• Title/Summary/Keyword: 분해반응속도

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The Photocatalytic Degradation of Textile Effluent Containing Azo-Dye by UV/TiO2 AOP

  • 이태경;나영수;송승구
    • Proceedings of the Korean Environmental Sciences Society Conference
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    • 2001.11a
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    • pp.97-98
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    • 2001
  • Acid Orange 7과 Methyl Orange의 경우, UV 빛을 조사하고 $TiO_2$ powder를 투여하였을 때 120분 이내에 탈색이 완전히 이루어짐으로써 색도를 80% 이상 제거할 수 있었다. 광촉매량이 증가할수록 촉매표면적이 증가하여 광반응 속도의 증가를 가져오나, 과도한 촉매량의 투입은 오히려 UV 빛의 효과적인 투과를 방해함으로써 광반응 속도를 감소시킨 것으로 사료된다. 초기 pH는 반응 속도에 큰 영향을 미치지 못하는 것으로 나타났으며, Orange II는 Methyl Orange보다 초기 pH에 다소 큰 영향을 받았다. 초기 농도가 낮을수록 초기 반응 속도는 증가하여 염료 분해 속도가 빠름을 알 수 있었다.

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Effects of pH, Amino Acids and Hydrolyzed Proteins on Caramelization of Starch Syrup (물엿의 Caramel 반응 중 아미노산과 가수분해 단백질 첨가의 영향)

  • Park, Cheon-Woo;Kang, Kun-Og;Lee, Jung-Kun;Kim, Woo-Jung
    • Applied Biological Chemistry
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    • v.42 no.2
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    • pp.152-155
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    • 1999
  • Effects of pH, amino acids, hydrolyzed protein and potassium phosphate on caramelization were investigated for improvement of its reaction rate. The caramelization was performed with starch syrup at $110^{\circ}C$ and the different color functions-metric saturation(Suv), 5-hydroxymethylfurfural (HMF) contents and absorbance at 420 nm were measured. As the pH was raised from 4 to 10, the reaction rate (Suv/hr) was increased by 31.9% along with significant increase in HMF content and absorbances at 420 nm. Among the several amino acids, arginine and glycine were very effective for improvement of caramelization, which may be due to Maillard reaction. When $K_2HPO_4$ were added in different ratio with arginine, glycine, HVP or HAP, the effects of arginine and HAP on thee rate were markedly enhanced while the effects of glycine and HVP were rather reduced.

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Application of Ultrasound for the Decomposition of Musty-Odorous Compounds in Water (수용액 중 Musty-Odorous Compound류의 분해에 따른 초음파의 응용)

  • 유영억;영전양웅;전전태소
    • Journal of environmental and Sanitary engineering
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    • v.13 no.1
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    • pp.1-8
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    • 1998
  • Musty-odorous compound (Geosmin, 2-Methylisobrneol) 수용액 중에 초음파 (200kHz, $6.0W/cm^{2}$)를 조사시켜 조사시간에 따른 농도 및 취기의 변화를 고찰했다. 초음파 조사에 의해 이 물질들은 빠르게 분해되었고 분해 형태는 농도에 대한 유사1차 반응을 나타내었다. 공기 포화 분위기에서 이들의 초기 분해속도는 각각 2.5 $10^{-3}{\;}Msec^{-1}$(2-MIB), 3.2 $10^{-3}{\;}Msec^{-1}$ (Geosmin)로 나타났다. 초음파 조사 시 포화가스 (Envelope gas)의 영향은 아르곤(Ar) 산소($O_{2}$) 공기(Air) 질소($N_{2}$) 순서로 순수한 아르곤(Ar) 분위기에서 musty-odorous compound 류의 분해가 가장 빠르게 진행되었고 그 분해생성물로 CO, $CO_{2}$ 그리고 HCOOH, $CH_{3}COOH$ 등의 저급 유기산류가 검출되었다. 또한 이들의 분해반응은 물의 초음파분해에 따라 생성된 hydroxylradical에 의한 radical반응, cavitation bubble내에서의 고온고압에 의한 열분해 및 직접연소반응으로 진행됨을 알 수 있었다.

