• Title/Summary/Keyword: entropy change

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Thermal and Optical Properties of Cellobiose Octa(cholesteryloxycarbonyl)alkanoates (셀로비오스 옥타(콜레스테릴옥시카보닐)알카노에이트의 열 및 광학 특성)

  • Jeong, Seung-Yong;Ma, Yung-Dae
    • Polymer(Korea)
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    • v.32 no.3
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    • pp.230-238
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    • 2008
  • The thermal and optical properties of cellobiose octa(cholestryloxycarbonyl)alkanoates CCCBn, $n=2{\sim}8$,10, the number of methylene units in the spacer) were investigated. All the samples formed monotropic cholesteric phases with left-handed helical structures. CCBn with n=2 or 10, in contrast with CCBn with $3{\leq}n{\leq}8$, did not display reflection colors over the full cholesteric range, suggesting that the helical twisting power of the cholesteryl group highly depends on the length of the spacer connecting the cholesteryl group to the cellobiose chain. The isotropic-cholestropic transition ($T_{ic}$) and glass transition temperatures decreased with increasing n and showed no odd-even effect. The transition entropy at $T_{ic}$ increased with increasing n from 2 up 6, but at n=7 it drops significantly and then increased again with increasing n from 8 to 10. The sharp change at n=7 may be attributed to a difference in arrangement of the side groups. The thermal stability and degree of order in the mesophase and the temperature dependence of the optical pitch observed for CCBn were significantly different from those reported for the cellulose tri(cholesteryloxycarbonyl)alkanoates and glucose penta(cholesteryloxycarbonyl)alkanoates. The results were discussed in terms of the differences in the degree of polymerization, the number of the mesogenic units per mole-glucose unit, and the conformation of the molecules.

Study on Equillibrium, Kinetic, Thermodynamic Parameters for Adsorption of Brilliant Green by Zeolite (제올라이트에 의한 Brilliant Green의 흡착에 대한 평형, 동역학 및 열역학 파라미터에 관한 연구)

  • Lee, Jong Jib
    • Korean Chemical Engineering Research
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    • v.56 no.1
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    • pp.112-118
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    • 2018
  • Adsorption equilibrium, kinetic and thermodynamic parameters of a brilliant green from aqueous solutions at various initial dye concentration (10~30 mg/L), contact time (1~24 h) and temperature (298~318 K) on zeolite were studied in a batch mode operation. The equilibrium adsorption values were analyzed by Langmuir, Freundlich and Dubinin-Radushkevich model. The results indicate that Langmuir and Freundlich model provides the best correlation of the experimental data. Base on the estimated values of Langmuir dimensionless separation factor ($R_L=0.041{\sim}0.057$) and Freundlich constant (1/n=0.30~0.47), this process could be employed as effective treatment method. calculated values of adsorption energy by Dubinin-Radushkevich model were 1.564~1.857 kJ/mol corresponding to physical adsorption. The adsorption kinetics of brilliant green were best described by the pseudo second-order rate model and followed by intraparticle diffusion model. Thermodynamic parameters such as activation energy, free energy, enthalpy and entropy were calculated to estimate nature of adsorption. negative Gibbs free energy (-10.3~-11.4 kJ/mol), positive enthalpy change (49.48 kJ/mol) and Arrehenius activation energy (27.05 kJ/mol) indicates that the adsorption is spontaneous, endothermic and physical adsorption process, respectively.

Thermal and Optical Properties of Poly{1-(Cholesteryloxycarbonylalkanoyloxy)ethylene}s (폴리{1-(콜레스테릴옥시카보닐알카노일옥시)에틸렌}들의 열 및 광학 특성)

