• Journal of Surface Science and Engineering
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• v.50 no.1
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• pp.46-54
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• 2017

Marcel Pourbaix에 의해 만들어진 Eh-pH 도표는 화학적으로 안정한 상을 pH와 전위 (Potential or Eh)의 관점으로 도시한 것으로서 수용액 내에서 일어나는 화학반응을 부식-방식의 관점에서 이해하데 유용하게 사용되어 왔다. pH (potential of hydrogen)는 수소이온의 농도의 함수이며, Eh는 표준수소전극 (SHE, standard hydrogen electrode) 에 대한 전위를 나타낸다. 수용액에서의 도금 반응은 부식반응의 역반응이라 할 수 있으므로 도금반응도 이 도표를 이용하면 반응에 대한 열역학적 예측이 가능하다. 국내외 전기화학 및 표면공학 관련 교재들을 보면 Eh-pH 도표로 대표되는 열역학이나 분극곡선으로 대표되는 속도론에 대한 설명은 주로 부식의 관점에서 설명이 되어있어 도금을 공부하는 학생들에게는 직접적인 이해가 쉽지 않은 것이 사실이다. 저자는 출연연구소에 근무하면서 새로 들어오는 학연생(대학원생)들의 Eh-pH 도표에 대한 이해도를 알아보면 이 도표를 이해하고 이용할 줄 아는 학생이 거의 없다는 점을 안타깝게 여겨왔다. 최근에는 단순한 금속 도금이 아니라 나노 분말 합성, 반도체 물질 합성 등 여러 가지 공정기술과 응용기술이 수용액에서의 산화-환원 반응을 이용하고 있기 때문에 Eh-pH 도표의 중요성은 더해가고 있음을 느끼고 있었다. 그러던 중, 일본의 표면 처리 학술지인 표면기술(表面技術) (2013년, 64권 2호)에 'Eh-pH 도표의 표면기술에의 응용'이라는 제하의 소특집이 발간되었다. 이 소특집은 6편의 논문으로 되어 있었다. 저자는 이 소특집을 읽는 순간 이 논문들을 번역하여 표면공학회지에 소개를 하면 도금이나 전기화학을 공부하는 학생들에게 큰 도움이 될 것이라는 생각을 하였다. 본 기술해설 논문은 저자가 이 소특집에 게재된 논문을 번역하고 일부 내용은 저자의 의견으로 가감하여 표면공학회 학생 회원 및 기업의 연구원들에게 소개하기 위하여 저역을 한 것이다. 이 논문은 매 호 한편씩 소개할 예정이며, 원문을 읽고 싶다면 표면기술(表面技術)을 참조하길 바란다.

• Journal of Surface Science and Engineering
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• v.50 no.2
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• pp.131-139
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• 2017

This article introduces how to use potential-pH diagram for the formation of metallic nanoparticles, based upon the data obtained from the experiments. It is important to measure the values of equilibrium potentials of the reactions for the use of potential-pH diagram in aqueous and non-aqueous solutions. This article includes how to obtain the potential-pH diagrams in solutions containing particles and in non-aqueous solutions.

• Journal of Surface Science and Engineering
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• v.5 no.3
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• pp.77-85
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• 1972

A method of preparation of synthetic ignorgaic coating on copper (patina) has been presented . An Eh--pH diagram was constructed for the present Cu-H2O-SO$_4$ system using the most recently available thermodynamic data. In the path of the patination at room temperature the general behaviour of copper in acidic copper sulfate solutions with potassium chlorate as an oxidizing agent appeared to follow those predictable in this Eh-pH diagram. In the presence 0.05 molar cupric sulfate at a temperature of about 28$^{\circ}C$ a green brochantite (CuSO$_4$$.$3Cu(OH)$_2$) layer was formed on copper sheet in 20 days. In a solution having an initial pH of 3.5 the development of a brochantite coating has been observed to take place in two stages. In the first, a layer of cuprous oxide formed on the copper at a relatively rapid rate. In the ensuing step the outer layer of cuptrite was oxidized at much slower rate to form brochantite. The syntetic coatings appeared to consist of crystal-lites of brochanitite growing perpendicular to the cuprose oxide surface. The outer tips of the -crystallites were reasily broken off and gave to the layer a rather chalky character. Underneath, at the brochantite Cu$_2$O interface, however, the green layers were firmely attached. The effect of reagent concentration , solution agitation , and moderate temperature increase were investigated to improve the quality of coating. So also in a qualitative way were the effect of light.

• Economic and Environmental Geology
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• v.41 no.1
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• pp.47-56
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• 2008

pH and Eh were measured at 25 points in the abandoned Dalcheon mine. And, major ion components $(Na^+,\;K^+,\;Ca^{2+},\;Mg^{2+},\;Cl^-,\;SO_4^{2-},\;CO_3^{2-},\;HCO_3^-)$ were analyzed through groundwater sampling at 41 points. pH and Eh were measured the highest concentration in serpentinite area. And, pH was between weak alkaline and intermediate values in study area. Groundwater in study area was dominated oxidation-reduction environment caused by reaction with carbonate rock. Because sulfur components contained in carbonate, serpentinite, arsenopyrite and pyrite was dissolved by groundwater, $SO_4^{2-}$ component was high in study area. And $Ca^{2+},\;Mg^{2+}$ of cations were high. Correlation coefficients of ion components in tailing dumps were 0.95 between $Ca^{2+}\;and\;SO_4^{2-}$, 0.86 between $Ca^{2+}\;and\;Mg^{2+}$, 0.85 between $Mg^{2+}\;and\;SO_4^{2-}$. Correlation coefficients of ion components in bedrock were 0.86 between $Mg^{2+}\;and\;SO_4^{2-}$, 0.68 between $Ca^{2+}\;and\;SO_4^{2-}$. Concentration range of $Ca^{2+}$ in tailing dumps was $6.85{\sim}323.58mg/L,\;and\;3.18{\sim}207.20mg/L$ in bedrock. Concentration range of $SO_4^{2-}$ in tailing dumps was $21.54{\sim}1673.17mg/L,\;and\;2.04{\sim}1024.64mg/L$ in bedrock. By the result of Piper diagram analysis with aquifer material, groundwater in tailing dumps was $Ca-SO_4$ type. Groundwater quality types with bedrock material were Mg-$SO_4$ and Mg-$HCO_3$ types in serpentinite area, Ca-$HCO_3$ type in carbonate area, Na-K and $CO_3+HCO_3$ types in hornfels, respectively. As a result of this study, groundwater in tailing dumps were dissolved $Ca^{2+},\;Mg^{2+}\;and\;SO_4^{2-}$ components with high concentration. Also, these ion components were transported into bedrock aquifer.

