• Title/Summary/Keyword: thermodynamic solution

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Experimental and theoretical investigation of micellization behavior of sodium dodecyl sulfate with cetyltrimethylammonium bromide in aqueous/urea solution at various temperatures

  • Hoque, Md. Anamul;Mahbub, Shamim;Rub, Malik Abdul;Rana, Shahed;Khan, Mohammed Abdullah
    • Korean Journal of Chemical Engineering
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    • v.35 no.11
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    • pp.2269-2282
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    • 2018
  • Mixed micelle formation behavior of cationic surfactant-cetyltrimethylammonium bromide (CTAB) and anionic surfactant sodium dodecyl sulfate (SDS) in aqueous as well as in urea medium from 303.15 K to 323.15 K at 5 K interval was carried out by conductometric method. The differences between the experimental values of critical micelle concentrations (cmc) and ideal critical micelle concentrations ($cmc^{id}$) illustrate the interaction between the amphiphiles studied. The values of micellar mole fraction ($X_1^{Rub}$ (Rubingh), $X_1^M$ (Motomura), $X_1^{Rod}$ (Rodenas) and $X_1^{id}$(ideal) of surfactant CTAB determined by different proposed models and outcome indicate high involvement of CTAB in SDS-CTAB mixed micellization, which enhance by means of the augment of mole fraction of CTAB. The negative value of interaction parameter (${\beta}$) showed an attractive interaction involving CTAB and SDS. Activity coefficients were less than unity in all case, which also reveals the presence of interaction between CTAB & SDS. The negative ${\Delta}G^0_m$ values imply the spontaneous mixed micellization phenomenon. The attained values of ${\Delta}H^0_m$ were positive at inferior temperature, while negative at superior temperature. The negative ${\Delta}H^0_m$ values in urea ($NH_2CONH_2$) medium illustrate exothermic micellization process. The magnitudes of ${\Delta}S^0_m$ were positive in almost all cases. The excess free energy of mixed micelle formation (${\Delta}G_{ex}$) was found to be negative, which indicates the stability of mixed micelle as compared to the individual's components micelles.

Solubilization of Cresol Isomers by the Cationic Surfactant of TTTAB in Aqueous Solution of n-Butanol and NaCl (n-부탄올 및 NaCl 수용액에서 양이온 계면활성제인 TTAB에 의한 크레졸 이성질체들의 가용화에 대한 연구)

  • Lee, Byung-Hwan
    • Journal of the Korean Applied Science and Technology
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    • v.38 no.3
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    • pp.832-839
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    • 2021
  • We tried to investigate the effects of substituent position, temperature, and additives such as NaCl and n-butanol on the solubilizations of cresol isomers by tetradecyltrimethylammonium bromide (TTAB), using the UV-Vis spectrophotometric method. The measured solubilization constants (Ks) values for each cresol isomer increased in the order o-cresolo and ∆Ho values for the solubilizations of cresols were all negative values but the ∆So values were all positive values within the measured ranges. The values of ∆Go increased also with increasing the concentration of n-butanol but decreased with increasing the concentration of NaCl. From these facts, we could conclude that both the enthalpy and entropy changes contribute together for the solubilizations of cresols isomers by cationic surfactant of TTAB and they are solubilized in the polar palisade region or at the surface of micelle.

Thermally-activated Mactra veneriformis shells for phosphate removal in aqueous solution

  • Yeon-Jin, Lee;Jae-In, Lee;Chang-Gu, Lee;Seong-Jik, Park
    • Membrane and Water Treatment
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    • v.14 no.1
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    • pp.1-10
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    • 2023
  • This study explored the feasibility of calcium-rich food waste, Mactra veneriformis shells (MVS), as an adsorbent for phosphate removal, and its removal efficiency was enhanced by the thermal activation process. The CaCO3 in MVS was converted to CaO by thermal activation (>800 ℃), which is more favorable for adsorbing phosphate. Thermal activation did not noticeably influence the specific surface area of MVS. The MVS thermally activated at 800 ℃ (MVS-800), showed the highest phosphate adsorption capacity, was used for further adsorption experiments, including kinetics, equilibrium isotherms, and thermodynamic adsorption. The effects of environmental factors, including pH, competing anions, and adsorbent dosage, were also studied. Phosphate adsorption by MVS-800 reached equilibrium within 48h, and the kinetic adsorption data were well explained by the pseudo-first-order model. The Langmuir model was a better fit for phosphate adsorption by MVS-800 than the Freundlich model, and the maximum adsorption capacity of MVS-800 obtained via the Langmuir model was 188.86 mg/g. Phosphate adsorption is an endothermic and involuntary process. As the pH increased, the phosphate adsorption decreased, and a sharp decrease was observed between pH 7 and 9. The presence of anions had a negative impact on phosphate removal, and their impact followed the decreasing order CO32- > SO42- > NO3- > Cl-. The increase in adsorbent dosage increased phosphate removal percentage, and 6.67 g/L of MVS-800 dose achieved 99.9% of phosphate removal. It can be concluded that the thermally treated MVS-800 can be used as an effective adsorbent for removing phosphate.

