• Title/Summary/Keyword: Activation energies

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Adsorption Characteristics of Flue Gas Components on Zeolite 13X and Effects of Impurity (제올라이트 13X에 의한 배가스 성분의 흡착 특성 및 불순물의 영향)

  • Suh, Sung-Sup;Lee, Ho-Jin
    • Korean Chemical Engineering Research
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    • v.54 no.6
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    • pp.838-846
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    • 2016
  • Most of combustion processess used in industries require recovering or removing flue gas components. Recently a new MBA (moving bed adsorption) process for recovering $CO_2$ using zeolite 13X was developed. In this study, adsorption experiments for carbon dioxide, nitrogen, sulfur dioxide, and water vapor on zeolite 13X were carried out. Adsorption equilibrium and adsorption rate into solid particle were investigated. Langmuir, Toth, and Freundlich isotherm parameters were calculated from the experiment data at various temperatures. Experimental results were consistent with the theoretically predicted values. Also $CO_2$ adsorption amount was measured under the conditions with impurities such as $SO_2$ and $H_2O$. Binary adsorption data were well fitted to the extended Langmuir isotherm using parameters obtained from pure component experiment. However, $H_2O$ impurity less than, roughly, ${\sim}10^{-5}H_2O\;mol/g$ zeolite 13X enhanced slightly $CO_2$ adsorption. Spherical particle diffusion model well described experimentally measured adsorption rate. Diffusion coefficients and activation energies of $CO_2$, $SO_2$, $N_2$, $H_2O$ were obtained. Diffusion coefficients of $CO_2$ and $SO_2$ decreased with small amount of preadsorbed impurity. Parameter values from this study will be helpful to design of real commercial adsorption process.

Changes in Available Lysine and Extractable Nitrogen, and Extent of Browning during the Storage of Dried Fish Meat (건어육저장중의 유효 Lysine 및 Ex분질소의 변화와 갈변)

  • LEE Kang-Ho;SONG Dong-Suck;You Byeong-Jin;KIM Mu-Nam
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.15 no.4
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    • pp.271-282
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    • 1982
  • The browning development, mainly through the Maillard reaction, occurring in the dried fish meat products during storage causes reduction of the nutritional value due to the loss of the essential amino acid such as available lysine as well as off -flavor resulting in the deterioration of the food quality thus shortening the shelflife. In the work, the changes in the amount of available lysine, extractable nitrogenous compounds (nonprotein-N, amino-N, trimethylamine oxide, trimethylamine, and free lysine) and development of browning were measured to assess the relationship between the shelflife and the quality loss in dried filefish under the steady state conditions (35,45, and $55^{\circ}C;a_{w}'s$ of 0.44 0.52, 0.65 and 0.75 at each temperature) and fluctuating temperature condition of $35/55^{\circ}C$ will. alternating 7 day periods at each water activity. The results indicated that the amount of available lysine and extractable nitrogenous compounds except TMA decreased rapidly with increasing temperatures and water activities while the rate of available lysine and extractable nitrogenous compounds must be involved in the initial stage of brown pigment formation. The available lysine loss of the dried filefish products stored under the fluctuating temperature conditions was greater than that stored under its fixed mean temperature, $45^{\circ}C$. The activation energies for lysine loss obtained from the Arrhenius plot ranged 6.9 to 4.4 Kcal/mol and $Q_{10}$ values at $40^{\circ}C$ were 1.4 to 1.2. The values for browning were 15.7 to 14.4 Kcal/mol and 2.2 to 2.0 respectively. Shelf-life, defined as the time to reach 0.15 O. D./g solid or the limit of off-color deterioration by browning reaction, was extented longer than the halflife of Iysine loss, actually corresponding $75\%$ loss of available lysine. This suggested that the halflife of lysine loss might not be adequate to assess the shelf-life of the food system with high potential of protein, nonproteinous nitrogen compounds, and lipids.

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Improved Preservation and Shelf-life Extension of Fish Cake by Modified Atmosphere Packaging (변형기체포장에 의한 어묵의 저장성 향상 및 유통기한 연장)

  • Park, Su Yeon;An, Duck Soon;Kang, Jun Soo;Lee, Dong Sun
    • KOREAN JOURNAL OF PACKAGING SCIENCE & TECHNOLOGY
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    • v.23 no.2
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    • pp.75-81
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    • 2017
  • Modified atmosphere packaging (MAP) of vacuum, 60% $N_2/40%$ $CO_2$, 100% $N_2$ and 100% $CO_2$ were examined to preserve fried fish cakes and extend their shelf life. When product packages in air were stored at 5, 10, and $15^{\circ}C$ with measurement in quality attributes, aerobic bacterial growth was found to be primary quality factor to determine the shelf life of the product. Huang's model was adopted to obtain the parameters for use in shelf life determination for a variety of packaging and storage conditions. Temperature dependence expressed in Arrhenius equation showed activation energies of 139.4 and 41.8 kJ/mol for inverse of lag time and growth rate of the microbial spoilage, respectively. MAP of 100% $CO_2$ could double the product shelf life at $10^{\circ}C$ compared to air package. High $CO_2$ concentration MAP at low temperature was found to be effective to prolong the shelf life.

Conduction Band Model of the System ${\alpha}-Fe_2O_3$-CdO at Extrinsic Region (외성영역에서 ${\alpha}-Fe_2O_3$-CdO 계의 전도띠 모델)

  • Keu Hong Kim;Seok Ho Yun;Young Sik Kwon;Jae Shi Choi
    • Journal of the Korean Chemical Society
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    • v.31 no.5
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    • pp.406-412
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    • 1987
  • The electrical conductivities of ${\alpha}-Fe_2O_3$ containing 2.5 and 5.0mol% of cadmium were measured from 300 to $900^{\circ}C$ under oxygen pressures of 10$^{-7}$ to 10$^{-1}$ atmosphere. Plots of log ${\sigma}$ vs. 10$^3$/T show the extrinsic conductivity at oxygen pressure higher than $5{\times}10$^{-2}$atm. The transition points appear at about 550$^{\circ}$C and the activation energies are 1.34 eV for the intrinsic region and 0.50 eV for the extrinsic region on 5mol% Cd-doped ${\alpha}-Fe_2O_3$. The extrinsic conductivity disappears at oxygen partial pressures lower than $5{\times}10$^{-2}$ atm, and the intrinsic conductivity predominates. The electrical conductivities decrease with increasing mol% of cadmium doped. The predominant defect of ${\alpha}-Fe_2O_3$ doped with Cd is believed to be Fe${2+}$ interstitial for the intrinsic, however, oxygen vacancy predominates for the extrinsic region. The electrical conduction mechanisms are proposed and the conduction band model is suggested for the extrinsic region.

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Exchange Reaction Mechanism of $Pb(II)-N_2O_m$ Macrocyclic Complexes by $^{207}Pb-NMR$ Spectroscopy ($^{207}Pb-NMR$ 분광법에 의한 $Pb(II)-N_2O_m$계 거대고리 리간드 착물형성 반응의 교환 메카니즘)

  • Kim, Jeong;Yun, Chang Ju;Yu, Han Jun;Kim, Geon;Kim, Si Jung
    • Journal of the Korean Chemical Society
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    • v.38 no.1
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    • pp.41-49
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    • 1994
  • Exchange reaction mechanisms of the Pb(II) ion for the complexes between Pb(II) ion and nitrogen oxygen donor macrocyclic ligands, such as 1,13-diaza-3,4 : $1011-dibenzo-59-dioxacyclohexa-decane(NtnOtnH_4)$, 1,15-diaza-3,4 : $1213-dibenzo-5811-trioxacycloheptadecane(NenOdienH_4)$, and 1,15-diaza-3,4 : $1213-dibenzo-5811-trioxacyclooctadecane(NtnOdienH_4)$, were studied by $^{207}Pb-NMR$ spectroscopy in N,N'-dimethylformamide(DMF) solutions. The associative-dissociative mechanism dominated in $NtnOtnH_4-Pb(II)$ and $NtnOdienH_4-Pb(II)$ system. For $NenOdienH_4-Pb(II)$ system, the bimolecular exchange mechanism prevailed below $-5^{\circ}C$, and both bimolecular exchange and associative-dissociative mechanism dominated above $+5^{\circ}C.$ The order of activation energies for dissociation was $NtnOdienH_4\;<\;NtnOtnH_4\;<\;NenOdienH_4$ which was reverse to the order of stabilities.

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Studies on the Semicarbazone Formation of Mono substituted Benzaldehydes (일치환 Bezaldehyde 의 Semicarbazone 생성 반응에 관한 연구)

  • Kim, Yong-In;Kim, Chang-Mean
    • Journal of the Korean Applied Science and Technology
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    • v.7 no.1
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    • pp.93-105
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    • 1990
  • Semicarbazone formation of nine monosubstituted benzaldehydes was studied kinetically in 20% methanol buffer solution at 15, 25, 35, and $45^{circ}C$. The rate of p-nitrobenzaldehyde semicarbazone formation is 2.7 times as fast as that of benzaldehyde, while p-hvdroxybenzaldehyde is 3.6 times as slow as that of benzaldehyde. Activation energies for p-chlorobenzaldehyde, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldshyde, p-hydroxybenzaldehyde, and p-dimethylaminobenzaldehyde semicarbazone formation are calculated as 5.80, 6.19, 6.57, 7.06, 8.03, and 6.46 kcal/mol respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ions but neutral molecules involving hydrogen bonding between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst, and concerted attack of the necleophilic reagent, free base on carbonyl compound. Also, the effect of solvent composition is small in 20% and 50% methanol (and ethanol) aqueous solutions. The ${\rho}-{\sigma}$ plots for the rates of semicarbazone formation at pH 7.1 show a linear ${\rho}-{\sigma}$ relationship (${\rho}=0.14l$, in contrast to that at pH 2.75 and pH 5.4 corresponding to ${\rho}-{\sigma}$ correlations reparted by Jencks. The rate of semicarbazone formation at pH 5.4 show a relationship which is convex upward, resulting in a break in the curve but at pH 2.75, slight difference from a linear relationship. As a result of studying citric acid catalysis, second-order rate constants increase linearly with citric acid concentration and show a 2 times increase as the catalyst concentration is varied from 0.025 to 0.1 mol/1 at pH 2,9, but slight increase at pH 5.3. The rate-determining step is addition below pH 5 but is dehydration between pH 5 and 7. Conclusively, the rate-determining step of the reaction changes from dehydration to addition in respect to hydrogen ion activity near pH 5. The ortho: para rate ratio of the hydroxybenzaldehydes for semicarbazone formation is about 17 at $15^{\circ}C$. It is concluded that the results constitute strong evidence in favor of greater stabilization of p- than o-hydroxybenzaldehyde by substituent which donate electrons by resonance and is due to hydrogen bonding between the carbon-bound hydrogen of the-CHO group and the oxygen atom of the substituent.

Rapid Fermentation of Fish Sauce and Its Kinetics (어장유의 속성발효와 동력학적 고찰)

  • KIM Byeong-Sam;PARK Sang-Min;CHOI Soo-Il;KIM Chang-Yang;HAN Bong-Ho
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.19 no.1
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    • pp.10-19
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    • 1986
  • A study on the rapid fermentation of fish sauce has been carried out for effective utilization of sardine. The frozen sardine was thawed at room temperature, chopped, homogenized with equal amount of water and then hydrolyzed by addition of commercial proteolytic enzymes such as bromelain, papaya protease, ficin and a enzyme mixture under different conditions of hydrolysis. The effect of wheat gluten for masking fishy odor and color development during thermal treatment were also tested. The reaction mixture was heated for 30 minutes at $100^{\circ}C$ for enzyme inactivation, pasteurization and color development and then centrifuged for 20 minutes at 4,000 rpm. Finally, table salt and benzoic acid were added for bacteriostatic effect. The results were summarized as follows ; 1. The hydrolyzing temperature, time, pH and the concentration of enzymes based on the weight of whole sardine for optimal hydrolysis were as follows: autolysis, $52.5^{\circ}C$, 4 hours, pH 8.0: with $0.25\%$ bromelain, $52.5^{\circ}C$, 4 hours, pH 6.6 :with $0.25\%$ ficin, $52.5^{\circ}C$, 4 hours, pH 6.8: with $0.3\%$ papaya protease, $52.5^{\circ}C$, 4 hours, pH 6.6: with $6\%$ enzyme mixture, $52.5^{\circ}C$, 4 hours, pH 6.9, respectively. But pH control was not much beneficial in increasing yield. 2. The hydrolytic reaction of chopped sardine with proteolytic enzymes could be interpreted as a first order reaction that devided into 2 periods with different reaction rate constsnts. $Q_{10}$ values of the first period prior to 4 hours were 1.23 to 1.31, and those of post 4 hours were 1.25 to 1.55. The corresponding activation energies were $1.81{\times}10^4\;to\;2.34{\times}10^4\;kJ/kmol$ and $1.92{\times}10^4\;to\;3.77{\times}10^4\;kJ/kmol$, respectively. 3. The reasonable amount of $75\%$ vital wheat gluten for addition was $9\%$ of chopped sardine. 4. The dark brown color was mainly developed during the thermal treatment for 30 minutes at $100^{\circ}C$ and not changed during storage.

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Rheological Properties of Rehydrated Suspensions of Freeze Dried Kochujang Powders (동결건조 분말고추장의 재수화시 리올로지 특성)

  • Kim, Suk-Shin;Chang, Kyu-Seob;Yoon, Han-Kyo;Lee, Sang-Kyu;Lee, Shin-Young
    • Korean Journal of Food Science and Technology
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    • v.19 no.2
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    • pp.81-88
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    • 1987
  • Rheological properties of rehydrated suspensions of two kinds of freeze dried Kochujang powders, processed at different freezing rates, were compared with raw Kochujang using Brookfield wide-gap rotational viscometer at $25^{\circ}C-60^{\circ}C$. Shear rates ranged from $0.1965\;sec^{-1}$ to $1.9650\;sec^{-1}$ and solid content ranged from 47% to 56%. Rehydrated suspensions of quickly frozen Kochujang powder and slowly frozen Kochujang powder, and raw Kochujang exhibited pseudoplastic behaviors with yield stress and presented thixotropic properties which followed the second-order kinetic behavior proposed by Tiu. Suspensions of Kochujang powders exhibited considerably higher decaying rates than raw Kochujang. The dependency of the equilibrium structure parameter on the shear rate was weak, and there were no significant differences among the values of structure parameters of three samples. The temperature dependency of the apparent viscosity of Kochujang suspension was fully expressed by Arrhenius equation and activation energies of suspensions of quickly frozen Kochujang powder and slowly frozen Kochujang powder, and raw Kochujang were 2.21, 2.18, and 2.32 Kcal/g.mole respectively. Consistency indices of three samples increased with solid content and decreased with temperature. Flow behavior indices of three samples showed no considerable dependency on the temperature and solid content. There were no significant differences in the rheological properties between two Kochujang powders.

