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    24 May 1986, Volume 7 Issue 5
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    Articles
    Studies on White Powdery Tungstic Acid (Ⅳ)—Preparation of Ammonium Metatungstate and Study on its Polycrystalline X-ray Diffraction Pattern
    Gu Yidong(Yih-Dong Ku), Song Yuan, Chen Minqin
    1986, 7(5):  383-386. 
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    After we succeeded in preparing white powdery tungstic acid hitherto not described in literature, we have found that on account of its reactivity, different from tungstic acid in yellow form, white powdery tungstic acid can be well used for preparing a variety of compounds including different kinds of salts of meta-tungstic acid as well as certain heteropoly tungstic acid and their salts.Ammonium metatungstate, AMT, prepared by neutralizing white powdery tungstic acid with ammonium bicarbonate gives a perfectly clear, rather concentrated solution, then well defined crystals at room temperature. Although the crystals thus prepared rather readily lose part of water of hydration, as revealed in thermal analysis, we have succeeded in measuring its X-ray diffraction pattern not yet revealed in literature. The diffraction pattern of AMTcrystal has been found as a =18.08Å, Z = 4. The molecular formula of AMTcan be expressed as (NH4)6[H2(W3O10)4]·20H2O.
    Bonding Model Studies for Nitric Oxide Complex of a Tailed Iron(Ⅱ) Porphyrin
    Cao Xizhang, Mu Xihai
    1986, 7(5):  387-390. 
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    Anew tailed iron( Ⅱ )porphyrin complex mcso-MDBPTPPFe( Ⅱ ), with a tailed Et2N-as axial base,reacts with nitric oxide to form adduct meso-MDBPTPPFe( Ⅱ ) NO. The N-Ostretching frequency for this adduct is 1671cm-1. Spectral results demonstrate that when meso-MDBPTPPFe( Ⅱ ) is coordinated by NOin the sixth coordination position the axial coordinated base is away from iron because the unpaired electron of NOhas to go into the antibonding orbital of sp3(N) + dz2(Fe). The observed three g values in meso-MDBPTPPFe( Ⅱ )NO EPRspectrum indicate that the dxz and dyz orbitals are nondegenerate and the iron-nitric oxide unite is bent.
    The Synthesis and Properties of AlPO4-5, AlPO4-11 and A1PO4-20 Molecular Sieves
    Xu Qinhua, Dong Jialu, Yan Aizhen, Jin Changtai
    1986, 7(5):  391-396. 
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    The AlPO4-5, AlPO4-11 and AlPO4-20 molecular sieves have been synthesized hydrothermally in the presence of organic amines or quaternary ammowum which acts as templcte. These samples were characterized by X-ray diffraction patterns and infrared spectra. It was found that the framework topology of AlPO4-11 is changed after calcinations. DTAshows no structural collapse below -950℃.The adsorption properties of water and hydrocarbons on the samples were studied. The results show that the water pore volumes are greater than the hydrocarbon pore volumes, reflecting the presence of additional pore volume accessible to H2Obut not to hydrocarbons.
    Complex of Cerium(Ⅳ) Nitrate with a Tetraoxadiaza Macrocycle
    Zhu Wenxiang, Li Qin, Zhang Aijun, Chen Botao, Zhao Jizhou, Jin Linpei
    1986, 7(5):  397-400. 
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    The 1: 1 solvated complex of cerium( Ⅳ ) nitrate with a tctraoxadiaza 18-membered. macrocycle has been synthesized under anhydrous conditions. The complex was characterized by elemental analysis, conductometric and spectral data. The properties of the complex has been studied.
    Complex Formation of Ce(Ⅳ) with the Pyrophosphate Ion
    Dong Wenji, Yang Rudong
    1986, 7(5):  401-405. 
