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    24 July 1988, Volume 9 Issue 7
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    Articles
    Synthesis and Magnetism of Copper(Ⅱ)-Cobalt(Ⅱ)Complexes with N,N'-Ethylenedisalicylamidatocuprate(Ⅱ)
    Liao Daizheng
    1988, 9(7):  647-650. 
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    New binuclear complexes of type [Cu(samen)Co(L)]2 were synthesized,where samen 4- denotes N,N'-ethylenedisalicylamidate anion and Ldenotes 2,2'-dipyridyl or 1,10-phenanthrolirie. Based on IR, elemental analyses and electronic spectra, the complexes are proposed to consist of a Cu(Ⅱ) in a distorted planar environment and Cod) in a distorted octahedron. The magnetisms of the Cu(Ⅱ)-Co(Ⅱ) complexes were well interpreted in terms of the susceptibility equation based on Heisenberg model.
    Studies on Tungsten Cluster Compounds(Ⅰ)——Structural Determination of M3W2CI9 by EXAFS and Single Crystal Diffraction
    Lu Gang, Chen Minqin, Ma Lidun, Jin Songlin, Gu Yidong
    1988, 9(7):  651-655. 
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    EXAFS measurements were performed on a 12-kWrotating anode X-ray spectrometer for K3W2Cl9, (NH4)3 W2Cl9 and (Bu4N)3W2Cl9. Through Fourier transformation and curve fitting processes, the bond lengths and coordination numbers were obtained. W-W 2.43(1) Å, CN 1, W-Clt 2.44(3) Å, CN 3.3; W- Clb2.49(3)Å, CN 3.8. In order to certify the EXAFSresults, the single crystal structure of (NH4)3W2Cl9 was determined on ENRAF-NONIUS CAD-4 four-circle X-ray diffractometer. (NH4)3W2Cl9 crystallizes in space group P6θ/m and contains two formula unit in a unit cell, a = 6 = 7.216Å, c=16.518Å, dc = 3.303g/cm3. Within experimental error, the structural parameters of W,Cl93- determined by EXAFS technique are in good agreements with those by single crystal diffraction. It is infered that, combined with +1 cations, the anion W2Cl93- has the structure of two octahedra sharing a face to give D3d symmetry, and the skeleton and bond lengths have no tremendous change due to the strong W—W multi-bond.
    Spin State and Axial Coordination of Dimethylamino Tailed Porphyrin Iron
    Xiu Zhengkun, Zhao Dongyuan, Cao Xizhang, Dong Qingchu
    1988, 9(7):  656-660. 
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    Atailed porphyrin iron complex, meso-mono-CO-(4-dimethylamino butylami-do) phenyl] triphenylporphyrin iron (Ⅲ) chloride has been prepared. Experimental results by EPR, UV,Raman, Mossbauer, MCDand cyclic voltammetry methods demonstrated that high-spin iron (Ⅲ)complex shows no intermolecular coordination of the terminal group on the metal ion while five-coordinate ferrous com-plexes are formed with axial ligands.
    Studies on the Colour Reaction of New Reagent p-Methyldibromoarsenazo with Rare Earths
    Li Xinyi, Zhang Huashan, Cui Jianchuan
    1988, 9(7):  661-664. 
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    Anew reagent,p-methyldjbronioarsenazo, was synthesized and a simple, rapid, seusitive and selective method for the spectro-protometric determination of rare earths was developed based upon the formation of p-methyldibromoarse-nazo-rare earth complexes.In HCl-NaAc medium, the reaction of rare earths with p-methyldibromoar-senazo forms blue violet complexes, which are stable over 24 hours. The absor-bance was measured at 635nm. The apparent molar absorptivity coefficient of rare earth complexes are very much the same (εLa= 1.38×105, εYb = 1.01 ×105, εY= 1.17×105). The composition of complex is La(Y):R= 1:2.The method has been successfully applied to the determination of micro amount of rare earths in wheat and aluminium alloy.
    Investigation on Triangular-wave AC Oscillopolarography(Ⅱ)——Theory of Single Electrode Reaction
    Qi Hong, Ma Xinsheng, Gao Hong(H. Kao)
    1988, 9(7):  665-669. 
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    The theory of single electrode reaction in triangular-wave ACoscillopola-rography is presented. Theoretical equation for E-t curve and incision height on concentration, current sweeping rate and other factors is confirmed with the experimental results very well.
