• Title/Summary/Keyword: Redox equilibrium

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Sulfur Redox Equilibrium in Mixed Alkali Silicate Glass Melts

  • Kim, Ki-Dong;Hwang, Jong-Hee
    • Journal of the Korean Ceramic Society
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    • v.48 no.3
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    • pp.205-210
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    • 2011
  • The dependence of sulfur redox behavior and its diffusivity on temperature and composition was studied in mixed alkali silicate melts by means of square wave voltammetry (SWV) at different frequencies in a temperature range of $1000^{\circ}C$ to $1400^{\circ}C$. The voltammograms showed two reduction peaks at high frequency but only one peak at low frequency. Irrespective of $K_2O/(Na_2O+K_2O)$, each peak potential due to reduction of $S^{6+}$ to $S^{4+}$ and $S^{4+}$ to $S^0$ moved toward a negative direction with temperature decrease, and the peak current showed a strong dependence on frequency at a constant temperature. However, the compositional dependence of the peak potential showed an inconsistent behavior with an increase of $K_2O$. The mixed alkali effect was not observed in sulfur diffusion. This inconsistency of both peak potential and diffusion for compositional dependence may be derived from the strong volatilization of sulfur in melts.

Redox Equilibrium of Antimony by Square Wave Voltammetry Method in CRT Display Glass Melts

  • Jung, Hyun-Su;Kim, Ki-Dong;Kim, Hyo-Kwang;Kim, Young-Ho
    • Journal of the Korean Ceramic Society
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    • v.44 no.1 s.296
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    • pp.1-5
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    • 2007
  • Fining and homogenization of melts during batch melting is closely related to the redox reaction of polyvalent element M (M: Sb, As etc), $M^{(x+n)+}+n/2O^{2-}{\rightarrow}M^{x+}+n/4O_2$. In this study, square wave voltammetry (SWV) measurements were performed to examine the redox behavior of an antimony ion in cathode ray tube (CRT) glass melts. According to results, well-separated two peaks are shown at low temperature while only one peak is shown at high temperature in voltammograms, which reveals that redox reaction of antimony consist of two steps: $Sb^{5+}/Sb^{3+}\;and\;Sb^{3+}/Sb^0$, depending on the temperature. Based on the peak potential shown in the voltammogram, the thermodynamic data and the redox ratio for two redox couple were determined.

Simulating Bioremediation of Uranium-Contaminated Aquifers

  • ;Peter R. Jaffe
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2002.09a
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    • pp.161-166
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    • 2002
  • Bioremediation of trace metals in groundwater may require the manipulation of redox conditions via the injection of a carbon source. To simulate the numerous biogeochemical processes that will occur during the bioremediation of trace-metal-contaminated aquifers, a reactive transport model has been developed. The model consists of a set of coupled mass balance equations, accounting for advection, hydrodynamic dispersion, and a kinetic formulation of the biological or chemical transformations affecting an organic substrate, electron acceptors, corresponding reduced species, and trace metal contaminants of interest, uranium in this study. The redox conditions of the domain are characterized by estimating the pE, based on the concentrations of the dominant terminal electron acceptor and its corresponding reduced specie. This pE and the concentrations of relevant species we then used by a modified version of MINTEQA2, which calculates the speciation/sorption and precipitation/dissolution of the species of interest under equilibrium conditions. Kinetics of precipitation/dissolution processes are described as being proportional to the difference between the actual and calculated equilibrium concentration.

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Effect of Batch Melting Temperature and Raw Material on Iron Redox State in Sodium Silicate Glasses

  • Mirhadi, Bahman;Mehdikhani, Behzad
    • Journal of the Korean Ceramic Society
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    • v.48 no.2
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    • pp.117-120
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    • 2011
  • In this study, the redox state of iron in sodium silicate glasses was varied by changing the melting conditions, such as the melting temperature and particle size of iron oxide. The oxidation states of the iron ion were determined by wet chemical analysis and UV-Vis spectroscopy methods. Iron commonly exists as an equilibrium mixture of ferrous ions, $Fe^{2+}$, and ferric ions $Fe^{3+}$. In this study, sodium silicate glasses containing nanoparticles of iron oxide (0.5% mol) were prepared at various temperatures. Increase of temperature led to the transformation of ferric ions to ferrous ions, and the intensity of the ferrous peak in 1050 nm increased. Nanoparticle iron oxide caused fewer ferrous ions to be formed and the $\frac{Fe^{2+}}{Fe^{3+}}$ equilibrium ratio compared to that with micro-oxide iron powder was lower.

