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Table of Content
24 December 1989, Volume 5 Issue 4
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Articles
Synthesis and Structure of Dibenzoyl-bissemicarbazone Neodymium(Ⅲ) Perchlorate
Huang Ling, Huang Chunhui, Xu Guangxian, Zheng Qitai, He Cunheng
1989, 5(4): 282-287.
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A new Schiff base Dibenzoyl-bissemicarbazone C
15
H
16
N
6
O
2
(L) and its complex with neodymium(Ⅲ ) perchlorate [NdC(H
2
O)
24
)
3
3.The final standard deviation R=0.0919.In the complex Nd is coordinated by four nitrogen and six oxygen atoms, of which four nitrogen and four oxygen atoms are provided by two neutral ligands L, and the other two oxygen atoms are provided by two water molecules, forming a ten-coordinated complex cation, which the perchlorate groups exist in the outer sphere.The coordination polyhedron takes a bicapped anti-square prism arrangement.
Studies on Volatilization of Zirconium from Electrothermal Graphite Furnace for Sample Introduction into Inductively Coupled Plasma
Huang Min, Jiang Zucheng, Zeng Yune
1989, 5(4): 288-292.
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Element zirconium reacted with polytetrafluoroethylene (PTFE) dispersed in isopropanol-water mixture to form volatile fluoride when heated in an electrothermal graphite furnace, and the fluorides formed subsequently were vaporized into ICP for atomization and excitation.The technique provides a picogram detectkm limit and adequate precision of 4% relative standard deviation.Linear dynamic range covers over three orders of magnitude.The process of sample preparation it very convenient.It is expected that the method proposed is suitable for determination of other refractory elements.
Studies on the Biomimetic Oxidation Catalyzed by the Model Compound of Cytochrome P-450 (Ⅶ) The Influence of the Axial Ligand X in TPPFe(Ⅲ)X on Its Catalytic Properties for the Oxygenation of Cyclohexane
Zhu Shenjie, Gui Mingde, Guo Cancheng
1989, 5(4): 293-298.
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In the study of cyclohexane monoxygenation with PhIO catalyzed by TPPFe( Ⅲ )X, we found the Influence of different axial ionic ligands X (X = F, Cl, Br, I, SCN, OR, R, CH
3
, C
2
H
6
, (CH
3
)
2
CH, (CH
2
)
3
C)in TPPFe( Ⅲ )X on the oxidation products distribution and the yields of cyclohexanol.This paper deals with the linear relationship between the catalytic activity of TPPFe(Ⅲ)X and both the electronic or/ and steric effects of the axial ligands OR in TPPFe(Ⅲ)OR on its catalytic activity.
In Situ FTIR Spectroscopic Study of Electrochemical Adsorption of Phosphate Ions on Gold
Zhou Zhihua
1989, 5(4): 299-303.
Abstract
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)
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Infrared reflection-absorption spectra for primary, secondary and tertiary orthophosphate anions on a gold electrode in aqueous solution were studied by in situ FTIR spectroscopy.The spectra show that H
2
PO
4
-
, HPO
4
2-
ions do not interact with the electrode surface as strong as PO
4
3-
do.According to the surface selection rule, we deduce the modes of adsorption of these anions on the electrode from these spectra.The experiment also confirms the affection to adsorption of ion on the electrode due to ion-migration into thin-layer cavity.
Studies on Kinetic Properties of Active Oxygen on the Surfaces of V
2
O
5
/SiO
2
, V
2
O
5
-MoO
3
/SiO
2
and V
2
O
5
-P
2
O
5
/SiO
2
Catalysts
Zheng Xiaoming, Zhu Yifei, Zhou Lihua
1989, 5(4): 304-312.
Abstract
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Applying the TPD-MS with a high sensitivity of determination, the TPD spectrum of surface oxygen of V
2
O
5
/SiO
2
, V
2
O
5
-MoO
3
/SiO
2
and V
2
O
6
-P
2
O
5
/SiO
2
catalysts was obtained.The surface oxygen of these catalysts can be divided into three groups according to the desorption temperature.O
2
--
from 673K to 873K and O
2-
at above 873K.The activation energy and frequency factor of all the three kinds of oxygen species were calculated.Based on these results, the mechanism of oxygen desorption and the influence of P
2
O
5
and MoO
3
on the properties of oxygen supply of V
2
O
5
/SiO
2
catalst were investigated.MoO
3
and a small amount of P
2
O
5
increase the number of supplying oxygen and increase the activity of O
-
species.A large amount of P
2
O
5
increases the number of supplying oxygen and restrains the activity of O
-
species.
The Applicaton of IAF Theory to the Study of Dissociation Equilibrium (Ⅱ)--The Calculation of Solubility Product Constant in Nonaqueous Solvents
Wang Fengyun
1989, 5(4): 313-318.
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This article reports a theoretical calculation of solubility product constant of several slightly soluble silver salts in a number of nonaqueous solvents according to the IAF (interaction force) theory based on the interaction free energy of electrostatic, orientation, induction and dispersion.The calculated values of pKsp are in good accordance with those from literature.
