• Title/Summary/Keyword: 열역학적양

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Electrocatalytic Effect on the Oxygen Reduction and Electrochemical Properties of Co(Ⅱ)-dimethyl Bipyridine Perchlorate (Co(Ⅱ)$(dimethyl bipyridine)_3(ClO_4)_2$의 전기화학적 성질과 산소환원에 대한 전극 촉매 효과)

  • Kim, Il Kwang;Park, Chong Sool;Han, Wan Soo;Kim, Youn Keun;Jeon, Il Cheol
    • Journal of the Korean Chemical Society
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    • v.41 no.8
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    • pp.385-391
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    • 1997
  • Diffusion Coefficient$(D_0)$ and electrode reaction rate Constant$(K_0)$ of Co$(dimethyl bipyridine)_3(ClO_4)_2$ were determined by cyclic voltammetry and chronoamperometry. It was also investigated that the effects of solvent, concentration, and scan rate, etc. on the diffusion coefficient and the temperature effect on the rate constant. The peak currents and diffusion coefficients were dcreased as increasing the viscosity of solvent. Diffusion coefficient was $5.54{\times}10^{-6 }cm^2/sec$ and the reaction rate constant was $2.39{\times}10^{-3 }/s$ at 25$^{\circ}C$. The thermodynamic parameters such as ${\Delta}G^{\neq},\;{\Delta}H^{\neq},\;and\;{\Delta}S$ were calculated from plotting the reaction rate constants versus the solution temperatures. This compound was shown the catalytic effect on the oxygen reduction that the reduction peak current of oxygen was greatly enhanced and the peak potential was shifted to +0.2 volt.

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Thermodynamics on the Mixed Micellar Formation of Dimethyldodecylamine Oxide in Water/n-Propanol (Dimethyldodecylamine Oxide 의 물/n-프로판올 용매에서 혼합미셸 형성에 관한 열역학적 연구)

  • Lee Byung-Hwan
    • Journal of the Korean Chemical Society
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    • v.37 no.6
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    • pp.562-569
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    • 1993
  • The pseudophase separation model is used to describe the effects of pH and n-propanol on the mixed micellar formation of protonated and unprotonated dimethyldodecylamine oxides. Dimethyl-dodecylamine oxide surfactant molecules may exist in aqueous solution in either nonionic (unprotonated) or cationic (protonated) form, and they can be modeled thermodynamically as a binary mixture of cationic and nonionic surfactants. The composition of the binary mixture is varied by adjusting the solution pH. And activities, micellar compositions, and monomeric compositions of two surfactant species can be calculated directly from the experimental titration data by applying pseudophase separation model to the micellar system of DDAO in water/n-propanol. The critical micellar concentrations and the p$K_a$ values of the binary mixture systems are dependent on the micellar composition of the protonated cationic surfactant (X); especially they show the minimum phenomena when they are plotted against the micellar composition of the protonated cationic surfactant (X). The critical micellar concentration of the binary mixed DDAO system is generally decreased when n-propanol is added to the binary mixture system, and the degree of decrease is dependent on the concentration of n-propanol.

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Influence of Sulfate on Thermodynamic Modeling of Hydration of Alkali Activated Slag (알칼리 활성 슬래그의 열역학적 수화모델링에 대한 황산염의 영향)

  • Lee, Hyo Kyoung;Park, Sol-Moi;Kim, Hyeong-Ki
    • Resources Recycling
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    • v.28 no.1
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    • pp.32-39
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    • 2019
  • The present study investigated hydration of alkali activated slag incorporating sulfate as a form of anhydrite by employing thermodynamic modeling using the Gibbs free energy minimization approach. Various parameters were evaluated in the thermodynamic calculations, such as presence of sulfide, precipitation/dissolution of AFt/AFm phase, and the effect of oxic condition on the predicted reaction. The calculations suggested no significant difference in the void volume and chemical shrinkage, which might influence the performance of the mixtures, in spite of various changes of the parameters. Although the types of hydration products and their amount varied according to the input conditions, their variations were smaller range than that induced by water-to-binder ratio. Moreover, it did not affect the amount of C-(N-)A-S-H which was the most important hydration product.

