Neue schnelle Ionenleiter vom Typ MMIIICl6 (MI = Li,Na, Ag; MIII = In,Y)

Novel Fast Ion Conductors of the Type M M^IIICl₆ (M^I = Li, Na, Ag; M^III = In, Y) The ternary chlorides Li₃InCl₆, Na₃InCl₆, Ag₃InCl₆, and Li₃YCl₆ have been studied by difference scanning calorimetry, high-temperature X-ray, infrared, and high-temperature Raman methods. Impedance spectroscopic measurements exhibit fast ionic conductivity increasing in the sequence Na₃InCl₆ < Li₃YCl₆ < Ag₃InCl₆ < Li₃InCl₆. In the range of 300°C, Li₃InCl₆ is the best lithium ion conductor known so far (σ = 0,2 Ω^?1 cm^?1 at 300°C). With the exception of Na₃InCl₆, the chlorides exhibit complicated order-disorder phase transitions.     

Trigonal-planare CuX3-Gruppen in Cu2Mo6X14, X = Cl,Br, I

Trigonal Planar CuX₃-Groups in Cu₂Mo₆X₁₄, X = Cl, Br, I Cu₂Mo₆Cl₁₄ (I), Cu₂Mo₆Br₁₄ (II) and Cu₂Mo₆I₁₄ (III) were synthesized by thermal treatment of corresponding mixtures of copper(I) and molybdenum(II) halides. The crystal structures were determined by single crystal X-ray analyses. I and II show isotypism, cubic, Pn3 (no. 201, sec. setting), Z = 4, I: a = 12.772(3) Å, II: a = 13.350(2) Å. III shows a new structural type, orthorhombic, Pbca (No. 61), Z = 4, a = 16.058(3) Å, b = 10.643(2) Å, c = 16.963(3) Å. Trigonal planar CuX₃ units were found in I? III. Structural behaviour relations are discussed, especially with regard to ionic conductivity.     

A potentiometric investigation of the hydrolysis of chromate (VI) ion in NaCl media to 175°C

The hydrolysis of chromate ion was studied potentiometrically in a concentration cell fitted with hydrogen electrodes by titrating basic NaCl–Na₂CrO₄ solutions with standardized HCl against a NaOH reference solution. The temperature was varied from 25 to 175°C at 25° intervals at the following ionic strengths (I): 0.1140, 0.2346, 0.5337, 0.9988, 2.940, and 5.239 (NaCl). Depending on the ionic strength, the molality of total chromium was varied from 0.001 to 0.100. The resulting titration curves could be resolved best in terms of three equilibria involving the formation of HCrO ₄ ^– (aq), Cr₂O^3– (aq), and CrO₃Cl^– (aq). The equilibrium quotients for all three reactions were fitted as a function of temperature and ionic strength, and the molal thermodynamic parameters that were computed from these relationships are tabulated at specific ionic strengths over the experimental temperature range.     

基于金属介导和离子液体的新型绿原酸印迹整体柱的制备及评价

选用1-乙烯基-3-乙基咪唑四氟硼酸盐([VElm]BF4,一种离子液体)作为功能单体,以Co2+为介导离子,结合1-丁基-3-甲基咪唑四氟硼酸盐([BMIM]BF4)/二甲基亚砜(DMSO)二元致孔体系制备了绿原酸印迹整体柱。经过对制备参数的考察,确定最佳比例为绿原酸:Co2+:[VElm]BF4:EDMA(乙二醇二甲基丙烯酸酯)(摩尔比)=1:1:5:20,[BMIM]BF4:DMSO=3:1(V/V),最大印迹因子达2.10。通过优化色谱条件,最终在乙腈:20 mmol/L乙酸钠缓冲液(pH 4.2)=70:30(V/V)时实现了绿原酸及其类似物的完全分离。由此可见,以离子液体为功能单体及致孔剂,在金属介导策略下制备的分子印迹聚合物可实现绿原酸的特异性识别及分离。     

Investigation of the behavior of arenediazonium salts with olefins in BmimPF6

The palladium-catalyzed reactions of olefins with arenediazonium salts in ionic liquids were investigated. For methyl acrylate and methyl acrylonitrile, normal Heck cross-coupling products are obtained in good yields. However, highly selective dimerization products are formed in excellent yields for styrenes. The catalyst system can be recycled.     

