• Journal of the Korean Chemical Society
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• v.24 no.1
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• pp.8-14
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• 1980

Solvolysis rate constants for methylchloroformate, $CH_3O$(CO)Cl, methylthiono-chloroformate, $CH_3O$(CS)Cl, and methylthiolchloroformate, $CH_3S$(CO)Cl, have been determined conductometrically in acetone-water and acetonitrile-water mixtures, and activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, have been derived. Results show that in water-rich regions the order of rate increases as $$CH_3O(CO)Cl while in dipolar aprotic solvent-rich region this order reverses. The plots of log k vs. solvent parameters, Y, $\frac{D-1}{2D+1}$ and log($H_2$) show that the order of rate increase in water-rich region is the results of increase in $S_N1$ character. It is concluded that $CH_3S$(CO)Cl solvolyzes via $S_N1$ mechanism whereas $CH_3O$(CO)Cl reacts via $S_N2$ and $CH_3O$(CS)Cl via intermediate mechanism in water-rich region.

• Journal of the Korean Chemical Society
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• v.37 no.11
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• pp.951-960
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• 1993

$Hg^{2+}$-induced aquation trans-[Co(3,2,3-tet)$X_2]^+$(3,2,3-tet = 4,7-diazadecane-1,10-diamine, $X_2\;=\;Cl_2,\;(NO_2)Cl,\;Br_2,\;(NO_2)Br,\;(NO_3)_2)$ complexes was investigated in aqueous solution. The products and the reaction mechanism were confirmed by chromatography, UV/Vis. spectrum, and circular dichroism (CD) spectrum. From the results, $Hg^{2+}$-induced aquation of 3,2,3-tet system has been produced cis-${\beta}$ complex via trans complex. The kinetic studies on $Hg^{2+}$-induced aquation of trans-[Co(3,2,3-tet)$Cl_2]^+$ complex and trans-[Co(3,2,3-tet)$(NO_2)Cl]^+$ complex were also carried out to study the reaction mechanism. The results show that trans-[Co(3,2,3-tet)$Cl_2]^+$ complex undergoes the D(dissociative)-mechanism and trans-[Co(3,2,3-tet)$(NO_2)Cl]^+$ complex $I_d$(interchange dissociavite)-mechanism. In order to confirm steric course for the reaction mechanism, $Hg^{2+}$-induced aquation on trans-[Co(R,R-3,2,3-tet)$Cl_2]^+$ complex to which chiral R,R-3,2,3-tet was coordinated instead of the racemic(R,R:S,S) 3,2,3-tet was used has been examined by CD spectrum. From the results, the final complex was confirmed to be ${\Delta}-cis-{\beta}$-[Co(R,R-3,2,3-tet)$(OH_2)_2]^{3+}$ complex indicating the chirality was retained through whole process.

• Bulletin of the Korean Chemical Society
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• v.11 no.4
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• pp.354-357
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• 1990

Synthesis of dichloro cobalt (Ⅲ) complexes of a flexible $N_2O_2-type$ tetradentate ligand, ethylenediamene-N,N'-di-${\alpha}$-isobutyric acid (eddib), has yielded two geometrical isomers, s-cis-$(Co(eddib)Cl_2)- and uns-cis-(Co(eddib)Cl_2)-.$ A series of substitution reactions, $(Co(eddib)Cl_2)^- {\to} (CO(eddib)Cl H_2O) {\to} (Co(eddib)CO_3)^- {\to} (Co(eddib(H_2O)_2)^+$ have been run for each of the two geometrical isomers. The reaction between the s-cis-(Co(eddib)Cl_2)^-$ complex and L-alanine (L-als) or S-methyl-L-cysteine (L-mcy) gave the meridional s-cis-[Co(eddib)(aa)) (aa = L-ala or L-mcy) complex. The S-methyl-L-cysteine was found to coordinate to cobalt (Ⅲ) ion via the nitrogen and oxygen donor atoms.

