• 한국세라믹학회지
• /
• 제48권3호
• /
• pp.205-210
• /
• 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.

• 한국세라믹학회지
• /
• 제44권1호
• /
• pp.1-5
• /
• 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.

• 한국지하수토양환경학회:학술대회논문집
• /
• 한국지하수토양환경학회 2002년도 추계학술발표회
• /
• pp.161-166
• /
• 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.

• 한국세라믹학회지
• /
• 제48권2호
• /
• pp.117-120
• /
• 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.

• 한국세라믹학회지
• /
• 제45권2호
• /
• pp.90-93
• /
• 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.

• 한국세라믹학회지
• /
• 제44권8호
• /
• pp.419-423
• /
• 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.

• 한국염색가공학회지
• /
• 제8권1호
• /
• pp.15-25
• /
• 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.

• 한국세라믹학회지
• /
• 제46권3호
• /
• pp.271-274
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• 제18권6호
• /
• pp.628-631
• /
• 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.

• 한국응용과학기술학회지
• /
• 제30권1호
• /
• pp.166-172
• /
• 2013

본 연구는 압연공정에서 발생하는 폐수 중에 함유되어있는 난분해성 COD 물질을 $80{\mu}m$ 두께의 극세사 형태로 제조된 Cu-Zn 금속합금의 산화 작용으로 인하여 발생하는 OH 라디칼을 이용하여 처리하는 방법에 관한 기초 연구이다. OH 라디칼은 유기화합물(RH) 속에 포함된 수소를 수소추출반응(H Abstraction) 또는 탄소와 탄소(C-C)의 불포화 결합에 첨가됨으로써 빠르고 비 선택적인 반응을 수행하는 것으로 알려진 것처럼 난 분해성 유기화합물의 처리에 효과적인 것으로 나타났다. 금속합금 반응 물질은 극세사 형태로 표면적이 넓어서 1회 처리만으로도 수용액의 pH를 평형에 도달하게 하여서 반응 효율성이 높은 것으로 나타났다. COD처리 효율은 중성 pH에 가까운 pH 7, pH 6에서 최고치를 보였으며 산성분위기인 pH 5이하 및 알칼리성 분위기인 pH 8이상에서는 낮은 효율을 보였다. 실제 압연 폐수의 응집 침전을 이용한 COD 처리에서도 redox 반응장치의 유무에 따라 2배 이상의 처리효율의 차이를 보였다.