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Correction for instrument time constant and baseline in determination of reaction kinetics

✍ Scribed by Clifford W. Hansen; Lee D. Hansen; Allen D. Nicholson; Marie C. Chilton; Nathan Thomas; Jared Clark; Jaron C. Hansen


Publisher
John Wiley and Sons
Year
2010
Tongue
English
Weight
263 KB
Volume
43
Category
Article
ISSN
0538-8066

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✦ Synopsis


Rates of reactions can be expressed as dn/dt = kf(n), where n is moles of reaction, k is a rate constant, and f(n) is a function of the properties of the sample. Instrumental measurement of rates requires c (dn/dt) = ckf(n), where c is the proportionality constant between the measured variable and the rate of reaction. When the product of instrument time constant, Ο„ , and k is 1, the reaction is much slower than the time response of the instrument and measured rates are unaffected by instrument response. When Ο„ k < 1, = 1, or >1, the reaction rate and instrument response rate are sufficiently comparable that measured rates are significantly affected by instrument response and correction for instrument response must be done to obtain accurate reaction kinetics. This paper describes a method for simultaneous determination of Ο„ , k, c , and instrument baseline by fitting equations describing the combined instrument response and rate law to rates observed as a function of time. When Ο„ cannot be neglected, 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 that increase as Ο„ k increases. Inclusion of instrument baseline as a fitting parameter significantly reduced variability in k and c compared with use of measured instrument baselines. The method was tested with data on the heat rate from acid-catalyzed hydrolysis of sucrose collected with three types of calorimeters. In addition, to demonstrate the generality of this method of data analysis, equations including Ο„ , k, c , and instrument baseline are derived for the relation between the reaction rate and the observed rate for first order, second order (first in each reactant), nth order in one reactant, autocatalytic, Michaelis-Menten kinetics, and the Ng equation.


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