A study on the zinc oxide crystalline powder synthesized by zinc chloride solution and sodium-based alkali precipitants (염화아연 수용액과 나트륨계 알칼리 침전제 종류에 따라 합성한 산화아연 결정 분말에 대한 연구)

  • Dae-Weon Kim;Dae-Hwan Jang;Bo-Ram Kim
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.33 no.1
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    • pp.15-21
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    • 2023
  • To prepare zinc oxide powder, three types of sodium-based alkali precipitants such as NaOH, Na2CO3, NaOH/NaHCO3 were compared to the differences in the manufacturing process of zinc oxide powder from zinc precipitate products like intermediates with the consideration of thermodynamic reaction. The prepared zinc precipitate products by the reaction with the sodium-based alkali precipitant were confirmed to respectively hydroxy zinc chloride (Zn5(OH)8Cl2·H2O) and zinc carbonate hydroxide (Zn5(OH)6(CO3)2·H2O) from XRD analysis. Zinc oxide particles were compared in heat treatment at 800℃ according to sodium-based alkali precipitants. The mixed NaOH and NaHCO3 of alkali precipitant reaction was contributed to synthesize the more uniform zinc oxide particles.

Corrosion Inhibition Performance of Two Ketene Dithioacetal Derivatives for Stainless Steel in Hydrochloric Acid Solution

  • Lemallem, Salah Eddine;Fiala, Abdelali;Ladouani, Hayet Brahim;Allal, Hamza
    • Journal of Electrochemical Science and Technology
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    • v.13 no.2
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    • pp.237-253
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    • 2022
  • The methyl 2-(1,3-dithietan -2- ylidene)-3-oxobutanoate (MDYO) and 2-(1,3-dithietan-2-ylidene) cyclohexane -1,3-dione (DYCD) were synthesized and tested at various concentrations as corrosion inhibitors for 316L stainless steel in 1 M HCl using weight loss, electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), surface analysis techniques (SEM / EDX and Raman spectroscopy) and Functional Density Theory (DFT) was also used to calculate quantum parameters. The obtained results indicated that the inhibition efficiency of MDYO and DYCD increases with their concentration, and the highest value of corrosion inhibition efficiency was determined in the range of concentrations investigated (0.01 × 10-3 - 10-3 M). Polarization curves (Tafel extrapolation) showed that both compounds act as mixed-type inhibitors in 1M HCl solutions. Electrochemical impedance spectra (Nyquist plots) are characterized by a capacitive loop observed at high frequencies, and another small inductive loop near low frequencies. The thermodynamic data of adsorption of the two compounds on the stainless steel surface and the activation energies were determined and then discussed. Analysis of experimental results shows that MDYO and DYCD inhibitors adsorb to the metal surface according to the Langmuir model and the mechanism of adsorption of both inhibitors involves physisorption. SEM-EDX results confirm the existence of an inhibitor protective film on the stainless steel surface. The results derived from theoretical calculations supported the experimental observation.