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Nucleophile Substitution von Arylmethylchloriden. Kinetische Untersuchung der Solvolyse von 9-Chlormethylanthracen in binaren Losungsmittelgemischen (염화아릴메틸의 친핵치환 반응. 이성분혼합용매내에서 9-클로로메틸안트라센의 가용매 분해반응의 속도론적 연구)

  • Wang-Ki Kim
    • Journal of the Korean Chemical Society
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    • v.24 no.6
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    • pp.413-420
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    • 1980
  • Die Geschwindigkeitskonstanten der Solvolyse-Reaktionen von 9-Chlormethylanthracen wurden bei verschiedenen Temperaturen in unterschiedlichen binadren Losungsmittelgemischen (Wasser/Aceton, Wasser/Acetonitril, Wasser/Methanol, Wasser/Athanol) mit Hilfe der Leitfahigkeitsmeßungen bestimmt. Die Aktivierungsparameter $E_a$, ${\Delta}H^{\neq}$ und ${\Delta}S^{\neq}$ wurden berechnet. Die Meßergebnisse deuten darauf hin, daß die Solvolyse von 9-Chlormethylanthracen in protonischen Losungsmitteln schneller ablauft als in aprotonischen Losungsmitteln; in den Meßreihen mit protonsichen bzw. mit aprotonischen Losungsmitteln steigt die Reaktionsgeschwindigkeit mit der Zunahme der Dielektrizitatskonstanten des Losungsmittels an, und die Aktivierungsparameter nehmen mit steigendem Wassergehalt zu. Es wurde festgestellt, daß die Reaktion nach einem $S_N1$-Mechanismus ablauft. Die experimentellen Daten deuten darauf hin, daß Wasser einerseits als Nucleophil und andererseits als allgemeine Base am Reaktionsmechanismus beteiligt ist.

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Comparison of the Hydrolysis Rate of Several Polyol Ester Oils as a Candidate for Environmentally Adapted Synthetic Base Oil (환경친화적인 합성기유 후보물질로서의 몇가지 폴리올에스터 오일의 가수분해속도 비교)

  • 한두희;마사부미마스꼬
    • Proceedings of the Korean Society of Tribologists and Lubrication Engineers Conference
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    • 2001.06a
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    • pp.162-177
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    • 2001
  • The hydrolysis rates of seven kinds of polyol ester base oils 〔POEs〕 of different branch shape were investigated by using a simple apparatus under mild acidic condition. Seven polyol ester base oils were made of poly hydric alcohols of two-four valence, normal or branched fatty acids of different carbon number. p-Toluene sulfonic acid was used as acid catalyst to accelerate the rate of hydrolysis. Partial esters and fatty acid produced by sequential hydrolysis of POEs were identified and their concentrations were determined by calibrated-internal standard method using Gas Chromatography. The rate constants of each step in sequential hydrolysis were determined by the least square method from rate equation and the concentration of each component, were compared with one another. It was shown that the rate of hydrolysis of POEs was strongly affected by whether molecular structure of fatty acid was straight chain or branch chain and which position was branched. The hydrolysis stability for all the POEs can be reasonably explained by using a steric hindrance effect anticipated fi:om their molecular structures affecting as water molecule makes an attack on the carbonyl carbon of POEs.

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Nucleophilic Displacement at a Carbonyl Carbon Atom (ⅩⅢ). Methanolysis of Thiochloroformate in $CH_3OH-CH_3CN$ Mixtures (카르보닐탄소원자의 친핵성 치환반응 (제13보). 메탄올-아세토니트릴 혼합용매에서 Thiochloroformate의 가메탄올 분해반응)

  • Sangmoo La;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.24 no.4
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    • pp.288-294
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    • 1980
  • Methanolysis rate constants were determined for $CH_3O(CO)Cl,\;CH_3S(CO)Cl\;and\;CH_3S(CS)Cl\;in\;CH_3OH-CH_3CN$ mixtures. Results show that the rates are not predominantly influenced by the bulk solvent properties but are partly influenced by specific electrophilic solvation.Polarity of the solvent is not a dominant factor but it nevertheless plays a role in charge stabilization of the $S_N1$ like transition state. The methanolysis proceeds through $S_N1$ mechanism for $CH_3S(CS)Cl$ for which both specific solvation of leaving group by methanol and charge stabilization by a high dielectric medium are important, while for $CH_3O(CO)Cl\;methanolysis occurs\;via\;S_N2$ mechanism in which both of the solvent effects are unimportant.

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Kinetics and Mechanism of the Hydrolysis of Phenyl N-Benzenesulfonylchloroformimidate Derivatives (Phenyl N-Benzenesulfonylchloroformimidate 誘導體의 加水分解 反應메카니즘과 反應速度論的 硏究)

