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    24 December 1980, Volume 1 Issue 2
    Articles
    STUDY OF TETRAVALENT PRASEODYMIUM COMPOUNDS--Ⅰ--PREPARATION OF Ce(Ⅳ)-Pr(Ⅳ)HETEROPOLYNUCLEAR OXIDE AT ROOM TEMPERATURE, AND THE BEHAVIOR OF TETRAVALENT PRASEODYMIUM IN SEVERAL ACID SOLUTIONS
    Gu Yidong(Ku Yih-tong), Song Yuan
    1980, 1(2):  1-13. 
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    Although quite a number of tetravalent praseodymium compounds have been prepared and well characterized,the solution chemistry of tetravalent praseodymium is little known.By means of "Carrier oxidation"through cerium from a 4:1 mixture of Ce (Ⅲ) and Pr (Ⅲ) nitrate in aqueous solution,using ozone as oxidizing agent at room temperature and at pHaround 6.5,a more reactive heteropolynuclear oxide hydrate with chocolate brown color was obtained.After drying in vacuo at a temperature not higher than 50℃,chemical analysis and X-ray diffraction pattern( Fig,1,2).confirmed the formation of PrO2in the mixed oxide.The degree of readiness for that heteropolynuclear oxide to get into solution differs markedly in con.HCl,con.HNO3and glacial acetic acid.The stability in those solutions also appearsdifferent.In con.HCl,solution formation is very easy;the blood red color due to Pr(Ⅳ) lasts for only a few minutes.Solution formation in con.HNO3is less easy,but the blood red color lasts much longer.In nitric acid solution,oxidation of MnO2·.H2O to MnO4- has been observed visually;transient formation of H2O2has been revealed in recording spectrophotometer(Fig.4,7).These phenomena substantiate the relative values of their respective electrode potentials given in literature.Solution of Ce(Ⅳ)-Pr(Ⅳ) heteropolynuclear oxide into glacial acetic acid needs brief warming;the blood red color can persist for a long time.Mixed complex compounds containing Ce(Ⅳ) and Pr(Ⅳ) can be obtained.
    STRUCTURAL CHANGE DURING THE SAPONIFICATION OF ORGANOPHOSPHORIC ACID EXTRACTANTS AND THE COMPOSITION OF THE EXTRACTED SPECIES
    Wu Jinguang, Chen Dian, Gao Hongcheng, Jin Tianzhu, Li Shengchong, Xu Guangxian
    1980, 1(2):  14-22. 
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    The change of structure during the saponification of D2EHPA and other organophosphoric acid extractants has been studied.It was found that the saponification is a process of the formation of a microemulsion of water-in-oil type,while the extraction of rare earth ions is a process of ion exchange in the water-oil interface forming a metal chelate,thus destroying the microemulsion.When 100% saponified D2EHPA was used to extract divalent metal ions,we obtained extracted species of composition MA2,instead of M(HA2)2,thus doubling the extraction capacity of D2EHPA.
    ACTION OF 1-PHENYL-3-METHYL -4-BENZOYL-PYRAZOLONE-5WITH THORIUM AND RARE-EARTHS-Ⅲ--STUDIES ON THE EXTRACTION OF RARE-EARTHS AND THE COMPOSITION AND PROPERTY OF SOLID COMPLEX COMPOUNDS
    Liu Jianmin, Yang Rudong, Ma Tairu
    1980, 1(2):  23-30. 
