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).

이온 센서

이흥락 경북대학교 센서기술연구소 1996 센서기술 Vol.3 No.1

용해기체 분석용 기체 감응막 이온선택성 전극 (제 1 보). 관형 PVC 막 pH 전극을 이용한 아질산이온의 연속·자동화 정량

이흥락,윤종훈,Heung Lark Lee,Jong Hoon Yun 대한화학회 1989 대한화학회지 Vol.33 No.4

기체 감응막전극을 이용하여 수용액 중의 아질산이온을 연속${\cdot}$자동화법으로 정량하는 방법을 개발하였다. 이 방법에서 최종검출기로 쓴 이온선택성 전극은 관형 PVC막 pH 전극이었다. 장치계의 최적조건에서 구한 아질산이온 표준시료에 대한 전극의 감응기울기는 63.5mV/decade 이었으며, 직선감응 범위는 $2.5{\times}10^{-4}\; M{\sim}7.5 {\times} $10^{-2}$M 이었고, 검출한계는 $8.0{\times} 10^{-5}$M이었다. 이 방법은 다른 정량법보다 산성기체종의 방해를 적게 받을 뿐만 아니라 정량에 필요한 시간도 훨씬 단축할 수 있었다. A continuous-automated method for the determination of nitrite ion using gas-sensing membrane electrode was developed. The pH electrode of tubular PVC membrane type was used as a detector of this system. The slope of linear response of the electrode measured at optimum conditions for the continuous-automated determination of nitrite ion was 63.5 mV/decade. The concentration range of linear response and detection limit were 2.5 ${\times}10^{-4}{\sim}\;7.5{\times}10^{-2}$M and $8.0{\times}10^{-5}$M, respectively. This detection system was not only less interfering to acidic gas species than other methods but also less time consumable for determination.

효소반응기와 암모늄이온선택성 전극을 이용한 L-Glutamic Acid의 연속정량

이흥락,윤종훈,정동숙 경북대학교 센서기술연구소 1992 센서技術學術大會論文集 Vol.3 No.1

용해기체 분석용 기체감응막 이온선택성 전극 (제 4 보) 관형 PVC막 pH전극을 이용한 황화이온의 연속 · 자동화 정량

이흥락,배준웅,오상협,Lee Heung Lark,Bae Zun Ung,Oh Sang-Hyub 대한화학회 1992 대한화학회지 Vol.36 No.5

황화이온검출기로서 2가지 형태의 연속 flow-through 전극계의 분석적 감응성질을 조사하고, 최적조건에서 그들의 감응특성을 직접 비교하였다. 두 검출계에 있어서 측정한 봉우리전위를 황화이온농도의 대수값과 관련지웠으며, 적어도 시간당 20개의 시료를 정량할 수 있었다. pH전극법에서는 투석기를 지나 흘러가는 recipient stream의 pH를 측정하였다. 장치는 연속흐름형의 기체투석기가 관형 polymer 막전극과 연결되도록 설계되어 있다. 이 방법의 최적실험조건은 recipient $5.0 {\times} 10^{-5} M NaOH + 5.0 {\times} 10^{-3} M$ NaCl과 diluent 0.10M $H_2SO_4$이며, recipient stream, diluent stream 및 시료의 유속은 모두 1.0ml/min이다. 황화이온 전극법에서는 시판하는 황화이온선택성 전극을 flow-through cell 속의 황화이온을 검출하는 데에 썼다. 이 방법의 최적실험조건인 황화이온 산화방지 완충제(1.0M NaOH 용액에 3.5g 아스코르브산과 7.6g $Na_2EDTA$를 용해)와 시료의 유속은 각각 1.4 ml/min와 1.0 ml/min이다. The analytical response properties of two types of continuous flow-through electrode system as fulfide ion detectors are examined and directly compared their reponse characteristics under the optimal conditions. In both detection systems, observed peak potentials are logarithmically related to the sulfide ion concentration and at least twenty samples per hour can be determined. In the pH electrode method, the pH of the flowing recipient stream leaving the dialyzer was monitored. The designed system involves the use of continuous flow gas dialyzer in conjunction with the tubular polymer membrane electrode. In this method, optimal experimental conditions are recipient of mixture of $5.0 {\times} 10^{-5} M NaOH + 5.0 {\times} 10^{-3} M$ NaCl and diluent of 0.10 M $H_2SO_4$, and all flow rates of recipient stream, diluent stream, and sample are 1.0 ml/min. In the sulfide ion electrode method, a commercially available sulfide ion-selective electrode was used to detect sulfide ion in the flow-through cell. The optimal flow rates of sulfide anti-oxidant buffer (3.5 g ascorbic acid and 7.6 g $Na_2EDTA$ dissolved in 1.0 M NaOH solution 1 l) and sample were 1.4 ml/min and 1.0 ml/min, respectively.

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.

새로운 효소반응기를 이용한 guanine의 연속·자동화 정량

李興洛,裵俊雄,梁昇泰,金榮喆 경북대학교 센서기술연구소 1991 센서技術學術大會論文集 Vol.2 No.1

Continuous automated system for the determination of guanine was developed. The system was composed of enzyme reactor, gas-dialyzer and tubular PVC-nonactin membrane ammonium ion-selectiveindicator electrode. The enzyme reactor was constructed to packed-bed form which filled with glass beads(pore diameter 500 Å, particle size 125 ~ 177 μm), which immobilized enzyme on, in teflon tube(2 mm I.D., 20 cm length). The response characteristics of the indicator electrode was superior to those of ammonia gas-sensing electrode. Guanine in 0.1 M tris-HCl buffer solution could be determined by using this system. The linear response range, response slope and detection limit for the determination of guanine in this buffer solution were found to be 1.0x10^(-3) ~ 1.0x10^(-1) M, 30.69 mV/decade and 5.8x10^(-4) M from the plot of cell emf vs. guanine concentration, respectively.

鹽析抽出法에 의한 Acetonitrile-물 混合溶液으로부터 鐵의 分光光度法的 定量

李興洛 慶北大學校 1981 論文集 Vol.32 No.-

Thirty compounds of one hundred and thirteen ones tested were possible salting-out agents for the separation of acetonitrile from aqueous solutions. Ammonium sulfate was superior in which they were efficient salting-out agents, its pH could be easily adjusted. The ferric acetylacetonate chelate was successfully extracted from ammonium sulfate solution into the acetonitrile phase. The absorbance of the organic phase was measured at 435 nm, which was the absorption maximum in the visible region. The effect of concentration of salting-out agent ammonium sulfate and extraction reagent acetylacetone on the extractability, the relation between pH of the aqueous phase and the extractability of erric acetylacetonate, and the calibration curve for the determination of iron(Ⅲ) have been evaluated and compared with the experimentally determined values.