Determination of ammonia based on the electro-oxidation of hydroquinone in dimethylformamide or in the room temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

The results detail a novel methodology for the electrochemical determination of ammonia based on its interaction with hydroquinone in DMF. It has been shown that ammonia reversibly removes protons from the hydroquinone molecules, thus facilitating the oxidative process with the emergence of a new wave at less positive potentials. The analytical utility of the proposed methodology has been examined with a linear range from 10 to 95 ppm and corresponding limit-of-detection of 4.2 ppm achievable. Finally, the response of hydroquinone in the presence of ammonia has been examined in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluormethylsulfonyl)imide, [EMIM][N(Tf)₂]. Analogous voltammetric waveshapes to that observed in DMF were obtained, thereby confirming the viability of the method in either DMF or [EMIM][N(Tf)₂] as solvent.     

凝胶型聚合物电解质的电导率与温度的关系

凝胶型聚合物电解质的电导率与温度的关系孙晓光，林云青，齐力，景遐斌，王佛松（中国科学院长春应用化学研究所长春１３００２２）关键词凝胶电解质，离子电导率，活化能无定形聚合物电解质电导与温度的依赖关系一般可用Ｖｏｇｅｌ－Ｔａｍｍａｎ－Ｆｕｌｃｈｅｒｃ（Ｖ...     

Study of the absorption spectra and ionic equilibria of cationic-anionic polymethine dyes

The absorption spectra of a number of cationic-anionic polymethine dyes in polar, low-polarity, and nonpolar solvents were studied. It was established that in polar solvents the absorption spectra represent the sum of the absorption spectra of the cation and anion, whereas in nonpolar and low-polarity solvents, in many cases the appearance of a short-wave absorption band is observed, due to interaction of the chromophores of the cation and anion in ion pairs. In solvents of intermediate polarity (for example, in chloroform and ethyl acetate), a concentration dependence of the absorption spectra is observed, determined by the equilibria of ionic dissociation. The ionic dissociation constants of a number of cationic-anionic dyes in chloroform and ethyl acetate were determined by a conductometric method. The thermodynamic data obtained are compared with the spectral data.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2524–2532, November, 1992.     

Hydroselenation of alkynes using NaBH4/BMIMBF4: easy access to vinyl selenides

A general and easy method for the synthesis of several vinyl selenides using NaBH₄ and BMIMBF₄ as a recyclable solvent is described. This efficient and improved method furnishes the corresponding vinyl chalcogenides preferentially with Z configuration. We also observed that when the same protocol was applied to phenyl acetylene, (E)-bis-phenylseleno styrene was obtained in good yield and with high selectivity.     

Utilisation of 1,3-dialkylimidazolium-2-carboxylates as CO2-carriers in the presence of Na and K: application in the synthesis of carboxylates, monomethylcarbonate anions and halogen-free ionic liquids

1,3-Dialkylimidazolium-2-carboxylate compounds have recently been fully characterised. Here we describe the utilisation of 1,3-dimethyl (1a) and 1-butyl-3-methyl-imidazolium-2-carboxylate (1b) in a carboxylation reaction with transfer of the CO₂ moiety to benzoylacetone and methanol for the synthesis, in high yield, of benzoylacetate and monoalkylcarbonate anions, respectively. Conversely, when compounds 1a and b are reacted with carbonylic substrates lacking C-H active bonds, a product resulting from nucleophilic attack of the 1,3-dialkylimidazol-2-ylidene species on the carbonyl moiety is obtained. The reported reactions can find applications in organic synthesis and in the synthesis of halogen-free ionic liquids.