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    In this paper we have studied the action of Ln(NO)3(Ln=La,Ce,Eu,Yb,and Lu) with PMBP-CHCL3.It was found that when the concentration of PMBP≥0.2M the distribution ratio is in inverse proportion to the third power of the concentration of hydrogen ions and in direct proportion to the fourth power of the concentration of PMBP,all the rare-earth ions are extracted into organic phase in the form of LnA3·HA,their extraction equilibrium constants(lgK) equal to La(-6.20),Ce(-4.30),Eu(-3.62),Yb(-2.90) and Lu(-3.20),respectively.Under the condition of extraction,all the rare-earth solid complexes (except pm) are obtained from organic phase,their composition is LnA3HA (LuA3for Lu) their crystals,infrared spectra and thermalgraph are also studied.In this paper we have studied the action of Ln(NO)3(Ln=La,Ce,Eu,Yb,and Lu) with PMBP-CHCL3.It was found that when the concentration of PMBP≥0.2M the distribution ratio is in inverse proportion to the third power of the concentration of hydrogen ions and in direct proportion to the fourth power of the concentration of PMBP,all the rare-earth ions are extracted into organic phase in the form of LnA3·HA,their extraction equilibrium constants(lgK) equal to La(-6.20),Ce(-4.30),Eu(-3.62),Yb(-2.90) and Lu(-3.20),respectively.Under the condition of extraction,all the rare-earth solid complexes (except pm) are obtained from organic phase,their composition is LnA3HA (LuA3for Lu) their crystals,infrared spectra and thermalgraph are also studied.
    STUDIES ON SILLICIC ACID AND ITS SALTS--Ⅺ--TEMPERATURE EFFECT ON AND ACTIVATION ENERGY OF THE GELATION PROCESS OF MONO-SILICIC ACID
    Chen Rongsan, Zhang Xueqin, Wang Baikang, Dai Anbang(Tai An-pong)
    1980, 1(2):  31-38. 
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    Using H3PO4,HAc and HCl as gelating agents,in a wide range of pH,temperature effect on the rate of gelation of silicic acid was studied at 0°,20°,30°,40°,50°,and 70°.Activation energy of gelation was obtained therefrom.The results indicated that the activation energy varied with the kind of gelating agents used and pHof the solution.It was found also that concentration of silicic acid had an effect on the activation energy of gelation,however,when the total salt concentration of the solution maintained constant,the activation energy would not change with the concentration of the acid.All these findings had been well explained by the theory of polymerization of silicic acid proposed previously.
    THE PHYSICO-CHEMICAL PROPERTIES OF THE HIGH TEMPERATURE ION-EXCHANGED INDIVIDUAL RARE EARTH Y TYPE ZEOLITES
    Xu Ruren(Hsu Rhu-reng), Lu Yuqin, Ma Shujie, Yu Guozhen, Li Shougui, Zhang Jianmin, Wang Lijie
    1980, 1(2):  39-47. 
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    We investigated systematically some of the main physicochemical properties of 13 individually ion-exchanged LnY zeolites (LaY,CeY,We investigated systematically some of the main physicochemical properties of 13 individually ion-exchanged LnYzeolites (LaY,CeY, PrY,NdY,SmY,EuY,GdY,DyY,HoY,ErY,TmY,YbY,and Y-Y),prepared by high temperature ion-exchange method (180℃)(10kg/cm2).It was found that there are some obvious rules and features among the main physico-chemical properties of high temperature ion-exchanged LnFzeolites.1.A11 rare earth elements (Ln+3) can exchange with Na+ on St-sites in β cage of NaF type zeolite at 180℃ and under treatment in autoclave.There is a very strong correlation between the degree of ion-exchange of individual LnYand their relative crystallinity2.From the change of various main physico-chemical properties of LnFwith the atomic mumber of elements,we found that the dependence of lattice constant,as,specific surface area (S.A.) and dehydration temperature upon the atomic number of elements show the similar features,and such features are particularly obvious for light and mid-rare earth elements and we also found the appearance of gadolinium break.Exist peaks among Gd,Dy and Ho on respective curves.We also found the similar phenomena in enthalpy change of individual Ln+3.3.The thermostabilities of LnFvary with the changing of θ-value (Z/r) of Ln+3 ions.Amuch higher thermostability of heavy LnYand Y-Yappears.We suggested that the reason of this phenomenon lies in the easiness of diffusion of heavy Ln+3ions with smaller radius from St-sites in β-cage onto that of double six-ring (D6R) in high temperatures.This fact leading to the structural stability has been identified by the increasing of infrared vibrational frequenies in D6R of heavy LnFand Y-Y.
