高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (8): 1537.

• 研究论文 • 上一篇    下一篇

Et2NH2[Nd(S2CNEt2)4]的晶体结构和生成反应焓变

高胜利, 陈三平, 任宜霞, 焦宝娟, 谢钢, 史启祯   

  1. 陕西省物理无机化学重点实验室, 西北大学化学系, 西安710069
  • 收稿日期:2003-07-03 出版日期:2004-08-24 发布日期:2004-08-24
  • 基金资助:

    国家自然科学基金(批准号:20171036);陕西省自然科学基金(批准号:01H08)资助

Crystal Structure and Enthalpy Change of Formation Reaction for Et2NH2[Nd(S2CNEt2)4]

GAO Sheng-Li, CHEN San-Ping, REN Yi-Xia, JIAO Bao-Juan, XIE Gang, SHI Qi-Zhen   

  1. Shaanxi Key Laboratory of Physic-Inorganic Chemistry, Department of Chemistry, Northwest University, Xi′an 710069, China
  • Received:2003-07-03 Online:2004-08-24 Published:2004-08-24

摘要: 在干燥氮气气氛下,以无水乙醇为溶剂,制备了低水合氯化钕与二乙氨基荒酸二乙铵(D-DDC)配合物,确定其组成为Et2NH2[Nd(S2CNEt2)4].单晶结构分析表明,配合物中4个二乙氨基荒酸根各通过2个硫原子与钕离子成键形成八配位十二面体阴离子,并与二乙铵阳离子形成缔合型分子.晶体属单斜晶系,空间群P21/n,a=1.37517(14)nm,b=2.1146(2)nm,c=1.44641(15)nm,β=102.028(2)°,Z=4.用微量热法测定了298.15K下水合氯化钕和D-DDC在无水乙醇中的溶解焓及二乙氨基荒酸钕液相生成反应焓变分别为(-17.89±0.096),(50.280±0.151)和(-10.116±0.065)kJ/mol,求得固相生成反应焓变.

关键词: 水合氯化钕, 二乙氨基荒酸二乙铵(D-DDC), 晶体结构, 微量热法, 热化学

Abstract: The solid complex of neodymium chloride hydrate with diethylammonium diethyldithiocarbamate(D-DDC) Et2NH2[Nd(S2CNEt2)4] was synthesized in dry N 2 atmosphere and absolute alcohol. The composition of the complex was determined by chemical and elemental analyses. The crystal structure showed that Nd 3+ was coordinated by eight sulfur atoms with four ligands. The coordination polyhedron can be described as a distorted dodecahedron. It crystallizes in a monoclinic system,space group P2 1/n with a=1.375 17(14) nm, b=2.114 6(2) nm, c=1.446 41(15) nm, β =102.028(2)°, Z=4. The enthalpies of solution of neodymium chloride hydrate and D-DDC in absolute alcohol at 298.15 K and the enthalpy change of liquid-phase reaction of formation for complex Et2NH2[Nd(S2CNEt2)4] was determined by a microcalorimeter as(-17.89±0.096),(50.280± 0.151 ) and (-10.116±0.065) kJ/mol, respectively. The enthalpy change of the solid-phase reaction of formation was obtained through a thermochemical cycle.

Key words: Neodymium chloride hydrate, Diethylammonium diethyldithiocarbamate(D-DDC), Crystal structure, Microcalorimetric method, Thermochemistry

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