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    24 August 1982, Volume 3 Issue 3
    Articles
    THE STABILITY OF COMPLEX COMPOUNDS FORMED BY GLYCYL GLYCINE, LEUCINE AND 2, 3, 5, 6-TETRAHYDRO-6-PHENYLIMIDAZO (2, 1-b)THIAZOLE WITH URANYLION (Ⅱ)
    Zhang Jianmin, Zhang Aiyou, Chen Baojiao, Wang wenming
    1982, 3(3):  281-286. 
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    The stability of complex compounds formed by glycyl glycine, leucine and 2,3,5,6-tetrahydro-6-phenylimidazo (2,1-6) thiazole with uranyl ion (II) has been investigated. The stepwise formation constants of these compounds were determined potentiometrically at 25℃ in aqueous solution in presence of 0.1 Mpotassium chloride.The adsorption theory of complex equilibria in solution which has been proposed by Hsu Kwang-hsien[4] , was introduced in treatment of the data determined by pH method.
    THE MECHANISM OF FORMATION AND CRYSTAL GROWTH OF MOLECULAR-SIEVE-ZEOLITE(I)——THE STUDY ON THE STRUCTURE OF FAUJASITE TYPE "DIRECTING-AGENT
    Xu Ruren(Hsu Rhu-reng), Zhang Jianmin
    1982, 3(3):  287-292. 
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    1. In this paper, the new and efficient broad line Na23-NMRtechnique was first applied to investigate the existence and growth of nucleation center with faujasite type structure in a highly disperse colloidal system and some interesting results were obtained. This technique supported a possibility to study the nucleation processes of zeolite in a colloidal system.2. The nucleation processes of the so-called "directing-agent" (highly disperse colloidal system with a composition of 16Na2O ·Al2O3· 15SiO2·320H2O) have been investigated by broad line Na23-NMR, X-ray diffraction, electron diffraction technique. The structure of the colloidal particles in the "directing-agent" system has been verified to be of the faujasite type. It is the nuclei that enable NaYtype zeolites to be formed in the starting mixture in which NaPtype zeolites should be formed.
    COMPLEX FORMATION OF RARE EARTH IONS WITH THIOCYANATE AND NITRATE IONS
    Huang Chunhui, Li Biaoguo, Zhou Yongfen, Zhang Hongjian, Li Junran, Hsu Kwang-Hsien
    1982, 3(3):  293-299. 
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    So far as the authors are aware, the stability constants of the rare earth ions with some inorganic ligands reported in the literature are quite inconsistent with one another.In this paper, the complex formation of all the rare earth ions (besides Ce and Pm) has been studied by ion exchange method at 25℃ in NaClO4 (2M) ionic medium. The stability constants were calculated by a special computer program written for this purpose in Beida 6912 language. In the case of thiocyanate the complexes were RECNS2+ , RE(CNS)2+, RE(CNS)3, but in the case of nitrate, almost only RENO32+. We use Y(1) to express the ratio (C0RE)/(RE3+) when (L-) = 1M, where (C0RE), (RE3+), (L-) represent the concentrations of the total metals, the free metals, and the total ligands respectively. The values of Y(1) were irregular but had a tendency of increasing with the increase of the atomic number in thiocyanate system and decreasing with the increase of the atomic number in nitrate system. The value of Y(1) of yttrium was the smallest both in thiocyanate and nitrate systems.
    A STUDY ON THE COLOUR REACTION OF MOLYBDENUM WITH SALICYLFLUORONE AND CETYL TRIMETHYL AMMONIUM BROMIDE
    Shen Hanxi, Wang Zhenqing
    1982, 3(3):  300-304. 