Characteristics of Equilibrium, Kinetics and Thermodynamics for Adsorption of Disperse Yellow 3 Dye by Activated Carbon (활성탄에 의한 Disperse Yellow 3 염료의 흡착에 있어서 평형, 동력학 및 열역학적 특성)

  • Lee, Jong-Jib
    • Clean Technology
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    • v.27 no.2
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    • pp.182-189
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    • 2021
  • The adsorption of disperse yellow 3 (DY 3) on granular activated carbon (GAC) was investigated for isothermal adsorption and kinetic and thermodynamic parameters by experimenting with initial concentration, contact time, temperature, and pH of the dye as adsorption parameters. In the pH change experiment, the adsorption percent of DY 3 on activated carbon was highest in the acidic region, pH 3 due to electrostatic attraction between the surface of the activated carbon with positive charge and the anion (OH-) of DY 3. The adsorption equilibrium data of DY 3 fit the Langmuir isothermal adsorption equation best, and it was found that activated carbon can effectively remove DY 3 from the calculated separation factor (RL). The heat of adsorption-related constant (B) from the Temkin equation did not exceed 20 J mol-1, indicating that it is a physical adsorption process. The pseudo second order kinetic model fits well within 10.72% of the error percent in the kinetic experiments. The plots for Weber and Morris intraparticle diffusion model were divided into two straight lines. The intraparticle diffusion rate was slow because the slope of the stage 2 (intraparticle diffusion) was smaller than that of stage 1 (boundary layer diffusion). Therefore, it was confirmed that the intraparticle diffusion was rate controlling step. The free energy change of the DY 3 adsorption by activated carbon showed negative values at 298 ~ 318 K. As the temperature increased, the spontaneity increased. The enthalpy change of the adsorption reaction of DY 3 by activated carbon was 0.65 kJ mol-1, which was an endothermic reaction, and the entropy change was 2.14 J mol-1 K-1.

Transient State Theory of Significant Liquid Structure applied to Binary Mixture, Benzene-Cyclohexane (이성분 액체 혼합물의 통계열역학적 연구)

  • Ahn, Woon-Sun
    • Journal of the Korean Chemical Society
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    • v.10 no.3
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    • pp.136-142
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    • 1966
  • The Transient State Theory of Significant Liquid Structure has been successfully extended to binary mixture, benzene-cyclohexane system, which gives positive deviation from Raoult's law. The partition function has been derived, and from it various thermodynamic properties, such as total and partial vapor pressures, molar volumes, and excess entropies have been calculated at the temperatures $303.15^{\circ},\;\313.15^{\circ},\;and\;343.15^{\circ}K$. The calculated values agree satisfactorily with the experimental data.

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정밀여과막의 공경 및 분포 제어

  • 홍재민;하성룡;강용수;안규홍;김은영
    • Proceedings of the Membrane Society of Korea Conference
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    • 1994.10a
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    • pp.76-76
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    • 1994
  • 일반적으로 다공성 비대칭막은 상분리법에 의하여 제조하는데, 분리막을 구성하는 고분자를 적절한 용매에 녹인 제막용액을 일정한 두께로 casting하고 이를 비용매에 담가서 binodal/spinodal decomposition이 일어나도록 하여 제조한다. 이 방법으로 제조된 다공성 분리막의 성능은 표면층에 존재하는 pore의 크기와 그 분포 및 porosity에 의해 결정된다. Casting된 고분자 용액을 비용매에 침지시켜 다공성막을 형성시킬 경우 막의 표면과 비용매 사이의 계면에서 용매와 비용매의 교환이 일어난다. 용매-비용매 교환이 일어나면 제막된 고분자 용액내의 비용매의 양이 증가되어 열역학적으로 불안정해져 상분리가 일어난다. 그런데, 이때 용매-비용매의 교환이 매우 빠른 속도로 일어나므로 pore-size 및 그의 분포를 조절하기가 매우 어렵다. 표면층의 pore size와 분포를 조절하기 위하여 그간 고분자 용액내의 고분자 농도조절, 첨가제의 사용, 비용매의 조성을 바꾸는 등의 여러가지 방법에 대한 연구가 진행되어 왔다.

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A study on neutron diffraction of amorphous Ni-Ta and Cu-Ta alloy powders prepared by mechanical alloying (기계적 합금화법으로 제조한 비정질 Ni-Ta 및 Cu-Ta 합금분말의 중성자회절에 관한 연구)

  • Lee, Chung-Hyo;Lee, Jin
    • Electrical & Electronic Materials
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    • v.8 no.6
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    • pp.715-720
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    • 1995
  • 기계적 합금화법에 의한 비정질화 과정을 Ni-Ta계 및 Cu-Ta계에 대하여 조사하였다. Ni-Ta합금계는 혼합엔탈피가 음이나, Cu-Ta계는 혼합엔탈피가 양인 열역학적으로 대조적인 합금계이다. 볼밀 중 발생하는 원자구조 변화를 중성자회절법을 이용하여 관찰하였다. 두 합금게에 있어서 기계적 합금화에 의한 비정질상이 생성되었다. 비정질 Cu-Ta합금의 local원자구조를 혼합엔탈피가 크게 음인 Ni-Ta계의 결과와 비교하였다. 그 결과, 대조적 특성을 가진 두 합금계임에도 불구하고 원자크기가 작은 Ni 및 Cu가 bcc Ta의 결정격자 속으로 우선적으로 침입함으로써 비정질화가 진행됨을 알 수 있었다.

