• 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.

• Bulletin of the Korean Chemical Society
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• 제33권5호
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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.

• 분석과학
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• 제8권4호
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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.

• 한국수소및신에너지학회논문집
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• 제2권1호
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• pp.7-13
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• 1990

광합성계를 모방한 인공물의 광분해기에는 광증감제, 전자공여체 및 전자수용체가 필요하다. 광합성계에서는 Mn-tetramer가 물의 산화를 담당하는 종이라는 것이 알려져 있으니 Mn 화합물의 반응성을 아는 것이 중요하다. 이 Mn-tetramer의 모델이 될 수 있는 지용성 및 수용성 Mn(III) porphyrin을 새로이 합성하였다. 지용성 Mn(III) porphyrin은 porphyrin 자체에 금속화하는 방법과 porphyrin 고리 자체를 합성 할 때 긴 탄소사슬을 넣는 방법을 이용하였다. 지용성이나 수용성 Mn(III) Porphyrin은 계면에서 거동이 다를 것으로 생각되기 때문에 그 합성에 의의가 있다고 하겠다. 이 합성된 Mn(III) porphyrin 유도체들은 아민이나 알코올이 존재하는데서 광환원된다는 사실을 알게 되었다. 이 사실은 광증감제와 더불어 이중으로 여기시킬 수 있다는 점에서 큰 의의가 있다.

• 대한환경공학회지
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• 제28권1호
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• pp.54-60
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• 2006

주문진사 및 석영사를 담체로 사용하여 코팅온도, 코팅시간, 및 초기 망간용액 주입농도를 변화시키면서 망간(IV)을 코팅시킨 모래흡착제($MnO_2$-Coated Sand, MCS)를 제조하였으며 As(III)의 산화효율을 비교하였다. MCS 제조의 최적조건은 코팅효율 및 As(III) 산화능으로 부터 선정하였다. 망간 코팅효율은 코팅시간에는 크게 영향을 받지 않았지만 코팅온도가 증가함에 따라 증가하였다. 반면 As(III)의 산화능은 코팅온도가 증가됨에 따라 크게 감소하여 나타났다. 이러한 결과들을 고려하여 MCS의 최적 코팅 조건을 $150^{\circ}C$ 온도조건과 1시간의 가열시간으로 선정할 수 있었다. Mn(II) 주입농도가 늘어남에 따라 망간 코팅효율은 뚜렷이 증가하였지만 As(III)의 산화능은 0.8 Mn(II) mol/kg sand 조건에서 최대값을 보여주었다. MCS로 부터의 망간의 용출은 pH가 감소함에 따라 크게 증가하여 나타났다. 최적 조건에서 제조한 MCS를 사용하여 As(III)의 산화반응 특성을 회분식 실험을 통하여 조사한 결과, MCS의 As(III) 산화특성은 MCS의 농도에 대하여 비례적인 반응속도를 보여주었으며 pH가 감소할수록 As(III)의 산화속도가 증가하였다.

• 한국지하수토양환경학회지:지하수토양환경
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• 제13권3호
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• pp.52-58
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• 2008

여러 조건으로 제조한 망간첨착활성탄(Mn-AC)을 유기물과 무기물이 함께 오염되어 있는 합성 폐수처리에 적용하였다. 유기물과 무기물의 대표물질로 각각 페놀과 3가 비소를 선정하였다. Mn-AC의 물리화학적 특성과 안정성을 분석한 후, 회분식 반응조에서 활성탄(AC) 및 Mn-AC에 의한 3가 비소 및 페놀 흡착 특성을 조사하였다. Mn-AC의 안정성 평가를 위해 pH 2에서 4의 산성용액에서 용출되는 망간의 농도로부터 평가하였다. pH 3 이하에서는 Mn-AC로부터 많은 양의 망간이 용출되었지만, pH 4에서는 청정지역 허용기준인 3 ppm 이하의 농도로 용출되었다. Mn-AC에 대한 X-선 회절기 분석결과 첨착된 망간은 $Mn_2O_3$로 밝혀졌다. Mn-AC를 이용한 3가 비소와 페놀의 동시처리 실험결과 3가 비소는 낮은 pH에서 AC보다 높은 산화율을 보였으나, 중성 이상의 pH에서는 AC가 더욱 높은 산화율을 보였다. 활성탄에 망간을 첨착시킴으로서, 비표면적이 13% 감소하였고 이로서 Mn-AC에 의한 페놀제거율은 AC에 비해 8% 정도 줄어들었다. 3가 비소 산화 및 페놀 흡착실험을 통하여 Mn-AC는 복합오염물을 갖는 폐수의 동시처리에 적용될 수 있음을 알 수 있었다.

• 대한화학회지
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• 제23권4호
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• pp.198-205
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• 1979

금속이온의 $d^2sp^3$ 혼성궤도함수와 리간드의 singIe basis set 궤도함수를 사용하여 팔면체 [M(II)O_3S_3]$형태 착물의 쌍극자모멘트를 계산하는 원자가결합법을 발전시켰다. [M(III)=V(III), Cr(III), Mn(III), Fe(III), Co(III), Ru(III), Rh(III) 및 Os(III)]. 이 새로운 방법에 있어서 금속이온의 valence basis sets와 리간드 궤도함수사이의 혼성계수가 같다고 가정할 필요가 없으며 이것이 근사분자궤도함수법에 의한 팔면체 전이원소 착물의 쌍극자모멘트를 계산하는 방법과 다른점이다. 원자가결합법에서는 근사분자궤도함수법에서 보다도 훨씬 쉽게 팔면체착물의 쌍극자 모멘트를 계산할 수 있으며 계산한 쌍극자 모멘트의 값이 또한 실험치 범위에든다.

• Journal of Microbiology and Biotechnology
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• 제14권6호
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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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• 제35권7호
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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.

• 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).