• Journal of the Mineralogical Society of Korea
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• v.28 no.1
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• pp.29-38
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• 2015

Cyanide can be leached out from the cyanidation method which has been used to extract high-purity gold and silver from ores, and it becomes a variety of cyanide complexes associated with heavy metals contained in ores. Such cyanide complexes are considered as persistent and non-degradable pollutants which cause adverse effects on humans and surrounding environments. Based on binding force between heavy metals and cyanide, cyanide complexes can be categorized weak acid dissociable (WAD) and strong acid dissociable (SAD). This study comparatively evaluated the performance of photo-catalytic process with regard to forms of cyanide complexes. In particular, both effects of UV LED wavelength and surface modification of photo-catalyst on the removal efficiency of cyanide complexes were investigated in detail. The results indicate that the performance of photo-catalytic oxidation is significantly affected by the form of cyanide complexes. In addition, the effect of UV LED wavelength on the removal efficiency was quite different between free cyanide and cyanide complexes associated with heavy metals. The results support that the surface modification of photo-catalyst, such as doping can improve overall performance of photo-catalytic oxidation of cyanide complexes.

• Clean Technology
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• v.19 no.4
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• pp.487-491
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• 2013

To efficiently desorb gold and copper-cyanide complexes adsorbed onto Dowex21K XLT resin, the mixed solvent with HCl and acetone which is a kind of dipolar aprotic solvent was used as a desorbing agent. The desorption efficiency for gold-cyanide complex was the highest as about 94% when the mixing ratio of HCl and acetone based on volume was the 7:3, however, the value decreased as the ratio of acetone increased. In the case of copper-cyanide complex, most of them was desorbed when the amount of HCl was relatively higher than that of acetone, however, desorption efficiency decreased as the ratio of acetone increased. The desorption efficiency for gold and copper-cyanide complexes was the 94 and 100%, respectively at the 0.6 M of HCl with the 7 (HCl) : 3 (Acetone) of mixing ratio and desorption efficiency for gold-cyanide complex not increased any more even though higher HCl concentration was used. And the desorption efficiency for gold and copper-cyanide complexes was about 100% at the S/L raio ${\leq_-}1.0$ whereas desorption efficiency for gold-cyanide complex was very low as about 20-29% at the S/L ratio > 1.0. Also, most of desorption process for gold and copper-cyanide complexes was completed within 120 min.

• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1581-1585
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• 2012

Two pyridinecarboxamide dicyanidecobalt(III) building blocks and two mononuclear seven-coordinated macrocycle manganese(II) compounds have been rationally selected to assemble cyanide-bridged heterobimetallic complexes, resulting in three cyanide-bridged $Co^{III}-Mn^{II}$ complexes. Single X-ray diffraction analysis show that these complexes $\{[Mn(L^1)][Co(bpb)]\}ClO_4{\cdot}CH_3OH{\cdot}0.5H_2O$ ($\mathbf{1}$), $\{[Mn(L^2)][Co(bpb)]\}ClO_4{\cdot}0.5CH_3OH$ ($\mathbf{2}$) and ${[Mn(L^1)][Co(bpb)]\}ClO_4{\cdot}H_2O$ ($\mathbf{3}$) ($L^1$ = 3,6-diazaoctane-1,8-diamine, $L^2$ = 3,6-dioxaoctano-1,8-diamine; $bpb2^{2-}$ = 1,2-bis(pyridine-2-carboxamido)benzenate, $bpmb2^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate) all present predictable one-dimensional single chain structures. The molecular structures of these one-dimensional complexes consists of alternating units of $[Mn(L)]^{2+}$ ($L=L^1$ or $L^2$) and $[Co(L^{\prime})(CN)2]^-$ ($L^{\prime}=bpb2^{2-}$, or $bpmb2^{2-}$), forming a cyanide-bridged cationic polymeric chain with free $ClO_4{^-}$ as the balance anion. The coordination geometry of manganese(II) ion in the three one-dimensional complexes is a slightly distorted pentagonal-bipyrimidal with two cyanide nitrogen atoms at the trans positions and $N_5$ or $N_3O_2$ coordinating mode at the equatorial plane from ligand $L^1$ or $L^2$. Investigation over magnetic properties of these complexes reveals that the very weak magnetic coupling between neighboring Mn(II) ions connected by the diamagnetic dicyanidecobalt(III) building block. A best-fit to the magnetic susceptibility of complex ${\mathbf}{1}$ leads to the magnetic coupling constants $J=-0.084(3)cm^{-1}$.

• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1675-1680
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• 2012

Three new cyanide-bridged $Cr^{III}Mn^{II}$ binuclear complexes, $[Mn(phen)_2Cl][Cr(bpmb)(CN)_2]{\cdot}H_2O$ ($\mathbf{1}$) (phen = 1,10-phenanthroline, $bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate), $[Mn(phen)_2Cl][Cr(bpmb)-(CN)_2]{\cdot}H_2O$ ($\mathbf{2}$) ($bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate), and $[Mn(phen)_2Cl]-[Cr(bpClb)(CN)_2]{\cdot}CH_3OH{\cdot}H_2O$ ($\mathbf{3}$) ($bpClb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate) were obtained based on $Mn(phen)_2Cl_2$ and a series of dicyanidechromate(III) building blocks. Single crystal X-ray diffraction analysis shows the structures of the three complexes are dimeric type with two different metal centers linked by a cyanide group from corresponding dicyanidechromate(III) building block. Magnetic investigations indicate the existence of relatively weak antiferromagnetic coupling between Cr(III) and Mn(II) ions with best-fit constants $J_{CrMn}=-2.78(5)cm^{-1}$ for $\mathbf{1}$, $J_{CrMn}=-3.02(2)cm^{-1}$ for $\mathbf{2}$ and $J_{CrMn}=-2.27(3)cm^{-1}$ for $\mathbf{3}$ based on the spin exchange Hamiltonian = $-2J_{CrMn}\hat{S}_{Cr}\hat{S}_{Mn}$. The magneto-structural correlation of cyanide-bridged $Cr^{III}Mn^{II}$ complexes has been discussed at last.

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2544-2548
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• 2011

Two pyridinecarboxamide cobalt dicyanide building blocks and Mn(III) compounds have been employed to assemble cyanide-bridged heterometallic complexes, resulting in three trinuclear cyanide-bridged $Co^{III}-Mn^{II}$ complexes: $\{[Mn(MeOH)_4][Co(bpb)(CN)_2]_2\}{\cdot}2MeOH{\cdot}2H_2O$ (1), $\{[Mn(MeOH)_4][Co(bpmb)(CN)_2]_2\}{\cdot}2MeOH{\cdot}2H_2O$ (2) and $\{[Mn(DMF)_2(en)_2][Co(bpb)(CN)_2]_2\}{\cdot}2DMF{\cdot}H_2O$ (3) ($bpb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)benzenate, $bpmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate, en = ethylenediamine). Single crystal X-ray diffraction analysis shows their similar sandwich-like structures, in which the two cyanide-containing building blocks act as monodentate ligands through one of their two cyanide groups to coordinate the Mn(II) center. For complex 3, it was further linked into one-dimensional structure by ethylenediamine acting as bridges. Investigation of the magnetic properties of complex 3 reveals weak antiferromagnetic coupling between the neighboring Mn(II) centers through the bridging ethylenediamine molecule. A best-fit to the magnetic susceptibilities of complex 3 gave the magnetic coupling constant J = -0.073(2) $cm^{-1}$.

• Journal of Korean Society of Environmental Engineers
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• v.29 no.12
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• pp.1381-1389
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• 2007

Wastewater discharged by industrial activities of metal finishing and electroplating units is often contaminated by a variety of toxic or otherwise harmful substances which have a negative effects on the water environment. The treatment method of heavy metal-cyanide complexes wastewater by alkaline chlorination have already well-known($1^{st}$ Oxidation: pH 10, reaction time 30 min, ORP 350 mV, $2^{nd}$ Oxidation: ORP 650 mV). In this case, the efficiency for the removal of ferro/ferri cyanide by this general alkaline chlorination is very high as 99%. But the permissible limit of Korean waste-water discharge couldn't be satisfied. The initial concentration of cyanide was 374 mg/L(the Korean permissible limit of cyanide is 1.0 mg/L max.). So a particular focus was given to the treatment of heavy metal-cyanide complexes wastewater by $Zn^{+2}/Fe^{+2}$ ion and coprecipitation after alkaline chlorination. And we could meet the Korean permissible limit of cyanide(the final concentration of cyanide: 0.30 mg/L) by $Zn^{+2}/Fe^{+2}$ ion and coprecipitation(reaction time: 30 min, pH: 8.0, rpm: 240). The removal of Chromium ion by reduction(pH: 2.0 max, ORP: 250 mV) and the precipitation of metal hydroxide(pH: 9.5) is treated as 99% of removal efficiency. The removal of Copper and Nickel ion has been treated by $Na_2S$ coagulation-flocculation as 99% min of the efficiency(pH: $9.09\sim10.0$, dosage of $Na_2S:0.5\sim3.0$ mol). It is important to note that the removal of ferro/ferri cyanide of heavy metal-cyanide complexes wastewater should be employed by $Zn^{+2}/Fe^{+2}$ ion and coprecipitation as well as the alkaline chlorination for the Korean permissible limit of waste-water discharge.

