Abstract
AbstractThe optimization of chemical processes that take place in a finite time constitutes an important application of finite‐time thermodynamics. In this study we investigate two generic optimal control problems for nucleation‐and‐growth based syntheses: the maximization of the amount of a crystalline solid phase generated via cooling from the melt within a finite time τ, and the maximization of the difference between two metastable crystalline modifications again synthesized by crystallization from a supercooled melt. In both cases the optimal temperature program consists in a bang‐bang solution with constant values of the temperature, where a switch from a temperature T1, where nucleation rates are high, to a temperature T0 > T1, where the growth rates of the crystallites are maximal, occurs. The location of the switching time ts* (0 ≤ ts* ≤ τ) is analyzed as function of the parameters of the models describing the chemical systems, and an application to the synthesis of glycerol crystals is given.
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