• Applied Chemistry for Engineering
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• v.31 no.5
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• pp.575-580
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• 2020

In this study, we simulated an amine regeneration process with heat-stable salts removal unit. We derived the optimal operating conditions considering the flow rate of waste, the removal rate of heat-stable salts, and the loss rate of MDEA (methyl diethanolamine). In the amine regeneration process that absorbs and removes acid gas, heat-stable salt impairs the absorption efficiency of process equipment and amine solution. An ion exchange resin method is to remove heat-stable salts through neutralization by using a strong base solution such as NaOH. The acid gas removal process was established using the Radfrac model, and the equilibrium constant of the reaction was calculated using Gibbs free energy. The removed amine solution is separated and flows to the heat-stable salts remover which is modeled by using the Rstoic model with neutralization reaction. Actual operation data and simulation results were compared and verified, and also a case study was conducted by adjusting the inflow mass of removal unit followed by suggesting optimal conditions.

• Clean Technology
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• v.26 no.2
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• pp.122-130
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• 2020

The isotherm, kinetic, and thermodynamic parameters of reactive blue 4 adsorbed by activated carbon were investigated for activated carbon dose, pH, initial concentration, contact time, and temperature data. The adsorption of the RB 4 dye by activated carbon showed a concave shape in which the percentage of adsorption increased in both directions starting from pH 7. The isothermal adsorption data were applied to Langmuir, Freundlich, and Temkin isotherms. Both Freundlich and Langmuir isothermal adsorption models fit well. From determined Freundlich separation factor (1/n = 0.125 ~ 0.232) and Langmuir separation factor (R_L = 1.53 ~ 1.59), adsorption of RB 4 by activated carbon could be employed as an effective treatment method. The constant related to the adsorption heat (B_T = 2.147 ~ 2.562 J mol^-1) of Temkin showed that this process was physical adsorption. From kinetic experiments, the adsorption process followed the pseudo second order model with good agreement. The results of the intraparticle diffusion model showed that the inclination of the first straight line representing the surface diffusion was smaller than that of the second straight line representing the intraparticle pore diffusion. Therefore, it was confirmed that intraparticle pore diffusion is the rate-controlling step. The negative Gibbs free energy change (ΔG = -3.262 ~ -7.581 kJ mol^-1) and the positive enthalpy change (ΔH = 61.08 kJ mol^-1) indicated the spontaneous and endothermic nature of the adsorption process, proving this process to be spontaneous and endothermic.

• Korean Chemical Engineering Research
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• v.54 no.6
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• pp.734-745
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• 2016

This review article described the electrochemical Frumkin, Langmuir, and Temkin adsorption isotherms of over-potentially deposited hydrogen (OPD H) and deuterium (OPD D) for the cathodic $H_2$ and $D_2$ evolution reactions (HER, DER) at Pt, Ir, Pt-Ir alloy, Pd, Au, and Re/normal ($H_2O$) and heavy water ($D_2O$) solution interfaces. The Frumkin, Langmuir, and Temkin adsorption isotherms of intermediates (OPD H, OPD D, etc.) for sequential reactions (HER, DER, etc.) at electrode/solution interfaces are determined using the phase-shift method and correlation constants, which have been suggested and developed by Chun et al. The basic procedure of the phase-shift method, the Frumkin, Langmuir, and Temkin adsorption isotherms of OPD H and OPD D and related electrode kinetic and thermodynamic parameters, i.e., the fractional surface coverage ($0{\leq}{\theta}{\leq}1$) vs. potential (E) behavior (${\theta}$ vs. E), equilibrium constant (K), interaction parameter (g), standard Gibbs energy (${\Delta}G_{\theta}{^{\circ}}$) of adsorption, and rate (r) of change of ${\Delta}G_{\theta}{^{\circ}}$ with ${\theta}$ ($0{\leq}{\theta}{\leq}1$), at the interfaces are briefly interpreted and summarized. The phase-shift method and correlation constants are useful and effective techniques to determine the Frumkin, Langmuir, and Temkin adsorption isotherms and related electrode kinetic and thermodynamic parameters (${\theta}$ vs. E, K, g, ${\Delta}G_{\theta}{^{\circ}}$, r) at electrode/solution interfaces.