• Bulletin of the Korean Chemical Society
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• v.13 no.2
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• pp.158-162
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• 1992

Hydrocarbon solution of $(PPh_3)_2(CO)MOSO_2CF_3(M=Rh$, Ir)reacts rapidly with Pyrazine or 4,4'-bipyridyl to yield dinuclear metal complexes $[(PPh_3)_3(CO)M({\mu}-pyrazine)M(CO)(PPh_3)_2](SO_3CF_3)_2$ (I: M= RhH; III: M=Ir) or [$(PPh_3)_2$(CO)M(${\mu}$-44'-bipyridyl)M(CO)$(PPh_3)_2](SO_3CF_3)_2$, (II: M=Rh; IV: M=Ir), respectively. Compounds, I, II, III, and IV were characterized by $^1H-NMR$, $^{13}C-NMR$, $^{31}P-NMR$, and infrared spectrum. Ethanol solution of $(PPh_3)_2(CO)MOSO_2CF_3$ (M=Rh, Ir) also reacts with $(TBA)_2$M'$(CN)_4$ (M'=Pd, Pt) to yield trinuclear metal complexes [$(PPh_3)_2$(CO)dM-NCM'$(CN)_2$CN-M(CO)$(PPh_3)_2]$ (V : M=Rh, M'=Pd; VI : M=Rh, M'=Pt; VII: M=Ir, M'=Pd; VIII: M=Ir, M'=Pt). The trinuclear metal complexes V, VI, VII, and VIII are bridged by the cyanide groups. The infrared spectrum of V, VI, VII, and VIII supports the presence of the bridged cyanide and terminal cyanide group.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2203-2206
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• 2013

• Bulletin of the Korean Chemical Society
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• v.35 no.9
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• pp.2684-2688
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• 2014

Two two-dimensional cyanide- and phenoxo-bridged heterometallic M(II)-Mn(III) (M = Ni, Pd) coordination polymers $\{[Mn(saltmen)]_4[Ni(CN)_4]\}(ClO_4)_2{\cdot}CH_3OH{\cdot}H_2O$ (1) and $\{[Mn(saltmen)]_4[Pd(CN)_4]\}(ClO_4)_2{\cdot}CH_3CN{\cdot}H_2O$ (2) ($saltmen^{2-}$ = N,N'-(1,1,2,2-tetramethylethylene)bis(salicylideneaminato)dianion) have been obtained by using $K_2[M(CN)_4]$ as building blocks and a salen-tpye Schiff-base manganese(III) compound as assembling segment. Single X-ray analysis reveals their isostrutural cyanide-bridged $MMn_4$ pentanuclear cationic structure. The four Schiff base manganese units of the pentanuclear entity are self-complementary through the phenoxo oxygen atoms from the neighboring complex, therefore forming cyanide- and phenoxo-bridged 2D sheet-like structure. Investigation over magnetic susceptibilities reveals the overall ferromagnetic coupling between the adjacent Mn(III) ions bridged by the phenoxo oxygen atoms with J = 2.13 and $2.21cm^{-1}$ for complexes 1 and 2, respectively.

• Journal of the Korean Chemical Society
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• v.33 no.2
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• pp.215-224
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• 1989

Electrochemical reductions of $trans-[Co(en)_2X_2](ClO_4)_n$ (where X is cyanide, nitrite, ammonia, and isothiocyanate) were investigated by cyclic voltammetry and polarography at mercury and glassy carbon electrode. $trans-[Co(en)_2(CN)_2]ClO_4$ was reduced to Co(II) complex followed by adsorption to the mercury electrode. Cyanide ion was not released from the reduced Co(II) complex but the cyanide and (en) were released after the reduction to metallic cobalt. The other complexes except $trans-[Co(en)_2(CN)_2]ClO_4$ were reduced to cobalt(II) complexes followed by release of monodendate ligand, and (en) was released at the reduction step to metallic cobalt. $trans-[Co(en)_2(NO_2)_2]ClO_4$ was reduced to cobalt(Ⅱ) complex, and $NO_2^-$ ion was released followed by electroreduction through ECE mechanism at pH 2. On glassy carbon electrode, all complexes of Co(III) were reduced to Co(II) complexes with irreversible one-electron diffusion controlled reaction in which (en) was not released at this step. Increasing absorption wave number of complexes caused to negative shift of peak potential.