• Applied Chemistry for Engineering
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• v.16 no.2
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• pp.206-211
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• 2005

Mediated electrochemical oxidation (MEO) of polyethylene glycols (PEGs) of molecular weight of 1000, 4000 and 20000, was carried out on both platinum (Pt) and titanium-iridium electrodes in 8.0 M nitric acid solution containing 0.5 M Fe(II) and Co(II) ion. The electrochemical parameters such as current densities, kinds of electrode, electrolyte concentration and removal efficiency were investigated in both Fe(III)/Fe(II) and Co(III)/Co(II) redox systems. The PEGs was decomposed into carbon dioxide by MEO in Fe(III)/Fe(II) and Co(III)/Co(II) redox system during 180 min and 210 min at the current density of $0.67A/cm^2$ on the Pt electrode. Removal efficiency of PEGs by MEO was better in Co(III)/Co(II) redox system than Fe(III)/Fe(II) redox system, indicating mediated electrochemical removal efficiency was 100%.

• Applied Chemistry for Engineering
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• v.16 no.5
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• pp.635-640
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• 2005

Mediated electrochemical oxidation (MEO) is an aqueous process which oxidizes organics electrochemicallly at low temperatures and pressures. The useful process can be used to treat mixed wastes containing hazardous organics. This paper have studied MEO of ethylene glycol (EG) in nitric acids by Fe(III)/Fe(II) and Co(III)/Co(II) system. It investigated current density, supporting electrolyte concentration, hydraulic retention time, removal efficiency of EG by MEO. Removal efficiency of EG by MEO was superior in Co(III)/Co(II) redox system than Fe(III)/Fe(II) redox system, where MEO removal efficiency was 100 percent. In case of EG, the reactions were fast and good yields of carbon dioxide formation was observed.

• Bulletin of the Korean Chemical Society
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• v.19 no.6
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• pp.654-660
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• 1998

$[Fe^{II}Fe^{III}BPLMP(OAc)_2](BPh_4)_2$ (1), a new model for the reduced form of the purple acid phosphatases, has been synthesized by using a dinucleating ligand, 2,6-bis[((2-pyridylmethyl)(6-methyl-2-pyridylmethyl)amino) methyl]-4-methylphenol (HBPLMP). Complex I has been characterized by X-ray diffraction method as having (μ-phenoxo)bis(acetato)diiron core. Complex 1 was crystallized in the monoclinic space group C2/c with the following cell parameters: a=41.620(6) Å, b=14.020(3) Å, c=27.007(4) Å, β=90.60(2)°, and Z=8. The iron centers in the complex 1 are ordered as indicated by the difference in the Fe-O bond lengths which match well with typical $Fe^{III}-O\; and\; Fe^{II}-O$ bond lengths. Complex 1 has been studied by electronic spectral, NMR, EPR, SQUID, and electochemical methods. Complex 1 exhibits strong bands at 592 nm, 1380 nm in $CH_3CN$ (ε = 1.0 × 103 , 3.0 × 102). These are assigned to $phenolate-to-Fe^{III}$ and intervalence charge-transfer transitions, respectively. Its NMR spectrum exhibits sharp isotropically shifted resonances, which number half of those expected for a valence-trapped species, indicating that electron transfer between $Fe^{II}\;and\;Fe^{III}$ centers is faster than NMR time scale. This complex undergoes quasireversible one-electron redox processes. The $Fe^{III}_2/Fe^{II}Fe^{III}\;and\;Fe^{II}Fe^{III}/Fe^{II}_2$ redox couples are at 0.655 and -0.085 V vs SCE, respectively. It has $K_{comp}=3.3{\times}10^{12}$ representing that BPLMP/bis(acetate) ligand combination stabilizes a mixed-valence $Fe^{II}Fe^{III}$ complex in the air. Complex 1 exhibits a broad EPR signal centered near g=1.55 which is a characteristic feature of the antiferromagnetically coupled high-spin $Fe^{II}Fe^{III}$ system $(S_{total}=1/2)$. This is consistent with the magnetic susceptibility study showing the weak antiferromagnetic coupling $(J= - 4.6\;cm^{-1},\; H= - 2JS_1{\cdot}S2)$ between $Fe^{II}\; and \;Fe^{III}$center.