• Asian-Australasian Journal of Animal Sciences
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• v.33 no.9
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• pp.1387-1399
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• 2020

Objective: The objective of this study was to estimate the genetic parameters and trends for milk, fat, and protein yields in the first three lactations of Thai dairy cattle using a 3-trait,-3-lactation random regression test-day model. Methods: Data included 168,996, 63,388, and 27,145 test-day records from the first, second, and third lactations, respectively. Records were from 19,068 cows calving from 1993 to 2013 in 124 herds. (Co) variance components were estimated by Bayesian methods. Gibbs sampling was used to obtain posterior distributions. The model included herd-year-month of testing, breed group-season of calving-month in tested milk group, linear and quadratic age at calving as fixed effects, and random regression coefficients for additive genetic and permanent environmental effects, which were defined as modified constant, linear, quadratic, cubic and quartic Legendre coefficients. Results: Average daily heritabilities ranged from 0.36 to 0.48 for milk, 0.33 to 0.44 for fat and 0.37 to 0.48 for protein yields; they were higher in the third lactation for all traits. Heritabilities of test-day milk and protein yields for selected days in milk were higher in the middle than at the beginning or end of lactation, whereas those for test-day fat yields were high at the beginning and end of lactation. Genetics correlations (305-d yield) among production yields within lactations (0.44 to 0.69) were higher than those across lactations (0.36 to 0.68). The largest genetic correlation was observed between the first and second lactation. The genetic trends of 305-d milk, fat and protein yields were 230 to 250, 25 to 29, and 30 to 35 kg per year, respectively. Conclusion: A random regression model seems to be a flexible and reliable procedure for the genetic evaluation of production yields. It can be used to perform breeding value estimation for national genetic evaluation in the Thai dairy cattle population.

• Bulletin of the Korean Chemical Society
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• v.29 no.5
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• pp.953-958
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• 2008

A novel anthraquinone diamino-bridged bis($\beta$ -cyclodextrin) 2 was synthesized. The inclusion complexation behaviors of the native $\beta$ -cyclodextrin 1 and the novel bis($\beta$ -cyclodextrin) 2 with guests, such as acridine red (AR), neutral red (NR), ammonium 8-anilino-1-naphthalenesulfonate (ANS), sodium 2-(p-toluidinyl) naphthalenesulfonate (TNS) and rhodamine B (RhB) were investigation by fluorescence, circular dichroism and 2D NMR spectroscopy. The spectral titrations were performed in phosphate buffer (pH 7.20) at 25 ${^{\circ}C}$ to give the complex stability constants (Ks) and Gibbs free energy changes (−${\Delta}G^0$) for the stoichiometric 1:1 inclusion complexation of host 1 and 2 with guests. The results indicated that the novel bis($\beta$ -cyclodextrin) 2 greatly enhanced the original binding affinity of the native $\beta$ -cyclodextrin 1. Typically, bis($\beta$ -cyclodextrin) 2 showed the highest binding constant towards ANS up to 34.8 times higher than that of 1. The 2D NMR spectra of bis($\beta$ -cyclodextrin) 2 with RhB and TNS were performed to confirm the binding mode. The increased binding affinity and molecular selectivity of guests by bis($\beta$ -cyclodextrin) 2 were discussed from the viewpoint of the size/shape-fit concept and multipoint recognition mechanism.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.387-387
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• 2013

