• Title/Summary/Keyword: Enthalpy and entropy

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The Study on Complex of Gallium Bromide with Ethyl Bromide in Aniline and in o-Chloroaniline under High Vacuum (고진공 상태에서 아닐린과 o-클로로 아닐린 용액중 브롬화갈륨과 브롬화에탄과의 착물형성에 관한 연구)

  • Young Cheul Kim;Se Kyung Kim;Deog Ja Koo;Jong Wan Lim
    • Journal of the Korean Chemical Society
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    • v.35 no.5
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    • pp.480-486
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    • 1991
  • The solubilities of ethyl bromide in aniline and o-chloroaniline have been measured at 5, 15$^{\circ}$ and 25$^{\circ}$C in the presence and the absence of gallium bromide. When gallium bromide does not exist in the system, the solubility of ethyl bromide in o-chloroaniline is greater than in aniline, indicating a stronger interaction of ethyl bromide with o-chloroaniline than that with aniline. It could be thought that ethyl bromide forms unstable complex with gallium bromide in the presence of gallium bromide in the system. This complex has been assumed in various ways and evaluated, that instability constant (K value) is relatively constancy under the assumption of 1 : 1 complex, $C_2H_5Br{\cdot}GaBr_3$. Therefore, the complex forms the following equilibrium in the solution: $C_2H_5Br{\cdot}GaBr_3\;{\rightleftharpoons}\;C_2H_5Br +1/2Ga_2Br_6$ The instability of the complex of ethyl bromide with gallium bromide is compared with similar complexes of gallium bromide with methyl bromide. The changes of enthalpy, free energy and entropy fcor the dissociation of the complex are also calculated.

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A Study on the Micellization of Sodium Dodecyl Sulfate in 𝜔-Phenylakylammonium Salt Solution (𝜔-Phenylalkylammonium Salt의 수용액에서 Sodium Dodecyl Sulfate의 미셀에 관한 연구)

  • Ryu, Yeanho;Oh, Jung Hee
    • Applied Chemistry for Engineering
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    • v.8 no.6
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    • pp.1041-1047
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    • 1997
  • The influence of $\omega$-phenylalkylammonium salt on the critical micelle concentration (CMC) of SDS has been examined using the electric conductivity method. CMC of SDS exhibited the tendency to decrease with the length of alkyl group of additives. The effect of temperature on CMC of SDS in additive solutions has been observed in the range of $18^{\circ}C-50^{\circ}C$. The free energy(${\Delta}G_m^{\circ}$) for the micellization of SDS is negative and the entropy(${\Delta}S_m^{\circ}$) is a large positive value. The enthalpy(ΔHm0is positive in low temperature($18^{\circ}C$) and negative in high temperature($>25^{\circ}C$). In the prensence of organic additives, the micellization of SDS was considered as a spontaneous process and to involve a phase transition. The values of ΔGm0has shown the tendency to increase but the values of ${\Delta}S_m^{\circ}$ and ${\Delta}H_m^{\circ}$ to decrease with the length of alklyl group of additive salts. The changes in ${\Delta}\kappa$(difference of specific conductivity) with increasing mole ratio of additives in the mixed solutions indicated the formation of mixed micelles between SDS and additives. The effect of the length of alkyl chain on the micellization of SDS demonstrated the penetration of organic additives into the palisade layer of the SDS micelle.

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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 Interaction of Gallium Iodide with n-Propyl Iodide in Nitrobenzene and m-Xylene on High Vacuum (고진공 상태에서 니트로벤젠과 m-크실렌용액중 요오드화갈륨과 1-요오드화프로판과의 상호작용)

  • Kim Young Choul;Koo Deog Ja
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.301-307
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    • 1991
  • The solubilities of the n-propyl iodide in nitrobenzene and m-xylene have been measured at 8$^{\circ}$, 15$^{\circ}$ and 25$^{\circ}C$ in the presence and the absence of gallium iodide. When gallium iodide does not exist in the system, the solubility of n-propyl iodide in m-xylene is greater than in nitrobenzene, indicating a stronger interaction of n-propyl iodide with m-xylene than that with nitrobenzene. It could be thought that n-propyl iodide forms unstable complex with gallium iodide in the presence of gaillium iodide in the system. This complex has been assumed in various ways and evaluated, that instability constant (K value) is relatively certain under the assumption of 1:1 complex, n-C$_3H_7I{\cdot}GaI_3$. Therefore, the complex would form the following equilibrium in the solution: n-C$_3H_7{\cdot}GaI _3{\rightleftharpoons}n-C_3H_7I+1/2Ga_2I_6$ the instability of the complex of n-propyl iodide with gallium iodide is compared with similar complexes of gallium iodide with methyl iodide. The changes of enthalpy, free energy and entropy for the dissociation of the complex are also calculated.

