Citation:
Xiaoming Wang, Huan Jiao, Xiping Jing. “非整比化合物”概念辨析[J]. University Chemistry,
;2022, 37(11): 211207.
doi:
10.3866/PKU.DXHX202112078
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“非整比化合物”是固体化学和材料化学等学科领域普遍接受的概念。然而,在文献中这个概念的含义是含混的。本文通过对一些实例的组成分析,廓清了晶格缺陷、固溶体及“非整比化合物”之间的关系。通过结构分析,阐明了“道尔顿体”和“柏托雷体”的区别及“柏托雷体”与其虚拟母体化合物的关系。在此基础上对“非整比化合物”的概念给予较为全面的说明。在一定的条件下,晶态无机物质(包括金属和化合物)的晶格中可以形成高浓度(用常规化学方法可定量检测)缺陷的状态,缺陷的主要种类有空位、填隙、取代和变价等。这种含有高浓度缺陷的物质可以用固溶体的形式表示其组成。在相图中,对于母体化合物组成处于固溶区边界的固溶体其母体称为“道尔顿体”,固溶体称为“道尔顿固溶体”;而母体组成不处于固溶体边界的固溶体称为“柏托雷体”,其母体可以看成是组成处在固溶体区域外某个组成的“虚化合物”。由于其组成可变,且各元素原子个数比偏离简单整数比,广义的“非整比化合物”包含“道尔顿固溶体”和“柏托雷体”。由于不存在真实的母体化合物,狭义的“非整比化合物”仅指“柏托雷体”。
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