• 제목/요약/키워드: Diffusion-influenced kinetics

검색결과 11건 처리시간 0.017초

Diffusion-Influenced Kinetics of Reactions Involving Polymers

  • Sung, Jae-Young;Park, Pyeong-Jun;Lee, Jin-Uk;Lee, Woo-Jin;Kim, Ji-Hyun;Lee, Sang-Youb
    • Bulletin of the Korean Chemical Society
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    • 제24권6호
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    • pp.843-852
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    • 2003
  • We present a brief account of the theory of diffusion-influenced kinetics of reactions involving polymers. The review will be based on the recent contributions from the authors. Both intrapolymer and interpolymer reactions are considered, and the effects of various physical factors, such as the chain length, chain stiffness, and hydrodynamic interactions, are described within a unified theoretical framework.

Memory Equations for Kinetics of Diffusion-Influenced Reactions

  • Yang, Mino
    • Bulletin of the Korean Chemical Society
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    • 제27권10호
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    • pp.1659-1663
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    • 2006
  • A many-body master equation is constructed by incorporating stochastic terms responsible for chemical reactions into the many-body Smoluchowski equation. Two forms of Langevin-type of memory equations describing the time evolution of dynamical variables under the influence of time-independent perturbation with an arbitrary intensity are derived. One form is convenient in obtaining the dynamics approaching the steady-state attained by the perturbation and the other in describing the fluctuation dynamics at the steady-state and consequently in obtaining the linear response of the system at the steady-state to time-dependent perturbation. In both cases, the kinetics of statistical averages of variables is found to be obtained by analyzing the dynamics of time-correlation functions of the variables.

작은 반응 매질에서 일어나는 촉매 반응 속도에 관한 연구 (Kinetics of Catalytic Reactions Occurring in a Small Reaction Volume)

  • 김중한;성재영
    • 대한화학회지
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    • 제52권3호
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    • pp.217-222
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    • 2008
  • 본 논문에서는 반응 매질의 부피가 촉매 반응 속도에 미치는 영향을 조사하였다. 단순하지만 정확한 모델에 대한 연구로부터 촉매 반응의 반응 속도 계수는 매질의 부피가 줄어들 수록 증가함을 알게 되었다. 평균 반응속도 상수(average reaction rate constant)는 Collins-Kimball 속도 상수의 일반화 된 형태로 얻어졌는데, 속도 상수는 부피의 효과를 보정해주는 인자를 포함하고 있다. 조사한 모델의 반응물 농도는 전통적 화학 반응론에서 예측되는 지수함수적 감소와는 상당한 차이를 보이는데 이는 기존 화학 반응속도론에서는 무시되는 반응분자 공간 분포의 비평형 확산운동(non-equilibrium diffusive dynamics)의 효과 때문이다. 반응 매질의 부피 가 유한한 점을 고려하면, 반응 시간이 충분히 오래 지났을 때, 기존의 확산지배 반응에서는 예측 되는 않는 지수 함수적 농도 감소가 얻어지는데, 그 속도 상수 역시 반응매질 크기에 의존한다.

Role of Diffusion in the Kinetics of Reversible Enzyme-catalyzed Reactions

  • Szabo, Attila;Zhou, Huan-Xiang
    • Bulletin of the Korean Chemical Society
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    • 제33권3호
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    • pp.925-928
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    • 2012
  • The accurate expression for the steady-state velocity of an irreversible enzyme-catalyzed reaction obtained by Shin and co-workers (J. Chem. Phys. 2001, 115, 1455) is generalized to allow for the rebinding of the product. The amplitude of the power-law ($t^{-1/2}$) relaxation of the free- and bound-enzyme concentrations to steady-state values is expressed in terms of the steady-state velocity and the intrinsic (chemical) rate constants. This result is conjectured to be exact, even though our expression for the steady-state velocity in terms of microscopic parameters is only approximate.

Theory of Diffusion-Influenced Bimolecular Reactions in Solution : Effects of a Stochastic Gating Mode

  • Kim Joohyun;Lee Sangyoub
    • Bulletin of the Korean Chemical Society
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    • 제13권4호
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    • pp.398-404
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    • 1992
  • We have investigated the kinetics of diffusion-influenced bimolecular reactions in which one reactant has an internal mode, called the gating mode, that activates or deactivates its reactivity intermittently. The rate law and an expression for the time-dependent rate coefficient have been obtained from the general formalism based on the hierarchy of kinetic equations involving reactant distribution functions. The analytic expression obtained for the steady-state reaction rate constant coincides with the one obtained by Szabo et al., who derived the expression by employing the conventional concentration-gradient approach. For the time-dependent reaction rate coefficient, we obtained for the first time an exact analytic expression in the Laplace domain which was then inverted numerically to give the time-domain results.

