烷氧基取代金属酞菁的合成和在有机溶液中聚集性质的研究

酞菁化合物的结构与卟啉类似,对光和热稳定性好,在可见光区有强的吸收,而且它还具有半导体性能和光生伏打效应。因此作为光导材料,信息记录和储存材料,以及在模拟光合作用研究光敏电子转移反应中作为光敏剂。引起人们广泛的兴趣。一般水溶性酞菁在水溶液中容易形成聚集体。聚集体与单体的性质有很大差别。因此了解酞菁     

SOLVENT EXTRACTION OF URANIUM(VI) AND THORIUM(IV) WITH A TETRA-CARBOXYLATED CALIX[4]ARENE AND EFFECT OF ALKALI IONS (Na+, K+)

ABSTRACT

The solvent extraction of uranium(VI) and thorium(IV) with a tetra-carboxylated calix[4]arene (LH₄) in chloroform has been studied in the presence or absence of alkali ions (M⁺=Na⁺, K⁺). When studied alone, UO₂ ²⁺ and Th⁴⁺ were extracted into chloroform as 2:2 and 1:1 metal:ligand complexes, respectively. The efficiency of extraction increases in the presence of alkali ions, due to the formation of heteronuclear complexes. For uranium(VI), the extracted species are found to be both 2:2:2 and 1:1:1 (uoi₂ ²⁺:M⁺:LH₄,) mixed complexes. For Th(IV) in the presence of Na⁺, the formation of a mixed complex in 1:1:1 (Th(IV):Na⁺:LH₄,) proportions has been evidenced. However, the exact nature of this species could not be determined. In practical grounds, LH. may be useful as a selective extracting agent for Th(IV) with respect to U(VI) since separation factor Th(IV)/U(VI) close to 1000 have been measured in competitive extraction, in the presence or absence of alkali ions.     

INTERFACIAL ACTIVITY OF HDEHP AND KINETICS OF NICKEL EXTRACTION IN VARIOUS DILUENTS

ABSTRACT

The interfacial behavior of HDEHP at various diluents/0.05M (H₂,Na₂)SO₄ interfaces was examined using the Drop Volume Method. Different adsorption isotherms such as the Gibbs and Szyszkowski were found as fits well to the experimental interfacial tension isotherms. The values of surface excess at saturated interface,calculated according to them by using the concentration of individual species (e.g. organic monomeric species),increase in the order: MIBK<chloroform <benzene～toluene～xylene<CCl₄ <n-hexane～n-heptane

The interfacial activity data were used to discuss the mechanism and kinetics of nickel extraction. It was shown that the interfacial mechanism is very probable and the extraction limiting step is the reaction between HDEHP molecules present near the interface and the intermediate 1:2 complex just as following

Ni(H₂O) ₄A_2(int,0) +2H₂A_2(int,0) =Ni(H₂O) ₂A₂˙2H₂A_2(int,0) +2H₂O_(int,0)

The investigation of the influence of diluent on the extraction rate supports the mechanism suggested.     

SURVEYING THE EXTRACTION OF CESIUM NITRATE BY 1,3-ALTERNATECALIX[4]ARENE CROWN-6 ETHERS IN 1,2-DICHLOROETHANE

ABSTRACT

The extraction of cesium nitrate from a mixture of alkali metal nitrates by calix7lsqb;4]arene crown-6 ethers in 1,2-dichloroethane diluent has been surveyed at 25 °C. The results reveal that smaller substituents (but larger than C₂,) at the phenolic positions of the calixarene opposite the crown ether increase both the extraction efficiency and the cesium selectivity. Benzo substituents on the crown ether tend to decrease extraction strength while increasing cesium-to-sodium selectivity. Conversely, a cyclohexano group on the crown ether has a negative impact on both extraction strength and selectivity.     

SOLUBILITY AND DIFFUSIVITY OF GASES IN AN ORGANIC SOLUTION OF AMINE

Solubilities and diffusivities of carbon dioxide and nitrous oxide in a mixture of toluene and isopropanol organic solution of cyclohexylamine were measured at 20°C in the range of pressures of solute from 1 to 3 bars. This was performed with an original chromatographic technique taking into account the presence of the product of the reaction.     

