• 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.

• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1675-1680
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• 2012

Three new cyanide-bridged $Cr^{III}Mn^{II}$ binuclear complexes, $[Mn(phen)_2Cl][Cr(bpmb)(CN)_2]{\cdot}H_2O$ ($\mathbf{1}$) (phen = 1,10-phenanthroline, $bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate), $[Mn(phen)_2Cl][Cr(bpmb)-(CN)_2]{\cdot}H_2O$ ($\mathbf{2}$) ($bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate), and $[Mn(phen)_2Cl]-[Cr(bpClb)(CN)_2]{\cdot}CH_3OH{\cdot}H_2O$ ($\mathbf{3}$) ($bpClb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate) were obtained based on $Mn(phen)_2Cl_2$ and a series of dicyanidechromate(III) building blocks. Single crystal X-ray diffraction analysis shows the structures of the three complexes are dimeric type with two different metal centers linked by a cyanide group from corresponding dicyanidechromate(III) building block. Magnetic investigations indicate the existence of relatively weak antiferromagnetic coupling between Cr(III) and Mn(II) ions with best-fit constants $J_{CrMn}=-2.78(5)cm^{-1}$ for $\mathbf{1}$, $J_{CrMn}=-3.02(2)cm^{-1}$ for $\mathbf{2}$ and $J_{CrMn}=-2.27(3)cm^{-1}$ for $\mathbf{3}$ based on the spin exchange Hamiltonian = $-2J_{CrMn}\hat{S}_{Cr}\hat{S}_{Mn}$. The magneto-structural correlation of cyanide-bridged $Cr^{III}Mn^{II}$ complexes has been discussed at last.

• Analytical Science and Technology
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• v.8 no.4
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• pp.569-574
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• 1995

In-situ spectroelectrochemical studies have been carried out on the oxidation of Mn(II) at platinum, gold, lead dioxide, and bismuth doped lead dioxide electrodes. The Mn(III), $MnO_2$, and/or ${MnO_4}^-$ species are produced depending on experimental conditions employed during electrolysis. Mn(III) is shown to be produced from a very early stage during the anodic potential scan and undergo disproportionation-conproportionation reactions depending on the relative concentration of each species near the electrode surface. An oxidation mechanism consistent with these observations is proposed.

• Journal of Hydrogen and New Energy
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• v.2 no.1
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• pp.7-13
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• 1990

We are interested in studying the artificial photolysis of water which mimics the natural plant photosynthesis. In the artificial system there should be a proper photosensitizer, electron donor and electron acceptor. Since Mn-tetramer is known to be the essential part for the oxygten-evolving system in the natural photosynthesis, it is important to know or study the reactivity of Mn-porphyrins. As a model for the Mn-tetramer in the natural photosynthesis, we prepared the lipophilic and hydrophilic Mn-porphyrins. For the lipophilic porphyrin with long hydrocarbon chain, the long hydrocarbon chain was inserted in the porphyrin ring formation step. For the hydrophilic porphyrin, the porphyrin was sulfonated with sulfuric acid. These syntheses of lipophilic and hydrophilic Mn-porphyrins are significant, since the behaviors of these compounds will be different in the microemulsions or vesicles. We also found that the Mn-porphyrins were photoreduced in the microemulsion and water in the presence of amines.

• Journal of Korean Society of Environmental Engineers
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• v.28 no.1
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• pp.54-60
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• 2006

[ $MnO_2$ ]-Coated Sand(MCS) was prepared with variation of coating temperature, coating time, and dosage of initial Fe(III) with two kinds of sands such as Joomoonjin and quartz sand. An optimum condition for the preparation MCS was determined from the coating efficiency as well as the oxidation efficiency of As(III). Coating efficiency of Mn was strongly dependent on the coating temperature but quite similar over the investigated coating time, showing an increased coating efficiency at higher coating temperature. In contrast to coating efficiency, the oxidation efficiency of As(III) by MCS was severely reduced as increase of coaling temperature. By considering these results, an optimum coating temperature and time for the preparation of MCS was selected as $150^{\circ}C$ and 1-hr, respectively. Coating efficiency increased as the dosage of initial Mn(II) increased, while As(III) oxidation was maximum at 0.8 Mn(II) mol/kg sand. The solution pH was identified as an important parameter affecting stability of MCS, and dissolution of Mn from MCS increased as pH decreased. Oxidation rate of As(III) increased as the dosage of MCS increased as well as solution pH decreased.

