자동차 배기정화용 촉매에 관하여 : NO와 CO제거를 위한 촉매제

박유철,오상오,김창수,구본권 경북대학교 교육대학원 1980 논문집 Vol.12 No.-

The reactions of nitric oxide with hydrogen, carbon monoxide and hydrogen-carbon monoxide mixture have been investigated over the catalysts supported on alumina. In NO-H_2 System the relative activity of catalysts was decreased in the order as Pd>Ru>Pt>Os, while it was Ru>Pd<Pt<Os in NO-CO system. The relative activity sequence of catalysts in NO-H_2-CO system was similiar to that in the mixture of nitric oxide and carbonmonoxide. The inverstigation on the effectiveness of air-fuel ratio for the purification of exhaust gases has also been carried out over alumina supported ruthenium and palladium. Of exhaust gases the nitric oxide conversions were decreased slowly with increasing the air-fuel ratio, while the carbon monoxide conversions were increased slowly under the same condition. In this experiment the best value of air-fuel ratio was 14.5. In the nitric oxide conversions, the ruthenium and palldium of catalysts used were not so much inhibited by carbon monoxide.

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.-

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.

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.

산성수용액에서 cis-aquo-bis(ethylenediamine)cobalt(Ⅲ) 착이온의 평형 및 착이온과 oxalate이온간의 치환반응에 미치는 압력영향

박유철,이동철 慶北大學校 1981 論文集 Vol.32 No.-

The chemical equilibrium of cis-aquo-bis(ethylenediamine)cobalt(Ⅲ) complex ion and the kinetics of nucleophilic substitution reaction between the complex and oxalate ions have been spectrophotometrically investigated in a aqueous solution. Measurements of the optical density at wave lengths 490, 510 and 520 nm were carried out to determine the values of the equilibrium constants for the reactions: [Co(en)_2(H_2O)_2]^3+??[Co(en)_2(OH)(H_2O)^2+ +H^=; K_1 [Co(en)_2(OH)(H_2O)^2+??[Co(en)_2(OH)_2]^+ +H^+; K_2 At 20℃ and in sodium nitrate media of unit ionic strength the equilibrium constants for these reactions, K_1 and K_2 were 7.36×10 exp(-6) and 3.81×10 exp(-10) respectively. The anation reaction between complex and oxalate ions studied as a funtion of total oxalate ion concentrations, [Ox]_T were carried out at a various pressures (1-1000bar) and 60℃. By analysis of pseudo-first ordor rate constants observed as [Ox]_T, it was found that the change of volume in the process ion-pair formation, ΔV_5 is 8.3㎤/mole and that in the process of rate determining step, ΔV_a^≠=5.7㎤/mole. In addition, the rate law of anation reaction in a wide range of pH was described. And by the change of volume determined the mechanism of anation was discussed.

산성수욕액에서 cis-aquo-bis(ethylenediamine)cobalt(Ⅲ) 착이온의 평형 및 착이온과 oxalate 이온간의 치환반응에 미치는 압력영향

박유철,이동철 慶北大學校 物理化學硏究所 1984 硏究論文集 Vol.5 No.-

The chemical equilibrium of cis-aquo-bis(ethylenediamine)cobalt(Ⅲ) complex ion and the kinetics of nucleophilic substitution reaction between the complex and oxalate ions have been spectrophotometrically investigated in a aqueous solution. Measurements of the optical density at wave lengths 490, 510 and 520 nm were carried out to determine the values of the equilibrium constants for the reactions: 〔Co(en)_2(H_2O)_2〕^3+ ⇔ 〔Co(en)_2(OH)(H_2O)〕^2+ + H^+; K_1 〔Co(en)_2(OH)(H_2O)〕^2+ ⇔ 〔Co(en)_2(OH)_2〕^+ + H^+; K_2 At 20℃ and in sodium nitrate media of unit ionic strength the equilibrium constants for these reactions, K_1 and K_2 were 7.36×10 exp(-6) and 3.81×10 exp(-10) respectively. The anation reaction between complex and oxalate ions studied as a function of total oxalate ion concentrations, 〔Ox〕_T were carried out at a various pressure (1-1000bar) and 60℃. By analysis of pseudo-first ordor rate constants observed as 〔Ox〕_T, it was found that the change of volume in the precess ion-pair formation, ΔV_5 is 8.3㎤/mole and that in the precess of rate determining step, ΔV_a^≠=5.7㎤/mole. In addition, the rate law of anation reaction in a wide range of pH was described. And by the change of volume determined the mechanism of anation was discussed.

