• Title/Summary/Keyword: Chelate formation

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Effects of the addition of chelate compound in phosphating surface conditioning solution (인산염 표면 조정액 중의 킬레이트제 첨가 영향)

  • 남궁성;허보영
    • Journal of the Korean institute of surface engineering
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    • v.34 no.4
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    • pp.281-288
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    • 2001
  • Phosphating treatments have been performed to improve paint adhesion and corrosion resistance of zinc and zinc alloy coated steels for a long time. In this work, the effects of the addition of chelate compound were studied to improve the stability of surface conditioning solution and properties of zinc phosphate films. The coalescence of colloidal Ti-compound and extraneous charged particles (alkaliearth metal cation such as $Mg^{2+}$ , $Ca^{2+}$ ) were suppressed by using a surface conditioning solution with chelate compound. Therefore, after surface conditioning solution containing chelate compound was left standing for one week at room temperature, the formation of a white sediment was decreased comparing to surface conditioning solution without chelate compound. The crystal size of phosphate film was fine and the whiteness value of phosphated zinc coated steel sheets was also high without the decrease of corrosion resistance and anti-patina. It was very effective to use chelate compound improving the stability of surface conditioning solution.

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Thermodynamics of Metal Chelate Formation of 8-Hydroxyquinoline-5-Sulfonic Acid (8-Hydroxyquinoline-5-Sulfonic Acid의 금속킬레이트 생성에 관한 열역학적 고찰)

  • Kun Moo LEE
    • Journal of the Korean Chemical Society
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    • v.13 no.1
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    • pp.5-8
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    • 1969
  • Acid dissociation constants and chelate stability constants of 8-hydroxyquinoline-5-sulfonic acid have been determined for divalent metal ions. Co (Ⅱ), Ni (Ⅱ) and Zn (Ⅱ) by means of the Calvin-Bjerrum technique at the various temperatures. The standard free energy changes for the reactions at $20^{\circ}$, $30^{\circ}$, $40^{\circ}$and $50^{\circ}C$ were calculated, and the corresponding values of ${\Delta}H^{\circ}$ and ${\Delta}S^{\circ}$ applying over this temperature range are reported. The results are interpreted on the basis of current theories of metal chelate formation in aqueous solution.

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Studies on the Properties of 2-Methoxy-5-Nitrophenol Complex Salts (2-Methoxy-5-Nitrophenol 금속착염의 화학적 성질에 관한 연구)

  • 김선덕;우세홍;김명운
    • Journal of Environmental Health Sciences
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    • v.1 no.1
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    • pp.21-27
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    • 1974
  • This work was carried out to investigate the chemical properties of the chelate compounds which were produced with 2-methoxy-5-nitrophenol(MNG) and metal salt such as copper nitrate and manganese nitrate. And obtained results were as in the followings. 1) The binding ratio of the chelate compounds formation were determined by using the molar ratio concentration method and their chemical structures were identified by IR-spectrum. 2) In the absorbance measuring, 2-methoxy-5-nitrophenol coordinated with manganese and copper showed the maximum absorbance at $430 m\mu$ and $410 m\mu$ respectively. 3) The binding ratio of chelated compounds were measured by molar ratio method and continuous variation method with spectrophotometer, which was identified as 1:2. 4) The conditional formation constant(log Kn value) of manganese and copper chelate compounds were 6.70, 6.75, respectively according to the equation of $log\frac{A-AM\circ n MNG}{AMm MNG-A}=n log (M\circ)+log Kn$ 5) The dissociations degree of manganese and copper chelate compound were $2, 300{\times} 10^{-7}$, $2, 346{\times} 10^{-7}$ respectively according to the molar calculation method.