• Bulletin of the Korean Chemical Society
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• v.20 no.1
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• pp.85-88
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• 1999

Me3NO selectively abstracts the proton from [IrH(CO)(PPh3)2L(A)]0.1+,2+ (1) (A: -CCPh, Cl-, CH3CN and L: CH3CN, Cl-, C1O4-) to give the trans-elimination products, Ir(CO)(PPh3)2(A) (2). The reductive elimination of H+ and Cl- from Ir(H)Cl2(CO)(PPh3)2 (lb) to give IrCl(CO)(PPh3)2 (2b) is first order in both lb and Me3NO. The rate law d[2b]/dt=kobs[lb]=k2[lb][Me3NO] suggests the formation of (PPh3)2(CI)2(CO)Ir-H-ON+Me3 in the rate determining step (k2) followed by the fast dissociation of both H-ON+Me3 and the trans ligand Cl-. The rate significantly varies with the cis liaand A and the trans ligand L and is slower with both A and L being Cl- than other ligands. Me3NO selectively eliminates CO from [Ir(H)2(CO)(PPh3)2L]0,+ (3) (L=CH3CN, C1O4-) to produce [Ir(H)2(PPh3)2L'(CH3CN)]+ (4) (L'=CH3CN, PPh3) in the presence of L. Me3NO does not readily remove either H+ or CO from cis, trans- and trans, trans-lr(H)(-CCPh)2(CO)(PPh3)2 and cis, trans-Ir(H)2Cl(CO)(PPh3)2. The choice whether hydridocarbonyls, 1 and 3 undergo the deprotonation or decarbonylation may be understood mostly in terms of thermodynamic stability of the products and partly by kinetic preference of Me3NO on proton and CO.

• Resources Recycling
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• v.11 no.6
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• pp.12-17
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• 2002

Solvent extraction experiments have been performed to separate copper from $CuCl_2$-$NiCl_2$-$CoCl_2$$ solutions using Alamine336 and LIX84. The complex formation tendency between metal ions and chloride ion had a great effect on the distribution coefficients of Cu, Co and Ni ions and separation factor of Cu to Co and Ni. In the experimental ranges of chloride ion concentration from 0.5 to 4.0 M, LIX84 was superior to Alamine336 in separating copper from cobalt. When the volume percentage of LIX84 and Alamine336 was varied from 5 to 40%, LIX84 was more effective than Alamine336 in separating Cu from Co and Ni in solutions in which the chloride ion concentration was 1.0 M.

• Journal of the Korean Chemical Society
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• v.41 no.12
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• pp.639-644
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• 1997

Novel carbonylruthenium (Ⅲ) complex Cp*Ru(CO)Cl2(2, Cp*=η5-C5Me5) was synthesized by the reaction of [Cp*RuCl2]2(1) with CO in toluene. The effective magnetic moment (Veff=1.81 B.M.) derived from the magnetic susceptibility measurement of the complex (2) was consistent with the presence of one "single" unpaired electron. Dibromocarbonylruthenium (Ⅲ) complex Cp*Ru(CO)Br2(3) was obtained by the reaction of complex (2) with KBr in toluene. Complex (2) was easily reduced by the reaction with phosphine in toluene to give the corresponding Ru (Ⅱ) complex Cp*Ru(CO)(PR3)Cl (4a∼4e, PR3=PMe3, PEt3, PMePh2, PPh3, PCy3).

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.13 no.3
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• pp.181-186
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• 2015

It is necessary to develop an effective waste salt treatment technology for the minimization of radioactive waste generation from the pyroprocessing of spent nuclear fuel. For this reason, the separation characteristics of NdCl₃ from LiCl-KCl eutectic salt in a reactive distillation process using Li₂CO₃ or K₂CO₃ were observed. NdCl₃ was converted into oxychloride (NdOCl) or oxide (Nd₂O₃) in the reaction model between NdCl₃ and the carbonates using HSC-Chemistry, and this result was confirmed in the reactive distillation test of the LiCl-KCl-NdCl₃ system using the carbonates. Based on these results, the reactive distillation process conditions were determined to separate NdCl₃ into an oxide form (Nd₂O₃) which can be easily fabricated into a final waste form.

