• Bulletin of the Korean Chemical Society
• /
• 제26권7호
• /
• pp.1044-1050
• /
• 2005

The reaction of cis-[Cr([14]-decane)($OH_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = isothiocyanate ($NCS^-$), azide ($N3^-$) or chloroacetate(caa)} leads to a new cis-[Cr([14]-decane)($NCS)_2]ClO_4{\cdot}H_2O$ (1), cis-[Cr([14]-decane)($N_3)_2]ClO_4$ (2) or cis-[Cr([14]-decane)($caa)_2]ClO_4$ (3). These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[Cr([14]-decane)($NCS)_2]ClO_4{\cdot}H_2O$ reveals that central chromium(III) has a distorted octahedral coordination environment and two $NCS^-$anions are bonded to the chromium(III) ion via the Ndonor atom in the cis positions. The angle $N_{axial}-Cr-N_{axial}$ deviates by 13$^{\circ}$ from the ideal value of 180$^{\circ}$ for a perfect octahedron. The bond angle N-Cr-N between the Cr(III) ion and the two nitrogen atoms of the isothiocyanate ligands is close to 90$^{\circ}$. The bond lengths of Cr-N between the chromium and $NCS^-$groups are 1.964(5) and 2.000(5) $\AA$. They are shorter than those between chromium and nitrogen atoms of the macrocycle. The IR spectra of 1, 2 and 3 display bands at 2073, 1344 and 1684 $cm^{-1}$ attributed to the $NCS^-$, ${N_3}^-$ and caa groups stretching vibrations, respectively.

• 대한화학회지
• /
• 제30권5호
• /
• pp.423-432
• /
• 1986

폐수 중의 6가크롬을 음이온 교환체인 aliquat-336(tri-caprylmethyl ammonium chloride)으로 이온쌍을 형성시켜 유기용매인 p-xylene으로 추출하여 원자흡수분광도법으로 정량하는 방법에 대하여 조사 검토하였다. Toluene을 용매로 사용하여 유기물을 제거한 폐수 100ml를 취하여 염산으로 pH 0.5 되게 산성화시킨 다음 aliquat-336을 0.01M되게 녹인 p-xylene 20ml로 6가크롬을 추출하였다. 표준물첨가법에 의해 air-acetylene 불꽃에서 용매중에 추출된 6가크롬을 정량하였다. Al(III), Fe(III), Cr(III)이온들은 6가크롬의 추출 및 흡광도 측정에 방해 하지 않았으며, Fe(III)이온이 6가크롬을 3가크롬으로 환원시키기 때문이다. 또한 유기물이 존재하면 6가크롬의 흡광도를 감소시키므로 이런 방해유기물을 toluene으로 추출 제거하였다. 최적 조건으로 분석한 결과는 96%이상의 회수율을 보여 주었고 이는 미량 분석에서 정확한 방법이라 할 수 있고, 상대평균편차가 3.95%로서 재현성도 비교적 좋았다.

• Journal of Microbiology and Biotechnology
• /
• 제31권11호
• /
• pp.1519-1525
• /
• 2021

Hexavalent chromium (Cr(VI)) is recognized to be carcinogenic and toxic and registered as a contaminant in many drinking water regulations. It occurs naturally and is also produced by industrial processes. The reduction of Cr(VI) to Cr(III) has been a central topic for chromium remediation since Cr(III) is less toxic and less mobile. In this study, fermentative Fe(III)-reducing bacterial strains (Cellu-2a, Cellu-5a, and Cellu-5b) were isolated from a groundwater sample and were phylogenetically related to species of Cellulomonas by 16S rRNA gene analysis. One selected strain, Cellu-2a showed its capacity of reduction of both soluble iron (ferric citrate) and solid iron (hydrous ferric oxide, HFO), as well as aqueous Cr(VI). The strain Cellu-2a was able to reduce 15 μM Cr(VI) directly with glucose or sucrose as a sole carbon source under the anaerobic condition and indirectly with one of the substrates and HFO in the same incubations. The heterogeneous reduction of Cr(VI) by the surface-associated reduced iron from HFO by Cellu-2a likely assisted the Cr(VI) reduction. Fermentative features such as large-scale cell growth may impose advantages on the application of bacterial Cr(VI) reduction over anaerobic respiratory reduction.