Electrochemical Approach in Plasma Display Panel Glass Melts doped with Sulfate and Sulfide I. Oxygen Equilibrium Pressure

  • Kim, Ki-Dong;Kim, Hyo-Kwang
    • Journal of the Korean Ceramic Society
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    • v.45 no.2
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    • pp.90-93
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    • 2008
  • The oxygen gas behavior in PDP (plasma Display Panel) glass melts doped with sulfate ($SO_4^{-2}$) or blast furnace slag (BFS, $S^{2-}$) or both by means of yttria-stabilized zirconia (YSZ) electrodes was observed after the first fining. The temperature dependence of oxygen equilibrium pressure ($P_{O2}$) in each melt showed typical behavior, namely $P_{O2}$ decreased as temperature decreased. This suggests that an oxidation of $S^{4+}$ to $S^{6+}$ took place. However, the $P_{O2}$-value at constant temperature increased in the following order: BFS$P_{O2}$ of the melt doped with sulfate+BFS was much lower than that of the melt with only sulfate, although only 10% of sulfur was added by the BFS. This behavior can be explained by the redox reaction between sulfide ions in the BFS and dissolved oxygen ions in the melt during the first fining.

Behavior of Oxygen Equilibrium Pressure in CRT Glass Melts doped with Sb and Ce ions from the Viewpoint of Fining

  • Kim, Ki-Dong;Kim, Hyo-Kwang;Kim, Jun-Hong
    • Journal of the Korean Ceramic Society
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    • v.44 no.8
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    • pp.419-423
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    • 2007
  • The behavior of oxygen gas participating in fining was observed in CRT (Cathode Ray Tube) glass melts doped with $Sb_2O_5\;or\;CeO_2$ by means of a yttria-stabilized zirconia (YSZ) electrode. The temperature dependence of the oxygen equilibrium pressure ($P_{o2}$) or the activity in both melts showed typical behavior corresponding to a theoretical redox reaction. In other words, the $P_{o2}$ value of melts with $CeO_2$ was lower than that of melts with $Sb_2O_5$ above $1250^{\circ}C$. The result implies that $Sb_2O_5$, is more efficient as a fining agent compared to $CeO_2$. On the other hand, melts from a batch containing $Sb_2O_5\;and\;KNO_3$ showed much higher $P_{o2}$ values compared to melts without $KNO_3$ above $1350^{\circ}C$. It is suggested that the addition of $KNO_3$ to CRT glass batch contributes partly to the first fining of the melts.

Dyeing Properties of Wool Using Hydrogen Peroxide/Glyoxal Redox System (과산화수소/글리옥살 산화환원계를 사용한 양모의 염색성)

  • Jeong, Dong Seok;Lee, Mun Cheul;Lee, Young Hee;Kim, Kyung Hwan
    • Textile Coloration and Finishing
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    • v.8 no.1
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    • pp.15-25
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    • 1996
  • Wool fabric and merino wool top were dyed with two dyes, C.I. Acid Red 13 and C.I. Direct Blue 1 in presence of hydrogen peroxide/glyoxal redox system at various conditions such as dyeing time, temperature and redox concentration. The pH of dye bath was 4.5 in buffer solution of $KH_{2}PO_{4}$ (0.1mol/1)/$Na_{2}HPO_{4}$ (0.1mol/1). Also dyeing of cotton fabric was carried out with C.I. Direct Blue 1 in absence or presence of redox system. The color depth(K/S) increased with redox concentration and dyeing temperature. The increases in dyeing rate and equilibrium dye exhaustion of Acid Acid 13 and Direct Blue 1 on wool fiber and fabric in the present of hydrogen peroxide/glyoxal have been caused by decreasing in pH value during dyeing process which due to the decomposition of hydrogen ion in glyoxal with the assistance of hydrogen peroxide. But the decreases in exhaustion of Direct Blue 1 on cotton may be attributed to repulsive interac ion between salt and salt.

