金屬이온의 폴라로그래프적 파라미터에 미치는 影響

李興洛,배준웅 慶北大學校 物理化學硏究所 1982 硏究論文集 Vol.3 No.-

The dependence of polarographic parameters on temperature and pressure for reduction of 5×10 exp (-4) molarity of CdCl_2 and NiCl_2 in 0.05 molarity of KCl aqueous solution at the dropping mercury electrode have been discussed. In this paper the temperature was varied from 25℃ to 35℃ and the pressure was ranging from 1 atmosphere to 1,500 atmospheres. With increasing pressure the half-wave potentials of the cadmium ion are shifted markedly to more negative values, 62 millivolts at 25℃ and 64 millivolts at 30℃. But in the case of the nickel ion the reduction potentials are changed to more positive values, 66-54 millivolts at 30-35℃, respectively, with pressure. And the reduction half-wave potentials for two metal ions are shifted to more positive values with increasing temperature. The diffusion currents of all metal ions are also observed to be sensitive to pressure and temperature. With increasing pressure and temperature the limiting currents of two metal ions become considerably larger, in keeping with the theory on the change of the physical properties, such as the compressibility, the viscosity, the dielectric constant, and the equivalent conductance etc., of 0.05M KCl aqueous solition. The slopes of the linear E vs. log(i_d-i/i) relation become much larger with increasing pressure, indicating more irreversible reduction. But the change of the log plot slopes is also observed to be less sensitive to temperature. The reduction currents are found to be diffusion-controlled. It is because the average temperature coefficient of the limiting currents over the range of temperatures from 25℃ to 35℃ are between about 1.6 and 1.7 percent/deg for two metal ions. Comparing the drop time of the dropping mercury electrode to the value at 1 atmosphere it is much longer with pressure and the electrocapillary maximum zeros are shifted to more negative potential values during the pressure change from 1 atmospher to 600 atmospheres.

Tubular Polymer막형 pH감응전극을 이용한 아질산이온의 연속·자동화정량

李興洛,尹鍾勳 慶北大學校 自然科學大學 1985 自然科學論文集 Vol.3 No.-

An electrode-based automated method for a rapid determination of nitrite ion is described. The system desinged utilizes a novel tubualr flow-throught PVC-tridodecylamine membrane electrode to sense hydrogen ion formed in a recipient stream as the sample passes through a gas dialyzer. Peak poentials observed are related to the nitrite ion concentration logarithmically. At least 30 samples per hour can be dtermined. Thorough investigations on the optimization of the system variables, such as flow rates of a diluent stream and a recipient stream, pH of a recipient stream, the concentration of the recipient electrolyte, etc. are described.

메탄올-물 혼합용매 중에서 1-(2-pyridylazo)-2-naphthol과 4-(2-pyridylazo-resorcinol의 폴라로그래프적 파라미터에 미치는 압력의 영향

이흥락,배준웅,윤종훈,서무룡 慶北大學校 物理化學硏究所 1983 硏究論文集 Vol.4 No.-

滴下水銀電極에서 메탄올-물의 混合溶液中에서 2.0 × 10 exp(-4) M의 1-(2-pyridylazo)-2-naphthol(PAN)과 5.0 × 10 exp(-4) M의 4-(2-pyridylazo)-resorcinol(PAR)의 還元에 대한 溫度와 壓力의 效果를 조사하였다. 이 實驗에서 溫度는 25℃에서 30℃로 변화시켰으며 壓力은 1氣壓에서 1,800氣壓까지 바꾸었다. 壓力이 증가함에 따라 半波電位는 陰電位쪽으로 이동하였고, 擴散電流는 溫度와 壓力에 따라 민감하게 변하였다. 곧 1氣壓에서 약 1,000氣壓까지는 壓力이 증가할수록 限界電流가 상당히 커지다가 1,000氣壓 이상에서는 오히려 줄어드는 傾向이 있었다. E와 log〔(i_d - i / i〕의 關係를 plot하여 얻은 直線의 기울기는 壓力이 증가함에 따라 더욱 증가하였다. 이것은 壓力 增加에 따라 還元反應이 더욱 非可逆的으로 됨을 뜻한다. 두 減極劑는 모든 實驗壓力 範圍에서 擴散支配的임을 알 수 있다. 이것은 平均溫度係數, l/i · di/dt × 100의 값이 1.1과 2.1%/deg 사이에 있기 때문이다. 實驗壓力(1∼1,800 atm) 範圍內에서는 限界電流와 濃度 사이에 直線性이 잘 성립하였다. The dependance of polarographic parameters on pressure and temperature for reduction of 2.0×10 exp(-4) molarity of 1-(2-pyridylazo)-2-naphtol (PAN) and 5.0×10 exp(-4) molarity of 4-(2-pyridylazo)-resorcinol (PAR) in buffered methanol-water mixed solution at the dropping mercury electrode, have been discussed. In this experiment the temperature was varied from 25℃ to 30℃ and the pressure was ranging from 1 atmosphere to 1,800 atmospheres. With increasing pressure the reduction half-wave potentials are shiffed to the more negative potentials. The diffusion currents of two depolarizers are found to be sensitive to pressure and temperature. With increasing the pressure from 1 atmosphere to about 1,000 atmospheres the limiting currents of two depolarizers become considerably larger, but above 1,000 atmospheres the limiting currents are getting smaller. The slopes of the linear E vs. log{(i_d-i)/i} relation become much larger with increasing with increasing pressure, indicating the more irreversible reduction. The reduction currents of two depolarizers are found to be diffusion controlled over all ranges of pressure. It is because the average temperature coefficients, 1/i·di/dt×100 of two depolarizers are between about 1.1 and 2.1 percent/deg. The linear relationship between limitting currents and the concentration of two depolarizers is good agreement over the range of pressure (1atm. ∼ 1,800atm).

