• Korea-Australia Rheology Journal
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• 제17권4호
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• pp.199-205
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• 2005

Carbon dioxide was absorbed into aqueous polyethylene oxide (PEO) solution containing AMP in a flat-stirred vessel to investigate the effect of non-Newtonian rheological behavior of PEO on the rate of chemical absorption of $CO_2$, where the reaction between $CO_2$ and AMP was assumed to be a first-order reaction with respect to the molar concentration of $CO_2$ and AMP respectively. The liquid-side mass transfer coefficient, which was obtained from the dimensionless empirical equation containing the properties of viscoelasticity of the non-Newtonian liquid, was used to estimate the enhancement factor due to chemical reaction. PEO with elastic property of non-Newtonian liquid made the rate of chemical absorption of $CO_2$ accelerate compared with Newtonian liquid based on the same viscosity of the solution.

• 대한화학회지
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• 제6권1호
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• pp.14-18
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• 1962

Solution to the diffusion layer for the first order reaction at a droping mercury electrode (D.M.E.) is presented. Equations are derived for polarographic currents for the reactions at the D.M.E. A factor which is applicable to the D.M.E. is derived, when we use the equations of the polarographic currents for the reactions at a plane electrode(P.E.), and the rate constants of the backward reactions are negligibly small. Polarographic currents from a combination of diffusions and reactions are obtained at the D.M.E. with special approximation. Rate constant for the reaction of ferrous ion with hydrogen-peroxide is determined at the D.M.E.,using the data of Kolthoff and Perry. The agreement of the equation with the data of Kolthoff and Perry for the kinetic current of ferric ion in the presence of hydrogen-peroxide is good. Ratios of diffusion layer at the D.M.E. to the diffusion layer at the P.E. are discussed and show that, when the rate constants of the backward reactions for the first order reactions are larger than 1/0.05 sec-1. and drop-time about 3 sec., these ratioes are about one.

• 대한기계학회:학술대회논문집
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• 대한기계학회 2004년도 추계학술대회
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• pp.1604-1610
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• 2004

A steady dilute premixed combustion at transonic speeds in a diverging channel is investigated. The model explores the nonlinear interactions between the near-sonic speed of the flow, the small changes in geometry from a straight channel, and the small heat release due to the one-step first-order Arrhenius chemical reaction. The reactive flow can be described by a nonhomogeneous transonic small-disturbance (TSD) equation coupled with an ordinary differencial equation for the calculation of the reactant mass fraction in the combustible gas. The asymptotic analysis results in the similarity parameters that govern the reacting flow problem. The model is used to study transonic combustion at various amounts of incoming, reactant mass, reaction rates, and channel geometries.

• 대한화학회지
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• 제33권3호
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• pp.309-314
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• 1989

산 용액내에서 cis-$[Co(en)_2(N_3)_2]^+$와 Fe(II)간의 산화-환원 반응속도를 UV/vis-분광광도계로 측정하였다. 여기서 촉매 $H^+$가 관여한 반응속도상수와 각 반응물의 반응차수 그리고 활성화파라메타를 구하여 이들 자료를 바탕으로 타당한 반응메카니즘을 제안하였다. 본 연구의 실험결과를 보면, Co(III)와 Fe(II) 그리고 $H^+$에 대해서 각각 1차로 총괄반응이 3차 반응이다. 이때 반응속도상수 $K_H^+$는 $3.27{\times}10^{-2}l^2{\cdot}mol^{-2}{\cdot}sec^{-1}$이였다. 그리고 활성화에너지 $E_a$는 14.8Kcal/mol, 활성화엔탈피 ${\Delta}H^{\neq}$는 14.2Kcal/mol, 활성화엔트로피 ${\Delta}S^{\neq}$는 -16.7e.u.였다. 이러한 실험적 사실을 바탕으로, 본 반응계에서 $H^+$가 촉매로 작용하여 내부권(inner-sphere) 메카니즘으로 산화-환원반응이 진행되는 타당한 반응메카니즘을 제안하였다.

• 한국미생물·생명공학회지
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• 제13권1호
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• pp.33-39
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• 1985

The effects of initial concentration, flow rate, and recycle ratio on the removal efficiency of phenol were studied in a tapered fluidized bed reactor packed with activated carbon which was attached with Candida tropicalis. The optimum conditions of Candida tropicalis were showed that pH was 7.0 and temperature was $30^{\circ}C$, and the specific growth rate of Candida tropicalis was satisfied with the Monod equation up to 500 mg/L of phenol, and beyond it the inhibition of substrate was found. According to the increases of initial concentration and flow rate, the removal efficiency was decreased, as the recycle ratio was increased, the removal efficiency was increased. In the case of flow rate of 10mL/sec and the recycle ratio of 2, the removal efficiency was 90% above for the all of initial concentration. The removal rate of phenol was the first order reaction in this system, and the rate equation of reaction was as follows.

