A population balance approach is used to model solid phase reactions in terms of nuclei of the product phase dispersed in the reactant matrix. A conversion-time relationship is obtained by the solution of a set of moment equations derived from the population balance. Some previously known solutions for both homogeneous and heterogeneous nucleation are developed by this approach to demonstrate the relative ease of so!ution when compared with previously uJed integral techniques. A model for nucleus impingement at low conversions is formulated and applied to published data on the oxidation of cuprous iodide to illustrate the practical use of this technique. The classical Avrami model (Avrami, 1939(Avrami, , 1940(Avrami, , 1941) is modified to include the initial volume of a nucleus, and it is shown that insensitivities in the original model are removed by this improvement. The need for direct measurements of nucleation and growth rates is emphasized.
1975) or lengrhy power series procedures (Von Goler andThe procedure developed here is generally easier than those ot the corresponding integral equations and has the added advantage that the size dependent interaction of nuclei can be readily incorporated through the use of birth and death rate functions. A procedure for the calculation of these functions is presented which is valid for the early stages of the reaction. The fit of the modified Avrami model to a specific set oi' experimental data is compared with that of a model presented in this paper to emphasize the importance of direct measurements of nucleation and growth rates in the determination of a correct impingement model.
CONCLUSIONS AND SIGNIFICANCEThe modeling of phase-transformation kinetics is approached through a balance over the number density of nuclei, which in-orporates birth and death functions that arise from nucleus impingement. This approach for obtaining the conversion-time relationship results in a set of first-order differential equations. The technique offers an advantage over the previously used methods becau;e of the relative ease of solution of these equations. It can also be used to calculate the nucleus size density for correIation with experimental data.For comparison purposes, the well-known Avrami model is modified to include a term for the initial volume ok a ical Engineers, 1979. growth nucleus in order to increase the sensitivity of the least-squares fit to the choice of parameter values. The two models are equally satisfactory in fitting a specific set of experimental data in the low to moderate conversion range, showing that conversion-time data alone are insufficient to distinguish between the two models for nucleuj impingement. Direct measurements of nucleation and growth rates are needed to identify the more accurate model.The simplified theory presented does not predict the sigrno:dal shape of the conversion-time curve since it does not account for the higher-order impingement among nuclei at high conversion. The consiraining effect of the outer surface of a reacting ...