铀的离子交换反应——Ⅱ.硫酸和盐酸介质中铀(Ⅵ)在阳离子交换树脂上的化学状态
ION EXCHANGE OF URANIUM Ⅱ. URANYL SPECIES SORBED ON CATION EXCHANGER FROM SULFURIC AND HYDROCHLORIC ACID
-
摘要: 本文用红外光谱法和当量计算法研究了在硫酸、盐酸介质中铀(Ⅵ)在阳离子交换树脂上的化学状态及其含量。结果表明,在阳离子交换树脂上,铀(Ⅵ)除了以UO_2~(2+)外,还可以(UO_2HSO_4)~+和(UO_2Cl)~+存在,但当酸的浓度低于 0.5N时,其量可忽略不计。即使在酸浓度相当大(2—3N)时,(UO_2HSO_4)~+和(UO_2Cl)~+也只占树脂交换容量的很小一部分。因此,在通常用的阳离子交换色层法富集铀同位素的工作中,可以按照阳离子交换树脂上只有 UO_2~(2+)来考虑同位素效应及计算分离因数。Abstract: Uranyl species sorbed on cation exchanger from H2SO4 and HCl solution are thoroughly studied by IR spectra and equivalent accounting. The spectra are recorded with DIGILAB FTS-15C infrared spectrometer. The assymetric stretch, v3 of the uranyl group is infrared active. UO2 2+ and (UO2HSO4)+ from H2SO4 solution and UO2 2+ and (UO2Cl)+ from HC1 solution are found to be sorbed on the cation resin. The species sorbed on cation exchanger shows only a single band at 945.3cm-1. or 949.2cm-1 when the equilibrium is carried out in the solution with very low concentration of H2SO4 or HC1 respectively. The species should be UO2 2+. However, a new band at 902.9cm-1 or 906.6 cm-1 is found when the equilibrium is carried out in the solution with high concentration of H2SO4 or HC1 respectively. With increasing the acidity of the equilibrium solution the gradual increase of intensity of the new band and the gradual decrease of intensity of the original one can be observed. As a cation exchanger selectively sorbs cation, the species now sorbed should be either (UO2HSO4)+ or (UO2Cl)+. But the amount of (UO2HSO4)+ or (UO2Cl)+ on the cation exchanger can be ignored with a concentration of acids less than 0.5 N, The equivalent accounting method is applied to the resin loaded with uranyl ion and hydrogen ion, together with cation uranyl complex species, under the conditions of negligible invasion of uarnyl species. A known amount of resin in hydrogen form is equilibrated in a batch process with a solution containing uranyl and sulfuric acid(or hydrochloric acid) at various ratios. It is found experimentally that the amount of (UO2HSO4)+ or (UO2Cl)+ sorbed on exchanger is so low that they can not be observed by the method within experimental errors.It may be concluded that the (UO2HSO4)+ or (UO2 Cl)+ sorbed on cation exchanger can be overlooked under the general conditions of the experiment.
-
-
[1] 44, 761 (1975) . [2] T. M. Florence, G. E. Batley et al., J. Inorg. Nucl. Chem., 37, 1961 (1975) . [3] H. Kakihana, Maso Aido, Bull. Tokyo Inst. Technol., 116, 39 (1973) . [4] 22, 473 (1980) . [5] H. Bist et al., Indian J. Pure Appl. Phys, 2, 107 (1964) . [6] C, Heitner-Wirguin et al.. J. Inorg. Nucl, Chem., 35, 3341 (1973) . [7] C. Heitner-Wirguin et al., Isr. J. Chem., 12, 723 (1974) . [8] 陶祖贻等,科学通报,19,1168(1981) . [9] C. Heitner-Wirguin et al., J. Phys. Chem., 71, 2556 (1967) . [10] S. K. Sarpal et al., Indian J. Chem., 16A, 55 (1978) . [11] S. P. McGlynn et al., J. Chem. Phys., 35, 105 (1961) . [12] A. N. Richard et al., Infrared Spectra of Inorganic Compound, Academic Press, New York and London, 1971, p. 145, p. 245． [13] Kazuo Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, 3rd. ed., John Wiley & Sons, New York, 1978, pp. 3-67． [14] C. Heitner-Wirguin, Ion Exchange and Solvent Extraction, Vol. 7, New York, 1977, pp. 116-152． [15] 48, 1448 (1979) . [16] 22, 534 (1980) . [17] 44, 577 (1970) . [18] Y. Marcus et al., Ion Exchange and Solvent Extraction of Metal Complexes, Wiley-Interscience, London, 1969, pp. 323-326． [19] Lars G. Sillen et al., Stability Constants of Metal Complexes, 2rd, ed., London, 1964, p. 239, p. 278． [20] T. F. Young et al., The Structure of Electrolytic Solution, N. Y., Wiley, 1959, p. 35． [21] O. O. Bonner et al., J. Phys. Chem., 61, 326 (1957) .
计量
- 文章访问数: 607
- HTML全文浏览量: 0
- PDF下载量: 1162
下载:
