• Title/Summary/Keyword: Activation energies

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Kinetics and Mechanism of the Selective Oxidation of Ethylene for Ethylene Oxide over Monolithic Silver Catalyst (모놀리스형 은촉매상에서 에틸렌선택산화반응의 속도론적 고찰)

  • Park, Rho-Bum;Kim, Sang-Chai;Sunwoo, Chang-Sin;Yu, Eui-Yeon
    • Applied Chemistry for Engineering
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    • v.2 no.2
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    • pp.165-174
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    • 1991
  • The kinetics and the mechanism for the selective oxidation of ethylene on the supported monolithic silver catalyst were experimentally investigated in a fixed bed tubular reactor. The formation rates of ethylene oxide and carbon dioxide were measured at the atmospheric pressure with various combinations of partial pressures of ethylene and oxygen at temperature range of $225-300^{\circ}C$, conversion with 1.2-7.5 %, and then the mechanism of the selective oxidation of ethylene was verified. Their formation rates fitted with the Langmuir-Hinshelwood mechnism. The ethylene oxide and carbon dioxide are produced by reation of adsorbed ethylene with monoatomic oxygen adsorbed on the active sites of Ag-surface, and their formation rate equation are expressed as : $R_{EO}={\frac{k_1K_0{^{1/2}}K_EK_SP_{02}{^{3/2}}P_E}{(1+{\sqrt{K_0P_{02}}}+K_EP_E+K_PP_P)^2(1+{\sqrt{K_SP_{02}})^2}}$ $R_C={\frac{k_2K_0{^3}K_EK_S{^{7/2}}P_{02}{^{13/2}}P_E}{(1+{\sqrt{K_0P_{02}}}+K_EP_E+K_PP_P)^7(1+{\sqrt{K_SP_{02}})^7}}$ The activation energies of ethylene oxide and dioxide and carbon dioxide formations can be estimated to be 12.25 and 17.85 Kcal/mol, respectively.

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Pyrolysis Characteristics of Sawdust and Rice Husk (톱밥과 왕겨의 열분해 특성 연구)

  • Park, Dong Kyoo;Seo, Myung Won;Goo, Jeong Hoi;Kim, Sang Done;Lee, See Hoon;Lee, Jae Goo;Song, Byung-Ho
    • Applied Chemistry for Engineering
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    • v.18 no.5
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    • pp.415-423
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    • 2007
  • Pyrolysis characteristics of sawdust and rice husk as biomass resources in a thermogravimetric analysis were determined. Experiments were carried out with a linear heating rate under inert atmosphere of $N_2$ gas. Pyrolysis of the biomass can be classified as a lower temperature reaction zone where the major component of holocellulose is thermally decomposed and a high temperature reaction zone where lignin is thermally decomposed. The obtained data was analyzed by the two-step consecutive reaction model. Activation energies of sawdust and rice husk are found to be respectively 82.5 kJ/mol and 85.1kJ/mol in the low temperature zone according to the first order reaction model and 19.7 kJ/mol, 22.0 kJ/mol in the high temperature zone according to the three-way transport model. The reaction rate constant with variation of heating rate can be well predicted by the kinetic compensation relation of Gaur-Reed.

Rheological Properties of Gelatinized Millet Starch Dispersions (국내산 조전분 호화액의 유동특성)

  • Kim, Nam-Soo;Nam, Young-Jung
    • Korean Journal of Food Science and Technology
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    • v.21 no.6
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    • pp.742-748
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    • 1989
  • Rheological properties of gelatinized millet starch dispersions were evaluated. Gelatinized nonwaxy and waxy millet starch dispersion were typical pseudoplastic fluids. At constant shear rate, gelatinized waxy millet starch dispersion showed higher shear stress than nonwaxy millet starch dispersion. Flow behaviours of gelatinized nonwaxy and waxy millet starch dispersion were well fitted to Herschel-Bulkley equation and flow behaviour index (n) and consistency index (K) were strongly concentration dependent. There was a linear relationship between concentration of gelatinized starch dispersion and square root of yield stress. The concentrations of gelatinized nonwaxy and waxy millet starch dispersion where yield stresses become zero were estimated as 2.19 and 1.69%, respectively. Pseudoplastic constant (m) approaches to a constant value in each type of millet starch when the concentration of gelatinized starch dispersion was increased. As the measuring temperatures increase, n value was increased, whereas, K value was decreased. The activation energies of gelatinized nonwaxy and waxy millet starch dispersion were 2.89 and 3.18kcal/mol, respectively.