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Redox Behavior of Sn and S in Alkaline Earth Borosilicate Glass Melts with 1 mol% Na2O

  • Kim, Ki-Dong;Kim, Hyo-Kwang
    • Journal of the Korean Ceramic Society
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    • v.46 no.3
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    • pp.271-274
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    • 2009
  • Redox investigation of Sn and S ion was attempted in alkaline earth borosilicate glass melts with only 1 mol% $Na_2O$ by means of Square Wave Voltammetry (SWV). According to voltammograms, there was only one peak due to $Sn^{4+}/Sn^{2+}$ in melt doped with $SnO_2$. The calculated standard enthalpy and entropy of the reduction of $Sn^{4+}$ to $Sn^{2+}$ were 116kJ/mole and 62 J/mol K, respectively. The determined redox ratio, [$Sn^{2+}$] / [$Sn^{4+}$] in the temperature range of $1300{\sim}1600^{\circ}C$ was in $0.4{\sim}2.1$. On the contrary, in the voltammogram of melt doped with $BaSO_4$ there was no peak due to $S^{4+}/S^o$ but shoulder that might be attributed to the adsorption of sulfur at the electrode. The absence of the peak related with $S^{4+}/S^o$ was discussed from the view-point of the thermal decomposition behavior of $BaSO_4$ in the glass batch.

Temperature-Dependent Redox Isomerism via Intramolecular Electron Transfer. Synthesis and Properties of Co(dmppz)₂(3,6-dbq)₂ (dmppz=1,4-dimethylpiperazine; 3,6-dbq=3,6-di-tert-butyl-1,2-quinone)

  • 정옥상;조두환;박성호;손윤수
    • Bulletin of the Korean Chemical Society
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    • v.18 no.6
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    • pp.628-631
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    • 1997
  • The preparation and characterization of $Co(dmppz)_2(3,6-dbq)_2$ (dmppz=1,4-dimethylpiperazine; 3,6-dbq=3,6-di-tert-butyl-1,2-quinone) are established. Temperature-dependent magnetic moments (100-400 K), variable-temperature IR, and electronic spectra are presented to show that the title complex exhibits an equilibrium via a catechol to cobalt intramolecular electron transfer. At temperatures below 350 K, the charge distribution of the complex is $Co^Ⅲ(dmppz)_2(3,6-dbsq)(3,6-dbcat)$ (3,6-dbsq=3,6-di-tert-butyl-1,2-semiquinonato; 3,6-dbcat=3,6-di-tert-butylcatecholato) whereas at the temperature beyond 390 K, the complex is predominantly Co^Ⅱ(dmppz)_2(3,6-dbsq)_2$ form in the solid state. At the temperature range of 350-390 K a mixture of Co(Ⅲ) and Co(Ⅱ) redox isomers exist at equilibrium. The transition temperature (Tc) of Co(Ⅲ)/Co(Ⅱ) in solution is approximately 50° lower than that in the solid state. In particular, thermal analysis on solid sample of the complex discloses that the transition for the Co(Ⅲ)/Co(Ⅱ) is accompanied by the change in heat content of 12.30 kcal/mol.

A Study on the Treatment of Refractory Organics by Redox Reaction of Cu-Zn Metal Alloy (Cu-Zn 금속 합금의 산화.환원 반응에 의한 난분해성 COD처리에 관한 연구)

  • Song, Ju-Yeong;Park, Ji-Won;Kim, Jong-Hwa
    • Journal of the Korean Applied Science and Technology
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    • v.30 no.1
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    • pp.166-172
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    • 2013
  • The purpose of this study is to evaluate the treatment ability of refractory organics in hot rolling precess waste water by redox(reduction and oxidation) reaction. Metal is oxidized in an aqueous solution to generate electron which can reduce water to generate hydroxy radical. These hydroxy radical is very effective to conduct hydrogen abstraction reaction and addition reaction to the carbon - carbon unsaturated link. The surface area of metal alloy reaction material is more than enough to get equilibrium at a single treatment. The efficiency of COD treatment by redox reaction showed maximum at mild pH of pH 7 and pH 6. But it was not effective in acidic atmosphere of pH 3, 4, 5 and basic atmosphere of pH 8 or over. Redox reaction system in much more helpful in a commercial coagulation sedimentation treatment than exclusive system.