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    24 March 1986, Volume 7 Issue 3
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    Articles
    A Study of Oxidizing Process of Cobalt(Ⅱ) in the Bis-(2-Ethylhexyl)Dithiophosphoric Acid-Pyridine Solvent Extraction System
    Huang Jinwang, Xia Jingmou, Yu Hancheng, Ji Liangnian
    1986, 7(3):  191-196. 
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    In general, the cobalt (Ⅱ) complex is oxidated quite easy in the bis(2-ethyl-hexyl)dithiophosphoric acid solvent extraction system by oxygen in air. The oxidizing process of cobalt( Ⅱ ) has been studied in the bis(2-ethylhexyl)dithiophosphoric acid-pyridine solvent extraction system by using the methods of the interfacial tension, visible spectrum and infrared spectrum. The experiments have demonstrated that pyridine and its some derivatives can restrain the oxidation of cobalt( Ⅱ ) complex because of forming the mixed type complexes when they are coordinated into the Co( Ⅱ ) complex and the restraint ability of oxidation depends on the stability of mixed type complex formed.
    Hetero-Atom Molecular Sieve (Ⅵ)—The Synthesis and the Properties of B-Si Pentasil Type Molecular Sieve in the System of Na2O-SiO2-H3BO3-H2O
    Li Guowen, Pang Wenqin, Huo Qisheng, Qiu Shilun, Zhu Xing, Xu Yihua
    1986, 7(3):  197-202. 
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    B-Si pentasil type molecular sieve has been synthesized in a Na2O-SiO2-H3BO3-H2Osystem, by using directing agent. The ternary crystallization area for the molecular sieve was obtained in the reaction mixture. The suitable ranges for the composition of the reaction mixtures have been found. The kinetic process of the crystal growth and transformation of metastable phase were investigated for the molecular sieve.By using high vacuum adsorption methods TGand DTA, the adsorption and the thermal stable properties were determined for this molecular sieve respectively.
    Preparations and Properties of Scadium and Yttrium Nitrate Complexes with Biuret
    Zhai Yingli, Tang Ning, Wang Dinbo, Tan Minyu
    1986, 7(3):  203-205. 
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    In this work, the solid complexes of scadium and yttrium nitrates with biuret have been synthesized in anhydrous ethanol medium. The composition of these complexes were determined as ScB4(NO3)3 and YB4(NO3)3 (where B = biuret) by the methods of elemental analysis, X-ray powder diffraction, electrical conductance measurement infrared spectrometer and DTA-TGanalysis. ScB4(NO3)3 and YB4(NO3)3 melt at 220℃ and 258℃ respectively, with decomposition. They are stadle in drv air.
    Studies on Highly Sensitive Colour Reactions of Noble Metals (Ⅶ)—Palladium(Ⅱ)-Potassium lodide-Rhodamine 6G-PVA System
    Ci Yunxiang, Zhang Jinghua, Su Wen
    1986, 7(3):  206-210. 
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    Anew highly sensitive colour reaction of palladium ( Ⅱ ) has been investigated, based on the formation of an aqueous soluble ion-association complex of palladium( Ⅱ ) with potassium iodide and rhodamine 6G(R6G) in the presence of polyvinylalcohol(PVA). The absorption maximum of the ion-association complex is at 560 nm, and its apparent molar absorptivity is 4.5×105 1·mole-1·cm-1 at 560 nm; Beer's law is obeyed for 0-80 ng/rnl of palladium. The interference of 40 dverse ions was studied. The proposed procedure was applied to the determination of palladium in anode slime.
    Investigations on Oscillopolarographic Titrations (XXⅦ)—Oscillopolarographic Chelometric Titrations on One Micro Pt-Electrode
    Yang Zhaoliang, Gao Hong(H. Kao)
    1986, 7(3):  211-215. 
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    Studies on oscillopolarographic chelometric titrations on one micro pt-electrode were carried out. It was found that in the presence of KBr and at lower frequencies of a. c. source, some metallic ions gave distinct incisions which can be used to indicate the end-point of chelometric titrations. The accuracy and precision of the method arc satisfactory.
    Studies on the Multi-Hole Ring Oven Technique(Ⅱ)—The Mechanism of the Continuous Elution Method in Hydrophobic Capillarity Beds
    Geng Xindu
    1986, 7(3):  216-220. 
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    Amodel calculating the hydrophobility and evaluating the flow rate of eluant on a hydrophobic capillarity beds has been presented. The influence factors caused by the change of the surface tension of the cluanl were discussed. This model was tested by experiment qualitatively and has laid the foundation for exploring multi-hole ring oven techniques.
    Study on the Colour-Forming System with High Sensitivity—The System Lanthanum-Carboxynitrazo-Anionic/Cationic Surfactants
    Zhou Zhiming, Hu Jie, Wang Yiwen
    1986, 7(3):  221-224. 