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Kinetic Study on the Color Deterioration of Crude Anthocyanin Extract from Schizandra Fruit (Schizandra chinensis fructus) (오미자 색소 추출물의 가열 변색에 대한 속도론적 연구)

  • Cho, Sung-Bin;Kim, Hyun-Jung;Yoon, Jong-Il;Chun, Hyang-Sook
    • Korean Journal of Food Science and Technology
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    • v.35 no.1
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    • pp.23-27
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    • 2003
  • The effects of temperature and pH on color deterioration of anthocyanin in Schizandra fruit (Schizandra chinensis fructus) were determined with temperature range of $80{\sim}100^{\circ}C$ and pH range of $2.0{\sim}5.0$. Browning index was used as an index of color deterioration of crude anthocyanin extract from Schizandra fruit. As pH of crude anthocyanin extract was increased, color deterioration was accelerated, showing pH-dependency of thermal stability of anthocyanin extract from Schizandra fruit. Anthocyanin degradation could be modeled as a second-order rate reaction, with rate of $3.2{\times}10^{-3}\;h^{-1}\;(pH\;2.0){\sim}4.1{\times}10^{-3}\;h^{-1}\;(pH\;5.0)\;at\;100^{\circ}C$. Temperature dependence of deterioration was described by the Arrhenius relationship. Activation energies for pH $2.0{\sim}5.0$ ranged from $24.87{\sim}42.54\;kJ/mol^{-1}$.

Studies on the Rheological Properties of Sugar Derivative Sweeteners (대체감미료 당유도체의 유변성에 관한 연구)

  • Lee, Cherl-Ho;Park, Choon-Sang;Han, Bok-Jin;Kim, Bong-Chan;Jang, Ji-Hyang
    • Korean Journal of Food Science and Technology
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    • v.22 no.7
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    • pp.852-857
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    • 1990
  • The rheological properties and food functionality of the novel sugar derivatives, fructo-oligosaccharide, high maltose syrup(HMS), maltitol and sorbitol were examined and compared to those of sucrose. All samples tested showed Newtonian fluid property at the concentration range of 10% to the original concentrated products containing $69{\sim}81%w/w$ solid. HMS showed the highest viscosity. The viscosity increased(r=0.8038) as the average molecular weight of sugar derivatives were increased. The viscosity increased exponentially as the concentration increased, and sugar alcohols had lower value of the exponent compared to HMS and fructo-oligosaccharide. The viscosity of sugar derivatives solutions decreased by the increasing temperature following the Arrhenius equation. The flow activation energies of sorbitol and HMS were higer than that of sucrose. Substitution of sucrose with fructo-oligosaccharide in apple jam processing did not change the textural characteristics, but in redbean jelly(yanggaeng) it reduced the hardness, adhesiveness, springiness and cohesiveness. When sucrose was 100% replaced by HMS, the texture of apple jam and redbean jelly was not changed, but by mixing sucrose and HMS 1 : 1 ratio, the hardness decreased substantially The sugar alcohols reduced the hardness, adhesiveness, springiness of apple jam and redbean jelly significantly. Addition of fructo-oligosaccharide and HMS to sucrose did not influence the solidifying rate of candy, but sorbitol, even at 10% addition, retarded the candy moulding.

