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Table of Content

    24 December 1984, Volume 5 Issue 6
    Preface
    A Study on the Mechanism of Extraction of Cobalt(Ⅱ) and Magnesium with Di(2-Ethylhexyl) Phosphoric Acid (HDEHP)
    Shen Jinglan, Gao Zili, Jiang Dehua
    1984, 5(6):  749-754. 
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    The extraction of cobalt (Ⅱ) and magnesium with di (2-ethylhexyl) phosphoric acid (HDEHP) in kerosine from 0. 1Msodium chloride solution has been studied at 25±1℃. The experimental results indicate that the reaction of extraction of Co(Ⅱ) and Mg(Ⅱ) with HDEHPis a cat-ionic exchange process.The general equation for extraction equilibria can be represented as  The method for calculating the free concentration of the extractant in the organic phase has been discussed.
    Articles
    The Phase Diagrams of LiF-KCl-KBr and KF-NaCl NaBr Systems
    Yan Lichenr, Zhu Yingying, Chen Nianyi
    1984, 5(6):  755-758. 
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    The phase diagrams of LiF-KCl-KBr and KF-NaCl-NaBr systems were determined. It was found that LiFformed positive deviated molten salt solution with KCl-KBr, and that KFformed negative molten salt solution with NaCl-NaBr system.This result was discussed based on some conclusion obtained from the Monte Carlo simulation method of molten salt mixture.
    The Mutual Transformation Between Erionite and Offretite in T-type Zeolite
    Wang Xingqiao, Xu Ruren
    1984, 5(6):  759-764. 
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    Some of T-type zeolite have been synthesized under different conditions and treated at some temperature. X-ray diffraction and electron diffraction patterns and crystal shape of these zeolite are all the same. Studies of the adsorption of cyclohexane allow to evaluate contents of Erionite and Offretite in T-type zeolite, and thus found out relation between Erionite and Offretite in the mutual transformation of them.
    The Studies on the Diagrams of the Molten Salt Systems of ZnCl2-LiCl and SnCl2-ZnCl2-LiCl
    Liu Shuqi, Liu Ying, Zhang Qiyun
    1984, 5(6):  765-768. 
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    By visual polythermal, DTAand X-ray powder diffraction methods,the phase diagrams of molten salt systems ZnCl2-LiCl and SnCl2-ZnCl2-LiCl have been investigated.
    Preface
    Studies on Silicic Acid and Its Salts (ⅩⅥ)——Dissociation Constants of Silicic Acid in Gelation Process
    Chen Rongsan, Chen Yuehua, Liu Haicheng, Tai Anpang
    1984, 5(6):  769-774. 
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    Using HOAc and H2SO4 as acidifying agents, the relationship of the gelation time and pH of the solution containing SiO2/Na2O ratio of 1.0, 2.0 and 3.0, has been studied.The curve which expresses the relationship is of N-shape. At the minimum point of the curve, the pHis equal to pK1,at maximum point, the pHis equal to (pK0 + pK1)/2 and on the right side of the minimum point where , the pHis equal to (pK1+pK2)/2. Therefore, from the structure of N-shape curves, dissociation constants of various species of silicic acid can be obtained.The results indicate that the dissociation constants of silicic acid in gelation process vary with the acidiffying agent, total salt concentration and the degree of polymerization of silicic acid, that when the total salt concentration of the solution maintained constant and the acidfying agent is same, the dissociation constants of silicic acid would not change with the concentration of the acid, and that the pK1 of silicic acid and ionic strength of its solution bear a linear relationship, in which the slop represents coordination energy of anion of the corresponding salt with silicic acid and the intercept represents dissociation constant of silicic acid in the gelation process when the salt effect is eliminated.
    Articles
    Investigation on Oscillopolarographic Titrations(ⅩⅪ) ——Oscillopolarographic Titrations at Pt-Electrodes
    Zhuang Jianyuan, Gao Hong(H. Kao)
    1984, 5(6):  775-780. 
