해수의 전기전도도에 미치는 압력의 영향(Ⅱ) : 활성화에너지와 활성화부피변화 The Activation Energy and the Activation Volume Change

황금소,황정의 한국수산학회 1977 한국수산과학회지 Vol.10 No.4

제 Ⅰ보에서 측정한 해수의 비전도도 값을 사용하여 본논문에서 저자들이 제안한 식으로부터 얻어진 당량 전도도를 Arrhenius plot 했을 때 활성화에너지, ΔE¹는 압력 및 농도변화에 따라 3.0∼4.0 Kcal/mole범위이었다, 압력변화에 따른 활성화 부피변화의 평균치는 측정된 온도와 압력에서 -0.27∼-1.30 ㎤/mole 범위였다. (염소량이 6.228‰,-1.65∼ -0.32 ㎤/mole: 9.063‰,-1.18∼-0.27 ㎤/mole; 11.628‰, -1.53∼-0.07 ㎤/mole; 14.311‰, -1.37∼-0.35㎤/mole; 16.408%, -1.18∼-0.47 ㎤/mole; 19.372‰, -1.53∼-0.29 ㎤/mole)이들값으로 해수의 성질과 물의구조를 정성적으로 밝힐 수 있었다. In this study, physical and chemical properties of sea water were investigated qualitatively from the data measured by means of the conductive method as described in the previous paper. The activation energy, ΔE¹, calculated from the suggested equation describing the electrical conductive property of sea water was about 3.0 to 4.0 Kcal/mole at a given pressure and concentration. The average values of the activation volume change, ΔV^M, over the pressure 1 to 1,200 bars decreased from -1.30 to -0.27㎤/mole as the temperature increased from 10 to 25℃.

백금전극에서 요오드 이온의 흡착특성과 반응기구

황금소 부산수산대학교 1990 부산수산대학교 연구보고(자연과학편) Vol.30 No.1-2

진한 염소나트륨의 전극반응에 관한 연구

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 $CIO_3^-\;{\longrightarrow_{n_c}}\;CIO^-\;{\longrightarrow_{n_a}}\;CIO_4^-$

산화피막전극을 이용한 디이소부틸니트로소아민의 전극반응

황금소 한국수산학회 1981 한국수산과학회지 Vol.14 No.2

해수에서 전기 전도성이 있는 산화 피막전극을 사용하여 금속 산화피막 전극들의 특성과 발암성 원인물질인 DBNA의 전극 반응성을 규명하는데 필요한 기초 자료를 potential drop방법과 galvanostatic방법으로 얻어서 다음과 같은 결론을 내렸다. 1) 9‰해수에 음극반응 억제제 DBNA를 첨가한 경우 알루미늄 산화피막 전극과 아연 산화피막 전극은 potential drop현상을 나타내지 못 했으나 납 산화 피막 전극과 구리 산화피막 전극은 피막전극으로서 적합한 기능을 가졌음을 알았다. 2) 제1단계 음극반응의 transition time이 0.22∼1.40sec범위의 1분이내 값이므로 산화피막을 통과한 양성자는 확산→흡착과정의 음극반응을 했다. 3) 0.5M NaCl수용액과 9‰해수에서 얻어진 transition time 값들이 대체로 일치한 것은 금속의 종류에 관계없이 산화피막을 통과한 양성자의 확산속도가 일정전류밀도 범위에서 일정하였기 때문이다. 4) 1.9×10^(-4)∼10^(-6) amp/㎠의 전류밀도 범위에서 해수와 해수에 억제제 DBNA를 첨가했을 때 얻어진 τ₁/4값들과 E₁/4값들의 차가 각각 0.06sec와 0.53v 였으므로, 억제 DBNA의 음극반응은 주로 흡착→확산과정 이었다. 5) 알루미늄 산화피막과 아연 산화피막의 표면에 흡착된 전해질의 흡착량이 납 산화피막과 구리 산화 피막보다 많은 것은 피막표면에 생성된 불규칙한 기공 생성 수가 증가 하였기 때문이다. To investigate the characteristics of anodic film formed on metals and the reactivities of organic inhibitor Di-iso-butylnitrosoamine (DBNA) in sea water, the cathodic reactions of anodic film formed on metals were carried out by using the potential drop method and galvanostatic method at 25℃. The investigated results are as follows: The anodic films formed on aluminum and zinc in 60mM DBNA+9‰ sea water did not show changes of potential drop. However, those formed on lead and copper were reasonable electrodes. It was conclude that cathodic reactivities of proton through the anodic film in aqueous solution were constant without regard to the kinds of metals used with anodic film electrode at operated current density ranges, because the values of transition time obtained in 0.5M sodium chloride solution and 9‰ sea water nearly coincided. The values of transition time of the first step by the galvanostatic method were obtained from 0.22 to 1.40 sec ranges far less than one minute. Therefore, it suggested that cathodic reactions of proton through the anodic film were mainly controlled by diffusion/adsorption process. The differences of between τ₁/4 in 9‰ sea water and τ₁/4 in 60m M DBNA +9‰ sea water, and between E₁/4 in sea water and E₁/4 in 60mM DBNA+9‰ sea water at the constant current density with 1.9×10^(-4)∼5.0×1O^(-5) amp/㎠ were 0.06 sec and 0.53 v. respectively and cathodic reactions of DBNA on the anodic film electrodes were chiefly controlled by adsorption/diffusion precess. The reason that adsorption quantities of proton on anodic film formed on aluminum and zinc in aqueous solutions were much more than those on lead and copper, seems to be due mostly to the number of porosity produced on anodic film used.

