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1.
叔胺N235萃取盐酸时酸度对产生第三相的影响 总被引:4,自引:2,他引:2
本文研究了三烷基胺N235-C12H26-HCl萃取体系,在无改性剂TBP(磷酸三丁酯)和含20% TBP两种情况下,初始HCl浓度对HCl萃取率、第三相体积和第三相电导率的影响。发现无TBP时,萃取入有机相的HCl按两阶段形式进入第三相。在nHCl(o)/nN235(o)≤1时,形成的第三相萃合物为R3N·(H2O)m·HCl(m<3)。在nHCl(o)/nN235(o)>1时,萃合物组成接近R3N·(H2O)m·2HCl。第三相的体积及电导率变化均在nHCl(o)/nN235(o)=1附近出现拐点。有机相含20% TBP后,在cHCl(init)≤4.0 mol·L-1范围不出现第三相,cHCl(init)≥5.0 mol·L-1则再次出现第三相,此第三相的组成推测为R3N·(H2O)m·HCl及TBP·(H2O)m·HCl两种离子溶液的混合物。 相似文献
2.
3.
通过柔性配体1, 3-丙二胺缩邻香兰素(H2L)与和La(NO3)3·6H2O反应, 合成了1个由2个H2L桥连的双核稀土配合物[La2(NO3)6(H2L)2] ·CH2Cl2 (1), 该配合物与(NH4)(PF6)继续反应生成了1个由2个NO3-离子桥连的双核配合物[La2(NO3)2(H2L)4] (PF6)4·4H2O·2CH2Cl2 (2), X-射线单晶衍射分析确定了2个配合物的晶体结构。配合物1和2为结构完全不同的2个双核结构, 因抗衡阴离子PF6-有去阴离子的作用, 配合物1中的NO3-离子被配体取代, 导致配合物1的结构翻转, 形成了1个新颖的双核结构2。 相似文献
4.
5.
合成了四氯合锌酸正九烷铵复合物(C9H19NH3)2ZnCl4(s) (C9Zn(s)), 并使用X射线单晶衍射、化学分析以及元素分析确定了其晶体结构和化学组成. 利用其晶体学数据推导了C9Zn(s)的晶格能UPOT=952.94 kJ·mol-1. 在298.15 K下, 利用恒温环境溶解-反应热量计测定了C9Zn(s)在不同质量摩尔浓度下的摩尔溶解焓. 在Pitzer电解质溶液理论基础上确定了C9Zn(s)的无限稀释摩尔溶解焓ΔsΗm∞=20.09 kJ·mol-1, 以及Pitzer焓参数组合(4βC9H19NH3,Cl(0)L+2βZn,Cl(0)L+θC9H19NH3,ZnL)和(2βC9H19NH3,Cl(1)L+βZn,Cl(1)L)的值. 相似文献
6.
五元体系Li+/Cl-,CO32-,SO42-,B4O72--H2O 298 K相关系实验研究 总被引:2,自引:0,他引:2
Zabuye saline lake, Tibet, China, is unrivalled in the world for its high concentration of chloride, sulfate, carbonate and borate of lithium, sodium and potassium. Always at the later stage of the evaporation of brines, most sodium and potassium salts are crystallized out, so the main components of brines can be described with the Li+, Mg2+/Cl-, SO42-, CO32-, B4O72--H2O system. As a part of study on the equilibrium of this complex system, the equilibrium solubilities and phase diagram of the quinary system Li+/Cl-,CO32-,SO42-,B4O72--H2O at 298 K were studied by isothermal dissolution equilibrium method. In the 3-dimentional solubility diagram or its projection diagram saturated with solid LiCl, there are four crystallization fields, four univariant curves and one invariant point. At the invariant point, the saturated solid salts are LiCl·H2O, Li2B4O7·3H2O, Li2CO3and Li2SO4·H2O. No double salt or solid solution is formed. 相似文献
7.
Five novel chiral dinuclear Salen complexes M2L (M = Fe3+Cl-, Mn3+Cl-, Co2+, Ni2+, Cu2+) and Ba2+-crown ether complex H4BaL(ClO4)2 were synthesized. The complexes were synthesized by reaction between ligand 3(H4L) and corresponding metal salts (FeCl3, Mn(OAc)2·4H2O, Co(OAc)2·4H2O, Ni(OAc)2·4H2O, Cu(OAc)2·H2O, Ba(ClO4)2·2H2O). The chiral two discrete Salen ligand 3 was condensed from 3,3′-[Oxybis(2,l-ethanediyloxy)]bis(2-hydroxybenzaldehyde) and (R,R)-1,2-diamino-cyclohexane. The structure of complexes is two discrete Salen unit bridged with crown ether from two sides. We found that ligand 3 had three complex cites. The two N2O2 cavities can found complexes with d-metals (compound 4), while the O10 cavity can found complex with alkali metals and alkaline-earth metals (compound 5). The compounds were characterized by elemental analyses, 1H NMR, Mass-spectra, FT-IR, UV-Vis and CD spectra. The FT-IR, UV-Vis and CD spectra property of complexes were minutely analyzed. 相似文献
8.
