溶剂萃取动力学的研究 Ⅱ.三辛基氧化膦从盐酸体系中萃取铀(Ⅳ)的速率

本文采用上升液滴法,研究了三辛基氧化膦(TOPO)-环己烷溶液从盐酸体系中萃取U(IV)的动力学.按实验结果在一定的盐酸浓度下,TOPO箤取U(IV)的速率可由下述萃取动力学方程式表示:R=K[U(IV)][TOPO]_(0)在[HCl]=3M和15℃时,计算得萃取速率常数K=3.7x10~(-5).在不同盐酸浓度的溶液中,TOPO萃取U(IV)的速率与盐酸浓度的3/2次方成正比.测定了温度(15～45℃)对萃取速率的影响,求得萃取反应的表观活化能为10.8 kcal/mol. 由实验结果推测,TOPO从盐酸体系中萃取U(IV)的反应可能按下列两步进行:UCl_4+TOPO_(0)=UCl_4·TOPO_(0) (1)UCl_4·TOPO_(0)+TOPO_(0)=UCl_4·2TOPO_(0) (2)而生成界面溶剂配合物的反应(1)是萃取速率的控制步骤.     

二甲庚基乙酰胺(N_(503))自盐酸溶液中萃取铟的研究

本工作研究了二甲庚基乙酰胺(N_(503))自盐酸溶液中萃取铟的性能,得出其萃取能力随着酸度的增加而增加。 经斜率法和化学分析法确定,N_(503)自盐酸溶液中萃取铟的反应为: In_(a)~(3+)+H_(a)~++4Cl_(a)~=+nN_(503)(O)?HInCl_4·nN_(503)(O)萃合物中的溶剂化数n随酸度而变化。IR和NMR研究证明,铟是以HInCl_4形式被N_(503)萃入有机相的。在盐酸体系中(HCl<2N),N_(503)对镓、铟、铊的萃取顺序为: Tl(Ⅲ)>Ga(Ⅲ)>In(Ⅲ)     

N,N（二甲庚基）乙酰胺萃钯机理研究

本文研究了N,N二甲庚基乙酰胺(N_(s03))从氯化物体系中萃取钯的机理。应用等摩尔系列法和斜率法确定萃合物组成为:(CH_3CONR_2H)_2PdCl_4。通过紫外-可见光谱法研究,证实N_(503)萃取钯的机理属阴离子交换反应,其萃取方程式为: 2CH_3CONR_2HCl_((o)) PdCl_4~(2-)(a)?(CH_3CONR_2H)_2PdCl_4(o) 2Cl~-(a)     

二甲庚基乙酰胺(N503)自盐酸溶液中萃取铟的研究

本工作研究了二甲庚基乙酰胺(N₅₀₃)自盐酸溶液中萃取铟的性能,得出其萃取能力随着酸度的增加而增加。经斜率法和化学分析法确定,N₅₀₃自盐酸溶液中萃取铟的反应为: 萃合物中的溶剂化数n随酸度而变化。IR和NMR研究证明,铟是以HInCl₄形式被N₅₀₃萃入有机相的。在盐酸体系中(HCl<2N),N₅₀₃对镓、铟、铊的萃取顺序为:Tl(Ⅲ)>Ga(Ⅲ)>In(Ⅲ)     

二已基-N,N-二乙基酰胺甲撑磷酸酯从盐酸介质中萃取钯(Ⅱ)的研究

研究了DHDECMP的二甲苯溶液从盐酸溶液中对钯(Ⅱ)的萃取。钯(Ⅱ)的分配比随水相盐酸浓度和有机相萃取剂浓度的增加而增加。当水相盐酸浓度大于0.5mol·l~(-1)时,萃取平衡可表示为 pd~(2 ) 2H~ 4Cl~- 2DHDECMP-(o)(?)[PdCl_4~(2-)·2H~ DHDECMP]_(o) DHDECMP以及萃取平衡后有机相的红外吸收谱表明,DHDECMP中的P=O基被质子化后与PdCl_4~(2-)缔合成离子对进入有机相而使Pd(Ⅱ)被萃取。     