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    Oscillopolarographic titrations are usually carried out at Hg-electrodeswith an applied potential of 0——2 volts. Such electrodes cannot be usedin redox titrations. It is also inconvenient to use them for titrations involving ions such as Ag+, Hg++,Cu++, Fe+++ which are reduced at near zero potentials. The use of micro Pt-electrode can solve these problems. T.itration of As(Ⅲ) .with KBrO3 in acidic solution gives very accurate results. Titration of Ag+ with I- also gives accurate results. Neutralization and complexation in titrations can also be carried out at Ptelec-trodes.
    Polarographic Study on Metal-4-(2-Pyridinylazo)-Resorcinol (PAR) Complex(Ⅰ)—— Polarographic Catalytic Wave in Vanadium(V)-PAR-NaClO3 System
    Song Junfeng, Liu Longbin, Hu Yinhua
    1984, 5(6):  781-786. 
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    The complex of vanadium(Ⅴ) with PARat pH2.1H2SO4 medium in the presence of NaClO3 produces a sensitive catalytic wave. The peak potential of this wave appears at -0.1 V(SCE). It is found that the catalytic wave is of both adsorption and kinetic characteristics.
    TLC Study of High-Valent Metal Ions on Crystalline Antimonic(V) Acid p-Sulfachlorophosphonazo Impregnated Thin Layer Plate
    Liu Jinchun, Huang Shouting, Liu Liangbin, Cheng Jieke
    1984, 5(6):  787-790. 
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    In this paper, a new TLC method is described, TLC behaviour of RE(Ⅲ), Ti(Ⅳ), Zr(Ⅳ), Nb(Ⅴ) and U(Ⅵ) in oxalic acid-alcohol rystems on C-SbA-P-SCP impregnated thin-layer plate was studied. Aseries of effective separation of binary and ternary mixtures were achieved. The method is simple, rapid and intuitional.Based on the experimental results, an empirical formula was proposed: Rf=a-b104/Z2r0 where Z and r0 are the atomic number and the bare ion radius of lanth-anide, respectively.The intercepts, slopes and linear relative coefficients(r) of curves were calculated for various developers.
    A New Sensitive Method for Determination of Chromium (Ⅵ) by Spectrophotometry ——A Study on the Color, System of Cr(Ⅵ)-Br-PF-CPB
    Zhang Fan, Chen Guonan, Yang Yiqiang, Hung Shaopeng
    1984, 5(6):  791-795. 
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    The color reaction of Cr (Ⅱ) -Br-PF-CPBis studied in detail. In the presence of CPB, Cr (Ⅱ) is found to be able to react with Br-PFand form a purple complex in the pHrange of 3.5-5.0 under heating in 50℃ water for 10 min. The molar ratio of the complex is 1:3, its wavelength of maximum absorbance is 586nm.The molar absorptivity is 1.44× 105. Beer's Law is obeyed for 0-2.5μg of Cr(Ⅱ) in 10ml solution. In the presence of CyDTA, the interferences of many ordinary ions are eliminated. Amethod for determining Cr in steel and water is developed. It has been applied to real sample analysis, and good results are obtained.
    Polarography of Phenol Red
    Liu Yanmin, Wang Erkang
    1984, 5(6):  796-798. 
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    Electroreduction of Phenol Red has been studied by polarography and voltammetry. The mechanism of electroreduction with disproportion reaction was suggested.
    A Method of Addition in the Emisson Spectrographic Analysis
    Liu Lixing
    1984, 5(6):  799-801. 
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    In this paper, two evaluation equations of method of addition in the emisson spectrographic analysis, i.e., evaluation equation of method of addition without background and with background correction have been derived. The former applies to evaluation of content in the spectrum lines measured without background, the latter with background.The relative analytical error is lower than ±10%.
    Syntheses of Phenol-Formaldehyde and Acetal Types Polymeric Crown Ethers Containing Benzo-15-Crown-5 and Their Complexing and Catalytic Properties
    Zhan Caimao, Dong Shihua, Xu Yuwu
    1984, 5(6):  802-806. 
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    In this paper, two types of polymeric crown ethers containing B-15-C-5 were reported. The phenol-formaldehyde type was prepared by condensation-polymerization of bis(B-15-C-5) dimethyl ether with phenol and formaldehyde, and the other, acetal type, was obtained by reaction of polyvinyl alcohol with 15-formyl-B-15-C-5. Their complexing capacity and phase-transfer catalytic activity were investigated,
    The Asymmetric Esterification of Ethylmethylmalonic Acid
    Zhu Xingpei, Wu Yongren, Yin Chenglie
    1984, 5(6):  807-811. 