• Journal of Korean Society of Environmental Engineers
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• v.29 no.7
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• pp.778-782
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• 2007

This study investigated the dechlorination mechanisms of TCE by Fe(II) associated with cement. Batch slurry experiments were peformed to investigate the behaviors of selected ions; Fe(II), Fe(III), $Ca^{2+}$, $SO_4^{2-}$ in cement/Fe(II) system. The kinetic experiments of TCE in cement/Fe(II) systems showed that injected Fe(II) was mostly sorbed on cement within 0.5 day and 90% of injected 200 mM sulfate was sorbed on cement within 0.5 day when $[TCE]_0$ = 0.25 mM and $[Fe(II)]_0$ = 200 mM. The kinetic experiments of TCE in hematite/CaO/Fe((II) systems were conducted for simulation of cement/Fe(II) system. Calcium oxide that is one of the major components in cement hydration reactions or has a reactivity in limited conditions. Hematite assumed the ferric iron oxide component of cement. The reactivities observed in hematite/CaO/Fe(II) system were comparable to those reported for cement/Fe(II) systems containing similar molar amounts of Fe(II). The behavior of Fe(II) and $SO_4^{2-}$ sorbed on solid phase at an early stage of reaction in hematite/CaO/Fe(II) system was similar to that of cement/Fe(II) system. Ferric ion was released from hematite at an early period of reaction at low pH. The experimental evidence of kinetic test using hematite/CaO/Fe(II) system implies that the reactive reductant is a mixed-valent Fe(II)-Fe(III) mineral, which may be similar to green rust. Fe(II) sorbed on cement can be converted to new mineral phase having a reactivity such as Fe(II)-Fe(III) (hydr)oxides in cement/Fe(II) systems.

• Journal of the Korean Chemical Society
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• v.55 no.3
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• pp.463-471
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• 2011

A novel $N_2O_2$ Schiff base ligand, N,N'-bis(4-methoxysalicylidene)phenylendiamine(4-$CH_3O$-Salphen), has been synthesized. It has been revealed that the compound is very useful for the spectrophotometric quantification of Fe(II) and Fe(III) ions in aqueous solutions, such as mineral water, hot spring water, sea water, and waste water. The optimum conditions for the quantitative analysis are the followings; [4-$CH_3O$-Salphen]=$4.0{\times}10^{-4}\;M$, DMF/$H_2O$=70/30(v/v), pH=3.4~3.8, T= at $55^{\circ}C$, and prereaction time=1.0 hr. The sample of single valence state was prepared by the preliminary oxidation or reduction using $H_2O_2$ ($5.0{\times}10^{-4}\;M$) and $NH_2OH{\cdot}HCl$ ($5.0{\times}10^{-4}\;M$). The quantitative analyses of Fe(II) and Fe(III) ion were performed by measuring the absorbance at 434 nm and 456 nm, respectively. The estimated mean values agreed well with the standard values within the range of 2.00~6.90%. The limit of detection was 27.9 ng/mL for Fe(II) and 55.8 ng/mL for Fe(III).

• Economic and Environmental Geology
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• v.42 no.5
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• pp.487-494
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• 2009

The purpose of this study was to investigate the feasibility of As(V) reduction by aqueous Fe(II), and subsequent As(III) immobilization by the precipitation of As(III) incorporated magnetite-like material [i.e., co-precipitation of As(III) with Fe(II) and Fe(III)]. Experimental results showed that homogeneous As(V) reduction did not occur by dissolved Fe(II) at various pH values although the thermodynamic calculation was in favor of the redox reaction between As(V) and Fe(II) under the given chemical conditions. Similarly, no heterogeneous reduction of sorbed As(V) by sorbed Fe(II) was observed using synthetic iron (oxy)hydroxide (Goethite, ${\alpha}$-FeOOH) at pH 7. Experimental results for the effect of As(V) on the oxidation of Fe(II) by dissolved oxygen showed that As(V) inhibited the oxidation of Fe(II). These results indicate that As(V) could be stable in the presence of Fe(II) under the anoxic or subsurface environments.

• KSCE Journal of Civil and Environmental Engineering Research
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• v.28 no.1B
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• pp.149-152
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• 2008

The reaction between iron oxide and ferrous iron is known to be the adsorption of ferrous iron onto the oxide surfaces that produces Fe(II)-Fe(III) (hydr)oxides and ferrous oxide oxidized to ferric ion which is the reducing agent of the target compounds. In our investigations on DS/S using ferrous modified steel slag, the results did not follow the trends. FeO and Fe(II), the major component of steel slag, were used to investigate the degradation of TCE. Degradation did not take place for the first and suddenly degraded after awhile. Degradation of TCE in this system was unexpected because Fe(II)-Fe(III) (hydr)oxides could not be produced in absence of ferric oxide. In this study, the characteristics of FeO/Fe(II) system as a reducing agent were observed through the degradation of TCE, measuring byproducts of TCE and the concentration of Fe(II) and Fe(III). Adsorption of ferrous ion on FeO was observed and the generation of byproducts of TCE showed the degradation of TCE by reduction in the system is obvious. However it did not correspond with the typical reducing mechanisms. Future research on this system needs to be continued to find out whether new species are generated or any unknown mineral oxides are produced in the system that acted in the degradation of TCE.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 1999.10a
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• pp.81-84
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• 1999

