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中文
Table of Content
24 August 1987, Volume 8 Issue 8
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Articles
Solubility Isotherm of H
3
BO
5
-MgCl-MgSO
4
-H
2
O Quarternary System at 288.15 K
Chen Huanchu, Yin Jingzhi
1987, 8(8): 671-675.
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In the present paper the solubility isotherm of three ternary systems MgCl
2
-MgSO
4
-H
2
O, H
3
BO
3
-MgCl
3
-H
2
O, H
3
BO
3
-MgSO
4
-H
2
O and quarternary system H
3
BO
3
-MgCl
3
-MgSO
4
-H
2
O at 283.15 K have been studied in detail.The existence of MgSO
4
·6H
2
O in system MgCl
2
-MgSO
4
-H
2
O was verified. The correlations of equilibrium phases and the salting-out effecis between components were discussed.
Study on the Synthesis, Structure and Properties of Magnesium Aluminophosphate Molecular Sieve
Han Shuyun, Zhang Wenhong, Li Liyun
1987, 8(8): 676-680.
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Magnesium aluminophosphate (MAPO-5) molecular sieve was synthesized by hydrothermal method. The crystal structure of MAPO-5 has been studied by X-ray diffraction, electron probe,
31
P-Nuclear Magnelic Resonance and infrared spectra. The parameters of the unite cell and chemical composition of MAPO-5 have been determined. Some physicochemical properties of MAPO-5 such as adsorption capacity, thermal stability and acid have been investigated. These results illustrates that Magnesium enter the framework of MAPO-5 molecular sieve.
The Chemical Activities of Paratungstate A and B and the Study for Their Rate of Transformation
Jiang Anren, Pang Zhen, Gu Yidong
1987, 8(8): 681-685.
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Taking advantage of their difference, the quantity of the non-active component, para B, in the acidified timgstate solution aged by heating can be determined. Making use of the method of H
2
O
2
-SO
2
, the rate of formation of para Bare determined at 80℃ with Zvalues (H
+
/W) equal to 0.667,0.850,1.00 and 1.14 respectively. It is found that expect the solution with Z=1.14 in which the disproportionation reaction may occured, in all the solutions with other Zvalues the formations of,para Eare very slow. The characters of the changing of the rates of para Bformation are linear, and the formation rate decreases as the Zvalue increases. The activity difference with H
2
O
2
between para A and B is explained according to their structure.
Detection of the Intermediate of the Electrocatalytic Reduction of Carbon Dioxide Using Optically Transparent Thin-Laver Electrode
Cao Xizhang, Zheng Guodong
1987, 8(8): 686-687.
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In this work, optically transparent thin-layer electrode (OTTLE) was used to detect the intermediate of electrocatalytic reduction of CO
2
The results showed that in the presence of imidazole (Im),the intermediate CO
2
·Co(Ⅰ) TMAPI·lm, was detected by UV/Vis absorption pectrum at -1.0V (SCE). The characteristic peaks were 434.0nm, 555.4nm and 603.6nm. We can come to the concolusion that CO
2
was activated by the formation of the intermediate CO
2
-Co(Ⅰ)-TMAPI.
Studies on New Inorganic Ion Exchanger Containing Phosphorous (Ⅳ)--Thin-Layer Chromatography Separation of Noble Metal Elements on Stannic Selenopyrophosphate
Liu Xu, Liu Jinchun, Liu Lianbin, Cheng Jieke
1987, 8(8): 688-692.
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Thin-layer chromatography of the noble metal elements on the inorganic ion exchanger stannic selenopyrophosphate has been studied systematically. The change regularity of the noble metals elements in the acidity medium,the ammonia-ammonium chloride, the trimethylamine and the trimethylamine-alcohol development systems has been discussed. Partial metal ions obey relationship R
m
=Alog C+B. A series of binary and ternary mixtures of the noble metal elements was separated successfully.
Differential Kinetics Analysis for Simultaneous Determination of Gadolinium and Dysprosium in a Mixture
Wang Lisha, Cai Ruxiu, Zeng Yun'e
1987, 8(8): 693-697.