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    Ethylmethylmalonic acid reacted with l-menthol to form the diastereo-meric l-menthyl hydrogen ethylmethylmalonates (Ⅰ).From(Ⅰ)the diaster-eomeric l-menthyl ethylmethylmalonamides(Ⅲ) were obtained in nearly quantitative yield. To saponify the amides(Ⅲ) with alkali, the partially optically active ethylmethylmalonanic acid(Ⅳ) were produced in 70% yield. (Ⅲ) were degraded to partially optically active a-amino-methylethylacetic acid (Ⅴ) (V,8.8%e.e S - (+) -isomer)by the Hoffmann degradaton.In DMFthe monobrucine salts of ethylmethylmalonic acid reacted with iodoethane and diazomethane to produce the optically inactive mono-ethyl ester (Ⅵ) and monomethyl ester (Ⅴ) respectively.
    Studies on Crystal and Molecular Structure of Bis(Methylcyclopentadienyl) Di(2, 6-dichlorophenoxy)hafnium
    Dou Shiqi, Chen Shoushan
    1984, 5(6):  812-816. 
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    In the present paper, the crystal and molacular structure of (η5-CH3C5H4)3Hf(OC6H3Cl3-2,6)3 have been determined by X-ray diffraction method. The crystallizes structure belongs to monoclinic system with space group C25h-P21/c and cell parameters a = 17.010(2)Å, b = 8.577(1)Å, c= 16.313(3)Å,β=101.52(3)°. There are four molecules in each unit cell, Z = 4. Within each molecule there is a non-crystallographic twofold axis which lies on the (010) plane through the Hf atom parting the molecule into two similar halves.Two methylcyclopentadienyl group and two oxygen atoms around the hafnium atom form a pseudo-tetrahedron.The angle between the two methylcyclopentadienyls is 125.33°. The angle O-Hf-Ois 103.71°.The bond length Hf-Ois 2.004-2.022Å, it is shorter than Hf-O single bond. The results show clearly that Hf-O bond is characteristic of some partial double bond.
    Preface
    Research on Organophosphorus Compounds(Ⅴ) ——The Reaction of Some Phosphorodithioates with Aldehydes and Ketones
    Wu Junhe, Huang Naiju, Zhang Changnian
    1984, 5(6):  817-822. 
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    a,β-Unsaturated acid derivatives, esters, amides and nitriles, have been prepared by the reaction of O,O-dialkyl phosphorodithioates with aldehydes and ketones in the presence of n-butyl lithium in good yields .
    Articles
    Mass Spectrometric Studies on Heterocyclic Compounds Containing Iodine
    Yuan Xizhao, Hou Zijie, Huang Wenkui(Hwang Wen-Kuei)
    1984, 5(6):  823-828. 
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    The experimental data show that the EImass spectra of 3,6-dinitro-dibenzopyriodonium halides (X = Cl, Br, I) and 3,6-dinitro-9-one-diben-zopyrdonium halides (X = Cl, Br, I) are the mixed mass spectra of their thermolysis products produced inside the instrument. The adsorbed solvent, formic acid, in the samples (Ⅳ-Ⅵ)takes part the thermolysis process. By the electron collision induced fragmentation, one can easily identify 2-halo-2' -iodo-4, 4' -dinitro-dibenzoketone, the main thermolysis product of 3,6-dinitro-9-one-dibenzopyriodonium halides (X = Cl, Br, I).
    Structure of the Benzoylation Product of the Morpholine Ename of Cyclohexanone
    Li Liangzhu, Chang Cheng
    1984, 5(6):  829-832. 
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    By catalystic hydrogenation, IR., NMR., MS., etc. supported the dibenzoylated enamine is (2-morpholino-4′-yl-2-cyclohexen-1-yl) phenyl ketone enol benzoate that was assigned by Helmers.
    Synthesis of Bis(methyl-cyclopentadienyl) Titanium Dichloride and Its Derivatives
    Zhou Yaokun, Feng Tiecheng
    1984, 5(6):  833-835. 
