• Bulletin of the Korean Chemical Society
• /
• 제33권3호
• /
• pp.963-970
• /
• 2012

We review novel chemical kinetics proposed for quantitative description of fluctuations in reaction times and in the number of product molecules in a heterogeneous biological system, and discuss quantitative interpretation of randomness parameter data in enzymatic turnover times of ${\beta}$-galactosidase. We discuss generalization of renewal theory for description of chemical fluctuation in product level in a multistep biopolymer reaction occurring in a dynamically heterogeneous environment. New stochastic simulation results are presented for the chemical fluctuation of a dynamically heterogeneous reaction system, which clearly show the effects of the initial state distribution on the chemical fluctuation. Our stochastic simulation results are found to be in good agreement with predictions of the analytic results obtained from the generalized master equation.

• Macromolecular Research
• /
• 제13권1호
• /
• pp.68-72
• /
• 2005

A low-molecular-weight poly(lactic acid) was synthesized through the condensation reaction of L-lactic acid. The effects that the catalyst and temperature have on the reaction rate were studied to determine the optimum reaction conditions. The reaction kinetics increased with temperature up to $210^{\circ}C$, but no further increase was observed above this temperature. Among a few selective catalysts, sulfuric acid was the most effective because it maximized the polymerization reaction rate. Reduction of the pressure was another important factor that enhanced this reactions kinetics.

• Korean Chemical Engineering Research
• /
• 제51권1호
• /
• pp.144-150
• /
• 2013

본 연구에서는 촉매로 zinc acetate를 사용하였고 dimethyl terephthalate(DMT)와 ethylene glycol(EG)의 에스테르 교환을 통하여 polyethylene terephthalate(PET)의 단량체인 bishydroxyethyl terephthalate(BHET)를 생성하는 반응에 대하여 알아보았다. 기존의 kinetics 연구는 에스테르 교환 반응에서 생성되는 메탄올이 반응계에서 제거되는 반회분식공정을 바탕으로 하여 이때 제거된 메탄올 양을 측정하여 역반응이 무시된 반응 kinetics 모델을 구성하였다. 본 연구에서는 회분식 반응기를 통하여 DMT와 메탄올의 양을 정량하여, 역반응을 고려한 보다 정확한 kinetics 모델을 제안하였고, 제안된 모델의 예측값들이 실험값들과 잘 일치하는 것을 보였다. 또한 모델과 실험값을 분석하여 여러 공정 변수들이 에스테르 교환 반응에 미치는 영향을 조사하였다.

• Korean Chemical Engineering Research
• /
• 제53권4호
• /
• pp.463-467
• /
• 2015

We investigated catalytic activity of ion-exchange resins in acetalization of 1,2-propylene glycol with acetaldehyde. The impacts of reaction variables, such as temperature, reaction time, catalyst loading and feedstock composition, on the conversion of 1,2-propylene glycol were measured. The life of the catalyst was also studied. Furthermore, the reaction kinetics of 1,2-propylene glycol acetalization was studied. It was found that reaction rate followed the first-order kinetics to acetaldehyde and 1,2-propylene glycol, respectively. Therefore, overall acetalization reaction should follow the second-order reaction kinetics, expressed as. Key words: 1,2-propylene Glycol, 2,4-dimethyl-1,3-dioxolane, Ion-exchange Resin, Polyhydroxy Compounds, Acetalization $r=kC^{nA}_AC^{nB}_B=19.74e^{\frac{-6650}{T}}C^1_AC^1_B$.

• Bulletin of the Korean Chemical Society
• /
• 제35권11호
• /
• pp.3313-3318
• /
• 2014

The reaction mechanism of Lead ions catalyzing complexation reactions between TIPP and metal ions was investigated by researching the kinetics of the formation of metalloporphyrins by UV/Vis-spectra, and verified by exploring the formation of metalloporphyrins catalyzed by acetic acid. Kinetics studies suggested that the fluctuations of reaction rate indicated the formation of metalloporphyrin was step-wise, including the pre-equilibrium step (the coordination of the pyrrolenine nitrogens to $Mn^+$) and the rate-controlling step (the deprotonation of the pyrrole proton). In the pre-equalization step, a sitting-atop (SAT) structure formed first with the complexation between larger radius of $Pb^{2+}$ and TIPP, changed the activation, then $Pb^{2+}$ left with the smaller radius of metal ions attacking from the back of the porphyrin ring center. In the rate-controlling step, two pyrrole protons dissociated to restore a stable structure. This was verified by adding acetic acid at different reaction times.

