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Abstract  

A theoretical approach has been used to show that, except for certain types of reaction mechanism, the ease with which it is possible to distinguish the form of the reaction mechanism by the reduced-time plot method depends particularly on the rate of transfer of heat into the sample. The original reduced-time plots [1] were calculated from model equatioons which assume that the sample is, from the outset, at a fixed temperature and remains under isothermal conditions throughout the reaction. The variations produced in the appearance of reduced-time plots when the sample is programmed to rise to a given fixed temperature through various temperature schedules have been investigated. It is shown that even relatively rapid temperature rises can produce distortion of the reduced-time plots for various reaction equations. If the reaction mechanism is known, however, fairly accurate values of the activation energy for the reaction can be determined, even when the furnace used has relatively poor heat-transfer characteristics.

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consistent when changing the reaction model. The used model fitting expressions are (5) (6) where g (α) is the integral reaction model ( Table 1 ). The reduced time plots ( Fig. 4 ) for the isothermal evaporation of TMSB were subjected to statistical

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corresponding t 0.5 to obtain the normalized curves. The generalized reduced time plots derived from the isoconversional curves have been compared with the generalized reduced theoretical ones reported in literature [ 30 , 32 ]. The reduced time plots for the

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