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Synthesis and Characterization of UV-curable Aliphatic Epoxy Acrylate (자외선 경화형 지방족 에폭시 아크릴레이트의 합성 및 특성분석)

  • Kim, Young Chul;Lee, Byung-Hoon
    • Journal of Adhesion and Interface
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    • v.10 no.4
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    • pp.191-198
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    • 2009
  • UV-curable aliphatic epoxy acrylates were prepared by the reaction of glycerol diglycidyl ether (GDE) with 2-carboxyethyl acrylate (2-CEA) or 2-hydroxyethyl acrylate (2-HEA). The structures of the epoxy acrylates were characterized by FT-IR, $^1H$-NMR, and $^{13}C$-NMR and the yield was obtained by prep-LC. The UV- and the thermal-curing behaviors of the product were investigated using photo-DSC and DSC, respectively. The reactivity of 2-CEA was higher than 2-HEA and the yield of the product (GEA-C) which was prepared using 2-CEA was about 83%. The maximum UV-curing time ($T_{max}$) of the GEA-C contained non-reactive components and by-product was about 10 seconds. The GEA-C showed low color difference (${\Delta}E^*$), low viscosity, and good thermal stability - its value was 2.51, 192 cps, and $299^{\circ}C$ (at 5% weight loss), respectively. The activation energies ($E_a$) of thermal-curing reaction calculated from Kissinger and Ozawa-Flynn-Wall method were 91~92 kJ/mol.

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Electrical Conductivity of the System NiO-$Y_2O_3$ (NiO-$Y_2O_3$계의 전기전도성)

  • Jae Shi Choi;Keu Hong Kim;Won Yang Chung
    • Journal of the Korean Chemical Society
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    • v.30 no.1
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    • pp.27-32
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    • 1986
  • Electrical conductivities of NiO-$Y_2O_3$ systems containing 0.8, 1.6, and 3.2 mol% NiO have been measured in the temperature range of 400 to 1100$^{\circ}$C at $PO_2$'s of 1 ${\times}10^{-5}$ to 2 ${\times}10^{-1}$ atm. Plots of $log\sigma$ vs 1/T at constant $PO_2$'s are found to be linear with an inflection at temperature around 650$^{\circ}$C. The slopes are steeper in the high temperature region above 650$^{\circ}$C than in the low temperature region below 650$^{\circ}$C. The average activation energies are 41.8kcal/mol in the high temperature region and 12.5kcal/mol in the low temperature region. $PO_2$'s dependence value, 1/n, is 1/5.1~1/5.4 in the high temperature region and 1/5.9~1/6.2 in the low temperature region. The NiO-$Y_2O_3$ systems are found to be an electronic p-type semiconductor. The predominant defects in the systems are believed to be triply ionized yttrium vacancy in the high temperature region and doubly ionized oxygen interstitial in the low temperature region. Ionic contribution to the total conductivity is found from ${\sigma}^{\propto}PO_2$ in the temperatures below 650$^{\circ}$C.

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The Kinetics of Non-Enzymatic Browning Reaction in Green Tea During Storage at Different Water Activities and Temperatures (온도와 수분활성을 달리한 녹차 저장중의 비효소적 갈변)

  • Kim, Young-Suk;Jung, Yeon-Hwa;Chun, Soon-Sil;Kim, Mu-Nam
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.17 no.3
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    • pp.226-232
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    • 1988
  • Non-enzymatic browning is a carbohydrate dehydration reaction, accelerated thorough the interaction of amino compounds. Reaction depends on several factors including temperature, reactant concentration, pH, water activity and specific ion concentrations, and result in progressive development of brown pigments in the affected food systems. The present study was designed to utilize a kinetic approach to analyze the effect of temperature and water activity on the browning development in green ten. The green tea was controlled at aw of 0.33, 0.44, 0.52 and 0.65 using saturated salt solutions and then stored at 35,45 and $55^{\circ}C$. Author portion of the sample of which the water activities were controlled in the same manner was stored at 35 and $55^{\circ}C$ alternately with 7 days interval. Simplified kinetic models were used to obtain the various kinetic parameters for browning development in green tea subjected to accelerated shelf-life tests(ASLT). The reaction of browning development was zero order. The activation energies calculated from Arrhenius plot ranged $1.5{\sim}2.4kcal/mole$ and $Q_{10}$ values were between 1.07 and 1.12. These kinetic parameters were then used to predict browning development under the nonsteady storage. Assessed from the parameters the shelf-lives at $25^{\circ}C$, the time to reach 1.02 O.D./g solid at which severe brown color change could be detectable, ranged 57 to 113 days and showed decrease with increase in aw. The predicted shelf-lives at different water activities were a little higher than actual values.

