• Analytical Science and Technology
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• v.20 no.5
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• pp.406-412
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• 2007

The formation of inclusion complexes between ${\beta}$-cyclodextrin and diethylenetriamine substituted-pyridine copper(II) perchlorate; [Cu(dien)(sub-py)] $(ClO_4)_2$, were studied by spectrophotometric methods. On account of charge-transfer band(MLCT) and $^2T_2{\rightarrow}^2E$, the two high peaks were observed as an inclusion complex for the [${\beta}$-CD]$[Cu(dien)(p-Cl-py)]^{2+}$ in the ultraviolet region of the spectrum. The ${\beta}$-CD and $[Cu(dien)(sub-py)]^{2+}$ ion formed a 1:1 complex, and the formation constants were decreased with the increasing temperatures, due to weak binding energy between ${\beta}$-CD and $[Cu(dien)(sub-py)]^{2+}$ ion. This reaction was controlled by enthalpy. In a correlation of the Hammett substituent constants and formation constants for the reaction, formation constants were increased by strong binding energy in the inclusion complexes when electron donating groups were substituted in pyridine ring.

• Journal of the Korean Chemical Society
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• v.46 no.6
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• pp.502-508
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• 2002

We have used PET chemosensors in the determination of N-carbamoylglycine. When N-carbam-oylglycine reacts with complex already made by the fluorophore and metal ion, the luminescence intensity can be changed and this phenomenon can be utilized in quantification. We used three metal ions, $Zn^{2+}$, $Ni^{2+}$, $Cu^{2+}$ and in order to investigate selectivity an acetic acid was used. $Ni^{2+}$ ion showed change in the eT mechanism by the anions. $Cu^{2+}$ ion showed the ability to distinguish N-carbamoylglycine from an acetic acid and it is noteworthy that $Zn^{2+}$ ion can change luminescence sensitively according to concentration.

• Journal of the Korean Chemical Society
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• v.35 no.2
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• pp.119-127
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• 1991

The protonation and the metal ion complexation of 15 to 18 membered diaza crown ether such as 1,12-diaza-3, 4 : 9, 10-dibenzo-5, 8-dioxacyclopentadecane(NtnOenH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-hydroxy-5,9-dioxacyclohexadecane(NtnOtnH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-15-hydroxy-5,9-dioxacyclohexadecane(Ntn(OH)OtnH$_4$), 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdienH$_4$) and 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane(NtnOdienH$_4$) were studlied by potentiometry and NMR spectroscopy. The protonation constants were used to predict basicity of crown ethers. The sequence of the basicity was NenOdienH$_4$ < Ntn(OH)OtnH$_4$ < NtnOenH$_4$ < NtnOtnH$_4$ < NtnOdienH$_4$. Changes on the basicity were explained in terms of the effects of substituents and the degree of twistness of the macrocyclic ring. The sequence of the complex stabilities were Co(II) < Ni(II) < Cu(II) < Zn(II) for the transition metal complexes and Cd(II) < pb(II) < Hg(II) for the post-transition metal complexes. These changes on the stabilities were dependent on the basicity of the ligand and cavity size of the ring. For the heavy post-transiton metal complexes and Zn(Ⅱ) complex, the former factor was predominent and for the other transition metal complexes, the latter was affected on the stabilities. $^1$H and $^{13}$C-NMR studies for heavy post-transition metal complexes indicated that the nitrogen atom has greater affinity on metal ions than oxygen atom and the planarity of the rings was losed by the complexation with metal ions.

• Analytical Science and Technology
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• v.12 no.6
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• pp.515-520
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• 1999

The spectrophotometric determination of Al(III) with thorin have been investigated. The optimum condition of pH, concentration of ligand and surfactant, and stability were evaluated. The thorin ligand offers selective separation of Al(III) from sample solution containing Fe(III), Ni(II), Cu(II), Pb(II) and Cu(II). Various surfactants were tested and Triton X-100 showed the best stability and the maximum absorbance in an aqueous solution of Al(III)-Thorin-Triton X-100 complex appears about 526 nm. The method was applied for the determination of Al(III) in mixed sample solution. Separation and preconcentration was performed with a short column filled with resorcinol-formaldehyde resin. Control of the pH during the column operation is essential because the adsorption capacities are very sensitive to change in pH. Their separation was carried out in 0.2 M acetic acid-sodium acetate buffer solution (pH 4.5) and 1.0 M $HNO_3$media.

