化学学报 ›› 1983, Vol. 41 ›› Issue (2): 117-127. 上一篇    下一篇

研究论文

Cr^3^+的水解聚合作用IV.两种"根+节"体系之间的过渡状态

罗勤慧;任建国;沈孟长;戴安邦   

  1. 南京大学配位化学研究所
  • 发布日期:1983-02-15

Studies on the hydrolytic polymerization of chromium (III) ion IV: The transition between two types of "core plus links" compounds.

LUO QINHUI;REN JIANGUO;SHEN MENGCHANG;DAI ANBANG   

  • Published:1983-02-15

关键词: 水解, 硝酸盐, 铬离子, 聚合, 铬化合物

The hydrolytic polymerization of chromium (III) ion in 0.040, 0.060, 0.080 and 0.160M Cr(NO3)3 solutions was studied pH-metrically in the medium of 0.5M NaNO3 at 40+/-1 C. The average number of OH- bound per Cr^3^+ at different pH was designated as Z, the gighest value of Z was found to be about 1.0. A family of curves of Z(pH)B, each at a definite concentration B of Cr(NO3)3, was obtained. The values of both B and pH were determined from the curves and a linear relationship between -lgB and pH was found for each value of Z. From the slope of each curve of-lgB(pH)z, a value of t was obtained, which increased from 1.51 to 2.06 when Z increased from 0.10 to 1.0. This implied that the polymerized hudrolysis products were of mixed types. The data of different Z value were treated by three different methods, namely, "core + links" method, project strip method and "homoligand formation constant" method. The results obtained showed the existence of "core + links" compounds not only with two hydroxyl bridges as Cr (Cr(OH)2)n^(^3^+^n^)^+(n = 1,2,3) but also with both one and two hydroxy bridges as Cr3(OH)3, indicating that the present system was a transition from t = 2 to t = 1. The hydrolysis constants of the above compounds are as follows: lgβ = -4.19, lgβ33 = -5.28, lgβ = -8.23, lgβ64 = 12.28. The above results are in agreement with those obtained at low and medium concentration of Cr(NO3)3. Furthermore, the constants obtained by means of different methods are in good agreement with each other as well as with those reported in previous papers.

Key words: HYDROLYSIS, NITRATE, CHROMIUM ION, POLYMERIZATION, CHROMIUM COMPOUNDS

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