• Bulletin of the Korean Chemical Society
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• v.19 no.3
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• pp.349-353
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• 1998

Solvolysis rates of substituted 2-aryl-1,1-dimethylethyl bromides (1) were determined in a variety of solvents such as aqueous mixtures of ethanol, acetone, 2,2,2-trifluoroethanol, and also mixtures of ethanol and TFE at 25 ℃, 35 ℃, and 45 ℃. The solvent effects were analyzed in terms of Winstein-Grunwald equation. The solvent effects of 1-4-MeO failed to give a single linear correlation against either Y or YCl (YBr), but exhibited a wide split pattern which could not be related to the solvent nucleophilicity. On the other hand 1-4-CH3 and 1-H gave a fairly good linearity. In the case of 1-4-MeO, a fairly good linearity was observed against YΔ defined from the solvolysis of 4-methoxyneophyl tosylate. It is assumed that resonance interaction between reaction site and aryl-π-system operates to give charge delocalization regardless of the different solvolysis mechanisms. The Hammett-Brown treatment of the solvolytic rate constant of compounds 1 was obtained non-linear two separated lines of - 1.06 to - 1.46, suggesting of mechanistic changeover from kc-ks to kΔ on going from electron-withdrawing to electron-donating substituents as a basis of 4-CH3 group.

• 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).

• Macromolecular Research
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• v.15 no.2
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• pp.167-172
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• 2007

The reduction behavior of silver ions to silver nanoparticles is an important topic in polymer/silver salt complex membranes to facilitate olefin transport, as this has a significant effect on the long-term performance stability of the membrane. In this study, the effects ofthe solvent type on the formation of silver nanoparticles, as well as the long-term membrane performance of a solid polymer/silver salt complex membrane were investigated. These effects were assessed for solid complexes of poly(N-vinyl pyrrolidone) $(PVP)/AgBF_4$, using either an ionic liquid (IL), acetonitrile (ACN) or water as the solvent for the membrane preparation. The membrane performance test showed that long-term stability was strongly dependent on the solvent type, which increased in the following order: IL > ACN >> water. The formation of silver nanoparticles was more favorable with the solvent type in the reverse order, as supported by UV-visible spectroscopy. The poor stability of the $(PVP)/AgBF_4$ membrane when water was used as the solvent might have been due to the small amount of water present in the silver-polymer complex membranes actively participating in the reduction reaction of the silver ions into silver nanoparticles. Conversely, the higher stability of the $(PVP)/AgBF_4$, membrane when an IL was used as the solvent was attributable to the cooperative coordination of silver ions with the IL, as well as with the polymer matrix, as confirmed by FTIR spectroscopy.

• Bulletin of the Korean Chemical Society
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• v.27 no.12
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• pp.2011-2018
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• 2006

We have investigated the solvent effects on $\Delta log\;K_s $(the difference of stability constant of binding) and the different free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6, i.e., the selectivity of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6 using a Monte Carlo simulation of statistical perturbation theory (SPT) in diverse solvents. The stability constant ($\Delta log\;K_s $) of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6, in $CH_3OH$ was calculated in this study as -1.06 agrees well with the different experimental results of -0.44~-0.6, respectively. We have reported here the quantitative solvent-polarity relationships (QSPR) studied on the solvent effects the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6. From the calculated coefficients of QSPR, we have noted that solvent polarity (ET) and Kamlet -Tafts solvatochromic parameters (b ) dominate the differences in relative solvation Gibbs free energies of $Nd^{3+}$ and $Eu^{3+}$ ions but basicity (Bj) dominates the negative values in differences in the stability constant ($\Delta log\;K_s $) as well as the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6 and acidity (Aj) dominates the positive values in differences in the stability constant ($\Delta log\;K_s $) as well as the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6.

• Journal of the Korean Chemical Society
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• v.20 no.3
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• pp.206-211
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• 1976

Equilibria equations, applicable to solvent of low dieletric constant, were derived for potentiometric neutralization titration. Effects of salt and solvent were studied in potentiometric neutralization titration using ethylenediamine as solvent. Good agreement was observed between theory and experimental results.

