeley, Robert A. Morris, A. A. Viggiano, Haobin Wang, William L. Hase

Chemistry and Biochemistry

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Abstract

The rate constants and products for the reactions of Cl^-(D₂O)(n) + CH₃Br (n = 1-3) have been measured. The n = 1 reaction was studied from 238 to 478 K. The rate constant is well described by k = (6.0 x 10^-10) exp(-1270/T) cm³ s^-1. We determined the reaction mechanism to be ligand switching to produce Cl^-(CH₃Br) followed by thermal decomposition of the complex. Cl^-(CH₃Br) decomposition produces greater than 90% Br^- + CH₃Cl with the remainder being Cl^- + CH₃Br. The Cl^-(CH₃Br) + He rate constant is well described by k = (4.5 x 10^-10) exp(-2260/T) cm³ s^-1. RRKM theory was used to model the decomposition of Cl^-(CH₃Br). The results are consistent with our experimental results if a central barrier height of 22.5 kJ mol^-1 is used. The n = 2 and 3 reactions also proceed by ligand switching followed by thermal decomposition. The n = 2 reaction was studied from 203 to 298 K. The rate constant is well-described by (4.4 x 10^-9) exp(-1329/T) cm³ s^-1. The main product observed was Cl^-(D₂O) with a smaller amount of Cl^-(D₂O)(CH₃Br) also detected. The n = 3 reaction was studied from 188 to 203 K. The reaction was about a factor of 1.8 faster than the n = 2 reaction. The main product was Cl^-(D₂O)₂ with smaller amounts of Cl^-(D₂O)₂(CH₃Br) and Cl^-(D₂O)(CH₃Br) also observed.

Original language	English
Pages (from-to)	577-584
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	119
Issue number	3
DOIs	https://doi.org/10.1021/ja960872u
State	Published - Jan 22 1997

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@article{8c3131e93fc6454e946503b387ed021d,

title = "Temperature dependence of the rate constants and branching ratios for the reactions of Cl- (D2O)1-3 with CH3Br and thermal dissociation rates for Cl-(CH3Br)",

abstract = "The rate constants and products for the reactions of Cl-(D2O)(n) + CH3Br (n = 1-3) have been measured. The n = 1 reaction was studied from 238 to 478 K. The rate constant is well described by k = (6.0 x 10-10) exp(-1270/T) cm3 s-1. We determined the reaction mechanism to be ligand switching to produce Cl-(CH3Br) followed by thermal decomposition of the complex. Cl-(CH3Br) decomposition produces greater than 90% Br- + CH3Cl with the remainder being Cl- + CH3Br. The Cl-(CH3Br) + He rate constant is well described by k = (4.5 x 10-10) exp(-2260/T) cm3 s-1. RRKM theory was used to model the decomposition of Cl-(CH3Br). The results are consistent with our experimental results if a central barrier height of 22.5 kJ mol-1 is used. The n = 2 and 3 reactions also proceed by ligand switching followed by thermal decomposition. The n = 2 reaction was studied from 203 to 298 K. The rate constant is well-described by (4.4 x 10-9) exp(-1329/T) cm3 s-1. The main product observed was Cl-(D2O) with a smaller amount of Cl-(D2O)(CH3Br) also detected. The n = 3 reaction was studied from 188 to 203 K. The reaction was about a factor of 1.8 faster than the n = 2 reaction. The main product was Cl-(D2O)2 with smaller amounts of Cl-(D2O)2(CH3Br) and Cl-(D2O)(CH3Br) also observed.",

author = "Seeley, {John V.} and Morris, {Robert A.} and Viggiano, {A. A.} and Haobin Wang and Hase, {William L.}",

year = "1997",

month = jan,

day = "22",

doi = "10.1021/ja960872u",

language = "English",

volume = "119",

pages = "577--584",

journal = "Journal of the American Chemical Society",

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Temperature dependence of the rate constants and branching ratios for the reactions of Cl^- (D₂O)_1-3 with CH₃Br and thermal dissociation rates for Cl^-(CH₃Br). / Seeley, John V.; Morris, Robert A.; Viggiano, A. A. et al.
In: Journal of the American Chemical Society, Vol. 119, No. 3, 22.01.1997, p. 577-584.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Temperature dependence of the rate constants and branching ratios for the reactions of Cl- (D2O)1-3 with CH3Br and thermal dissociation rates for Cl-(CH3Br)

AU - Seeley, John V.