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Elution Behavior of Pd(II) - Isonitrosoethylacetoacetate Imine Chelates by Reversed Phase High Performance liquid Chromatography (역상 액체 크로마토그래피에 의한 Pd(II) - Isonitrosoethylacetoacetate Imine 유도체 킬레이트들의 용리 거동)

  • Kim, In-Whan;Shin, Han-Chul;Lee, Man-Ho;Yoon, Tai-Kun;Kang, Chang-Hee;Lee, Won
    • Analytical Science and Technology
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    • v.5 no.4
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    • pp.389-399
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    • 1992
  • Liquid Chromatographic behavior of Pd(II) in Isonitrosoethylacetoacetate lmine, $Pd(IEAA-NR)_2$ (R=H, $CH_3$, $C_2H_5$, $n-C_3H_7$, $C_6H_5-CH_2$, $n-C_4H_9$) chelates were investigated by reversed-phase HPLC on Micropak MCH-5 column using methanol/water as mobile phase. The optimum conditions for the separation of $Pd(IEAA-NR)_2$ chelates were examined with respect to the effect of the flow rate, sample solvent, mobile phase strength and column temperature. It wass found that metal chelates were properly eluted in an acceptable range of capacity factor value($0{\leq}log\;k^{\prime}{\leq}1$). The dependence of the logarithm of capacity factor(k') on the volume fraction of water in the binary mobile phase was examined. Also, the dependence of k' on the liquid-liquid extration distribution ratio($D_c$) in methanol-water/n-alkane extration system was investigated. Both kinds of dependence are linear, which susggests that the retention of the electroneutral metal chelate is largely due to the solvophobic effect. Standard adsorption enthalpy changes (${\Delta}H^{\circ}$) and standard adsorption entropy changes (${\Delta}S^{\circ}$) of Pd(II) Isonitrosoethylacetoacetate imine chelates on Micropak MCH-5 column were calculated by measuring capacity factor with changing temperature of the column.

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Chemical Reaction of Solvated Electrons in Binary Mixture (이성분계 $(THF-H_2O)$에서 용매화전자의 화학반응속도)

  • Yu-Chul Park
    • Journal of the Korean Chemical Society
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    • v.27 no.3
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    • pp.201-207
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    • 1983
  • The rate constants for solvated electrons with benzene in the binary mixture (tetrahydrofuran-water) were measured at a various temperatures$(-18{\circ}C{\sim}+51{\circ}C)$ by photolysis. From Arrhenius plots of rate constants it was observed that the activation energies were decreased with increasing tetrahydrofuran(THF) content. Decreasing the viscosity of solvent mixtures by adding water, the rate constants were also decreased. It indicates that the reaction of solvated electrons are not controlled by diffusion. The change of activation enthalpy in kcal $M^{-1}$ and the rate constants in$ M^{-1}sec^{-1}$ were 4.90 and $8.80{\times}10^8$ for 30M% of THF, 2.80 and $5.14{\times}10^8$ for 49M% of THF, and -0.30 and %1.43{\times}10^8$ for 75M% of THF, respectively. The slope of the linear plot of activation enthalpies against activation entropies was $244{\circ}K$, which supports the reaction parameter is the change of activation entropy in the range of the experimental temperature. From the solvent effect on the activation energy, it was found that the step of the reaction, ${e_s}^-+B{\rightleftharpoons}B^-$ shifted to the exothermic reaction with increasing THF content.