• Bulletin of the Korean Chemical Society
• /
• 제33권3호
• /
• pp.941-952
• /
• 2012

In the present contribution the Encounter Theory (ET) (the prototype of the classical Collision Theory in rarefied gases) concepts for widely occurring diffusion assisted irreversible bulk reactions A + A ${\rightarrow}$ C and A + B ${\rightarrow}$ C in liquid solutions examined by the authors in the literature are analyzed and compared with each other for these different types of reactions. It is shown that for a particular case of equal initial concentrations $[A]_0=[B]_0$ in the reaction A + B ${\rightarrow}$ C, when the kinetics of both reactions A + A ${\rightarrow}$ C and A + B ${\rightarrow}$ C in the framework of formal chemical kinetics and ET are the same, the accumulation of macroscopic correlations breaking the concepts of independent encounters and leading to the Generalized Encounter Theory (GET) are drastically different. The influence of the force interaction and the decay of nonstable reactants on the time behavior the macroscopic correlations is also briefly discussed.

• Korean Chemical Engineering Research
• /
• 제56권1호
• /
• pp.103-111
• /
• 2018

본 연구에서는 PET (Poly Ethylene Terephthalate)의 단량체인 BHET (bis (2-Hydroxyethyl) Terephthalate)와 1,4-BD(1,4-Butanediol)의에스테르교환반응을활용하여 PBT (Poly Butylene Terephthalate)의단량체인 BHBT (Bis (4-Hydroxybutyl Terephthate)를 생성하는 반응에 대하여 조사하였다. 이 반응의 촉매로 Zinc Acetate를 사용하였다. 회분식 반응기를 통하여 BHET, EG (Ethylene Glycol), THF (Tetrahydrofuran)의 양을 정량하여 반응 kinetics 모델을 구성하였다. 제시된 모델을 통하여 반응속도와 반응물의 조성 분포를 조사하였고, 이 모델의 예측 값과 실험 값들이 잘 일치함을 보였다.

• 연구논문집
• /
• 통권29호
• /
• pp.151-162
• /
• 1999

In general, manufacturing processes of thermosetting composites consist of mold filling and resin cure. The important parameters used in modeling and designing mold filling are the permeability of the fibrous preform and the viscosity of the resin. To consolidate a composite, resin cure or chemical reaction plays an essential role. Cure kinetics. Therefore, is necessary to quantify the extent of chemical reaction or degree of cure. It is also important to predict resin viscosity which can change due to chemical reaction during mold filling. There exists a heat transfer between the mold and the composite during mold filling and resin cure. Cure kinetics is also used to predict a temperature profile inside composite. In this study, a new scheme which can determine cure kinetics from dynamic temperature scaning was proposed. The method was applied to epoxy resin system and was verified by comparing measurements and predictions.

• Bulletin of the Korean Chemical Society
• /
• 제32권5호
• /
• pp.1679-1684
• /
• 2011

Interfacial reactions kinetics often differ from kinetics of bulk reactions. Here, we describe how the density change of an immobilized reactant influences the kinetics of interfacial reactions. Self-assembled monolayers (SAMs) of alkanethiolates on gold were used as a model interface and the Diels-Alder reaction between immobilized quinones and soluble cyclopentadiene was used as a model reaction. The kinetic behavior was studied using varying concentrations of quinones. An unusual threshold density of quinones (${\Gamma}_c$ = 5.2-7.2%), at which the pseudo-first order rate constant started to vary as the reaction progressed, was observed. This unexpected kinetic behavior was attributed to the phase-separation phenomena of multi-component SAMs. Additional experiments using more phase-separated two-component SAMs supported this explanation by revealing a significant decrease in ${\Gamma}_c$ values. When the background hydroxyl group was replaced with carboxylic or phosphoric acid groups, ${\Gamma}_c$ was observed at below 1%. Also, more phase-separated thermodynamically controlled SAMs produced a lower critical density (3% < ${\Gamma}_c$ < 4.9%) than that of the less phaseseparated kinetically controlled SAMs (6.5% < ${\Gamma}_c$ < 8.9%).

• 한국수소및신에너지학회논문집
• /
• 제29권1호
• /
• pp.90-96
• /
• 2018

Reaction characteristics and kinetics of a oxygen carrier (OCN717-R1SU) for chemical looping combustion (CLC) have been investigated using TGA by changing gas concentration (10-30 vol.% $CH_4$) and reaction temperature ($825-900^{\circ}C$). Reaction rate of OCN717-R1SU increased as temperature increased and it was found that reaction is delayed at the initial reaction regime. Johnson-Mehl-Avrami (JMA) model was adopted to explain the reaction phenomenon. The activation energy (E) determined by JMA model in reduction reaction of OCN717-R1SU is $151.7{\pm}2.03kJ/mol$ and pre-exponential factor and JMA exponent were also obtained. The parameters calculated in this study will be applied in design of the reactor and operation conditions for CLC process.