• Bulletin of the Korean Chemical Society
• /
• 제33권5호
• /
• pp.1675-1680
• /
• 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.

• 한국표면공학회지
• /
• 제21권4호
• /
• pp.160-167
• /
• 1988

Electrochemical behaviors od chromium electrodeposition from 0.05M chromium (III) sulface complexes in aqueous solutions using sodium formate-glycine mixtures as a complexing agent were studied. In the cathodic current-potential cures, it is found that the intial limiting current of Cr(III) is proportional to square root of scan rate and activiation energy from Arrhenius plot is s obtained 3.05Kcal/mol. From this results, the reaction is considered, Cr3++e longrightarrow Cr2+, which is controlled diffusion of Cr (III). It is also found that the chromium is deposited when the potential reaches to hydrogen evolution potential. Effects of NaSCN as a catalyser in the electrolyte were investigated NCS- anion seems to react strongly by specific absorption at the inner HelmholtZ layer, so that, it is considered to suppress the electrodeposition reaction reaction for chromjum, and also it is considered multipe-bridge such as Cr(III)-NCS---M(M;cathode).

• Bulletin of the Korean Chemical Society
• /
• 제25권7호
• /
• pp.977-982
• /
• 2004

The reaction of $cis-[Cr([14]-decane)(OH_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = benzoate(bz) or chlorobenzoate(cbz)} leads to a new compound $[Cr([14]-decane)(bz)_2]ClO_4$ or $[Cr([14]-decane)(cbz)_2]ClO_4$. These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. The crystal structure of $[Cr([14]-decane)(cbz)_2]^+$ was determined. The complex shows a distorted octahedral coordination environment with the macrocycle adopting a folded cis-V conformation. The angle $N_{axial}-Cr-N_{axial}$ deviates by $14.5^{\circ}$ from the ideal value of $180^{\circ}$for a perfect octahedron. The bond angle cis-O-Cr-O between the Cr(III) ion and the two carboxylate oxygen atoms of the monodentate p-chlorobenzoate ligands is close to 90$^{\circ}$. The FAB mass spectra of the $cis-[Cr([14]-decane)(La)_2]ClO_4$ display peaks due to the molecular ions $[Cr([14]-decane)(bz)_2-H]^\;,\;[Cr([14]-decane)(cbz)_2-2H]^$ at m/z 578, 646, respectively.

• 대한화학회지
• /
• 제46권2호
• /
• pp.145-150
• /
• 2002

자동흐름분석법으로 lucigenin을 발광시약으로 이용하여 화학발광의 세기를 측정함으로써 수용액 중의 Cr(III)을 정량하는 방법에 대하여 연구하였다. pH, 시료의 주입 양과 속도, lucigenin의 농도 및 방출파장이 방출세기에 미치는 영향을 조사하였다. Lucigenin과 과산화수소의 화학발광 반응에서 Cr(III)를 첨가하였을 때 방출세기가 현저히 증가함을 관찰하였다. Cr(III) 이온 검정곡선의 직선감응범위와 검출한계는 들뜸 파장, pH 및 lucigenin과 과산화수소의 농도가 각각 473 nm, 12.8 및 1.0${\times}10^{-6}$M과 2.0M였을 때, 1.0${\times}10^{-6}$M∼1.0${\times}10^{-3}$M 및 5.2${\times}10^{-8}$M이었다.

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

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

• Bulletin of the Korean Chemical Society
• /
• 제33권11호
• /
• pp.3691-3695
• /
• 2012

Photocatalytic reduction of hexavalent chromium (Cr(VI)) in ferric-tartrate system under irradiation of visible light was investigated. Effects of light resources, initial pH value and initial concentration of various reactants on Cr(VI) photocatalytic reduction were studied. Photoreaction kinetics was discussed and a possible photochemical pathway was proposed. The results indicate that Fe(III)-tartrate system is able to rapidly and effectively photocatalytically reduce Cr(VI) utilizing visible light. Initial pH variations resulte in the concentration changes of Fe(III)-tartrate complex in this system, and pH at 3.0 is optimal for Cr(VI) photocatalytic reduction. Efficiency of Cr(VI) photocatalytic reduction increases with increasing initial concentrations of Cr(VI), Fe(III) and tartrate. Kinetics analysis indicates that initial Fe(III) concentration affects Cr(VI) photoreduction most significantly.