    ANALYSIS OF ORGANOMETALLIC COMPOUNDS-Ⅰ--THIN-LAYER CHROMATOGRAPHY OF FERROCENE DERIVATIVES
    Yang Xuejin, Xie Zhenzhen, Ni Fengshu, Shi Shujian
    1980, 1(2):  48-60. 
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    Forty-two ferrocene derivatives (including hydrocarbons,ethers,aldehydes,ketones,alcohols,amines,benzenesulfonamides,carboxylic acids,and acrylonitriles) have been separated by thin-layer chroma-tography using silica gel as adsorbent,and toluene-petroleum ether--acetone (15:1:1 or 15:1:3),benzene-alcohol (15:1) or toluene-petroleum ether-alcohol(15:1:1) as development.The following rules have been obtainedⅠ.The relations between the structures of the compounds and their Rs values:1.The Rs values decrease with the increase of the polarity of the substituents of the same series.2.The Rs values decrease with the increase of the number of the substituents of the same type.The Rs values of the monosubsti tuted coinpounds>those of the disubstituted ones.Ⅱ.The Rs values increase with the increase of the polarity of the development.The fact that some ferrocenes derivatives containing side chain hydroxy-group do not obey the rules mentioned above has been explained by means of their IRand NMRspectra.
    HSIEC SEPARATION OF HEAVY METAL AND DETERMINATION OF COPPER AND ZINC
    Liu Mancang, Fan Biwei, Hu Zhide
    1980, 1(2):  61-66. 
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    A flow coulometric detector was applied to a study of the separation of heavy metal ions by cation-exchange chromatography using tartrate,lactate and citrate as the eluents.The separation of a six-component mixture of metal ions (copper,zinc,nickel,cobalt,cadmium,and manganese) was completed within one hour under suitable conditions.The effects of composition and flow rate of the eluents on the retention time and column efficiency was investigated.The relation of plate height and flow rate of the eluents was agreeable to the Snyder equation.It was observed that the electrolytic efficiency varied with the kind of ions and the size of the sample.The method was applied to the determinations of copper and zinc in a brass and waste water.Aflow coulometric detector was applied to a study of the separation of heavy metal ions by cation-exchange chromatography using tartrate,lactate and citrate as the eluents.The separation of a six-component mixture of metal ions (copper,zinc,nickel,cobalt,cadmium,and manganese) was completed within one hour under suitable conditions.The effects of composition and flow rate of the eluents on the retention time and column efficiency was investigated.The relation of plate height and flow rate of the eluents was agreeable to the Snyder equation.It was observed that the electrolytic efficiency varied with the kind of ions and the size of the sample.The method was applied to the determinations of copper and zinc in a brass and waste water.
    STUDIES ON NITROXIDES--Ⅱ--THE SOLVENT EFFECT OF NITROXIDES AND THEIR MOLECULAR STRUCTURE
    Liu Youcheng, Jiang Zhiqin, Wu Shaping
    1980, 1(2):  67-74. 
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    The electron spin resonance spectra of 4-oxo-2,2,6,6-telramethy 1-piperidine-1-oxyl in twenty-six solvents of different polarity were deter mined.It was found that the hyperfinc splitting constant ANincreased with the increase of the polarity of the solvent while the g value showed a tendency of slight decrease.There was a linear correlation of the ANvalue with Reichardt ET and Kosower Z,but no such correlation was found with e or μ Since ET,Zare microscopic solvent polarity parameters for model reactions whereas ε,μ macroscopic solvent polarity parameters for nonmodel reactions,ANcan thus be used as a microscopic solvent polarity parameter for nonmodel reactions.The bonding molecular orbital energy and antibonding molecular orbital energy of the hcteronuclear diatomic three electron bond in nitroxide were calculated by HMOmethod,using the semi-empirical value of hiand kiiparameters for heteroatoms given by Streitwieser,and it was shown that the delocalization energy was within the range of 0.4-0.5β,comparable to that for butadiene (HMOmethod).The results could account for the stability of nitroxide radical and also the solvent effect upon the distribution of π-electron density.