• Journal of Soil and Groundwater Environment
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• v.13 no.3
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• pp.52-58
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• 2008

Mn-impregnated activated carbon (Mn-AC) prepared at different conditions was applied in the treatment of synthetic wastewater containing both organic and inorganic contaminants. Phenol and As(III) was used as the representative organic and inorganic contaminants, respectively. After evaluation of the physicochemical characteristic and stability of Mn-AC, oxidation of As(III) as well as adsorption of phenol by activated carbon(AC) and Mn-AC were investigated in a batch reactor. To investigate the stability of Mn-AC, dissolution of Mn from each Mn-AC was measured pH ranging from 2 to 4. Although Mn-AC was unstable at a strong acidic condition, the dissoluted Mn was below 3 ppm at pH 4. XRD analysis of Mn-AC indicated that the mineral type of the impregnated manganese was $Mn_2O_3$. From the simultaneous treatment of As(III) and phenol by AC and Mn-AC, As(III) oxidation by Mn-AC was greater than that by AC at lower pH, while the reverse order was observed at higher pH. After impregnation of Mn onto AC, 13% decrease of the surface area was observed, causing 8% reduction of phenol removal. Considering removal properties of As(III) and phenol, Mn-AC could be applied in the simultaneous treatment of wastewater contaminated with multi-contaminants.

• Journal of the Korean Chemical Society
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• v.23 no.4
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• pp.198-205
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• 1979

A valence bond method of calculation of the dipole moments for octahedral $(M(III)0_3S_3)$ type complexes are developed, using $d^2sp^3 $hybrid orbitals of the central metal ions and the single basis set orbital of ligands. (M (III) =V (III), Cr (III), Mn (III), Fe (III), Co (III), Ru (III), Rh (III) and OS (III)). In this method the mixing coefficient of the valence basis sets for the central metal ion with the appropriate ligand orbitals is not required to be the same, differently from the molecular orbital method. The valence bond method is much more easier to calculate the dipole moments for octahedral complexes than the approximate molecular orbital method and the calculated results are also in the range of the experimental vaues.

• Journal of Microbiology and Biotechnology
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• v.14 no.6
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• pp.1120-1128
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• 2004

The SCBFC was composed of bilayered cathode, the outside of which was modified with $Fe^{3+}$ (graphite-Fe(III) cathode) and the inside of which was porcelain membrane, and of an anode which was modified with $Mn^{4+}$ (graphite­Mn(lV) anode). The graphite-Fe(III), graphite-Mn(IV), and porcelain membrane were designed to have micropores. The outside of the cathode was exposed to the atmosphere and the inside was contacted with porcelain membrane. In all SCBFCS the graphite-Fe(III) was used as a cathode, and graphite-Mn(IV) and normal graphite were used as anodes, for comparison of the function between normal graphite and graphite-Mn(IV) anode. The potential difference between graphite-Mn(IV) anode and graphite-Fe(III) cathode was about 0.3 volt, which is the source for the electron driving force from anode to cathode. In chemical fuel cells composed of the graphite-Mn(IV) anode and graphite-Fe(III) cathode, a current of maximal 13 mA was produced coupled to oxidation of NADH to $NAD^{+}$ the current was not produced in SCBFC with normal graphite anode. When growing and resting cells of E. coli were applied to the SCBFC with graphite-Mn(IV) anode, the electricity production and substrate consumption were 6 to 7 times higher than in the SCBFC with normal graphite anode, and when we applied anaerobic sewage sludge to SCBFC with graphite-Mn(IV) anode, the electricity production and substrate consumption were 3 to 5 times higher than in the SCBFC with normal graphite anode. These results suggest that useful electric energy might possibly be produced from SCBFC without electron mediators, electrode-active bacteria, and extra energy consumption for the aeration of catholyte, but with wastewater as a fuel.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.1965-1969
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• 2014

A new tetranuclear Mn(III) complex $[Mn^{III}{_4}(sae)_4({\mu}_3-O)({\mu}_{1,1}-N_3)(OH)(H_2O)_2]{\cdot}H_2O$ (1) ($H_2sae$ = 2-salicylideneamino-1-ethanol) has been synthesized by the reaction of $MnCl_2{\cdot}4H_2O$, $H_2sae$ and sodium azide in the mixed solvent of methanol, acetonitrile and water. The X-ray diffraction analysis shows that the four Mn(III) ions in complex 1 have a unique adamantine arrangement, whereas the coordination environment of each Mn(III) ions is different. Magnetic studies indicate that complex 1 manifests antiferromagnetic behaviors. The magnetic susceptibilities of complex 1 have been fitted by two magnetic models based on the suitable analysis of its magnetic structural topology.

• 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).