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化学学报
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化学学报 ›› 1993, Vol. 51 ›› Issue (9): 874-879. 上一篇    下一篇

研究论文

稀土(Ⅲ)-冠醚配位作用的热力学性质Ⅱ:臂式15-冠-5和臂式18-冠-6与稀土(Ⅲ)硝酸盐在无水乙腈溶液中配位的量热滴定

刘育;鲁统部;谭民裕;井上佳久;白子忠男   

  1. 中国科学院兰州化学物理研究所;兰州大学化学系;日本姬路工业大学物质科学系;日本姬路工业大学应用化学系
  • 发布日期:1993-09-15

Complexation thermodynamics of rare earth(Ⅲ)-crown ether.Ⅱ.calorimetric of complexation of the arm type 15-crown-5 and arm type 18-crown-6 with rare earth(Ⅲ)nitrates in anhydrous acetonitrile

LIU YU;LU TONGBU;TAN MINYU;JING SHANGJIAJIU;BAI ZIZHONGNAN   

  • Published:1993-09-15

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363

本文用量热滴定研究了N-苄基-单氮杂-15-冠-5与稀土(Ⅲ)硝酸盐(La,Ce,Pa,Nd,Sm,En,Gd,Tb,Dy,Ho,Er,Yb)和N-苄基-单氮杂-18-冠-6与稀土(Ⅲ)硝酸盐(La和Ce)在无水乙腈溶液中,298.15K时配位作用的热力学性质、化学计量法表明,所有稀土硝酸盐均与臂式冠醚形成1:1配合物.实验中,由联接的计算机直接算出了配合物 的稳定常数和配位反应的热焓,进而算出了配位自由能和配位熵.从热力学的观点,讨论了冠醚环的尺寸效应、空间构型等对配位稳定性的影响.

关键词: 热力学性质, 氮杂环化合物, 稳定常数, 冠式化合物, 硝酸盐, 熵, 焓, 空间效应, 稀土化合物, 乙腈

Calorimetric titrns. at 298.15 K in anhydrous acetonitrile were used to determine the stability constants and thermodn. parameters for 1:1 complexes of rare earth (III) nitrates with N-benzyl-monoaza-15-crown-5 and N-benzyl-monoaza-18-crown-6 (the latter with La and Ce only). The stability constants, heats and entropies were calculated from data obtained by precision calorimetry. The effect of the crown ether size, spatial arrangement and other factors influencing the stability of the complexes are discussed.

Key words: THERMODYNAMIC PROPERTIES, NITROGEN HETEROCYCLICS, STABILITY CONSTANT, CROWN ETHER COMPOUNDS, NITRATE, ENTROPY, ENTHALPY, STERIC EFFECT, RARE EARTH COMPOUNDS, ACETONITRILE

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