以双四唑胺(H2bta)、NdCl3·6H2O、KOH为原料,用水热法合成了1个一维异核的Nd3+配合物[KNd(bta)2(H2O)6]·H2O。通过X-射线单晶衍射、元素分析、红外光谱对该配合物进行了结构表征。该化合物属于单斜晶系,P21/m空间群。每个Nd3+与2个来自bta2-离子的4个氮原子和5个水分子形成了1个盖帽的四方双锥,通过bta2-和水分子桥联配体把Nd3+和K+连接成一维链状结构,链与链之间通过O-H…N和N-H…O氢键作用形成三维超分子结构。紫外吸收光谱和荧光光谱表征结果显示该配合物的水溶液在292和412 nm表现出双四唑胺的特征吸收峰和荧光发射特征峰。 相似文献
9.
采用等温蒸发法研究五元体系Li+,Na+//CO32-,SO42-,B4O72--H2O 288 K介稳相平衡关系,测定在288 K条件下的介稳平衡溶液中各组分的溶解度和溶液密度,根据实验数据绘制相应的介稳平衡相图及密度组成图。研究结果表明该五元体系介稳相平衡中有复盐Na3Li(SO4)2·6H2O生成,其介稳相图中有4个共饱点,9条单变量曲线,6个Li2CO3饱和的结晶区分别为LiBO2·8H2O,Na2B4O7·10H2O,Na2CO3·10H2O,Na2SO4,Li2SO4·H2O和复盐Na3Li(SO4)2·6H2O。 相似文献
10.
采用溶液法合成了2例由O—P—O单元桥联的锰-席夫碱(SB)新型三核配合物,即[Mn3(salen)3(L)]ClO4·H2O (1)和[Mn3(salpn)3(L)]ClO4(2),其中salen2-=N,N''-乙二胺缩双水杨醛,salpn2-=N,N''-丙二胺缩双水杨醛,H2L=(5-(乙氧基羰基)萘-1-基)膦酸。通过单晶X射线衍射、红外光谱、粉末X射线衍射对其进行了表征。配合物1和2是同构的,均是由膦酸酯配体中的O—P—O桥联3个[Mn (SB)]+构成一个三核结构单元[Mn3(SB)3(L)]+,一个无序的ClO4-作为平衡阴离子存在。这些[Mn3(SB)3(L)]+三聚体通过π-π相互作用和相邻的分子形成超分子一维波形链。配合物1和2的磁性研究表明,不对称结构中的3个Mn(Ⅲ)离子分别是2个高自旋和1个低自旋,而Mn(Ⅲ)离子之间主要存在反铁磁相互作用。 相似文献
11.
Kun Huang Jing Chen ChengFeng Zhang ZhiHong Li QingHua Pan Yan Sun ShaoXuan Liu XueXin Liu WeiHong Li ZhanLan Yang ShiFu Weng TianDou Hu YiZhuang Xu JinGuang Wu 《中国科学:化学(英文版)》2009,52(11):1825-1834
In this paper, we have investigated the formation of the third-phase in tertiary amine (N235)-PtCl 6 2? -HCl system and the microscopic phase structural evolution of platinum-loaded organic phases before and after the occurrence of the third-phase. The third-phase is characterized by various spectroscopic techniques, and the small angle X-ray scattering (SAXS) experiments demonstrate the appearance of nano-aggregates, i.e., water-in-oil reversed micelles, in the third phase. The experimental results indicate that (1) formation of the third phase is related to the aggregation behaviors of nano-reversed micelles in which a super-concentrated hydrochloric acid formed with the H+ to H2O molar ratio being much higher than that of the conventional 37 wt% saturated hydrochloric acid. (2) The occurrence of the super-concentrated HCl results in a great amount of H+ and Cl? ions enriched and confined within the nano-water pools of W/O reversed micelles in third phase. Therefore, the coordination behaviors of platinum complex ions in that super-concentrated hydrochloric acid are very different from their corresponding behaviors in bulk aqueous solutions. It is possible that H+ ions participate in the formation of such complexes as H m PtCl 6 z+ in the super-concentrated hydrochloric acid. (3) The relative contents of various H m PtCl 6 z+ complexes are different corresponding to the H+ ion concentrations in confined nano-water pools. The association ability of the acidified tertiary amine N235 molecules (R3NH+) with various H m PtCl 6 z+ complexes plays an important role in affecting the platinum extraction behaviors. 相似文献
12.
