单糖酸与生命金属元素的配位行为及其在溶液中相互作用的热化学研究

Precision calorimetry is playing the more important role as an unique research method in solving many scientific problems. This project is proposed so that the relationship between the coordination features and thermodynamic properties will be deeply understood on the basis of the synthesis, structure characterization, and thermodynamic research of the complexes of single sugar acids with life metallic elements. By accurately measuring some thermodynamic properties, such as low-temperature heat capacities, enthalpies of dissolution, and enthalpies of combustion, comparative standard of energy enhancement and evaluation system of thermodynamic properties will be established. By the principle of solution thermodynamics, a new computational formula of activity coefficient will be derived, and a new method using precision adiabatic calorimetry to determine the activity coefficient of the electrolyte solution will be set up by the measurement of low-temperature heat capacities in a wide temperature region and enthalpy of phase transition of the aqueous solution of the complexes. Using the theory and method in statistical thermodynamics, the parameters of crystal structures will be linked with thermodynamic properties of the complexes, the relationship between the structures and properties of the complexes will be investigated from the thermodynamic theory. The regularity of interaction between single sugar acids and metal ions will be revealed. The effect of energy and biology of these complexes as sinsible heat chemical energy storage materials and new food additives will be explored. The relationship between the structural specificity and the performance of sensible heat chemical energy storage and biological activity of the complexes will be clarified. A thermodynamic theoretical basis will be founded for the purpose of application development of new generations of sensible heat chemical energy storage materials and new kinds of food additives.

精密量热法作为一种独特的研究方法在解决诸多科学问题中的作用愈显重要。本项目拟在单糖酸与生命金属元素配合物合成、结构表征和热力学研究的基础上，深入了解它们的配位特征与热力学性质之间的关系。通过准确测量配合物的低温热容、溶解焓和燃烧焓等热力学性质，建立此类物质能量增强的比较标准和热力学性质的评价体系。利用溶液热力学的原理，推导出新的活度系数计算公式，利用精密绝热量热法测量配合物水溶液的宽温区热容和相变焓，建立一种用绝热量热法确定配合物水溶液活度系数的新方法。利用统计热力学的理论和方法，将晶体结构与热力学性质相关联，从理论上研究配合物的结构与性质间的关系，揭示单糖酸根与金属离子相互作用的规律性，探索此类配合物作为显热类储能材料和新型营养添加剂的能量和生物学效应，阐明其结构特异性与储能性能和生物活性间的联系，为新一代无毒、高效、高能和实用的化学储能材料和营养添加剂的应用开发奠定热力学理论基础。

本项目经过四年的潜心研究，我们课题组完成了以下四个方面的研究内容：.1、合成了6个系列的目标配合物，包括葡萄糖酸、丙酮酸、乳酸、苹果酸、富马酸、水杨酸等单糖酸与生命金属元素如碱金属钾、钠、钙、镁、锌、铁等的配合物，共计40余个样品，纯化并培养成单晶。所合成的新颖配合物有各种各样奇特的结合方式和空间结构，用X-射线单晶衍射法确定这些配合物的晶体结构和配位方式。.2、用我们与中国科学院大连化学物理研究所热化学实验室合作研制的精密自动绝热量热法确定这些化合物在78-400 K温区的宽温区摩尔热容、相变行为和标准热力学函数。用溶解-反应和燃烧量热法确定配合物的溶解焓、燃烧焓和标准摩尔生成焓。用Pitzer电解质溶液理论确定配合物的无限稀释摩尔溶解焓、水化焓、相对偏摩尔焓和Pitzer参数，并确定活度系数和渗透系数与温度的关系。用电导测定法测定配合物水溶液的摩尔电导率，确定其在水中的电离常数和无限稀释摩尔电导率。.3、用绝热量热法准确测量配合物稀水溶液的固-液相变温度和相变焓，利用稀溶液热力学理论确定配合物在水溶液中的平均活度系数。.4、用统计热力学和溶液化学的原理和方法，将热力学参数与晶体结构相关联，探索配合物结构与性质间的关系。. 通过本项目的实施，深入揭示了单糖酸根与金属离子相互作用的规律性，建立了用绝热量热法确定稀溶液平均活度系数的新方法，为新型无毒高效营养添加剂的应用开发和相关的理论研究建立热力学理论基础。这些研究成果对于这些物质作为营养添加剂的应用开发和相关的理论研究具有重要的指导作用。