• Journal of Korean Society of Environmental Engineers
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• v.35 no.3
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• pp.179-191
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• 2013

This study was conducted to comparatively assess quantitative indicating factor for biomineralization characterizing $CO_2$ mineralization on three type of minerals (i.e., $CaCl_2$, $MgCl_2$, $CaCl_2-MgCl_2$) in an aqueous solution amended with Bacillus pasteurii or indigenous microorganisms for a S landfill cover soil. For given three types of minerals, $NH_4{^+}$ (urease activity) was released at the highest of 88 mg/L for $MgCl_2$, then 85 mg/L for $CaCl_2$, and the lowest of 42 mg/L for $CaCl_2-MgCl_2$. $CO_2$ gas in the head space was completely removed after 12, 12, and 24 hr for $CaCl_2$, $MgCl_2$ and $CaCl_2-MgCl_2$, respectively. $Ca^{2+}$ concentration in $CaCl_2$ solution was the quickest and the greatest decreased 92% for 12 hr whereas that in $CaCl_2-MgCl_2$ solution was lower at 85% for 36 hr. $Mg^{2+}$ concentration in $MgCl_2$ was more efficiently decreased at 46% for 48 hr than that of $CaCl_2-MgCl_2$ solution of 38.5% for 72 hr. Regardless of types of minerals or their concentration, pH was changed from 5.5 to 9 by biomineralization being progressed. Microbial activity ($OD_{600}$) was also changed from 0 to 0.6. SEM images indicated that spheroidal and trapezoid shape crystal were formed, which were identified as of $CaCO_3$ (Calcite) and $MgCO_3$ (Magnesite) by X-ray diffraction. In the long run, $NH_4{^+}$ (urease activity), $CO_2$ gas, $OD_{600}$, pH, $Ca^{2+}$ and $Mg^{2+}$ would be suitable for reasonable indicating factor in order to assess the degree of biomineralization efficiency.

• Journal of the Korean institute of surface engineering
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• v.53 no.1
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• pp.1-8
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• 2020

Sulfamate-chloride baths were fabricated to study the properties of the electrodeposited Ni and NiCo thin films. The dependences of current efficiency, deposit composition of Ni and Co, residual stress, surface morphology and microstructure of electrodeposited Ni and NiCo thin films on CoCl₂ concentration in sulfamate-chloride baths were investigated. The current efficiency was measured to be more than about 90%, independent of the changes of CoCl₂ concentration in the baths. Residual stress of Ni and NiCo thin films was increased from about 45 to about 250 MPa with varying CoCl₂ concentration from 0 to 0.210 M CoCl₂ in the baths and then reached to a plateau, about 250 MPa above 0.420 M CoCl₂ concentration. Nodular surface morphologies were observed at most CoCl₂ concentrations in the baths except 0.210 M. NiCo thin film electrodeposited from the bath with 0.210 M CoCl₂ concentration showed an acicular surface morphology. Pure Ni thin film consists of FCC(111), FCC(200), FCC(220), and FCC(311) peaks without any preferred orientation. On the other hand NiCo thin films make up of HCP(100), FCC(111), HCP(101), FCC(200), FCC(220) or HCP(110), FCC(311) or HCP(112) and FCC(222) peaks. It was revealed from the analysis of XRD result that FCC(111) peak at the NiCo thin film electrodeposited from the bath with 0.084 M CoCl₂ concentration can be regarded as the preferred orientation. However the peak of the preferred orientation was changed to FCC(220) or HCP(110) above 0.084 M CoCl₂ concentration in the baths. Then the intensity of FCC(220) or HCP(110) peak was gradually decreased with increasing CoCl₂ concentration further. The crystalline size of pure Ni thin film was observed to be about 53 ㎛ and those of NiCo thin films were in the range of 35~45 ㎛.

• Journal of the Korean Chemical Society
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• v.30 no.4
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• pp.335-450
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• 1986

The thermodynamic dissociation constants of $[Co(en)]_3Cl_3\;and\;[Co(NH_3)_6Cl_3$ in aqueous solutions at $25{\circ}$ and at the pressure from 1 bar to 2000 bars were measured by conductometric method. The dissociation constants were increased with pressure elevation because of volume decreasing by the formation of charged ions during dissociation reaction. That is, the $pK^T$ values of $[Co(en)]_3Cl_3$ were 2.16 for I bar, 2.08 for 500 bars, 2,08 for 1000 bars, 2.05 for 1500 bars and 2.03 for 2000 bars, respectively and those of $[Co(NH_3)_6Cl_3$ were 2.02 for 1 bar 1.96 for 500 bars, 1.90 for 1000 bars, 1. 88 for 1500 bars and 1. 87 for 2000 bars, respectively. Comparing and analyzing the values of Stokes' radii and $K^T$, the formation of ion pair compound was affected by not only the electrostatic interaction, but also the Interal Conjugate Base(ICB), which was increased by the elevation of the pressure.