Currently, the flash memory and the dynamic random access memory (DRAM) have been used in a variety of applications. However, the downsizing of devices and the increasing density of recording medias are now in progress. So there are many demands for development of new semiconductor memory for next generation. Magnetic random access memory (MRAM) is one of the prospective semiconductor memories with excellent features including non-volatility, fast access time, unlimited read/write endurance, low operating voltage, and high storage density. MRAM is composed of magnetic tunnel junction (MTJ) stack and complementary metal-oxide semiconductor (CMOS). The MTJ stack consists of various magnetic materials, metals, and a tunneling barrier layer. Recently, MgO thin films have attracted a great attention as the prominent candidates for a tunneling barrier layer in the MTJ stack instead of the conventional Al2O3 films, because it has low Gibbs energy, low dielectric constant and high tunneling magnetoresistance value. For the successful etching of high density MRAM, the etching characteristics of MgO thin films as a tunneling barrier layer should be developed. In this study, the etch characteristics of MgO thin films have been investigated in various gas mixes using an inductively coupled plasma reactive ion etching (ICPRIE). The Cl2/Ar, CH3OH/Ar, and CH4/Ar gas mix were employed to find an optimized etching gas for MgO thin film etching. TiN thin films were employed as a hard mask to increase the etch selectivity. The etch rates were obtained using surface profilometer and etch profiles were observed by using the field emission scanning electron microscopy (FESEM).

• Journal of Nuclear Fuel Cycle and Waste Technology
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• v.1 no.1
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• pp.65-73
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• 2013

Temperature-dependent hydrolysis behaviors of aqueous U(VI) species were investigated with time-resolved laser fluorescence spectroscopy (TRLFS) in the temperature range from 15 to $75^{\circ}C$. The formation of four different U(VI) hydrolysis species was measured at pHs from 1 to 7. The predominant presence of $UO{_2}^{2+}$, $(UO_2)_2(OH){_2}^{2+}$, $(UO_2)_3(OH){_5}^+$, and $(UO_2)_3(OH){_7}^-$ species were identified based on the spectroscopic properties such as fluorescence wavelengths and fluorescence lifetimes. With an increasing temperature, a remarkable decrement in the fluorescence lifetime for all U(VI) hydrolysis species was observed, representing the dynamic quenching behavior. Furthermore, the increase in the fluorescence intensity of the further hydrolyzed U(VI) species was clearly observed at an elevated temperature, showing stronger hydrolysis reactions with increasing temperatures. The formation constants of the U(VI) hydrolysis species were calculated to be $log\;K{^0}_{2,2}=-4.0{\pm}0.6$ for $(UO_2)_2(OH){_2}^{2+}$, $log\;K{^0}_{3,5}=-15.0{\pm}0.3$ for $(UO_2)_3(OH){_5}^+$, and $log\;K{^0}_{3,7}=-27.7{\pm}0.7$ for $(UO_2)_3(OH){_7}^-$ at $25^{\circ}C$ and I = 0 M. The specific ion interaction theory (SIT) was applied for the extrapolation of the formation constants to infinitely diluted solution. The results of temperature-dependent hydrolysis behavior in terms of the U(VI) fluorescence were compared and validated with those obtained using computational methods (DQUANT and constant enthalpy equation). Both results matched well with each other. The reaction enthalpies and entropies that are vital for the computational methods were determined by a combination of the van't Hoff equation and the Gibbs free energy equation. The temperature-dependent hydrolysis reaction of the U(VI) species indicates the transition of a major U(VI) species by means of geothermal gradient and decay heat from the radioactive isotopes, representing the necessity of deeper consideration in the safety assessment of geologic repository.

• Journal of Electrochemical Science and Technology
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• v.8 no.1
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• pp.43-52
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• 2017