• 대한화학회지
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• 제38권10호
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• pp.705-709
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• 1994

1M 황산용액에서 세륨(Ⅳ) 이온에 의한 말론산의 산화반응에 관한 반응속도를 분광광도법으로 연구하였다. 말론산이 과량으로 존재하는 조건하에서 측정된 유사일차 속도상수, $k_{obs}$는 말론산의 농도, [MA]에 따라 크게 의존함을 보였으며 $k_{obs}$ = (0.592[MA])/(1+14.5[MA]$^2$)의 관계를 만족하였다. 이에 근거하여 반응메카니즘을 제안하였다. 말론산의 산해리에 의해 생성된 enolate형 음이온과 Ce(Ⅳ)간의 전자이동반응이 반응속도 결정단계이며, MA의 고농도하에서 Ce(Ⅳ)과 enolate형 음이온간의 1:2 chelate생성반응에 의하여 Ce(Ⅳ)의 농도가 감소하여 산화반응이 억제됨을 알 수 있었다. 본 연구에서 제안된 메카니즘에 근거하여 Sengupta 등에 의해 연구된 pH 의존성을 설명할 수 있었다.

• Environmental Engineering Research
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• 제12권1호
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• pp.30-35
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• 2007

Fenton system using homogeneous iron catalyst is very powerful in the degradation of organic compounds, but has a disadvantage to remove Fe ions from water after wastewater treatment. Thus, iron catalyst was bounded to support such as inorganic and polymer materials. The PVP supporting iron catalyst showed a good catalytic performance in degradation of phenol contained in waste water and iron catalyst supported on ${SO_4}^{2-}$ type PVP (KEX 511) showed the best catalytic performance. Also, reaction kinetic study was carried out in this system. Reaction constants on various catalysts was obtained from the pseudo first order equation. Reaction rate constants with the heterogenized $FeCl_2/PVP$ catalyst is a three-fold smaller than that of $FeCl_2$ catalyst.

• 한국응용과학기술학회지
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• 제9권1호
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• pp.41-46
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• 1992

The transesterification of dimethylphthalate by 1,4-butanediol was kinetically investigated In the presence of various metal acetate catalysts at 180$^{\circ}C$. The quantity of dimethylphthalate reacted in the reaction flask was measured by gas chromatography. The transesterification was assumed to obey first-order kinetics with respect to dimethylphthalate and 1,4-butanediol, and a rate equation was derived. The linear relationship was shown between apparent rate constant and reciprocal absolute temperature, the activation energy has been calculated as 7.4kcal with lead acetate. The maximum reaction rate was appeared at the range of 1.5${\sim}$1.6 of electronegativity of metal ions.

• Bulletin of the Korean Chemical Society
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• 제24권3호
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• pp.306-310
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• 2003

Hydrolysis reactions of S-phenyl-S-vinyl-N-p-tosylsulfilimine (VSI) and its derivatives at various pH have been investigated kinetically. The hydrolysis reactions produced phenylvinylsulfoxide and p-toluene sulfonamide as the products. The reactions are first order and Hammett ρ values for pH 1.0, 6.0, and 11.0 are 0.82, 0.45, and 0.57, respectively. This reaction is not catalyzed by general base. The plot of k vs pH shows that there are three different regions of the rate constants $(k_t)$ in the profile.; At pH < 2 and pH > 10, the rate constants are directly proportional to the concentrations of hydronium and hydroxide ion catalyzed reactions, respectively. The rate constant remains nearly the same at 2 < pH < 10. On the bases of these results, the plausible hydrolysis mechanism and a rate equation have been proposed: At pH < 2.0, the reaction proceeds via the addition of water molecule to sulfur after protonation at the nitrogen atom of the sulfilimine, whereas at pH > 10.0, the reaction proceeds by the addition of hydroxide ion to sulfur directly. In the range of pH 2.0-10.0, the addition of water to sulfur of sulfilimine appears to be the rate controlling step.

• Bulletin of the Korean Chemical Society
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• 제20권10호
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• pp.1213-1217
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• 1999

Hydrolysis reactions of 2-phenyl-4H,5H,6H-3-methyl-3-thiazinium perchlorate (PTP) and its derivatives at various pH have been investigated kinetically. The hydrolysis is quantitative, producing N-3-mercaptopropyl-N-methylbenzamide as the only product in the all pH ranges. The observed rate of hydrolysis of PTP was always of the first-order. For hydrolysis from PTP, Hammett ρvalues were 0.53, 0.84 and 1.13 for pH 5.0, 8.0, and 10.0, respectively. Bronsted βvalue was 0.53 for general base catalysis. This reaction is catalyzed by general w acetate concentration. However, as the amount of base becomes larger, the rate of hydrolysis reaction approaches the limiting values. The plot of log k vs. pH shows that the rate constants (kt) are two different regions in the profile; one part is directly proportional to hydroxide ion concentration and the other is not. On the bases of these result, the plausible hydrolysis mechanism and a reaction equation were proposed: Below pH 4.5, the hydrolysis was initiated by the addition of water to α-carbon. Above pH 9.0, the hydrolysis was proceeded by the addition of hydroxide ion to α-carbon. However, in the range of pH 4.5-8.0, these two reactions occured competitively.