凝聚液态水溶液中的化学反应

Chemical Reactions in Aqueous Solutions with Condensed Liquid State

液态水是进行化学反应的最重要介质与溶剂之一,也是研究在凝聚(液)态中进行化学反应的主要对象。在不同的外界条件下(特别是极端条件下),液态水的组成、结构与性能会发生很大的变化,促使在其中进行的化学反应呈现不同的特点,因而形成了温和条件下、水热条件下(Hydrothermal condition)与超临界水热条件下(Supercritical water codition)三大类型反应的凝聚态化学。本文立足凝聚态,讨论了在温和(一般)条件下,液态水与水溶液的组成、结构与性能对发生于其中的化学反应(包括溶解与结晶反应、盐类复分解反应、酸碱反应、沉淀反应、成胶与晶化反应、水解反应、氧化-还原反应以及配位化学反应)的影响,包括对反应物存在状态与化学活性,化学反应的过程与机理,反应的中间与最后产物的组成、结构等造成的影响,以及产生的结果与规律等有关的反应化学。通过这些讨论我们提出应从凝聚态的角度看待发生于液态水溶液中的化学反应,并希望这种新视角对研究在其他类型液体(诸如有机溶剂、离子液体、分子熔体等)中进行的化学反应时有所帮助,同时能加强彼此间的交流、讨论与批判,协力为推动以液态为主要研究对象的凝聚态化学的研究与学科建设提供有益的基础。

Liquid water is one of the most important media and solvent for chemical reactions,which is also the main object in scholarly investigation of the chemical reactions occurring in condensed(liquid)matter.The composition,structure,and characteristics of water may vary significantly under different conditions,especially under extreme conditions,which may change both the rates(kinetics)and favorability(thermodynamics)of individual chemical reactions in solution.Thus,the condensed matter chemistry under(normal)mild conditions,hydrothermal conditions,and supercritical water conditions may differ considerably.In this review,we discuss the influences of the composition,structure,and characteristics of liquid water and solution on the chemical reactions within,which includes the state and reactivity of the reactants,processes and mechanisms of reactions,compositions and structures of the intermediate and final products.Examples of these reactions are dissolution and crystallization,double decomposition reaction of salts,acid-base reaction,precipitation,gelation and crystallization,hydrolysis,redox reaction,and coordination reactions.In our discussions,we emphasize that it is essential to consider the chemical reactions occurring in aqueous solutions at the level of condensed matter physical science;and similarly it is also essential to investigate chemical reactions occurring in other types of liquids such as organic solvents,ionic liquids,and molecular substances in molten state.We well understand that this review will result in more in-depth discussions and possibly criticisms about the topics of condensed matter chemistry as well as our perspectives among our peer researchers,which will definitely advance this emerging science in liquids and possibly serve as a base for establishing the new discipline of condensed matter chemistry.