蒽和咔唑在有机溶液中溶解度的研究

利用液 -固相平衡装置 ,测定了蒽和咔唑分别在 DMF、吡啶、苯和甲苯中的溶解度并作出溶解度曲线 .发现 DMF对蒽和咔唑的分离具有很好的效果 ,对工业上应用有重大意义 .测温误差为 0 .0 5 K,还从理论上对溶解度进行了探讨     

SOLUBILITY AND DIFFUSIVITY OF GASES IN AN ORGANIC SOLUTION OF AMINE

Solubilities and diffusivities of carbon dioxide and nitrous oxide in a mixture of toluene and isopropanol organic solution of cyclohexylamine were measured at 20°C in the range of pressures of solute from 1 to 3 bars. This was performed with an original chromatographic technique taking into account the presence of the product of the reaction.     

三辛胺萃取草酸的第3相特性

以三辛胺（TOA）萃取草酸时出现第3相的基本规律为研究对象,实验测定了无水溶剂及液液萃取平衡有机相中草酸的溶解度及其随TOA和正辛醇浓度的变化规律.结果显示,正辛醇对草酸及其与TOA形成的缔合物在溶剂中的溶解度影响显著;随正辛醇含量的增加,草酸及其缔合物在溶剂中的溶解度提高,因而溶剂对草酸的萃取能力随之增大;在TOA与草酸以1∶1的化学计量比饱和后,草酸溶解度出现阶跃现象,这与形成草酸二聚体的缔合物有关;相比之下,液液萃取平衡实验中有机相对草酸的溶解度大于无水溶剂的结果,溶剂中水的存在有助于缔合物溶解.同时建立了描述液液萃取平衡有机相中草酸及其缔合物溶解度的数学模型,并通过参数寻优求得了相应的模型参数.     

REMOVAL OF NITRIC ACID FROM CONCENTRATED PHOSPHORIC ACID BY EXTRACTION WITH METHYL ISOBUTYL KETONE IN AROMATIC DILUENTS

The extraction of nitric acid from concentrated phosphoric acid solutions by methyl isobutyl ketone (MIBK) dissolved in aromatic diluent has been studied. Nitric acid can be effectively removed by MIBK from the solutions containing 50–75% H₃P0₄. With increasing the concentration of either H₃PO₄ or MIBK, the distribution coefficient of HN0₃ increases but the separation factor for HN0₃ against H₃PO₄ decreases. However, it is possible to achieve a complete removal of HN0₃ in a few of stages and the coextraction of H₃PO₄ can be limited to less than 1%.     

不同煤阶煤的CS2-NMP萃取率及与煤性质的关联

对6种不同变质程度煤(包括气煤、弱黏煤、肥煤、焦煤和瘦煤)常温常压下用CS2-NMP混合溶剂进行了萃取实验.结果表明,挥发分(Vdaf)为35%左右的煤具有最高的萃取率,达到43.05%,不同煤阶煤的萃取率与其奥压膨胀度及塑性温度区间近似呈线性关系.通过对原煤、萃取残渣和生成焦粒的红外对比分析表明,不同变质程度煤经过萃取后,残渣中脂肪烃和脂环烃含量有所减少,矿物质大都在残渣中,氢键缔合峰的强弱随不同煤种表现不同,肥煤和气煤氢键缔合的极性键都位于煤中的大分子上,而焦煤和弱黏煤中的极性键大都在小分子化合物上.     

不同烧结助剂制备的Si_3N_4陶瓷的氧化行为

以α-Si3N4粉末为原料,分别以Y2O3-La2O3和Y2O3-CeO2为烧结助剂,利用热压烧结法制备了Si3N4陶瓷。研究了Si3N4陶瓷样品在空气中高温下的氧化行为。结果表明:原始的α-Si3N4在烧结过程中完全转化为β-Si3N4。在1000～1350℃氧化100h后,用Y2O3-La2O3烧结助剂制备的样品表现为质量增加趋势,质量变化小于0.389mg/cm2,其氧化过程符合抛物线规律。用Y2O3-CeO2烧结助剂制备的样品,在1000℃氧化后表现为质量减小,为-0.248mg/cm2;在1230℃和1350℃表现为质量增加,分别为0.024mg/cm2和0.219mg/cm2,并且其氧化过程不符合抛物线规律。样品的氧化过程主要受2个扩散过程的控制,即稀土元素的向外扩散与氧的向内扩散。     