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    A new colour reaction of the molybdenum with salicylfluorone and cetyl trimethyl ammonium bromide has been studied. In a dilute hydrochlpride acid medium (0.2-0.8N) molybdenum can form a red-colour tenary complex with the above-mentioned reagents. The complex exhibits maximum absorption at 530nm, and the value of apparent molar absorption coefficient is found to be 1.40×105. The constituent of the complex is also established as Mo:SAF:CTMAB = 1:2:2 by the methods of isomolar continuous variation and slop ratio, as well as triple diagram.Ahigh sensitive and selective spectrophotometric method is developed for the determination of molybdenum. The Beer's law is obeyed in the range of 0-8μg Mo/25ml. Most metal ions do not interfere with the determination of molybdenum. Oxidized metal ions, such as Fe(III), Cr(VI), V(Y) and Mn(VII), must be reduced with ascorbic acid. The ions of tin (IV) were reduced by sodium hypophosphite in the presence of mercuric ions as catalyst. The ions of zirconium were masked by EDTA. Only the ions of tungsten and titanium interfere seriously. The method is used in the determination of molybdenum in some high alloy steel with satisfactory results.
    INVESTIGATIONS ON DIFFERENTIAL PULSE POLAROGRAPHY(Ⅱ)——THEORY OF CATALYTIC CURRENTS AND ITS EXPERIMENTAL VERIFICATION
    Chang Tsow-shein, Gao Qijia
    1982, 3(3):  305-313. 
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    The equation of catalytic current in differential pulse polarography is described.
    STUDIES ON COLOR REACTIONS OF QUATERNARY COMPLEXES OF RARE-EARTH METALS
    Sun Shusheng
    1982, 3(3):  314-318. 
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    The color reactions of quaternary complexes of rare-earth metals with chromazurol S (CAS), 4,7-diphenyl-l,10-phenanthroline and cetyltrimethyl ammonium bromide (CTAB) have been investigated. The absorption maxima of these green complexes appear at 628-642 nm, and their molar absorpti-vities are 1.21×105-1.49×105·mole-1 · cm-1. The composition of the green complex of lutetium is Lu3+:CAS: 4, 7-dp-phen: CTAB = 1:2:1:4. In the presence of ethyl alcohol(7ml),the absorption maxima of the green complexes show that the bathochromic shift and the molar absorptivities become larger. In this system, CTABexerts either the sensitization effect or the decoloration effect on the color complexes of rare-earth metals at different concentrations. The amount of CTABrequired for complete decoloration of different rare-earth complexes is different. Satisfactory results have been obtained by the application of the quaternary complexes in the spectropho-tometric determination of small amounts of gadolinium in the presence of lanthanum.
    SPECTROPHOTOMETRIC-COMPLEXOMETRIC TITRATIONS(Ⅰ)——THE TITRATION OF MICRO-QUANTITIES OF IRON(Ⅲ)
    Chen Yongzhao, Chen Huanguang
    1982, 3(3):  319-326. 
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    The stability constant of Fe(III)-EDTAcomplex is rather large (logK = 25.1). Iron should be titrated at as low as pH 1, but owing to no suitable indicator to give a sharp end point, it has to be titrated at pH 2-3, which minimizes the selectivity of the titration. Through the comparison of the absorption curves of Bi-xylenol orange complex at different pHvalues, we found that at a wave length of 540 nm and at pH 0,8, the end point of the spectrophotometric titration of bismuth still was very clear. So we chose bismuth nitrate as the back titrant in the back titration of iron at a much lower pHvalue.This paper reports the optimum conditions for the spectrophotometric titration of 3-100Mg of iron in about 30 ml volume. The selectivity of this method is very high. 1 to 2 mg of Al, Ti(IV), Cr(III), Cu, Pb, Zn, Mn, La, Ce(III), W(VI), Mo(VI), V(Y), As(I), Mg, Ca and Ag, and 100ug of Hg, Sb(III), Ni and Th, as well as large amounts of chloride, fluoride and phosphate anions do not interfere. Using ammonium fluoride as a masking agent, 10 mg of Al, 200 ,ug of Zr and 100 Mg of Sn(IV) can be tolerated. Sodium sulfate can mask thorium up to 500 Mg. Co(II) is the only cation that interferes, and in the presence of EDTAit is easily oxidized to Co(III), which is cotitrated with iron.Micro-quantities of iron in quartz, tap water, aluminium alloys and pure aluminium, without preliminary separation, can be successfully and accurately determined with this method.