Study of Cathodic Polarization Curves During Pulse Plating of Chromium
Zhang Hengbin, DerTau Chin
1989, 5(4): 319-324.
Abstract
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)
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A study has been made of the cathodic polarization curves during the pulse plating of chromium from an aqueous chromic acid bath containing 250 g/L CrO
3
and 2.5 g/L H
2
SO
4
at 22℃ over the range of pulse periods from 1 ms to 50 ms.The duty cycle was kept at 50%.The methods of potentiostatic pulse potential control and galvanostatic pulse current control were used to determine the polarization curves of a platinum and a copper rotating disk electrode in the chromium plating solution.The results indicated that pulse potential and pulse current inhibited the formation of a cathode film and shifted the potential of the hydrogen evolution reaction toward the positive direction by about 500 mV.The potential and current pulses behaved as a depolarter of H
+
reduction reaction.The present results agreed with a previous experimental observation that the coulombic efficiency of the chromium deposition reaction was reduced and the coulombic efficiency of the hydorgen evolution reaction was increased in pulse plating of chromium.
Ab Initio Study on the Isomerization and Dehydrogenation of Methylnitrene
Chen Bin, Zhao Chengda, Fu Qiang, Huang Jingan
1989, 5(4): 325-330.
Abstract
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)
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The ab initio calculations were performed at the RHF/4-31G level with the reaction pathways of the iso-merization and dehydrogenation of methylnitrene by the intrinsic reaction coordinate method.The results show that the transformation from methylnitrene to methylenimine would be very easy.This accountes for the experimental fact that one couldn't find the methylnitrene, but only obtained the methylenimine in the pyrolysis of methyl azide.The mode-selective study reveals the reaction coordinates (IRC) of isomerization and dehydrogenation of methylnitrene are associated with the molecular deformation mode of 1191 cm
-1
and the methyl group unsymmetrical stretch mode, respectively.The coupling between normal coordinates is favourable to select the reaction channel of isomerization.
CNDO Studies on the Intermolecular Coulomb Interaction in TCNQ-Stack
Huang Zonghao, Zhao Chengda
1989, 5(4): 331-335.
Abstract
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)
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The coulomb interaction among TCNQ-molecules in different stack structures was calculated by quantum chemistry CNDO method.The results of the calculation would be used to explain the change rule of the electricity property of the TCNQ complex very well.
The Effective Hamiltonian and Electron Correlation Energy
Deng Conghao, Feng Dacheng, Deng Lu, Li Dazhong
1989, 5(4): 336-343.
Abstract
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)
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An effective,hermitian hamiltonian is derived in amodel space.Its perturbation expressions to third order approximation are given.The correlation energy is also given to the third order approximation.The effective hamiltonian deviates form the actual one by the presence of acorrelation operator.The cprrelation operatop is given in an explicit form.
On the Construction of n-Electron States with Symplectic Symmetry
Sun Jiazhong(Sun Chiachung), Li Baifu, Zeng Zonghao, Liu Chengbu
1989, 5(4): 344-356.
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Under quasispin scheme, a complete group theoretical classification of fermion states with symplectlc symmetry is proposed.Furthermore, the first and second order irreducible tensor operators are investigated in detail to approach the fermion states with explicit forms.
Synthesis of Polymer-Supported Heteronuclear Rhodium-Cobalt Bimetallic Carbonyl Cluster Catalysts and Their Hydroformylation Properties
He Binglin(Ho PingLum), Sun Juntan, Li Hong, Sang Junjie, Zhao Fenzhi
1989, 5(4): 357-362.
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)
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Tetranuclear Rh-Co bimetallic cluster was synthesized and characterized by IR and XPS.The properties of the anchored catalysts, its stability and the ligand effect were also studied.The experimental results show that the optimal conditions for the hydroformylation of hexene-1 are as follows: the temperature is 80℃, reaction time 8 h, pressure 5.88×10
5
Pa, and molar ratio of H
2
/CO 1.2/1.0.Functional groups attached to the donor atom(N) possess more or less some influence on the catalytic behavior.Compared with the homogeneous cluster, the polymer-supported bimetallic cluster is more stable.After the catalytic reaction, the structure of the anchored catalysts was not destroyed.X-ray photoelectron spectroscopy characterization indicates that there is a weak interaction between the polymer support and the active metals.
Studies on the Formation Mechanism of Silica-Sodalite in the System of Sodium Hydroxide-Silica-Ethylene Glycol
Feng Shouhua, Xu Jianing, Xu Ruren, Ma Shujie, Ding Hong
1989, 5(4): 363-367.
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A New Synthetic Method of Meso-Tetrakis (4-sulfonatophenyl) porphyrin
Zhang Zhoupeng
1989, 5(4): 368-372.
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)
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Editor-in-Chief:
Jihong YU
ISSN 1005-9040
CN 22-1183/O6
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