J. Chem. Soc., Perkin Trans 2, 2000, 365-373.
© The Royal Society of Chemistry, 2000
John Andraos,* Edward C. Lathioor, and William J. Leigh
Contribution from the Department of Chemistry, University of Toronto, Toronto, ON M5S 3H6 and the Department of Chemistry, McMaster University, Hamilton, ON Canada L8S 4M1
Abstract: The absorbance extremum method introduced to resolve the rate
constant-reaction step ambiguity problem in two step consecutive reactions is applied to
cases where the rate constant in each step is pseudo first order and dependent on catalyst
concentration. In particular, acid and base catalyzed reactions of substrates in aqueous
solution are examined. Resultant simultaneous pH-rate profile functions are treated in the
context of the ambiguity problem and a detailed account of the possible interactions
between pH-rate profiles is also given. The merits of this method include its general
scope, its applicability to reactions for which it may be experimentally difficult to
resolve the ambiguity assignment by other means, and its use of rate data acquired from
original kinetic traces without requiring additional information. The theoretical analysis
is verified and tested experimentally for the hydration of fluorenylideneketene in dilute
aqueous perchloric acid solutions.
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