    ELECTROANALYTICAL CHEMICAL STUDIES ON RARE EARTH ELEMENTS (V)——SINGLE SWEEP POLAROGRAPHIC STUDIES OF YTTRIUM-RHODAMINE B-DIPHENYL-GUANIDINE SYSTEM
    Jiao Kui, Gao Xiaoxia(Kao Sheau-shya)
    1982, 3(3):  327-335. 
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    This paper reports the polarographic behavior of the complex of Y3+ with basic dye rhodamine B.Near-1.5V (SCE) rhodamine Bhas a large adsorptive single sweep polarographic wave in the presence of ammonium chloride and diphenylg-uanidine. Y3+ decreases the height of this derivative wave. Under the optimum conditions, such as 0.4.Mammonium chloride, 8.0×10-5 Mrhodamine B, 1.0×10-4 Mdiphenylguanidine, pH 4.5-5.0, there is a linear relationship between 1× 10-7-l×10-6M Y2+ and the decrease of the wave heights. Heavy rare earth elements behave similarly as Y3+ , thus the total amount of them may be determined.The mechanism of this system has been studied by means of dc, dpp, single sweep normal and derivative polarographys. The results indicated that Y3+ may form an ion-association complex with rhodamine Band diphenylguanidine as shown in the following.
    COMPUTER ANALYSIS OF UV-IR SPECTRA FOR MIXTURES CONTAINING A UNKNOWN COMPONENT
    Hu Hsing-yao, Zhang Liangping, Lu Weiqin
    1982, 3(3):  336-340. 
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    For mixtures containing a unknown component, computer quantitative analysis has been investigated. It can be applied to herbal drugs, synthetic material,environmental monitor and biochemical samples etc.This method is based on UVor IRspectra of mixtures. Firstly, the quantities- of known components are calculated by linear-programming method, then the subtrac-tive spectrum of a unknown component is solved on computer.
    THE SYNTHESIS AND REARRANGEMENT OF 4-ALLYLOXYPYRIDINE-1-OXIDE
    Zhou Chengdong, Hsu Xiangong
    1982, 3(3):  341-344. 
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    4-Allyloxypyridine-l-oxide(IV)has been synthesized in good yield by tre ating 4-chloropyridine-l-oxide with sodium aliyloxide in allyl alcohol under mild condition. On heating under vacuum, (IV) is found to be transformed into N-allyl-4-pyridone (V) and 3-allyl-4-hydroxypyridine-1-oxide (VI) by Ciaisen rearrangement.
    A STUDY ON ISOMERIZATION OF L(+)-ψ-EPHEDRINE IN GLACIAL ACETIC ACID
    Cheng Dongliang, Li Zhixiao, Guo Hongda, Zhu Ziqing(Chu Tze-Tsin)
    1982, 3(3):  345-350. 
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    L(+)-ψ-ephedrine could be isomerized to D(-)-ephedrine in glacial acetic acid. The method of isomerization was rather easy as follows:A 5% solution of L(+)-ψ-ephedrine in glacial acetic acid was refluxed for twenty hours, then acetic acid was removed immediately from the mixture under diminished pressure. The residue was hydrolyzed with 2.5 N NaOHsolution. The D(-)-ephedrine oxalate was first prepared from the product of hydrolyzation and finally converted to its hydroehloride. The yield of pure product was about 31.2% of the theoretical based on the L(+)--ephedrine.
    STUDIES ON BORON COMPOUNDS (Ⅲ)——THE REACTIONS OF B10H102-、B12H122- AND B3H8- WITH FERROCENYL QUATERNARY AMMONIUM SALTS
    Zhang Guomin, Zhu Hong, Ding Qiang
    1982, 3(3):  351-358. 
