Table of Content

24 November 1985, Volume 1 Issue 2

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Articles

THE THEORY OP BOUNDARIES IN ISOBARIC ISOPLETHS(Ⅰ)--REGULAR SECTIONS

Zhao Muyu, Kang Hongye

1985, 1(2):  1-8. 

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According to the theory of the relation between neighboring phase regions abbreviated to NPRs) and their boundaries in isobaric phase diagrams,we discuss systematically the relation between the characteristics of boundaries and the combinations of the phases of NPRs in isobaric isopleths.There are only three types and seven subgroups of boundaries of different character and the concrete characteristics of them have been determined.

STUDIES ON BORON COMPOUNDS (Ⅱ)--SYNTHESIS AND PROPERTIES OF BORON CONTAINING BIS(π-ARENE)IRON(Ⅱ)COMPOUNDS

Zhang Lun, Fang Xingin, Zhang Guomin

1985, 1(2):  9-15. 

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Thirteen bis(π-arene)iron(Ⅱ) compounds were synthesized.They are [Ar FelB₁₂H₁₂(Ar=C₆H₆;MeC₆H₅;EtC₆H₅;n-PrC₆H₅;t-Pr-C₆H₅;p-Me₂C₆H₄,o-Me₂C₆H₄; 1,2,4-Me₃C₆H₃;1,3,5-Me₃C₆H₃;and 1,2,4,5-MeC₆h₂)and [Ar₂Fe][PF6]₂(Ar=p-Me₂C₆H₄;and These compounds have all been identified by elemental analysis and IRspectra,some of them by MS and ¹HNMR.The thermal behavior of these compounds has been investigated by DTA-TGmethod and IRspectroscopy,and their thermal stability was described.

STUDIES OK TRANSFORMATION FOR ZEOLITE CRYSTAL(Ⅲ)--THE STABILITY OF ZEOLITE NaY AND THE STRUCTURE OF ZEOLITE NaPc

Ha Shujie, Li Liansheng, Xu Ruren, Ye Chaohui

1985, 1(2):  16-22. 

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We investigated the crystallization of NaYand especially the transformation for NaY to NaPc type zeolite from an initial gel of the batch composition 3.3Na₂O·Al₂O₃·10SiO₂·200H₂O at 100℃and the changes of zeolite structures in the process of the transformation crystal using the modern techniques,Amore detailed liquid phase transportation mechanism of the transformation was suggested.

THEORETICAL EQUATIONS OF MULTIPLE SEMIDIFFERENTIAL ANODIC STRIPPING ELECTROANALYSIS WITH MERCURY FILM ELECTRODE

Wang Yaoguang

1985, 1(2):  23-30. 

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In this paper,the theoretical curve equations of multiple semidifferential anodic stripping electroanalysis with TMFE are established.The theoretical curves and performance parameters are obtained with a digital computer.Experimental results are in good oyreement with theory.The multiple semidifferential electroanalysis provides much better sensitivity and resolution than semidifferential electroanalysis.

STUDY ON THE ANION-EXCHANGE BEHAVIOUR OF MOLYBDENUM(Ⅵ) AND TUNGSTEN(Ⅵ)IN MIXED ORGANIC-AQUEOUS SOLVENTS

Cai Shulian(Tsai Shu Lien), Zhou Zhiming

1985, 1(2):  31-36. 

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THE FRONTIER ORBITAL ENERGV LIVEL AND ELECTRON SPECTRA OF SOME UNSVMMETRICAL BISAZO DERIVATIVES OF CHROMOTROPIC ACID CONTAINING HALOGEN GROUPS

Chen Qiong, Luo Mingdao, Cai Ruxiu, Chen Shukang, Lin Zhixin

1985, 1(2):  37-43. 

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The π electron molecular orbital energy level and electron spectra of some unsymmetrical bisazo derivatives of chromotropic acid containing halogen group were studied by HMO method.Results of calculations show that the wavelength of the maximum absorptive peak differs from experimental value by 8nm and the substituting position of electrophilic group agrees well with experimental value.We also discussed the red shift of electron spectra and the substituting position of e:lectrophilic group from these results.