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Study of Magnetic Field Shielded Sputtering Process as a Room Temperature High Quality ITO Thin Film Deposition Process

  • Lee, Jun-Young;Jang, Yun-Sung;Lee, You-Jong;Hong, Mun-Pyo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.288-289
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    • 2011
  • Indium Tin Oxide (ITO) is a typical highly Transparent Conductive Oxide (TCO) currently used as a transparent electrode material. Most widely used deposition method is the sputtering process for ITO film deposition because it has a high deposition rate, allows accurate control of the film thickness and easy deposition process and high electrical/optical properties. However, to apply high quality ITO thin film in a flexible microelectronic device using a plastic substrate, conventional DC magnetron sputtering (DMS) processed ITO thin film is not suitable because it needs a high temperature thermal annealing process to obtain high optical transmittance and low resistivity, while the generally plastic substrates has low glass transition temperatures. In the room temperature sputtering process, the electrical property degradation of ITO thin film is caused by negative oxygen ions effect. This high energy negative oxygen ions(about over 100eV) can be critical physical bombardment damages against the formation of the ITO thin film, and this damage does not recover in the room temperature process that does not offer thermal annealing. Hence new ITO deposition process that can provide the high electrical/optical properties of the ITO film at room temperature is needed. To solve these limitations we develop the Magnetic Field Shielded Sputtering (MFSS) system. The MFSS is based on DMS and it has the plasma limiter, which compose the permanent magnet array (Fig.1). During the ITO thin film deposition in the MFSS process, the electrons in the plasma are trapped by the magnetic field at the plasma limiters. The plasma limiter, which has a negative potential in the MFSS process, prevents to the damage by negative oxygen ions bombardment, and increases the heat(-) up effect by the Ar ions in the bulk plasma. Fig. 2. shows the electrical properties of the MFSS ITO thin film and DMS ITO thin film at room temperature. With the increase of the sputtering pressure, the resistivity of DMS ITO increases. On the other hand, the resistivity of the MFSS ITO slightly increases and becomes lower than that of the DMS ITO at all sputtering pressures. The lowest resistivity of the DMS ITO is $1.0{\times}10-3{\Omega}{\cdot}cm$ and that of the MFSS ITO is $4.5{\times}10-4{\Omega}{\cdot}cm$. This resistivity difference is caused by the carrier mobility. The carrier mobility of the MFSS ITO is 40 $cm^2/V{\cdot}s$, which is significantly higher than that of the DMS ITO (10 $cm^2/V{\cdot}s$). The low resistivity and high carrier mobility of the MFSS ITO are due to the magnetic field shielded effect. In addition, although not shown in this paper, the roughness of the MFSS ITO thin film is lower than that of the DMS ITO thin film, and TEM, XRD and XPS analysis of the MFSS ITO show the nano-crystalline structure. As a result, the MFSS process can effectively prevent to the high energy negative oxygen ions bombardment and supply activation energies by accelerating Ar ions in the plasma; therefore, high quality ITO can be deposited at room temperature.

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Formation of amorphous and crystalline phase, phase sequence by solid state reaction in Co/Si multilayer thin films (Co/Si 다층박막에서의 고상반응에 의한 비정질상과 결정상의 생성 및 상전이)

  • Sim, Jae-Yeop;Park, Sang-Uk;Ji, Eung-Jun;Gwak, Jun-Seop;Choe, Jeong-Dong;Baek, Hong-Gu
    • Korean Journal of Materials Research
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    • v.4 no.3
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    • pp.301-311
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    • 1994
  • The growth of amorphous and first crystalline phase, and phase sequence by solid state reaction were examined in Co/Si multilayer thin films by DSC and XRD. The experimental results were compared with the results expected by effective driving force models, PDF and effective heat of formation models.Amorphous phase growth was not observed in Co/Si system and it was consistent with the predicted result by effective driving force. It was observed that the first crystalline phase is CoSi. According to the PDF and effective heat of formation models, the first crystalline phases were CoSi and $CO_2Si$, respectively. The experiemental results were coincident with the PDF model considering structure factors. In case of the atomic concentration ratios of 2Co : 1Si and 1Co : 2Si, the phases sequences were $CoSi\to Co_2Si$ and $CoSi \to Co_2Si \to CoSi \to CoSi_2$, respectively and it was analysized through the effective heat of formation model. The formations of CoSi, $CO_2Si$ and $COSi_2$ in initial stage were controlled by nucleation and the activation energies for the nucleation of three phases were 1.71, 2.34 and 2.79eV.

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