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Cure Behaviors and Fracture Toughness of PEl/Difunctional Epoxy Blends (PEI/DGEBA 블랜드계의 열적특성 및 파괴인성)

  • Park, Soo-Jin;Jin, Sung-Yeol;Kaang, Shinyoung
    • Journal of Adhesion and Interface
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    • v.4 no.3
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    • pp.33-40
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    • 2003
  • In this work, diglycidyl ether of bisphenol A (DGEBA)/polyetherimide (PEI) blends were cured using 4,4-diaminodiphenyl methane (DDM). And the effects of addition of different PEI contents to neat DGEBA were investigated in the thermal properties and fracture toughness of the blends. The contents of contents of containing PEI were varied in 0, 2.5, 5, 7.5, and 10 phr. The cure activation energies ($E_a$) of the cured specimens were determined by Kissinger equation and the mechanical interfacial properties of the specimens were performed by critical stress intensity factor ($K_{IC}$). Also their surfaces were examined by using a scanning electron microscope (SEM) and the surface energetics of blends was determined by contact angles. As a result, $E_a$ and $K_{IC}$ showed maximum values in the 7.5 phr PEI. This result was interpreted in the increment of the network structure of DGEBA/PEI blends. Also, the surface energetics of the DGEBA/PEI blends showed a similar behavior with the results of $K_{IC}$. This was probably due to the improving of specific or polor component of the surface free energy of DGEBA/PEI blends, resulting in increasing the hydrogen bonding of the hydroxyl and imide groups of the blends.

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Dosimetric Properties of LiF:Mg,Cu,Na,Si TL pellets (LiF:Mg,Cu,Na,Si TL 소자의 선량계적 특성)

  • Nam, Young-Mi;Kim, Jang-Lyul;Chang, Si-Young
    • Journal of Radiation Protection and Research
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    • v.26 no.1
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    • pp.7-12
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    • 2001
  • Sintered LiF:Mg,Cu,Na,Si thermoluminescence (TL) pellets were developed for application in radiation dosimetry. In the present study, the TL dosimetric properties of LiF:Mg,Cu,Na,Si TL pellets have been investigated for emission spectrum, dose response, energy response, and fading characteristics. LiF:Mg,Cu,Na,Si TL pellets were made by using a sintering process, that is, pressing and heat treatment from TL powders. Photon irradiations for the experiments were carried out using X-ray beams and a $^{137}Cs$ gamma source at the Korea Atomic Energy Research Institute (KAERI). The average energies and the dose were in the range of 20-662 keV and $10^{-6}-10^{-2}\;Gy$, respectively. The glow curves were measured with a manual type TLD reader(System 310, Teledyne) at a constant nitrogen flux and a linear heating rate. For a constant heating rate of $5^{\circ}C\;s^{-1}$, the main dosimetric peak of glow curve appeared at $234^{\circ}C$, the activation energy was 2.34 eV and frequency factor was $1.00{\times}10^{23}$. TL emission spectrum is appeared at the blue region centered at 410 nm. A linearity of photon dose response was maintained up to 100 Gy. The photon energy responses relative to $^{137}Cs$ response were within ${\pm}20%$ at overall photon energy region. The fading of TL sensitivity of the pellets stored at the room temperature was not found for one year.

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