web-publishedsupplement.docVIP

Web-Published Supplement This supplement presents a detailed derivation of the dimensionless model used in this work. The method of moments is originally due to Hulbert and Katz.1 Additional background information is available in reference texts.2-6 The units used in this derivation assume that the crystal size distribution function and its moments are defined on a volume of suspension basis, i.e. is the number of crystals per unit volume of suspension (#/m3), is the volume of crystals per unit volume of suspension (m3/m3), and is the rate of nucleation per unit volume of suspension (#/m3s). We further assume that the total volume of the suspension does not change significantly over the course of the batch. However, all of the analysis presented in this paper will work regardless of the basis that is used (e.g. volume of clear liquid or solvent mass) as long as that basis is used consistently. 1. Basic Equations In the absence of agglomeration and breakage, a general statement of the population balance for a well-mixed batch crystallization system is: (1) where is the crystal size distribution (CSD) function, B is the nucleation rate (#/m3s) and G is the crystal growth rate (m/s). Equation 1 is subject to an initial condition based on the properties of the seeds at the beginning of the batch ( is given) and to a left boundary condition: (2) The driving force for both nucleation and growth is the supersaturation: (3) In this work concentration is defined as the mass of dissolved solute per unit volume of suspension. Common forms for the expressions for crystal growth rate and secondary nucleation are: (4) (5) Where , , and are empirically determined kinetic parameters and is the third moment of the CSD. The moments of the CSD are determined according to: (6) And it can be shown (if the crystal growth rate is independent of size) that: (7) (8) A mass balance on the solute shows that the time rate of change of the concentration, C, is given