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Kinetics of Ligand Substitution Reactions in Vanadium(III) Complexes with Multidentate Ligand
김정성,HIROSHI TOMIYASU 大邱大學校附設 基礎科學硏究所 1993 基礎科學硏究 Vol.10 No.-
The kinetics of ligand substitution reactions in V(Gly)3 (Gly = Glycine) with various multidentate ligands, nitrilotriacetate (NTA) and ethylendiaminetetraacetate (EOM) have been atudied spectre photometrically. The rates of EDTA and NTA substitutions depend on the entering species. The value of the second order rate constants are k11= 3.0 x 10-2 M-1 s-1(1 M = 1 mol dm 3) for H2edta, k21 = 0.24 M-1 s'1 for Hnta and 1.9 x 10-2 M-1 s-1 for H2nta as an entering ligand, respectively at 250C. Large negative values of activation entropies are interpreted by associative mechanism.
김정성,박윤열,HIROSHI TOMIYASU 大邱大學校附設 基礎科學硏究所 1993 基礎科學硏究 Vol.10 No.-
Unusual kinetic behavior was observed in the substitutions of hemin with imidazole and cyanide ion under conditions of [L] S 2[hemin] (L=substituting ligand) in N,N--dimethylformamide. The rates of these reactions were much slower than those the formations of mono- and bis-coordinate complexes. Based on the kinetic results, these slow reactions were interpreted in terms of the dissociations of mono-coordinate complex to solvated hemin. The activation volume was determined to be 24.3 -- 0.4 cm3 mol'1 for the reaction with imidazole by the high pressure stopped flow method. The large positive value of the activation volume strongly supports a limiting dissociative mechanism.
개량된 초임계수 산화법에 의한 염소계 유기물 (PCB, 4-DCBz)의 완전분해반응
이상환,박기철,박윤열,양종규,김정성,富安博 한국환경과학회 2005 한국환경과학회지 Vol.14 No.5
For the destruction of toxic chlorinated organic compounds, this study proposes improved supercritical water oxidation method (multistep oxidation) using sodium nitrate as an oxidizer. This method solves the problems involved in the existing supercritical water oxidation method. Multistep oxidation means that NaNO₃ is oxidized to N₂ via NaNO₂ and NO. Toxic and hard to destroy organic substances like para-dichlorobenzen(4-DCBz), polychlorinate biphenyl(PCB) ware oxidized to non toxic substances in a condition, in which rapid pressure and temperature rise is restrained as much as possible. 4-dichlorobenzene(4-DCBz) and Polychlorinate biphenyl(PCB) in condition(450℃, p_(w)=0.25g/cm³, 30min) Was discomposed perfectly.