Free radical addition to olefins. Part 1. - Addition of bromotrichloromethane to ethylene

J. M. Tedder; J. C. Walton

doi:10.1039/TF9646001769

Free radical addition to olefins. Part 1. - Addition of bromotrichloromethane to ethylene

J. M. Tedder^*, J. C. Walton

^*Corresponding author for this work

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Abstract

The light-induced addition of bromotrichloromethane to ethylene has been studied in a series of gas-phase experiments in which relative concentration, temperature and light intensity have been varied. The reaction is shown to involve the following process. CCl₃+hv→CCl₃· +Br· (1) CCl₃·+E→CCl₃E· (2) CCl₃E·+CCl₃Br→CC₃EBr+CCl ₃· (3) CCl₃·+CCl₃·→ C₂Cl₆ (4) Br·+E→EBr· (5) CCl ₃·+CCl₃·→(CCl₃E) ₂. (7) When bromotrichloromethane is in excess, reaction (4) is the predominant chain-termination process, and using literature data for k ₄, the value k₂ = 4.17×10⁵ exp (-3240/RT)l. mole^-1 sec^-1 was determined. With ethylene in large excess, reaction (7) becomes the main chain termination process, and assuming A₇≈10⁸ and E₇≈0, the value k₃≈10⁵ exp (-3400/RT)l. mole^-1 sec ^-1 was determined.

Original language	English
Pages (from-to)	1769-1774
Number of pages	6
Journal	Transactions of the Faraday Society
Volume	60
DOIs	https://doi.org/10.1039/TF9646001769
Publication status	Published - 1 Jan 1964

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@article{a3f97e1c17084d98a73184782b0742e2,

title = "Free radical addition to olefins. Part 1. - Addition of bromotrichloromethane to ethylene",

abstract = "The light-induced addition of bromotrichloromethane to ethylene has been studied in a series of gas-phase experiments in which relative concentration, temperature and light intensity have been varied. The reaction is shown to involve the following process. CCl3+hv→CCl3· +Br· (1) CCl3·+E→CCl3E· (2) CCl3E·+CCl3Br→CC3EBr+CCl 3· (3) CCl3·+CCl3·→ C2Cl6 (4) Br·+E→EBr· (5) CCl 3·+CCl3·→(CCl3E) 2. (7) When bromotrichloromethane is in excess, reaction (4) is the predominant chain-termination process, and using literature data for k 4, the value k2 = 4.17×105 exp (-3240/RT)l. mole-1 sec-1 was determined. With ethylene in large excess, reaction (7) becomes the main chain termination process, and assuming A7≈108 and E7≈0, the value k3≈105 exp (-3400/RT)l. mole-1 sec -1 was determined.",

author = "Tedder, \{J. M.\} and Walton, \{J. C.\}",

year = "1964",

month = jan,

day = "1",

doi = "10.1039/TF9646001769",

language = "English",

volume = "60",

pages = "1769--1774",

journal = "Transactions of the Faraday Society",

issn = "0014-7672",

publisher = "Faraday Division of the Chemical Society",

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TY - JOUR

T1 - Free radical addition to olefins. Part 1. - Addition of bromotrichloromethane to ethylene

AU - Tedder, J. M.

AU - Walton, J. C.

PY - 1964/1/1

Y1 - 1964/1/1

N2 - The light-induced addition of bromotrichloromethane to ethylene has been studied in a series of gas-phase experiments in which relative concentration, temperature and light intensity have been varied. The reaction is shown to involve the following process. CCl3+hv→CCl3· +Br· (1) CCl3·+E→CCl3E· (2) CCl3E·+CCl3Br→CC3EBr+CCl 3· (3) CCl3·+CCl3·→ C2Cl6 (4) Br·+E→EBr· (5) CCl 3·+CCl3·→(CCl3E) 2. (7) When bromotrichloromethane is in excess, reaction (4) is the predominant chain-termination process, and using literature data for k 4, the value k2 = 4.17×105 exp (-3240/RT)l. mole-1 sec-1 was determined. With ethylene in large excess, reaction (7) becomes the main chain termination process, and assuming A7≈108 and E7≈0, the value k3≈105 exp (-3400/RT)l. mole-1 sec -1 was determined.

AB - The light-induced addition of bromotrichloromethane to ethylene has been studied in a series of gas-phase experiments in which relative concentration, temperature and light intensity have been varied. The reaction is shown to involve the following process. CCl3+hv→CCl3· +Br· (1) CCl3·+E→CCl3E· (2) CCl3E·+CCl3Br→CC3EBr+CCl 3· (3) CCl3·+CCl3·→ C2Cl6 (4) Br·+E→EBr· (5) CCl 3·+CCl3·→(CCl3E) 2. (7) When bromotrichloromethane is in excess, reaction (4) is the predominant chain-termination process, and using literature data for k 4, the value k2 = 4.17×105 exp (-3240/RT)l. mole-1 sec-1 was determined. With ethylene in large excess, reaction (7) becomes the main chain termination process, and assuming A7≈108 and E7≈0, the value k3≈105 exp (-3400/RT)l. mole-1 sec -1 was determined.

UR - https://www.scopus.com/pages/publications/2542614878

U2 - 10.1039/TF9646001769

DO - 10.1039/TF9646001769

M3 - Article

AN - SCOPUS:2542614878

SN - 0014-7672

VL - 60

SP - 1769

EP - 1774

JO - Transactions of the Faraday Society

JF - Transactions of the Faraday Society

ER -

Free radical addition to olefins. Part 1. - Addition of bromotrichloromethane to ethylene

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