Sobczak Szymon, Ratajczyk Paulina, Katrusiak Andrzej
Department of Materials Chemistry, Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznańskiego 8, 61-614, Poznań, Poland.
Chemistry. 2021 Apr 26;27(24):7069-7073. doi: 10.1002/chem.202005121. Epub 2021 Mar 4.
New polymorphs β and γ of bis-3-nitrophenyl disulphide, crystallized above 0.3 GPa, are less dense than the ambient-pressure polymorph α. This counterintuitive density relation results from the high-entropy nucleation and subsequent kinetic crystallization. The work performed by pressure compensates the high entropy and temperature product, substantiated in varied conformers and increased chemical potential. Pressure-increased viscosity promotes the kinetic polymorphs, in accordance with empirical Ostwald's rule of stages. It contrasts to mechanochemical techniques, favouring high-density polymorphs.
双-3-硝基苯基二硫化物的新多晶型物β和γ在0.3 GPa以上结晶，其密度低于常压多晶型物α。这种违反直觉的密度关系源于高熵成核和随后的动力学结晶。压力所做的功补偿了高熵和温度乘积，这在不同的构象体和增加的化学势中得到证实。压力增加导致的粘度增加促进了动力学多晶型物的形成，这与经验性的奥斯特瓦尔德阶段规则一致。这与机械化学技术相反，后者有利于高密度多晶型物的形成。