Baranova O. V. Kosmynin V. V. Savelova V. A. Shendrik A. N. Korotkikh N. I. Raenko G. F. Popov A. F. 《Russian Journal of Organic Chemistry》2002,38(3):378-384
Onium salts QZ (Z = Cl, Br) having a lipophilic (Q = R3NR', where R' = C16H33) or readily extractable (into organic phase) cation (Q = Ph4P) exhibit a high catalytic activity in phase-transfer alkaline hydrolysis of N-benzyloxycarbonylglycine 4-nitrophenyl ester in the two-phase system chloroform-borate buffer (pH 10). No catalytic effect is observed in the presence of hydrophilic ammonium salts [Et4NCl, Et3PhCH2NCl, Me2(NH2)+NCH2CH2+N(NH2)Me2·2Br-] and those insoluble in organic solvents [(Me)3+NNH(CH2)2COO-·2H2O, Me2(NH2)+NCH2CO-, Me2(NH2)+N(CH2)3SO3
-]. These data suggest extraction mechanism of the process. The activity of lipophilic cation Q is determined mainly by two factors: its extractibility, on the one hand, and the ability to form micelles, on the other. 相似文献
13.
Extraction equilibria for the 4-(2-Pyridylazo)-Resorcinol-Nickel(II)-Quaternary-Ammonium salt system
The extraction equilibria of nickel(II)-PAR complexes with tetradecyldimethylbenzylammonium chloride(Q+Cl?) are investigated. Two kinds of nickel complex are extracted by chloroform: Ni(HR)2,nQ+Cl?(0)(?500 = 3.73·104l mol?1cm?1) at about pH 5 and 2Q+ NiR2-2(o)(?500 = 8.08·104 l mol?1 cm?1) at above pH 8.5. The extraction constant for 2Q+ NiR2-2(o) was evaluated as [2Q+ NiR2-2]0/[NiR2-2] [Q+]2 = 1011.16 at μ = 0.1 (Na2SO4. Synergic extraction studies of the Ni(HR)2 species under slightly acidic conditions show that the species is Ni(HR)2(H2O)2in auqeous solution and is extracted into chloroform as the adduct Ni(HR)2(TBP)2 (?535 = 3.57·104 l mol?1 cm?1. Based on the extraction behavior of these complexes, the structures of the Ni2+—PAR complexes are discussed. 相似文献
14.
NH4[Re3Cl10(OH2)2] · 2 H2O: Synthesis and Structure. An Example for “Strong” N? H …? O and O? H …? Cl Hydrogen Bonding The red NH4[Re3Cl10(OH2)2] · 2 H2O crystallizes from hydrochloric-acid solutions of ReCl3 with NH4Cl. It is tetragonal, P41212, No. 92, a = 1157.6, c = 1614.5 pm, Z = 4. The crystal structure contains “isolated” clusters [Re3Cl10(OH2)2]?. These contain Cl…?H? O? H…?Cl units with “very strong” hydrogen bonds: distances Cl? O are only 286 pm. NH4+ has seven Cl? as nearest neighbours and, additionally, one H2O which belongs to a cluster [d(N? O1) = 271 pm] and one crystal water [d(N? O2) = 286 pm]. 相似文献
15.
D. Naoufal P. Selucký B. Grüner B. Bonnetot H. Mongeot 《Journal of Radioanalytical and Nuclear Chemistry》2005,266(1):145-148
Summary New anion derivatives of the closo-decaborate [B10H10]2- bearing amine or phosphine groups were tested for the extraction of radioactive cesium cations in acidic medium. The technique used is the liquid-liquid extraction based on the complexation of Cs+ by these anions to form neutral compounds which are extracted by organic solvents (diluents) of medium polarity. Promising results were obtained with the anion [1-(C6H5CH2)2(C6H5)NB10H9]- (3) soluble in many organic solvents. The most efficient diluent for the extraction is nitrobenzene. Using hydrochloric acid or sulfuric acid in the aqueous medium instead of nitric acid does not significantly affect the efficiency of Cs+ extraction. 相似文献
16.
