冠醚-1,2-二氯乙烷在苦味酸体系中对轻希土元素的萃取

本文在文献[1]的基础上,研究了二环己基-18-冠-6(DC18C6)和二环己基-15-冠-5(DC15C5)在苦味酸体系中对La~(3+),Ce~(3+),Pr~(3+),Nd~(3+),Sm~(3+),Eu~(3+),Gd~(3+)七个轻希土元素的萃取,求得了萃合常数和萃合物在有机相中的离解常数,并测定了苦味酸在水相对七个希土元素的一级络合常数。     

冠醚萃取钍(Ⅳ)的化学平衡及其萃合物的红外光谱

本文研究了数种冠醚的1,2-二氯乙烷溶液从硝酸、盐酸和苦味酸等水溶液中萃取钍的行为。在硝酸介质中,钍与二环己基-18-冠-6(DC18C6)或二环己基-24-冠-8(DC24C8)形成了萃合物Th(NO_3)_4·2L·HNO_3(L为冠醚)。其相应的萃取平衡常数(25℃)经测定分别为:K_(DC18C6)=3.98和K_(DC24C8)=6.30。 测定了萃合物Th(NO_3)_4·2DC18C6·HNO_3和Th(NO_3)_4·2DC24C8·HNO_3的红外光谱。差示光谱的特征吸收峰表明,金属离子和冠醚环上氧配位原子之间可能存在直接的键合,以及萃合物中NO_3根参与配位。     

二环己基-18-冠-6萃取铀、钚和镅的研究

本文叙述了溶剂种类、酸度和冠醚浓度诸因素对二环己基18冠6(DCH 18 C 6)萃取铀、钚等元素的影响,着重研究了常量铀的萃取行为。结果表明,1,1,2—三氯乙烷作溶剂时,DCH18 C 6对微量铀或常量铀均能萃取。在硝酸体系形成的萃合物中,Pu(Ⅳ)和U(Ⅵ)与二环己基18冠6的分子比分别为2和1。DCH 18 C 6-1,1,2—三氯乙烷能够从含有U(Ⅵ)和U(Ⅳ)的3—5 M HCl溶液中单独萃取U(Ⅵ)而不萃取U(Ⅳ)。     

二环己基-18-冠-6对锶的萃取

为了解二环己基-18-冠-6(DCH18C6)在酸性介质中对锶的萃取行为,考察了DCH18C6的浓度、不同酸介质、不同稀释剂、硝酸浓度对锶分配比的影响.结果表明,该萃取体系在硝酸介质中能够有效的萃取锶,当DCH18C6浓度为0.1 mol/L时,萃取率高于92%,用去离子水反萃时,反萃率可达100%.采用双对数斜率法确定了DCH18C6萃取锶的萃合物组成,当c(DCH18C6)＜8 mmol/L时,DCH18C6同锶萃合物的组成为1∶2应占主要份额.当c(DCH18C6)≥8 mmol/L时,此时DCH18C6同锶萃合物的组成为1∶1应占主要份额.     

冠醚萃取氯化铀酰的研究

研究了五种冠醚的1,2-二氯乙烷溶液从盐酸水溶液中萃取铀(VI)的行为。实验表明,铀(VI)分配比与水相盐酸浓度、LiCl浓度、有机相冠醚浓度有关。用斜率法和等摩尔系列法确定了18-冠-6、二苯并-18-冠-6、二苯并-24-冠-8、二环己基-18-冠-6、二环己基-24-冠-8与铀(VI)萃合物的组成比,并求得它们的萃取平衡常数。     

二环己基-18-冠-6对镎(Ⅳ)的萃取

本文研究了硝酸体系中十种不同结构的冠醚在不同硝酸浓度下对镎(Ⅳ)的萃取,实验结果表明,镎(Ⅳ)的萃取与有机相中萃合物的形式、多醚环上取代基的结构以及水相硝酸浓度等因素有很大关系,其中以二环已基-18-冠-6为最好。 研究了11种稀释剂并观察了分配比与介电常数之间的关系,最后选择强极性溶剂1,2-二氯乙烷为稀释剂。在1,2-二氯乙烷-7.5M HNO_3 条件下,初步实验结果表明络合物的组成为1:1。同时测定了其它金属离子的分配比,并计算了相应的分离系数。     

二苯并-18-冠-6从盐酸溶液中萃取铀(Ⅳ)和铀(Ⅵ)

