Freezing first-order

For systems where the bulk freezing transition is well understood, one may want to go one step further and investigate the modifications of the phase transition and the sohd phases in the event of external influence on the system. Flow does freezing happen in a confined situation where external boundaries are present What is freezing in porous media like A related question is What does the interface between sohd and liquid look like This is an intrinsic inhomogeneity that the system builds up by itself (if, as usual, the transition is first order). Let us describe some papers dealing with freezing under external influence. 

The freezing of droplets of a given size follows a first-order equation that can be written as [76]... 

The latter number incorporates just the chemical step(s) of formation of triazole within cucurbituril. Since the product release step apparently is at least 100-fold slower than the actual cycloaddition, the net catalytic acceleration should be adjusted downward by that amount. An instructive alternative estimation of kinetic enhancement is to compare the extrapolated limiting rate for cycloaddition within the complex (i.e. cucurbituril saturated with both reactants, k — 1.9xl0 s ) with the uncatalyzed unimolecular transformation of an appropriate bifunctional reference substrate as in Eq. (3) (k, = 2.0x 10 s ). Such a comparison of first-order rate constants shows that the latter reaction is approximately a thousandfold slower than the cucurbituril-engendered transformation. This is attributable to necessity for freezing of internal rotational degrees of freedom that exist in the model system, which are taken care of when cucurbituril aligns the reactants, and concomitantly to an additional consideration which follows. 

Figure 12 The correlation of storage stability with protein structure as determined by Fourier transform infrared spectroscopy (FTIR) apparent first-order rate constants for aggregation of freeze dried rlL-2. (O) 45°C storage. ( ) 29°C storage. (Data from [67].)...

---