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Table of Content

    24 January 1986, Volume 7 Issue 1
    Articles
    The Study of Extraction of Ag with Di-2-Ethylhexylphosphoric Acid (D2EHPA) and Di-2-Ethylhexyldithiophoric Acid (D2EHDTPA)
    Shong Kuiyuan, Shong Yulin, Li Hongtu
    1986, 7(1):  1-6. 
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    The extraction and strip of Ag+ from nitric acid solution with Di-2-ethylhe-xylphosphoric acid(D2EHPA)and Di-2-ethylhexyldithio-phosphoric acid(D2EHDTPA) were studied.The composition of extracted complex was determined by the methods of saturation and molecular ratio. The bonding of extracted species is discussed on the basis of its IRand NMR.It is explained satisfactorily that the extraction capacities of Ag ion in the two cxtractants are quite differient by quantum chemical EHMOmethod.
    Studies on Carbon Monoxide Complex of a New Tailed Porphyriniron
    Cao Xizhang, Mu Xihai
    1986, 7(1):  7-11. 
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    The carbon monoxide adduct of Fe complex of meso-mono[o-(4-dietheyla-mino) butyramidophenyl] triphenylporphyrin (tailed porphyrin, meso-MDBPTPP) is reported. The equilibrium constant of the adduct was measured by spectrophoto-metric method and the COvibration was obtained by using differential spectrum technique. Experimental results demonstrate that the fifth ligand affects the equilibrium constant dramatically.
    Kinetics of Hydrolysis of TiCl4 in Hydrochloric Acid
    Wang Fuyuan, Bi Guixin, Liang Dongsheng
    1986, 7(1):  12-14. 
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    The kinetic behavior of hydrolysis of TiCl4 in the solution of hydrochloric acid of ilmenite was studied; the relation between the degree of hydrolysis and concentration of Ti(Ⅳ), temperature of hydrolysis, quantity of seed added and acidic concentration have been found and the following relation dn/dt = 0.lC-1:5· ·n0.6 (at η = 25%) was discovered, where Cis the initial concentration of Ti(Ⅳ), n the quantity of seed added.The calculated value of action energy which was obtained from the relation of temperature and the degree of hydrolysis was 201.9kJmol-1.
    Study on Adsorptive Complex Wave of Aluminium-Pyrocatechol
    Li Qilong, Xing Jingna
    1986, 7(1):  15-18. 
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    In a supporting electrolyte containing 3.5·10-5Mpyrocatechol, 0.015 NH4Ac and at pH 4.7, an adsorptive complex wave of aluminium-pyrocatechol was obtained by single-sweep polarography. The peak potential of the polarographic wave was -0.85V (vs, SCE). The linear relationship between wave height and concentration of Al+3 held in the range of 1 ·10-6- 1. 2·10-5M.The composition of the complex in the ratio 1:1 was determined. This wave was proved to be an adsorptive wave by several experiments. The mechanism of the electrode reaction was discussed.
    Study of Atomization Process in Graphite Furnace Atomizer (Ⅱ)—Effects of Matrices on Atomization of Aluminium
    Zheng Yansheng, Zhu Feng
    1986, 7(1):  19-22. 
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    In the paper the effects of matrices of chlorides (such as CaCl2, MgCl2 NaCl, FeG3, NiCl2 and CoCl2), HNO3 and HCl on aluminium absorption signal in the pyrolytic graphite coating tube, Zirconium-coated and tungston-coated pyrolytic graphite tubes were studied, and the interference mechanism was discussed as well.
    The Analysis of Copper by Absorption Spectroelectrochemistry
    Huang Ganquan, Luo Huanguang, Wang Zhi
    1986, 7(1):  23-26. 
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    The behavior of absorption spectroelectrochemistry of copper and the effects of instrumental equipment as well as measurement conditions on the sensitivity of copper were investigated. Results show that the best sensitivity (0.029ppm) was obtained when the electrolytic cell with double electrodes and hollow cathode light source in place of the electrolytic cell with single work electrode and deuterium lamp was used for measurement of absorption spectroelectrochemistry of copper. The technique yields increased in sensitivity of copper of 2.5-fold, in comparison to the west method.
    The Studies of Chloride, Bromide and Iodide by Reversed-Phase Chromatography
    Hu Zhide, Liu Mancang, Chen Ruizhen
    1986, 7(1):  27-29. 
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    The conditions of separation of Cl-, Br- and I- by reversed-phase chromatog-hy using N235-silica gel or N263-silica gel as stationary phase were studied. ions were separated within32 minutes by using NaNO3 as mobile phase. The ride and bromide contents of some samples were simultaneously determined. The hods of determining Vm were studied in detail. The chromatographic behaviour Cl-, Br- and I- on N235 and N263 was investigated. An empirical formula of ulating retention values was obtained.
    Spectrophotometric Study on the Reaction of meso-Tetra-(3-Methylphenyl) Porphyrin with Cadmium
    Tong Shenyang, Zhao Fenglin, Liu Hong
    1986, 7(1):  30-32. 