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    The colour-forming reaction of lanthanum with carboxynitrazo was studied in the presence of anionic and cationic surfactants, sodium dodecyl benzene sulfonate (SDBS) and tetradecyl pyridine bromide (TPB). Strong sensitization was observed under the cooperative action of both surfactants near the equimolar([SDBS] : [TPB] = 1.2:1.0).The apparent molar absorptivity at 730 nm reaches as high as 3.00×105 l/mol·cm. The mechanism of the sensitization was discussed.
    Spectrophotometric Study of the β-Type Color Reaction of Rare Earths-Amino C Acid Chlorophosphorazo
    Guo Nairong, Luo Qingyao, Zeng Yun' e
    1986, 7(3):  225-227. 
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    In a HC1 medium, amino Cacid chlorophosphorazo reacts with rare earth elements, forming β-type complexes. The color reactions arc related to the acidity of the solutions both initial and final, the kinds and concentrations of the RE.The Ce-sub group demonstrates more strong trend than the Y-sub group one in forming β-type complexes. All of this is different from the other color reagents of this kind. It is seldom seen that the REdevelops color in such high acidity.
    The Synthesis of the Parapheromones of Rice Stem Borer Moth,Chilo Suppressalis
    Li Zhengming, Liu Tianlin, Liu Ziping, Go Husen, Yao Enyun
    1986, 7(3):  228-232. 
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    (Z)-Hcxadeccnes, their cpoxidcs and aryl analogs have stcrcospccifically been prepared by Wittig reaction of alkylidenetriphenylphosphorancs with alkylaldehydcs or arylaldehydes, respectively. (E)-5-Hexadecene is obtained from the conversions of (Z)-5-hcxadccenc via the addition of bromine and then elimination-reduction with NaNH2/NH3(1). These compounds arc active in EAGresponses.
    Study on Organo-Iodoso Compounds(Ⅰ)—The Steric Effect of Ortho-n-Alkyl Group on the Stability of Ortho-n-Alkyl Iodosobenzene
    Zhu Shenjie, Zhang Chunhao
    1986, 7(3):  233-238. 
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    Ascries of ortho-n-alkyl iodosobenzenes were synthesized from the corresponding n-alkyl iodobenzenes. Under the same conditions,it was found that with increasing in the carbon chain length of n-alkyl group, the formation of the corresponding ortho-n-alkyl iodosobenzene became more difficult and their stability decreased accordingly. Attempts for synthesizing ortho-n-alkyl iodosobenzene with carbon atoms more than five in the n-alkyl group were not successful. The structures of some ortho-n-alkyl iodosobenzenes were analyzed by ir and nmr spectra. The steric effect of the long chain n-alkyl groups in the formation of more stable polybridged structure was discussed.
    The Synthesis of Cytidylyl (2'-5') Cytidylyl (2'-5') Adenosine
    Zhang Lihe, Xu Chen, Tong Weimin
    1986, 7(3):  239-242. 
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    The synthesis of C2'p5'C2'p5'A, an analogue of adenylyl (2'-5') adenylyl (2'-5') adenosine, was described. This is the first report of a new analogue of A2'p5'A2'p5'Acontaining pyrimidine base instead of purine base.
    The Synthesis of Bis (Alkylcyclopentadienyl)Dithiocyano of Titanium,Zirconium and Hafnium
    Chen Shoushan, Li Jinshan, Wang Jitao
    1986, 7(3):  243-244. 
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    Using different method, the bis(alkylcyclopentadicnyl)dithiocyano of titanium, zirconium and hafnium, (η5-RC5H4)2M(NCS)2 (where M = Ti, Zr, Hf; R = CH3, C2H5, n-C3H7, n-C4H9) have been prepared. Their 1H NMRspectrum has been discussed.
    A Study of Bioactivitive Phosphorus-Containing Compounds—The Synthesis of N-(O,O-Dialkylthiophosphoryl)-α-Aminoacetic Esters with an Essentially Asymmetric Structure
    Zhang linglin, Chen Shizhi, Lu Haiyan
    1986, 7(3):  245-247. 
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    Fifteen ethyl N-(O,O-dialkylthiophosphoryl)-α-aminoacclic esters with two different alkoxy-groups on phosphorus atom were synthesized.
    Studies on the Kinetics of Solvent Extraction Process(Ⅱ)—Extraction of Zn(Ⅱ) from Sulfate Solution with HEH[EHP]
    Xi Zhengkai, Zhang Tiauhong, Shen Jinglan
    1986, 7(3):  248-250. 
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    Kinetics of Zinc(II ) extraction from aqueous sulfate solution with HEH[EHP] in benzene has been studied by means of the classical polarography. The effects of the stirring-speed, interfacial area between two phases, and the concentrations of Zn2+, H+ , SO42- and HEH[EHP] on the extraction rate for the titled, system have been investigated. The results indicate that extraction process is controlled by the interfacial reaction when the stirring-speed is over 200 rpm.
