• 제목/요약/키워드: Kinetic determination

검색결과 121건 처리시간 0.028초

Determination of the Frumkin and Temkin Adsorption Isotherms of Hydrogen at Nickel/Acidic and Alkaline Aqueous Solution Interfaces Using the Phase-Shift Method and Correlation Constants

  • Chun, Jang-H.
    • 전기화학회지
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    • 제15권1호
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    • pp.54-66
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    • 2012
  • The phase-shift method and correlation constants, which are unique electrochemical impedance spectroscopy techniques for studying the linear relationship between the phase shift ($90^{\circ}{\geq}-{\varphi}{\geq}0^{\circ}$) vs. potential (E) behavior for the optimum intermediate frequency ($f_o$) and the fractional surface coverage ($0{\leq}{\theta}{\leq}1$) vs. E behavior, are proposed and verified to determine the Frumkin, Langmuir, and Temkin adsorption isotherms and the related electrode kinetic and thermodynamic parameters. At Ni/0.5 M $H_2SO_4$ and 0.1M LiOH aqueous solution interfaces, the Frumkin and Temkin adsorption isotherms (${\theta}$ vs. E) of H for the cathodic hydrogen ($H_2$) evolution, interaction parameters (g), equilibrium constants (K), standard Gibbs energies (${\Delta}G^0_{\theta}$) of H adsorption, and rates of change (r) of ${\Delta}G^0_{\theta}$ with ${\theta}$ have been determined using the phase-shift method and correlation constants. A lateral repulsive interaction (g>0) between the adsorbed H species appears. The value of K in the alkaline aqueous solution is much greater than that in the acidic aqueous solution.

A Chemometric Aided UV/Vis Spectroscopic Method for Kinetic Study of Additive Adsorption in Cellulose Fibers

  • Chal, Xin-Sheng;Zhou, Jinghong;Zhu, Hongxiang;Huang, Xiannan
    • 한국펄프종이공학회:학술대회논문집
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    • 한국펄프종이공학회 2006년도 PAN PACIFIC CONFERENCE vol.1
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    • pp.137-140
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    • 2006
  • This paper describes a technique combining chemometrics with UV spectroscopy for the determination of the concentra tions of two tissue additives (i.e., wet strength and softening agents) in a cellulose fiber containing solution. In single as ent solutions, the concentration of the additive can be measured by UV spectroscopy at the wavelength where the species having absorption. For a binary (i.e., containing two additives) solution system, the spectral characterization is very complicated. However, if aided by a chemometrical calibration technique, each additive in the binary solution can be quantified simultaneously. The present method is very rapid and simple, it can easily perform a continuous measurement in the changes in the additives' concentration after fiber addition, and therefore this becomes a valuable tool for the adsorption kinetics study of chemical additives onto the cellulose fibers. The time-dependent adsorption behaviors of the wet-strength, softening agent, and their both on fiber were also presented.

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부타디엔 고무로 결합된 탄소반죽 바이오센서를 이용한 과산화수소의 전기화학적 정량 (Electrochemical determination of hydrogen peroxide using carbon paste biosensor bound with butadiene rubber)

  • 윤길중
    • 분석과학
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    • 제23권5호
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    • pp.505-510
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    • 2010
  • 톨루엔에 녹인 폴리부타디엔을 탄소가루의 결합재로 사용하였을 때, 탄소반죽은 전극 제작 후 용매 증발에 의하여 기계적 물성을 보였으며, 이 성질은 탄소반죽전극 실용화의 선행조건을 충족시키는 것이었다. 부타디엔 고무를 결합재로 사용하여 새로운 효소전극을 제작하고, 그것이 정량적인 전기화학적 행동을 보이는지 확인하기 위하여 여러 가지 전기화학 속도론적 파라메터 즉 대칭인자, 교환전류밀도, 이중층의 축전용량, 시간상수, 최대전류, Michaelis 상수 등을 구하였다. 이 결과들은 부타디엔 고무가 탄소반죽전극 실용화에 추천할 만한 위한 결합재임을 보여 주는 것이었다.

LDPE 광분해 반응의 속도 상수 결정 (Determination of Photodegradation Rate Constant of LDPE)

  • 김현주;정일현;홍인권;이재동
    • 공업화학
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    • 제5권4호
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    • pp.637-645
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    • 1994
  • 254nm 이상의 파장을 갖는 자외선 램프가 설치된 광조사장치를 이용하여 상용성 저밀도 폴리에틸렌을 100시간 동안 광분해시켰다. 20여 단계가 넘는 복잡한 광분해 반응단계 중에서 필름의 물성을 크게 저하시키는 중요 3단계로 정하고 간단하게 변수를 정의하여 반응 모델식을 설정하였으며, IR스펙트럼을 이용하여 광분해 과정중에 생성되는 과산화물과 카르보닐기의 흡광도를 시간의 함수로 해석하여 각 단계에서의 속도상수와 활성화 에너지를 구하였다. 이들 자료로부터 논란이 되고 있는 반응 메카니즘을 정리할 수 있었으며 속도 결정 단계를 정하였다.