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    Properties of mcso-(3-mcthylphenyl) porphyrin and its complex formation reaction with cadmium (Ⅱ) were studied. The dissociation constant of the reagent was calculated by PC-8001 Bcomputer according to A~pHcurve, pK3.4 = 5.67 ± 0.07. The complex has an absorption maximum at 432nm, and the maximum absorbancc was obtained in the pH 9.2 to 10.0. The apparent molar absorptivity of the complex is 3.8×105.
    Study on Coordination Equilibrium of Cu(Ⅱ) and Some α-Amino Acids in Solution by Ion-Selective Electrode Method
    Chen Jingtang, Su Li, Guo Dewei, Fan Chunmei
    1986, 7(1):  33-35. 
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    In this paper the coordination equilibrium constants of Cu (Ⅱ) and several α-amino acids and thermodynamic functions of Cu( Ⅱ )-asparamide system in solution were determined by Ion-selective electrode method.
    Phosphorylation Reactions of Benzothiazolone
    Chen Kejian, Zhang Jingling
    1986, 7(1):  36-41. 
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    This paper reports the reactions of benzothiazolone with phosphites, hexaalkyl phosphorous amides and bis-(dialkylamino)-phenylphosphines. Benzothiazolone could not react with various phosphites, but it gave N-phosphorylated products with phosphorous amides. The restricted rotation about P-Nbond at room temperature was observed and discussed.
    Synthesis and Analysis of Titanate Coupling Agants of Lactic Acid Type
    Jin Zhengzhong, Zhou Qingli
    1986, 7(1):  42-46. 
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    In this paper, seven new type titanate coupling agents of lactic acid have been synthesized, ND-81 has been synthesized by the reaction of the isopropyl titanate with lactic acid and dioctyl pyrophosphate. Stable aqueous solution of its ammonium salt(ND-84) has been made by the reaction of ND-81 with bis(hydrox-yethyl) amine. The Ti-O-Pbond in the titanate compounds containing Phas been identifid by IRspectrum. Anew method of gravimetric analysis has been researched. It may analyse the contents of Ti and Psimultaneously in organic compounds in which Ti and Pcoexist.
    The Solvent Effects on UV-Vis Spectra of Some 1,4 Bis[β-(4-Substituted Phenyl)-Ethenyl] Benzene Derivatives
    Xue Jieyou, Zhi Jinfang, Zhang Yibao, Yang Xuejin
    1986, 7(1):  47-53. 
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    In this paper, the UV-Vis spectra of some 1, 4-bisβ-(4-substituted phenyl)-ethenyl] benzene derivatives in seventeen solvents or binary nonpolar mixed solvents (e.g., benzene-cyclohexane, bezene-n-hexane, carbon disulfide-cyclohexane, etc.) have been measured. In general, the absorption maxima λmax have a bathochromic shift with increasing refractive index n of the solvent. Some linear relationships between vmax and n or (n2 -1)/(2n2 +1) are obtained, respectively.
    Vapor Pressures and Excess Gibbs Free Energies of Benzene-Cyclohexane, Benzene-n-Heptane and Gyclohexane-n-Heptane
    Sun Yaping, Yen Wenxing
    1986, 7(1):  54-58. 
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    The vapor pressures of benzcne-cyclonexane (313.25K), benzene-n-heptane (308.1119K) and cyclohexane-n-heptane (298.15K) were measured with a tensi-meler. By correlating the vapor pressures with their respective solution compositions, excess Gibbs free energies were calculated by Wilson and Redlich-Kister cquations, in good agreement with published data.
    Route of Aromatic Ring Acetylation Calculated by CNDO/2 Method
    Guo Jinbo, Huang Zhiqing, Wang Li
    1986, 7(1):  59-62. 
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    The paper deals with the study about reaction mechanism of acetylation in aromatic ring catalyzed with AlCl3 by method of CNDO/2. The calculation found: (1) a more preferable route of reaction process and activation energy, (2) the generation of δ-complex alone in the course of the reaction process and no π-compkcx formation. The paper further shows that on accout of the solvent effect activation energy has been decreased.
    Hetero-Atom Molecular Sieves (Ⅸ)—Studies on Syntheses, Structure and Physicochemical Properties of Zr-Si Pentasil Type Molecular Sieve
    Fang Wenqin, Qiu Shilun, Ge Ying
    1986, 7(1):  63-68. 
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    Zr-Si pentasil type molecular sieve was synthesized with tetraethyl orthosilicate or water glass as the silica source and zirconium oxychloride as the zirconium source, and tetrapropylammonium hydroxide (TPAOH), 1, 6-hexandiamine (HDA), tetracthylammonium hydroxide (TEAOH) or tetrabutylammonium bromide (TBABr) as the templating agent. The structure of the molecular sieve has been studied by means of X-ray diffraction, X-ray electron probe and IR. The parameters of unit cell of Zr-Si pentasil type molecular sieve were obtained by step scanning procedure with step size of 0.01°(2θ) on X-ray diffractometer. The results indicate that Zr is introduced into framework. The ability of adsorption, thermal stability, specific surface and acidity for the molecular sieve were also studied.