• Proceedings of the Mineralogical Society of Korea Conference
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• 2001.06a
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• pp.44-44
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• 2001

구리(II)의 전자상자성공명 흉수선의 모양과 선 폭에 대한 해석을 통해 석영-물 계면에서의 구리(II) 및 흡착수와 석영 표면과의 상호 작용에 대해 연구하였다. 두 가지 흡수선이 중첩하여 흡수선을 구성하며 따라서 석영 표면에 적어도 두 종류의 구리(II)가 존재함을 알 수 있었다. 하나는 g=2.18에 중심을 둔 초미세 갈라짐이 분해되지 않는 등방성 단일 흡수선을 보여 주는 구리(II) 이온이다. 이는 수용액 중에서와 유사한 빠른 자유 회전 운동이 가능한 상태로 표면에 매우 약하게 결합된 구리 이온(Cu($H_2O$)$_{6}$$^{2+}$)인 것으로 해석된다. 다른 하나는 축 대칭 흡수선 $g_{∥}$=2.40, $g_{⊥}$=2.08)을 가지는 구리(II)로서 이는 표면에 강하게 결합된 것으로 해석된다. 본 결과는 흡착 현상에 대한 열역학적 접근법인 표면 착물화 모델들이 제시하는 광물 표면에서의 금속 이온 흡착 모델이 거시적 관점에서 흡착 현상을 잘 모사할지라도 분자 수준의 미시적 관점에서 흡착 메커니즘을 규명하기 위해서는 독립적인 분광학적 정보가 제시되어야함을 보여 준다.다.

• Journal of the Korean Chemical Society
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• v.50 no.2
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• pp.99-106
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• 2006

The electronic absorption spectra of [3-(2-thenoyl) 3-(p-NO2-phenylhydrazone) ethyl pyruvate] (I), p-Br (II) and p-CH3 (III) were studied in ethanol and the spectra comprise four absorption bands which assigned to the corresponding electronic transition. The pK values of these compounds have been determined spectrophotometrically and pH-metrically, the results shown that the interval range for color change of compound (I) is (8-10) similar to that of phenolphethalin indicator, indicating that this compound can be used as acid-base indicator. The successive stability constants of the compounds under study with some transition elements (Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), UO2(II), La(III) and Zr(IV) have been determined pH- metrically. Stoichiometric complexes with ratios 1:1 and 1:2 (M: L) were formed for all metals. The pK of the three derivatives and the values of the stability constant (logK) of the complexes have the order; III > II > I. Also conductometric titrations have been carried out and the results show that this titration can be used for determination of both the metal ion and the ligand concentrations by each others.

• 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.

• Analytical Science and Technology
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• v.6 no.1
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• pp.57-63
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• 1993

Spectrophotometric determination of cobalt by flow injection method is described. 2-(5-Bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino) aniline rapidly forms a water-soluble complex with cobalt in $NH_3-NH_4Cl$ buffer solution at pH 10.5. The absorption maxima of this complex is at 545 nm with molar absorptivity of $58000L\;mol^{-1}\;cm^{-1}$. The calibration curve of cobalt is linear over the range of 0.1 to 0.6ppm and the detection limit is 25ppb. The relative standard deviation is ${\pm}0.72%$ for 0.5ppm and the sampling rate is $60samples\;hr^{-1}$. The interfering effect of some cations and anions was investigated. Ni(II), Cu(II), Fe(III) and $CN^-$ interfered severely. The interfering effect of these matallic ions could be decreased by adding $1.0{\times}10^{-3}M$ EDTA solution to the carrier stream.

• Analytical Science and Technology
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• v.10 no.4
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• pp.256-263
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• 1997

The new naphthol-containing hexadentate ligands, 1,12-bis (2-naphthol)- 2,5,8,11-tetraazadodecane 4HCl (nptr) and 1,14-bis(2-naphthol)- 2,6,9,13- tetraazatetradodecane .4HCl (npptr) were synthesized and characterized by elemental analysis, IR, NMR, and mass spectrometry. Acid dissociation constants and stability constants of Co(II), Ni(II). Cu(II), and Zn(II) complexes were determined at $25.0^{\circ}C$ and ionic strength ($\mu$)=0.10M($KNO_3$) by potentiometry. The relationship between basicity and stability constants of ligands containing aliphatic amines and 2-naphthol were studied.

• Journal of Environmental Health Sciences
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• v.24 no.3
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• pp.1-5
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• 1998

A spectrophotometric method was developed for the acidic solution stripped after an extraction of 0.5 to 2.5 ppm of Lead(II) from 50 mL of $Na_2S_2O_3$ solution into chloroform as the ion-pairs formed between their thiosulfate complexes and alkylamine, Aliquat336. Pb(II) in the stripped solution forms an complex with DDTC in pH 7.3 buffer solution, and was developed in yellow by copper replacement. The ydlow-colored solution have the maximum absorbance at 435 nm in the measurement of absorbance by UV-Visible spectrophotometer. The interference ions such as Fe(III), Hg (II), Al(III), Co, Cu, Ni, Zn, Ca, Sn, have great effects on the extraction, but they were overcomed by the usage of adequate masking agents before an extraction. At last, a good result was obtained in applying this method to synthetic water.