    STUDIES OF ACTIVITY COEFFICIENTS OF NONELECTROLYTES IN AQUEOUS SALT SOLUTIONS-XI--THE DISTRIBUTION OF n-PROPIONIC ACID AND n-BUTYRIC ACID BETWEEN BENZENE AND AQUEOUS SOLUTIONS OF SALTS WITH SMALL IONS
    Xic Wenhui, Liu Wen, Liu Zhenyi, Ma Diankun, Fan Qijia, Huang Ziqing
    1980, 1(2):  75-85. 
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    The distribution coefficients of n-propionic acid and n-butyric acid have been determined in the benzene phase in equilibrium with the water as well as the aqueous salt solution phases,thus enabling us to get the activity coefficient of each of the acids.The salts used are LiCl,NaCl,KCl,SrCl2,BaCl2,LiBr,NaBr,and KBr.Following the Randall and Failley's treatment of the weak acid,we have calculated the concentrations of its ions and obtained the concentration and finally the activity coefficient of the undissociated part of the acid fuThe salt concentrations Cs used are 0→1 mol e/1.When we plot log fu vs.Csfor the salts,the results obtained are all straight lines.On comparison of the slopes of these lines,the salting-out order is SrCl2> BaCl2>LiCl≈NaCl>LiBr≈NaBr>KCl>KBr for propionic acid,and is SrCl2>BaCl2>NaCl≈LiCl>NaBr≈KCl≈LiBr>KBr for butyric acid.We have calculated the salting-out constants of these acids in the solutions of alkaline and alkaline-earth halides by the formula of (1) Debye-McAulay,(2) McDevit-Long,and (3) Conway-Desnoyes-Smith.With the exception of the lithium salts,they all give the right salting order of the salts,but formula (3) gives the results in better agreement with the experiment than those of (1) and (2).
    CONFIGURATIONAL SEQUENCE DISTRIBUTION OF VINYL POLYMER
    Yan Deyue, Shen Jiacong, Tang Aoqing
    1980, 1(2):  86-98. 
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    Generally,the theoretical treatment of configurational sequence distribution has been made by statistical method.In this paper,we solve the kinetic equations of living copolymerization in Bernoulli and Markov processes with the aid of linear differential technique and obtain the sequence distribution,the functions for number average length,weight average length and sequence fraction.On the basis of these,we propose the decision equations of Bernoulli process as follows.which are a modification of Bovey's map.If the reaction system falls under Bernoulli process,fraction of isotac-tic,syndiotactic and heterotactic configuration PI,PS,PHdoes not depend on reaction time,monomer conversion and initial concentration of monomer.Alternatively,in the case of the first Markov proces,fraction of configuration varies with time,monomer concentration and approaches a definite limit as propagation parameter x→∞ It is proved that the theoretical results are in agreement with experimental data.
    THE INVESTIGATION ON THE GAS PHASE DOPING EPITAXIAL GROWTH OF GaN
    Meng Guangyao, Peng Dingkun, Hu Keao, Lou Jiren, Xi Lanzhi, Han Xing
    1980, 1(2):  99-108. 
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    This paper deals with the investigation of the doping growth of GaNby using Ga-HCl-NH3-H2-Ar system.The experimental results indicate that the incorporation of Zinc into epitaxial layers and the morphology of the layers are significantly effected by each of deposition parameters,especially by the deposition temperature.It was found that there is a narrow range of temperature (ca.970-1000℃) in which Zinc incorporates abruptly into the epitaxial layers and the layers grown have better quality.In addition an initial test of doping growth with both Zinc and phosphorus as dopants was carried out.The result suggests the value of further rese-(re-search) search on it.The measurement of the impurity distributions in the depth of the layers grown showed the difference in the incorporation behaviours of Zinc and phosphorus.On the basis of these experimental facts the mechanisms of Zinc-doping and crystal growth processes are presented and a desirable procedure for doping epitaxial growth is suggested.