STUDY ON THE CONSTITUENTS OF SAUSSUREA INVOLUCRATA KAR.ET KIN.(Ⅱ)

Li Yu, Jia Zhongjian, Du Mei, Chu Tsetsin

1985, 1(2):  44-47. 

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A new β-glucoside of sesquiterpene lactone was isolated from Saussurca Involucrata Kar.et kin.hydrolysis of this compound gave a new quaianolide,named as involu-cratolactone.

RESEARCH ON 2-(2'-SUBSTITUTED VINYL)-5-BIPHENYLYL OXAZOLES

Pan Jiaxing, He Jiaqi, Kao Chen-heng

1985, 1(2):  48-54. 

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Fifteen of the 2-(2'-substituted vinyl)-5-biphenylyl oxazoles were synthesized respectively by the condensation of corresponding 2-methyl-5-biphenylyl oxazole with benzaldehyde,substituted benzaldehydes or furfural in the presence of alkali or acid.Their m.p.,infrared spectra,λ_max of UV spectra and fluorescence spectra,fluorescence quantum yields as well as laser conversion efficiency of the compounds are listed in tables.

SYNTHESIS AND SPECTRAL STUDIES OF(μ-PHENYLTHIO) (μ-ALKYLTHIO) HEXACARBONYLDIIRON COMPLEXES

Song Licheng, Hu Qingmei, Liu Xiangyang, Wang Jicao

1985, 1(2):  55-62. 

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Through reductive reaction between PhL₁and μ-S₂Fe(CO)₆,tollowed by nucleophilicsubstitution of the intermediate (μ-PhS)(μ-LaS)Fe₂(CO)₆toward RX,nine Fe-S Clus-ter Complexes of (μ-PhS)(μ-LaS)Fe₂(CO)₆series have been synthesized. The influence of RX structures on the activities in nucleophilic substitution has been examined and possible steroisomers and isomer ratios of the complexes determined.

THEORY OF GAS-PHASE ACIDITY(Ⅰ)CORRELATION OF DEPROTONATION ENERGY WITH HYDROGEN CHARGE

Chen Zhixing

1985, 1(2):  63-68. 

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The charge distributions of various acids and their conjugate bases are calculated by using CNDO/2 and MNDO with full geometry optimization.The deprotonation energy is found to be better correlated with the charge on the acidic hydrogen than with the charge on the atom linking to the hydrogen and with the charge on the nucleophilic atom of the conjugate base.This shows that the charge on the acidic hydrogen has an important effect on acidity,whereas the effect of the charge on the linking atom and on the nucleophilic atom of the conjugate base is not important.It can thus be deduced that the view of stabilization of the anio'n due to dispersion of the negative charge is not a significant explanation of acidity.

STUDIES ON THERMOKINETICS.(Ⅰ)THEORY AND METHODS OP THERMOKINETICS

Deng Yu

1985, 1(2):  69-75. 

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A chemical reaction taking place in a calorimeter is called a thermokinetic system.The recording curve of its temperature during the reaction is called a thermogram.It is very interesting to study the reaction kinetics from.its thermogram but the theory and methods of thermokinetics have not been developed into perfection yet.In this article,the thermokinetic equations of a reacting system are derived in the light of nonequilibrium thermodynamics.And the analytical expression of a thermogram can be derived from the thermokinetic equations.On this theoretical basis,a new research method in thermokinetics has been suggested

A STUDY OF THE REDOX CHARACTERISTICS OF THE TERNARY CLATHRATE COMPOUND Mo[S₂CN(C₂H₅)₂]₄}⁺{FeCl₄}^-C₆H₅CH₂SSCH₂C₆H₅

Huang Chubao, Guo Chunxiao, Zhang Zhigui, Xu Lijuan

1985, 1(2):  76-81. 