아세톤-물혼합용매에서 trans-[Co(en)_2Cl_2]^+ 및 trans-[Co(1,3-pn)_2Cl_2]^+ 이온의 가용매 분해 반응에 미치는 압력과 용매조성의 영향

朴裕哲,卞鍾轍,金京美,趙靈濟 慶北大學校 物理化學硏究所 1985 硏究論文集 Vol.6 No.-

The rates of solvolysis of trans-[Co(en)_2Cl_2]^+ and trans-[Co(1,3-pn)_2Cl_2]^+, in which en and 1,3-pn are ethylenediamine and 1,3-propylenediamine resepectively, have been investigated using conductometric and spectrophotometric methods at various pressures up to 2,000 bar in acetone-water mixture. The activation volumes obtained from the pressure effect on rate constants were small and positive values in both complexes of trans-[Co(en)_2Cl_2]^+ and trans-[Co(1,3-pn)_2Cl_2]^+. These results are discussed in terms of dissociative mechanism (S_NI) for the solvolysis of both complexes. The importance of solvent composition on the reaction is further confirmed by application of a free energy cycle. It is concluded from the free energy cycle that the effect of solvation of transition state in the solvolysis of both complexes is more dominant than that of initial state. In addition to that, it is shown that the character of S_NI is further increased with increasing the content of acetone.

물-에탄올 혼합용매에서 Co(Ⅱ)-THPP(THPP: tetrakis-(ortho-hydroxy)phenylporphyrin) 착화합물 생성반응

朴裕哲,孫景千 慶北大學校 自然科學大學 1987 自然科學論文集 Vol.5 No.-

5, 10, 15, 20-tetrakis(ortho-hydroxy)phenylporphyrin(THPP) was synthesized by refluxation of (ortho-hydroxy)benzaldehyde with pyrrol in propionic acid. The protonation constants(K^H) of THPP were studied by spectrophotometric method at λ=540nm. From the results of this experiment, it showed that THPP exists in three ionic speces, THPPH_3^+, THPPH_2 and THPPH^- in pH=2∼11. The values of the protonation constants were THPPH^-+H^+??THPPH_2 ; K_2^H=3.421×10^5 THPPH_2+H^+??THPPH_3 ; K_3^H=1.887×10^9 The rate constants of the complex formation reaction of Co(Ⅱ) with THPP were studied in ionic strength of 0.1M NaCIO_4 at pH=3.5. The rate constants(sec^-1) were 1.440×10^-4, 1.380×10^-3, 5.400×10^3 and 1.220×10^-2 at T=25, 30, 35 and 40℃, respectively. The activation parameters, ΔH^≠ and ΔS^≠ were 53 kcal·mol^-1 and 102cal·mol^-1·deg^-1, respectively.

철(Ⅱ)에 依한 클로로코발트(Ⅲ) 錯物의 還元反應에 關한 硏究

朴裕哲,吳相午 慶北大學校 文理科大學 1974 文理學叢 Vol.2 No.-

The kinetics and mechanisms for the reduction of cis-[Co(NH_3)_4H_2OCl]^+2 complexion by Fe^+2 have been investigated. The rate constants in various Fe^+2 concentration an the activation parameters of Co(Ⅲ)-Fe(Ⅱ) reaction have been measured at 14.1℃ and ionic strength of 1.0. It is estimated from a result of the entropy of activation (-43cal mole^-1 deg^-1 at 14.1℃) that the effect upon the surrounding solvent-the electrostriction effect-is a prime factor in determining the entropy of activation in this reaction. And all kinetic experiments were run under pseudo-first-order conditions with respect to Fe^+2 concentration. The reaction order in Fe^+2 varied from first order to zero order.