• Bulletin of the Korean Chemical Society
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• v.22 no.8
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• pp.842-846
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• 2001

Solvolyses of N-methyl-N-phenylcarbamoyl chlorides in aqueous binary mixtures of acetone, ethanol, methanol and in water, D2O, and 50% D2O-CH3OD are investigated at 25.0 $^{\circ}C.$ The Grunwald-Winstein plots of first-ord er rate constants for N-methyl-N-phenylcarbamoyl chlorides with YCl (based on 2-adamantyl chloride) show a dispersion phenomenon. The ring parameter (I) has been shown to give considerable improvement when it is added as an hI term to the original Grunwald-Winstein and extended Grunwald-Winstein correlations for the solvolyses of N-methyl-N-phenylcarbamoyl chlorides. This study has shown that the magnitude of l, m and h values associated with a change of solvent composition is able to predict the dissociative SN2 transition state. The kinetic solvent isotope effects determined in deuterated water are consistent with the proposed mechanism of the general base catalyzed and/or a dissociative SN2 mechanism channel for N-methyl-N-phenylcarbamoyl chlorides solvolyses.

• Journal of the Korean Chemical Society
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• v.32 no.3
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• pp.211-226
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• 1988

Liquid chromatographic behavior of several metal ions in dithiocarbamate(DTC) chelates were investigated by reversed phase high performance liquid chromatography on Novapak $C_{18}$ and ${\mu}$-Bondapak $C_{18}$ columns. The optimum conditions for the separation of DTC-metal chelate were examined with respect to the pH, shaking time, flow rate, extraction solvent, and mobile phase strength. The metal ions in mixtures at trace level, chelated with some dithiocarbamate derivatives were separated successfully on Novapak $C_{18}$ column using acetonitrile/methanol/water or acetonitril/water mixtures as mobile phases. It was found that all DTC metal chelates studied were eluted in an acceptable range of capacity factor values ($0{\leqq}log\;k'{\leqq}1$). Although several foreign metal ions were coexisted, high recovery and good precision were attained ; 97.0-106.7 % for the recovery and 0.98-3.41% for the coefficient of variation. Under the optimum analytical conditions, trace metal ions in the composite water samples were determined sucessfully with in relative error of about {\pm}$6.7 %.

• Bulletin of the Korean Chemical Society
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• v.23 no.1
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• pp.123-131
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• 2002

Solvolyses rate constant of 1- and 2- naphthoyl chlorides (1 and 2) are reported for aqueous binary mixtures with methanol, ethanol, fluorinated alcohol, acetonitrile and dioxane. Kinetic solvent isotope effects (KISE) in methanol and product selectivities (S) of 2-naphthoyl chloride (2) in alcohol-water are also reported. Dispersions in Grunwald-Winstein correlations $(r{\leq}0.901)$ are discussed by multiple regression analysis incorporating ionizing power $(Y_{Cl})$ scale and rate-rate profiles. Major causes for these phenomena are investigated as an aromatic ring solvation effects, in conjunction with weakly nucleophilic solvation effects ($S_N2$ character), for solvolyses of 1 and for solvolyses of 2, as dual reaction channels, described as $S_N1$-$S_N2$ and $S_AN$-$S_N2$ processes. Distinct border lines between the two pathways are derived from solvolyses rates of 2 in 18 solvent using the results of $log(k/k_o)=mY_{Cl}+lN_T+hI$ plot with values of 1.13 for m, 0.37 for l and 0.15 for h value in 5 aqueous fluorinated alcohol mixtures. Using rate-product correlation, the validity of a third order model based on a general base catalyzed by solvent and contribution from these rate constants, $k_{aa},\;k_{aw}$ and $k_{aw}$, are investigated for $S_AN$-$S_N2$ solvolyses of 2 favored in more rich alcohol media and gradual addition of water to alcohol solvent shows a great shift away from stoichiometric solvation to predominantly medium effects. Rate-rate correlation between solvolyses of 2 and trimethyl acetylchloride (5) with alkyl group in the 29 aqueous solvent mixtures shows appreciable linearity (slope = 0.84, r = 0.987), caused by the same pathway ($S_N1$-$S_N2$ process), even if this correlation coincides with appreciable dispersion (different solvation effect).

