Kinetic compensation effect: discounting the distortion provoked by accidental experimental errors in the isokinetic tem
- PDF / 1,218,284 Bytes
- 12 Pages / 595.276 x 790.866 pts Page_size
- 100 Downloads / 152 Views
ORIGINAL PAPER
Kinetic compensation effect: discounting the distortion provoked by accidental experimental errors in the isokinetic temperature value Joaquin F. Perez‑Benito1 · Iker Alburquerque‑Alvarez1 Received: 21 January 2020 / Accepted: 10 November 2020 © Springer-Verlag GmbH Austria, part of Springer Nature 2020
Abstract Random experimental errors are known to provoke the appearance of false isokinetic enthalpy–entropy relationships under some circumstances. In this contribution, it is shown that the observation of a false error-caused isokinetic plot, with a slope close to the mean working temperature (Tm), does not necessarily preclude the occurrence of a real isokinetic temperature (Tik) that might be quite different from Tm, for that particular homologous reaction series. However, since accidental errors cause a shift in the value of parameter Tik toward that of Tm, different numerical simulation methods have been tried to discount this effect and so obtain the most probable (extrapolated) value of Tik. The method leading to the best results was that of shifting the maximum probability curve for each reaction series until it matched the experimental point (defined by both the Tik value and the activation enthalpy mean fitting error). Finally, the applicability of this method has been checked out for 17 reaction families selected from chemical bibliographic sources. According to the results found in this study, when the experimental isokinetic temperature is higher than the mean working temperature (Tik,exp > Tm) the most probable value should be looked for in the high temperature range (Tik,sim > Tik,exp), and when Tik,exp
Data Loading...
