The compensation effect

Abstract

This paper is a rebuttal to the paper of Zsak6 and Somasekharan. It has been shown that the criticisms of Zsak6 and Somasekharan are baseless. The procedure proposed earlier by Agrawal to distinguish between true and false compensation effect is reasonable and gives good results. To establish true c.e., it has been reaffirmed that both T~s o and In kiso are prerequisite.In a recent paper, Zsak6 and Somasekharan [1] have criticized the procedures proposed by Agrawal [2] to distinguish between the true and false compensation effect (c.e.). Their criticism was directed at four related issues: (i) questioning the use of Arrhenius equation and the definition of mole of solids; (ii) commenting on the calculation of k from A and E obtained from non-isothermal data; (iii) questioning the criterion In kiso ~ 0, and claiming that this depends on the units of k; and (iv)suggesting that a concurrence point depends on the correlation coefficient. I disagree with all the issues raised by Zsak6 and Somasekharan [1].

Kinetic compensation effect in the thermal degradation of polymers

“…The isokinetic temperature has been regarded either as the temperature at which relative rates within a group roup of reactions undergo inversion, or as the temperature at which the rate constants of all the reactions in the series have the same value [ 17]. However, Agrawal [22] suggested an alternate method for detecting true compensation behavior via an Arrhenius plot of ln(k) vs. (l/T) for a series of related reactions. Accordingly, true compensation behavior is displayed when the Arrhenius plots show a point of concurrence.…”

Role of metal oxides in the thermal degradation of bisphenol a polycarbonate

“…However, it has been suggested [13,14] that true compensation effect will be observed only when Ink vs. liT plots exhibit a point of concurrence. However, the TG data on PC do not exhibit such point of concurrence as shown in the Fig.…”

Practical kinetic modeling of petroleum generation and expulsion

“…(Some of these diagnostics have been discussed in greater detail in other review papers on compensation effects, such as Agrawal, 1986;Bond et al, 2000;Exner, 1964;Krug et al, 2006).…”