• Membrane Journal
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• v.25 no.4
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• pp.327-331
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• 2015

Poly(vinyl alcohol) (PVA) membranes cross-linked with sulfosuccinic acid (SSA) in which poly(4-styrene sulfonic acid-co-maleic acid) (PSSA_MA) was blended to endow more ion exchange capacity were prepared to measure the permselectivities of water-alcohol mixtures by pervaporation separation technique. The feed mixtures of binary aqueous methanol, ethanol and iso-propyl alcohol solution by 90 wt% alcohol portion were used. Typically, for PVA10/SSA9/PSSA_MA90 membrane, the flux of 202.6, 47.8, $20.2g/m^2hr$ for aqueous methanol, ethanol and iso-propyl alcohol solutions was shown while the best separation factors of 34.2, 291 and 991 were given by PVA10/SSA11/PSSA_MA80 membrane. More details are discussed in main text of this article.

• Korean Membrane Journal
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• v.10 no.1
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• pp.39-45
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• 2008

Polyelectrolyte complex based on two anionic polysaccharides, composed of sodium alginate and carrageenan, were prepared by interacting with divalent calcium ions in solution. The effects of annealing on the structural deformation of polyelectrolyte complex and on their characteristics at removing water from a methanol mixture from the point of molecular sieve were investigated and discussed. The result showed that the structural deformation of the annealed polyelectrolyte complex has an effect on the free volume between these polymer chains and the chelate segments such a shrinking of the overall morphology, which act as a molecular sieve in the separation of methanol and water mixtures.

• Bulletin of the Korean Chemical Society
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• v.34 no.9
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• pp.2711-2719
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• 2013

Hydrogen bonding interaction between alcohols and water molecules is an important characteristic in the aqueous solutions of alcohols. In this paper, a series of molecular dynamics simulations have been performed to investigate the aqueous solutions of low molecular weight alcohols (methanol, ethylene glycol and glycerol) at the concentrations covering a broad range from 1 to 90 mol %. The work focuses on studying the effect of the alcohols molecules on the hydrogen bonding of water molecules in binary mixtures. By analyzing the hydrogen bonding ability of the hydroxyl (-OH) groups for the three alcohols, it is found that the hydroxyl group of methanol prefers to form more hydrogen bonds than that of ethylene glycol and glycerol due to the intra-and intermolecular effects. It is also shown that concentration has significant effect on the ability of alcohol molecule to hydrogen bond water molecules. Understanding the hydrogen bonding characteristics of the aqueous solutions is helpful to reveal the cryoprotective mechanisms of methanol, ethylene glycol and glycerol in aqueous solutions.

• Journal of the Korean Chemical Society
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• v.20 no.3
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• pp.185-192
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• 1976

Equivalent conductances of ammonium salts such as $NH_4Cl,\;CH_3NH_3Cl,\;(CH_3)_2NH_2Cl,\;(CH_3)_3NHCl\;and\;(CH_3)_4NCl$ have been measured in methanol-water mixtures of various composition (0.0${\sim}$0.6-mole frcation: m. f.) in the concentration range from 0.01 to 0.04 M at $25^{\circ}C$, and limiting equivalent conductances (${\Lambda}_0$) are determined by the analysis of Fuoss Onsager's semiempirical equation.The experimental results are discussed in terms of varing the size of ${\Lambda}_0$ due to the salts species and solvent composition. It has been observed in quite common over all salts that ${\Lambda}_0$ decreases with the increase of m. f. methanol, and the maximum decrement in ${\Lambda}_0$ shows between water and 0.1 m. f., while the plot of ${\Lambda}_0$ vs. m. f. goes through a minimum at 0.4 m. f. and then turns slightly upward. On the other hand, the ${\Lambda}_0$ decrease with the increase of the size of ammonium cation and the larger values ${\Lambda}_0$ are showed in comparison with those of values observed for the corresponding $n-RNH_3Cl$ under the same experimental procedure. All these behaviors are considered to be closely correlated with the structures of solvents and solutes and the significant similarities are compared with the behaviors of partial molar volumes for amine salts in same solvent system.

