• Title/Summary/Keyword: Enthalpy of activation

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Molecular Theory of Superplastic Deformation (초소성변형의 분자론)

  • Chang Hong Kim;Taikyue Lee
    • Journal of the Korean Chemical Society
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    • v.23 no.4
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    • pp.217-236
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    • 1979
  • The author's theory for plastic deformation was applied to superplastic alloys (Zn-Al eutectoid, Al-Cu, Pb-Sn, Sn-Bi, Mg-Al eutectics). The plastic deformation of the superplastic alloys could be described by two Maxwell models connected in parallel which represent two grain boundary flow units. The flow units are characterized by the two parameters $X_{gj}/{\alpha}_{gj}\;and\;{\beta}_{gj}$ (j=l or 2, g signifies the grain boundary) the values of which were obtained by applying our flow equation [Eq. (5)] to experiment. We confirmed that our flow equation describes the superplasticity very well. The curve of strain rate sensitivity m (=${\partial}\;In\;f/{\partial}\;In\;\dot{s})\;vs.\;-In\dot{s}$, where f and s are stress and strain rate, respectively, showed two peaks corresponding to flow unit gl and g2, the separation of the two peaks is determined by the difference between ${\beta}_{g1}\;and\;{\beta}_{g2}$. The condition of superplasticity is also determined by ${\beta}_{gj}$, which satisfies $\dot{s}_{mj}{\leqslant}1.53}{\beta}_{gj}$ [Eq.(13)], where $\dot{s}_{mj}$ is the s of the jth unit at the peak. The grain size dependence of ${\beta}_{gj}$ is described by $ln({\beta}_{gj})^{-1}$=alnx+b [Eq. (16)], where x is the grain size, and a and b are constants. The activation enthalpy for each flow unit, ${\Delta}H_{gj}^{\neq}$ was also determined from the temperature dependence of ${\beta}_{gj}$ which is proportional to the relaxation time of the j th unit. Since the superplasticity is determined by Eq. (13), and since ${\beta}_{gj}$ and ${\Delta}H_{gj}^{\neq}$ are related, we obtained the conclusion that superplasticity occurs in the system having small ${\Delta}H_{gj}^{\neq}$ values. The Aej values were equal to the activation enthalpies of grain boundary self-diffusion of the component atoms of the alloys, this accords with our proposed flow mechanism. The ${\Delta}H_{gj}^{\neq}$ value increases with grain size as expected from Eq. (16).

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KINETIC STUDIES OF LACTIC ACID FERMENTATION(PART 2) INFLUENCE OF TEMPERATURE ON FERMENTATION (유산균 발효에 관한 동력학적 연구(제2보) 발효에 미치는 온도의 영향)

  • LEE Keun-Tai;LEE Myeong-Sook;HAN Bong-Ho
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.12 no.3
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    • pp.161-166
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    • 1979
  • To know the influence of temperature on the fermentation process, a strain of Lactobacillus bulgarius was experimentally cultured three different temperature conditions of $39^{\circ}C,\;42^{\circ}C\;and\;45^{\circ}C$, pH 5.8 and mechanical agitation of 500rpm. During 20 hour's fermentation, the microbial growth attained the maximum concentration under the conditions mentioned above. However, the culturing conditions resulted different outcomes in terms of maximum concentration of the microbes and the residual concentration of substrate. Among the three temperature conditions, the fermentation at $45^{\circ}C$ was most effective and the maximum specific growth temperature conditions, the fermentation at $45^{\circ}C$ was most effective and the maximum specific growth rate was 0.58/hr. Activation energy deduced from the Arrhenius equation was 9,220cal/mole and entropy was $-33.74\;cal/^{\circ}K$ mole. Activation enthalpy was 9,845 cal/mole and free energy was 19,800 cal/mole.

