• Proceedings of the Petrological Society of Korea Conference
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• 1999.06a
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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).

• Journal of Environmental Science International
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• v.23 no.5
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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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• v.11 no.4
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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.

• Korean Journal of Environmental Agriculture
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• v.20 no.5
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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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• v.39 no.4
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• pp.309-317
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• 2004

Synthesis of fullerene oxides [$C_{70}O_n$] ($n=1{\sim}3$ or n=1) in solid state by fullerene [$C_{70}$] and several oxidants such as 3-chloroperoxy benzoic acid, chromium(VI) oxide, benzoyl peroxide, and trichloroisocyanuric acid was taken place under microwave irradiation. The reactivity in solid state oi fullerene [$C_{70}$] with various oxidants under same microwave condition increased in the order of 3-chloroperoxy benzoic acid > chromium(VI) oxide > trichloroisocyanuric acid ${\simeq}benzoyl$ peroxide. The MALDI-TOF-MS, UV-visible spectra and HPLC analysis confirmed that the products of fullerene oxidation were [$C_{70}O_n$] ($n=1{\sim}3$ or n=1).

• Bulletin of the Korean Chemical Society
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• v.19 no.2
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• pp.265-267
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• 1998

• 한국연소학회:학술대회논문집
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• 1997.06a
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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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• v.41 no.1
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• pp.89-94
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• 1998

Various Mn-oxides can oxidize Cr(III) to Cr(VI). Behaviors of chromium species in the oxidation system, especially on the oxide surface, are expected to control the reaction. During Cr(III) oxidation by birnessite and pyrolusite, Cr species in the reaction system were determined to elucidate their effects on the oxidation. Capacities of Cr oxidation of the two Mn-oxides were quite different. Solution pH and initial Cr(III) concentration also had significant effects on the Cr(III) oxidation by Mn-oxides. Chromium oxidation by pyrolusite was less than 5% of the oxidation by birnessite. The high crystallinity of pyrolusite could be one of the reasons and the difficulty of Cr (III) diffusion to the positive pyrolusite surface and Cr(VI) and Cr(III) adsorption seems to be other controlling factors. At pH 3, adsorption or precipitation of Cr species on the surface of birnessite were not found. Small amount of Cr(VI) adsorption was found on the surface of pyrolusite, but arty Cr precipitation on the oxide surface was not found. Therefore Cr(III) oxidation at pH 3 seems to be controlled mainly by the characteristics of Mn-oxides. Chromiun oxidation by Mn-oxides is thermodynamically more favorable at higher solution pH. However as solution pH increased Cr oxidation by birnessite was significantly inhibited. For Cr oxidation by pyrolusite, as pH increased the oxidation increased, but as Cr(III) addition increased the reaction was inhibited. Under these conditions some unidentified fraction of Cr species was found and this fraction is considered to be Cr(III) precipitation an the oxide surface. Chromium(III) precipitation on the oxide surface seems to play an important role in limiting Cr(III) oxidation by armoring the reaction surface on Mn-oxides as well as lowering Cr(III) concentration available for the oxidation reaction.

• Journal of Surface Science and Engineering
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• v.34 no.1
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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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• v.41 no.4
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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.