• Analytical Science and Technology
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• v.20 no.5
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• pp.448-451
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• 2007

A new bis(dicyclohexylammonium) chromate dihydrate complex, $[(C_6H_{11})_2NH_2]_2[CrO_4]{\cdot}2H_2O$, (I), has been synthesized and its structure analyzed by FT-IR, EDS, elemental analysis, ICP-AES, and single crystal X-ray diffraction methods. The Cr(VI) complex (I) is tetragonal system, I${\bar{4}}$2d space group with a = 12.5196(1), b = 12.5196(1), c = $17.3796(3){\AA}$, a = ${\beta}$ = ${\gamma}$ = $90^{\circ}$, V = $2724.09(6){\AA}^3$, Z = 4. The crystal structure of complex (I) consists of tetrahedral chromate $[CrO_4]^{2-}$ anion, two organic dicyclohexylammonium $[(C_6H_{11})_2NH_2]^+$ cations and two lattice water molecules. The chromate anion and protonated dicyclohexylammonium cation is mainly constructed through the ionic bond. The cyclohexylammonium rings of the dicyclohexylammonium cation take the chair form and vertical configuration with each other. The N-H${\cdot}$O and O-H${\cdot}$O hydrogen bond networks between the $N_{dicyclohexylammonium}$, $O_{water}$ and $O_{chromate}$ atom lead to self-assembled molecular conformation and stabilize the crystal structure.

• Korean Journal of Crystallography
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• v.6 no.2
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• pp.75-79
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• 1995

The crystal structure of Tris(ethylenediamine)nickel(II)Chromate has been determined by X-ray crystallography. Crystal data : a=9.027(2)Å, c=9.751(5)Å이며, Z=2, V=687.9(2)Å3, Dc=1.714gcm-3, μ=21.635-1. The intensity were collected with Mo-Kα radiation (λ=0.7107Å) on an automatic four-circle diffractometer with a graphite monochromator. The structure was solved by Patterson method and refined by full matrix least-square methods using unit weights. The final R and S values were R=0.029, Rw=032, Rall=0.049 andS=0.018 for 342 observed reflections. The chromate ions are located at position of point of point symmetry 32 and their oxygens are sixfold disodered in an unusual way. Extensive strong hydrogen bonds between complex cations and chromatic anions are found in axial and equatorial directions.

• Journal of the Korean Chemical Society
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• v.30 no.2
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• pp.231-236
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• 1986

Oxidation of $[Mo_2O_4(C_2O_4)_2(OH_2)_2]^{2-}$ with hydrogen chromate yields the molybdenum (VI) complex, $[Mo_2O_4(C_2O_4)_2(OH_2)_2]^{2-}$. Stoichiometry for the reaction of $[Mo_2O_4(C_2O_4)_2(OH_2)_2]^{2-}$ with hydrogen chromate are expressed as ${3Mo_2}^V+2Cr^{VI}\;{\rightleftharpoons}\;{3Mo_2}_{VI}+2Cr^{III}$. Observed rate constants are dependent on $[H+]^2$. The kinetic data are consistent with a mechanism in which three successive single-electron steps convert $Cr^{VI}$to $Cr^{III}$ by way of intermediate Cr^V$ and $Cr^{IV}$. Mechanism of the reaction are presented and discussed.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.13 no.1
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• pp.462-469
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• 2012

Cr(VI)-4,4'-bipyridine complex(4,4'-bipyridinium dichromate) was synthesized by the reaction of 4,4'-bipyridine with chromium trioxide in H2O, and characterized by IR, ICP. The oxidation of benzyl alcohol using 4,4'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order: cyclohexene$CH_3$, H, m-Br, m-$NO_2$) smoothly in N,N'-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.63(303K). The observed experimental data have been rationalized as follows; the proton transfer occurs after the prior formation of a chromate ester in the rate determining step.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.14 no.11
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• pp.6039-6046
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• 2013

Cr(VI)-heterocyclic complex[Cr(VI)-2-methylpyrazine] was synthesized by the reaction between of heterocyclic compound(2-methylpyrazine) and chromium trioxide, and characterized by IR and ICP analysis. The oxidation of benzyl alcohol using Cr(VI)-2-methylpyrazine in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order : cyclohexene${\rho}$) was Cr(VI)-2-methylpyrazine= -0.65(308K). The observed experimental data have been ratiolized. The hydride ion transfer causes the prior formation of a chromate ester in the rate-determining step.