• The Journal of Engineering Geology
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• v.17 no.2 s.52
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• pp.187-196
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• 2007

The Dalseong acid mine drainage were studied focused on the characters of schwertmannite that controls geochemistry of the stream. Besides chemical analysis of stream water, particle size analysis, XRD SEM and TEM were performed on precipitates of streams and on wasted metalliferous ores. The AMD discharged from the abandoned mine reveals a decrease of pH and EC downward stream. Euhedral sulfur occurs as equigranular aggregates on the altered pyrite while fine acicula goethite coalesces to form cross, star, or starfish-like shapes. Water chemistry plotted on the Eh-pH diagram shows that schwertmannite and ferrihydrite are stable phases. Reddish brown precipitates consist of mostly schwertmannite with less goethite, whereas yellowish brown precipitates are composed of geothite with less schwertmannite. The particle size of precipitates ranges $d(0.1)\;0.861{\mu}m{\sim}3.769{\mu}m,\;d(0.5)\;3.984{\mu}m{\sim}15.255{\mu}m,\;and\;d(0.9)\;9.875{\mu}m{\sim}56.726{\mu}m$. Schwertmannite is characterized by equigranular spheric form. Pincushion or spicule with 100nm width and $200{\sim}300nm$length form on schwertmannite sphere with radial growth patterns. It is highly probable that reddish or yellowish brown precipitates formed in many AMDs may contain schwerhnannite. Because it can serve as sink for removing heavy elements by adsorption in AMD system, there is a need to correctly identify schwertmannite in precipitates and to characterize its phase stability.

• Economic and Environmental Geology
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• v.43 no.1
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• pp.43-52
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• 2010

The geochemical and nitrogen isotopic analyses for shallow groundwater of Ogcheon area were carried out to characterize the geochemical characteristics of the groundwater and to identify the source of nitrate. Groundwater shows a neutral pH to weakly alkalic condition with pH values ranging from 6.9 to 8.4. The average of EC, Eh and DO is $344.2\;{\mu}s/cm$, 195 mV, 4 mg/L, respectively. According to piper diagram, chemical composition of groundwater is dominantly characterized by Ca-$HCO_3$ type. On the other hand, groundwater type in the study area include Ca-Cl+$NO_3$ type that were highly influenced by agricultural activities. $NO_3$-N concentration of the collected samples(n=45) range from 12.4 to 34.2 mg/l. These data show that the $NO_3$-N concentration exceeds Korea Drinking Water Standard (10 mg/l). The $\delta^{15}N-NO_3$ values range from $2.7^{\circ}/_{\circ\circ}$ to $18.8^{\circ}/_{\circ\circ}$. The enrichments of heavy isotope in the groundwater indicate that major origin of nitrate pollution were associated with animal and human waste. Also the denitrification may have partly contributed as one of the sources of nitrogen.

• The Journal of Engineering Geology
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• v.23 no.4
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• pp.477-491
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• 2013

Natural radionuclides in groundwater in the Danyang area were investigated to characterize the behaviors of uranium and radon with respect to lithology and physico-chemical components, which can aid our understanding of their occurrence, properties, and origins. To this end, a total of 100 groundwater samples were collected and analyzed, and radionuclide levels were used to construct detailed concentration maps. The water type of the groundwater, assessed using a Piper diagram, is mainly Ca-Na-$HCO_3$. The concentrations of uranium range from 0.02 to $251.0{\mu}g/L$ (average, $3.85{\mu}g/L$) and only 1% exceed USEPA's MCL (Maximum Contaminant Level). Uranium is enriched in groundwaters of Cretaceous granites and Precambrian metamorphic rocks, whereas it is depleted in groundwaters of sedimentary rocks. The concentrations of radon range from 13 to 28,470 pCi/L (average, 2397 pCi/L). Only 15% of the samples exceed AMCL (Alternative Maximum Contaminant Level) of 4000 pCi/L. The radon concentration is highest in groundwater of Cretaceous granites and lowest in groundwater of sedimentary rocks. In conclusion, the distribution and occurrence of radionuclides are intimately related to the basic geological characteristics of the rocks in which the radiogenic minerals are primarily contained. The behavior of uranium is only weakly related to that of radon (correlation coefficient = 0.15). There are also weak correlations between radionuclides and the main chemical components, pH, EC, Eh, and well depth. Of note, the correlation coefficient between radon and $SiO_2$ is 0.68, and that between radon and $HCO_3$ is -0.48. Factor analysis shows that radionuclides behave somewhat independently of each other because there are no significant factors that control the behavior of chemical components as well as radionuclides. The detailed concentration maps during this study will be used to establish useful database of radionuclide distribution and geological properties throughout Korea.