VALENCE STATE EQUILIBRIA BETWEEN COBALT AND MANGANESE IONS AND MAGNETIC-PROPERTIES OF LACO0.9MN0.1O3

According to the thermodynamic equilibria between the low spin state Co(III) (t2g6e(g)0) ion and the high spin state Co3+ (t2g4e(g)2) ion and between the cobalt and manganese ions with different valence state and spin state, an approximate semiempirical f

THE SYNTHESIS AND PHYSICAL-PROPERTIES OF THE NEW LAYERED LANTHANIDE ALKALINE-EARTH COBALT OXIDES [LN2MCO2O7 (LN=SM,GD M=SR,BA)]

Three new oxides Sm2SrCo2O7, Sm2BaCo2O7 and Gd2SrCo2O7 have been successfully synthesized by a solid state reaction method.The X - Ray diffraction spectra show that they are all isostructural with Sr8Ti 2O7, Ln2SrCo2O7(Ln=Sm, Gd) crystallized in the tetra

SPIN AND VALENCE STATE EQUILIBRIA OF COBALT AND MAGNETIC-PROPERTIES OF LACOO3

On the basis of the spin and valence state equilibria and superexchange interaction of the various cobalt ions in LaCoO3, an approximate semiempirical formula has been proposed and used to calculate magnetic susceptibilities of LaCoO3 over a wide temperature range (100-1200 K). The results indicate that there are thermodynamic equilibria between the low spin state Co(III) (t2g6e(g)0) ion, the high spin state Co3+ (t2g4e(g)2) ion, the Co(II) (t2g6e(g)1) ion and the Co(IV) (t2g5e(g)0) ion in LaCoO3. The energy difference between the low spin state Co(III) and the high spin state Co3+ is about 0.006 eV. The content of the low spin state Co(III) ion is predominant in LaCoO3 and the content of the high spin state Co3+ ion varies with temperature, reaching a maximum at about 350 K, then decreasing gradually with increasing temperature. At low temperature the contents of the Co(II) ion and the Co(IV) ion in LaCoO3 are negligible, while above 200 K the contents of both the Co(II) ion and the Co(IV) ion increase with increasing temperature; however, the content of the Co(II) ion always is larger than that of the Co(IV) ion at any temperature. These calculated results are in good agreement with experimental results of the Mossbauer effect, magnetic susceptibility and electrical conductivity of LaCoO3.

ELECTROCHEMICAL DETECTION OF COBALT IN HAIR FOLLOWING ON-COLUMN DERIVATIZATION WITH 1-(2-PYRIDYLAZO)-2-NAPHTHOL-6-SULFONIC ACID AND REVERSED-PHASE LIQUID-CHROMATOGRAPHY

A method for the specific determination of cobalt based on reversed-phase liquid chromatography with amperometric detection via on-column complex formation has been developed. A water-soluble chelating agent, 1-(2-pyridylazo)-2-naphthol-6-sulphonic acid (PAN-6S), is added to the mobile phase and aqueous cobalt solutions are injected directly into the column to form in situ the cobalt-PAN-6S chelate, which is then separated from other metal PAN-6S chelates and subjected to reductive amperometric detection at a moderate potential of -0.3 V. Because the procedure eliminates the interference of oxygen and depresses the electrochemical reduction of the mobile phase-containing ligand PAN-6S, by virtue of the quasi:reversible electrode process of the cobalt-PAN-6S complex, a low detection limit of 0.06 ng can be readily obtained. Interference effects were examined for sixteen common metal species, and at a 5- to 8000-fold excess by mass no obvious interference was observed. The feasibility of the method as an approach to the specific analysis of cobalt in a hair sample has been demonstrated.

ELECTROCATALYSIS AND DETERMINATION OF HYDRAZINE COMPOUNDS IN LIQUID-CHROMATOGRAPHY AT A MIXED-VALENT COBALT OXIDE CYANOCOBALTATE FILM ELECTRODE

A glassy carbon electrode coated with an electrodeposited film of mixed-valent cobalt oxide/cyanocobaltate (Co-O/CN-Co) enabled hydrazine compounds to be catalytically oxidized at the greatly reduced overpotential and in a wide operational pH range (pH 2.0-7.0). Electrocatalytic activity at the Co-O/CN-Co modified electrode was evaluated with respect to solution pH, film thickness, supporting electrolyte ions, potential scan rate, operating potential, concentration dependence and other variables. The Co-O/CN-Co film electrode was completely compatible with a conventional reversed-phase liquid chromatographic (RP-LC) system. Practical RP-LC amperometric detection (RP-LCEC) of hydrazines was performed. A dynamic linear response range over three orders of magnitude and a detection limit at the pmol level were readily obtained. The Co-O/CN-CO film electrode exhibited excellent electrocatalytic stability in the flowing streams.