• Korean Journal of Air-Conditioning and Refrigeration Engineering
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• v.16 no.10
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• pp.942-951
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• 2004

This paper presents the results of a theoretical study of the effect of radiation during free convective laminar film boiling for methanol/water binary mixtures on an isothermal vertical wall at atmospheric pressure. With the well-known boundary layer theory as a basis, a theoretical model has been formulated into consideration for mass diffusion at liquid phase. The equations are numerically solved by a similarity method to investigate the effects of radiation emissivity on the surface with various parameters such as wall superheat and composition of more volatile component at liquid phase far from the wall. From the results, the distributions of the physical quantifies are investigated in both phases. New correlations are proposed to predict the heat transfer coefficient of binary mixtures. It is shown that the proposed correlations are in good agreement with numerical results and with Bromley's correlation within maximum $11\%$ errors. It is also found that as the wall superheat is increased, radiation effect becomes more important.

• Journal of Microbiology and Biotechnology
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• v.8 no.6
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• pp.656-662
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• 1998

To make a distinction between the influence of the dielectric constant and of methanol concentration on trypsin-catalyzed hydrolysis and methanolysis at $0^{\circ}C$, a model reaction of $N^u$-benzyloxycarbonyl-L-lysine p-nitrophenyl ester with water-methanol mixtures was chosen and a kinetic study done. The $k_{cat}$ values increased with methanol concentration, in a linear manner whereas $K_{M}$ values increased in a log-linear fashion. However, the $k_{cat},$_{M}$ ratio increased at lower methanol concentrations than 30% and then began to decrease at higher concentrations. The decrease in $k_{catK_M}$observed at higher than 30% methanol concentrations is attributed to the hydrophobic partitioning effect on substrate binding. On the other hand, the increase in $k_{catK_M}$ in the 0~30% methanol concentration range seems to be due to the effect of nucleophilic cosolvent on $k_{cat}$ and of the dielectric constant on $k_m$. This explanation was verified by measuring the effect of varying the dielectric constant of the medium on kinetic constants with isopropyl alcohol chemically unrelated to the enzyme reaction as the methanol concentration is maintained at a constant level. Therefore, we conclude that the effect of increasing the methanol concentration in the model reaction on the kinetic parameters $k_{cat \;and\;{K_M}}$ is caused by changes in both the nucleophilicity and the dielectric constant of the medium. Based on product analysis, the increase in $k_4, k_3$by decreasing the temperature can be accounted for by the suppression of hydrolytic reactions. This observation indicates that the nucleophile is favored by low temperatures. There was no loss of trypsin activity over a 10 h period in 60% methanol concentration at $pH^＊\; 5.5,\; 0^{\circ}C$.EX>.

• Bulletin of the Korean Chemical Society
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• v.24 no.4
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• pp.431-436
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• 2003

Solvolytic rate constants at 25℃ are reported for solvolyses of cinnamyl bromide (1) in binary mixtures of water with acetone, ethanol, methanol, methanol-d, and 2,2,2-trifluoroethanol. Product selectivities are reported for solvolyses of 1 in aqueous ethanol and methanol. Rate ratios in solvents of the same $Y_{Br}$ value and different nucleophilicity provide measures of the minimum extent of nucleophilic solvent assistance (e.g. $[k_{40EW}/k_{97TFE}]$Y = 2.88, EW = ethanol-water). With use of the extended Grunwald-Winstein equation, the l and m values are similar to the values of 0.43 and 0.88 obtained for the solvolyses of 1 using the equation (see below) which includes a parameter (I) for solvation of aromatic rings. The magnitude of l and m values associated with a change of solvent composition predicts the $S_{N1}$ reaction mechanism rather than an $S_{N2}$ channel. Product selectivities (S), defined by S = [ether product]/[alcohol product]×[water]/[alcohol solvent] are related to four rate constants for reactions involving one molecule of solvent as nucleophile and another molecule of solvent as general base catalyst. A linear relationship between 1/S and molar ratio of solvent is derived theoretically and validated experimentally for solvolyses of the above substrates from water up 75% 1/S = $(k_{wa}/k_{aw})$([alcohol solvent]/[water]) + $k_{ww}/k_{aw}$ alcohol-water. The results are best explained by product formation from a “free” carbocation intermediate rather than from a solvent-separated ion pair.