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    This paper deals with the reaction of binary polyhedral borane anion quaternary ammonium salts BnHn2- (in which n is 10 or 12) and tetraethyl-ammonium octahydrotriborate B3H8- with (ferrocenylmethyl) N-alkyl-N,N-dimethylammonium halide C5H5FeC5H4CH2N (R) Me2X (in which Ris CH3—, C2H5—, n-C3H7—, CH3=CHCH2— or CH = CCH2—, respectively) and 1,1'-bis-(N-alkyl-N, N-dimethylaminomethyl) ferrocene dihalide Fe(C5H4CH2-N (R) Me2X)2 (in which Ris CH3—, C2H5—, n-C3H7—, CH2=CHCH2 and CH = CCH2— respectively), and with the effect of ratios of reactants on products. In each of the reactions, irrespective of the ratios of the reactants, only one product is obtained (in good yields 90.2—98.5%). Apparently, the above mentioned experimental results were explained by the HSABprinciple. 30 new compounds have been synthesized and characterized (their physical properties,IRspectra, yields and analysis data are given). All these compounds are stable to hydrolysis.
    RESEARCH ON 2,5-DISUBSTITUTED OXAZOLES
    Kao Chen-heng, Cheng Jinpei, Li Xiang
    1982, 3(3):  359-366. 
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    2-Phenyl-5-(4'-biphenyl)-oxazole and thirty one 2-substituted phe-nyl-5-(4'-biphenyl)-oxazoles are synthesized. Among them, thirty are new compounds. The M.P., λmax of UV absorption spectra and fluorescence emission spectra, as well as laser properties of the compounds are given in tables. It is found that twenty three of the titled compounds are better than 2,5-diphenyl oxazole (PPO) in using as laser dye in near UVregion.Abrief discussion on the relation between the substituent effects and spectral properties of the compounds is given.
    STUDIES ON THE SYNTHESIS OF 3-SUBSTITUTED AND-1, 3-DISUBSTITUTED PYRAZOLES THROUGH CONDENSATION OF β-CHLOROVINYL KETONES WITH HYDRAZINES
    Huang Zaifu, Wei Daimu, Peng Wenli, Wang Guoliang, He Haiquan
    1982, 3(3):  367-373. 
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    This paper describes a simple method for synthesizing pyrazoles from β-chlorovinyl ketones.Aseries of pyrazoles (3-halomethyl pyrazoles, 3-unsaturated alkyl pyrazoles, 3-(2-furyl) pyrazoles and 1-hydroxyethyl 3-alkylpyrazoles), have been synthesized by treating various β-chlorovinyl ketones with appropriate hydrazines. Yields are good in most cases.
    THE VACUUM ADIABATIC CALORIMETRY OF ANHYDROUS URANYL SULPHATE AND URANYL NITRATE TRIHYDRATE
    Feng Shiyan, Zhang Zhiying, Zhang Suichun
    1982, 3(3):  374-380. 
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    A vacuum adiabatic calorimeter has been established in our laboratory. In order to ascertain the precision and the accuracy of the whole apparatus, the heat capacity of KCl was measured from 60K to 300K. The difference between the weights of the samples used in the two series of experiments is 18.6255g. Except for a few points, the deviation of the experimental points from the smooth curve does not exceed ±0.3 per cent.The selected values of molar heat capacity of KCl are tabulated from 60 K to 300 K, and are compared with the values given by other authors. Our result is in agreement with the literature values with the deviation not exceeding±0.3 per cent, which shows our calorimeter is reliable.The heat capacities of UO2SO4 and UO2(NO3)2. 3H2O have been measured from 60K to 300K by the above-mentioned calorimeter. No thermal anomalies were found. Except for a few points, the deviation of the experimental points from the smooth curves for the two compounds does not exceed ±0.2 per cent.
    PHOTOELECTROCHEMICAL BEHAVIOR OF N-TYPE GaAs1-xPx
    Xu Ping, Zhang Wenbao, Wu Haoqing
    1982, 3(3):  381-388. 
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    Studies of n-type GaAs1-xPx-based photoelectrocherriical cell using S2-/SrR2- relectrolyte under the nitrogen atmosphere are reported for values of x (0.15, 0.29, 0.34, 0.40, 0.46, 0.52, 0.59, 0.65).The open circuit photovoltages(VOC) and the short circuit photocurrent densities(JSC) were determined under an illumination intensity of 35.2mW/cm2.
