Polyaminocarboxylatonickelate(Ⅱ)와 Cu(Ⅱ)이온의 금속치환 반응속도에 관하여

박유철 경북대학교 교육대학원 1979 논문집 Vol.11 No.-

The metal-ion substitution reactions of polyaminocarboxylatonickelate(Ⅱ) (iminodiacetic acid and nitrilotriacetic acid) with Cu(Ⅱ) ion have been studied. In iminodiacetatonickelate(Ⅱ)-Cu(Ⅱ) system the kinetics has been investigated spectrophotometrically at the ionic strength 2.0, temperature 25℃ and pH 3.0∼5.0. From the observed rate constants the over-all rate law of metal-ion substitution reaction is expressed as follows: Rate=(k_01'+k_02'[Cu(Ⅱ)+k_03[H^+]) [Ni(Ⅱ)L] where L is iminodiacetic acid. The values of rate constants, k'_01 k'_02 and k_03' are 2.1×10 exp(-4) sec^-1, 1.8×10 exp(-2) M^-1 sec^-1 and 1.2M^-1 sec^-1, respectively. The reaction between nitrilotriacetatonickelate(Ⅱ) and Cu(Ⅱ) ion have been investigated by polarography at ionic strength 1.0, temperature 50℃ and pH 2.6∼3.5. Experimental results are consistent with the rate law as follows; Rate=(k_01''+k_02''[H^+]+k_03''([H^+]/[Ni(Ⅱ)]))[Ni(Ⅱ)L] where L is nitrilotriacetic acid. The values of rate constants, k_01'', k_02'' and k_03'' are 1.2×10 exp(-3) sec^-1, 0.43 M^-1 sec^-1 and 4.41×10 exp(-3) sec^-1, respectively. In both substitution reactions, reactionpathway and mechanisms are discussed.

Cu(Ⅱ)이온과 meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane간의 착화합물형성 반응에 관한 연구

朴裕哲,李承姬 慶北大學校 自然科學大學 1985 自然科學論文集 Vol.3 No.-

The complex formation of Cu(Ⅱ) ion with meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazac-yclotetradecane in acidic aqueous solution was investigated at the range of pH=3∼7 in which the blue complex could be formed. Under this experimental contidion, the reaction of blue-to-red conversion was not observed. The rates of formation of the blue complex have been measured using spectrophotometric method at 0.1M of ionic strength are 25∼35℃ of temperature. The rate constants were determined rfom Guggenheim plots. The rate constant of the comple xation increased with increasing the total concenturation of copper ion, pH an and temperature. The rate law obtained from the experimental results was the follows : Rate=k_1[Cu^2+][LH^+]+k_2[CuCO_2Me^+][LH^+]+k_3[CuCO_2Me^+][LH_2^2+] It was also found that the formation of blue complex was controlled by the positive enthalpy of activation. The isckiretic relationship between the enthalpy and the entropy of activation was shown, from which the isokinetic temperature(338.7°K) was obtained. From these results the mechanism of complexation could be discussed.

meso-[Co(trans-Me_6[14]dieneN_4)Cl_2]^+과 meso-[Co(trans-Me_6[14]dieneN_4)Br_2]^+ 착이온의 가수분해반응

朴裕哲,卞鍾轍,宋哲鎬 慶北大學校 1988 論文集 Vol.45 No.-

The rates of hydrolysis of meso-[Co(trans-Me_6[14]dieneN_4)X_2]^+ (Me_6[14]dieneN_4; 5,7,7,12, 14, 14-hexamethyl-1, 4, 8, 11-tetraazacyclotetradeca-4, 11-diene) have been investigated using spectrophotometric method according to various method content(v/v%; 60,70,80,90) and the pressure (1,500,1000,1500 bar). The results for the hydrolysis rate showed that the more methanol composition and pressure increase, the more the rates increase. The reaction mechanism was discussed using the activation parameters(ΔH^≠, ΔS^≠, and ΔV^≠) and the rate change with varying dielectric constant(D) and ionizing power(Y) of the mixture solvents.

물-아세톤 혼합용매에서 trans-[Co(N-Eten)_2Cl_2]^+착이온의 가용매분해 반응속도에 미치는 온도 및 압력의 영향

박유철,김경미 慶北大學校 1983 論文集 Vol.36 No.-

The rates of solvolysis of the complex ion, trans-Co(N-Eten)_2Cl_2+, in water-acetone mixture have been investigated using spectrophotometric method at various pressures and temperatures. The rate constants in aqueous acetone solutions are analyzed with the solvent compositions which gave been characterized in terms of Y parameter representing solvent ionizing power. The logarithms of rate constants are non-linearly correlated with parameter, Y. It suggested that the effects of solvent compositions on the reaction mechanism are important. The activation parameters are determined using transition state theory. The pressure effects on the rate of solvolysis of the complex have also been studied in water-acetone mixture, yielding +0.3~+1.5ml/M of activation volumes at 1~2,000bar and 25℃. The activation volumes are dependent on the solvent compositions and pressures. The established solvent composition of isoactivation volume are about 7%(v/v) acetone in this mixture.