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We have studied the kinetics of the complex formation reaction between rare earths and dibromochloroarsenazo, and presented a differential kinetic method for simultaneous determination of gadolinium and dysprosium in a mixture.The reaction rate constants of rare earths decrease with increasing their atomic numbers. A "Gd broken" phenomenon was found for the first time. The kinetics equations of Gd and Dy were deduced, and that the active energies of Gd and Dy are 29.216 kJand 53.35 kJrespectively was reported. Linear regression and graphical extrapolation appraochs have been applied to treatment of the kinetic analysis data. The comprision of the two methods shows that linear regression appra-och is better for the Gc
3+
/Dy
3+
-Dibromochloroarsenazo syslem, which has been used to determine Gd and Dy in a synthetical n ixture sample down to 10
-7
M with accuracy of 0 to 13.5%.
Anion-Sensitive Membrane Electrodes Based on Quaternary Phosphonium Sites
Wang Kemin, Yu Ruqin
1987, 8(8): 698-702.
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The quaternary phosphonium compounds are promising site materials for the preparation of anion-sensitive electrodes. Many phosphonium counter-parts of quaternary ammonium salts are difficult to be synthesized and the simplified methods searching for synthesis of useful quaternary phosphonium site materials are of considerable interest. Several such phosphonium compounds have been synthesized and compared as site materials for anion-sensitive membranes. Hexadecyltriphenylphosphonium iodide (HTPP) was recommended as especially suitable substance for this purpose. Asimple method for synthesis of HTPPfrom triphenylphosphine and hexadecyl iodide was worked out. The electrodes prepared from HTPP are equal or superior in sensitivity to the early quaternary ammonium site versions. The membrane composition for various anions was optimized. The potentiometric selectivity coefficients of the prepared electrodes and their correlation with various ionic parameters have also been investigated.
Trace Analysis of Silver by Catalytic-Kinetic Spectrophotometry
Dai Guozhong, Jiang Zhiliang
1987, 8(8): 703-705.
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In the presence of the activator ethylenediamine, the catalytic effect of Ag
+
on the coloration reaction based on the oxidation of reduced phenolphthalein with (NH
4
)
2
S
2
O
8
was studied. Anew catalytic-kineitc spectrophotometric method for determining Ag was developed and its optimum conditions were established. satisfactory result was obtained when the method was applied to trace analysis of Ag in water and waste water.
Quantitative Structure-Activity Study on a Series of Insecticidal O-Alkyl O-Aryl Phosphoramidothioates
Chen Ruyu, Wang Huilin, Cao Ruzhen, Zhang Zhengpu, Shao Jiushu, Zhu Lanhui, Chen Xueren, Yang Huazheng
1987, 8(8): 706-711.
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19 O-Alkyl O-aryl phosphoramidothioates were synthesized by the reaction of O-alkyl O-aryl phosphorochloridothioates with aqueous ammonia and the quantitative relationship between their structures and insecticidal activities was analyzed using physicochemical parameters of the substituents in the benzene ring by regression analysis. It was found that the electronic and hydrophobic effects of the substituents are important to the activity.
The Synthesis of Hydrocarbyl Substituted Penta-methoxycarbonylcyclopentadienes
Qiu Changlong, Wu Minyang, Zhou Zhihong
1987, 8(8): 712-713.
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Two new hydrocarbyl substitued pentamethoxycarbonylcyclopcntadienes have been synthesized from hydrocarbyl halides and potassium or thallium pentametho-xycarbonylcyclopentadiene.The identification of these compounds show that they all have carbon linkage at the ring carbon of cyclopentadiene.
Study on the Chemical Ingredients of Essential Oil of Fruit of Alpinia Galanga (L.) Swartz
Xue Dunyuan, Chen Yaozu, Li Zhaolin, Zhai Jianjun, Su Yibing, Yan Suyun
1987, 8(8): 714-719.