    The Adsorption-Desorption Study for the Low Temperature Water Gas Shift Reaction System by TPD
    Duan Xue, Zhuang Xinyu, Gao Zhengzhong, Wang Qi
    1986, 7(1):  69-74. 
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    The adsorption and desorption of CO, H2O(g), CO2 and H2 in the water gas shift reaction on the Cu/ZnO/Al2O3 catalyst were studied by TPD. And a similar discussion was made for six samples which bore analogy definite to Cu/ZnO/ A12O3 catalyst. It was discovered through analyzing qualitativly to TPDspectra had been got that the adsorption and desorption action were different for the water gas shift reaction conponents on the compositions of Cu/ZnO/Al2O3.Different compositions had an adsorption and desorption characteristic in itself. All the results gave useful informations for an explanation of the mechanism of the low temperature water gas shift reaction.
    Non-Empirical Calculation of Spin-Orbit Coupling Constants of Diatomic Molecules NS(X2Ⅱ) and SiF(X2Ⅱ)
    Guo Hua, Tian Anmin, Yan Guosen
    1986, 7(1):  75-76. 
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    Aprogram has been developed for calculation of the spin-orbit coupling constants of molecules. With this program we calculated the spin-orbit coupling constants of two diatomic molecules NS(X2Ⅱ) and SiF(X2Ⅱ).Excellent agreement between experimental and calculated values has been obtained if the core polarization is considered.
    The Modified H uckel Molecular Orbital Method (Ⅶ)—Studies on Linear Alternant Polyenes
    Ren Dehou, Lin Huixin
    1986, 7(1):  77-79. 
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    In this paper, we reported a modified Huckel molecular orbital (MHMO) method, which is driected to the calculations for linear alternant polyenes.MHMOcalculations for linear alternant polyenes with nc =4-50 were carried out by DJS-21 electronic digital computer. we have obtained pi-electron energies, MHMOcoefficients, et al.. Comparison of predicted and observed longest-wave length absorptions (or wave numbers) for linear alternant polyenes shows fair agreement with experiment. These predicted results are close to that which is calculated by the SCF MO. It is a most distinct improvement compared with HMO.
    Approximate Formulas of Kinetics in Process of Temperature Program Desorption
    Shi Shouheng, Li Dershan
    1986, 7(1):  80-82. 
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    During last decades, TPDmethod is used for determining heat of desorption of the gases adsorbed on the surface of solid catalyst and for testing state of the gases adsorbed. Even now the method is used in the thermal decomposition reaction. Generally, re-adsorption is ignored in treatment of TPDexperiment data. In the same appraximation condition, it is convenient to calculate the coverage θ if we let (1+βt/T0)1 = 1-βt/T0, where t is the time of reaction, β is the rate of raising temperaiure, and T0 is the temperature where t = 0.
    Studies on the Gompatibilizing Effect of High-Speed Stirring upon Poly ( Ethylene Oxide)/Polyacrylamide System
    Wang Qi, Li Huilin, Xu Xi
    1986, 7(1):  83-88. 
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    The compatibility of poly ( ethylene oxide) (PEO)/Polyacrylamide(PAM) system and the compatibilizing effect of PEO-PAMblock copolymcr formed during highspeed stirring of PEO/PAMmixture in its aqueous solution were studied. As viewed from thermodynamics, PEO/PAMis incompatible; the same is true of the conclusions drawn from contrast microscopy, TEM, SAXSand stress-strain behavior testing. It is found, however, that PEO-PAMblock copolymer is an effective compati-bilizer, which could cut down the dimension of the domains, reduce the heterogeneity of the system, increase the thickness of transition layer and improve the mechanical properties of the polyblend.
    Study of Gelation Reaction by Laser Light Scattering ( Ⅱ,Ⅲ )--The Network Copolymerization of Styrene with Ethylene Glycol Dimethacrylate and Divinylbenzene
    Zuo Ju, Han Xinhua, Zhou Yimin
    1986, 7(1):  88-94. 
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    According to the method presented in the previous paper, the most prominent features of the method are its high sensitivity and making use of the scanning technique, the network copolymerization of styrenc with cthylene glycol dimcthacry-late and divinyibenzene were studied here by means of laser light scattering. Several parameters characterizing the properties of network copolymerization, the speed and point of gelation, the point of phase separation, the correlation coefficient α ard the mean squared average dielectric constant fluctuation62, were obtained. And some comparisons among the three systems were studied. Based on the experiments and the comparisons, this method makes possible to understand the properties of network copolymerization and ihc activity of monomers at quantitative level conveniently. Therefore, the law of the kind of chemical reactions could be understood letter.