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The Kinetics of Complexation of Nickel(II) and Cobalt(II) Mandelates in Aqueous Solution

  • Choi, Ki-Young;Yun, Sock-Sung;Kim, Mal-Jin
    • Bulletin of the Korean Chemical Society
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    • v.12 no.6
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    • pp.629-632
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    • 1991
  • The rate constants for the formation and dissociation of nickel(II) and cobalt(II) complexes with mandelate have been determined by the pressure-jump relaxation study. The forward and reverse rate constants for the mandelate complex formation reactions were obtained to be $k_f=3.60{\times}10^4\;M^{-1}s^{-1}$ and $k_r=1.73{\times}10^2\;s^{-1}$ for the nickel(II), and $k_f=1.75{\times}10^5\;M^{-1}s{-1}$ and $2.33{\times}10^3\;s^{-1}$ for the cobalt(II) in aqueous solution of zero ionic strength ($(\mu{\to}0)\;at\;25^{\circ}C$. The results were interpreted by the use of the multistep complex formation mechanism. The rate constants evaluated for each individual steps in the multistep mechanism draw a conclusion that the rate of the reaction would be controlled by the chelate ring closure step in concert with the solvent exchange step in the nickel(II) complexation, while solely by the chelate ring closure step for the cobalt(II) complex.

Optical Resolution of DABS-Amino Acids with Mobile Chiral Chelate Addition (키랄킬레이트 이동상첨가법에 의한 답실아미노산의 광학이성질체 분리)

  • Lee, Seon Haeng;O, Dae Seop;Byeon, Seong Gu
    • Journal of the Korean Chemical Society
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    • v.34 no.4
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    • pp.345-351
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    • 1990
  • Optical isomers of DABS-amino acids have been separated in a reversed phae high performance liquid chromatography by adding Cu (Ⅱ)-L-Proline chelate to the mobile phase. The retention behaviors for the DABS-amino acids are discussed in terms of pH of the mobile phase and the concentrations of acetonitrile, Cu (Ⅱ) complex, and buffer. The selectivity of the optical isomers of DABS-amino acids increases with the pH of the mobile, and the concentration of the chelate, but decreases with concentration of the oganic modifier. The concentration of buffer does not affect the optical separation selectivity. A separation mechanism is illustrated by cis and trans formation based on the steric effect of the ligand exchange reaction between DABS-amino acids and the copper chelate.

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The Kinetics of Complexation of Manganese(Ⅱ), Cobalt(Ⅱ) and Nickel(Ⅱ) Ions with Some Dicarboxylates in Aqueous Solution

  • Yun Sock Sung;Doh Jae-Bum;Choi Ki Young
    • Bulletin of the Korean Chemical Society
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    • v.13 no.6
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    • pp.659-662
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    • 1992
  • The pressure-jump relaxation method has been used to determine the rate constants for the formation and dissociation of maganese(Ⅱ), cobalt(Ⅱ), and nickel(Ⅱ) with some dicarboxylates in aqueous solution at zero ionic strength. The carboxylate ligands used are 3-nitrophthalate, 4-nitrophthalate, and phenylmalonate. The activation parameters have alse been obtained from the temperature dependence of the rate constants. A dissociative interchange mechanism with a chelate ring closure step as rate determining is employed to interpret the kinetic data of manganese(Ⅱ) and cobalt(Ⅱ) complexes. The rates of formation of nickel(Ⅱ) complexes are controlled by both the solvent exchange step and the chelate ring closure step.

Synthesis and Solution Properties of La(III)-N-ethylmorpholine Complex

  • Anwar, Zeinab M.;Sung, Yong-Kiel
    • Bulletin of the Korean Chemical Society
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    • v.26 no.4
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    • pp.614-618
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    • 2005
  • The complex of the composition LaL(N$O_3)_3\;(H_2O)_2$ is prepared by the reaction of La($NO_3)_3{\cdot}6H_2O$ with Nethylmorpholine in aqueous medium. The ligand is involved in the complex as a neutral species where the chelation occurs via the oxygen of the ligand moiety and the nitrate groups as bidentate ligand. The chemical structure of the studied complex is confirmed through IR, XRD, and thermal analysis data. The complexation equilibria of La(III) with N-ethylmopholine is studied in aqueous medium at ionic strength I = 0.1 mol${\cdot}dm^{-3}\;KNO_3$ and at 25, 35 and 45 ${^{\circ}C}$, respectively. The thermodynamic parameters $\Delta$G, $\Delta$H and $\Delta$S values were calculated to prove the association with the complex formation. It is clearly observed that the process is accompanied by absorption of heat, i.e. endothermic process, while the entropy does not change greatly attributed to the release of constant number of water molecules during chelate formation.