Effect of T6 heat treatment on the microstructure and mechanical properties of AA365 alloy fabricated by vacuum-assisted high pressure die casting (고진공 고압 다이캐스팅으로 제조된 AA365 합금의 미세조직과 기계적 특성에 미치는 T6 열처리의 영향)

  • Junhyub Jeon;Seung Bae Son;Seok-Jae Lee;Jae-Gil Jung
    • Journal of the Korean Society for Heat Treatment
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    • v.37 no.3
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    • pp.121-127
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    • 2024
  • We investigate the effect of T6 heat treatment on the microstructure and mechanical properties of AA365 (Al-10.3Si-0.37Mg-0.6Mn-0.11Fe, wt.%) alloy fabricated by vacuum-assisted high pressure die casting by means of thermodynamic calculation, X-ray diffraction, scanning and transmission electron microscopy, and tensile tests. The as-cast alloy consists of primary Al (with dendrite arm spacing of 10~15 ㎛), needle-like eutectic Si, and blocky α-AlFeMnSi phases. The solution treatment at 490 ℃ induces the spheroidization of eutectic Si and increase in the fraction of eutectic Si and α-AlFeMnSi phases. While as-cast alloy does not contain nano-sized precipitates, the T6-treated alloy contains fine β' and β' precipitates less than 20 nm that formed during aging at 190℃. T6 heat treatment improves the yield strength from 165 to 186 MPa due to the strengthening effect of β' and β' precipitates. However, the β' and β' precipitates reduce the strain hardening rate and accelerate the necking phenomenon, degrading the tensile strength (from 290 to 244 MPa) and fracture elongation (from 6.6 to 5.0%). Fractography reveals that the coarse α-AlFeMnSi and eutectic Si phases act as crack sites in both the as-cast and T6 treated alloys.

Optimization of Ascorbic Acid Encapsulation in PLA Microcapsules Using Double Emulsion Process (이중유화법을 이용한 PLA 마이크로캡슐 내부로의 아스코르브산 캡슐화 공정 최적화)

  • Ji Won Yun;Young Mi Chung
    • Applied Chemistry for Engineering
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    • v.35 no.2
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    • pp.115-121
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    • 2024
  • This study analyzed the influence of process variables affecting the thermodynamic equilibrium and fluid dynamics of interfaces such as reverse micelle, salt concentration, interfacial tension, and viscosity of fluids to optimize the microencapsulation process using the W1/O/W2 double emulsion method. The process variable with the greatest impact on encapsulation efficiency was found to be the difference in osmotic pressure between the W1 and W2 phases. It was observed that increasing the salt concentration in the W2 phase or decreasing the ascorbic acid concentration in the W1 phase resulted in higher encapsulation efficiency. Additionally, a larger difference in osmotic pressure led to increased damage to the surface of the microparticles, as confirmed by SEM images. The introduction of reverse micelles, which was anticipated to increase encapsulation efficiency, either had a low contribution or even decreased encapsulation efficiency. The yield of microcapsules was expressed as a universal function, applicable to all process conditions or solution compositions. According to this universal function, no further increase in yield was observed beyond the Ca (capillary number) of approximately 20.

A Study of Fluoride Adsorption in Aqueous Solution Using Iron Sludge based Adsorbent at Mine Drainage Treatment Facility (광산배수 정화시설 철 슬러지 기반 흡착제를 활용한 수용액상 불소 흡착에 관한 연구)

  • Lee, Joon Hak;Kim, Sun Joon
    • Economic and Environmental Geology
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    • v.54 no.6
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    • pp.709-716
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    • 2021
  • In this study, an adsorbent prepared by natural drying of iron hydroxide-based sludge collected from settling basin at a mine drainage treatment facility located in Gangneung, Gangwon-do was used to remove fluoride in an artificial fluoride solution and mine drainage, and the adsorption characteristics of the adsorbent were investigated. As a result of analyzing the chemical composition, mineralogical properties, and specific surface area of the adsorbent used in the experiment, iron oxide (Fe2O3) occupies 79.2 wt.% as the main constituent, and a peak related to calcite (CaCO3) in the crystal structure analysis was analyzed. It was also identified that an irregular surface and a specific surface area of 216.78 m2·g-1. In the indoor batch-type experiment, the effect of changes in reaction time, pH, initial fluoride concentration and temperature on the change in adsorption amount was analyzed. The adsorption of fluoride showed an adsorption amount of 3.85 mg·g-1 16 hours after the start of the reaction, and the increase rate of the adsorption amount gradually decreased. Also, as the pH increased, the amount of fluoride adsorption decreased, and in particular, the amount of fluoride adsorption decreased rapidly around pH 5.5, the point of zero charge at which the surface charge of the adsorbent changes. Meanwhile, the results of the isotherm adsorption experiment were applied to the Langmuir and Freundlich isotherm adsorption models to infer the fluoride adsorption mechanism of the used adsorbent. To understand the thermodynamic properties of the adsorbent using the Van't Hoff equation, thermodynamic constants 𝚫H° and 𝚫G° were calculated using the adsorption amount information obtained by increasing the temperature from 25℃ to 65℃ to determine the adsorption characteristics of the adsorbent. Finally, the adsorbent was applied to the mine drainage having a fluoride concentration of about 12.8 mg·L-1, and the fluoride removal rate was about 50%.