    Investigation of Enhancement Sensitivity of Ytterbium by Surfactants in Atomic Absorption Spectrometry
    Wei Jizhong, Mu Huiling, Shi Huiming
    1988, 9(7):  670-675. 
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    In this paper, we studied the effect of surfactants on the sensitivity of Yb in the C2H2-Air flame. The absorption of Ytterbium was increased by about 10 or 50 times in the presence of sodium dodecyl sulfate (SDS) or SDSwith the sulfosalicylic acid(SSA), respectively. The interference from other rare earth elements and some acids was greatly depressed,especially from SO42- and PO43-,in the presence of SDSand SSA. Moreover, the mechanism of enhancement of surfactants was also studied. The detective limit of Yb was fallen down to 0.031μg/mLin the presence of SDSand SSA,and the relative standard deviation was 3.0% in the range of 0.05-2.0μg/mL Yb.
    Determination of Components and Stability Constants of Metal Chelates by Anodic Stripping Voltammetry
    Hang Taijun, Peng Cizhen
    1988, 9(7):  676-680. 
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    Anodic stripping voltammetry method was used in the study of metal chelates. The systems of Pb(Ⅱ), Cd(Ⅱ) and Zn(Ⅱ) with EDTA, Pb(Ⅱ) with NTAand Pb(Ⅱ), Cd(Ⅱ) with TTHA have been investigated. The components of these chelates were determined and the stability constants were calculated. They are in good agreement with literature results.
    The Determination of Ultratrace Amounts of Iron by Catalytic Decolorizing Method as a New Indicator Reaction
    Zhang Zhenhui
    1988, 9(7):  681-686. 
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    In this paper, that iron(M) can catalyze the decolorizing reaction which results from the oxidation of calconcaboxylic acid sodium salt by hydrogen peroxide in acetic acid is studied. In this method, Sandell sensitivity of catalytic spectrophotometry is 2.92×10-5μg/cm2. Beer's law is obeyed in the range of 0 to 500ng Fe per 25mL.The apparent activation energy of catalytic reaction is 79.80kJ/mol, which was calculated by using Arrhenius Formula. This new method has been successfully applied to the determination of ultratrace amounts of iron in water, foods, and human hair samples, respectively.
    Identification and the Mechanism of Formation of the Radicals in Friedel-Crafts Reactions
    Dang Haishan, Liu Youcheng, Hu Wensu, Chen Wei
    1988, 9(7):  687-691. 
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    Friedel-Crafts reactions of a series of alkyl halides with benzene gave well-resolved ESRspectra which originated from 9,10-disubstituted anthracene radical cations formed through one-electron oxidation of the parent compounds by Lewis acid. Asimple method for the formation of 9,10-disubstituted anthracene radical cations has been developed and an ESRspectrum of a new radical cation 1,2,3, 4,5,6,7,8-octadeuteroanthracene is reported.
    Keto-Enol Tautomerism of a Stable Free Radical——ESR and ENDOR Study on Tri(2-Deoxy-2-L-Ascorbyl) Amine Radical Anion
    Wu Longmin, Liu Zhongli, Wang Lijuan, Liu Youcheng, Cheng Jinlong
    1988, 9(7):  692-695. 
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    ESR and ENDOR studies were accomplished on the free radical obtained from the oxidation of tri(2-deoxy-2-L-ascorbyl)amine in pH 8.95buffer solution. It is concluded that a keto-enol tautomeric equilibrium of the amine radical anion existed in the solution,which is believed to be the first example of keto-enol tauto-merism concerning a stable free radical.
    Studies on Organoarsenic Compounds(X)——The Mass Spectrum of α-Thenoylacylmethyltriphenylarsine and Its Reactions with Acid Anhydrides and Acyl Halides
    Tao Wentian, Yang Tingxian, Zhang Yinhua
    1988, 9(7):  696-699. 