甲基膦酸二(1-甲基庚基)酯萃取金(Ⅲ)的紫外光谱研究

中性含磷萃取剂萃取贵金属已有报道.Tocher等研究了磷酸三丁酯(TBP)和三辛基氧膦(TOPO)对HAuCl_4和HAuBr_4的萃取,用分配比法测定了萃合物的组成为H_3O~+·3R·yH_2O…AuX_4~-.陈景等研究了TBP和烷基氧膦(TAPO)对铂族金属萃取,发现TBP萃取HIrCl_6时,IrCl_6~(2-)萃取前后的中心离子光谱没有发生变化;萃取H_2PtCl_6时,纯TBP及萃合物红外光谱中P=O的振动频率几乎无改变.由此推断,萃取剂未与被萃离子发生配位作用,而是形成了离子缔合物2(H~+·nTBP·yH_2O)…MCl_6~(2-).可见,这类萃取剂在萃取贵金属时,首     

HPMTFP与1,10—菲罗啉(Phen)等中性萃取剂对Co(Ⅱ)的协同萃取

本文研究了以1-苯基-3-甲基-4-4-三氟乙酰基吡唑啉酮-5(HPMTFP)与1,10菲罗啉(Phen)。三辛基氧磷(TOPO)、三苯基氧磷(Ph_3PO)、三丁基磷酸酯(TBP)和二戊基亚砜(DASO)的氯仿溶液对CO(Ⅱ)的协同萃取.协萃图上发现,HPMTFP与Phen协萃效应显著,与TOPO、Ph_3PO协萃效应较小,而与TBP、DASO基本上无协萃效应.本文由协萃图数据斜率分析和求协萃反应平衡常数的方法,推断萃合物组成为Co(PMTFP)_2·B(B分别为Phen、TOPO、Ph_3PO),求得的各协萃反应的平衡常数如下:Co~(2+)+2HPMTFP_(0)+Phen_(0) Co(PMTFP)_2·Phen_(0)+2H~+ β_(12)=9.57Co~(2+)+2HPMTFP_(0)+TOPO_(0) Co(PMTFP)_2·TOPO_(0)+2H~+ β_(12)=9.56×10~(-3)Co~(2+)+2HPMTFP_(0)+PH_3PO_(0) Co(PMTFP)_2·PH_3PO_(0)+2H~+ β_(12)=5.01×10~(-3)根据模拟萃合物Co(PMTFP)_2·2C_2H_5OH和萃合物Co(PMTFP)_2·Phen的单晶X-射线结构研究结果,讨论了萃合物的结构和产生协萃效应的原因。     

溶剂萃取动力学的研究——Ⅲ.氯化铀酰在盐酸和磷酸三丁酯之间的传质过程

本文采用上升液滴法,研究了氯化铀酰在盐酸介质和磷酸三丁酯(TBP)之间的传质过程.在一定浓度的盐酸溶液中,TBP 萃取铀的速率与[U]和[TBP]_(0)~2成正比;反萃速率与[U]_(0)成正比,而与[TBP]_(0)成反比.在温度为20～40℃范围内分别测定了萃取和反萃反应的活化能,它们的差值与由萃取平衡分配比与温度关系测得的焓变相符.可以认为,萃合物 UO_2Cl_2·2TBP 的生成和离解都是分步进行的,中间产物是 UO_2Cl_2·TBP;萃取速率的控制步骤是 UO_2Cl_2·2TBP 的生成反应,而反萃速率的控制步骤是 UO_2Cl_2·TBP 的离解反应.     

