• Bulletin of the Korean Chemical Society
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• v.34 no.3
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• pp.777-782
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• 2013

In order to further reduce the sulfur content in liquid hydrocarbon fuels, a desulfurization process by adsorption for removing dimethyl sulfide (DMS) and propylmercaptan (PM) was investigated. Bentonite adsorbents modified by $CuCl_2$ for the desulfurization of model oil was investigated. The results indicated that the modified bentonite adsorbents were effective for adsorption of DMS and PM. The bentonite adsorbents were characterized by X-ray diffraction (XRD) and thermal analysis (TGA). The acidity was measured by FT-IR spectroscopy. Several factors that influence the desulfurization capability, including loading and calcination temperature, were studied. The maximum sulfur adsorption capacity was obtained at a Cu(II) loading of 15 wt %, and the optimum calcination temperature was $150^{\circ}C$. Spectral shifts of the ${\nu}$(C-S) and ${\nu}$(Cu-S) vibrations of the complex compound obtained by the reaction of $CuCl_2$ and DMS were measured with the Raman spectrum. On the basis of complex adsorption reaction and hybrid orbital theory, the adsorption on modified bentonite occurred via multilayer intermolecular forces and S-M (${\sigma}$) bonds.

• Korean Journal of Crystallography
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• v.9 no.1
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• pp.6-10
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• 1998

The complex[Cu(L)](ClO4)2 (1) (L:3,5,10,12-Tetramethyl-1,4,8,11-tetraazacyclotetradecane) has been synthesized and structurally characterized. The complex 1 crystallizes in the monoclinic system, space group P21/n with cell parameters a=8.208(2)Å, b=13.339(6) Å, c=10.752(5) Å, β=111.02(4)˚ Z=2. Least-squares refinement of 1 led to a R(RW)factor of 0.073 (0.142) for 617 observed reflections of F0>40(F0). The crystal structure of 1 has a square-planar geometry and adopts the trans-III conformation.

• Bulletin of the Korean Chemical Society
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• v.5 no.3
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• pp.108-112
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• 1984

Interactions between metal ions and chitosan in solution were studied by spectroscopic and viscometric measurements. $Cu^{++}$-chitosan complex exhibited an absorption band at 265 nm, whereas D-glucosamine complex showed one at 245 nm. The difference in ${\lambda}_{max}$ was attributed to the different amine to $Cu^{2+}$ ratios of the complexes, that is, 2 : 1 for chitosan and 1 : 1 for D-glucosamine. The molar absorptivities and binding constants of the complexes were evaluatatled. The binding of $Cu^{2+}$ to chitosan was cooperative near pH 5, and both intra- and intermolecular chelations depending on chitosan and $Cu^{2+}$concentrations were observed, The intermolecular chelation was stabilized by addition of salts. The cooperative intermolecular chelation of $Ni^{++}$ was also observed at pH 6.2. No significant binding of other divalent ions was observed. The reported high adsorption abilities of chitosan particles for these ions were attributed to the deposition of metal hydroxide aggregates in pores of chitosan particles rather than chelation to amine groups.

• Bulletin of the Korean Chemical Society
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• v.11 no.4
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• pp.281-286
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• 1990

The kinetics and mechanism of reduction of Cu(II) with an excess D-penicillamine have been examined at pH = 6.2 and 0.60M in ionic strength. The reaction at the initial stage is biphasic with a rapid complexation process to give "red" transient complex of $[Cu(II)(pen)_2]^2$- that is partially reduced to another transient "brown" intermediate. The "brown" intermediate is finally reduced to diamagnetic "yellow" complex, $[Cu(I)(Hpen)]_n$. The final reduction process is pseudo-first order in ["brown" transient] disappearance $with {\kappa} = {{\kappa}_{3a} + {\kappa}_{3b}[pen]^{2-}},$ where ${\kappa}_{3a} = (5.0{\pm}0.8){\times}10^{-3}sec^{-1}$ and ${\kappa} = (0.14{\pm}0.02) M^{-1}sec^{-1}$ at $25^{\circ}C$. The activation parameters for the $[H_2pen]$-independent and $[H_2pen]$-dependent paths are ${\Delta}H^{\neq} = (52{\pm}5)kJmol^{-1},$ and ${\Delta}S^{\neq} = ( - 27{\pm}3)JK^{-1}mo^{l-1},$ and ${\Delta}H^{\neq} = (56{\pm}2)kJmol^{-1}$ and ${\Delta} S^{\neq} = ( - 18{\pm}0.7)JK^{-1}mol^{-1}$ respectively. The nature of "brown" intermediate is not clearly identified, but this intermediate seems to be in the mixed-valence state, judging from the kinetic and spectroscopic informations.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.2043-2048
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• 2014

