• 제목/요약/키워드: order of reaction

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Dependence of an Interfacial Diels-Alder Reaction Kinetics on the Density of the Immobilized Dienophile: An Example of Phase-Separation

  • Min, Kyoung-Mi;Jung, Deok-Ho;Chae, Su-In;Kwon, Young-Eun
    • Bulletin of the Korean Chemical Society
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    • 제32권5호
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    • pp.1679-1684
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    • 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%).

고온/고압 조건에서의 석탄 촤 내부 및 외부 가스화 반응효과 (Impact of Internal/External Diffusion on Gasification Reaction Rate Analysis of Coal Char in High Temperatures and Elevated pressures)

  • 김경민;김진호;리산디케빈요하네스;김량균;김규보;전충환
    • 한국연소학회지
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    • 제21권4호
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    • pp.23-29
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    • 2016
  • Reactivity of gasification defined by bouardard reaction is critical parameter in efficiency of the gasifier. In this study, char reactivity of the gasification was derived from the experiments using the intrinsic reaction kinetics model. Pressurized wire mesh heating reactor (PWMR) can produce high temperature and high pressure conditions up to 50 atm and 1750 K, respectively and PWMR was designed to evaluate the intrinsic reaction kinetics of $CO_2$ gasification. In this study, Kideco and KCH (sub-bituminous Indonesian coal) were pulverized and converted into char. Experiments used the PWMR were conducted and the conditions of the temperature and pressure were 1373~1673 K, 1~40 atm. To distinguish the pressure effect from high pressurized condition, internal and external effectiveness factors were considered. Finally, the intrinsic kinetics of the Kideco and KCH coal char were derived from $n^{th}$ order reaction rate equations.

Amino산-Xylose 갈변반응 물질의 항산화성 1. 아미노산과 갈변 반응 물질의 항산화성 (Antioxidant Activity of Amino Acid-Xylose Browning Reaction Products 1. Antioxidant Activity of Various Amino Acids and Their Browning Reaction Products)

  • 유병진;이강호;김장량;이종호
    • 한국수산과학회지
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    • 제19권1호
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    • pp.1-9
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    • 1986
  • In order to isolate and clarify the antioxygenic substances from the browning reaction products, the antioxidant activity of various amino acids and their browning reaction products were measured when they were reacted with xylose. Among nonpolar amino acids Met and Trp appeared to have stronger antioxidant effect than others. Most of polar and basic amino acids, however, did not have antioxidant activity. Ser and Cys showed a rather slight prooxidant effect. The browning reaction products of Trp and His had a higher level of antioxidant activity than that they were reacted as free amino acids. But the browning product of Met did not show the antioxidant activity. When all amino acids were divided on their polar characteristics, the higher optical density of the browning reaction products showed, the stronger antioxidant activity revealed.

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Comparison of local reaction at injection site following intramuscular administration with three commercial atrophic rhinitis vaccines in pigs

  • Kim, Myung-Hyee;Kwon, Taeyong;Yoo, Sung J.;Seo, Sang won;Park, Jun Woo;Lyoo, Young S.
    • 한국동물위생학회지
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    • 제41권4호
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    • pp.251-255
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    • 2018
  • Bordetella bronchiseptica and Pasteurella multocida are two main pathogens responsible for atrophic rhinitis (AR), which causes considerable economic losses in swine industry worldwide. Commercial vaccine has been widely used to prevent the damage from AR in Korea. Adverse effects of vaccination at the injection site have been reported, which results in the numerous complaint from farms. However, data on about local reaction at the injection site remains limited. In this study, we compared the local adverse effects of three commercial vaccines following intramuscular injection. The results showed that no gross lesion was founded at the injection sites of all three vaccines. In histopathologic examination, a various level of lesions was identified. Especially, the local reaction of vaccine including saponin as an adjuvant showed the lowest level of histopathological lesions, when compared to those of oil-based and vitamin E-based vaccines. Therefore, this study would provide the information about the extent of local reaction at the injection site and help the farmer to select AR vaccine in order to avoid adverse reaction due to vaccination.

Si-N 전구체를 이용한 에폭시/실리카 나노복합재료의 제조 (Novel Preparation of Epoxy/Silica Nanocomposite Using Si-N Precursor)

  • 김이주;윤호규;이상수;김준경
    • 폴리머
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    • 제28권5호
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    • pp.391-396
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    • 2004
  • 기존의 에폭시/실리카 나노복합재료의 제조 방법에서 나타나는 문제점인 경화 반응 중의 휘발성 부산물 생성에 의한 미세기공 형성 및 치수 불안전성 등을 극복하고자 Si-N 전구체를 사용한 새로운 방법을 제안하고자 한다. 실리카 전구체로 부산물이 형성되지 않는 메틸트리페닐실란 (MTPS)을 합성하고 이를 이용하여 솔-젤 반응과 에폭시 경화 반응이 병행되는 동시 복합화 반응을 통하여 무기상의 고른 분산상태를 지닌 에폭시/실리카 나노복합재료를 제조하였으며, 이로부터 뛰어난 투명성뿐 아니라 기계적 물성과 열적특성에서 탁월한 물성의 증가를 얻을 수 있었다.