납 산화피막 전극의 특성과 디이소부틸니트로소아민의 전극반응성

황금소 한국수산학회 1981 한국수산과학회지 Vol.14 No.2

해수에서 납 산화 피막전극들의 특성과 DBNA의 음극반응성을 조사하기 위해 constant current-potential 방법으로 실험하여 다음과 같은 결론을 얻었다. 1). 대체로 인산 수용액에서 만들어진 산화 피막전극에 의한 양성자의 제1단계 환원반응은 DBNA에 의하여 크게 억제되었다. 그러나 30℃, 0.5M NaCl 수용액과 6‰ 해수에서 DBNA의 첨가 유무에는 관계없이 제2단계의 환원반응이 일어났다. 2). 0.5M NaCl수용액에 DBNA를 첨가했을 때 수산 수용액에서 만들어진 산화피막에 의한 음극반응은 일어나지 않았다. 이 현상은 억제제 DBNA가 수산에서 만들어진 산화피막과 결합하여 완전 절연체를 형성하였기 때문이다. 3). 0.5M NaCl수용액과 6‰ 해수에 DBNA를 첨가하여 인산수용액에서 만들어진 산화 피막전극으로 음극반응 시키면 (∂ΔE_H^+/∂T)_(i=const)의 값은 각각 -0.006 V/℃와 -0.005 V/℃로서 거의 같았지만, (∂E_0/∂T)_(i=0)의 값은 각각 0.002 V/℃와 -0.002V/℃로서 대조적인 현상을 나타내었다. 4). 일련의 관계식을 유도하여 몇가지 상수 및 열역학적 값을 구하였든 바, 0.5M NaCl수용액, 6‰ 해수 및 6‰해수에 60mM DBNA를 첨가한 수용액에서 산화 피막전극이 의한 양성자의 환원 반응성을 설명할 수 있었다. The cathodic reactions of lead anodic films formed in phoaphoric acid, oxalic acid and sodium hydroxide solutions and the reactivities of Di-iso-butylnitrosoamine (DBNA) in sea water at 15∼35℃ were studies by means of constant current-potential method. Besides, various contants and thermodynamic quantities obtained in the experiment were also described to explain the reactivities of protons that entered in the anodic film by being transferred across the metal-oxide interface. The electrode reactions of lead anodic film formed in sodium hydroxide solution in 60mM DBNA +0.5M NaCl did not occur because of complete insulator formed on anodic film. The values of (∂ΔE_H^+/∂T)_(i=const) estimated with lead anodic films formed in phosphoric acid in 60mM DBNA+0.5M NaCl and 60mM DBNA+6‰ sea water were -0.006 V/℃ and -0.005 V/℃, thus being nearly coincided, but the values of (∂E_0/∂T)_(i=0) were 0.002 V/℃ and -0.002 V/℃, being completely inversed.

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 ??.

염화요오드 수용액의 전극반응

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.

디메틸포름아미드 중에서 디이소부틸니트로소아민의 음극 반응

황금소 부산수산대학교 1979 부산수산대학교 연구보고(자연과학편) Vol.19 No.1

염화요오드 수용액의 전극반응

황금소 부산수산대학교 1978 부산수산대학교 연구보고(자연과학편) Vol.18 No.1-2