    A Study on Simulation Kinetics of Oligomers Reaction During Thermal Polymerization of Styrene
    Chang Mian, Zhang Xiqing, Yu Zhaofei
    1986, 7(3):  251-254. 
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    During the thermal Polymerization of styrene small quantities of dimeric and trimeric styrene are usually formed. In this paper the kinetic character of dimeric and trimeric at temperatures of 137℃ and 180℃ are studied by means of simulation method of an approximate curve of 'S' type. The corresponding kinetic equation is obtained, which is simple in form and clear in physical significance. Compared with Kirchner's theoretical model, this model is in better agreement with experimental results.
    A Statistical Mechanical Treatment of Hydrogen Evolution Reaction on FCC Metal
    Su Wenduan, Wu Yuanyun, Wu Jidao
    1986, 7(3):  255-260. 
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    The kinetics of electrolytic hydrogen evolution reactions ( H.E.R. ) on FCCmetals is considered in terms of statistical mechanics, assuming that the processes obey the catalytic mechanism. Amethod is proposed to calculate the inter-repulsed potentials between the hydrogen atoms adsorbed on crystal surfaces,and the theoretical η-lg(i) curves for H.E.R. on Ni, Pi, Ag, Cu, Au, and Pd arc plotted, respectively.The results show that the theoretical Tafel slope ( ?η/ ?lg(i) = b ) is determined by inter-repulsion between the adsorbed hydrogen atoms, and the intercept a is dependent on the atomic radius and lattice array of metal, and heat of adsorption of hydrogen, etc.
    Crystal Structure of Sulfatoaquo-2,3-Dimethyl-2,3-Butyldiamineplatinum
    Guo Dongyue, Wang Fengshan, Qu Yun, Tang Wenxia
    1986, 7(3):  261-264. 
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    [Pt DMBA SO4H2O]·H2Ocrystals belong to orthorhombic system, a= 11.073 (3), b = 9.672(2), c=21.156(7)Å, space group C2cd, Z = 8. The diffraction data (MoKa) were collected with Nicolet R3 fourcircle diffractometer. The structure was determined by heavy atom method and refined by the least square program, R = 0.0716.
    Analytical Potential Function for Polyatomic Systems—Application to SSO and SOS
    Z. H. Zhu
    1986, 7(3):  265-270. 
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    It is considerable interest to notice that a stable structure SSOis in Cs symmetry, but its melastable structure SOSin C2v symmetry. Using the contracted split-type Gaussian base sets with polarization functions, SOSwas discovered for the first time at HFSCFlevel. There have been no detailed studies, of the SSOsurface, although it was examined by a microwave spectrum as early as 1959. In this paper an analytical potential function based on the many-body expansion has been derived for both the SSOand the SOSsurfaces,which are adequate accuracy in the whole region for the dynamical research.
    Open Metallocene (Ⅳ)—Electron Structure of Bis(dimethylpentadienyI)Vanadium
    Zhao Wenyun, Liu Juzhen
    1986, 7(3):  271-274. 
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    Bis(2,4-dimethylpentadienyl)vanadium, an open vanadocene, and its adducts of various Lewis bases bave been analyzed in detail by EHMOprocedure, and the obtained results could reasonably explain their magnetism, stability, the effect of substitutive methyl on pentadienyl and Lewis bases, and configuration as well. Moreover the formation and properties of similar compounds have been predicted.
    The Determination of Composition and Sequence Distribution in Polysulfone-Polyesters Block Copolymers by 1H NMR
    Ding Youjun, Chen Qi, Pan Jingqi
    1986, 7(3):  275-280. 
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    High resolution NMRspectra of several kinds of Polysulfone-Polyesters(PSF-PPT, PSF-PBT, PSF-PHT, PSF-PDET, PSF-PTET) block copolymers were measured.The composition and sequence distribution of Polysulfonc-Polyesters block copolymers were studied. Proton signals due to helerolinkages could be observed in these block copolymers, and the average sequence length (L) and the degree of Randomness (B) in the Polysulfone-Polyesters block copolymers were calculated from the intensities of their signals.Bof block copolymers lie in the region of 0<B<1.
    A Lewis Acid Catalyst Supported by Polymer:Polystyrene-Stannic Chloride Complex—Preparation and Application in Organic Synthesis
    Ran Ruicheng, Jiang Shuojian, Shen Ji
    1986, 7(3):  281-285. 
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    Stannic chloride is protected with polystyrene-divinylbenzene (7%) copolyme beads in CS2 to form a stable complex containing 10.8% of chlorine. The SnCl4 supported by the polystyrene is resistant to water and is Prolonged Storing in air at least one year. The complex catalyst (PS-SnCl4) is a strong solid Lewis acid. The Lewis acid supported by polymer can be used to catalyze a lot of organic synthetic reactions in high yield, such as esterfications, acetal formations, ketal formations, etherifications and Friedel-Crafts alkylations.
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