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    This paper presents the mass spectrum of α-thenoylacylmethyltriphenylarsine (1) and its reactions with acid anhydrides and acyl halides. The fragment peaks pf arspnium ylide (1) are shpwn.Arspnium ylide (1) reacted with a variety pf acid anhydrides tp fprm new stable derivatives pf the corresppnding diketoarsonium ylides (2a-d) at 30-60℃; in benzene. Acylation of arsonium ylide (1) with acyl halides in benzene led to enol-ester derivatives (3a-f). We alsp found that when arsonium ylides (3c,d) was heated in basic trichloromethane, diketoarsonium ylides (4d) and arsonium ylide (1) was obtained. The structures of products have been ascertained by elemental analysis, IRand 1H NMRspectroscopies.
    The Method of Determination for the force Constants of General Valence Force Field in Vibration of Large Molecules
    Yan Guosen, Sun Zemin, Xiao Shenxiu, Xue Ying
    1988, 9(7):  700-705. 
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    At first, the method for defining the force constants of GVFFfrom that of UBFFhas been set up in this paper.Through a serial transforms,we can conveniently obtain Fs force constants matrix in symmetric coordinates in UBFF. According to the idea that in the local symmetry force field there is the . transferability of force constants related to different functional groups in the molecules having similar structure, and we transfer the FS matrix from UBFFto GVFFfor the same molecule, that is: (FS)GVFF = (FS)UBFF. Then the (FS)GVFF is transformed by the-converse transform of the Umatrix to the Fr in GVFF, which--is used as the initial force constant F° in Wilson's equation. In this paper, we still further study the method of kinematically defined fore constants. This method starts from the determination of force constants by the factorization of Gmatrix and vibrational frequencies. Yan Guosin etc. have discussed the., problem of- the-ordering of eigenvalues λi in Λ matrix. The advance- here for it has made in the two respects; in the using, the higher dimensional matrix FS has- calculated, by an above rule, and the dimension of symmetry species have expanded to 16.In the method,we give a solution on the new problem that two frequencies belong tothe same symmetric coordinates, if frequencies vi and vi belong to Si and Si, while vk and vl to Sk and Sl,the four possible orderings were considered and the correspond force constants were calculated by those orderings respectively. It had been shown that in Born-Oppenheimer approximation the force constants of the molecule due to isotopic substitution are invariable, then, we calculate .the vibration-al frequencies of the isotopic molecule with the several set of force condtants given above and compare them with the observed isotopic frequencies respectively. The ordering in which the frequency error is smallest would be choosed. The normal vibrational analyses of the molecules M(NH2CSeNH2)42+, {M = Pd(Ⅱ), Pt(Ⅱ)} are carried out by the above methods.
    A Study of Pulsed Light-Induced Transient Behavior at n-InP Electrode in Fe3+/Fe2+
    Qian Daosun, Sun Lizhong, Sun Birou
    1988, 9(7):  706-710. 
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    In this paper the effects of electrode potential and current on the transient behavior of n-InPin Fe3+/Fe2+ using pulsed light technique are studied.The rules of the values at the peak response are in accordance with the stable state. The influence of the electrode potential and the current on the time-constant can be explained by back-diffusion mechanism.The light intensity does not influence the time-constant. An overrush phenomenon is observed when the electrode potential is near the flatband potential. The output electric quantities are determined and the results are explained.
    Molecular Orbital Study of the Interaction of Benzene Molecules with Rh(111) Surface
    Gao Guorong, Guo Chunxiao
    1988, 9(7):  711-715. 
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    The chemisorption behavior and bonding properties of benzene molecules adsorbed on Rh(111) surface have been studeid by EHMOprogram reduced by group theory. The metal cluster of Rh7 is used to imitate Rh(111) surface. The calculated binding energy is 41 kJ/mol and the distance between the adsorbed benzene ring plane and Rh(111) surface is 2.60Å.The present authors consider that the interaction between π- electron pf the adsorbed benzene molecules and d orbital of Rh atoms on surface enables the benzene molecules to activate, which is favorable for the reaction of benzene on Rh(111) surface.
    Studies on Mass Spectrometry of Methylated Pentadiene
    Yang Yinghua, Jiang Yunfei, Zhao Bing, Liu Juzheng
    1988, 9(7):  716-720. 
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    For pentadiene and methylated pentadiene, CH3CH=C(CH3) CH=CH2(1), CH5C(CH3)=CHCH=CH2 (2),CH3CH=C(CH3)C(CH3)=CH2(3),CH3C(CH3) =CHC(CH3)=CH2 (4), CH3C(CH3)=C(CH3) C(CH3)=CH2 (5), and CH3CH=CHCH=CH2 (6), EI, CI, mass spectra were recorded,and the samples (1), (3), (5) of them were determined by metastable and high resolution technique simultaneously. On the basis of these, the fragmentation rules and mechanisms of methylated pentadiene have been suggested.