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33 chemical ingredients of the essential oil of fruit of Alpinia galanga(L.) swartz have been identified and estimated by [GC]
2
and [GC]
2
/MS.The results of flash-vaporization-gas chromatography and conventional steam distillation-GC have been compared. The former method possesses such advantages as:rapidity, simplicity in manipulation and micro quantity of herb sample(about 5 mg) used. Acomponent was isolated from the essential oil by preparative TLCand identified by means of IR,
1
H-NMR and MS as 1'-acetoxy-chavicol-acetate, of which the fragmentation of mass spectra was studied through high resolution mass spectrometry and B/Elinking scanning technique. Its hydrolytic product has been isolated and identified
Thermal Isomerizations of meso- and dl-Diethyl 2,3-Dicyano-2,3 -Diphenylsuccinate
Yang Dilun, Liu Youcheng, Gao Sulian
1987, 8(8): 720-725.
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The kinetics and activation parameters of thermal isomerization of the meso-isomer (1) and the dl-isomer(2) of diethyl 2,3-dicyano-2,3-diphenylsuccinate in 1,1,2, 2-tetrachloroethane were determined by means of HPLC. The experimental results showed that dl-isomer(2) was more stable than the meso-isomer(1). This fact was explained from the point of view of configuration and the ability to the formation of space bonds.
Surface Adsorption and Micelle Formation of the Mixed Aqueous Solutions of Fluorocarbon and Hydrocarbon Surfactants(Ⅳ)--Nonionic-Nonionic System
Ding Huijun, Chen Xin, Zhao Guoxi
1987, 8(8): 726-730.
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The surface adsorption and micelle formation of the mixed aqueous solution of fluorocarbon and hydrocarbon chains nonionic surfactants (C
10
F
19
O(C
2
H
4
O)
9
H and C
8
H
l7
C
6
H
4
O(C
3
H
4
O)
10
H) have been investigated. The surface tension of the mixed solution has been determined by the drop-volume method.The results indicate that(1) there is no completely miscible micelle but essentially the individual micelle(C
10
F
19
O(C
3
H
4
O)
9
H and(C
8
H
l7
C
6
H
4
O(C
3
H
4
O)
10
H) in the mixed aqueous solution, (2) surface mole fractions calculated by both methods are essentially consistent with each other, (3) the molecular interaction parameters (βσ) are of positive values. All of these indicate the real existence of "mutual phobicity" between the fluorocarbon and hydrocarbon chains in the mixed system.
Studies on the Structure and Properties of Perovskite Type Materials in Catalysis--La
k-x
Sr
x
Co
0.75
Me
0.25
○
3-δ
Series
Huang Qing, Li Wan, Zhang Wanjing, Lu Guanglie, Lin Bingxiong
1987, 8(8): 731-736.
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The structure and lattice strain of a series of [(La
1-y
Sr
y
)
1-z
□
z
][Co
0.75
Me
0.25
]○
3-δ
□
δ
] ABO
3
type compounds have been studied by polycrystalline X-ray diffrac tome try. In this structure, La
3+
,Sr
2+
and Ca 14% vacancaies occupy Asites randomly. Co and Me ions distributed at random in the Bsites and O
2-
and its vacancies in the ○ sites. While the Sr
2+
content in the Asite increases, some of the Co ions change their valence from Ⅱ to Ⅲ and finally to Ⅳ, at this time both the lattice strain <ε
110
2
>
1/2
and the activity for COoxidation rapidly increases. Therefore the lattice stain <ε
110
2
>
1/2
could be regarded as a parameter to characterize the modifying effect of Asite substitution on the catalytic properties of these compounds.
Electronic Structure and Chemical Bond of the Cluster Ions Te
6
4+
and P
6
4-
Chen Zhida, Lin Yingzhang, Xu Guangxian
1987, 8(8): 737-740.
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The extended-Huckel molecular orbital approach has been applied to a calculation of the electronic structures of the Te
6
4+
and Pf
6
4-
ions. The difference of the bonding property between Te
6
4+
, Pf
6
4-
and prismane, benzene with the same configuration has been studied by the coefficients and energy levels of their occupied molecular orbitals. It is shown that the weak antibonding orbitals with slightly higher energy level than p orbitals of the free atom Te and Pare occupied by their extra valence electrons of Te
6
4+
and Pf
6
4-
. The interpretation of the stability of the Te
6
4+
and Pf
6
4-
ions was proposed.
