• Journal of the Korean Chemical Society
• /
• v.23 no.4
• /
• pp.187-197
• /
• 1979

The molar optical rotation of poly(cis-5-methylproline) was measured in solvent mixtures of chloroform and chloroethanol. After proper allowance for time-dependent mutarota-tions, equilibrium states between form A and form B were observed to occur with a solvent composition of 0.5~10 % chloroethanol in chloroform by volume. From the equilibrium constants, which were calculated by optical rotations at equilibrium measured at three different temperatures (5, 25, and 45 $^{circ}$C), the thermodynamic parameters-free enthalpy, enthalpy and entropy changes for the mutarotation-were evaluated. It was found that starting with equimolar concentrations of form A and form B, the forward mutarotation occurred in the solvent compositions of chloroethanol greater than 3 % by volume, whereas the reverse mutarotation resulted in solvent compositions of chloroethanol less than 3 % by volume. The changes in enthalpy and entropy for the forward mutarotation were found to be positive, while those were for the reverse mutarotation were negative. The driving forces for the forward mutarotation were found to be the increase in entropy, whereas that for the reverse mutarotation was the negative enthalpy change. The thermodynamic data were explained by the interaction between polymer and solvent, i.e., preferential hydrogen bonding of chloroethanol with the carbonyl group in form B over form A, and by difference in conformational energies between form A and form B.

• Korean Chemical Engineering Research
• /
• v.45 no.3
• /
• pp.219-225
• /
• 2007

The equilibrium solubilization capacity of pure hydrocarbon oils by 2.5 wt% $C_{12}E_8$ nonionic surfactant solution was measured at $30^{\circ}C$ by gas chromatography (GC) analysis. Experimental results indicated that the molar solubilization ratio (MSR) for pure alkanes was found to decrease almost linearly with the alkane carbon number (ACN) of the hydrocarbon oil. For the binary mixture systems of the hydrocarbon oils both selective and nonselective solubilization behaviors were observed depending on the difference in carbon number of the two hydrocarbon oils. Equilibrium solubilization tests for the two n-octane/n-nonane and n-nonane/n-decane mixture systems in $C_{12}E_8$ surfactant solutions suggest slightly selective solubilization in favor of n-octane, but the small difference in solubilization rates between two hydrocarbon oils does not allow ruling out non-selective solubilization for these particular systems. This is certainly not the case for the n-octane/n-decane mixture, for which selective solubilization was conclusively demonstrated by GC analysis data.

• Korean Chemical Engineering Research
• /
• v.48 no.5
• /
• pp.632-637
• /
• 2010

Liquid-liquid equilibrium data for the quaternary system water +tetrahydrofuran + butyl acetate + isoamyl alcohol mixture were measured at 298.15 K and atmospheric pressure. Binodal curves, tie-lines, distribution, and selectivity for the quaternary system have been determined in order to investigate the effect of using binary solvents, butyl acetate and isoamyl alcohol, on extracting tetrahydrofuran from aqueous solution. In addition, these experimental tie-line data were also compared with the values predicted by the UNIFAC model. For the quaternary system, an average root-mean-square deviation for the system in 75/25, 50/50, and 25/75 mass ratios as mixed solvents are(3.35, 5.21 and 5.65) %, respectively.

• Korean Chemical Engineering Research
• /
• v.47 no.6
• /
• pp.755-761
• /
• 2009

To a first approximation, phase behavior of a system becomes increasingly skew in proportion to the boiling point difference of system-forming constituents. Therefore, phase behavior data of a system of a large boiling point difference are to be experimentally measured for thorough understanding of the thermodynamic characteristics of such system. In this work, isobaric vapor-liquid equilibrium of a mixture consisting of toluene and cresol, which shows a large boiling point difference of nearly $100^{\circ}C$ and is consequently expected to be considerably nonideal, was measured by using a recirculating equilibrium cell at various subatmospheric pressures ranging from 10 kPa to 60 kPa. The measured VLE data were correlated with NRTL and UNIQUAC models in a satisfactory manner and the accompanying thermodynamic consistency test represented soundness of the measurements. In addition, the excess molar volume of the mixture was also measured with a vibrating densitometer and correlated with a Redlich-Kister polynomial. A negative excess volume prevailed over the whole concentration range, which indicates a favorable attraction between toluene and cresol isomers and results in an extensive miscibility.

• Bulletin of the Korean Chemical Society
• /
• v.13 no.2
• /
• pp.184-187
• /
• 1992

Regeneration methods of oximes, hydrazones, and N,N-dimethylhydrazones to the related carbonyl compounds were effected using various dicarbonyl compounds which are activated with electron withdrawing substituents such as trifluoromethylated $\beta-diketones$, $\beta-acylpyruvates$, and $\alpha-diketones$ via an equilibrium exchange reaction. The chemical transformations of the dicarbonyl compounds in the exchange reaction were investigated by various spectroscopic methods.