Two isomers of a new tetraaza macrotricycle 2,2,4,9,9,11-hexaazamethyl-1,5,8,12-tetraazatricyclo[$10.2.2^{5.8}$]-octadecane ($L^2$) containing additional N-$CH_2CH_2$-N linkages, C-meso-$L^2$ and C-racemic-$L^2$, have been prepared by the reaction of 1-bromo-2-chloroethane with C-meso-$L^1$ or C-racemic-$L^1$ ($L^1$ = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). Both C-meso-$L^2$ and C-racemic-$L^2$ react with copper(II) ion to form $[Cu(C-meso-L^2)]^{2+}$ or $[Cu(C-racemic-L^2)]^{2+}$ in dehydrated ethanol, but do not with nickel(II) ion under similar conditions. Crystal structure of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ shows that the complex has distorted square-pyramidal coordination geometry with an apically coordinated water molecule. Unexpectedly, the Cu-N distances [2.016(3)-2.030(3) ${\AA}$] of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ are longer than those [1.992(3)-2.000(3) ${\AA}$] of [Cu(C-racemic-$L^1$)($H_2O$)]$(ClO_4)_2$. As a result, $[Cu(C-racemic-L^2)(H_2O)]^{2+}$ exhibits weaker ligand field strength than $[Cu(C-racemic-L^1)(H_2O)]^{2+}$. The copper(II) complexes readily react with CN- ion to yield the cyano-bridged dinuclear complex $[Cu_2(C-meso-L^2)_2CN]^{3+}$ or $[Cu_2(C-racemic-L^2)_2CN]^{3+}$. Spectra and chemical properties of $[Cu(C-meso-L^2)]^{2+}$ and $[Cu_2(C-meso-L^2)_2CN]^{3+}$ are not quite different from those of $[Cu(C-racemic-L^2)]^{2+}$ and $[Cu_2(C-racemic-L^2)_2CN]^{3+}$, respectively.

• Journal of the Korea Institute of Military Science and Technology
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• v.3 no.1
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• pp.164-175
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• 2000

Three compounds of Cu(II)-loaded N,N,N'-trimethylethylenediaminated Merrifield-type polymers were synthesized with yields higher than 80%, and the hydrolysis reaction rates of O-isopropylmethyl-phosphonofluoridate(GB) and O-pinacolylmethylphosphonofluoridate (GD) catalyzed by them have been surveyed. GB and GD hydrolysis by Cu(II)-loaded polymers occurs via intermediate complex mechanism where rapid equilibrium to form intermediate complex between substrate and Cu(II)-loaded polymers($K_f$) is followed by rate determining hydrolysis step($k_1$). The measured activation parameters for $k_1$ are ${\Delta}H^{\ddag}$ : $17.75{\pm}0.98kJ/mol$ ${\Delta}S^{\ddag}$ / : $-218.42{\pm}3.35J/mol$ K, $E^{\circ}_a$ : $20.22{\pm}0.98kJ/mo1$ for GB and ${\Delta}H^{\ddag}$ / : $11.16{\pm}1.15kJ/mol,$${\Delta}S^{\ddag}$ /: $-258.57{\pm}3.93J/mol$ K, $E^{\circ}_a$ : $13.64{\pm}1.15 kJ/mol$ for GD. Standard enthalpy/entropy changes corresponding to the intermediate complex formation constant $K_f$ are ${\Delta}H^{\circ}$ : $37.05{\pm}2.19 kJ/mo1,$$ {\Delta}S^{\circ}$ : $163.12{\pm}7.49 J/mol$ K and ${\Delta}H^{\circ}$ : 418.59{\pm}2.04 kJ/mol,$ ${\Delta}S^{\circ}$ : 4111.92{\pm}6.98 J/mol$ K for GB and GD, respectively, The electron push-pull mechanism by Cu(II)-loaded polymers lowers the P-F bond breaking energy(~400 kJ/mol) to less than 1/20 compared to the case in which no Cu(II)-loaded resin presents. Analysis of $K_f$ and 4k_1$ over pH=6.5~8.0 range suggest that the GB and GD hydrolysis occurs intramolecularily with $pK_a$ =7.29 for ligated $H_2O$ and $t_{1/2}$=36.9 sec, $pK_a$ = 7.06 and $t_{1/2}$=177.7 sec for GB and GD, respectively.

