• 제목/요약/키워드: Reaction Rate Constant (k)

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Estimating Diffusion-Controlled Reaction Parameters in Photoinitiated Polymerization of Dimethacrylate Macromonomers

  • Choe, Youngson
    • Macromolecular Research
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    • 제11권5호
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    • pp.311-316
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    • 2003
  • The kinetics of photoinitiated polymerization of dimethacrylate macromonomers have been studied to determine the diffusion-controlled reaction parameters using attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). A predicted kinetic rate expression with a diffusion control factor was employed to estimate an effective rate constant and to define the reaction-controlled and diffusion-controlled regimes in the photopolymerization. An effective rate constant, k$_{e}$, can be obtained from the predicted kinetic rate expression. At the earlier stages of polymerization, the average values of kinetic rate constants do not vary during the reaction time. As the reaction conversion, $\alpha$, reaches the critical conversion, $\alpha$$_{c}$, in the predicted kinetic expression, the reaction becomes to be controlled by diffusion due to the restricted mobility of dimethacrylate macromonomers. A drop in value of effective rate constant causes a drastic decrease of reaction rate at the later stages of polymerization. By determining the effective rate constants, the reaction-controlled and diffusion-controlled regimes were properly defined even in the photopolymerization reaction system.m.m.

인삼사포닌 및 인삼수용성 추출물이 비둘기 가슴근육으로부터 분리된 Malate Dehydrogenase에 미치는 안정화효과 (Stabilizing Effect of Ginseng Saponin and Water Extract on Malate Dehydrogenase from Pigeon Breast Muscle)

  • 김두하;신문희;홍순근
    • Journal of Ginseng Research
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    • 제7권1호
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    • pp.88-93
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    • 1983
  • Studies were carried out to elucidate the protein stabilizing effect of ginseng. Malate dehydrogenase (EC 1.1.1.37) was used as a protein and the rate constant of the enzyme inactivation was determined under the heat denaturation condition. There was an optimum pH for the enzyme stability, the rate constant of the enzyme inactivation was minimum at BH 8.8. The rate constant was increased at lower and higher pH regions than the optimum pH. The inactivation reaction followed the Arrehnius law and the activation energy was measured as 36.8kcal/mole. The reaction rate was not affected by the enzyme concentration and thus it was assumed to be unimolecular first order reaction. The water extract of red ginseng decreased the rate constant of Malate dehydrogenate under heat inactivation condition to stabilize the enzyme activity. Purified ginseng saponin also stabilized the enzyme against heat inactivation.

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메틸메타크릴레이트와 디에탄올아민과의 에스테르 교환반응에 관한 연구 (A Study on the Transesterification Reaction Between Methyl Methacylate and Diethanolamine)

  • 손병청;박근호;정순욱;남기대
    • 한국응용과학기술학회지
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    • 제3권2호
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    • pp.41-47
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    • 1986
  • The transesterification reaction between diethanolamine and methyl-methacrylate was kinetically investigated in the presence of various metal acetate catalysts at $120^{\circ}C$. The quantity of methylmethacrylate reacted in the reaction flask was measured by gas chromatography and liquid chromatography, and the reaction rate was investigated by measuring of the quantity of products and reactnts under various catalysts. The transesterification reaction was carried out in the first order reaction kinetics with respect to the concentration of diethanolamine and methylmethacrylate, respectively. The apparent rate constant was found to obey first-order kinetics with respect to the concentration of catalyst. The linear relationship was shown between apparent rate constant and reciprocal absolute temperature, and by the Arrhenius plot, the activation energy has been calculated as 11.08 Kcal with zinc acetate catalyst, 17.99 Kcal without catalyst. The maximum reaction rate was appeared at the range of 1.4 to 1.6 of electronegativity of metal ions and instability constant of metal acetates.

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.

Quantitative Evaluation of the First Order Creatine-Kinase Reaction Rate Constant in in vivo Shunted Ovine Heart Treated with Oxandrolone Using Magnetization Transfer 31P Magnetic Resonance Spectroscopy (MT-31P-MRS) and 1 H/31P Double-Tuned Surface Coil: a Preliminary Study

  • Thapa, Bijaya;Dahl, Marjanna;Kholmovski, Eugene;Burch, Phillip;Frank, Deborah;Jeong, Eun-Kee
    • Investigative Magnetic Resonance Imaging
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    • 제22권1호
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    • pp.26-36
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    • 2018
  • Purpose: Children born with single ventricle physiology demonstrate poor growth rate and suffer from malnutrition, which lead to increased morbidity and mortality in this population. We assume that an anabolic steroid, oxandrolone, will promote growth in these infants by improving myocardial energy utilization. The purpose of this paper is to study the efficacy of oxandrolone on myocardial energy consumption in these infants. Materials and Methods: We modeled single ventricle physiology in a lamb by prenatally shunting the aorta to the pulmonary artery and then postnatally, we monitored cardiac energy utilization by quantitatively measuring the first order reaction rate constant, $k_f$ of the creatine-kinase reaction in the heart using magnetization transfer $^{31}P$ magnetic resonance spectroscopy, home built $^1H/^{31}P$ transmit/receive double tuned coil, and transmit/receive switch. We also performed cine MRI to study the structure and dynamic function of the myocardium and the left ventricular chamber. The spectroscopy data were processed using home-developed python software, while cine data were analyzed using Argus software. Results: We quantitatively measured both the first order reaction rate constant and ejection fraction in the control, shunted, and the oxandrolone-treated lambs. Both $k_f$ and ejection fraction were found to be more significantly reduced in the shunted lambs compared to the control lambs, and they are increased in oxandrolone-treated lambs. Conclusion: Some improvement was observed in both the first order reaction rate constant and ejection fraction for the lamb treated with oxandrolone in our preliminary study.