The Epoxy-metal Interphase and Its Incidence on Practical Adhesion

  • Roche, Alain Andre;Aufray, Maelenn
    • Journal of Adhesion and Interface
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    • v.4 no.2
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    • pp.1-9
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    • 2003
  • Epoxy-amine liquid prepolymers are extensively applied onto metallic substrates and cured to obtain painted materials or bonded joint structures. Overall performances of such systems depend on the created interphase between the organic layer and the substrate. When epoxy-amine liquid mixtures are applied onto more or less hydrated metallic oxide layer, concomitant amine chemical sorption and hydroxide dissolution appear lending to the chelate formation. As soon as the chelate concentration is higher than the solubility product, these species crystallize as sharp needles. Moreover, intrinsic and thermal residual stresses are developed within painted or bonded systems. When residual stresses are higher than the organic layer/substrate adhesion, buckling, blistering, debonding may occur leading to a catastrophic drop of system performances. Practical adhesion can be evaluated with either ultimate parameters (Fmax or Dmax) or the critical strain energy release rate, using the three point flexure test (ISO 14679-1997). We observe that, for the same system, the ultimate load decreases while residual stresses increase when the liquid/solid time increases. Ultimate loads and residual stresses depend on the metallic surface treatment. For these systems, the critical strain energy release rate which takes into account the residual stress profile and the Young's modulus gradient remains quite constant whatever the metallic surface treatment was. These variations will be discussed and correlate to the formation mechanisms of the interphase.

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Separation of D and L Amino Acids by High-Performance Liquid Chromatography

  • Lee, Sun-Haing;Ryu, Jae-Wook;Park ,Kyoung-Sug
    • Bulletin of the Korean Chemical Society
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    • v.7 no.1
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    • pp.45-50
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    • 1986
  • Separation of optical isomers of some derivatives of amino acids by reversed-phase HPLC has been accomplished by adding a chelate of an optically active amino acid to copper(Ⅱ) to the mobile phase. Cu(Ⅱ) complexes of L-proline and L-hydroxyproline in the mobile phase showed different degrees of separation. Optical isomers of DNS derivatives of amino acids are selectively separated, but those of several other derivatives are not at all. The kinds of buffer agents, the pH, and the concentrations of acetonitrile and the Cu(Ⅱ) ligand all affect the separations. The elution behavior between D and L DNS-amino acids appears to depend on the alkyl side chain of the amino acids. A chromatographic mechanism is proposed that is based on a stereospecificity of the formation of ternary complexes by the D, L-DNS-amino acids and the chiral additive associated with the stationary phase. The steric effects of the ligand exchange reactions are related with the feasibility of cis and/or trans attack of the amino acids to the binary chiral chelate retained on the stationary phase.

Stability Constants of Copper Sulfa-Drug Complexes in Dimethylformamide Aqueous Solution (Dimethylformamide 수용액중에서의 Sulfa제-Cu 착화합물의 안정도정수)

  • 이왕규
    • YAKHAK HOEJI
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    • v.9 no.1_2
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    • pp.4-7
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    • 1965
  • Acid dissociation constants of sulfamethoxypyridazine, sulfadimethoxine, sulfamerazine, sulfathiazole and sulfadiazine, and stability constants for formation of copper chelate were calculated from their titration curves in 80% dimethylformamide with ionic strength 0.1 at $25{\deg}$ It was found that the acid dissociation constants (pKa) of sulfa-drugs were in the range of 9.33 - 10.05, and the stability constants (log $k_{1}$, $k_{2})$ of their copper chelates were in the range of 9.33-9.71.

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