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Correction for instrument time constant in determination of reaction kinetics

Hansen, Clifford H.

Rates of reactions can be expressed as dn/dt = kcf(n) where n is moles of reaction, k is a rate constant, c is a proportionality constant, and f(n) is a function of the properties of the sample. When the instrument time constant, ?, and k are sufficiently comparable that measured rates are significantly affected by instrument response, correction for instrument response must be done to obtain accurate reaction kinetics. Correction for instrument response has previously been done by truncating early data or by use of the Tian equation. Both methods can lead to significant errors. We describe a method for simultaneous determination of ?, k, and c by fitting equations describing the combined instrument response and rate law to rates observed as a function of time. The method was tested with data on the heat rate from acid-catalyzed hydrolysis of sucrose.