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Lecture on Crystallization

By Prof. Sanjay Mahajani Dept of Chem Engg IIT Bombay

Introduction
Crystallization is the formation of solid particles within a homogeneous phase For crystallization to occur, solution must be supersaturated Supersaturation means that at a given temperature, the actual solute concentration exceeds the saturation concentration A supersaturated solution is metastable and contain clusters of molecules. Clusters grow large with time. Eventually will grow large enough for nucleation to occur.

Supersaturation
Supersaturation can be achieved by several methods:
a) Cooling b)Evaporation c) Solvent addition

Fractional and molar supersaturation are defined as

Fractional and molar supersaturation are related as

Concentration ratio () and fractional supersaturation (s) are related as

Supersaturation and Temperature Potential

Steps in Crystallization
Nucleation Birth of a new crystal Crystal Growth growth of existing crystal Ratio of rate of nucleation to growth controls the size distribution of product obtained General factors that affect nucleation and growth kinetics
Supersaturation Solvent Temperature Impurities Solution viscosity, surface tension

Objectives of Crystalization
Yield Purity Crystal strength Nonaggregation Uniformity in size

Effect of Supersaturation on Crystal Growth Quality and Type of Nucleation


For MgSO4. 7H2O

Kelvin Equation
Sequence of stages in the evolution of crystal Solubility of substance is related to particle size as

Rate of Nucleation
Rate of Nucleation is given as

Types of Nucleation
Homogeneous Nucleation Heterogeneous Nucleation Secondary Nucleation
Fluid Shear Nucleation Contact Nucleation

Crystal Growth
Equation for mass transfer

Equation for surface reaction Overall resistance for the two steps

Growth Rate and L Law


Equation for Growth Rate (G or dL/dt) is obtained as

L law states that rate of growth of crystal is independent of crystal size

MSMPR Model
An idealized crystallizer model Served well as a basis for identifying the kinetic parameters and showing how knowledge of them can be applied to calculate the performance of such a crystallizer

Assumptions in MSMPR Model


Steady state operation At all times the crystallizer contains a mixedsuspension magma, with no product classification At all times uniform super saturation exists throughout the magma L law applicable No size-classified withdrawal system is used No crystals in the feed The product magma leaves the crystallizer in equilibrium, so the mother liquor in the product magma is saturated No crystal breakage into finite particle size occurs

Assumptions in MSMPR Model


Constant nucleation rate at all points in the magma Constant growth rate and independent of crystal size and location All volume elements of mother liquor contain a mixture of particles ranging in size from nuclei to large particles Particle size distribution is independent of location in the crystallizer and is identical to the size distribution in the product

Population Density
Basic quantity in the theory of the Crystal Size Distribution The population density nis defined as the slope of the cumulative distribution curve (N/V vs. LN/L) at size L N = no of crystals of size L and smaller in the magma V = volume of mother liquor in the magma L = crystal size At L=0, N=0 and L=LT, N=NT

Cumulative Number Density vs Length

at L=0, n=n0 at L=LT, n=0 n = function of L and invariant in both time and location in the magma Dimensions of n: Number/Volume-Length

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