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Removal of Cs by Adsorption with IE911 (Crystalline Silicotitanate) from High-Radioactive Seawater Waste (IE911 (crystalline silicotitanate) 의한 고방사성해수폐액으로부터 Cs의 흡착 제거)

  • Lee, Eil-Hee;Lee, Keun-Young;Kim, Kwang-Wook;Kim, Ik-Soo;Chung, Dong-Yong;Moon, Jei-Kwon
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.13 no.3
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    • pp.171-180
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    • 2015
  • This study was performed on the removal of Cs, one of the main high- radioactive nuclides contained in the high-radioactive seawater waste (HSW), by adsorption with IE911 (crystalline silicotitanate type). For the effective removal of Cs and the minimization of secondary solid waste generation, adsorption of Cs by IE911 (hereafter denoted as IE911-Cs) was effective to carry out in the m/V (ratio of absorbent weight to solution volume) ratio of 2.5 g/L, and the adsorption time of 1 hour. In these conditions, Cs and Sr were adsorbed about 99% and less than 5%, respectively. IE911-Cs could be also expressed as a Langmuir isotherm and a pseudo-second order rate equation. The adsorption rate constants (k2) were decreased with increasing initial Cs concentrations and particle sizes, and increased with increasing ratios of m/V, solution temperatures and agitation speeds. The activation energy of IE911-Cs was about 79.9 kJ/mol. It was suggested that IE911-Cs was dominated by a chemical adsorption having a strong bonding form. From the negative values of Gibbs free energy and enthalpy, it was indicated that the reaction of IE911-Cs was a forward, exothermic and relatively active at lower temperatures. Additionally, the negative entropy values were seen that the adsorbed Cs was evenly distributed on the IE911.

Kinetics for the Transformation of Outer Charge Transfer Complex to Inner Complex (Outer Charge Transfer Complex가 Inner Complex로의 변환에 따른 속도론적 연구)

  • Kwon Oh-Yun;Paek U-Hyon;Kim Eung-Ryul
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.343-349
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    • 1991
  • Formation of charge transfer complex between iodine and substituted aniline [aniline, N,N-dimethylaniline(N,N-DMA), 2,6-dimethylaniline(2,6-DMA), 2,4,6-trimethylaniline(2,4,6-TMA)] in CHCl$_3$, CH$_2$Cl$_2$ : CHCl$_3$ (1 : 1), and CH$_2$Cl$_2$ have been studied kinetically by using conductivity method. In the transformation of initially formed outer charge transfer complex to inner complex, the effects of substituted aniline as electron donor and polar medium on the reaction were investigated. The rate of transformation depend on the dielectric contribution of medium and pK$_a$ value of substituted aniline. The order of rate increasing is 2,4,6-TMA, 2,6-DMA, aniline, and N,N-DMA. The activation enthalpy ${\Delta}H^{\neq}$ for 2.5 M-substituted aniline in CHCl$_3$ at 25$^{\circ}C$ is respectively N,N-DMA, 3.47 kcal/mol; aniline, 4.25 kcal/mol; 2,6-DMA, 7.79 kcal/mol and 2,4,6-TMA, 7.96 kcal/mol; and activation entropy ${\Delta}S^{\neq}$ is large and negative value of -41 ~ -55 cal/mol${\cdot}$K.

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Thermal Stability of Israeli Carp Actomyosin and Its Protection by Chemical Additives (이스라엘 잉어 Actomyosin의 열안정성과 그 보호)

  • NAM Taek-Jeong;CHOI Yeung-Joon;PYEUN Jae-Hyeung
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.17 no.4
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    • pp.271-279
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    • 1984
  • Effects of temperature and additives on the stability of actomyosin extracted from skeletal muscle of Israeli carp, Cyprinus carpio nudus, were studied by analyzing free SH-group, ATP-sensitivity and Ca-ATPase activity. The used additives were sucrose, sorbitol, Na-glutamate and L-cysteine. Furthermore, the denaturation constant($K_D$), protective effect(${\Delta}E/M$) and the other thermo-dynamic parameters on protein denaturation are systematically discussed. The actomyosin showed $4.12{\sim}4.68 mg/ml$ in protein concentration, $2.63{\sim}2.93\%$ in ribonucleic acid to the protein, $1:2.20{\sim}2.63$ in the binding ratio of myosin and actin, $4.33{\sim}5.26\%$ in fat content, 109.78 in ATP-sonsitivity, $0.159{\sim}0.201\;{\mu}M-Pi/min/mg-protein$ in Ca-ATPase activity and $3.3{\sim}3.4M/10^5$g-protein in free SH-group content. The first-order rate plots were obtained on the decrease of Ca-ATPase activity and ATP-sensitivity with an increase in temperature, while the free SH-group was increased to $60^{\circ}C$ and decreased rapidly above the temperature. The half-life of Ca-ATPase activity on the actomyosin Ca-ATPase was 280 min at $12^{\circ}C$, 125 min at $20^{\circ}C$, 55 min at $30^{\circ}C$ and 13 min at $40^{\circ}C$, and activation energy, activation enthalpy, activation entropy and free energy of the proteins at $20^{\circ}C$ wene 5,395 cal/mole, 4,814 cal/mole, -40.42 e.u. and 17,626 cal/mole, respectively. The protective effect of the additives on the actomyosin Ca-ATPase showed that the most effective material is $3\%$ sorbitol and followed in the order of $8\%$ Na-glutamate, $1\%$ sucrose and $1\%$ L-cysteine. The actomyosin was more stable at $-30^{\circ}C$ than at $0^{\circ}C$ and $-20^{\circ}C$. and when the additives were used in the low temperature storage, $8\%$ Na-glutamate was the most effective. $3\%$ sorbitol, $1\%$ sucrose and $1\%$ L-cysteine was to become lower in the order.