Graham Smith 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(3):315-319
The structures of ammonium 3,5‐dinitrobenzoate, NH4+·C7H3N2O6−, (I), ammonium 4‐nitrobenzoate dihydrate, NH4+·C7H4NO4−·2H2O, (II), and ammonium 2,4‐dichlorobenzoate hemihydrate, NH4+·C7H3Cl2O2−·0.5H2O, (III), have been determined and their hydrogen‐bonded structures are described. All three salts form hydrogen‐bonded polymeric structures, viz. three‐dimensional in (I) and two‐dimensional in (II) and (III). With (I), a primary cation–anion cyclic association is formed [graph set R43(10)] through N—H...O hydrogen bonds, involving a carboxylate group with both O atoms contributing to the hydrogen bonds (denoted O,O′‐carboxylate) on one side and a carboxylate group with one O atom involved in two hydrogen bonds (denoted O‐carboxylate) on the other. Structure extension involves N—H...O hydrogen bonds to both carboxylate and nitro O‐atom acceptors. With structure (II), the primary inter‐species interactions and structure extension into layers lying parallel to (001) are through conjoined cyclic hydrogen‐bonding motifs, viz.R43(10) (one cation, an O,O′‐carboxylate group and two water molecules) and centrosymmetric R42(8) (two cations and two water molecules). The structure of (III) also has conjoined R43(10) and centrosymmetric R42(8) motifs in the layered structure but these differ in that the first motif involves one cation, an O,O′‐carboxylate group, an O‐carboxylate group and one water molecule, and the second motif involves two cations and two O‐carboxylate groups. The layers lie parallel to (100). The structures of salt hydrates (II) and (III), displaying two‐dimensional layered arrays through conjoined hydrogen‐bonded nets, provide further illustration of a previously indicated trend among ammonium salts of carboxylic acids, but the anhydrous three‐dimensional structure of (I) is inconsistent with that trend. 相似文献
17.
E. S. Stoyanov 《Journal of Structural Chemistry》1994,34(5):714-721
Using IR spectroscopy we have shown that at digerent equilibrium concentrations of HCl in aqueous phases, its tributyl phosphate @acts contain: 1) at CHcl
a < 2.3 M, micelle-like associates H5O2
+(H2O)n–2(TBP)mCl–·(H20·TBP)2 (n 26 and m 13), the structure of micelles is discussed 2) at 2.3 M < CHCl
a < 5.6 M, dimer associates [H5O2
+(H2O)2Cl–(H2O·TBP)2]2; 3) at 5.6 M < CHCl
a < 8.5 M, H-bonded molecular fragments H5O2
+(TBP)2/3Cl–(A); and 4) at CHCl
a > 8.5 M, considerable amounts of the H3O+ tisolvate start to form in molecular fragments H3O+(TBP)1/3Cl
–(B) H-bonded with the nearest neighbors. At CHcl
a > 5.6 M, almost no free TBP molecules occur in the extracts and a structured liquid forms from the A fragments; and at CHcl
a > 8.5 M, from the B fragments.Institute of Catalysis, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturmoi Khimii, Vol. 34, No. 5, pp. 72–79, September–October, 1993.Translated by K. Shaposhnikova 相似文献
18.
The Crystal Structures of [Cu2Cl2(AA · H+)2](NO3)2 and [AA · H+]Picr? (AA · H+ = Allylammonium; Picr? = Picrat) By an alternating current electro synthesis the crystal-line π-complex [Cu2Cl2(AA · H+)2](NO3)2 has been obtained from CuCl2 · 2H2O, allylamine (AA), and HNO3 in ethanolic solution. X-ray structure analysis revealed that the compound crystallized in the monoclinic system, space group P21/a, a = 7.229(3), b = 7.824(3), c = 26.098(6) Å, γ = 94.46(5)°, Z = 4, R = 0.025 for 2 023 reflections. The crystal structure is built up of CunCln chains which are connected by π-bonding bidentate AA · H+ …? ON(O)O …? H+ · AA units. For comparision with the above complex the structure of [AA · H+]Picr? (Picr? = picrate anion) is also reported. 相似文献
19.
E. Makrlík P. Selucky P. Vaňura P. Toman R. Rathore 《Journal of Radioanalytical and Nuclear Chemistry》2011,287(2):497-500
From extraction experiments and γ-activity measurements, the extraction constants corresponding to the general equilibrium M+(aq) + 1·Cs+(nb)
\rightleftarrows \rightleftarrows
1·M+(nb) + Cs+(aq) taking part in the two-phase water–nitrobenzene system (1 = hexaarylbenzene-based receptor; M+ = H3O+, NH4
+, Ag+, K+, Rb+, Tl+; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Furthermore, the stability constants of the ML+ complex species in nitrobenzene saturated with water were calculated; they were found to increase in the series of Rb+ < K+ < Ag+, Tl+ < H3O+, NH4
+. 相似文献
20.
T. Omori M. Tadokodo Y. Suzuki H. Suganuma K. Yoshihara 《Journal of Radioanalytical and Nuclear Chemistry》1994,181(1):71-76
Solvent extraction mechanism of pertechnetic acid with TBP from perchloric acid solutions is discussed. When cyclohexane is used as a diluent of TBP, perchloric acid can be extracted in the form of HClO4(TBP)2 into the organic phase. The TBP extraction of pertechnetic acid competes with perchloric acid and its equilibria are expressed as follows: HTcO4+3TBPHTcO4(TBP)3 and HTcO4(TBP)3+TBPHTcO4(TBP)4. 相似文献