    PHOTO ELECTRON SPECTROSCOPY AND THE LINEAR RULE OF THE HOMOLOGOUS ENERGY FACTOR (Ⅱ)——NON-CONJUGATED HOMOLOGOUS SYSTEM
    Sun Yukun, Xu Guangxian(Hsu Kwang-hsien), Li Lemin
    1982, 3(3):  389-397. 
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    In the present investigation we have collected 60 sets of vertical ioniza-tion potentials of normal paraffins CnH2n+2 and other 19 sets of non-conjugated homologous series from UV photo electron spectroscopy and found to fit the following linear equation Ip(n,k)=a+bX(n,k) where IP(n, k) is the kth ionization potential of the nth member of the homologous series, a and b are constants, X(n,k)is called the homologous energy factor and is equal to X(n,k)=[(2k-1)/k]sin(kπ/(2n+1)] 83.3% of the correlations are of the "excellent" grades with correlation factor r≥0.99, and 16.7% of the "good" grade with r≥0.95.
    A NEW CATALYST FOR NITROGEN FIXATION——POLYVINYLPYRIDINE-COORDINATED CLUSTER OF MOLYBDENUM AND IRON
    Sun Chunting, Li Shuqin, Huang Qijun, Niu Shuyun
    1982, 3(3):  398-402. 
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    A new catalyst for nitrogen fixation has been prepared. This catalyst may be regarded as a cluster of molybdenum and iron bonded to a poly-vinylpyridine carrier. 'The initial rate of acetylene on the new catalyst is l.3mol/mol.min and as high as the same type complex catalyst of dextrin-supported molybdenum-cysteine. This catalyst is so stable that there appears only a little decrease in activity upon repeated use. The relationship of catalystic activity with elementary composition has been tabuleted, which implies the role of the components of the nitrogenase active center. The results mentioned above are helpful for understanding the mechanism of nitrogen fixation.
    CATALYTIC PROPERTIES OF RARE EARTH INTERMETALLIC COMPOUNDS——HYDROGENATION OF CO AND UNSATURATED GASEOUS ALIPHATIC HYDROCARBONS ON LaNi5
    Chen Yu, Zhou Jianlue, Chen Shuzi, Zhang Mengcheng, Wang Wen-zhuo
    1982, 3(3):  403-408. 
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    The catalytic hydrogenation of CO, C2H4, C2H2 and C6H6 on the intermetallic compound LaNis has been investigated by means of the chro-matographic pulse technique wiih a microreactor. The reaction was also carried out on pure Ni in the same apparatus. The experimental results show(1) The catalytic activity of LaNi5 depends on the character of hydro-genated substances. The catalytic efficiency of LaNi5 compared with Ni decreases in the order CO>C2H4>C2H2>C6H6, but the activity of LaNi5 for the hydrogenation of C6H6 is lower than that of pure Ni.(2) The catalytic activity of LaNi5 pretreated at 200℃ in flow hydrogen is higher than that of LaNi5 without treatment.(3) Methanation reactions of CO on both LaNi5 and pure Ni are first order and the activation energies are 15.5 Kcal/mole on LaNi5 and 31 Kcal/ mole on pure Ni, respectively.
    Preface
    THE KINETICS OF PHOTOPOLYMERIZATION OF β-HYDROXYETHYL METHACRYLATE
    Liang Zhaoxi, Chen Yonglie, Wang Zhan, Ye Tingen, He Yi, Li Manfu
    1982, 3(3):  409-417. 