气相中C_(60)与多氯代乙烷的反应

在质谱仪离子源化学电离条件下.C_(60)分别与1,2-二氯乙烷、1,1,2-三氯乙烷、1,1,1-三氯乙烷及1,1,2,2-四氯乙烷的主要碎片离子反应,生成多种C_(60)的加合离子.显示了气相中C_(60)的化学活泼性.

中性氧化铝用于碳-60、碳-70柱分离的探讨

自90年实现实验室合成C_(60)/C_(70)以来,碳原子簇化学引起世界各国科学家的广泛兴趣,纷纷开展与其相关的各项研究。由电阻加热法、电孤法产生的烟灰经过甲苯(或苯)抽提便可得到C_(60)/C_(70)混合溶液,但其大量分离却很困难。Hawkins等用苯基甘氨酸做基底的HPLC方法和Jinno等用多取代苯基修饰的二氧化硅作固

富勒烯碳-60,碳-70的电化学研究进展

短短的几年,随着各种物理与化学研究方法的相继介入,以C_(60)和C_(70)为代表的富勒烯研究取得了令人瞩目的成就。跟踪最新进展,引文41篇,本文就其电化学方面的研究工作做了系统的综述。

气相C_(60)与甲苯、氯化苄和对二甲苯反应研究

在质谱离子源内,气相C_(60)分别与甲苯、氯化苄、对二甲苯产生的主要碎片离子及自由基反应,生成了C_(60)的多种气相衍生物离子,表明气相下C_(60)具有很活泼的化学性质。

C_(60)与苯及氘代苯的气相反应

1985年Kroto首先用质谱在激光蒸发石墨的氦气氛中检测到丰度占优势的以C_(60)和C_(70),从而以质谱法为主要手段的C_(60)研究迅速开展起来。一系列实验结果支持了Kroto猜测的C_(60)球形结构,并对C_(60)的气相反应行为有所认识。 1990年实现宏观量制取C_(60)后,气相C_(60)离子的研究内容更加广泛,Frieser在气相中

C_(60)与卤代卡宾的气相离子-分子反应

足球状全碳烯 C_(60)具有丰富的化学性质,可以做为活泼的自由基捕捉试剂,在质谱常规化学电离源内气相 C_(60)可与 CCl_4,CHCl_3,CH_2Cl_2和 CHBr_3等产生的碎片发生化学反应,生成了[C_(60)CX_2]~+等多种气相衍生物离子.单独引入 CCl_4的离子源内存在着CCl_3~+(m/z117,100%),CCl_2~+(m/z82,22%),CCl~+(m/z47,24%)和 Cl+(m/z35,14%)阳离子、多种阴离子及 CCl_3,CCl_2,Cl 等自

C_(60)系列化合物的磁学性质

本文概述了C_(60)系列化合物的NMR谱、磁化率、磁性的某些进展。

STUDIES ON ELECTROGENERATION, INSITU ELECTROCHEMISTRY AND SPECTROELECTROCHEMISTRY OF ALKYL COBALT PORPHYRIN

Methyl-, ethyl-, propyl- and n-butyl cobalt porphyrins were electrochemically synthesized and studied byIn-situ cyclic voltammetry and UV-Visible spectro-el ectrochemistry. Rate constants for the alkylations were determined. It was found that the four alkyl saturated tetraphenylchlorin cobalt complexes were formed after electrochemical reduction of the alkyl cobalt porphyrins.

MEASUREMENT OF CATALYTIC ACTIVITY VARIATION FOR H2O2 OXIDATION AT A COBALT PORPHYRIN COATED ELECTRODE

A rapid rotation-scan method was used for the electrocatalytic oxidation of H2O2 at a cobalt protoporphyrin modified pyrolytic graphite electrode (CoPP/PG). The rate constant of H2O2 oxidation at the CoPP/PG electrode at different potentials and in different pH solutions was measured. The variation of catalytic activity with reaction charges (Q) passed through the electrode was analyzed. This provided a convenient electrochemical method to study the passivation and poisoning of catalytic sites with time.