• 한국암석학회:학술대회논문집
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• 한국암석학회 1999년도 춘계학술대회
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• pp.25-29
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• 1999

Manganese (Mn) oxides in soils and sediments differ in structure and composition. The influence of that diversity on the chromium (Cr) oxidation is the subject of this report. Oxidation of Cr(III) to Cr(VI) by coarse clay size Mn oxides (synthetic pyrolusite and natural lithiophorite, todorokite, and bimessite) was studied. Chromium oxidation by Mn oxides was initially fast and followed by a slow reaction. More Cr was oxidized by the Mn oxides at lower pH and higher initial Cr(III) concentration in solution. Birnessite had the highest chromium oxidation capacity per unit external surface area (COCUESA) and lithiophorite had the lowest COCUESA. The kinetics of Cr oxidation and COCUESA of Mn oixdes were apparently controlled by reactivity of surface Mn, mineralogy, and solution properties (pH and Cr(III) concentration).

• 한국환경과학회지
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• 제23권5호
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• pp.829-837
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• 2014

Titania-supported chromium oxides with different loadings have been embarked in catalytic oxidation of trichloroethylene (TCE) to inquire association of the formation of crystalline $Cr_2O_3$ with catalytic performances. A better activity in the oxidative TCE decomposition at chosen temperatures was represented when chromium oxides ($CrO_x$) had been dispersed on pure anatase-type $TiO_2$ (DT51D) rather than on phase-mixed and sulfur-contained ones such as P25 and DT51. The extent of TCE oxidation at temperatures below $350^{\circ}C$ was a strong function of $CrO_x$ content in $CrO_x$/DT51D $TiO_2$, and a noticeable point was that the catalyst has two optimal $CrO_x$ loadings in which the lowest $T_{50}$ and $T_{90}$ values were measured for the TCE oxidation. This behavior in the activity with respect to $CrO_x$ amounts could be associated with the formation of crystalline $Cr_2O_3$ on the support surface, that is less active for the oxidation reaction, and an easier mobility of the surface oxygen existing in noncrystalline $CrO_x$ species with higher oxidation states, such as $Cr_2O_8$ and $CrO_3$.

• Corrosion Science and Technology
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• 제11권4호
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• pp.141-150
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• 2012

Stress corrosion cracks in Alloy 600 compact tension specimens tested at $325^{\circ}C$ in a simulated primary water environment of pressurized water reactor were analyzed by analytical transmission electron microscopy and secondary ion mass spectroscopy (SIMS). From a fine-probe chemical analysis, oxygen was found on the grain boundary just ahead of the crack tip, and chromium oxides were precipitated on the crack tip and the grain boundary attacked by the oxygen diffusion, leaving a Cr/Fe depletion (or Ni enrichment) zone. The oxide layer inside the crack was revealed to consist of a double (inner and outer) layer. Chromium oxides existed in the inner layer, with NiO and (Ni,Cr) spinels in the outer layer. From the nano-SIMS analysis, oxygen was detected at the locations of intergranular chromium carbides ahead of the crack tip, which means that oxygen diffused into the grain boundary and oxidized the surfaces of the chromium carbides. The intergranular chromium carbide blunted the crack tip, thereby suppressing the crack propagation.

• 한국환경농학회지
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• 제20권5호
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• pp.346-351
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• 2001

Oxidation of Cr(III) to Cr(VI) can increase availability and toxicity of chromium. In this study, possible mechanisms by which pH and organic matter can control the chromium oxidation and reduction in soil system were examined using four soils of different pHs and organic matter contents. Reduction of Mn-oxides occurred in the soils of higher organic matter content (4.0%), but Mn-oxide was quite stable during the incubation in the soil of pH 7.0 and 0.5% organic matter content. Manganese oxides can be reductively dissolved at lower pH and higher organic matter conditions. The soil of pH 7.0 and 4.0% organic matter content showed the highest Cr-oxidation potential. Reduction of soluble Cr(VI) was observed in all the soils examined. The most rapid reduction was found in soil of pH 5.5 and 4.0% organic matter content, but the reduction was slow in soil of pH 7.0 and 0.5% organic matter content. Thus, the reductive capacity of organic matter added soils was much higher as compared to other two soils of lower organic matter content. In all the soils examined, the reductive capacity of soluble chromium was much higher than the oxidative capacity. Organic matter was found to be the most important controlling factor in the chromium oxidation and reduction. Reduction of Cr(VI) to Cr(III) could be a potentially useful remediation or detoxification process, and availability and toxicity of chromium in soil would be controlled by controlling organic matter content and pH of the soils.