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The Study of Bulk Emulsion Blends Consisting of Emulsion and ANFO (벌크 에멀젼 블랜드 폭약의 특성 고찰)

  • 정천채
    • Explosives and Blasting
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    • v.18 no.3
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    • pp.15-28
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    • 2000
  • 국내에서는 Heavy ANFO로 더 잘 알려져 있는 Emulsion Blends는 왁스 대신 오일을 사용 하여 상온에서 펌핑이 가능하도록 한 에멀젼과 ANFO(또는 초안)의 혼합물을 일컫는다. ANFO는 저렴하고 안전하며 장약이 쉽고 밀장전되는 장점이 있지만, 내수성이 거의 없고 폭발 속도가 느리며 장약 비중이 0.75∼0.90g/cc 정도로 낮아 폭약으로서 그 위력이 작은 단점을 갖고 있다. Blends는 수용성 ANFO 입자 사이의 빈 공간을 내수성 에멀젼이 태우고 있는 형태로서 에멀젼 함량 25%부터 내수성이 나타나기 시작하여 에멀젼 함량 40% 이상에서는 완전한 내수성을 갖게 되며, 에멀젼의 함량이 증가할수록 폭발속도는 카트리지 에멀젼 폭약에 근접하게 된다. 장약 비중은 에멀젼의 함량이 증가하여 45% 근처에서 1.25∼ 1.30g/cc의 최대 값을 갖지만, 그 이상의 에멀젼 함량에서는 기폭 감도 저하로 예감제를 사용하여 비중을 감소시키는 것이 바람직하다. Blends는 자체에 물을 함유하고 있으므로 열역학적으로 계산된 단위 중량당 반응열은 ANFO에 비해 매우 적지만, 폭발속도, detonation pressure(폭굉압), borehole pressure(폭발압력) 등이 ANFO에 비해 크므로 폭발압력에서부터 암석의 파괴가 가능한 압력가지의 단위 중량당 유효한 에너지의 양은 암석의 강도가 커질수록 ANFO에 비해 매우 적지만, 폭발속도, ANFO와 비슷해진다. 따라서 장약 비중이 ANFO의 130∼145%로 높은 Blends는 동일한 천공에 더 많이 장약할 수 있어 단위 천공당 암석 파괴에 이용되는 유효 에너지의 총 양이 커지게 되므로, 공간격과 저항선을 늘릴 수 있어 총 천공수를 감소시킬 수 있다. 결론적으로, Blends의 장점은 내수성과 함께 비장약량은 비슷하거나 약간 증가하는데 비해, 천공수는 크게 감소하여 전체적으로는 발파 현장의 경제성이 향상된다는데 있다.

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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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Thermodynamics of the Micellization of Cetylpyridinium Bromide in Some Aqueous Alcohol Solutions (몇 가지 알코올-수용액에서 Cetylpyridinium Bromide의 미셀화의 열역학적 성질)

  • Chung Jong-Jae;Lee Sang-Wook;Choi Joon-Ho
    • Journal of the Korean Chemical Society
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    • v.37 no.1
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    • pp.49-54
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    • 1993
  • The effects of added alcohols on the critical micelle concentration(CMC) of cetylpyridinium bromide(CPB) were investigated by the UV-Vis spectrophotometer at the temperature range of 8∼45$^{\circ}C$. The CMC of CPB was increased with the addition of methanol in the whole temperature region studied, while decreased with the addition of ethanol and propanol. The increase of CMC with the addition of methanol may be attributable to the increasing solvent power of the methanol-water mixture, because methanol was scarcely solubilized into the palisade layer of the micelle of CPB. The decrease of CMC with the inclusion of ethanol and propanol may be derived from the solubilization of alcohols into the micelles. On the other hand, the CMC was decreased with the temperature rise in the low-temperature region below about 25$^{\circ}C$, and the CMC was increased in the high-temperature region above that. The thermodynamic parameters (${\Delta}G_M^{\circ},\;{\Delta}H_M^{\circ},\;and\;{\Delta}S_M^{\circ}$) of the micellization of CPB were obtained in some aqueous alcohol solutions. In the whole temperature region (8∼45$^{\circ}C$), the values of ${\Delta}G_M^{\circ}$ were negative, while those of ${\Delta}S_M^{\circ}$ were positive. And in the temperature region below about 25$^{\circ}C$ the ${\Delta}H_M^{\circ}$ values were positive, while in the temperature region above that the values were negative.

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