The influence of the mass transfer phenomena on the thermal decomposition of calcium carbonate powders under vacuum was investigated through a detailed kinetic analysis by the constant transformation rate thermal analysis (CRTA). Reliable kinetic curves, free from the mass transfer problems, can be obtained by CRTA under vacuum, but within a restricted range of small sample sizes, <10 mg. The influence of mass transfer phenomena on the apparent kinetic parameters is discussed in relation to the distribution of fractional reaction a of the individual particles in a sample assemblage. Only when the distribution of α is maintained constant among a series of experimental kinetic curves, can a reliable activation energy, E, be obtained by one of the isoconversion methods. In this respect, a single cyclic CRTA permits the α distribution to be maintained constant between the two adjacent data points with different decomposition rates. In the present study, an apparent E value of about 223 kJ mol-1 was obtained by the Friedman method from a series of CRTA curves with sample sizes less than 10 mg and by the rate jump method from a single cyclic CRTA curve with sample size of about 40 mg. The first-order (F1) law was determined to be the most appropriate kinetic model function, from a series of CRTA curves, instead of the ideal contracting geometry (R3) law formalized for the three-dimensional shrinkage of the reaction interface in the respective particles. The particle size distribution of the sample particles is suggested to be one possible reason for the apparent agreement with the F1 law. A kinetic exponent M of the nth-order law that deviated from unity was obtained from the CRTA curves with sample sizes larger than 10 mg, due to an additional distribution of α produced by mass transfer phenomena. Because the α distribution due to the mass and heat transfer phenomena cannot be expressed practically in an analytical function, a meaningful kinetic model and preexponential factor are difficult to estimate from kinetic data that are influenced by the transfer phenomena. © 1998 John Wiley & Sons, Inc.
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