• Applied Chemistry for Engineering
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• v.25 no.6
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• pp.648-653
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• 2014

Cr(VI)-heterocyclic complex (2,4'-bipyridinium chlorochromate) was synthesized by the reaction between heterocyclic compound(2,4'-bipyridine) and chromium trioxide, and characterized by IR and ICP analysis. The oxidation of benzyl alcohol using 2,4'-bipyridinium chlorochromate in various solvents showed that the reactivity increased with the increase of the dielectric constant (${\varepsilon}$), in the order : N,N-dimet-hylformamide (DMF) > acetone > chloroform > cyclohexene. In the presence of DMF solvent with acidic catalyst such as hydrochloric acid (HCl solution), 2,4'-bipyridinium chlorochromate oxidized benzyl alcohol (H) and its derivatives (p-$CH_3$, m-Br, m-$NO_2$). Electron-donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.67 (303 K). The observed experimental data have been rationalize the proton transfer occurred followed the formation of a chromate ester in the rate-determining step.

• Journal of the Korean Chemical Society
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• v.30 no.3
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• pp.307-311
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• 1986

The rates of hydrolysis of the complex, $trans^-[Cr(en)_2F(H_2O)]^{2+}$, have been investigated using spectrophotometric method at various temperatures and pressure. Temperature was 30${\circ}C$ to 50${\circ}C$ and pressure was varied up to 1500bar. The rate constant measured at 30${\circ}C$ is $2.632{\times}10^{-5}sec^{-1}$. The rate constants are decrease with increasing pressure at constants temperature. Activation volume and other activation parameters are calculated from these rate constants. The activation volumes are all positive and lie in the limited range 0.447 ∼ 3.152$cm^3$/mol and the activation entropies are small values. From the results, it was found that this reaction was endothermic and enthalphy controlled reaction in the experimental temperature.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.14 no.11
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• pp.6000-6007
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• 2013

Cr(VI)-heterocyclic complex[Cr(VI)-isoquinoline] was synthesized by the reaction between of heterocyclic compound(isoquinoline) and chromium trioxide, and characterized by IR and ICP analysis. The oxidation of benzyl alcohol using Cr(VI)-isoquinoline in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order : cyclohexene$CH_3$, m-Br, m-$NO_2$). Electron- donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.69(308K). The observed experimental data have been ratiolized. The hydride ion transfer causes the prior formation of a chromate ester in the rate-determining step.

• Journal of the Korean Chemical Society
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• v.30 no.1
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• pp.57-62
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• 1986

Oxidation of $[Mo_3O_4(C_2O_4)_3(H_2O)_3]^{2-}$ with HCr$O_4^-$ yields the molybdenum(Ⅳ) complex, $[Mo_2O_5(C_2O_4)_2(H_2O)_2]^{2-}$. Stoichiometry for the reaction of $[Mo_3O_4(C_2O_4)_3(H_2O)_3]^{2-}$ with HCr$O_4^-$ are expressed as $2Mo_3^{IV} + 4Cr^{VI} {\to} 3Mo_2^{VI} + 4Cr^{III}$. Observed rate constants are dependent on hydrogen ion concentration. The kinetic data are consistent with a mechanism in which three successive single-electron steps convert $Cr^{VI}$to $Cr^{III}$ by way of intermediate $Cr^V$ and $Cr^{IV}$. Detailed mechanisms are presented and discussed.

• Journal of Korean Society of Environmental Engineers
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• v.31 no.3
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• pp.179-185
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• 2009

In this research, the removal capacity of Cr(VI) by the reused powdered wastes (RPW) containing aluminium oxides was studied. As a pre-treatment process for the preparation of calcined wastes, calcination was conducted at $550^{\circ}C$ to remove organic fraction in the raw wastes. In order to study the adsorption trend of Cr(VI) ions from aqueous solutions, the pH-edge adsorption, adsorption kinetic and adsorption isotherm were investigated using a batch reactor in the presence of four different background electrolytes($NO_3\;^-,\;CO_3\;^{2-},\;SO_4\;^{2-},\;PO_4\;^{3-}$). Cr(VI) adsorption was greatly reduced in the presence of $SO_4\;^{2-}$ and $PO_4\;^{3-}$ over the entire pH range. Meanwhile the inhibition effect by $NO_3\;^-$ and $CO_3\;^{2-}$ was relatively lower than that by $SO_4\;^{2-}$ and $PO_4\;^{3-}$. Cr(VI) adsorption was maximum around pH 4.5 in the presence of $NO_3\;^-$ and $CO_3\;^{2-}$. As the concentration of background electrolytes increased, Cr(VI) adsorption decreased. This result mightly suggests that adsorption between the surface of RPW and Cr(VI) occurs through outer-sphere complex. Cr(VI) adsorption onto the RPW was well described by second-order kinetics. From the Langmuir isotherm at initial pH 3, the maximum adsorbed amount of Cr(VI) onto the RPW was 11.1, 10, 3.3, 5 mg/g in the presence of $NO_3\;^-,\;CO_3\;^{2-},\;SO_4\;^{2-}$, and $PO_4\;^{3-}$, respectively.