• Nuclear Engineering and Technology
• /
• v.52 no.11
• /
• pp.2543-2551
• /
• 2020

Calculations of chemical equilibrium for multicomponent aqueous systems of the HyBRID dissolution of magnetite were performed by using the HSC Chemistry. They were done by using a Pitzer-based aqueous solution model with the recipe of raw materials in experiments conducted at KAERI. The change in the amounts of species and ions and the pH values of the solution at equilibrium was observed as functions of temperature and raw amount of CuSO₄. Precipitation of Cu₂O occurred at a large amount of CuSO₄ added to the solution, while no precipitation of Cu(OH)₂ was found at any amounts of CuSO₄. The E-pH diagrams for Cu were constructed at various Cu concentrations to provide the effect of the Cu concentration on the pH values at boundaries where the coexistence of Cu⁺ ion and Cu₂O solid occurred. To prevent Cu⁺ ions from being precipitated to Cu₂O, the raw amount of CuSO₄ should be adjusted so that the pH value of the solution from the equilibrium calculation is less than that from the E-pH diagram. We provided guidelines for the raw amount of CuSO₄ and the pH value of the solution, which prevent the formation of Cu₂O precipitates in the HyBRID dissolution experiments for magnetite.

• Journal of Energy Engineering
• /
• v.2 no.2
• /
• pp.225-230
• /
• 1993

Isothermal vapor-liquid equilibrium data have been measured for binary systems n-dodecane-1-defanol, n-doderane-1-dodecanol, and 1-decanoi-1-dodecanol at 140$^{\circ}C$ by using head space gas chromatography (H.S.G.C) as a static method. The activity coefficients, calculated taking into acount the nonideality of the liquid phase, were correlated with the conventional g$\^$E/ model, Margules, van Laar, Wilson, NRTL equations. These equilibrium data were thermodynamically consistent by Rrdlich- kister test, among these data, system n-dodecane-1-detanoi has minimum azeotrope.

• Korean Membrane Journal
• /
• v.5 no.1
• /
• pp.68-74
• /
• 2003

Methane steam reforming (MSR) reaction for hydrogen production was studied in a membrane reactor (MR) using two tubular membranes, one Pd-based and one of porous alumina. A higher methane conversion than the thermodynamic equilibrium for a traditional reactor (TR) was achieved using MRs. The experimental temperature range was 350-500$^{\circ}C$; no sweep-gas was employed during reaction tests to avoid its back-permeation through the membrane and the steam/methane molar feed ratio (m) varied in the range 3.5-5.9. The best results (the difference between the MR conversion and the thermodynamic equilibrium was of about 7%) were achieved with the alumina membrane, working with the highest steam/methane ratio and at 450$^{\circ}C$. Silica membranes prepared at KRICT laboratories were characterized with permeation tests on single gases (N$_2$, H$_2$ and CH$_4$). These membranes are suited for H$_2$ separation at high temperature.

• Korean Chemical Engineering Research
• /
• v.53 no.4
• /
• pp.450-456
• /
• 2015

In the present study, modelling and optimization of ethanol-benzene separation process were performed using pressure-swing distillation. Order to obtain a reliable results, vapour-liquid equilibrium (VLE) experiments of ethanol-benzene binary system were performed. The parameters of thermodynamic equation were determined using experimental data and the regression. The pressure-swing distillation process optimization was performed to obtain high purity ethanol and high purity benzene into a low-high pressure columns configuration and a high-low pressure columns configuration. The heat duty values of the reboiler from simulation were compared, and the process was optimized to minimize the heat duty.

• Macromolecular Research
• /
• v.12 no.3
• /
• pp.269-275
• /
• 2004

To graft N-isopropylacrylamide (NIPAAm) onto alginate, varying dosages of ${\gamma}$-rays were irradiated onto alginate films in deionized water and methanol media, which are non-solvents of alginate. We investigated the hydrogels graft ratio, mechanical strength, swelling kinetics and ratio, and behavior with respect to drug release. The graft yield of NIPAAm increased upon increasing the irradiation dose. The use of the aqueous solution increased the graft yield relative to that obtained in methanol. The mechanical strength of the grafted hydrogels increased after grafting with NIPAAm. In a study of the swelling kinetics, we found that all hydrogels reached an equilibrium swollen state within 3 h. The equilibrium swelling ratio of the hydrogels decreased upon increasing the irradiation dose. The swelling ratio of the hydrogels decreased dramatically between 30 and 35$^{\circ}C$ because phase separation of NIPAAm occurred at 32$^{\circ}C$. The swelling process, with respect to the temperature change, was repeatable. An NIPAAm-grafted alginate containing a drug sustained its release rate until 3 h after an initial high drug release caused by a burst effect.