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Characteristics of Equilibrium, Kinetics, and Thermodynamics for Adsorption of Acid Black 1 Dye by Coal-based Activated Carbon (석탄계 활성탄에 의한 Acid Black 1 염료의 흡착에 있어서 평형, 동력학, 및 열역학적 특성)

  • Lee, Jong-Jib
    • Clean Technology
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    • v.27 no.3
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    • pp.261-268
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    • 2021
  • Equilibrium, kinetics, and thermodynamics of adsorption of acid black 1 (AB1) by coal-based granular activated carbon (CGAC) were investigated with the adsorption variables of initial concentration of dye, contact time, temperature, and pH. The adsorption reaction of AB1 by activated carbon was caused by electrostatic attraction between the surface (H+) of activated carbon and the sulfite ions (SO3-) and nitrite ions (NO2-) possessed by AB1, and the degree of reaction was highest at pH 3 (97.7%). The isothermal data of AB1 were best fitted with Freundlich isotherm model. From the calculated separation factor (1/n) of Freundlich, it was confirmed that adsorption of AB1 by activated carbon could be very effective. The heat of adsorption in the Temkin model suggested a physical adsorption process (< 20 J mol-1). The kinetic experiment favored the pseudo second order model, and the equilibrium adsorption amount estimated from the model agreed to that given by the experiments (error < 9.73% ). Intraparticle diffusion was a rate controlling step in this adsorption process. From the activation energy and enthalpy change, it was confirmed that the adsorption reaction is an endothermic reaction proceeding with physical adsorption. The entropy change was positive because of an active reaction at the solid-liquid interface during adsorption of AB1 on the activated carbon surface. The free energy change indicated that the spontaneity of the adsorption reaction increased as the temperature increased.

Effect of Metal Ions and Substrate on the Thermostability of ${\alpha}-Amylase$ from Bacillus licheniformis (Bacillus licheniformis가 생산하는 ${\alpha}-Amylase$의 열안정성에 미치는 금속이온 및 기질의 영향)

  • Yoon, Jong-Won;Park, Kwan-Hwa
    • Korean Journal of Food Science and Technology
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    • v.24 no.4
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    • pp.371-375
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    • 1992
  • The ${\alpha}-amylase$ from Bacillus licheniformis was purified and its thermostability in the presence of substrate and metal was ions investigated. Comparing D-values of the enzyme obtained in the presence of $Ca^{++}$, $B^{+++}$ and both $Ca^{++}$ and $B^{+++}$, the thermostability of the enzyme was markedly enhanced by the addition of metal ions. $Ca^{++}$ and $B^{+++}$ exhibited a protective action, the former ion being more effective, and both ions showed a synergistic effect. The enthalpy of activation for the thermal inactivation in the presence of metal ion was 320.2 kJ/mole for $Ca^{2+}$ ion, 212.9 kJ/mole for $B^{+++}$, while it was 183.9 kJ/mole in the absence of metal ions. In the thermal inactivation for 30 min at $96^{\circ}C$, the residual activity in the presence of 30% (w/w) starch was 51.0%, whereas the presence of $Ca^{++}$ ion additionally provided a remarkable thermo-resistance.