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    In this paper, the bis(methyl-cyclopentadienyl) titanium dichloride is prepared by means of reaction of methyl-cyclopentadienyl lithium with titanium tetrachloride. Some new dimethylcyclopentadienyl compounds of titanium such as (MeCp)2Ti (OR)2 and (MeCp)2Ti (OR') Cl (R = C6H3Me2-2,4, C6H4NO2-3, C6H4NO2-4; R' = C6H3Me2-3,5) have also been synthesized. Their IR and 1HNMR spectra are given.
    Acid-Catalyzed Cyclization of 1,1-Dichloro-4,8-Dimethylnona-,3,7-Triene
    Xu Linxiao, Tao Fenggang, Wu Junhe
    1984, 5(6):  836-838. 
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    Cyclization of 1,1-dichloro-4, 8-dimethylnona-1, 3, 7-triene (Ⅳ) under the catalysis of boron trifluoride-etherate at room temperature gave a-isomer (Ⅴ) as the unique product in 90% yield. It was suggested that the cause leading to above result may be much more steric strain due to intramolecular crowding with the bulky dichlorovinyl group and adjacent three methyl groups in β-isomer (Ⅵ) than in a-isomer (Ⅴ),
    Separation and Determination of Isomers of Mono-, Di- and Trinitrotoluene Using a Shorter Capillary Column
    Fu Ruonong, Tian Linxiang
    1984, 5(6):  839-841. 
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    A new method is described for the separation of 15 isomers of mono-, di- and trinitrotoluene on a shorter glass capillary column coated with OV-225 as stationary phase. Relative retention ratio and resolution of these isomers were determined on this column, and it shows that all the isomers can be separated and determined in less than 12 mins.Acolumn 9.2m long is suitable for determination of all the isomers and a column 5.8m long for rapid separation of the isomers of TNT at 195℃ within 10 min.
    Synthesis, Ultraviolet and Fluorescence Spectra of 2-(1- or 2-Naphthyl)-5-Substituted Benzoxazoles
    Pan Jiaxing, Wang Minzhen, Zhang Suipo, Qin Yuanxi, Chen Jingshan, Wang Shenxiu
    1984, 5(6):  842-844. 
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    Ten 2-(1-naphthyl)-5-substituted benzoxazoles as well as ten 2-(2-naphthyl)-5-substituted benzoxazoles are synthesized and their λmax of UV spectra and fluorescence spectra are reported.
    Studies on Nitroxides (ⅩⅤ)——The ESR Anisotropism of 2,2, 6,6-Tetramethyl-4-Hydroxy- Piperidine-1-oxy Radical
    Wang Yukun, Liu Youcheng
    1984, 5(6):  845-846. 
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    Single crystals of 2,2, 6, 6-tetramethyl-4-hydroxypiperidine (1) were prepared, in which the 2, 2, 6, 6-tetramethyl-1-hydroxypiperidine-l-oxy radical was as an impurity. The Atensor of nitroxide radical cited above (2) has been determined and the eigenvalues of tensor Aare calculated to be 7.2, 5.2, and 33.8 Grespectively. The ESRspectra of (2) observed indicate the existence of six lines corresponding to two types of paramagnetic centers with different orientations in the matrix of (1), each of which contributing its triplet.
    Resonance Raman Spectra of Tetraphenylporphyrin and Rare Earth Acetylacetonate-α,β,γ,δ- Tetraporphyrin
    Zhao Yongnian, Liu Guofa, Wang Guifu, Wang Yutian
    1984, 5(6):  847-852. 
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    The Resonance Raman Spectra of TPP and MTPP acac were measured with 4579Å and 5145Å of Ar+ laser. Resonance speciality of spectra and structure symmetry were discussed. The band near 370cm-1 was assigned to M-Obond symmetric stretching vibration.
    The Application of Scaled Particle Theory in Calculation for Free Energy of Ionic Solvation
    Yang Jiazhen, Liu Ruilin
    1984, 5(6):  853-856. 