Synthesis of TiO2 Fine Powder by Sol-Gel Process and Reaction Mechanism(II) : Hydrolysis of Titanium n-Propoxide (졸-겔법에 의한 TiO2미분말 합성과 반응메카니즘(II): Titanium n-propoxide의 가수분해)

  • Myung, Jung-Jae;Park, Jin-koo;Chung, Yong-Sun;Kyong, Jin-Bum;Kim, Ho-Kun
    • Applied Chemistry for Engineering
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    • v.8 no.5
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    • pp.777-783
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    • 1997
  • $TiO_2$ powders were synthesized via hydrolysis reaction of titanium n-propoxide in n-propanol solvent and the reaction rates were studied by use of UV-vis spectroscopic method. Concentration of water, reaction temperature, reaction time and acid-base effects of the solution were investigated to determine the optimum conditions for $TiO_2$ powder synthesis. The reaction were controlled to proceed to pseudo-first orders reaction in the presence of excess water in n-propanol solvent. The rate constants which varied with temperature and concentration of water were calculated by Guggenheim method. Reaction using $D_2O$ was also carried out to determine the catalytic character of water. $TiO_2$ powders were synthesized only in the neutral and basic solution and those were almost spheric forms having average particle size of $0.4-0.7{\mu}m$ diameter. Particle size decreased with increasing concentration of water and reaction temperature, however, increased with increasing reaction time. Associative $S_N2$ mechanism for the hydrolysis was proposed from the data of n-value in the transition state and thermodynamic parameter. $D_2O$ solvent isotope effect showed that $H_2O$ molecules reacted as nucleophilic catalysis.

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Determination of Adsorption Isotherms of Hydroxide ata Platinum Electrode Interface Using the Phase-Shift Method and Correlation Constants

  • Chun, Jin-Y.;Chun, Jang-H.
    • Journal of the Korean Electrochemical Society
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    • v.10 no.3
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    • pp.219-228
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    • 2007
  • The phase-shift method and correlation constants, i.e., the electrochemical impedance spectroscopy (EIS) techniques for studying linear relationships between the behaviors (${\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and those (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}{\theta}{\geq}0$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at noble and transition-metal/aqueous solution interfaces. At the Pt/0.1 MKOH aqueous solution interface, the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=5.6{\times}10^{-10}\;mol^{-1}\;at\;0{\leq}{\theta}<0.81$, $K=5.6{\times}10^{-9}{\exp}(-4.6{\theta})\;mol^{-1}\;at\;0.2<{\theta}<0.8$, and $K=5.6{\times}10^{-10}{\exp}(-12{\theta})\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$, interaction parameters (g = 4.6 for the Temkin and g = 12 for the Frumkin adsorption isotherm), rates of change of the standard free energy ($r=11.4\;kJ\;mol^{-1}$ for g=4.6 and $r=29.8\;kJ\;mol^{-1}$ for g=12), and standard free energies (${\Delta}G_{ads}^0=52.8\;kJ\;mol^{-1}\;at\;0{\leq}{\theta}<0.81,\;49.4<{\Delta}G_{\theta}^0<56.2\;kJ\;mol^{-1}\;at\;0.2<{\theta}<0.8$ and $80.1<{\Delta}_{\theta}^0{\leq}82.5\;kJ\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$) of OH for the anodic $O_2$ evolution reaction (OER) are also determined using the phase-shift method and correlation constants. The adsorption of OH transits from the Langmuir to the Frumkin adsorption isotherm (${\theta}\;vs.E$), and vice versa, depending on the electrode potential (E) or the fractional surface coverage (${\theta}$). At the intermediate values of ${\theta}$, i.e., $0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms and related electrode kinetic and thermodynamic parameters. They are useful and effective ways to study the adsorptions of intermediates (H, OH) for the sequential reactions (HER, OER) at the interfaces.