• Bulletin of the Korean Chemical Society
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• v.19 no.5
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• pp.561-564
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• 1998

Solvent effects on the reactions of DANSYL and BANSYL chlorides with substituted pyridines have been investigated using two parameters of Taft's solvatochromic correlation and four parameters of Kirkwood-Onsager, Parker, Marcus, Hildebrand equation. The acetonitrile molecules accelerate charge separation of the reactants and stabilize the transition state. The coefficient of the solvent parameters provide a good information to predict and to analyze the reaction mechanism. The nucleophilic substitution reaction of DANSYL and BANSYL chlorides with substituted pyridines are ruled by the contribution of the change in dipole moment term and polarity-polarizability term.

• Journal of Environmental Science International
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• v.6 no.2
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• pp.133-139
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• 1997

The solvent extraction method was applied on the wastewater produced during malonate(malonic acid esters) process to recover cobalt. DEHPA and PC88A were used as organic solvent From separation funnel experiment(batch experiment), the effects of vari- ous parameters (pH, cobalt concentration, reaction rate, and stripping temperature) on solvent extraction were examined and these data were used to derive equilibrium curve. A mixer-settler experiment (continuous experiment) of bench scale was also carried out for the plant construction and a Mccabe-Thiele diagram was obtained. The results of these experiments indicate that cobalt is recoverable above 99 oyo and that its purity as cobalt sulfate Is higher than 99.9 wt%.

• Bulletin of the Korean Chemical Society
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• v.26 no.3
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• pp.384-392
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• 2005

Solvent effects on the kinetics of bromophenol blue fading have been investigated within a temperature range in binary mixtures of methanol, ethanol, 1-propanol, ethylene glycol and 1,2-propanediol with water of varying solvent compositions up to 40% by weight of organic solvent component. Correlation of logk with reciprocal of the dielectric constant was linear. Finally a mechanism was proposed for the bromophenol blue fading upon SESMORTAC (study of effect of solvent mixture on the one-step reaction rates using the transition state theory and cage effect) model, by means of this model, the fundamental rate constants of the fading reaction in these solvent systems were calculated.

• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.610-616
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• 2014

The influence of solvent polarity on the absorption spectra of some synthesized azo dye with heterocyclic moieties and ${\beta}$-naphthol (1-3) have been investigated using a UV-Visible spectrophotometer. The spectral characteristics of the azo dyes (1-3) in different solvents at room temperature were analyzed. The solvatochromic empirical variables like ${\pi}^*$, ${\alpha}$, and ${\beta}$ have been used to discuss the solvatochromic behaviour of the dyes and to evaluate their contributions to the solute-solvent interactions. A multi-parameter regression model for quantitative assessment of the solute/solvent interaction and the absorption has been used to explain the solvent effect on azo dyes (1-3).

• Journal of the Korean Society of Food Science and Nutrition
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• v.29 no.2
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• pp.204-210
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• 2000

The antioxidative effects of solvent fractions of kimchi on LDL oxidatiojn in vitro as well as hypolipidemic effects of these fractions in rabbit fed atherogenic diet were studied. Methanol extract of deffated kimchi was fractionated sequentially with dichloromethane, ethylacetate, butanol and water. All solvent fractions of kimchi inhibited Cu2+-induced LDL oxidation. Among these fractions, the dicholoromethane fraction at the concentration of 25$\mu\textrm{g}$/mL showed the highest antioxidant effects against LDL oxidation in the aspect of inhibiting TBARS production by 28.03% or prolonged lag phase duration 2-fold compared to those of control. Based on the results from in vitro study, New Zealand White Rabbits grouped six each were fed for 8 weeks either basal diet containing 1% cholesterol or experimental diet containing dichloromethane, ethylacetate or water fraciton added to the basal diet. The amount of solvent fraction of kimchi added to the experimental diet was equivalent to 5% of freeze-dried kimchi. The hypolipidemic effects was observed from all experimental gropus, especially from dichloromethane fraction added group. The plasma and LDL cholesterol levels of this group were decreased by 49% and 47%, respectively while that of HDL increased by 91% compared to those of control. The calculated atherogenic index for the dichloromethane group was the lowest among groups. However, TG lowering effect of experimental group was not observed since solbent fraction of kimchi was used instead of freeze-dried kimchi. The TBARS concentration of LDL isolated from rabbit fed dichloromethane fraction was decreased 21% than that of control. These results indicate that active principles responsible for inhibiting LDL oxidation and lowering plasma cholesterol may present abundantly in dichloromethane fraction of kimchi.