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The redox characteristics of the ternary clathrate compound {Mo[S₂CN(C₂H₅)₂]₄}⁺{C₆H₅CH₂SSCH₂C₆H₅}^-was studied by electrochemical measurement and quantum-chemical calculations.The cyclic voltammogram of this ternary clathrate compound in 0.1M KClO₄-DMF with a platinum electride had 2.pairs of redox peak.Both the electrochemical parameters derived from the voltammogram and the results of EHMO calculations indicate that the pair of redox peak at relatively positive potentials corresponds to the redox reaction of Fe(Ⅲ)/Fe(Ⅱ) which is irreversible in nature,while the pair of redox peak at more negative potentials corresponds to the redox reaction of Mo(Ⅴ)/ Mo(Ⅱ) which is semi-reversible.The calculations from experiment measurements are fairly agreement with the theoretical calculations.

DETERMINATION OF THE DEGREE OF BONDED PHASE ON THE SURFACE OF SILICA GEL BY XPS

Huang Huizhong, Guo Qinlin, Gui Linlin, Wang Qinwei, Duan Xiaoqing

1985, 1(2):  82-86. 

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Attention is being increasingly paid to the new material prepared by bonding organic molecules on the surface of silica gel in the preparation of catalyst or packing material for liquid chrotnatographic column.There has not been a quantitative method for determination or characterizing the degree of bonded phase on surface of silica gel yet.This paper provides a new semi-quantitative method.

DETERMINATION OF DEGREE OF BONDED PHASE AT SILICA,GEL SURFACE USED FOR CHROMOTOGRAPHIC PACKING MATERIALS

Wang Qingwei, Duan Xiaoqing, Qian Jiuxin

1985, 1(2):  87-92. 

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Most of the packing materials used for liquid chtomototyraphy takes silica,gel as base The surface cf silica gel is modified by grafting of various functional bond phase to meet the purpose of separation and analysis.In some literatures,only the grafting method and the elemental analysis of bonded phase were reported.No detail quantitative determination has yet been published.This article describes the quantitative determination of material grafted on silica gel prepared by coupling reaction of silica gel with different concentrations of v-glycidoxyproplsiyl(P-GOPS) in water by differential thermal analysis(DTA) thermogravimetry(TG),element analysis(EA) and solution adsorption method.The results obtained are in agreement with those obtained by X-ray photon scat tering(XPS) method

STUDY ON ELECTROOXIDATION OF TRACE CO(Ⅰ) REACTION KINETICS ON Pt/C CATALYST

Zhang Huixin, Xu Xingzhong, Li Zuojun

1985, 1(2):  93-99. 

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We have determined experimentally the reaction kinetics of the electrocatalytic oxidation of the trace carbon monoxide on Pt/C catalyst in aqueous sulphuric acid.At the constant potential 0.947V vs.NHE,the overall rate equation may be expressed by i=k_aP_coC_H3O⁺exp(-E_a/RT)where y is a parameter relating to the concentration of H₃O⁺.Assuming that the rate of the electrocatalytic oxidation of carbon monoxide is controlled by the edectrochemical reaction of the adsorbed COand adsorbed OHand that t the surface of catalyst is homogeneous,we can obtain a theoretical rate equation which is formally the same as the empirical rate equation.Recently,instruments for monitoring trace toxic gases in atomosphere based on electrochemical principles have been reported The determinable gases may involve CO,SO₂H₂S,nitrogen oxides,various gaseous paraffins,and so on.This new method raises wide interests for its many cdvantages,for instance,the price is cheap: the operation is simple and it can be used directly to monitor atmospheric toxic gases in situs.So far,however,the researches in these processes axe still primary The Kinetics of the electrocatalytic oxidation or reduction relating to the trace toxic gases has not been reported yet.In this paper,we shall provide the kinetic information of the electrocatalytic oxidation of the trace carbon monoxide on Pt/Cwhich may be useful for screening and improvement of electrocatalysts and also a general method for the studies of these kinetic problems.