착물 CoCIL(en)_2^+, ++의 산가수분해에 미치는 압력의 영향

이흥락 慶北大學校 物理化學硏究所 1981 硏究論文集 Vol.1-2 No.-

The hydrolysis constants of complex cis-〔CoCl_2(en)_2〕Cl, cis-〔CoCl(en)_2H_2O〕SO_4, and trans-〔CoCl(NO_2)(en)_2〕NO_3 in acidic (0.1 molarity of 〔H^+〕) aqueous solution have been measured at various pressures and temperatures. The aquation rate constants were increased with increasing temperature and with decreasing pressure. The activation columes were detemined from the stope and intercept of the plot of (∂lnk_p/∂_p)T vs. pressure variation at constant temperature. The other activation parameters, such as activation enthalpy, activation entropy, and activation energy, were estimated from the plot of ln(K_p/T) vs. T^-1 variation at constant pressure. The positive activation parameters (ΔV^≠, ΔS^≠) show that the complex ions released ligand Cl^- at the activated state. And the reaction mechanism were controlled by the activation enthalpy.

金屬이온의 폴라로그래프法的 파라미터에 미치는 壓力의 影響 Ⅱ

李興洛,裵俊雄,尹鐘勳 慶北大學校 1985 論文集 Vol.39 No.-

The dependence of polarographic parameters on the pressure for the reduction of Ni(Ⅱ)→Ni(0), Zn(Ⅱ)→Zn(0), Bi(Ⅲ)→Bi(0), and Sb(Ⅲ)→Sb(0) in 0.05 M KCI, 0.1 M KCI, 1 M HNO_3, and 1 M HCI solution, respectively, at dropping mercury electrode has been discussed. In this experiment the temperature was varied from 25℃ to 35℃ and the pressure was ranging from 1 atmosphere to 1,800 atmospheres. With increasing the pressure the reduction half-wave potentials of nickel ion and bismuth one are shifted to more positive values, but zinc ion and antimony one are shifted to more negative ones. The diffusion currents of all metal ions except zinc ion become considerably larger with increasing the pressure, in keeping with the theory on the change of physical properties, such as the compressibility, the viscosity, the dielectric constant, and the equivalent conductance, etc. of the electrolytic solution. The slopes of the linear relationship between E and log (i_d-i)/i become much larger with increasing the pressure, indicating more irreversible reduction reactions. The temperature coefficients observed over the range of the temperature from 25℃ to 35℃ are inconsistent with the pressure.

새로운 효소반응기를 이용한 Sucrose의 전류법적 정량

이흥락,양윤형,추고연 경북대학교 센서기술연구소 1994 센서技術學術大會論文集 Vol.5 No.1

The continuous amperometric determination method of sucrose using new enzyme reactors and the glassy carbon working electrode was developed. The principle of measurements was based on the amperometric detection of ferrocyanide ion formed when glucose to be inverted by invertase reactor was oxidized specifically by the GO_(x)/MUT enzyme reactor immobilized glucose oxidase and mutarotase, in the presence of ferricyanide ion as an electron acceptor. The optimal conditions were as follows: applied potential, 0.70 volt vs. silver/silver chloride reference electrode(sat'd KCl); flow rate of carrier solution(1.0 x 10^(-2) M K_(3)Fe(CN)_(6) + 0.80 M phosphate buffer of pH 7.3), 0.18 ml/min; injection volume of sample solution, 20 μl and temperature of enzyme reactors, 30 ℃.

