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중성 및 알카리성수용액에서 Cupferron 의 전극환원메카니즘
황금소,황정의 한국어업기술학회 1975 수산해양기술연구 Vol.11 No.1
The ammonium salt of N-Nitrosophenylhydroxiamine, namely Cupferron, is a well-known analytical reagent which precipitates a great number of metal ions in acid medium. Various structures of electrode reduction for N-Nitrosophenylhydroxiamine have been suggested in acid and alkaline media by many researchers, but not in neutral medium. So the mechanism of electrode reaction of Cupferron was investigated by both chronopotentiometric and polarographic methods. It was estimated that the reduction of Cupferron occurs in a three-step mechanism through which a chemical step is interposed between two charge transfer, the ECE (charge transfer-chemical reaction-charge transfer) mechanism, over a range of neutral and alkaline media. The chemical reaction of the process was assumed to be acid-base catalyzed from the fact that kapp (over all rate constant) of chemical reaction is pH dependent.
황금소,Hwang, Geum So 대한화학회 1974 대한화학회지 Vol.18 No.4
Galvanostatic double pulse 방법으로 백금전극을 사용해서 염소산이온의 전극반응기구를 조사하였다. double current pulse(음극펄스를 먼저 주고 다음에 양극펄스를 주었을 때)를 주었을 때 전류밀도 20∼25ma/$cm^2$ 범위에서 염소산이온의 전극반응기구가 다음과 같이 가정되었다. 더 높은 전류밀도 40∼90ma/$cm^2$ 범위에서, 염소산이온의 전극반응기구는 다음과 같이 가정되었다.$CIO_3^-\;{\longrightarrow^{I}_{n_{1c}}\;CIO_2^-\;{\longrightarrow^{II}_{n_{2a}}\;CIO^-\;{\longrightarrow^{I'}_{n_{1a}}\;CIO_2^-\;{\longrightarrow^{II'}_{n_{2a}}\;CIO_4^-$ 더 높은 전류밀도 40~90ma/$cm^2$ 범위에서, 염소산 이온의 전극 반응 기구는 다음과 같이 가정되었다.$CIO_3^-\;{\longrightarrow^{III}_{n_c}}\;CIO^-\;{\longrightarrow^{I'}_{n_{1a}}\;CIO_2^-\;{\longrightarrow^{II'}_{n_{2a}}\;CIO_4^-$ 혹은 $CIO_3^-\;{\longrightarrow_{n_c}}\;CIO^-\;{\longrightarrow_{n_a}}\;CIO_4^-$ The mechanisms of the electrode reaction of chlorate ion were investigated, using Pt-electrode, by means of the technique of galvanostatic double pulses. For double current pulses (a cathodic pulse followed by an anodic pulse), the mechanism of the electrode reaction of chlorate ion over a current density range from 20 ma/cm2 to 25 ma/cm2 was suggested as the following: $CIO_3^-\;{\longrightarrow^{I}_{n_{1c}}\;CIO_2^-\;{\longrightarrow^{II}_{n_{2a}}\;CIO^-\;{\longrightarrow^{I'}_{n_{1a}}\;CIO_2^-\;{\longrightarrow^{II'}_{n_{2a}}\;CIO_4^-$ For a higher current density from 40 ma/cm2, it was suggested as the following: $CIO_3^-\;{\longrightarrow^{III}_{n_c}}\;CIO^-\;{\longrightarrow^{I'}_{n_{1a}}\;CIO_2^-\;{\longrightarrow^{II'}_{n_{2a}}\;CIO_4^-$ or $CIO_3^-\;{\longrightarrow_{n_c}}\;CIO^-\;{\longrightarrow_{n_a}}\;CIO_4^-$
디메틸포름아미드 중에서 디이소부틸니트로소아민의 음극 반응
黃金小 釜山水産大學校 1979 釜山水産大學 硏究報告 Vol.19 No.1
By chronopotentiometric and potential-current methods, the cathodic reactions of di-iso-butylnitroscamine (Di-iso-BNA) were investigated in nonaqueous electrolyte, 0.1M NaClO₄in dimethylformamide, on the platinum electrode process of Di-iso-BNA was ranged from ??. The E¼ value (-0.264v) of 1mMDi-iso-BNA obtained with S.C.E. reference electrode in dimethylformamide(DMF) was -0.122v larger than the value measured by Pb-Pb(Ⅱ) reference electrode in it at ??. The transfer coefficient(α), diffusion coefficient (D) and Tafel slope in cathodic reaction of Di-iso-BNA were 0.17, ??, and -0.771v respectively. As increasing cathodic current density upto ??, short transition times of 5mM Di-iso-BNA were decreased reversely-that is, chronopotentiometric constants, K values were decreased. Similarly, in accordance with the increase of the concentration of Di-iso-BNA upto 0.1∼5.0mM, the E¼ values were decreased at the constant current density of ??.