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Determination of the Frumkin and Temkin Adsorption Isotherms of Underpotentially Deposited Hydrogen at Pt Group Metal Interfaces Using the Standard Gibbs Energy of Adsorption and Correlation Constants

  • Chun, Jinyoung;Jeon, Sang K.;Chun, Jang H.
    • 전기화학회지
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    • 제16권4호
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    • pp.211-216
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    • 2013
  • At Pt(111), Pt(100), Pt, and Rh interfaces, the Frumkin adsorption isotherm of underpotentially deposited hydrogen (UPD H) and related electrode kinetic data are determined using the standard Gibbs energy of adsorption. The Temkin adsorption isotherm of UPD H correlating with the Frumkin adsorption isotherm of UPD H is readily determined using the correlation constants between the Temkin and Frumkin or Langmuir adsorption isotherms. At the Pt(111), Pt(100), Pt, and Rh interfaces, the lateral repulsive interaction between the UPD H species is interpreted using the interaction parameter for the Frumkin adsorption isotherm. The lateral repulsive interaction between the UPD H species at the Pt(111), Pt(100), Pt, and Rh interfaces is significantly different from the lateral attractive interaction between the overpotentially deposited hydrogen (OPD H) species at Pt, Ir, and Pt-Ir alloy interfaces.

Polymer (Polydimethylsiloxane (pdms)) Microchip Plasma with Electrothermal Vaporization for the Determination of Metal Ions in Aqueous Solution

  • Ryu, Won-Kyung;Kim, Dong-Hoon;Lim, H.B.;Houk, R.S.
    • Bulletin of the Korean Chemical Society
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    • 제28권4호
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    • pp.553-556
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    • 2007
  • We previously reported a 27.12 MHz inductively coupled plasma source at atmospheric pressure for atomic emission spectrometry based on polymer microchip plasma technology. For the PDMS polymer microchip plasma, molecular emission was observed, but no metallic detection was done. In this experiment, a lab-made electrothermal vaporizer (ETV) with tantalum coil was connected to the microchip plasma for aqueous sample introduction to detect metal ions. The electrode geometry of this microchip plasma was redesigned for better stability and easy monitoring of emission. The plasma was operated at an rf power of 30-70 W using argon gas at 300 mL/min. Gas kinetic temperatures between 800-3200 K were obtained by measuring OH emission band. Limits of detection of about 20 ng/mL, 96.1 ng/mL, and 1.01 μ g/mL were obtained for alkali metals, Zn, and Pb, respectively, when 10 μ L samples in 0.1% nitric acid were injected into the ETV.

Apoptotic Cell Death in TrkA-overexpressing Cells: Kinetic Regulation of ERK Phosphorylation and Caspase-7 Activation

  • Jung, Eun Joo;Kim, Deok Ryong
    • Molecules and Cells
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    • 제26권1호
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    • pp.12-17
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    • 2008
  • The TrkA tyrosine kinase is activated by autophosphorylation in response to NGF, and plays an important role in cell survival, differentiation, and apoptosis. To investigate its role in cell fate determination, we produced stable TrkA-inducible SK-N-MC and U2OS cell lines using the Tet-On system. Interestingly, TrkA overexpression induced substantial cell death even in the absence of NGF, by stimulating ERK phosphorylation and caspase-7 activation leading to PARP cleavage. TrkA-mediated cell death was shown by the annexin-V binding assay to be, at least in part, apoptotic in both SK-N-MC and U2OS cells. Furthermore, the truncated form (p18) of Bax accumulated in the TrkA-induced cells, suggesting that TrkA induces mitochondria-mediated apoptosis. NGF treatment augmented the cell death induced by TrkA overexpression. This TrkA-induced cell death was blocked by the tyrosine kinase inhibitors, K-252a and GW441756. Moreover, TrkA overexpression inhibited long-term proliferation of both the neuronal SK-N-MC cells and the non-neuronal U2OS cells, suggesting a potential role of TrkA as a tumor suppressor.

Removal of ciprofloxacin from aqueous solution by activated carbon prepared from orange peel using zinc chloride

  • Koklu, Rabia;Imamoglu, Mustafa
    • Membrane and Water Treatment
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    • 제13권3호
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    • pp.129-137
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    • 2022
  • In this study, the removal of Ciprofloxacin (CPX) from aqueous solutions was investigated by a new activated carbon adsorbent prepared from orange peel (ACOP) with chemical activation using ZnCl2. The physicochemical properties of orange peel activated carbon were characterized by proximate and ultimate analysis, scanning electron microscopy, BET surface area determination and Fourier transformation infrared spectroscopic studies. According to Brunauer-Emmett-Teller isotherm and non-local-density functional theory, the cumulative surface area, pore volume and pore size of ACOP were determined as 1193 m2 g-1, 0.83 cc g-1 and 12.7 Å, respectively. The effects of contact time, pH, temperature and ACOP dose on the batch adsorption of CPX were studied. Adsorption equilibrium data of CPX with ACOP were found to be compatible with both the Langmuir and Freundlich isotherms. CPX adsorption capacity of ACOP was calculated as 181.8 mg g-1 using Langmuir isotherm. The CPX adsorption kinetics were found to be harmonious with the pseudo-second-order kinetic model. Conclusively, ACOP can be assessable as an effective adsorbent for the removal of ciprofloxacin (CPX) from aqueous solutions.