• Elastomers and Composites
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• 제39권4호
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• pp.309-317
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• 2004

풀러렌[$C_{70}$]을 3-chloroperoxy benzoic acid, chromium (VI) oxide, benzoyl peroxide, trichloroisocyanuric acid 등의 산화제를 사용하여 마이크로파 조건에서 반응시켜 풀러렌 난화물[$C_{70}O_n$] ($n=1{\sim}3$ or n=1)을 합성하였다. 동일한 마이크로파 조건에서 여러가지 산화제와 풀러렌[$C_{70}$]의 고체상태 반응성은 3-chloroperoxy benzoic acid > chromium(VI) oxide > trichloroisocyanuric acid $\simeq$ benzoyl peroxide 순으로 증가함을 나타냈다. MALDI-TOF-MS, UV-visible, 그리고 HPLC를 사용하여 분석한 결과 생성된 풀러렌 산화물은 [$C_{70}O_n$] ($n=1{\sim}3$ or n=1)임을 알 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제19권2호
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• pp.265-267
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• 1998

• 한국연소학회:학술대회논문집
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• 한국연소학회 1997년도 제15회 KOSCO SYMPOSIUM 논문집
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• pp.61-68
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• 1997

The morphology and size distribution of chromium oxides and the concentration measurement of atomic arsenic have been studied in laminar diffusion flames. Nitrogen was added to vary flame temperatures in hydrogen flames. Ethene flames were used in order to investigate the potential for interaction between the soot aerosol that is formed in these flames and the chromium aerosol. Two sources of chromium compounds were introduced: chromium nitrate and chromium hexacarbonyl. A detailed investigation of the morphology was carried out by scanning electron microscopy (SEM). The amounts of Cr(VI) and total Cr were determined by a spectrophotometric method and by X-ray fluorescence spectrometry, respectively. Also, LIF was used for the measurement of atomic arsenic, which was excited at 197.2 nm and was detected at 249.6 nm. Results showed that the morphology of the particles varied with the flame temperature and with the chromium source. The particles were characterized by porous structures, cenospheres and agglomerated dense particles when chromium nitrate solution was added to the flames. At low to moderate temperatures, porous sintered cenospheric structures were formed, in some cases with a blow hole. At higher temperatures, an agglomerated cluster which was composed of loosely sintered submicron particles was observed. It was also found that the emission of Cr(VI) from the undiluted $H_2$ flame was more than 10 times larger than in the 50% $H_2$ / 50% $N_2$ flame on a mass basis. Single point LIF measurement of atomic arsenic indicated that arsenic exist only in the low temperature, fuel rich region.

• Applied Biological Chemistry
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• 제41권1호
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• pp.89-94
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• 1998

