Chiral symmetry breaking in unstirred crystallization

Abstract

AbstractStatistics of nucleation of chiral forms of sodium bromate from unstirred aqueous solutions was studied. It was established that bimodal, trimodal and unimodal distributions of enantiomers are obtained in unstirred crystallization. It was also found out that probabilities of the creation of L or D crystals and racemates R, as well as the presence of D, L, and R peaks in distributions depend on crystallizer size, supersaturation and temperature. Nucleation at low supersaturations in small, closed crystallizers leads to the formation of pure enantiomers, and to bimodal distributions with D and L peaks at any temperature. At high supersaturations in large, open crystallizers the formation of racemates and unimodal distributions with racemate R peaks results. In open crystallizers at the lowest temperatures and at the highest temperatures used in crystallization from aqueous solution racemates of sodium bromate are preferentially formed, but in a wide range of intermediate‐temperatures apart from racemates, pure enantiomers are efficiently formed which leads to trimodal distributions. The spontaneous formation of pure enantiomers in crystallization from unstirred, unseeded solutions is caused by the chiral symmetry breaking phenomenon, the same as that discovered in stirred crystallization. The conservation of chiral symmetry is, in unstirred crystallization, one of the two possibilities, and the other one is the breakage of symmetry. Both of them occur in nature. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)