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Study of Equilibrium, Kinetic and Thermodynamic Parameters about Fluorescein Dye Adsorbed onto Activated Carbon (활성탄을 이용한 플루오레세인 염료 흡착에 대한 평형, 동력학 및 열역학 파라미터의 연구)

  • Lee, Jong-Jib;Um, Myeong Heon
    • Applied Chemistry for Engineering
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    • v.23 no.5
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    • pp.450-455
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    • 2012
  • The paper includes the utlization of an activated carbon as a potential adsorbent to remove a hazardous fluorescein dye from an aqueous solution. Batch adsorption experiments were carried out for the removal of fluorescein dyes using a granular activated carbon as an adsorbent. The effects of various parameters such as pH, amount of adsorbent, contact time, initial concentration and temperature of the adsoprtion system were investigated. The experimental results revealed that activated carbon exhibit high efficiencies to remove fluorescein dyes from the aqueous solution. The equilibrium process can be well described by Freundlich isotherm in the temperature range from 298 K to 318 K. From adsorption kinetic experiments, the adsorption process followed a pseudo second order kinetic model, and the adsorption rate constant ($k_2$) decreased with increasing the initial concentration of fluorescein. The free energy of adsorption ${\Delta}G^0$), enthalpy ${\Delta}H^0$), and entropy (${\Delta}S^0$) change were calculated to predict the nature adsorption. The estimated values for ${\Delta}G^0$ were -17.11~-20.50 kJ/mol over an activated carbon at 250 mg/L, indicated toward a spontaneous process. The positve value for ${\Delta}H^0$, 33.2 kJ/mol, indicates that the adsorption of fluorescein dyes on an activated carbon is an endothermic process.

Study on Adsorption Equilibrium, Kinetic and Thermodynamic Parameters of Murexide by Activated Carbon (입상 활성탄에 의한 Murexide의 흡착 평형, 동력학 및 열역학 파라미터에 관한 연구)

  • Lee, Jong-Jib
    • Clean Technology
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    • v.25 no.1
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    • pp.56-62
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    • 2019
  • The equilibrium, kinetic and thermodynamic parameters of adsorption of murexide by granular activated carbon were investigated. The experiment was carried out by batch experiment with the variables of the amount of the adsorbent, the initial concentration of the dye, the contact time and the temperature. The isothermal adsorption equilibrium was best applied to the Freundlich equation in the range of 293 ~ 313 K. From the separation factor (${\beta}$) of Freundlich equation, it was found that adsorption of murexide by granular activated carbon could be the appropriate treatment method. The adsorption energy (E) obtained from the Dubinin- Radushkevich equation shows that the adsorption process is a physical adsorption process. From the kinetic analysis of the adsorption process, pseudo second order model is more consistent than pseudo first order model. It was found that the adsorption process proceeded to a spontaneous process and an endothermic process through Gibbs free energy change ($-0.1096{\sim}-10.5348kJ\;mol^{-1}$) and enthalpy change ($+151.29kJ\;mol^{-1}$). In addition, since the Gibbs free energy change decreased with increasing temperature, adsorption reaction of murexide by granular activated carbon increased spontaneously with increasing temperature. The entropy change ($147.62J\;mol^{-1}\;K^{-1}$) represented the increasing of randomness at the solid-solution interface during the adsorption reaction of murexide by activated carbon.

A Study on the chemical analysis of synthesized Li-AGICs with changes of intercalant contents (Intercalant 함량 변화에 따라 합성된 Li-AGICs의 화학적 분석에 관한 연구)

  • Oh, Won-Chun;Shim, Sang-Kyun
    • Analytical Science and Technology
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    • v.10 no.3
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    • pp.209-215
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    • 1997
  • Li-AGICs as a anode of secondary battery were synthesized by high-pressure method as a function of the Li-contents. The characteristics of these prepared compounds were determined from the studies with X-ray diffraction method, UV/VIS spectrophotometric and differential scanning calorimeter(DSC) analysis. From the results of X-ray diffraction, it was found that the lower stage intercalation compounds were formed with increase of Li-contents. The mixed stages in these compounds were also observed. In the case of the $Li_{30wt%}$-AGIC, the compounds in the stage 1 structure were formed predominantly, but the structure of only pure stage 1 for structural defect of artificial graphite is not observed. According to UV/VIS spectrophotometric analysis, $Li_{30wt%}$-AGIC shows distinguishable energy state spectrum with the position of $R(%)_{min}$ values, but the characteristic spectra of almost all Li-AGICs are not observed. The enthalpy and entropy changes of the compounds can be obtained from the differential scanning calorimetric analysis results. From the results, it was found that exothermic and endothermic reactions of Li-AGICs are related to thermal stability of lithium between artificial graphite layers.

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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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