A system of physical chemistry. Kinetics by Lewis

By Lewis

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Extra resources for A system of physical chemistry. Kinetics

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Such acid-catalysed halogenation is observed with both bromine and, to a lesser extent, chlorine. In the presence of "halogen-carriers", such as iodine or pyridine, further kinetic complexities result. 11) and can be recognisedH7 ReJivmr'es pp. 3 INTERHALOGEN ADDITION The two interhalogens, ICl and IBr, have been used extensively to measure unsaturation, but the kinetics of their reaction with olefins has received very little attention. 12) They also found the order of reactivity I, e IBr < Br, < ICI < BrCl and showed that hydrogen chloride decreased the rate of addition of iodine monochloride to allyl acetate, presumably due to the formation of HICI,.

6. mole-l, AS* = - 16. eu. 4 eu. mole-’. 7 eu. 7 eu. g8 Bz = COPh. hh PNB = p-nitrobenzoyl. 5-dinitrobenzoyl. mole-l. Rate coefficient with olefin in great excess. mole-I. nn k , = 8k,. mole-l. pp k, = 8k,. mole-l. q q pH indicated in parenthesis. rr m-Nitrobenzoate ion = X-. 3) It was subsequently suggested that there was a parallel between the susceptibilities of olefins towards attack by bromine (a known electrophile) and that towards attack by per acid^'^^, and these suggestions were put on to a quantitative basis by the work of Lynch and P a u ~ a c k e r ' ~ who ~ , studied the effects of substituents upon both the peracid and the substrate (stilbene) in the reaction in benzene solution.

9 kcalmole-'. mole-'. 1 Kinetic expression is in fact very complex. mole-I. mole-I. 4-trimethyl- 1- and 2-pentenes; apparently the former isomer was predominant in the mixture used. 'I Reaction follows the kinetics of eqn. 3); X 2 refers to the second-order process. The data in ref. I03 contains results obtained cissuming a pure second-order reaction. A :S * = -28eu. 5 k ~ a l . mole-';AS-t=-27eu. 083 (eqn. 2 1 ). mole-'. 1 truns-n-3-Undecene. 7 truns-n-4-Undecene. 7 cis-n-5-Undecene. mole-I, ASt.

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