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Study on Kinetics and Thermodynamics of Rotary Evaporation of Paclitaxel for Removal of Residual Pentane (파클리탁셀의 잔류 펜탄 제거를 위한 회전증발의 동역학 및 열역학에 관한 연구)

  • Han, Jang Hoon;Ji, Seong-Bin;Kim, Ye-Sol;Lee, Seung-Hyun;Park, Seo-Hui;Kim, Jin-Hyun
    • Korean Chemical Engineering Research
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    • v.55 no.6
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    • pp.807-815
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    • 2017
  • This study investigated the removal efficiency of residual pentane from paclitaxel according to the drying temperature in the case of rotary evaporation, and performed a kinetic and thermodynamic analysis of the drying process. At all the temperatures (25, 30, 35, 40, and $45^{\circ}C$), a large amount of the residual solvent was initially removed during the drying, and the drying efficiency increased when increasing the drying temperature. Five drying models (Newton, Page, modified Page, Henderson and Pabis, Geometric) were then used for the kinetic analysis, where the Henderson and Pabis model showed the highest coefficient of determination ($r^2$) and lowest root mean square deviation (RMSD), indicating that these models were the most suitable. Furthermore, in the thermodynamic analysis of the rotary evaporation, the activation energy ($E_a$) was 4.9815 kJ/mol and the standard Gibbs free energy change (${\Delta}G^0$) was negative, whereas the standard enthalpy change (${\Delta}H^0$) and standard entropy change (${\Delta}S^0$) were both positive, indicating that the drying process was spontaneous, endothermic, and irreversible.

Nonstoichiometry of the Ytterbium Oxide (산화 이테르븀의 비화학양론)

  • Chul Hyun Yo;Hyung Rak Kim;Kwon Sun Roh;Kyu Hong Kim;Eung Ju Oh
    • Journal of the Korean Chemical Society
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    • v.36 no.4
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    • pp.511-516
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    • 1992
  • The x-values of the nonstoichiometric compound YbO$_x$ have been measured in a temperature range of 600 to 1150$^{\circ}C$ under oxygen partial pressure of 1.00 ${\times}$ 10$^{-2}$ atm∼atmospheric air pressure. The values are varied between 1.55453 and 1.60794 in the conditions. The enthalpy of the formation for x' in YbO$_{1.5+x'}$(${\Delta}$H$_f$) was 1.55, 1.18, and 1.05 kJ/mol under the above conditions, respectively. The electrical conductivities of the oxides or ${\sigma}$ have been measured in the temperature range from 600 to 1100$^{\circ}C$ under oxygen partial pressure of 1.00 ${\times}$ 10$^{-5}$ ∼ 2.00 ${\times}$ 10$^{-1}$ atm. They varied from 10$^{-9}$ to 10$^{-5}$ ohm$^{-1}$ cm$^{-1}$ within the semiconductor range. The Arrhenius plots of the electrical conductivities show a linearity and the activation energy for the conduction was about 1.7eV. The oxygen partial pressure dependence of the conductivity or 1/n value increases with the pressure. The nonstoichiometric conduction mechanism of the oxide was discussed in terms of the x values, ${\sigma}$ values, and the thermodynamic data.

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Thermodynamic Analysis of Phenol Adsorption by Powdered Activated Carbon (활성탄에 의한 페놀 흡착의 열역학적 연구)

  • Kim, Hwanik;Lee, Myoung-Eun;Kang, Seoktae;Chung, Jae-Woo
    • Journal of Korean Society of Environmental Engineers
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    • v.35 no.3
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    • pp.220-225
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    • 2013
  • The adsorption characteristics of phenol by the powdered activated carbon (PAC) were investigated by series of batch experiments. The pseudo-second-order model described the adsorption kinetics adequately with correlation coefficients over 0.999, indicating chemical adsorption as the rate-limiting step. The kinetic rate constants were from 0.55 to 19.81 mg $mg^{-1}min^{-1}$. The adsorption isotherm followed the Langmuir isotherm, indicating the homogeneous mono-layer adsorption onto the surface of the adsorbent. The values of activation energy, enthalpy and entropy were 17.44 kJ $mol^{-1}$, -8.26 kJ $mol^{-1}$ and -18.94 J $mol^{-1}K^{-1}$, respectively. The Gibbs free energy was in the range of -2.89~-2.14 kJ $mol^{-1}$. The results show that the phenol adsorption is physical, spontaneous and exothermic reaction.