크롬의 산화는 자연계에 존재하는 여러 가지의 Mn-oxide에 의해 일어나며 산화과정에 존재하는 크롬 화학종들은 반응계 내에서 흡착, 침전 현상을 유발할 수 있고 결과적으로 산화반응을 조절할 수 있을 것이다. 본 연구에서는 birnessite와 pyrolusite에 의한 크롬의 산화에서 크롬 화학종이 반응에 미치는 영향을 조사하였다 Mn-oxide는 그 종류에 따라 크롬 산화력에서 큰 차이를 보였으며 용액의 pH와 초기 3가 크롬 첨가량도 산화반응에 큰 영향을 미쳤다. 동일 표면적당의 산화력을 비교하면 pyrolusite의 산화력은 birnessite의 5% 정도에 불과하였다. 이는 pyrolusite 의 결정도에 크게 기인하며 또한 양으로 하전된 표면 특성 때문에 반응물인 3가 크롬의 접근이 어렵고 반응산물인 6가 크롬의 흡착 등에 기인하는 것으로 보인다. Birnessite에 의한 산화반응에서 pH 3에서는 oxide의 표면에서의 크롬 화학종들의 흡착이나 침전 현상은 발견되지 않았으며 pyrolusite의 경우 일부 6가 크롬의 흡착이 나타났으나 침전현상은 발견되지 않았다. 따라서 pH 3의 경우 산화반응은 Mn-oxide의 특성에 따라 결정된다. Mn-oxide에 의한 크롬의 산화는 열역학적으로 용액의 pH가 높아질수록 더 진행되어야 한다. Birnessite의 경우 pH 5에서 오히려 산화반응이 현저히 저해되었는데 이는 birnessite의 표면에 형성되는 3가 크롬의 침전이 반응표면을 감소시킴으로써 나타나는 현상으로 판단된다. Pyrolusite의 경우 pH 3보다 pH 5에서 크롬의 산화는 더 일어나나 초기 3가 크롬의 첨가량이 많아지면서 반응이 억제된다. 일부 3가와 6가 크롬의 흡착이 일어나나 이 경우도 역시 pyrolusite의 표면에 형성되는 3가 크롬의 침전이 반응을 조절하는 주 요인으로 생각된다. Mn-oxide의 표면에 형성되는 3가 크롬의 침전은 산화가 일어날 수 있는 반응표면을 감소시키고 또한 반응물의 농도를 낮춤으로써 용액의 pH가 높고 3가 크롬의 첨가량이 많아질 때 크롬의 산화반응을 억제하는 주 요인이 되는 것으로 판단된다.

• 한국표면공학회지
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• 제34권1호
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• pp.49-55
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• 2001

The addition of organic compound containing -COOH, X$800_2$, -CHO group such as formic acid, formamide, formaldehyde or diethyleneamine to a chromium electroplating bath results in a chromium deposit in which carbon is incorporated. Such deposits have fewer defects than chromium layers produced by a conventional method. It was found that the as-deposited layers were amorphous and auger electron spectroscopy (AES) showed that carbon is distributed uniformly in the deposit. During heat treatment, Cr-C deposits began to crystallize at $400^{\circ}C$, and at $800^{\circ}C$ they were crystallized into chromium carbides and oxides. The effects of current density, amount of additives, applied current waveform on Cr-C alloy electroplating were examined.

• Applied Biological Chemistry
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• 제41권4호
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• pp.241-245
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• 1998

Two oxidation states of chromium commonly occur in natural soil/water systems, Cr(III) and Cr(VI). The oxidized form, Cr(VI), exists as the chromate ion and is more mobile and toxic than Cr(III). Therefore oxidation of Cr(III) by various Mn-oxides in natural systems is a very important environmental concern. Organic substances can inhibit the Cr(III) oxidation by binding, Cr(III) strongly and also by dissolving Mn-oxides. Most of Cr(III) oxidation studies were carried out using in vitro systems without organic substances which exist in natural soil/water systems. In this study effect of organic acids - oxalate and pyruvate - on Cr(III) oxidation by $birnessite({\delta}-MnO_2)$ was examined. The two organic acids significantly inhibited Cr(III) oxidation by birnessite. Oxalate showed more significant inhibition than pyruvate. As solution pH was lowered in the range of 3.0 to 5.0, the Cr(III) oxidation was more strongly depressed. Addition of more organic acids reduced the Cr(III) oxidation mare extensively. Different inhibition effects by the organic acids could be due to their ability of reductive dissolution of Mn-oxides and/or Cr(III) binding. Organic acids dissolved Mn-oxide during the Cr(III) oxidation by the oxide, Dissolution by oxalic acid was much greater than that by pyruvate, and the dissolution was more extensive at lower pH. Inhibition of Cr(III) oxidation was parallel to the dissolution of Mn-oxide by organic acids. Although the effect of Cr(III) binding by organic acids on Cr(III) oxidation is not known yet, Mn-oxide dissolution by organic acids could be a main reason for the inhibition of Cr(III) oxidation by Mn-oxide in presence of organic acids. Thus oxidation of Cr(III) to Cr(VI) by various Mn-oxides in natural systems could be much less than the oxidation estimated by in vitro studies with only Cr(III) and Mn-oxides.