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    In this paper we have studied the reaction between the aqueous solution of P2O74- and Ce ( Ⅳ ) obtained by chemical oxidation of the corresponding trivalent species in an alkaline aqueous pyrophosphatc solution using ozonc. under different conditions three solids of Ce P2O7·x H2O, K2(Ce(HP2O7 )2)·4H2Oand K4(Ce(P2O7)3)·3H2Owere obtained from the solution of Ce( Ⅳ)-P274- with different methods. The compositions and the properties of these solids were studied by chemical analysis, thermal analysis, infra-red spectrum and the determination of molar conductivities and charges of the complex ion.
    Study of the Mechanism of Synergic Sensitizing Effect on Color Reactions by Mixed Ionic Nonionic Surfactants
    Qi Wenbin, Zhu Lizhong
    1986, 7(5):  406-410. 
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    The synergic sensitizing effects of mixed ionic-nonionic surfactants on both Cd-PARand Al-CASsystems have been investigated. It was deduced that besides mixed micelles of the surlaclanls affecting the reaction microenvironmenl, the synergic pertubatinal effect of the surfactants on electron distributions in conjugated system is also an important cause of synergic sensitizing effect.
    Studies on Inorganic Ion Exchanger Containing Phosphorus(Ⅱ)—Synthesis and Properties of Stannic Selenopyrophosphate
    Liu Xu, Liu Jinchun, Cheng Jieke
    1986, 7(5):  411-416. 
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    Anew inorganic ion exchanger—stannic selenopyrophosphate has beensynthesized. The studies on its chemical composition, ion exchange capacity, pHtitration,thermal and chemical stability,distribution coefficients of thirty seven metal ions, IR, Raman spectrometry and X-ray analysis show that it is a polyfunctional cation exchanger possessing high ion exchange capacity and good chemical stability. It has a high affinity for Ag(Ⅰ), Pb( Ⅱ ), Ba( Ⅱ ), Bi( Ⅲ ) and Zr(Ⅳ).An empirical formula representing the relationship of ion exchange capacity of alkali and alkaline earth metal ions with bare radii and charges has been proposed. And a possible chemical formula of stannic selenopyrophosphate has also been inferred.
    The Synthesis of 4-Fluoro-3-Hydroxy-1-Substituted Phenyl-6-Pyridazinones and Their Derivatives
    Cui Yingshe, Lin Chengji, Tian Guanrong
    1986, 7(5):  417-420. 
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    4-Fluoro-3-hydroxy-1-substituted phenyl-6-pyridazinones were prepared by the condensation of fluoro maleic anhydride ( Ⅰ ) with substituted phenyl hydrazines [Substituents: R(Ⅱ)=m-CF3; R(Ⅲ) = p-CH3; R(Ⅳ)=o-CH3; R(Ⅴ) = p-Br]. It was identified that compounds ( Ⅱ ), (Ⅲ), (Ⅳ) and (Ⅴ) exist in the form lactim and the fluorine atoms in these compounds are at C4 position in pyridazine ring. The reaction of ( Ⅰ ) with m-trifluoro methyl phenyl hydrazine in dilute hydrochloric acid gave N-(m-trifluoro methyl anilino)-fluoro maleimide (Ⅳ) which can be converted into ( Ⅱ ) in concentrated hydrochloric acid. The reaction of (Ⅲ) and (Ⅴ) with phosphorus oxy chloride gave corresponding3,4-dichloro substituted compounds (Ⅶ) and (Ⅷ) respectively. The reaction of (Ⅲ) with methyl sulfate gave 3 ,4-dimethoxy-l-(p-tolyl)-6-pyridazinone(Ⅸ ). Compounds ( Ⅱ ), ( Ⅲ ) and (Ⅷ) have a good effect on preventing the rice-blast, anti-intestinal spasm and tuberculostatic activity, respectively.
    The Solvent Effects on the Electronic Spectra of 1,4-Bis (5’-(2’-Phenyl Oxazolyl))Benzene and Its 2’-(4"-t-Butyl Phenyl) Derivative
    Wang Mingzhen, Jing Naiyong, Gao Zhenheng(Kao Chenheng)
    1986, 7(5):  421-425. 