    STUDIES ON THE La-Ni SYSTEM OF HYDROGEN ABSORPTION COMPOUNDS--Ⅰ--A CHEMICAL SYNTHETIC METHOD AND HYDROGEN ABSORPTION PROPERTIES OF LaNi5
    Shen Panwen, Wang Gcnshi, Zhang Yunshi. Song Deying, Zang Taoshi, Yu Suqing
    1980, 1(2):  109-112. 
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    In this paper a new route to the preparation of LaNi5by chemical synthetic method is presented.Lanthanum Nickel oxalate was first prepared by coprecipitation reactions from aqueous solutions,and the oxalate formed after dehydration was reduced by CaH2at 950℃ to give LaNi5.The reaction was studied in detail and the lattice parameters ofLaNi5were found a0=5.003Å and c0=3.987Å.The LaNi5thus prepared shows excellent absorption ability for hydrogen and the hydride formed has the composition corresponding to LaNi5H6.1The method seems to have general utility for chemical preparation of some transition metal alloys and intermetallic compounds.
    AN ERROR EQUATION OF SINGLE INCREMENT METHOD IN ION-SELECTIVE ELECTRODE
    Zhao Zaofan, Zhou Xingyao
    1980, 1(2):  113-116. 
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    In this paper,an error equation of single increment method has been derived as follows: ε=-2.3/S(10ΔE/s)/(10ΔE/s-1)Δ(ΔE)According to this equation,the optimum conditions of method are : the difference of potentials ΔE should be larger than about 40 mV (for mono-valent ions) or about 30 mV(divalent ions),and the volume of standard solution should not be over 10% of sample solution.
    Preface
    RESEARCH ON ORGANOPHOSPHORUS COMPOUNDS--THE SYNTHESIS OF N-ETHYLENEIMINO,ALKYLOXY (AMINO, SUBSTITUTED AMINO) THIOPHOSPHORYLAMIDES
    Yang Shixian(Yang Shih-hsien), Chen Tianchi, Li Yugui, Gao Jinsheng
    1980, 1(2):  117-120. 
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    The present communication deals with the preparation of three groups of compounds which are synthesized according to the following chemical equation The ethyleneiminizing reaction proceeds under the lower temperatures.Some physical constants of these compounds were recorded.The LD50of compounds Ps5,and Ps9 were respectively reported as l,000mg/kg and 500 mg/kg.Their chemosterilant action for insects remains to be tested.
    Articles
    THE RELATIONSHIP BETWEEN STRUCTURE AND PROPERTIES OF ORGANIC COMPOUNDS
    Lai Chengming, Gao Zhenheng(Kao Chen-heng)
    1980, 1(2):  121-124. 
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    The energy of excitation of eight homologous series was calculated by means of PMO method.The results are in agreement with the rule of homologous linearity.The energy of excitation of eight homologous series was calculated by means of PMO method.The results are in agreement with the rule of homologous linearity.
    LASER ACTION OF SOME 1,4-BIS-(β-STYRYL) BENZENE DERIVATIVES
    Wang Xiaolan, Zhang Yufan, Xue Jieyou
    1980, 1(2):  125-127. 
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    Laser action has been studied by pumping solutions of seven 1,4-bis-(β-styryl)benzene derivatives with a nitrogen laser.Being capable of giving higher relative energy transfer efficiency than PPO(2,5-dipheny-loxazole),the compounds (1),(2),(3),(5),and(7) may be used as dye lasers in between 4000Aand 5000A.Laser action has been studied by pumping solutions of seven 1,4-bis-(β-styryl)benzene derivatives with a nitrogen laser.Being capable of giving higher relative energy transfer efficiency than PPO(2,5-dipheny-loxazole),the compounds (1),(2),(3),(5),and(7) may be used as dye lasers in between 4000Aand 5000A.