The kinetic compensation effect observed in heterogeneous non-isothermal kinetics is only an apparent effect. In general,
the correlation derived between the kinetic parameters E and log A from TG curves can be described by means of a non-linear
compensation law, expressed by Eq. (14). This equation may become approximately linear in certain particular cases, i.e. it
may change into an isokinetic relation. The validity of the non-linear compensation law has been tested by using over 1000
sets of kinetic parameters reported earlier.
Shape and position parameters △Δ and τ are proposed for the characterization of TG curves and are defined by Eqs (6), (7) and (8), respectively. These parameters being reduced to the standard ”conditions”n=0 andq=1/6 K sec−1, the nomogram given in Fig. 1 can be constructed by means fo Eqs (9), (11) and (12). An iteration method is proposed, allowing derivation of the kinetic parametersn, E andZ of simple thermal decomposition reactions, from the parameters n,E andZ, by using the empirica formulae (9), (10), (11) and (12) and the nomogram. Table 3 contains data necessary to construct this nomogram.
Doyle's isothermal method is analysed by using it for deriving activation energies from theoretical curves. Empirical formulae are given for the time correctiontc, as well as for the factorr in the following equation:Ea=−rm cal/mole. An iterative procedure is suggested, which eliminates the inaccuracy of Doyle's method and permits the derivation of activation energies with an accuracy of ±0.1 kcal/mole in ideal cases.
Four many curves methods, viz. calculation techniques based on Eqs (30), (31), (34) and (36), respectively, for deriving kinetic parameters from several TG curves recorded with different heating rates are tested on two sets of theoretical TG curves. The maximum reaction rate temperature and conversion, as well as the approximate formulae used for their calculation are discussed. Some aspects of the kinetic compensation effect are analysed. The final conclusion is that the use of the many curves methods is not reasonable.
Computer programs are given in Fortran language for three integral methods of deriving kinetic parameters from TG curves. Method 1 is a computerized variant of Doyle's curve-fitting method and performs the calculation of the exponential integralp(x) by means of author's empirical formula. Methods 2 and 3 are variants of the Coats-Redfern linearization method. Testing of the methods on both theoretical and experimental TG curves shows them to be almost equivalent as far as the results obtained are concerned, but Method 1 needs a ten-fold higher computer time.