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    The solvent effects of 1,4-bis(5'-(2'-phenyl oxazolyl)) benzene and its 2’-(4"-t-butyl phenyl) derivative in nineteen solvents were studied by using UVand FLspectra. The results indicated that the action of the solvents on the ground states and the excited states of the two compounds are almost the same. The dipole moment of the excited states of the compounds was discussed.
    Polyethylene Glycols Used as Phase Transfer Catalyst for Darzens Glycidic Ester Condensation
    Xiong Liceng, Yu Lingchong
    1986, 7(5):  426-429. 
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    The Darzens glycidic ester condensation of aldehydes can be carried out in moderate yield under solid-liquid phase transfer condition with potassium carbonate as base, toluene as solvent and polyethylene glycol-600 as phase transfer catalyst. The yield of aromatic glycidic ester is 50-77%.
    Preparation of Optically Active Silatranes
    Yang Yunyun, Yin Chenglie
    1986, 7(5):  430-433. 
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    Twelve pairs of optically active silatranes ( Ⅱ ) were prepared by cyclization of alkyltrielhoxysilane with Dor L N,N-dihydroxyethyl-2-amino-butanol- 1 in the presence of alkaline hydroxide as catalyst.
    The Calculation of the Conjugated Bonding of Diphenylmercury
    Luo Xincai, Lai Chengming, Gao Zhenheng
    1986, 7(5):  434-435. 
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    EHMOmethod is used to siudy the conjugated property of diphcnylmercury , the results obtained from the calculation indicate that there exists the conjugated system in the molecule.
    Ligand Field Analysis of the Electronic Spectra of Tetragonal Distrorted Cobalt (Ⅱ) Complex
    Liao Daizheng, Zhang Zhiyong, Wang Genglin
    1986, 7(5):  436-440. 
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    Electronic spectra of 14-membered hexaaza macrocyclic Co ( Ⅱ ) complex, [CoL(SCN)2]·5H2O, have been treated by the ligand field theory. Values of the various ligand field parameters have been obtained and their chemical significance was discussed. The transition energies have been derived form the parameters and d7 energy matrices.Fairly good agreement has been obtained between the calculated and experimental values.
    Electronic Structure and Chemical Bonding of Trisindenyl Samarium
    Ren Jingqing, Xu Guangxian
    1986, 7(5):  441-447. 
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    The electronic structure and chemical bonding of Sm(Ind)3 have been studied by INDOcalculation. The results show that the 6s, 6p and 5d orbitals of Sm are mixed with the atomic orbitals of ligands to some extent while the 4f orbitals of Sm are strongly localized, participating in bonding less than 2%. The HOMOand the LUMOare of π-type. The chemical bonds of Sm(Ind)3 are considerably covalent in character. The net charge distribution on the carbon atoms of the indenyl group is unequal. Based on packing of ligands the possibility of existence of Sm-C σ bonds in Sm(Ind)3·THFwas discussed.
    E-R Localized Molecular Orbital Methods and Molecular Binding Energy
    Sun Weiguo, Xie Yaoming, Tian Anmin, Yan Guosen
    1986, 7(5):  448-452. 
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    According to the principle of localized Molecular Orbitals (LMOs)[1], the LMOs of HF, BH,LiH, Li2,Be2, CO and CH4 are obtained by using our program. Since a better unitary transformation is determined, these LMOs are more rational than those given by other papers[8,10]. In this article, we also computed the LMOenergy s, the addition energy E'and the molecular binding energy E"[2]. By analizing the value of E", three conclusions are obtained. First, the intercation energy between the chemical bonds can not be negnected. Second, the exchange energy between LMOs is smaller than that between canonical mocecular orbitals (CMOs), so the LMOis much nearer to the classical chemical picture. Third, the larger the electron number is, the greater the exchange energy among electrons will be.
    The Adsorption of Oxy-Aromatic Compounds from Cyclohexane onto Silica Gel
    Zhao Zhenguo, Wu Yin, Lin Yao
    1986, 7(5):  453-456. 