새로운 지시약 반응에 의해 극미량 수준의 망간 측정을 위한 촉매 반응의 분광 광도 측정법 (Catalytic Spectrophotometry for the Determination of Manganese at Trace Levels by a Novel Indicator Reaction)

  • Gurkan, Ramazan;Caylak, Osman
    • 대한화학회지
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    • 제54권5호
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    • pp.556-566
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    • 2010
  • 새로운 동적 분광 광도 측정법은 천연의 물 샘플에서 망간(II)의 측정을 위해 개발되었다. 그 방법은 620 nm에서 활성화제로서 nitrilotriacetic acid (NTA)를 사용하면서 $KIO_4$에 의한 갈로시아닌(Gallocyanin)의 산화와 함께 망간(II)의 촉매 효과에 기초했다. 최적조건은 갈로시아닌(Gallocyanin) $4.00{\times}1^{-5}\;M$, $KIO_4$ $1.00{\times}10^{-4}\;M$, NTA $1.00{\times}10^{-4}\;M$, pH = 3.50인 0.1 M HAc/NaAc 완충용액, 5분의 반응시간 그리고 $30^{\circ}C$의 온도에서 얻어졌다. 최적조건 하에서 제안된 방법은 $0.1\;-\;4.0\;ng\;mL^{-1}$의 범위에서 망간(II)의 측정을 허용했고 $0.025\;ng\;mL^{-1}$이하의 검출한계를 가지고 있다. 표준 망간(II) 용액을 측정하는 것에서 회수율은 98.5 - 102% 범위에 있다. 그리고 상대표준편차(RSD)는 0.76 - 1.25%의 범위에 있다. 새롭게 개발된 동적 방법은 약간의 주위의 물과 만족할 만한 결과를 갖는 JAC-0031의 공인된 표준 기준 강물 샘플 둘 다에서 망간(II)의 측정에 성공적으로 응용되었다. 또한, 얼마 안 되는 양이온과 음이온은 망간(II)의 측정을 방해한다. 다른 촉매-동적 방법과 기기적 방법과 비교했을 때, 제안된 동적 방법은 상당히 좋은 선택성과 감도, 낮은 가격, 저렴함, 낮은 검출한계와 신속함을 보인다. 상대적으로 낮은 염분을 갖는 진짜 물 샘플과 병으로 된 마시는 물, 차갑고 뜨거운 용천수, 호수, 강물 샘플 같은 복잡한 모체들에 적용하는 것은 쉽고 성공적으로 적용될 수 있다.

Determination of Adsorption Isotherms of Hydrogen on Zirconium in Sulfuric Acid Solution Using the Phase-Shift Method and Correlation Constants

  • Chun, Jang-H.;Chun, Jin-Y.
    • 전기화학회지
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    • 제12권1호
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    • pp.26-33
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    • 2009
  • The phase-shift method and correlation constants, i.e., the unique electrochemical impedance spectroscopy (EIS) techniques for studying the linear relationship between the behavior ($-{\varphi}$ vs. E) of the phase shift ($90^{\circ}{\geq}-{\varphi}{\geq}0^{\circ}$) for the optimum intermediate frequency and that ($\theta$ vs. E) of the fractional surface coverage ($0{\leq}{\theta}{\leq}1$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at noble metal (alloy)/aqueous solution interfaces. At a Zr/0.2 M ${H_2}{SO_4}$ aqueous solution interface, the Frumkin and Temkin adsorption isotherms ($\theta$ vs. E), equilibrium constants (K = $1.401{\times}10^{-17}\exp(-3.5{\theta})mol^{-1}$ for the Frumkin and K = $1.401{\times}10^{-16}\exp(8.1{\theta})mol^{-1}$ for the Temkin adsorption isotherm), interaction parameters (g = 3.5 for the Frumkin and g = 8.1 for the Temkin adsorption isotherm), rates of change of the standard free energy (r = $8.7\;kJ\;mol^{-1}$ for g = 3.5 and r = $20\;kJ\;mol^{-1}$ for g = 8.1) of H with $\theta$, and standard free energies ($96.13{\leq}{\Delta}G^0_{\theta}{\leq}104.8\;kJ\;mol^{-1}$ for K = $1.401{\times}10^{-17}\exp(-3.5{\theta})mol^{-1}$ and $0{\leq}{\theta}{\leq}1$ and ($94.44<{\Delta}G^0_{\theta}<106.5\;kJ\;mol^{-1}$ for K = $1.401{\times}10^{-16}\exp(-8.1{\theta})mol^{-1}$ and $0.2<{\theta}<0.8$) of H are determined using the phase-shift method and correlation constants. At 0.2 < $\theta$ < 0.8, the Temkin adsorption isotherm correlating with the Frumkin adsorption isotherm, and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are probably the most accurate, useful, and effective ways to determine the adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at highly corrosion-resistant metal/aqueous solution interfaces.