VARIATIONS IN THE SOLVENT EXTRACTION BEHAVIOR OF BIFONCTIONAL PHOSPHORUS-BASED COMPOUNDS MODIFIED WITH TBP

ABSTRACT

The solvent extraction of americium from nitric acid by several modified bifunctional extractants in CCl₄has been investigated. For all the compounds examined, addition of a modifier such as tributylphosphate (TBP) enhances distribution ratios at high aqueous acidities. The effect of the modifier at lower acidities varies depending on the basicity of the bifunctional extractant. While the most basic extractants show significantly reduced distribution ratios from lower acid solutions upon TBP addition, for the less basic compounds only slight reductions or, in some cases, even moderate increases in extraction are observed. Studies of the effect of modifier basicity on extraction behavior have also been carried out. The changes in distribution ratios with modifiers fall within the range of variations observed for diluent effects with extractants of this type. Increases in high acid distribution ratios upon TBP addition to an extractant as simple as trioctylphosphine oxide indicate that this modification of extraction behavior may be of general use for a wide range of neutral extractants     

超声波和微波辐射下萃取煤的有机硫形态分析

用超声波和微波辐射法在四氯乙烯体系下,采用气相色谱／质谱仪对北京煤、王庄煤、兖州煤和临汾煤进行了萃取液分析．结果表明,不同煤样在超声波作用下的脱硫效果不同,不同煤样四氯乙烯萃取物中分别含有苯并噻唑、苯并噻吩、噻克索酮、2-甲基-4-叔丁基苯硫酚、噻唑基嘧啶、甲苯噻嗪、5-乙氨基-噻唑基嘧啶、4-氨基-噻嗪、4-甲氧基-2-甲基-1-甲硫醚基苯、2-甲硫基-苯并噻唑和2-甲硫基-苯甲酸甲酯等硫化物。     

GAS-AGITATED LIQUID AND OXIDATIVE EXTRACTION IN THE ALKYL ANTHRAQUINONE PROCESS FOR THE PREPARATION OF HYDROGEN PEROXIDE

As preliminary investigations on oxidative extraction in the alkyl anthraquinone process for the production of hydrogen peroxide, the air-agitated liquid extraction of hydrogen peroxide from the working solution was studied and the dynamics of the extraction was measured as a function of the oil/water ratio and gas flow rate. The investigations were carried out either in an empty column or in a packed column. The results proved that the use of gas-agitated oxidative liquid extraction was a good way to integrate the oxidative operation unit with the extraction unit in the alkyl anthraquinone process for the preparation of hydrogen peroxide.     

OXIDATION AND REDUCTION OF MANGANESE ACETYLACETONATE COMPLEXES IN SOLVENT EXTRACTION SYSTEMS AND IN ORGANIC SOLVENTS BY ATMOSPHERIC OXYGEN

Partial oxidation of manganese(II) and Partial reduction of manganese(III) in acetylacetonate complexes occured in liqudd-liquid systems containing carbon tetrachloride and an aqueous sodium perchlorate solution buffered by sodium hydrogenecarbonate solution equilibrium was assumed to be established after a two phase agitation for several days. Howeve, when the manganese(II) complex was dissolved in air-saturated nonpolar organic solvents such as carbon tetrachloride benzene, and chloroform, it was quantitatively oxidized to the trivalent complex within one hour and the rate was dependent on both the oxygen and ligand. The rate was lower when the solvent was polar and also when an adduct-forming ligand with the bis-chelate such as trioctylphosphine oxide was added into carbon tetrachloride.     

EXTRACTIVE PROPERTIES TOWARDS RARE-EARTH METAL IONS OF CALIX[ 4] ARENES SUBSTITUTED AT THE NARROW RIM BY PHOSPHORYL AND AMIDE GROUPS

ABSTRACT

The extractive properties of the cone and partial-cone isomers of 5,11,17,23-tetra-?ert-butyl-25,27-bis( diethylcarbamoylmethoxy)-26,28-bisi( diphenylphospninoylmethoxy) calyx[ 4] arene ( cone-1 and partial-cone -1) in 1,2-dichloroethane towards rare-earth metal ions in nitrate media at 25 ° C were investigated. The analysis of the extraction equilibrium obtained from a mixture of four rare-earths ( La, Eu, Er and Y) revealed that the extracted species have a 1 1 metal/ ligand ratio for both ligands. The intra-group separation efficiercies of the ligandls have been evaluated in a competitive extraction process of 11 rare-earth metal ions ( La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb and Y). Significantly higher extractive properties were found for cone-1 with respect to partial-cone-1, suggesting the crucial role of the phosphoryl groups in the complexation of the rare-earth ions. These findings were