溶剂萃取动力学的研究III. 氯化铀酰在盐酸和磷酸三丁酯之间传质过程

本文采用上升液滴法, 研究了氯化铀酰在盐酸介质和磷酸三丁酯(TBP)之间的传质过程. 在一定浓度的盐酸溶液中, TBP 萃取铀的速率与[U] 成正比; 反萃速率与[U] 成正比, 而与[TBP] 成反比. 在温度为20~40 范围内分别测测定了萃取和反萃反应的活化能, 它们的差值与由萃取平衡分配 温度关胤系测得的焓变相符,可以认为, 萃合物UO2Cl2TBP 的生成和离解都是分步进行的中间 物是CU2Cl2TBP; 萃取速率的控制步骤是UO2Cl22TBP 的生成反应, 而反萃速率     

P_(350)萃取剂泡沫塑料富集及原子吸收光度法测定矿石中微量金

P_(350)(甲基膦酸二仲辛酯)广泛用于稀土元素的萃取分离。本文提出用P_(350)萃取剂泡沫塑料(聚醚型聚氨酯泡沫塑料)从试样溶液中富集微量金。实验证明,P_(350)浓度为10％(苯为稀释剂),水相盐酸浓度为10％,在室温下用约0.2g泡沫塑料为载体,搅拌或振荡萃取10—20min,水相体积为100—1000ml中微量的金均能被定量富     

Separation of uranium(vi) by liquid-solid extraction with tri-n-octylphosphine oxide diluted with naphthalene

Liquid-liquid distribution with tri-n-octylphosphine oxide (TOPO)and molten naphthalene has been investigated for the extraction of 20 metals from nitric acid and hydrochloric acid solutions. Uranium is quantitatively extracted from 1 M nitric acid or hydrochloric acid by using 100 mg of TOPO and 200 mg of naphthalene and shaking for 5 min at 80°C, and separated from transition metals, alkaline earth metals and rare earth metals (except scandium). Addition of naphthalene increases the extraction efficiency.     

Separation of Zr from Hf in acidic chloride solutions by using TOPO and its mixture with other extractants

Liquid–liquid extraction of Zr and Hf from chloride solutions was performed by using TOPO extractant in kerosene. An effective extraction of Zr from Hf was achieved selectively at 2.5–3 M HCl condition. Moreover, a mixture of TOPO with DOS, D2EHPA, Aliquat 336, Alamine 336 and Alamine 308 were tested in order to investigate the extraction behavior of Zr and Hf. The mixture of TOPO and D2EHPA was found to increase the extraction of Zr and Hf. In the extraction by the mixture of TOPO and amine, the extraction percentage of Zr and Hf was decreased with the increase of amine concentration due to the preferential extraction of HCl. Finally, among the mixtures of TOPO and other extractants tested in this study, the TOPO alone system was found to be better for the mutual separation of Zr and Hf in hydrochloric acid media.     

溶剂萃取动力学的研究 II: 三辛基氧化膦从盐酸体系中萃取铀(IV)的速率

The kinetics of the oxtraction of U(IV) chloride in the TOPO-HCl system has been studied using the single drop technique, The effects of the concentrations of U(IV, TOPO and HCl on the extraction rate for U(IV) have been examined. The extraction rate measured were found to be of first order with respect to (U(IV)) and (TOPO) (0). Moreover, the rate varied with (HCl)^3^/^2 between 2-7M hydrochloric acid. The extraction rate equation can be written as R=K(U(IV))(TOPO)(0) The rate constant K was evaluated to be 3.7X10^-^5 at 3M HCl and 15`C. The extraction rate was increased with increasing temperature. The apparent activation energy was found to be 10.8 kcal/mol between 15 to 45`C. It is suggested that the rate-controlling step may be the chemical reaction of UCl4 with TOPO at the interface and the formation of the interfacial complex UCL4.TOPO.     