Drying Characteristics of Korean-type Rehmannia (Jiwhang) Noodle

  • Rhim, Jong-Whan
    • Food Science and Biotechnology
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    • 제18권1호
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    • pp.202-206
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    • 2009
  • Drying characteristics of fresh Korean-type rehmannia (jiwhang) noodle was investigated to determine drying kinetic parameters under the experimental conditions of 5 temperatures (30, 40, 60, 80, and $90^{\circ}C$). Drying curve of the noodle showed a biphasic pattern of decrease in drying rate with initial rapid drying followed by slow dehydration as the progress in drying. In all drying conditions, only falling drying rate period was observed and the drying rate of the noodle was greatly influenced by the drying temperature. The effective diffusion coefficients ($D_{eff}$) were determined by the diffusion model and their temperature dependency was determined using an Arrhenius equation. The activation energy ($E_a$) values for the drying of the noodle were 19.94 and 21.09 kJ/mol at the initial and the latter stage of dehydration, which were comparable to those of pasta or Japanese udong dehydration.

저탄소${\cdot}$저합금 강의 연속 냉각 변태에 미치는 Ni의 영향 (Effects of Ni addition on continuous cooling transformation behavior of low carbon HSLA steels)

  • 강주석;전현조;박찬경
    • 한국소성가공학회:학술대회논문집
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    • 한국소성가공학회 2005년도 추계학술대회 논문집
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    • pp.456-459
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    • 2005
  • Continuous cooling transformation behaviors were studied fur low carbon HSLA steels containing three different level $(1\~3\;wt\%)$ of Ni addition. Thermo-mechanical processing (TMP) simulations to construct continuous cooling (CCT) diagram were conducted by using Gleeble system. As cooling rate increased, pearlite, granular bainite, acicular ferrite, bainitic ferrite and lath martensite were transformed from deformed austenite. Fully bainitic microstructure were developed at all cooling rate condition in high Ni containing steel due to hardenability increasing effects of Ni. Ni also influenced the transformation kinetics. At the slowest cooling rate of $0.3^{\circ}C/s$, transformation delayed with decreasing Ni contents because of the diffusion of substitutional alloy elements. However, cooling rate slightly increased to $1^{\circ}C/s$, transformation kinetics accelerated with decreasing Ni contents because nucleation of bainite was sluggish due to hardening of residual austenite.

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Reversible Excited-State Proton Transfer: Effect of the Switching of Interaction Potential by Reaction

  • Lee, Jin-uk;Uhm, Je-sik;Lee, Woo-Jin;Lee, Sang-youb;Sung, Jae-young
    • Bulletin of the Korean Chemical Society
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    • 제27권2호
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    • pp.197-202
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    • 2006
  • In the reaction A + B $^\rightarrow_\leftarrow$ C, where A and B are ionic reactants having opposite charges, a B molecule approaching an A will experience a switching of the interaction potential when the A molecule is captured by one of the other B molecules in the medium. In the reversible case, the former B molecule still has a chance to react with the A, so that one needs to take into account the switched interaction between the reactant B and the product C as well as that between the reactants to treat the kinetics accurately. It is shown that this kind of interaction potential switching affects the relaxation kinetics in an intriguing way as observed in a recent experiment on an excited-state proton transfer reaction.

Nonequilibrium Distribution Function Theory of Many-Particle Effects in the Reversible Reactions of the Type A+B ↔ C+B

  • Lee, Jin-Uk;Uhm, Je-Sik;Lee, Woo-Jin;Lee, Sang-Youb;Sung, Jae-Young
    • Bulletin of the Korean Chemical Society
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    • 제26권12호
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    • pp.1986-1990
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    • 2005
  • We study the relaxation kinetics of reversible reactions of the type A + B $^\leftarrow_\rightarrow$ C + B by applying the manyparticle kernel theory, which we have developed to investigate many particle effects on general diffusioninfluenced reactions. It is shown that for the target model, where A and C molecules are immobile and their interconversion is induced by the encounter with the B molecules that are present in much excess, the manyparticle kernel theory gives a result that coincides with the known exact result.

FORMATION OF AMORPHOUS NICKEL-PHOSPHORUS ALLOY FILM

  • Yamashita, Tsugito;Komiyama, Toyohiko
    • 한국표면공학회지
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    • 제29권6호
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    • pp.720-723
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    • 1996
  • The behavior of electrodeposition of amorphous nickel-phosphorus has been studied from the point of deposition mechanism, kinetic parameters, morphology and formation of alloy films. The electorode reaction and electrode kinetics of deposition of nickel were significantly influenced by the content of phosphorus. The cathodic deposition of nickel-phosphorus alloy might be governed by the diffusion process of phosphorous acid. The direction of growth layer of the nickel-phosphorus alloy was different with substrate material. The formation of nickel-phosphorus alloy films was affected considerably by the solution compositions, electrolytic conditions and properties of the material as an underlayer.

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