AU - Morris, Robert A.

AU - Viggiano, A. A.

AU - Wang, Haobin

AU - Hase, William L.

PY - 1997/1/22

Y1 - 1997/1/22

N2 - The rate constants and products for the reactions of Cl-(D2O)(n) + CH3Br (n = 1-3) have been measured. The n = 1 reaction was studied from 238 to 478 K. The rate constant is well described by k = (6.0 x 10-10) exp(-1270/T) cm3 s-1. We determined the reaction mechanism to be ligand switching to produce Cl-(CH3Br) followed by thermal decomposition of the complex. Cl-(CH3Br) decomposition produces greater than 90% Br- + CH3Cl with the remainder being Cl- + CH3Br. The Cl-(CH3Br) + He rate constant is well described by k = (4.5 x 10-10) exp(-2260/T) cm3 s-1. RRKM theory was used to model the decomposition of Cl-(CH3Br). The results are consistent with our experimental results if a central barrier height of 22.5 kJ mol-1 is used. The n = 2 and 3 reactions also proceed by ligand switching followed by thermal decomposition. The n = 2 reaction was studied from 203 to 298 K. The rate constant is well-described by (4.4 x 10-9) exp(-1329/T) cm3 s-1. The main product observed was Cl-(D2O) with a smaller amount of Cl-(D2O)(CH3Br) also detected. The n = 3 reaction was studied from 188 to 203 K. The reaction was about a factor of 1.8 faster than the n = 2 reaction. The main product was Cl-(D2O)2 with smaller amounts of Cl-(D2O)2(CH3Br) and Cl-(D2O)(CH3Br) also observed.

AB - The rate constants and products for the reactions of Cl-(D2O)(n) + CH3Br (n = 1-3) have been measured. The n = 1 reaction was studied from 238 to 478 K. The rate constant is well described by k = (6.0 x 10-10) exp(-1270/T) cm3 s-1. We determined the reaction mechanism to be ligand switching to produce Cl-(CH3Br) followed by thermal decomposition of the complex. Cl-(CH3Br) decomposition produces greater than 90% Br- + CH3Cl with the remainder being Cl- + CH3Br. The Cl-(CH3Br) + He rate constant is well described by k = (4.5 x 10-10) exp(-2260/T) cm3 s-1. RRKM theory was used to model the decomposition of Cl-(CH3Br). The results are consistent with our experimental results if a central barrier height of 22.5 kJ mol-1 is used. The n = 2 and 3 reactions also proceed by ligand switching followed by thermal decomposition. The n = 2 reaction was studied from 203 to 298 K. The rate constant is well-described by (4.4 x 10-9) exp(-1329/T) cm3 s-1. The main product observed was Cl-(D2O) with a smaller amount of Cl-(D2O)(CH3Br) also detected. The n = 3 reaction was studied from 188 to 203 K. The reaction was about a factor of 1.8 faster than the n = 2 reaction. The main product was Cl-(D2O)2 with smaller amounts of Cl-(D2O)2(CH3Br) and Cl-(D2O)(CH3Br) also observed.

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U2 - 10.1021/ja960872u

DO - 10.1021/ja960872u

M3 - Article

AN - SCOPUS:0031017428

SN - 0002-7863

VL - 119

SP - 577

EP - 584

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 3

ER -

Temperature dependence of the rate constants and branching ratios for the reactions of Cl^- (D₂O)_1-3 with CH₃Br and thermal dissociation rates for Cl^-(CH₃Br)

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