Analysis of Fluorescent Spectrum of Tb(Ⅲ) in KTbP
4
O
13
Crystal by Ligand Field Theory
Li Bofu, Li Yanxin, Bai Yubai, San Jiazhong
1987, 8(8): 741-742.
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The irreducible tensor methods of ligand field theory has been applied to analyse the fluorescent spectrum of Tb (Ⅲ) in KTbP
4
O
12
The optimized parameters, 5 crystal field parameters and 8 relativistic parameters, were obtained based upon both the approximate C
4
v symmetry of the environment of Tb (Ⅲ) and the experiment magnitude of the spectrum. The result of calculation is agreement with experiment very well.
The Solvent Effect on Two Menschutkin's Reactions
Jin Songshou, Hu Kecheng, Yu Jieqin, Lu Keshao, Liang Enming, Yang Xjaodong
1987, 8(8): 743-745.
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The effects of methanol, ethanol, acetone, nitromathane, dimethylformamide, dimethyl sulfoxide and other above twenty solvents upon the rates for two Mens-chutkin's reactions of triethylamine and benzyl chloride, pyridine and benzyl chloride have been investigated. The data obtained show that the solvation seems to have bearing the interaction between characteristic groups on the reaCtant molecules and those on solvent molecules.
Some Problems in Curing Theory of Polymer--The Cross-Linking Reaction of A
α
Type
Li Zeiheng, Tang Xinyi, Sun Jiazhong, Tang Aoqing
1987, 8(8): 746-751.
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Jn this paper, the curing process of A
α
-cross-linking reaction is discussed in detail. It contains the three forms of gel point, the varying situation of the sol and gel fraction, the weight average degree and Z-average degree of polymerization in the whole curing process, as well as the scaling problem in the curing theory.
Studies on the Copolymerization of Propylene and Butadiene with Supported Titanium Catalysts (Ⅱ)--Copolymerization with low Butadiene-content and Graft on Copoiymers
Wu Qing, Lu Zejian, Lu Yun, Lin Shangan
1987, 8(8): 752-757.
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Copolymerization of propylene with small amount of butadiene by using TiCl
4
/MgCl
2
/AlEt
3
/EB catalyst has been carried out. The influences of polymerization temperature, solvent species and concentration of titanium, triethylalu-minum, EBon ca:alytic efficiency, buiadiene unit content, and reduced viscosity of copolymers have been investigated.The copolymer containing 8mol% butadiene unit can be chemically grafted with polar vinyl monomers such as maleic anhydride and methyl methacrylatc in toluene solution in the presence of benzoyl peroxide with ease.
The Synthesis of Polymers of Polyvinyl Alcohol Linking 5-FU
Zhou Chaohua, Zhang Wei
1987, 8(8): 758-760.
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By the reactions of three kinds of sodium poly vinyl alcohol of different average molecular weight with 1-(chloroacetyl)-5-fluorouracil(AF) or l-(2-chloro-propionyl)-5-fluorouracil (PF) in absolute DMSO, six kinds of new polymers were prepared. Meanwhile, the influence of reaction conditions and average molecular weight of polyvinyl alcohol on the new polymers was studied systematically. The structural characteristics of the new polymers were investigated by IR and UV; hydrolysis of the new polymers in various buffer solutions (pH1.5, 7.0 and 9.0) was measured by UV, and it was obvious that the new polymers could release out 5-FU.
Study of Resolution of DL Amino Acids with Ligand Exchange Chiral Resins
He Binglin, Jin Renhua
1987, 8(8): 761-765.
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In this paper, resolution of DL-phc,PL-Phser, DL-Tyr, DL-Trp, DL-His etc was studied by liquid chromatography using L-Pro grafted resins coordinated with copper(Ⅱ) as stationary phase. Except DL-His, another amino acids mentioned above could be completely resolved and Dforms were eluated in front of Lforms Through determination of IR spectra of L-Pro-PGMA-Cu (Ⅱ) resin, its possible coordinated model of structure of resin and mechanism of resolution were presented.
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