二苯并-18-冠-6-硝基苯,从高浓度的盐酸或氯化物溶液中,能有效地萃取铀(Ⅳ)和铀(Ⅵ)。不同碱金属阳离子对萃取的影响,符合冠醚与阳离子络合作用的顺序:K~ >Na~ >Li~ ,少量钾离子的引入能显著提高对铀的萃取效果。通过对有机相中铀性质的研究和固体萃合物的成份分析,指出在被萃取的离子对中铀(Ⅳ)和铀(Ⅵ)是以氯络阴离子[UCl_6]~(2-)、[UO_2Cl_4)~(2-)的形式存在。采用饱和萃取法和等克分子系列法,确定了在盐酸体系中萃合物的组成为:H_2UCl_6·2DBC、H_2UO_2Cl_4·2DBC。当有与冠醚络合作用强的阳离子存在时,萃合物中的氢将被该阳离子所取代。     

硝酸介质中二环己基18-冠-6对锶的萃取

利用冠醚二环己基-18-冠-6（DCH18C6）作为萃取剂在硝酸介质中对锶的萃取性能进行了系统研究,考察了稀释剂、硝酸浓度、振荡时间、温度对锶萃取的影响,结果表明,该萃取体系与硝酸的浓度有关,当萃取剂浓度为0.01mol/L,以1,1,2,2-四氯乙烷为稀释剂,硝酸浓度为1mol/L时,锶的萃取率可高达92%左右,利用纯水作为反萃剂,反萃率可达(99.56±1.7)%左右。该萃取反应动力学比较快,可在10min 达到平衡,热力学实验表明该萃取反应是一个放热反应。同时选择性萃取实验结果表明,冠醚二环己基-18-冠-6能有效地从多种离子共存的体系中选择性地萃取锶。     

冠醚萃取同位素砹-211

为深入了解砹的化学性质,探索用冠醚作相转移催化剂来标记砹的化合物的可能性,采用冠醚二环己基-18-冠-6(DC18C6)于各种溶液中进行砹的萃取研究。 盐酸浓度变化显著影响DC18C6对~(211)At的萃取。随HCl浓度增加,萃取率急剧上升,在2mol·l~(-1)HCl时,萃取率可达99％。而用异丙醚萃取At需在8mol·l~(-1)HCl下进行,在2mol·l~(-1)     

冠醚萃取法从高放废液中去除锶

报道了用二环己基18冠6(DC18C6)-正辛醇萃取法从模拟高放废液中去除锶的研究。系统地研究了DC18C6-正辛醇对Sr~(2 )以及废液中其它阳离子 Na~ ,K~ ,Cs~ ,Ni~ ,Fe~ ,Al~(3 ),Cr~(3 ),Mo~(6 )的萃取性能。结果表明,DC18C6对Sr~(2 )有着良好的萃取选择性,除K~ 和Mo~(6 )等个别离子可被DC18C6部分萃取外,其它阳离子几乎都不被萃取。其中Al~(3 )和Fe~(3 )对Sr~(2 )的萃取起盐析作用;Na~ 在低酸时也起盐析作用,但在高酸时则起着竞争作用。在上述研究的基础上,建立了用DC18C6-正辛醇从高放浓缩液中去除锶的工艺流程,并进行了模拟料液的串级实验。经过3级萃取,1级洗涤,4级反萃后,锶的去除率接近99％,产品中锶的重量百分比为76％(原始料液中为0.6％)。该流程具有简单、高去除率、高选择性等优点,适用于从我国高放浓缩液中去除或回收锶。     

Influence of Gamma-Irradiation on Extraction and Cation-Transport of Uranium(VI) and Plutonium(IV) by Dicyclohexano-18-Crown-6

Changes of the extraction behaviour and cation-transport of U (VI) and Pu (IV) nitrates with r-irradiated DC18C6 in toluene have been investigated. The effect of radiation damage to DC18C6 for extraction and permeation at excessively higher doses (70 Mrads) has been studied systematically. No deterioration in its performance is noted at lower doses. Hydrolytic stability of the macrocycle/diluent system in the presence of nitric acid and radiolytic stability of immobilized liquid membrane using ‘Enka’ Accurel flat sheet polypropylene membrane films as solid support are also examined.     

Calibration of new I&C at VR-1 training reactor

The paper describes a calibration of the new instrumentation and control (I&C) at the VR-1 training reactor in Prague. The I&C uses uncompensated fission chambers for the power measurement that operate in a pulse or a DC current and a Campbell regime, according to the reactor power. The pulse regime uses discrimination for the avoidance of gamma and noise influence of the measurement. The DC current regime employs a logarithmic amplifier to cover the whole reactor DC current power range with only one electronic circuit. The system computer calculates the real power from the logarithmic data. The Campbell regime is based on evaluation of the root mean square (RMS) value of the neutron noise. The calculated power from Campbell range is based on the square value of the RMS neutron noise data. All data for the power calculation are stored in computer flash memories. To set proper data there, it was necessary to carry out the calibration of the I&C. At first, the proper discrimination value was found while examining the spectrum of the neutron signal from the chamber. The constants for the DC current and Campbell calculations were determined from an independent reactor power measurement. The independent power measuring system that was used for the calibration was accomplished by a compensated current chamber with an electrometer. The calculated calibration constants were stored in the computer flash memories, and the calibrated system was again successfully compared with the independent power measuring system. Finally, proper gamma discrimination of the Campbell system was carefully checked.     

