Nucleation as a function of Super-cooling or the heat of removal

A numbers of equations are available relating nucleation rate and supercooling (super saturation) for both homogeneous and heterogeneous nucleation. These equations are complex, still undergoing refinement and are of limited value for quantitatively describing the rate of heterogeneous nucleation in specific biological samples. Inadequate information concerning: 1) The mean interfacial energy between ice and water, 2) The nature and distribution of biological nucleants, is largely responsible for the situation. It seems preferable therefore 5to deal only with qualitative relationship between nucleation rate and supercooling. All rate equation for homogenous and heterogeneous nucleation predict that the rate of nucleation will remain very low and nearly independent of sample temperature while the degree of supercooling is small then as temperature is lowered (supercooling increase) if some critical value characteristic of the system rate of nucleation will suddenly increase from and almost negligible value 104 nuclei/cm3/sec or more. This general behaviors which is illustrated schematically in fig-1, is observed in practice the curves for homogenous and heterogeneous system are in correct relative position since it is known that at any given supercooling heterogeneous nucleation (whenever possible) will occur in preference to homogenous nucleation. Little significance should be attached to the exact lateral positioning of the curves, since a Number of factors can influence the point at which nucleation begins. For eg. Sample size, over quite a broad range can have rather pronounced effect

2) Rate of crystal growth

Crystal growth can occur at temperatures very near the melting point and Growth rate increase moderately with increasing rates of heat removal until at some very low specimen temperature, mass transfer difficulties cause growth rates to decline.

3) Crystal size
By comparing the crystal growth super cooling relationships (fig-2) with the super cooling relationship we can device the logical explanation for the well known fact that rapidly frozen foods and living specimens contain ice crystals which are small and numerous, where as similar specimens which have been slowly frozen than contain ice crystal which are large and few in number. To aid this comparison, fig-1 and fig-2 have been combined in fig-3. In unseeded system maintained at temperature between the melting point and point N, only few nuclei will form and each will grow extensively. This corresponds to slow freezing (slow removal of heat energy), during which the

sample temperature remains at or near the solid-liquid equilibrium temperature. On the other hand, if an unseeded liquid system is cooled to temperature well below point N (fast removal of heat energy and rapid freezing), many nuclei will form and each will grow to a limited extent. The size of the completed crystal therefore varies inversely with the number of nuclei. Conclusion: Control of crystal size and uniformity is most easily accomplished if the system is mixed during freezing, since this help to achieve a uniform temperature and growth environment. Vigorous stirring encourages the formation of small crystal, probably by increasing the rate of heat removal so that the temperature decreases to a point more favorable for nucleation and by fragmenting growing crystals.

Rate of nucleation

0oC

-150OC

Temperature (OC) Initial supercooling Rate of heat removal Fig-1: The rate of water nucleation as influenced by supercooling and rate of heat removal.

Rate of crystal growth

00 C

-1500 C

Temperature (0C) Fig 2: growth rates of ice crystal as influenced by super-cooling and rate of heat removal

Heterogeneous nucleation Rate

growth

00 C Temperature

-500 C

Fig 3: comparative rates of nucleation and crystal growth of water as influenced by supercooling and rate of heat removal.