  • Jeong, Seung-Yong;Ma, Yung-Dae
    • Polymer(Korea)
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    • v.33 no.2
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    • pp.144-152
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    • 2009
  • The thermal and optical properties of poly {1-(cholesteryloxycarbonylalkanoyloxy) ethylene}s (PCALEn, n=2$\sim$8,10, the number of methylene units in the spacer) were investigated. All of the homologues formed monotropic cholesteric phases with left-handed helical structures. PCALEn with n=2 or 10, in constrast with PCALEn with $3{\leq}n{\leq}8$, did not display reflection colors over the full cholesteric range, suggesting that the helical twisting power of the cholesteryl group highly depends on the length of the spacer connecting the cholesteryl group to the polyethylene chain. The glass transition temperatures decreased with increasing n. The isotropic-cholesteric phase transition temperatures decreased with increasing n up to 7 and showed an odd-even effect. However it became almost constant when n is more than 7. This behavior is rationalized in terms of the change in the average shape of the side chain on varing the parity of the spacer. This rationalization also accounts for the observed variation of the entropy gain for the clearing transition. The thermal stability and degree of order in the mesophase and the temperature dependence of the optical pitch observed for PCALEn were significantly different from those reported for cellulose tri(cholesteryloxycarbonyl)alkanoates. The results were discussed in terms of the differences in the chemical structure and flexibility of main chain and the number of the mesogenic units per repeating unit.

Analysis for Adsorption Equilibrium, Kinetic and Thermodynamic Parameters of Aniline Blue Using Activated Carbon (활성탄을 이용한 아닐린 블루의 흡착평형, 동역학 및 열역학 파라미터에 대한 해석)

  • Lee, Jong Jib
    • Korean Chemical Engineering Research
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    • v.57 no.5
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    • pp.679-686
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    • 2019
  • Characteristics of adsorption equilibrium, kinetic and thermodynamic of aniline blue onto activated carbon from aqueous solution were investigated as function of initial concentration, contact time and temperature. Adsorption isotherm of aniline blue was analyzed by Langmuir, Freundlich, Redlich-Peterson, Temkin and Dubinin-Radushkevich models. Langmuir isotherm model fit better with isothermal data than other isotherm models. Estmated Langmuir separation factors ($R_L=0.036{\sim}0.068$) indicated that adsorption process of aniline blue by activated carbon could be an effective treatment method. Adsorption kinetic data were fitted to pseudo first order model, pseudo second order model and intraparticle diffusion models. The kinetic results showed that the adsorption of aniline blue onto activated carbon well followed pseudo second-order model. Adsorption mechanism was evaluated in two steps, film diffusion and intraparticle diffusion, by intraparticle diffusion model. Thermodynamic parameters such as Gibbs free energy, enthalpy and entropy for adsorption process were estimated. Enthalpy change (48.49 kJ/mol) indicated that this adsorption process was physical adsorption and endothermic. Since Gibbs free energy decreased with increasing temperature, the adsorption reaction became more spontaneously with increasing temperature. The isosteric heat of adsorption indicated that there is interaction between the adsorbent and the adsorbate because the energy heterogeneity of the adsorbent surface.

Thermotropic Liquid Crystalline Properties of α,ω-Bis(4-cyanoazobenzene-4'-oxy)alkanes (α,ω-비스(4-사이아노아조벤젠-4'-옥시)알케인들의 열방성 액정 특성)

  • Jeong, Seung Yong;Kim, Hyo Gap;Ma, Yung Dae
    • Applied Chemistry for Engineering
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    • v.22 no.4
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    • pp.358-366
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    • 2011
  • A homologous series of linear liquid crystal dimers, the ${\alpha},{\omega}$-bis(4-cyano-azobenzene-4'-oxy)alkanes (CATWETn, where n, the number of methylene units in the spacer, is 2~10) were synthesized, and their thermotropic liquid crystalline phase behavior were investigated. The CATWETn with n of 3 and 6 exhibited monotropic nematic phases, whereas other derivatives showed enantiotropic nematic phases. The nematic-isotropic transition temperatures of the dimers and their entropy variation at the phase transition showed a large odd-even effect as a function of n. This phase transition behavior was rationalized in terms of the change in the average shape of the spacer on varying the parity of the spacer. The thermal stability and degree of order in the nematic phase and the magnitude of the odd-even effect of CATWETn were similar to those for the methoxy-, nitro-, and pentyl-substituted dimers, while they were significantly different from those for the monomesogenic compounds, 1-{4-(4'-cyanophenylazo)phenoxy}alkylbromides and the side-chain liquid-crystalline polymers, the poly[1-{4-(4'-cyanophenylazo)phenoxyalkyloxy}ethylene]s. The results were discussed in terms of 'virtual trimer model' by Imrie.

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.