An alternative to the concept of variable activation energy

被引:10
|
作者
Simon, Peter [1 ]
Dubaj, Tibor [1 ]
Cibulkova, Zuzana [1 ]
机构
[1] Slovak Univ Technol Bratislava, Inst Phys Chem & Chem Phys, Fac Chem & Food Technol, Radlinskeho 9, Bratislava 81237, Slovakia
关键词
General rate equation; Isoconversional methods; Arrhenius equation; Kinetic compensation effect; Complex processes; ENTROPY GENERATION ANALYSIS; CONVECTION HEAT-TRANSFER; MHD NANOFLUID FLOW; THERMAL-RADIATION; THERMOPHYSICAL PROPERTIES; VERTICAL MICROCHANNEL; TRANSFER ENHANCEMENT; POROUS-MEDIUM; SLIP-FLOW; UNCERTAINTIES;
D O I
10.1007/s10973-023-12711-2
中图分类号
O414.1 [热力学];
学科分类号
摘要
It is demonstrated here that the concept of variable activation energy is mathematically not fully correct. Further it is shown that general rate equation is a formal mathematical tool for the description of thermoanalytical kinetic data. The temperature function, k(T), is not the rate constant in general and the conversion function, f(alpha), may not reflect the mechanism in case of complex processes. Both, k(T) and f(alpha), are functions enabling to describe the kinetic hypersurface. For the complex processes, the physical meaning of parameters occurring in both functions is unclear. Hence, no mechanistic conclusions should be drawn from the values of an individual kinetic parameter; particularly, just from the values of activation energy. The conclusions can be drawn from the quantities with a clear physical meaning such as the values of isoconversional times, isoconversional temperatures, conversion, reaction rate, etc., i.e., the quantities that can be accessible experimentally. These quantities can be recovered and modeled from known kinetic parameters. It is proved here that the right temperature function may not be necessarily the Arrhenius equation for a complex process.
引用
收藏
页码:11507 / 11516
页数:10
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