    Syntheses and Properties of Graft Copolymer of Starch-Sulfomethylated Polyacrylamide
    Yao Kejun, Wang Yao
    1988, 9(7):  721-725. 
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    The graft copolymer of starch-sulfomethylated polyacrylamide(S-g-SPAM) was prepared by the sulfomethylation of graft copolyrner of starch-poly-acrylamide (S-g-PAM) with paraformaldehyde and sodium sulfite. The structure of the sul-fomethylated copolytner was identified by IR.The effects of their molecular structure on flocculation of Kaolin suspension were studied. The results are as follows.(1) The ability of flocculation of S-g-SPAMis better than that of S-g-PAM, HP AM, and much better than that of PAM.(2) S-g-SPAMshowed that the ability increases with increased molecular weight of grafted polymer.(3) Amid-degree of sulfomethylation (30%) is effective for Kaolin suspension.The rheological behaviour of S-g-SPAM aqueous solution showed pseudoplastic flow in the range of concentration of 0.1-1.0%. The metal ions (such as Na+, Mg2+, Ca2+) cause reduction in apparent viscosity (ηα), the order of influence is as follows:Na+<Mg2+<Ca2+.
    The Phase Diagram of BaCl2-LiCl-NaF System
    Yan Licheng, Yang jinxiu, Zhu Yingying
    1988, 9(7):  726-728. 
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    By visual polythermal, DTA aad X-ray powder diffraction methods, the phase diagram of molten salt system BaCl2-LiCl-NaF have been determined.
    A Dry Way Synthesis of EuSO4 and Its Crystal Structure
    Lin Pingdi, Wu Guoqing, Liu lianping
    1988, 9(7):  729-731. 
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    EuSO4 was prepared by a dry way reaction for the first time as follows:EuCl2 (s)+HgSO4(s) EuSO4(s) 3×10-4Pa.Ar/773K.72h→EuSO4+HgCl2(g) was obtained, orthorhombic barite structure (Prima, Z=4), with a=838.69± 0.15pm, b=534.95±0.09pm, c=688.18±0.13pm. Atom positions of Eu,S and O were proposed, resulting in a set of calculated intensities coincided well with the observed.
    Studies on the Fluorescence Reaction of Ninhydrin with Lysine
    Wang Huaigong, Ji Hongtao
    1988, 9(7):  732-734. 
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    This paper describes a new method for fluorometric determination of Lysine(Lys) with ninhydrin. The quantum yield of reaction is 0.51. The 1Rand NMRspectra of product formed were determined. The mechanism of reactionwas discussed, preliminary,too. The other amino acid interference was discoussed.The method is simple and rapid. The Lysine in sample was determined withsatisfactory and precision.
    Study on Nitrogen-Fixation Activity of Some Unstable Cp2TiAr2 Under Mild Conditions
    Liu Yiyin, Cao Xiaomin
    1988, 9(7):  735-736. 
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    The formation of some unstable Cp2TiAr2 (1) was proved by means of determination of produced X- ions in the reaction process. The nitrogen-fixation activity of Iunder room temperature and normal pressure was studied. Some of 1 show good nitrogen-fixation catalysis. The mechanism of ammonia formation is discussed.
    The Reaction of Tetracoordinated Thiophosphoryl Compounds with Catechol
    Liu Lunzu, Cao Ruzhen, Gai Baozhong, Yang Xiaohui
    1988, 9(7):  737-739. 
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    The reaction of a series of phosphorochloridothioates with catechol in the presence of triethylamine yields a hexacoordinated phosphorus, compound Ⅱ. Phenyl thiophosphonyl chlorides reacted with catechol to produce a pentacoordina-ted phosphorus compound Ⅴ. Phenyl. pyrophosphonothioate reacts with catechol to give Ⅱ and Ⅴ. The mechanism of these reaction were discussed, too.
    Studies on Chemical Ingredients of Aconitum Karakolicum var. Patentipilum
    Wang Rui, Chen Yaozu, Yu Jianxin
    1988, 9(7):  740-742. 