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    The adsorption isotherms for benzyl alcohol, anisole, benzaldehyde and benzoic acid on silica gel from cyclohexane have been measured at 15℃ and 30℃. The standard changes of free energy △G°, enthalpy △H° and entropy △S° in adsorption processes have been calculated from the Langmuir parameters. The results indicate that △S° is all positive. The shifts △VOHof the adsorption band of the stretching frequency of free hydroxyl groups on silica gel at high surface coverages were determined. The results show that △H0 is linear function of △vOHor △vOH1/2.
    Multiplicity, Stability and Reproducibility of Chemical Equilibria
    Li Rusheng
    1986, 7(5):  457-461. 
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    The multiplicity, stability and reproducibility of chemical equilibria in nonideal chemical reaction systems are discussed by using a kinetic method. The dependent relations between experimental results (chemical equilibrium states) and initial conditions and other kinetic processes are analysed. The importance of the problem of multiplicity and stability of chemical equilibria in some practical problems and engineering design are also briefly discussed.
    A Study on the Choice of the Electrolyte for Nonaqueous Battery of Li/MnO2
    Ding Yunchang, Xia Guanguang, Han Guofang, Zhang Junxia, Yu Dajie, Wu Dapeng
    1986, 7(5):  462-464. 
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    Aimitative battery of Li/MnO2 has been designed and made by the writer. By the simulated experiments of the battery the relation between electrolyte composition and electric performance of the battery has been found. The reuslts show that the electrolyte which is 1M LiClO4 in propylene carbonate: dimethoxyethune in the 3:7 ratio is desirable for Li/MnO2 battery.
    Behavior of Short Ghemotherapeutic Polyelectrolytes Solution
    Zhang Lina, Qiu Dajian, Feng Yonggui
    1986, 7(5):  465-469. 
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    Polyphosphonatester salts PPAand PPB (2400<M<3700) containing 5-fluo-rouracil in the main chain have been studied by improved Bruss rnenbranc osmometer and dynamic osmomctry, viscometry, conductivity method. It was indicated from experiment, that the molecular conductance of infinite dilution ∧0 of the samples in DMSOis small, so normal osmotic pressure behavior were observed. The number average molecular weight Mn and second virial coefficient A2 wene obtained. Dissolving them in pure water or in methanol, the condition, ∧0 of PPBthe samples become large and the solutions exhibit properties of polyelectrolyle solution. But at high dilutions, both curves of ηSP/C-Cand ∧0-Cappear anomaly.
    The Preparation and Properties of Bromo-Substituted Poly-N-Vinylcarbazole
    Liu Zhijie
    1986, 7(5):  470-474. 
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    In the present work author have studied the preparation of polymono-bromo-N-vinylcarbazole(PBVK) and polydibromo-N-vinylcarbazole(PDBVK) from poly-N-vinylcarbazol(PVK). Their 1Rand UVspectra were determined. The photoconducting sensitizing behavior of 2 ,4 ,7-Trinilrofluorenone (TNF), 2 ,4 ,6-triphenylthio-pyrylium perchlorate(TPT) and <<SS>dye to PVK, PBVKand PDBVKhas also been studied.
    Kinetics of the Ziegler-Natta Polymerization of 1-Octene (Ⅰ)—The Kinetics of the Stationary Period
    Yang Shilin, Fan Zhiqiang, Feng Linxian
    1986, 7(5):  475-477. 
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    The kinetic behavior of polymerization of 1-octcne in n-heptane based on α-TiCl3-AlEt3 (or -Al(i-Bu)3, -AlEt3Cl) catalysts was studied. The rate curves could be divided into 1 to 3 stages and corresponding1 to 3 stationary periods, in which the stationary rates increase in the approximate ratios 1:2:4, The phenomenon was caused by the corresponding stair-like rising of the number of active centers, and was suggested to be the result of the breaking of TiCl3 crystals under the effect of propagating chains.
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