Ion-exchange thin-layer chromatography of metal lons in organic solvent — Hydrochloric acid — Complexing agent media

Summary Thin-layers of strongly basic or strongly acidic ionexchange resins (Dowex 1 or Dowex 50), mixed with a plain cellulose, Avicel SF, have been used to investigate the chromatographic behaviour of 40 metal ions in acetic acid — hydrochloric acid — complexing agent media. The CIESE (combined ion-exchange-solvent extraction) effect, proposed by Korkisch, is noticed for scandium and thorium in the anion-exchange system involving trioctylphosphine oxide (TOPO) as the complexing agent, the system providing a basis on the specific separation of both elements. In the cation-exchange system involving TOPO, the metal ions are distributed chromatographically, so that the system allows multicomponent separations to be carried out. The system also reveals the CIESE effect for zirconium and hafnium.     

The extraction of divalent cobalt,copper, zinc,and cadmium from hydrochloric acid solutions by tri-n-octyl phosphine oxide

The partitions of divalent cobalt, copper, zinc and cadmium between hydrochloric acid solutions and solutions of tri-n-octyl phosphine oxide (TOPO) in benzene or kerosene have been investigated under different conditions. Further the absorption spectra of both the aqueous and organic phases have been examined, and the infra-red spectra of the organic phases have been studied. As a result, it is found that the order of the extraction efficiency of TOPO for divalent metals is Zn > Cd > Cu > Co at low aqueous acidity; Zn > Cd > Co > Cu at higher acidity. The mechanism of extraction is discussed on the basis of the results obtained.     

Synergistic extraction of uranium(VI) with 1-phenyl-3methyl-4-(2′-chlorobenzoyl)pyrazolone-5 and neutral extractants

The synergistic extractions of uranium(VI) from hydrochloric acid solution and sulfuric acid solution with 1-phenyl-3-methyl-4-(2-chlorobenzoyl)-pyrazolone-5 (PMCBP) together with the neutral extractants: tributyl phosphate(TBP), di-octyl sulfoxide(DOSO) and trioctylphosphine oxide(TOPO) in chloroform have been investigated. A high synergistic extraction effect was found. The formulas of the extracted species have been shown to be UO₂A₂B (where A=PMCBP, B=neutral extractant). The synergistic extraction power increases as follows: PMCBP-TOPO>PMCBP-DOSO>PMCBP-TBP. The equilibrium constants have been calculated. Models for the extraction mechanism are also discussed.     

Solvent extraction and separation of gallium, indium and thallium with N-benzylaniline

A simple and rapid method is proposed for the separation of tervalent gallium, indium and thallium by solvent extraction with N-benzylaniline in chloroform from different concentrations of hydrochloric acid. Thallium and gallium are extracted from 1M and 7.0-7.5M hydrochloric acid respectively. Indium is finally extracted from hydriodic acid. These metals in the final extracts are determined complexometrically. Interference from some cations can easily be eliminated by reduction with sulphite, followed by selective oxidation of thallium(I) to thallium(III) with saturated bromine water, and from others by the use of thioglycollic acid as a masking agent in the extraction of gallium and indium. Most common anions cause no interference. Log-log plots of distribution coefficients vs. concentration of amine for gallium, indium and thallium indicate a 2:1 limiting mole ratio of amine to these metals.     

Photometric determination of gallium with rhodamine b

Gallium is extractable as rhodamine B chlorogallate with benzene from 6M hydrochloric acid, and can be determined absorptiometrically or fluorimetrically in the extract. The interference of iron(III) is avoided by first separating gallium by extraction with isopropyl ether from hydrochloric acid solution containing titanous chloride. Traces of gallium can be determined in the presence of aluminium, indium, zinc, antimony, thallium, tungsten and other elements.     

Extraction-spectrophotometric determination of thallium in high-purity indium

Trace amounts of thallium in high-purity indium are separated from the matrix by extraction from 6M hydrochloric acid by di-isopropyl ether. On shaking the extract with Brilliant Green in 0.15M hydrochloric acid, an ion-association complex is formed in the organic phase. Interference of other elements is removed by their reduction with metallic copper and scrubbing. The proposed method permits determination of 10(-5)-10(-6)% thallium in high-purity indium with good precision and accuracy.