• Title/Summary/Keyword: Gibbs′ free energy

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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.

The Computer-Aided Simulation Study on the Gasification Characteristics of the Roto Coal in the Partitioned Fluidized-Bed Gasifier (상용모사기를 이용한 로토석탄의 분할유동층 가스화기 가스화 특성 모사)

  • Park, Young Cheol;Moon, Jong-Ho;Lee, Seung-Yong;Lee, Dong-Ho;Jin, Gyoung Tae
    • Korean Chemical Engineering Research
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    • v.50 no.3
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    • pp.511-515
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    • 2012
  • In this study, we used a commercial simulator to investigate the gasification characteristics of Roto coal in the partitioned fluidized-bed gasifier, which consists of 4 parts such as coal pyrolysis, char gasification, tar/oil gasification and char combustion. The heating medium was exchanged between the combustion part and the gasification part in order to supply the energy needed for pyrolysis and gasification. The correlation model from experimental data in relation to the reaction temperatures, the reaction gases and the coal feed rates was derived for the coal pyrolysis. The equilibrium model was used for the gasification and the combustion model for the char combustion. In order to compare the reaction behavior of the partitioned fluidized-bed gasifier, the single-bed gasifier was also simulated. The cold gas efficiency of both partitioned fluidized-bed gasifier and single-bed gasifier was almost the same. The $H_2$ and $CH_4$ contents of the syngas in the partitioned fluidized-bed gasifier slightly increased and the CO and $CO_2$ contents slightly decreased, compared with the singlebed gasifier. In order to verify the model, ten cases of the single-bed gasification experiment have been simulated. The contents of CO, $CO_2$, $CH_4$ in the syngas from the simulation corresponded with the experimental data while those of $H_2$ was slightly higher than experimental data, but the tendency of $H_2$ content in the syngas was similar to the experiments. In the coal conversion, the simulation results were higher than the experiments since equilibrium model was used for the gasification so that the residence time and contact time in the model is different from the experiments.

Carbon Dioxide Reforming of Methane over a Ni/KIT-1 Catalyst (Ni/KIT-1 촉매를 이용한 메탄의 이산화탄소 개질반응 연구)

  • Ryn, Seong-Yun;Ahn, Wha-Seung;Park, Sang-Eon
    • Applied Chemistry for Engineering
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    • v.9 no.7
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    • pp.1070-1078
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    • 1998
  • Thermodynamic analysis on carbon dioxide reforming of methane was performed using a computer program which can handle condensed species in the products, and the reforming experiments were conducted over $Al_2O_3$, $La_2O_3$, ZSM-5, MCM-41, KIT-1 supported nickel catalysts, and a commercial ICI 46-1. It was estabished that a system which consists of $CH_4$, $CO_2$, CO, $H_2$, $H_2O$, and C is appropriate for theoretical equilibrium calculations and addition of water vapor or oxygen was found to diminish the contribution of carbon dioxide in reforming. Silicate molecular sieve-supported catalysts such as Ni/ZSM-5, Ni/MCM-41, Ni/KIT-1 were effective for high $CH_4$ and $CO_2$ conversions as well as for high CO yield. Coke formation was suppressed when CaO was added as a promoter. Ni/Ca/KIT-1 which contains 10% Ni with 3% Ca showed conversion approaching equilibrium levels above $650^{\circ}C$ and maintained constant activity over 20 h. Despite increased space velocity, relatively high conversion and CO yield were observed.

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Basic Study on the Recycling of Waste Tungsten Scraps by the Oxidation and Reduction Process (산화·환원법에 의한 폐텅스텐 스크랩의 재활용에 관한 기초연구)

  • Kim, Sang-Uk;Yun, Ji-seok;Kim, Tae-Wook;Cho, Bong-Hwi;Kim, In-Ho;Kim, Sang-Mu;Song, Chang-Bin
    • Journal of Powder Materials
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    • v.24 no.1
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    • pp.34-40
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    • 2017
  • This study is carried out to obtain basic data regarding oxidation and reduction reactions, originated on the recycling of waste tungsten hard scraps by oxidation and reduction processes. First, it is estimated that the theoretical Gibbs free energy for the formation reaction of $WO_2$ and $WO_3$ are calculated as ${\Delta}G_{1,000K}=-407.335kJ/mol$ and ${\Delta}G_{1,000K}=-585.679kJ/mol$, from the thermodynamics data reported by Ihsan Barin. In the experiments, the oxidation of pure tungsten rod by oxygen is carried out over a temperature range of $700-1,000^{\circ}C$ for 1 h, and it is possible to conclude that the oxidation reaction can be represented by a relatively linear relationship. Second, the reduction of $WO_2$ and $WO_3$ powder by hydrogen is also calculated from the same thermodynamics data, and it can be found that it was difficult for the reduction reaction to occur at $1,027^{\circ}C$, in the case of $WO_2$, but it can happen for temperatures higher than $1127^{\circ}C$. On the other hand, $WO_3$ reduction reaction occurs at the relatively low temperature of $827^{\circ}C$. Based on these results, the reduction experiments are carried out at a temperature range of $500-1,000^{\circ}C$ for 15 min to 4 h, in the case of $WO_3$ powder, and it is possible to conclude that the reduction at $900^{\circ}C$ for 2h is needed for a perfect reduction reaction.

