• Journal of the Korea Academia-Industrial cooperation Society
• /
• v.11 no.12
• /
• pp.5221-5231
• /
• 2010

The complex formation from Ni(II) ion and 2-(2-Hydroxyethylamino)-2-(hydroxymethyl)-1,3-propanediol(Monotris) in aqueous solution at $25^{\circ}C$ and at ionic strength of 0.10M has been studied potentiometrically. In the Monotris(L) comlex $NiL^{2+}$, hydroxyl oxygen atom as well as the amine nitrogen of the ligand are coordinated to the Ni(II) ion.. The complex $NiL^{2+}$ undergoes further dissociation as the pH is increased forming triply deprotonated dinuclear complex $Ni_2L_2H_{-3}^+$.

• Journal of the Korean Chemical Society
• /
• v.31 no.4
• /
• pp.334-343
• /
• 1987

The Chemical reactions between $NiL_m{^{2+}}\{$Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;Ni(1[14]4-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}$}\and\ CN^-$ ion were studied by the spectrophotometric method. The equilibrium constants (K_1$) for the 1:1 complex ion, $[NiL_m(CN)]^+\;with\;NiL_m{^{2+}}\;and\;CN^-$ ion were determined in the range of 3 to $25^{\circ}C$. The $K_1\;for\;Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;Ni(1[14]4-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}\;at\;15^{\circ}C$ was 4.7, 5.3, 6.2, 7.5, 9.4, and 9.8, respectively. The values of $K_1$ decreased with increasing temperature. From the temperature effect on equilibrium constant ($K_1$), thermodynamic parameters $({\Delta}H^{\circ},\;{\Delta}S^{\circ},\;{\Delta}G^{\circ})$ for reaction were evaluated and the reaction of $NiL_m{^{2+}}\;and\;CN^-$ ion was exothermic. $NiL_m{^{2+}\;reacts\;with\;CN^-$ ion to give $Ni(CN)_4{^{2-}}$ ion and macrocyclic ligand $(L_m)$. The kinetics of formation of the $Ni(CN)_4{^{2-}}$ ion of varying the $[CN^-],\;[HCN],\;and\;[OH^-]$ have been investigated at 3∼$25^{\circ}C\;and\;0.5M\;NaClO_4$. Maintaining a constant $[CN^-],\;k_{obs}/[CN^-]^2$ increases linearly with increasing [HCN]. In the presence of large quantities of $[OH^-],\;k_{obs}/[CN^-]^2$ also increases linearly with $[OH^-]$. From the temperature effect on kinetic constant (k_{obs})$, parameter of activation $({\Delta}H^{\neq},\;{\Delta}S^{\neq})$ of reaction of $NiL_m{^{2+}}\;with\;CN^-$ ion were determined. For the $Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}\;series\;{\Delta}H^{\neq}$ gradually decrease as the d-d transition energy, $ν(cm^{-1})$ decrease. And the reaction of the five $NiL_m{^{2+}}\;with\;CN^-$ ion take place by way of equal paths.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.10
• /
• pp.1905-1910
• /
• 2008

The reaction of 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.0$0^{1.18}.0^{7.12}$]docosane ($L^1$) with formaldehyde in warm methanol yielded 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.$1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^7$) containing one 1,3-diazacyclohexane subunit. In methanol, $L^7$ readily reacts with $Cu^{2+}$ ion to form [$CuL^7(H_2O)$]$^{2+}$ which is extremely inert against methanolysis. In the solution containing $Ni^{2+}$ ion, however, $L^7$ reacts with methanol to yield [$NiL^3$]$^{2+}$ ($L^3$ = 2-(methoxymethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.$0^{1.18}.0^{7.12}$]- docosane), in which one N-$CH_2OCH_3$ pendant arm is appended. The copper(II) complex [$CuL^7(H_2O)$]- $(ClO_4)_2{\cdot}3H_2O\;(I{\cdot}3H_2O)$ has a severely distorted trigonal bipyramidal coordination geometry with a 4-5- 6-5 chelate ring sequence. The crystal structure of [$NiL^3$]$(PF_6)_2{\cdot}2H_2O$ (IIb) shows that the N-$CH_2OCH_3$ pendant arm is not coordinated to the metal ion in the solid state. In various solvents (S), however, the nickel(II) complex exists as a mixture of [$NiL^3$(S)]$^{2+}$, in which the N-$CH_2OCH_3$ group as well as S is coordinated to the metal ion, and [$NiL^3$]^{2+}.