STUDIES ON THE CHEMICAL CONSTITUENTS OF THE CHINESE MEDICINAL HERB ANEMONE RADDEANA REGEL(Ⅲ)

Wu Fenge, Zun Ziqing

1985, 1(2):  100-105. 

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Triterpenoid saponin R₁as well as glucose and cane sugar have been isolated from the Chinese herb Anemone raddeana Regel R₁was identified as 3-O-[a-L-rharnnopyranosyl-(1-4)-a-L-arabinopyranosyl-oleanolic acid by spectres copy and chemical transformations It is a new saponin,which was named as raddeanin B.

FAST ATOM BOMBARDMENT MASS SPECTROMETRY OF BILE ACIDS AND THEIR SUCCINYL DERIVATIVES

Da Shilu, D. Fraisse

1985, 1(2):  106-113. 

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The new technique of fast atom bombardment mass spectrometry has.been applied to the investigation of some free bile acids and their succinyl derivatives using glycerol or thioglycbl as "matrix compatible solvent".The pseudomoiecular species are observed giving molecular weight information.In negative ion mass spectra the(M-1)-ion is the most intense ion which is the base peak for each of the samples.Additionally,dimer ions and adduct ions with species which are from the matrix are obtained with low intensity.The technique allows the determination of the mixture of bile acids and the pseudomoiecular species observed to give molecular weight information for the component.

STUDIES ON METHYL METHACRYLATE POLYMERIZATION INITIATED WITH PIPERIDINE DERIVATIVES AND ORGANIC PEROXIDE SYSTEMS

Zhang Jingyi, Qiu Kunyuan, Feng Xinde

1985, 1(2):  114-120. 

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The polymerization of methyl methacrylate(MMA) initiated with piperidine derivatives,such as,piperidine(P),2,2,6,6-tetramethyl-4-hydroxyl piperidine(TMP),N-ethyl iperidine(NEP),1,2,2,6,6-pentamethyl-4-hydroxyl piperidine(PMP),and organic peroxides,such as,benzoyl peroxide(BPO),lauryl peroxide(LPO),f-butyl hydroperoxide (TBH),t-butyl peroxybenzoate(TBPB) systems was studied and discussed in this paper.The polymerization rate equation and the activation energy of polymerization were determined respectively.

STUDIES ON THE DYNAMIC MECHANICAL BEHAVIOR OF POLYMERIZATION OF BIS(4-(4-ETHYNYLPHENOXY)PHENYL)SULFONE AND ITS POLYMERS

Zeng Hanmin, Mai Kaneheng, Ye Lanxie

1985, 1(2):  121-128. 

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The dynamic mechanical behavior and structural characteristics of polymerization bis(4-(4-ethynylphenoxy)phenyl)sulfine(ESF) and its polymers were investigated by means of tcrsional braid analysis(TBA) and infrared spectroscopy.Results show that the multiple transitions including the melting,low-temperature and high-temperature reactions of ESF oligomers,glass transition and decomposition reaction of resulted polymer can be characterized in the TBA spectra.The glass transition tempe: atures and structural characteristics of ESF polymers depend upon the conditions of polymerization.

COIL PROPERTIES OF RING SHAPED POLYMER CHAINS IN GOOD SOLVENT(Ⅰ)--THEORETICAL CALCULATION AND EXPERIMENTAL DETERMINATION OF r_equ.ring r_equ.openand f_ring～f_open

Huang Jiaxian, Li Chunrong, Wang Linfu, He Binglin

1985, 1(2):  129-134. 

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Two correlation stations,.r_equ.ring/r_equ.open=1/([η]_open/[η]_ring)^1/3and f_ring/ f_open^-1/([η]_open/[η]_ring)^1/3of the ring shaped and linear shaped polymer coils with the same monomer and molecular weight in a dilute solution have been derived.If leave excluded volume effect out of consideration.