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    This paper has calculated ionic solvation free energies of KCl, KBr, NaCl, NaBr, CsCl and CsBr in seven solvents namely DMSO, DMF MeOH, MeCN, (CH3)2CO, EtOH and H2O. The results agree with observed values pretty well. Aone-layer continuum model was adopted in calculation, the nonelectrostatic term was calculated by the equation of scaled particle theory.
    The Study of the Surface Structure of the catalyst of the Systems NiO-Cr2O3-SiO3 NiO-SiO3 and by Using the Molecale Probe Method
    Tang Xinshuo, Liu Song, He Yabo, Jiang Yimin
    1984, 5(6):  857-862. 
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    This paper describes how the surface structure of the catalysts of the systems NiO-SiO2 and NiO-Cr2O3-SiO2 is studied and determined by using the molecule probe method.The conclusions obtained with the method have been verified to be correct by means of TPD, X-ray diffraction and magnetic analyses etc. And as a result the method is proved to be a new effective one for studing the surface structure.This method is characterized by rapidly gathering information about surface structure of adsorption centre of catalysts in a convenient way under Closely practical conditions of reaction.
    Configuration Interaction and the Woodward-Hoffmann Rules——Eleclrocydic Reaction of Butadiene
    Feng Jikang, Li Zhiru, Tian Yongchi, Li Yanxin, Zhang Chunshan, Sun Chiachung
    1984, 5(6):  863-868. 
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    In this article, two groups {E, C2} and {E, σv} are proposed to describe the orbital symmetry of the whole reaction paths with respect to the conrotatory and disrotatory electrocyclic reaction of butadiene. Furthermore, the symmetries of the two groups are extended to the systems as a many-body treatment based on spin-free theory. The effect of full configuration interaction is investigated using the Huckel-Hubbard approximation. The many-body treatment is generalized to the case in which the Gel'fand bases take the molecular orbitals as the starting point.We obtain singlet and triplet reaction paths-energy reaction surfaces, from which the activiation energies of thermal and photochemical reactions can be calculated. The results are compared with the values of other authors'and can explain the selection rules established by Woodward and Hoffmann.
    Study on the Organometallic Compounds of Transition Metals Containing Pentahaloaryl Ligands(Ⅱ)——The Kinetics and Mechanisms of Nucleophilic Substitution Reactions of Bis (diphenylalkylphosphine) pentachlo-RophenvInickeK (Ⅱ)Halides
    Chen Rongti, Zhang Qiyan, Wang Xianhong, Wang Xukun, Zhang Zhengchi
    1984, 5(6):  869-873. 
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    The kinetics of nuclcophilic substitution reactions of bis(diphenyl-alkylphosphine) pentachlorophenylnickel (Ⅱ) halides with NO2- and SCN- in MeOH EtOH and DMF was studied by spectrophotometric method. The results indicated that the reactions followed a two-term reaction rate law, that is, r = (k1 + k2[L]) [complex], k1, and k2 values were determined at different temperatures and the corresponding activated thermodynamic parameters △H and △S were evalualed. Reaction mechanisms have been proposed and factors influencing the reaction rate such as solvent effect, nature of the leaving and entering groups, different alkyl groups in the phosphine ligand, etc, have been discussed.
    Adsorption from of Solutions(Ⅹ)——The Adsorption of Some Organic Solutes from Binary Mixed Solvents
    Zhao Zhenguo, Liang Wenping, Peng Xiangdong
    1984, 5(6):  874-878. 
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    In this paper, we have studied the adsorption of benzoic acid and anthracene from binary mixed solvents; on silica gel and activated carbon. The experimental results show that the adsorption of solutes from non-polar mixed solvents depends simply on their solubilities. However, when the adsorption of solutes from polar non-polar or polar-polar mixed solvents was dealt with, the situation is very complex. From constant boiling mixtures with a maximum (for example chloroform-acetone; 1, 2, 2-tetrachloroethane-cyclohexanone eto.),the, adsorption of anthracene varies with, the composition of mixed solvents, and a positive deviation from straight line is observed. From constant boiling mixtures with a minimum, the adsorption of solutes also varies with the composition of mixed solvents, but a negative deviation is observed. Based on the interaction between molecules in mixed solvents, the experimental results may be explained qualitatively.
    pH-Electrometric Determination of Thermodynamical Parameters of Mn(Ⅱ),Co(Ⅱ),Ni(Ⅱ) Mandelate Complexes
    Jiang Lianfen, Sun Lingyi
    1984, 5(6):  879-880. 