黃金小 釜山水産大學校 1978 釜山水産大學 硏究報告 Vol.18 No.1
The electrode reactions of iodine monochloride aqueous solution on the platinum electrode were investigated to clarify the electrode reactions in the cathodic and the anodic processes using the anodic current density after applying the cathodic current density which came to the constant potential (the chronopotentiometric method). The essential current density range for investigating the electrode process was from 2.0 to 0.9 mΑ/㎠. The cathodic reaction in electrolysis at the constant current density was found to be consisted of three successive steps, the EEE mechanism. Discharging of hydrogen ion to form the adsorbed hydrogen atom with regard to the first step proceeds as a diffusion controlled process, while the last step which occurs as a result of iodine reduction is more influenced by the adsorption than the second step. Thus the second is supposed as the electrochemical process of the hydrogen evolution reaction. However, the anodic reaction takes place by a three-step mechanism (the ECE mechanism) in which a chemical step is interposed between two charge transfers-i. e., the first step may be occurred by the adsorption of the reactant and the last step according to the kinetically controlled process. The mechanisms of the cathodic electrode reaction at a high current density within 8.0-9.0mΑ/㎠ could be considered as follows: The first step, ?; the second step, ?; the third step, Ⅰ₂(aq.)+2e→?
전기 이중층 내에서 양성자와 디이소부틸니트로소아민의 용매 치환과 흡착 반응기구
黃金小 釜山水産大學校 1983 釜山水産大學 硏究報告 Vol.23 No.2
NaCl 수용액과 해수 수용액에 유기물질, DBNA를 첨가하고 Pb-hydroxide 산화 피막을 음극으로 사용한 constant current-potential 방법과 potentiodynamic cathodic polarization 방법에 의해서 얻어진 실험 결과는 다음과 같다. 1) Pb-hydroxide 산화 피막 전극으로 NaCl 수용액과 해수 수용액에서 구한 분자 크기, 피복율 및 열역학적 값들은 납-인산 피막 전극에서 얻은 값과 많은 차이를 나타내었다. 2) 반응 물질이 높은 전위값에서 환원되는 것을 Pb-hydroxide 산화 피막의 구성이 metal(Pb)/semiconducting inner film(PbO)/ionically conducting outer film(PbOH)/electrolyte 로 되어 있기 때문에 생긴 것 같다. 3) 수소의 흡착 반응 기구는 주로 화학 결합에 의해서 일어났지만, Pb-hydroxide 산화 피막 표면에서 수소가 발생할 때는 심한 피막 손실을 가져왔다. Substitutional adsorption mechanism was discussed with solvent displacement and relative factor( χ) of adsorbate and solvent and hydrogen coverage(θ) on the Pb-hydroxide anodic film electrode in NaCl solution and the sea water at 15∼35℃ were studied by means of constant current-potential method and potentiodynamic cathodic polarization method. In this experiment, various constants and thermodynamic quantities calculated from the coverage of hydrogen atoms studied with the Pb-hydroxide anodic film electrode in aqueous solutions were very different values than those of Pb-phosphate anodic film electrode. The Pb-hydroxide film electrode formed in alkaline solution was suggested with being consisted of metal(Pb)/semiconducting inner film(PbO)/ionically conducting outer film(PbOH)/electrolyte at interface. The adsorption mechanism of the hydrogen evolution was progressed as the chemical combination process according to the embrittlement of surface.