Zinc-ferrite의 용해 속도론에 미치는 황산 용액의 온도와 농도의 영향 (Effect of Solution Temperature and Bath Concentration on the Kinetics with Dissolution Reaction of Zinc-Ferrite)

  • 오이식;김천조
    • 자원리싸이클링
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    • 제12권4호
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    • pp.30-37
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    • 2003
  • 황산 용액에서 Zinc-ferrite의 용해에 대한 반응속도론을 황산 용액의 반응온도와 농도 변화에 대해 조사하였다. 반응율(R)과 겉보기 반응 속도상수(K)는 황산 용액의 온도와 농도가 클수록 증가한다. Zinc-ferrite의 반응속도는 반응초기에서 $1-(1-K)^{1/3}=Kt$와 같은 속도식을 적용할 수 있다. 용해에 대한 활성화 에너지는 황산 용액의 농도에 관계없이 약 16.3kcal/mole 이다. Zinc-ferrite가 황산 용액에서 용해할 때는 Zinc-ferrite의 화학 양론적 조성으로 용해되며, Fe 또는 Zn의 단독으로는 용해되지 않는다.

TTABr 미셀 용액속에서 2-알킬벤즈이미다졸 음이온에 의해 추진되는 디페닐-4-니트로페닐 포스페네이트(DPNPIN)의 탈인산화반응 (Dephosphorylation of Diphenyl-4-Nitrophenyl Phosphinate(DPNPIN) onto 2-Alkylbenzimidazolide Anion in TTABr Micellar Solution)

  • 김정배
    • 한국환경과학회지
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    • 제24권8호
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    • pp.981-992
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    • 2015
  • This study is mainly focused on micellar effect of tetradecyltrimethyl ammonium bromide(TTABr) solution including alkylbenzimidazole(R-BI) on dephosphorylation of diphenyl-4-nitrophenylphosphinate(DPNPIN) in carbonate buffer(pH 10.7). Dephosphorylation of DPNPIN is accelerated by $BI^{\Theta}$ ion in $10^2$ M Carbonate buffer(pH 10.7) of $4{\times}10^{-4}$ M TTABr solution up to 80 times as compared with the reaction in Carbonate buffer by no benzimidazole(BI) solution of TTABr. The value of pseudo first order rate constant($k_{\psi}$) of the reaction in TTABr solution reached a maximum rate constant increasing micelle concentration. The reaction mediated by $R-BI^{\Theta}$ in micellar solutions are obviously slower than those by $BI^{\Theta}$, and the reaction rate were decreased with increase of lengths of alkyl groups. It seems due to steric effect of alkyl groups of $R-BI^{\Theta}$ in Stern layer of micellar solution. The surfactant reagent, TTABr, strongly catalyzes the reaction of DPNPIN with R-BI and its anion($R-BI^{\Theta}$) in Carbonate buffer(pH 10.7). For example, $4{\times}10^{-4}$ M TTABr in $1{\times}10^{-4}$ M BI solution increase the rate constant($k_{\psi}=99.7{\times}10^{-4}1/sec$) of the dephosphorylation by a factor ca. 28, when compared with reaction($k_{\psi}=3.5{\times}10^{-4}1/sec$) in BI solution(without TTABr). And no TTABr solution, in BI solution increase the rate constant($k_{\psi}=3.5{\times}10^{-4}1/sec$) of the dephosphorylation by a factor ca. 39, when compared with reaction ($k_{\psi}=1.0{\times}10^{-5}1/sec$) in water solution(without BI).

Vanillylidene imine 유도체의 가수분해 반응에 관한 속도론적 연구 (A study on the Kinetics velocity for hydrolysis reaction of vanillylidene imine derivatives)

  • 성기천;김기준
    • 한국응용과학기술학회지
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    • 제12권2호
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    • pp.145-150
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    • 1995
  • The Kinetics velocity for hydrolysis reaction of vanillylidene imine derivatives has been measured by ultra-violet ray spectrophotometer in 20wt% $dioxane-H_2O$ at $25^{\circ}C$. It was measured the reaction rate Constant of vanillylidene imine derivatives that can be applied widely following to pH-change at $25^{\circ}C$. Final products that hydrolyzed the vanillylidene imine certified in vanillin and aniline derivative, and the effect of substitution radical that has affected on hydrolysis reaction was largely promoted to reaction rate by electron attrating group in acidity and electron donoring group in basic. From the results of rate constant to hydrolysis reaction, substituent radical effect and final products. It has certified the hydrolysis reaction mechanism of vanillylidene imine derivatives.

메틸메타크릴레이트와 디에탄올아민과의 에스테르 교환반응에 관한 연구(II) (A Study on the Transesterification Reaction between Methyl Methacrylate and Diethanolamine (II))

  • 손병청;박근호;정순욱
    • 한국응용과학기술학회지
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    • 제4권1호
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    • pp.67-71
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    • 1987
  • The transesterification reaction between diethanolamine and methyl methacrylate was kinetically investigated in the presence of various metal acetate catalysts at $120^{\circ}C$. The amount of reacted methyl methacrylate was measured by gas chromatography and liquid chromatography, and the reaction rate also measured from the amount of reaction products and reactants under each catalyst. The transesterification reaction was carried out in the first order with respect to the concentration of diethanolamine and methyl methacrylate, respectively. The over-all order is 2nd. The apparent rate constant was found to obey first-order kinetics with respect to the concentration of catalyst. The maximum reaction rate was appeared at the range of 1.4 to 1.6 of electronegativity of metal ions and instability constant of metal acetates.