이온 센서

이흥락 경북대학교 센서기술연구소 1996 센서기술 Vol.3 No.1

효소센서에 의한 생체관련 화합물의 정량1 : 연속자동화법과 이온선택성전극에 의한 아미노산류의 정량분석

李興洛,裵俊雄,梁昇泰,孫豪振 경북대학교 센서기술연구소 1990 센서技術學術大會論文集 Vol.1 No.1

효소반응기와 관형 PVC막 암모늄이온선택성 전극을 써서 연속·자동화법으로 아미노산류를 정량하는 방법을 연구하였다. 연속·자동화 장치는 효소반응기와 기체투석기 및 지시전극으로 구성되어 있다. 효소반응기는 효소를 고정화시킨 나일론-6 입자(42-48 mesh)를 teflon관(안지름 2 mm, 길이 30 cm)에 채워서 packed-bed의 형태로 만들었다. 이 효소반응기는 나일론-6관의 내면에 효소를 결합시킨 효소반응기와 효소전극보다 분해율이 크고,지시전극의 감응특성이 암모니아기체감응 전극보다도 우수하므로 연속·자동화 정량계의 감응특성이 개선되었다. 생체시료인 혈청 속의 아미노산 정량에 이 방법을 적용하여 보았더니 L-asparagine과 L-glutamine의 정량 가능한 농도범위는 각각 1.0 X 10^(-5) ~ 2.8 X 10^(-) M 와 6.5 X 10^(-5) - 2.4 X 10^(-3) M 이었다. Continuous automated system with reactor and tubular PVC-nonactin membrane ammonium ion-selective electrode for the deternination of amino acid species was studied. The system was composed of enzyme reactor, gas dialyzer and indicator electrode. The enzyme reactor was constructed to packed-bed form which filled with nylon-6 bead(42-48 mesh), immobilized enzyme on, in teflon tube(2 mm I.D., 20 cm length). The response characteristics of this system were inproved because the enzyme reactor had higher conversion efficiency than reactors made by immobilizing enzyme on inner surface of nylon-6 tube and enzyme electrodes, and the response chracteristics of the indicator electrode was superior to those of ammonia gas-sensing electrode. Amino acid species in physiological sample could be determined by using this system. The possible concentration range of determination of L-asparagine and L-glutamine in blood serum was 1.0 x 10^(-5) - 2.8 x 10^(-3) M and 6.5 x 10^(-5) - 2.4 x 10^(-3) M, respectively.

金屬이온의 폴라로그래프法的 파라미터에 미치는 壓力의 影響

李興洛,裵俊雄,尹鍾勳 慶北大學校 物理化學硏究所 1985 硏究論文集 Vol.6 No.-

滴下水銀電極에서 0.1M KCl 수용액에 포함되어 있는 單純金屬이온 In(Ⅲ), Cr(Ⅲ), Cd(Ⅱ), Pb(Ⅱ), Mn(Ⅱ), Co(Ⅱ), Tl(Ⅰ)의 還元에 대한 폴라로그래프법적 파라미터의 壓力에 따른 變化를 조사하였다. 溫度는 25℃에서 35℃까지 變化시켰으며, 壓力은 1氣壓에서 1,800氣壓까지 300氣壓 單位로 바꾸었다. 壓力이 增加함에 따라 모든 金屬이온의 還元半波電位가 8㎶/atm∼66㎶/atm 정도 陰電位쪽으로 移動하였으며, 擴散電流의 값은 1.3×10 exp(-3)%/atm∼2.3×10 exp(-2)%/atm 정도 增加하였다. 또한 壓力이 增加함에 따라 각 加電壓 E와 log(i_d-i/i)를 plot하여 얻은 直線의 기울기가 커지는 것으로부터 壓力을 增加함에 따라 還元反應의 可逆性이 減少한다는 事實을 알 수 있었다. 한편 25℃∼35℃의 범위에서 구한 溫度係數는 壓力增加에 따라 크게 변하지 않았다. The dependence of polarographic parameters on the pressure for the reduction of In(Ⅲ), Cr(Ⅲ), Cd(Ⅱ), Pb(Ⅱ), Mn(Ⅱ), Co(Ⅱ), Tl(Ⅰ) in 0.1M KCl aqueous solution at the dropping mercury electrode have been discussed. In this experiment the temperature varied from 25℃ to 35℃ and the pressure ranges from 1 atmosphere to 1,800 atmospheres. By increasing the pressure the reduction half-wave potentials of all metal ions are shifted markedly to more negative values and the diffusion currents of all metal ions become considerably larger. The slope on the linear relationship of E vs. log(id-i/i) become much larger with increase in pressure, which indicates more irreversible reduction. The temperature coefficients observed over the range of the temperature from 25℃ to 35℃ are not sensitive with increase in pressure.

TBAP의 Acetylacetone 非水溶液 中에서 金屬 Acetylacetonate의 擴散係數에 對한 펄스폴라로그래프法的 評價

李興洛 慶北大學校 1981 論文集 Vol.31 No.-

A study has been made to evaluate diffusion coefficients of metal chelates in acetylacetone as a non-aqueous solvent by pulse polarography. Solutions of acetylacetonates of manganese(Ⅲ), cobalt(Ⅲ), iron(Ⅲ), copper(Ⅱ), uranium(Ⅳ), and nickel(Ⅱ) in tetrabutylammonium perchlorate as the supporting electrolyte of varing concentrations(0.025, 0.050, 0.10, 0.15, 0.20 molarity) at 25℃ have been employed. There were three types in the change of the diffusion coefficients of metal acetylacetonates by increasing the concentration of the supporting electrolyte. Manganese(Ⅱ) acetylacetonate has decreased according to the theory. Chelates of cobalt(Ⅱ), copper(Ⅱ), uranium(Ⅳ), and nickel(Ⅱ) have showed maxima at 0.1 molarity of supporting electrolyte. But iron(Ⅱ) complex has increased by representing a sigmoid flexure.