• Bulletin of the Korean Chemical Society
• /
• v.34 no.7
• /
• pp.2125-2130
• /
• 2013

A new nickel(II) complex $[NiL^1]^{2+}$ ($L^1$ = 1-(2-aminoethyl)-3-(N-{2-aminoethyl}aminomethyl-1,3-diazacyclohexane) containing one 1,3-diazacyclohexane ring has been prepared selectively by the metal-template condensation of formaldehyde with N-(2-aminoethyl)-1,3-propanediamine and ethylenediamine at room temperature. The complex reacts with nitroethane and formaldehyde to yield the pentaaza macrocyclic complex $[NiL^2]^{2+}$ ($L^2$ = 8-methyl-8-nitro-1,3,6,10,13-pentaazabicyclo[13.3.1]heptadecane) bearing one C-$NO_2$ pendant arm. The reduction of $[NiL^2]^{2+}$ by using Zn/HCl produces $[NiL^3(H_2O)]^{2+}$ ($L^3$ = 8-amino-8-methyl-1,3,6,10,13-pentaazabicyclo[13.3.1]heptadecane) bearing one coordinated C-$NH_2$ pendant arm that is readily protonated in acid solutions. The hexaaza macrocyclic complex $[NiL^4]^{2+}$ ($L^4$ = 8-phenylmethyl-8-nitro-1,3,6,8,10,13-hexaazabicyclo[13.3.1]heptadecane) bearing one N-$CH_2C_6H_5$ pendant arm has also been prepared by the reaction of $[NiL^1]^{2+}$ with benzylamine and formaldehyde. The nickel(II) complexes of $L^1$, $L^2$, and $L^4$ have square-planar coordination geometry in the solid states and in nitromethane. However, they exist as equilibrium mixtures of the square-planar $[NiL]^{2+}$ (L = $L^1$, $L^2$, or $L^4$) and octahedral $[NiL(S)_2]^{2+}$ species in various coordinating solvents (S); the proportion of the octahedral species $[NiL(S)_2]^{2+}$ is strongly influenced by the ligand structure and the nature of the solvent. Synthesis, spectra, and chemical properties of the nickel(II) complexes of $L^1-L^4$ are described.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.8
• /
• pp.2565-2570
• /
• 2011

The reaction of bromoacetonitrile with 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[$16.4.1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^{10}$) containing a N-$CH_2$-N linkage produces 17-cyanomethyl-3,14-dimethyl-2,6,13,17-tetraazatetracyclo-[$16.4.1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^{11}$). The mono-N-functionalized macrocyclic complexes $[ML^2]^{2+}$ (M = Ni(II) or Cu(II); $L^2$ = 2-cyanomethyl-5,16-dimethyl-2,6,13,17-tetraazatricyclo[$16.4.0.0^{7.12}$]docosane) can be prepared by the reaction of $L^{11}$ with nickel(II) or copper(II) ion in acetonitrile. The N-$CH_2CN$ group attached to $[ML^2]^{2+}$ readily reacts with water or methanol to yield the corresponding complexes of $HL^3$ bearing one N-$CH_2CONH_2$ pendant arm or $L^4$ bearing one $N-CH_2C(=NH)OCH_3$ group. The $N-CH_2CONH_2$ or $N-CH_2C(=NH)OCH_3$ group of each complex is coordinated to the central metal ion. Both $[NiL^4(H_2O)]^{2+}$ and $[CuL^4]^{2+}$ are quite stable in acidic aqueous solutions, but undergo hydrolysis to yield $[Ni(HL^3)(H_2O)]^{2+}$ or $[Cu(HL^3)]^{2+}$ in basic aqueous solutions. In contrast to $[Cu(HL^3)]^{2+}$, $[Ni(HL^3) (H_2O)]^{2+}$ is readily deprotonated to form $[NiL^3 (H_2O)]^+$ ($L^3$ = a deprotonated form of $HL^3$) in basic aqueous solutions.

• Journal of the Korean Chemical Society
• /
• v.35 no.5
• /
• pp.527-533
• /
• 1991

Template condensation reactions of formaldehyde with appropriate tetramines and diamines in the presence of N(II) or Cu(II) ion produce square planar complexes of hexaaza macrotricyclic and macrotetracyclic ligands $[M(L)]^{2+}$(M = Ni(II) or Cu(II); L = 4-methyl-1,3,6,8,11,14-hexaazatricyclo[12,2,1,$1^{8,11}$]octadecane(C), 1,3,10,12,15,18-hexaazatetracyclo[16,2,1,$1^{12,15},0^{4,9}]$docosane(D) 4-methyl-1,3,6,8,12,15-hexaazatricyclo[13,3,1,$1^{8,12}$]eicosane(F), or 1,3,10,12,16,19-hexaazatetracyclo[l7,3,1,$1^{12,16},0^{4,9}]$tetracosane(G). These complexes contain two 1,3-diazacyclopentane or 1,3-diazacyclohexane rings in the six-membered chelate rings. The complexes of C and F contain one methyl group and those of D and G one cyclohexane ring in the five-membered chelate ring. Synthesis and characterization of the Ni(II) and Cu(II) complexes are presented. The effects of the ligand structure on the equilibrium $[Ni(L)]^{2+}2H_2O{\rightleftharpoons}[Ni(L)(H_2O)_2]^{2+}$ in aqueous solutions are described.