Effect of Water-Activity Depressor on the Enzymatic Synthesis of Maltosyl-$\beta$-Cyclodextrin through the Reverse Reaction of Pullulanase (Water-Activity Depressor가 Pullulanase의 역반응에 의한 Maltosyl-$\beta$-Cyclodextrin의 합성에 미치는 영향)

  • 이용현;한일근
    • Microbiology and Biotechnology Letters
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    • v.20 no.4
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    • pp.422-429
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    • 1992
  • The effect of various water-activity depressors, such as pol yo Is, sugars, and polymers, on the conversion yields of the enzymatic synthesis of maltosyl-$\beta$-cyclodextrin from $\beta$-cyc1odextrin and maltose through reverse reaction of pullulanase was investigated. PEG 6000 of concentration of 10% (w/w) was found to be the most acceptable water-activity depressor resulting for increment of conversion yield from 43.0% to 55.9%, corresponding maltosyl-$\beta$-cyc1odextrin concentration of 3.02 g/100 ml H20. Water activity was changed from initial 0.966 to 0.914 upon addition of 20% (w/w) of PEG 6000. The conversion yields were inversely proportional to the water activities, and the increased conversion yield was caused by water activity depression which inhibited the hydrolysis reaction of maltosyl-$\beta$-CD to maltose and $\beta$-cyc1odextrin. The changes of enthalpy ($\Delta$H), entropy ($\Delta$S), and Gibbs free energy ($\Delta$G) were calculated to be 36.788 kJ/mole, 0.067 kJ/mole K. and 14.433 kJ/mole, respectively. The synthesis of maltosyl-$\beta$-CD could be increased substantially by the intermittent feeding of $\beta$-cyclodextrin. PEG 6000 could be separated effectively from reaction mixture using ultrafiltration membrane for reutilization.

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Applicability of Theoretical Adsorption Models for Studies on Adsorption Properties of Adsorbents(III) (흡착제의 흡착특성 규명을 위한 흡착모델의 적용성 평가(III) - 열역학적 특성을 중심으로)

  • Na, Choon-Ki;Jeong, Jin-Hwa;Park, Hyun-Ju
    • Journal of Korean Society of Environmental Engineers
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    • v.34 no.4
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    • pp.260-269
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    • 2012
  • The aim of this study is to evaluate the applicability of adsorption models for understanding the thermodynamic properties of adsorption process. For this study, the adsorption isotherm data of $NO_3$-N ion onto a commercial anion exchange resin obtained at various experimental conditions, i.e. different initial concentrations of adsorbate, different dosages of adsorbent, and different temperatures, were used in calculating the thermodynamic parameters and the adsorption energy of adsorption process. The Gibbs free energy change (${\Delta}G^0$) of adsorption process could be calculated using the Langmuir constant $b_M$ as well as the Sips constant, even though the results were significantly dependant on the experimental conditions. The thermodynamic parameters such as standard enthalpy change (${\Delta}H^0$), standard entropy change (${\Delta}S^0$) and ${\Delta}G^0$ could be calculated by using the experimental data obtained at different temperatures, if the adsorption data well fitted to the Langmuir isotherm model and the plot of ln b versus 1/T gives a straight line. As an alternative, the empirical equilibrium constant(K) defined as $q_e/C_e$ could be used for evaluating the thermodynamic parameters instead of the Langmuir constant. The results from the applications of D-R model and Temkin model to evaluate the adsorption energy suggest that the D-R model is better than Temkin model for describing the experimental data, and the availability of Temkin model is highly limited by the experimental conditions. Although adsorption energies determined using D-R model show significantly different values depending on the experimental conditions, they were sufficient to show that the adsorption of $NO_3$-N onto anion exchange resin is an endothermic process and an ion-exchange process.