Metalloporphyrin 착물과 Nitrogenous Bases간의 화학평형반응

朴裕哲,卞鍾轍,羅勳吉 慶北大學校 1991 論文集 Vol.51 No.-

The axial ligation of nitrogenous bases(pyridine, imidazole, 1-methylimidazole, 2,6-lutidine) to the four coordinated metallo-tetrakis(ortho-chlorophenyl)porphyrin and metallotetraphenylporphyrin are studied in a noncoordinating solvent, dichloromethane. Equilibrium constants for the ligation reactions of metalloporphyrin were determined using the spectrophotometric method. The order of the coordination capability of the ligands was given by; 1-Methylimidazole>Imidazole>Pyridine>2, 6-Lutidine For the equilibria of reactions of ZnTPP and Zn(o-Cl)TPP with polar solvents(DMF, DMSO), the equilibrium constants(logK) were 2.74 and 1.39 for DMSO, and 1.89 and 1.22 for DMF Nitrogenous bases (1-Melm, 1m, Py, 2,6-Lut) to the four coordinated Zn(o-Cl)TPP and ZnTPP have been investigated in various solvents, dimethylformamide, dimethylsulfoxide, dirhlorome-thane, acetone, and chloroform at several temperature(15℃, 25℃ and 35℃) The values of thermodynamic parameters, ΔH(kcal/mol) and ΔS(eu) were determined from the temperature effect on the equilibrium constants. In addition to the temperature effect, the solvent effects on the equilibrium constant of ligation reaction were discussed. For the case of a coordinating solvent(DMSO and DMF), the solvent effects on the equilibrium reaction between the metalloporphyrin and nitrogenous bases were able to explain in terms of a competition between the nitrogenous bases and solvent for the vacant coordination site of ZnTPP and Zn(o-Cl)TPP.

Ga(III)-Porphyrin 착물을 촉매제로한 올레핀 산화반응

朴裕哲,羅勳吉,金聖洙 경북대학교 기초과학연구소 1994 慶北大學敎 基礎科學硏究所 硏究論文集 Vol.15 No.-

Trends of groundwater data from the Korean National Groundwater Monitoring Stations: indication of any change?

박유철,Yun-Ju Jo,이진용 한국지질과학협의회 2011 Geosciences Journal Vol.15 No.1

Widespread climate change can impact on groundwater conditions. We evaluated the groundwater data for 1996–2008 obtained from the National Groundwater Monitoring Stations (NGMS), in the context of the global warming effect. Indications of air temperature and sea level rises were evident in the period. The groundwater levels were generally decreasing and most of this decrease was attributed to increased pumping nationwide, but no indication for any effect of sea level rise on groundwater level in coastal aquifers was found. The electrical conductivity (EC) values of groundwaters were very high in metropolitan and industrial areas, which were indicative of anthropogenic groundwater contamination and progressive groundwater quality deterioration. A systematic EC rise in coastal groundwaters, as a possible result of the sea level rise, was not observed. The groundwater temperature variation was the most striking. The majority of the monitored shallow and deep groundwaters exhibited increasing trends at mean rates of 0.04–0.09 °C/yr. The widespread and prevailing increase in groundwater temperature nationwide, with increasing air temperature, is strongly indicative of the effect of global warming. The increasing trend became more distinctive every year. However, these significant conclusions require further groundwater monitoring and re-evaluation.

유전 알고리즘을 이용한 유기오염물질 정화 최적화 모델링

박유철,정의평,송산 대한지질학회 2011 대한지질학회 학술대회 Vol.2011 No.10

물-메타놀 混合 溶媒에서 Pb-Acetate의 熱力學的 性質에 關한 硏究

朴裕哲,吳相午,郭永右 慶北大學校 1973 論文集 Vol.17 No.-

Activity coefficients and solubility products of Pb-Acetate(10^(-1)∼10^(-4) mole/l) from aqueous solution to the solution of water-methanol mixtures are investigated by electromotive force measurements at 25℃. The effect of dielectric constant of various solvents on these physical constants have been considered on quantitative basis. We are suggested that the relationship between the meen activity coefficients(r^*_±) and solubility products(k^*_s) in a reference solvent and those in other solvents is represented as follows; logr^s_±=logr^*_±+n, where n is -logr^*_s/k^s_s. Futher, we estimated the difference of the free energy change of transfer of Pb-Acetate from aqueous solution to the solution of water-methanol mixtures and the ion-size parameter of Pb-Acetate. The values of the ion-size parameter varies from 3.8Å to 4.4Å. Considering the free energy change, it is possicle to assume that the salt in the solvent of higher dielectric constant may be dissolved by electrostatic force rather than non-electrostatic force.

Styrene 유도체의 산화반응에서 전이금속착물 (Ni, Pd, Pt)의 촉매활성

朴裕哲 경북대학교 환경과학연구소 1993 環境科學論文集 Vol.7 No.1