• Journal of the Korean Chemical Society
• /
• v.30 no.6
• /
• pp.526-531
• /
• 1986

The stability constants of 1,15-diaza-3,4:12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdien H$_4$, L) with transition metal ions such as $Co^{2+},\;Ni^{2+},\;Cu^{2+},\;and\;Zn^{2+}$ have been determined by potentiometry in 95% methanol solution at 25$^{\circ}$C. The complex formation of the NenOdien $_4$ with the transition metal ions depends on the basicity of the donor atoms. The order of complex stability was Co(II) < Ni(II) < Cu(II) > Zn(II). The geometries of the complexes in solid state were discussed by visible-near infrared and infrared spectrophotometry, elemental analysis and electro-conductivity. The results suggest that the geometries of the solid complexes are octahedral for $[CoL_2(OH_2)Cl]Cl{\cdot}2H_2O$, $[NiL_2(OH_2)Cl]Cl{\cdot}2H_2O$, and $[ZnLCl_2]{\cdot}\frac{1}{2}H_2O$ and square pyramidal for [CuLCl]Cl, respectively.

• Korean Journal of Crystallography
• /
• v.8 no.2
• /
• pp.124-126
• /
• 1997

The comples of [Ni(L)](ClO4)2 (L:3,5,10,12-tetramethyl-1,4,8,12-tetraazacyclotetradecane), C14H32Cl2N4NiO8, has a NiN4 square planar geometry and adopts a thermodynamically most stable trans-III conformation.

• Membrane and Water Treatment
• /
• v.10 no.3
• /
• pp.201-206
• /
• 2019

In this study, we performed an electrowinning process for effective removal of metals (Cu and Ni) in solution and their recovery as solid forms. A complete removal of Cu and Ni (1,000 mg/L) was observed during four times recycling test, indicating that our electrowinning system can ensure the efficient metal removal with high stability and durability. In addition, we investigated effect of operation parameters (i.e., concentration of boric acid only for Ni, variation of pH, concentration of electrolyte ($H_2SO_4$), and cell voltage) on the efficiency of metal removal (Cu and Ni) during the electrowinning. The addition of boric acid significantly enhanced removal efficiency of Ni as the concentration of boric acid increased up to 10 g/L. Compared to negligible pH effect (pH 1, 2, and 4) on the Cu removal, we observed the increase in removal efficiency of Ni as the pH increased from 1 to 4. The electrolyte concentration did not significantly influence the removal of Cu and Ni in this study. We also obtained great removal rates of Cu and Ni at 2.5 V and 4.0 V, which were much faster than those at lower voltages. Finally, almost 99% of each Cu and Ni (1,000 mg/L) was selectively removed from the mixture of metals by adjusting pH and addition of boric acid after the completion of Cu removal. The findings in this study can provide a fundamental knowledge about effect of important parameters on the efficiency of metal recovery during the electrowinning.

• Membrane Journal
• /
• v.21 no.3
• /
• pp.290-298
• /
• 2011

The influence of co-existing gases on the hydrogen permeation was studied through a Pd-coated $V_{53}Ti_{26}Ni_{21}$ alloy membrane. The hydrogen permeation characteristics of Pd-coated $V_{53}Ti_{26}Ni_{21}$ alloy membrane have been investigated in the pressure range 1-3 bar under pure hydrogen and hydrogen mixture gas with carbon dioxide and carbon monoxide at $450^{\circ}C$. Preliminary hydrogen permeation experiments have been confirmed that hydrogen flux was $5.36mL/min/cm^2$ for a Pd-coated $V_{53}Ti_{26}Ni_{21}$ alloy membrane (thick: 0.5 mm) using pure hydrogen as the feed gas. In addition, hydrogen fluxes were 4.46, 5.20, $3.91mL /min/cm^2$ for$V_{53}Ti_{26}Ni_{21}$ alloy membrane using $H_2/CO_2$, $H_2/CO$ and $H_2/CO_2/CO$ as the feed gas respectively. Therefore, the hydrogen permeation flux decreased with decrease of hydrogen partial pressure irrespective of temperature and pressure when $H_2/CO_2$, $H_2/CO$ and $H_2/CO_2/CO$ mixture applied as feed gas respectively and permeation fluxes were satisfied with Sievert's law in different feed conditions. It was found from XRD results after permeation test that the Pd-coated $V_{53}Ti_{26}Ni_{21}$ alloy membrane had good stability and durability for various mixtures feeding condition.