  • Nack-Do Sung;Ki-Sung Kwon;Tae-Rin Kim
    • Journal of the Korean Chemical Society
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    • v.28 no.5
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    • pp.328-334
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    • 1984
  • A series of phenyl N-benzenesulfonylchloroformimidate derivatives (p-H, p-Cl, p-CH3 & p-OCH3) were prepared and the hydrolysis of these compounds were studied kinetically at various pH by UV spectrophotometry in 1 ; 4 dioxane-water at $25^{\circ}C$. Hammett ${\rho}$ values measured at pH 5.0 (${\rho}$ = -0.45) and pH 10.0 (${\rho}$ = 0.40) indicate that the reaction proceeds via an azocarbonium ion intermediate in the acidic medium, whereas, it involves direct attack by hydroxide ion on the azomethine carbon atom occurs under the basic medium. The formation of stabilized azocarbonium ion species at pH 5.0 is also consistent with the large solvent effect(m = 1.3-1.5 & n = 5.0-5.5). On the basis of these findings, we may concluded that the hydrolysis of phenyl N-benzenesulfonylchloroformimidate derivatives proceeds by $SN_1$ below pH 8.0, however, above pH 10.0, the hydrolysis proceeds through $SN_2$ and in the range of pH 8.0-10.0, these two reactions occur competitively.

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Effect of Hydrogen Peroxide on the Acid Hydrolysis of Inulin (Inulin의 산 가수분해 반응에 과산화수소가 미치는 영향)

  • 윤석준;김성배최주홍박영철
    • KSBB Journal
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    • v.10 no.3
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    • pp.298-303
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    • 1995
  • Hydrogen peroxide has a characteristic of being dissociated rapidly into atomic oxygen and water when it is contacted with organic materials, resulting in a decrease in molecular weight of a polymer like carbohydrate. This effect on inulin hydrolysis under ultrasound irradiation was investigated. Maximum effect of hydrogen peroxide appeared at the H2O2 concentration of 2.3%(w/v) under the range of $50∼60^{\circ}C$ and 0.1∼0.3%(w/w) HCl. Compared to control reactions, the promotion effect reached 9∼43%. The activation energy, 26kca1/mo1, of inulin hydrolysis with H2O2 addition was similar to that without H2O2 addition, 25kca1/mo1. This implies that the rate enhancement of inulin hydrolysis with H2O2 addition is due to the increase of frequency factor.

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Hydrolysis of Phosphate Diesters as Nucleic Acid Model (핵산 모델로서 Phosphate Diester들의 가수분해 반응)

  • Sung, Nack-Do
    • Applied Biological Chemistry
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    • v.37 no.6
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    • pp.447-450
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    • 1994
  • Rate of hydrolysis ethylene phosphate, dimethylphosphate and hydroxyethylmethylphosphate in neutral water have been measured. Hydrolysis of ethylene phosphate proceeds with P-0 bond cleavage $(k_{obs}=3{\times}10^{-7}s^{-1}\;at\;100^{\circ}C,\;{\Delta}H{\neq}=24\;kcal,\;{\Delta}S{\neq}=25.5\;eu)$. In constrast, hydrolysis of dimethylphosphate proceeds with C-O bond cleavage $(k_{obs}=3{\times}10^{-7}s^{-1}\;at\;150^{\circ}C)$. The rate constant for P-O bond cleavage of dimethylphosphate is estimated at $1{\times}10^{-11}s^{-1}\;at\;150^{\circ}C,\;({\Delta}H{\neq}=36\;kcal,\;{\Delta}S{\neq}=25.5\;eu)$. A phosphodiesterase catalyzed hydrolysis of dimethylphosphate is $10^{17}$ times faster than the simple water rate. The observed rate of hydrolysis of hydroxyethylmethylphosphate is comparable to that of dimethylphosphate indicating C-O bond cleavage $(k_{obs}=6{\times}10^{-7}s^{-1}\;at\;150^{\circ}C)$.

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Kinetic Studies on the Mechanism of Hydrolysis of ${\alpha}$-Nitrobenzaldehydephenylhydrazone (${\alpha}$-Nitrobenzaldehydephenylhydrazone의 가수분해에 대한 반응속도론적 연구)

  • Tae-Rin Kim;Won-Sik Choi
    • Journal of the Korean Chemical Society
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    • v.22 no.1
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    • pp.30-36
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    • 1978
  • The kinetics of hydrolysis of ${\alpha}$-nitrobenzaldehydephenylhydrazone derivatives (p-$NO_2$, m-$NO_2$, p-Cl, p-$CH_3$) have been investigated by UV spectrometry in 25% dioxane-water at $25^{\circ}C$ and a rate equation which can be applied over wide pH range was obtained. From the rate equation and the effect of solvent, substituent and pKa on the rate equation, the following reaction mechanisms were proposed. Below pH 3.0 the hydrolysis of ${\alpha}$-nitrobenzaldehydephenylhydrazone proceeds by $S_N1$ mechanism, while above pH 4.0 the hydrolysis proceeds through 1,3-dipole ion mechanism. In the range of pH from 3.0 to 4.0 these two reactions occur competitively.

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