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    Five alkaloids have been isolated from the roots of aconitum karakolicum var. patentipilum W. T. Wang, which was collected from Xinjiang province in China. They were identified as deoxyaconitine, songorine, aconitine, neoline and karacoline. All these alkaloids were found first time in this herb.
    Synthesis of S- and R-Timolol Maleate
    Zhou Zhishan, Zhu Juliang
    1988, 9(7):  743-745. 
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    The S- and R-timblol were prepared by optical resolution of racemic timolol. Thus, the treatment of glycerol with HCl afforded 3-chloro-l,2-propanediol(1). 1 undergoes condensation with tertiary butylamine to give dl-3-t-butylamino-1, 2-propanediol(2) in 70.9% yield. The treatment of 2 with benzaldehyde afforded the oxazolidine derivative(3) in 79% yield. Racemic timolol(4) could be obtained in 53% yield from 3 by treatment with 3-chloro-4-morpholino-1,2,5-thiadiazole and t-BuOKin t-BuOHand hydrolization. 4 is resolved with d-tartaric acid to give S-timolol-d-tartaric acid . salt and R-timolol-d-tartaric acid salt. Then the treatment of these salts with NaOHand maleic acid afforded S-timolol and R-timolol maleate, respectively.
    Studies on Thermokinetics (Ⅵ)——Thermokinetics for Ring-Opening Reaction of the Epichlorohydrin
    Huang Qizhong, Zhang Yuanqin, Zeng Xiancheng
    1988, 9(7):  746-748. 
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    On the theoretical basis of thermokinetics proposed in previous articles, the thermokinetics for ring-opening reaction of the epichlorohydrin with potassium iodide has been studied at 20℃ in buffer solution with the method of dimension-less parameter for the second order reaction. The reproducibility of experimental results is very good, and the rate constant is in fair agreement with the values in literature.The influences of the concentration and pHvalues of the buffer solution on the rate constant of measured reaction have been also discussed.
    Frequency Property of Piezoelectric Crystal in Solutions with a Transistorized Oscillator and Its Chemical Applications
    Yao Shouzhuo, Zhou Tiean
    1988, 9(7):  749-751. 
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    Solution properties of the piezoelectric quartz crystal were studied using a transistorized oscillator. Frequency shift increases linearly with the increasing electrolyte concentration with a slope which is common for the electrolyte salts. Grounding the detection cell, it results 'in a wider linearity range. Anew frequency shift method has been developed for rapid determination of total electrolyte concentration in natural waters.
    A Study of H-F Force for Multicentre Bridge Bond in Electronic Deficient Molecule Boranes
    Du Qishi, Peng Zhouren
    1988, 9(7):  752-754. 
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    The bridge force term in partition the H-Fforce is defined, which means the force acting on a nucleus Acoming from the overlap of electronic charge density, between atoms Band C. The bridge forces in molecules B2H6 and C2H4 etc. are computed by means of quantum chemical ab initio method. The results show that the effect of bridge force in normal molecules (e.g.C,H4) can be neglected, but it may play a important role in multicentre bridge bond of electronic deficient molecules (e.g.B2H6). The equivalent point charge of the overlap force and its position in molecule B2H6 are calculated. According to these data a electronic charge distribution diagram of molecule B2H6 is drawn, which may clearly represent the character of chemical bond in a molecule.
    Synthesis of Ferrocene-Containing Poiyanlides, Polyureas and Polyesters in Their Backbones by the Interfacial Technique
    Lin Zhanru, Gonsalves. K.
    1988, 9(7):  755-757. 
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    Monomers, 1, 1'-bis(β-aminoethyl) ferrocene (1) and 1,1,-bis (β-hydro-xyethyl) ferrocene were synthesized starting frpm ferrocene via acetylation, hydrolysis, esterification, cyanidation and reduction, yields obtained were 73% and 98%, respectively. Monomer (1) then, reacted with diacid chlorides as well as with diisocyanates, and monomer (2) reacted with terephthaloyl chloride, leading to ferrocene-containing polyamides, polyureas and polyesters in their backbones under the interfacial polymerization condition.TGanalysis of the ferrocene-containing polyamide, in contrast, with the poly urea and polyester, showed weight loss only 1.0 to 1.5% at 300℃ and 3.0 to 6.0% at 400℃, respectively.
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