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    The stability constants of 1:1(Me2+ : mandelic acid) complex have been determined by pHmetrically at an ionic strength 0. 1 M KNO3 and at 10℃, 15℃,20℃,25℃, 30℃. The constants are in the order of NiL+ > CoL+>MnL+ at each temperature. The free enthalpy changes are NiL+< CoL+<MnL+,and the enthalpy change and entropy change are calculated graphically,
    The Standard Electrode Potential of Standard Cadmium Amalgam Electrode at 298 K
    Zhu Xunzhi(Hsun-Chih Chu), Qu Jin
    1984, 5(6):  881-883. 
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    This paper deals with the determination of the electrode potential of six different concentration cadmium amalgam (Cd concentration varies from 0.00510 to 0.52775 m) in a saturated CdSO4 solution. Two reference electrodes, i.e., the Hg-Hg2SO4 electrode and 10% Cd amalgam electrode, were used during the measurement. The result of the potential measurement for each Cd amalgam electrode was agreed to be ± 2μV.
    Determination of Molecular Weight for Polymers by Simple Osmometry
    Zhang Lina, Zou Congyan, He Congle, Tian Li
    1984, 5(6):  884-888. 
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    The number average molecular weight for polystyrene standards, poly-vinylchloride fraction and unfraction, vinyl chloride/vinyl acetate/vinyl alcohol copolymer, polymethylmethacrylate and polyacrylonitryle have been determined by a improved osmometer included one membrane and two chambers, and a simple dynamic osmometry. The osmotic pressure was determined by passing a flow of solvent through the membrane into the solution and extrapolating to zero flow rate. THF, acetone and DMFhave been used satisfactory as solvent in the measurement. The method is co-vennient to operate, rapid and reliable. Individual molecular weight measurements are accurete within ± 5 %.
    Copolymerization of 1, 3-Butadiene and Styrene by n-BuLi-THF Initiation (Ⅱ)——Kinetics and Reactivity of Reactive Species
    Cheng Zi sheng, Yu Feng nian, Ying Sheng-Kang
    1984, 5(6):  889-894. 
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    As cheme of complex equilibrium and cross propagations between the living species in butadiene-styrene anionic copolymerization by n-BuLi-THFinitiation has been proposed. Accordingly, a copolymer composition equation has been derived and the implications of the apparent monomer reactivity ratio have been discussed. Moreever, the relationship between apparent rate constants (kB, kS) and the concentration of THF has been established. Finally, the probability of the vinyl group formation in poly-butadiene chain in copolymer from mono-THF coordinated reactive spe-eies has been estimated.
    A Study of the Poly condensation Process of Poly (Phenylene Ether Sulfone)
    Yu Tongyin, Li Shanjun, Fu Shoukuan, Ji Caigui
    1984, 5(6):  895-900. 
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    The present paper reports the studies of the alkaline polycondensation kinetics of poly (phenylene ether sulfone). The related monomers and their model compounds for polymers were synthesized, then their reaction velocity constants were determined. The chief results obtained are. (1) when two series (m,n) of substituted benzene derivatives are reacted with each other, the velocity constant kmn is equal to the product of velocity constant km0 and kn0.(2) For polycondensation reaction, when the reactivities of the monomers and the polymers are different, as in the case of polycondensation of poly (phenylene ether sulfone),it is not quite accurate to use a single velocity constant to derive the kinetic equation, instead, two or more reaction velocity constants must be used so as to conform to the experimental facts.
    The Effects of Chain Structure and Frequence on the Dielectric Spectra of Segmented Poly(ether-urethane) Copolymer
    Chen Zhusheng, Duan Xiaoqing, Huang Zuxiu, Zhang Daofan, Zhu Yong
    1984, 5(6):  901-903. 
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    In this paper, the dielectric spectra of different chain structure of segmented poly(ether-urethane) copolymer have been investigated. All relaxation phenomena were greatly influenced by the molecular weight of the prepolymer. Conditions of the micro-phase separation have been discussed. The apparent activation energies of relaxation processes were determined.