velocity of the reaction of 1-Br at infinite [Br'], where the solvolysis reaction would proceed solely by the capture of the ion-pair intermediate [2• ']. This limiting velocity is only 0.06% (±0.02%) of the value of = 0.049 s'1 for the solvolysis reaction of 1-Br in the absence of bromide ion.The substitution of bromide ion for perchlorate ion is expected to destabilize 2 relative to 1-Br because of the specific bromide ion salt effect (see above). This would be expected to lead to a decrease in fecalc for the reaction of 1-Br through the carbocation intermediate 2. There is a 42% decrease in the observed first-order rate constant for the solvolysis of 1-1 when 5.00 M NaBr is substituted for NaC104 at I = 6.00 (NaC104). If there were a similar specific bromide ion salt effect on fccalc (Table I), then (*obsd~^caic) would be increased to 9.0 X 10~5 s'1.
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