HNO3-H2C2O4体系中Np和Pu的分离研究

研究了30％TBP-煤油在不同的硝酸-草酸混合溶液中对Np,Pu各价态的萃取分配,在HNO     

Gamma-ray irradiation impact of humic substances on apparent formation constants with Cu(II)

Aqueous solution samples of humic acid and fulvic acid were irradiated with gamma-rays in the dose range of 0–500 kGy at two dose rates, 0.1 and 1 kGy/h. The brownish solutions discolored with 500 kGy irradiation indicating degradation by radiolysis, and the index of degree of humification (as the absorbance ratio at 400 nm and 600 nm) was studied using UV-Visible spectroscopy. Apparent formation constants of Cu(II) with humic substances (HSs) in 0.1 M NaClO₄ were determined at 298 K by potentiometric titration using Cu ion selective electrode (ISE), and the effect of gamma irradiation on the constants is herein discussed. To calculate formation constants, the acid dissociation constants of HSs were also measured by potentiometric titration and used as the degree of dissociation. Though the concentration of carboxylic groups decreased drastically with high radiation exposure, no significant change in apparent formation constants was found.     

Hydrogen Isotope Separation by Self-displacement Chromatography Using Palladium Particles

Formation constants of a trivalent f-element, europium, with a series of carboxylates containing neutral donors such as amine and alcohol oxygen were determined by solvent extraction method in 0.1 M NaClO₄ at 25°C. Thirteen carboxylates were adopted for a systematic study of the effect of the functional groups on the complex stabilization. In order to analyze the trend of formation constants, a simple model was developed in which these ligand molecules were considered as composed of a certain number of fragment components of functional groups and chemical bridges each of which differently contributes to the formation constant. All parameter values for electrostatic and steric effects of the fragments were successfully determined by using the formation constants obtained experimentally. The present model is useful for predicting the formation constants of similar multidentate ligands by combining the fragment components and parameter values.     

Strontium Isotope Effect in Liquid-Liquid Extraction of Strontium Chloride Using a Crown Ether

Isotope effects in a liquid-liquid extraction of strontium with dicyclohexano-18-crown-6 (DC18C6) were investigated. Unit mass enrichment factors were observed to increase with concentrations of strontium salt in an aqueous phase. Isotope distinguishing ability of DC18C6 to strontium isotopes was calculated as an intrinsic separation factor to be K _c =1.00051±0.00004. An odd mass number isotope, ⁸⁷Sr, was recognized to behave differently from even mass number isotopes, ⁸⁴Sr, ⁸⁶Sr and ⁸⁸Sr. The enrichment factor induced by a nuclear property (odd or even mass number) other than the mass difference was ε_O/E = ?8.0 × 10^?4 which was observed with 3.2M Sr aqueous solution. Isotope shift of energy state for 5S-orbital of strontium produces the isotope shift in vibrational energy between the strontium ion and the DC18C6.     

冠醚溶剂萃取碱金属

用大环多醚溶剂萃取碱金属和碱土金属阳离子已有不少报道。大环多醚与碱金属的阳离子能形成稳定的络合物。在这类络合物中,金属阳离子处于多醚环孔穴的中心,依靠离子-偶极静电作用相互结合。被络合的阳离子的直径和多醚环孔径的吻合程度是影响络合物稳定性的主要因素。通过多醚对碱金属和碱土金属萃取行为的研究,得出萃取平衡常数与金     

用三烷基(C_6-C_8)氧磷(TRPO)从强放废液中萃取锕系、镧系元素的研究

本文研究了三烷基(C_6-C_8)氧膦(TRPO)对锕系、镧系元素及裂变产物的萃取行为;测得了铀、镎、钚、镅、锔等20余种离子在30％TRPO-煤油-硝酸溶液中的分配比以及部分离子的被萃络合物形式;测定了稀释剂、萃取剂浓度、温度、盐析剂等因素对TRPO萃取三价锕系和镧系元素的影响,为用TRPO萃取剂从强放废液中提取有用元素提供了基础数据。