• YAKHAK HOEJI
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• v.27 no.2
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• pp.177-179
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• 1983

A copper complex of $\epsilon$-N-[(2-chloroethyl)carbamoyl]-L-lysine was prepared by the treatment of the L-lysine copper complex with 2-chloroethyl isocyanate in cold water. Within the L-lysine copper complex molecule, the $\alpha-amino$ and carboxyl groups are bounded to $Cu^{2+}$ but the $\epsilon-amino$ group is free and can react with carbamoylating agents. A potential antitumor agent, $\epsilon-N-[(2-chloroethyl)$ nitrosocarbamoyl]-L-lysine was synthesized by nitrosation of this copper complex with Na $NO_{2}$ in anhydrous formic acid, followed by the passage of $H_{2}$S gas.

• Journal of Powder Materials
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• v.5 no.2
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• pp.145-153
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• 1998

W-Cu alloy is attractive to thermal managing materials in microelectronic devices because of its good thermal properties. The metal injection molding (MIM) of W-Cu systems can satisfy the need for mass production of the complex shaped W-Cu parts in semiconductor devices. In this study, the application of MIM process of the mechanically alloyed (MA) W-Cu composite powders, which had higher sinterability were investigated. The MA W-Cu powders and reduction treated (RT) powders were injected by using of the multicomponent binder system. The multi-stage debinding cycles were adopted in $N_2$ and $H_2$ atmosphere. The isostatic repressing treatment was carried out in order to improve the relative density of brown parts. The brown part of RT W-Cu composite powder sintered at 110$0^{\circ}C$ had shown the higher sinterability compared to that of MA powder. The relative sintered density of all specimens increased to 96% by sintering at 120$0^{\circ}C$ for 1 hour. The relationship between green density and the sintering behavior of MA W-Cu composite powder was analyzed and discussed on the basis of the nanostructured characteristics of the MA W-Cu composite powder.

• Bulletin of the Korean Chemical Society
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• v.9 no.5
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• pp.298-303
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• 1988

Kinetic studies on cupric ion ($Cu^{2+}$) oxidation of 1-benzyl- and 1-aryl-1,4-dihydronicotinamides (XNAH) in aqueous solution were performed. In the presence of dioxygen ($O_2$), the reaction followed first order kinetics with respect to both XNAH and $Cu^{2+}$. The oxidation reaction was found to be independent and parallel to the acid-catalyzed hydration reaction of XNAH. The catalytic role of $Cu^{2+}$ for the oxidation of XNAH in the presence of $O_2$ was attributed to $Cu^{2+}/Cu^+$ redox cycle by the reactions with XNAH and $O_2$. The second order rate constants of the Cu2+ oxidation reaction kCu, and acid-catalyzed hydration reaction $k_H$ were strongly dependent on the nature of the substituents in 1-aryl moiety. The slopes of log $k_{Cu}$ vs log $K_H$ and log $k_{Cu}$ vs ${\sigma}_p$ of the substituents plots were 1.64 and -2.2, respectively. This revealed the greater sensitivity of the oxidation reaction rate to the electron density on the ring nitrogen than the hydration reaction rate. A concerted two-electron transfer route involving XNAH-$Cu^{2+}$ complex was proposed for mechanism of the oxidation reaction.

• Korean Journal of Metals and Materials
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• v.47 no.5
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• pp.297-303
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• 2009

Solvent extraction experiments of cupric and cuprous chloride with Alamine336 have been performed from HCl solution. In order to identify the solvent extraction reaction, distribution diagram of cupric and cuprous species with HCl concentration was obtained by considering complex formation reaction and the activity coefficient of solutes with Pitzer equation. Analysis of the solvent extraction data by graphical method together with the distribution diagram of copper indicated that solvent extraction reaction of copper with Alamine336 depends on HCl concentration. In strong HCl solution of 3 and 5 M, ${CuCl_4}^{2-}$ and ${CuCl_3}^{2-}$ took part in the solvent extraction reaction as Cu(II) and Cu(I), respectively. When HCl concentration was 1 M, ${CuCl_2}^-$ was extracted into the organic phase in the case of Cu(I) while adduct formation between $Cu^{2+}$ and Alamine336 was responsible for the solvent extraction reaction of Cu(II).