In this paper, for the first time, the electroanalytical study of Triethylenediamine, TEDA was done on a typically graphene modified carbon paste electrode (Gr/CPE) in pH=10.5 of phosphate buffer solutions (PBS). The surface morphology of the bare and modified electrodes was characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The electro-oxidation of TEDA was investigated at the surface of modified electrode. The results revealed that the oxidation peak current of TEDA at the surface of Gr/CPE is 2.70 times than that shown at bare-CPE. A linear calibration plot was observed in the range of 1.0 to 202.0 ppm. In this way, the detection limit was found to be 0.18 ppm. The method was then successfully applied to determination of TEDA in aqueous samples obtained from two kinds of activated carbon from the masks of war. On the other hand, density functional theory (DFT) method at B3LYP/6-311++G** level of theory and a conductor-like Polarizable Continuum Model (CPCM) was used to calculate the $pK_a$ values of TEDA. The energies of lowest unoccupied molecular orbital ($E_{LUMO}$) and highest occupied molecular orbital ($E_{HOMO}$), gap energy (${\Delta}E$) and some thermodynamic parameters such as Gibbs free energy of TEDA and its conjugate acid ($HT^+$) were calculated. The results of calculated $pK_a$ were found to be in good agreement with the experimental values.

• Journal of the Korean Chemical Society
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• v.42 no.4
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• pp.383-390
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• 1998

The interaction of phenoxide anion with several cationic surfactant micelles (DTAB, TTAB, CTAB, CDEAB, and CTAC) was studied by UV/Vis spectrophotometric method. The solubilization constants of phenoxide anion into the cationic micellar phase and the critical micelle concentration of these surfactants in the presence of the phenoxide anion could be determined from the absorbance changes. The measured solubilization constants were changed according to the following order: $K_s(CTAC)>K_s(CDEAB)>K_s(CTAB)>K_s(TTAB)>K_s(DTAB).$ Effects of salts(NaCl and NaBr) and n-alcohols(butanol, pentanol, and hexanol) on the solubilization of phenoxide anion by the TTAB system have been also measured and analyzed. There was a great decrease of solubilization constant and CMC with these additives. The standard Gibbs free energy, enthalpy, and entropy changes for the solubilization of phenoxide anion by the TTAB system were calculated from the temperature dependence of $K_s$ values.

• Bulletin of the Korean Chemical Society
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• v.2 no.4
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• pp.142-147
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• 1981

A blend polymeric system composed of poly(methyl methacrylate) (PMMA or PM) and polystyrene (PS) dissolved in chloroform was rheologically studied. The viscosities ${\eta}_{bl}$ of the blend system with various blending ratios ${\chi}$ changing from zero (pure PS solution) to unity (pure PMMA solution) were measured at $25{\circ}C$ as a function of shear rates ${\dot{s}}$ by using a Couette type viscometer. ${\eta}_{bl}$ at a given ${\dot{s}}$ decreased exponentially with ${\chi}$ reaching asymptotic constant value of ${\eta}_{bl}$ ; ${\eta}_{bl}$ at a given ${\chi}$ is greater at a smaller ${\dot{s}}$. These results are explained by using Ree-Erying's theory of viscosity, ${\eta}_{bl}=(x_1{\beta}_1/{\alpha}_1)_{b}_1＋ (x_2{\beta}_2/{\alpha}_2)_{bl}[sinh^{-1}{\beta}_2(bl) {\dot{s}}]/{\beta}_2(bl){\dot{s}}$. The Gibbs activation energy ${\Delta}G_i^\neq$(i = 2 for non-Newtonian units) entering into the intrinsic relaxation time ${\beta}$ is represented by a linear combination ${\Delta}G_i^\neq(bl) ={\chi}{\Delta}G_i^{\neq}_{iPM}+(1-{\chi}){\Delta}G_i^{\neq}_{iPS}$;the intrinsic shear modulus$[[\alpha}_i]^{-1}$ is also represented by $[{\alpha}_i(bl)]^{-1}={\chi}[{\alpha}_{iPM}]^{-1}+(1-{\chi})[{\alpha}_{iPS}]^{-1}$ and the fraction of area on a shear surface occupied by the ith flow units $x_i(bl)$ is similarly represented, i.e., $x_i(bl) = {\chi}x_{iPM}+(1-{\chi})x_{iPS}$. By using these ideas the Ree-Eyring equation was rewritten which explained the experimental results satisfactorily.