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    Photopolymerization of β-hydroxyethyl methacrylate (HEMA) under UVlight at 30℃ with the use of benzoin derivatives as the photoinitiators has been studied by a recording dilatometer. For each photoinitiator (hydroxy-methyl benzoin methyl ether or benzoin ethyl tther), in aqueous solution, the initial rates of polymerization (Vp) were determined as a function of (photoinitiator), (HEMA) and light intensity. The kinetic data showed that the dependence of rates on initiator and incident light intensity was approximate to usual free radical kinetics with square-root dependence, but the monomer exponent was much lower than unity in both cases. This deviation from normal kinetics has been interpreted as that bimolecular termination of chain radicals were interrupted by the poor solvent as polymerization media, especially when the diluent concentration was higher, so the polymerization rate was unusually higher and thus lowering the monomer exponent. Through kinetic studies, tentative mechanism of HEMA polymerization in H2O was proposed. In addition, the effect of temperature and solvent on polymerization rate and post polymerization rate was also investigated. The overall activation energy of polymerization for the two systems were evaluated to be zero.
    Articles
    THE CURING PROCESS OF BIS(2,3-EPOXYCYCLOPENTYL) ETHER WITH AROMATIC DIAMINES
    Huang Jifu, Wang Derun, Zhang Baolong, Lu Yanling
    1982, 3(3):  418-424. 
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    The curing process of bis (2,3-epoxycyclopentyl) ether with aromatic diamines has been studied by differential scanning calorimetry (DSC) and torsional braid analysis (TBA).The DSCscans show that there are two separate exothermal peaks, both of which are proved to be the curing behavior of the reaction system. So it is suggested that the whole curing process proceeds in two stages.The mechanism concerning the two stages cure is discussed.From the isothermal cure curves obtained by TBAas a function of time, the results for the time needed to go to gel point fit Arrhenius relation, but two different slopes are obtained for the higher and lower isothermal cures curves, which might be related to the heterogenity of the reactive systems at lower isothermal cures, and homogenity at higher isothermal cures, where the reactive components are dissolved mutually and mixed intimately on a molecular level.Finally, the gelation-vitrification phase diagram is constructed and discussed.
    THE REACTIONS OF ALKYL DICHLOROPHOSPHITE WITH POLYVINYL METHYL KETONE AND ITS DIVINYLBENZENE COPOLYMERS
    Ho Plng-Lum, Ye Ker
    1982, 3(3):  425-429. 
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    This Paper consists of two parts. The first part is to find out the optimum conditions, such as the reaction temperature, reaction time, different solvent etc,for preparing the polypropenyl-α-hydroxyl-α-methyl-monobasic phosphonic esters.The second part is to prepare the cross-linked polypropenyl-α-hydroxyl-α-methyl-monobasic phosphonic esters.
    ASTUDY ON THE SYNTHESIS OF ZEOLITE ZSM-5 IN THE SYSTEM OF NH4+-TPA+-SiO2 -Al2O3 -H2O
    Han ShuYun, Xu Ruren
    1982, 3(3):  430-432. 
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    Zeolite HZSM-5 has been found to possess excellent quality as a catalyst. It can usually be prepared by exchange reaction between HCl or NH4 Cl and NaZSM-5.The product Thus obtained is HZSM-5 or NH4ZSM-5 respectively; the latter is capable of being transformed into HZSM-5 by heating. We report here a new procedure for synthesis of Zeolite HZSM-5. The NH4 ZSM-5 is prepared in the systems of NH4+-tetrapropylamonium bromide without the presence of NaOHand reaction of ion exchange. The reaction temperature from 1.00℃ to 160℃ is good enough for the synthesis of NH4 ZSM-5; the range of SiO2/Al2O3 ratio of the product is from 52to 180.The lower mole limit of TPABr used is 0.02 mole. The thermal stability of the product is good. It is shown by curves of TGAand DTAthat there is no phase transform peak in the range of temperature up to 1200℃. Its scanning electron micrographs,X-ray diffraction patterrn and the results of adsorption measurement are given.
    SUBSOLIDUS PHASE RELATIONSHIPS IN THE SYSTEM LaOBr-BiOBr
    Su Mianzeng, Wang YanJi
    1982, 3(3):  433-435. 
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    In order to seeking new possible phosphor hosts a method of synthesizing BiOBr and samples of the system La1-xBixOBr has been developed. The subsolidus phase relationships in that system have been determined by lattice parameter measurements. The solid solubility at 800℃ in that binary system was confined to the regions within x-<0.45 and x>0.59.