Maillard Browning Reaction of D-Psicose as Affected by Reaction Factors

  • Baek, Seung-Hee;Kwon, So-Young;Lee, Hyeon-Gyu;Baek, Hyung-Hee
    • Food Science and Biotechnology
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    • 제17권6호
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    • pp.1349-1351
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    • 2008
  • This study examined the effects of temperature, D-psicose concentration, pH, and various amino acids on the Maillard browning reaction of D-psicose and glycine mixture and compared browning color intensity with those of other sugars, such as sucrose, D-glucose, D-fructose, and D-tagatose. When D-psicose (0.1 M) and glycine (0.1 M) mixture was heated at $70-100^{\circ}C$ for 5 hr, the absorbance at 420 nm increased with increasing reaction temperature and time. The Hunter a, b values, and color difference (${\Delta}E$) increased with increasing D-psicose concentration and pH within the range of pH 3-7 except at pH 6, while the L value decreased. The rate of Maillard browning reaction was in order of D-tagatose>D-psicose $\fallingdotseq$ D-fructose>D-glucose>sucrose. The browning color intensity of the D-psicose-basic and non-polar amino acids mixtures was higher than that of the D-psicose-acidic amino acids.

Ethyl Silicate를 고순도 $\beta$-SiC미분말 합성에 관한 연구(I) 반응조건과 $\beta$-SiC의 생성율 및 특성 (A Study on Synthesis of High Purity $\beta$-SiC Fine Particle from Ethylsilicate(I) -Reaction Conditon, Yeild and Properties of $\beta$-SiC-)

  • 최용식;박금철
    • 한국세라믹학회지
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    • 제25권5호
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    • pp.473-478
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    • 1988
  • In order to obtain the high purity $\beta$-SiC powder that possesses the excellent sinterability and is close to the spherical shape, the carbon black was mixed into the composition of Si(OC2H5)4-H2O-NH3-C2H5OH which the monodispersed spherical fine particles is formed the hydrolysis of Ethylsilicate and the mixture was carbonized under an argon atmosphere. Particle shpae, size and the yield of $\beta$-SiC powder were investigated according to the molar ratio of carbon/alkoxide and variations of reaction temperature and reaction time. The results of this study are as follow ; 1) The yield of $\beta$-SiC gained from the reaction for one hour at 150$0^{\circ}C$ almost got near 100% and the particle size of $\beta$-SiC from the reaction for 15 hrs at 150$0^{\circ}C$ was 0.2${\mu}{\textrm}{m}$ on the average and close to the spherical shape agglomerate state. 2) When the molar ratio carbon/alkoxide is over 3.1 and the reaction occurs at 145$0^{\circ}C$ for 5hrs, the carbon content has not an effect on the kind of crystal of product.

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장쇄(長鎖)알킬 아세탈형(型) 비(非)이온성(性) 계면활성제합성(界面活性劑合成)에 관한 반응속도론적(反應速度論的) 연구(硏究) (Kinetics of the Reaction of Long Chain Alkyl Acetal Type Nonionic Surfactants)

  • 손주환;이승렬;남기대;노승호
    • 한국응용과학기술학회지
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    • 제5권1호
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    • pp.41-51
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    • 1988
  • Aliphatic aldehyde polyoxyethylene glycol acetals were synthesised through the reaction of aliphatic aldehydes such as caproic aldehyde, capryl aldehyde, capric aldehyde and lauric aldehyde with excess diethylene glycol, triethylene glycol and tetraethylene glycol, respectively. The acetal formation, in which water was azeotropically distilled by adding benzene to the reaction system, was gained a good yield of acetal type compounds. This reaction is found pseudo first order reaction at various temperatures such 70, 80, 90 and $97^{\circ}C$. Also these activation energies of reaction of acetal type products such as caproic aldehyde diethylene glycol acetal, capryl aldehyde diethylene glycol acetal, capric aldehyde diethylene glycol acetal, lauric aldehyde diethylene glycol acetal, caproic aldehyde triethylene glycol acetal and caproic aldehyde tetraethylene acetal were 17.3, 19.6, 21.2, 21.6, 15.5 and 14.7 Kcal/mole.

2-Amino-2-Methyl-1-Propanol이 용해한 극성 용매에서 이산화탄소의 흡수 (Absorption of Carbon Dioxide into Polar Solvents of 2-Amino-2-Methyl-1-Propanol)

  • 손영식;허남환;이성수;박상욱
    • Korean Chemical Engineering Research
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    • 제47권3호
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    • pp.380-385
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    • 2009
  • 평판형 교반기를 사용하여 2-amino-2-methyl-1-propanol(AMP)가 용해된 methanol, ethanol, n-propanol, n-butanol, ethylene glycol, propylene glycol, 및 propylene carbonate와 같은 극성 용매에서 이산화탄소($CO_2$)의 흡수속도를 측정하였다. $CO_2$의 흡수속도와 carbamate 생성 반응 메커니즘을 사용하여 기-액 불균일반응계의 빠른 반응영역에서 $CO_2$-AMP의 반응속도론을 해석하였으며 용매의 용해도 매개변수와 반응속도상수와의 상관관계를 제시하였다.

Reactivity of Superoxide Ion with Halogenonitriles and Dihalocarbons in Aprotic Media

  • 전승원;최용국
    • Bulletin of the Korean Chemical Society
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    • 제16권11호
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    • pp.1060-1064
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    • 1995
  • The reactivity of superoxide ion (O2-.) with halogenated substrates is investigated by cyclic voltammetry and rotated ring-disk electrode method in aprotic solvents. The more positive the reduction potential of the substituted nitrile, the more facile is nucleophilic displacement by O2-.. The reaction rates of halogenonitriles with O2-. vary according to the leaving-group propensity of halide (Br > Cl > F). The relative reaction rates of other substituted nitriles are in the order of electron-withdrawing propensity of the substituent group (CN > C(O)NH2 > Ph ≒ CH2CN). The reaction of O2-. with dihalocarbons indicates that five-membered rings can be rapidly formed by the cyclization of substrate and O2-., and the relative rates of cyclization depend on the number of methylenic carbons {Br(CH2)nBr, [n=1 < 2 < 3 > 4 > 5]}. Mechanisms are proposed for the reaction of O2-. with halogenated substrates.