The aqueous geochemical characteristics of Cr(III) and Cr(Ⅵ) in environmental systems are very different from one another: Cr(Ⅵ) is highly soluble, mobile and toxic relative to Cr(III) Reduction of Cr(Ⅵ) to Cr(III) are beneficial in aquatic systems because of the transformation of a highly mobile and toxic species to one having a low solubility in water, thus simultaneously decreasing chromium mobility and toxicity. Fe(II) species are excellent reductants for transforming Cr(Ⅵ) to Cr(III), and in addition, keeping Cr(III) concentrations below the drinking water standard of 52 ppb at pH values between 5 and 11. Investigations of the effects of NOM on Cr(Ⅵ) reduction are for examining the feasibility of using ferrous iron to reduce hexavalent chromium in subsurface environments. Experiments in the presence of soils, however, showed that the solid phase consumes some of the reducing capacity of Fe(II) and makes the overall reduction kinetics slower. The soil components bring about consumption of the ferrous iron reductant. Particular attention is devoted to the complexation of Fe(II) by NOM and the subsequent effect on Cr(Ⅵ) reduction. Cr(Ⅵ) reduction rate by Fe(II) was affected by the presence of NOM (humic acid), The effects of humic acid was different from the solution pH values and the concentration of humic acid. It was probably due to the reactions between humic acid and Cr(Ⅵ), humic acid and Fe(II), and between Cr(Ⅵ) and Fe(II), at each pH.

• Bulletin of the Korean Chemical Society
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• v.20 no.12
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• pp.1428-1432
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• 1999

[Fe$^{II}$(BLPA)DBCH]BPh₄ (1), a new functional model for the extradiol-cleaving catechol dioxygenases, has been synthesized, where BLPA is bis(6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine and DBCH is 3,5-di-tert-butylcatecholate monoanion. ¹H NMR and EPR studies confirm that 1 has a high-spin Fe(II) (S = 2) center. The electronic spectrum of 1 exhibits one absorption band at 386 nm, showing the yellow color of the typical [Fe$^{II}$(BLPA)] complex. Upon exposure to O₂, 1 is converted to an intense blue species within a minute. This blue species exhibits two intense bands at 586 and 960 nm and EPR signals at g = 5.5 and 8.0 corresponding to the high-spin Fe(III) complex (S = 5/2, E/D = 0.11). This blue complex further reacts with O₂ to be converted to (μ-oxo)Fe$^{III}_2$ complex within a few hours. Interestingly, 1 affords intradiol cleavage (65%) and extradiol cleavage (20%) products after the oxygenation. It can be suggested that 1 undergoes two different oxygenation pathways. The one takes the substrate activation mechanism proposed for the intradiol cleavage products after the oxidation of the $Fe^II\;to\;Fe^{III}$. The other involves the direct attack of O₂ to $Fe^{II}$ center, forming the $Fe^{III}$-superoxo intermediate which can give rise to the extradiol cleavage products. 1 is the first functional Fe(II) complex for extradiol-cleaving dioxygenases giving extradiol cleavage products.

• Bulletin of the Korean Chemical Society
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• v.21 no.10
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• pp.969-972
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• 2000

[Fe II Fe III $BPLNP(OAc)_2](BPh_4)_2$ (1), a new model for the reduced form of the purple acid phosphatases, has been synthesized by using a dinucleating ligand, 2,6-bis[((2-pyridylmethyl)(6-methyl-2-pyridylmethyl)ami-no)methyl]-4-nitrophenol (HBPLNP) . Complex 1 has been studied by electronic spectral, NMR, EPR, SQUID, and electrochemical methods. Complex 1 exhibits two strong bands at 498 nm $(\varepsilon=$ 2.6 ${\times}10^3M-^1cm-^1)$ and 1363 nm $(\varepsilon=$ 5.7 ${\times}10^2M-^1cm-^1)$ in $CH_3CN.$ These are assigned to phenolate-to-FeIII and intervalence charge-transfer transitions, respectively. NMR spectrum of complex 1 exhibits sharp isotropically shifted resonances, which number is half of those expected for a valence-trapped species, indicating that electron transfer between FeⅡ and FeⅢ centers is faster than NMR time scale at room temperature. Complex 1 undergoes quasireversible one-electron redox processes. The $FeIII_2/FeIIFeIII$ and $FeIIFeIII/FeII_2$ redox couples are at 0.807 and 0.167 V ver-sus SCE, respectively. It has Kcomp = 5.9 ${\times}$10 1s(acetato) ligand combination sta-bilizes a mixed-valence FeIIFeIII complex in the air. Interestingly, complex 1 exhibits intense EPR signals at g = 8.56, 5.45, 4.30 corresponding to mononuclear high-spin FeⅢ species, which suggest a very weak magnetic coupling between the iron centers. Magnetic susceptibility study shows that there is a very weak antiferromag-netic coupling (J = $-0.78cm-^1$, H = $-2JS_1${\times}$S_2)$ between FeII and FeIII centers. Thus, we can suggest that complex 1 has a very weak antiferromagnetic coupling between the iron centers due to the electronic effect of the nitro group in the bridging phenolate ligand.