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机构地区:[1]西北大学化学系,西安710069
出 处:《化学学报》1994年第8期789-796,共8页Acta Chimica Sinica
基 金:陕西省自然科学研究基金资助的项目
摘 要:本文研究了四元体系MCl-GdCl_3-HCl-H_2O(M=K,Rb,Cs;20℃)在不同酸浓度下的溶度,绘制了相应的溶度图,当M=K,HClwt%=14~23%的平行截面时,体系中无化合物形成;当M=Rb,HClwt%=13%时,体系中无化合物形成,但在HClwt%=22的平行截面时,体系中形成固液异组成的化合物RbCl·GdCl_3·4H_2O(1);当M=Cs,在HClwt%分别为13%和20%的条件下,体系均形成4CsCl·GdCl_3·H_2O(2)和2CsCl·GdCl_3·7H_2O(3)两种化合物.2在两种酸浓度下都是固液异组成的化合物,3随酸浓度由低到高的变化,从固液同组成化合物转变为固液异组成化合物.化合物1,2未见文献报道.本文的研究结果为Meyer的合成反应提供了热力学相平衡基础和新的机理解释,并可以更好地应用和指导Meyer合成反应.同时,首次提出了合成RbGd_2Cl_7、Cs_3Gd_2Cl_9两个化合物的可能性.In this paper, the solubilities of saturated solutions of quaternary systems: MCl-GdCl3-HCl-H2O (M = K, Rb, Cs; 20℃) at different acid concentrations have been determined and the corresponding equilibrium diagrams were constructed. When M = K, at the parallel sections of HCl%(wt)= 14- 23, in the system no compounds were formed; when M = Rb, at HC1% (wt)=13, any new phases were not discovered, but at the parallel section of HCl%(wt) = 22, the incongruent soluble compound RbCl · GdCl3 · 4H2O (1) was formed; when M = Cs, at HC1% (wt) = 13 and 20 of saturated solutions, two typical compounds 4CsCl ·GdCl3 · H2O (2) and 2CsCl · GdCl3 · 7H2O (3) were formed. The compound (2) is incongruent soluble compound at the two acid concentrations. When acid concentration was changed from low to high, the compound (3) would change from congruent soluble to incongruent soluble.The compounds 1, 2 and 3 have been also characterized by X-ray diffraction and thermoanalysis. The compounds 1 and 2 have not yet been reported in literatures.
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