• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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• 2001.06a
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• pp.1289-1289
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• 2001

Water-methanol and water-acetonitrile mixtures are frequently used as HPLC solvent system and strong hydrogen bonding is well-known. But a detailed aspect of water-methanol and/or water-acetonitrile mixtures have not been shown with direct spectral evidence. Recently, near infrared spectroscopy and chemometric data refinery have been successfully combined in many applications. On the basis of factor analytical methods, the spectral features of water-methanol and water-acetonitrile mixtures were studied to reveal the detail of mixtures. Water-methanol and water-acetonitrile mixtures were prepared with varying concentration of each constituent and near infrared spectral data were acquired in the range of 1100-2500nm with 2-nm interval. The data matrices were analysed with ITTFA(Iterative Target Transform Factor Analysis) algorithm implemented as MATLAB codes. As a result, the concentration profiles of water, methanol and water-methanol complex were resolved and the spectra of water-methanol complexes were calculated, which cannot be acquired with pure complexes. A similar result was obtained with NIR spectral data of water-acetonitrile mixtures. Moreover, pure spectra of hydrogen-bonding complexes of water-methanol and water-acetonitrile can be computed, while any other usual physical methods cannot isolated those complexes for acquiring pure component spectra.

• YAKHAK HOEJI
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• v.48 no.1
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• pp.6-12
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• 2004

Near-infrared spectra of methanol-water mixtures and acetonitrile-water mixtures were acquired to find interactions between solvents widely used for reverse-phase liquid chromatography. Mixtures were prepared to give a series of increasing mole fractions of methanol or acetonitrile in water. Data matrices of acquired spectra were analyzed to determine the proper number of principal components of each mixture system using Malinowski's factor indicator function. Initial guess of score matrix and loading matrix were calculated by nonlinear iterative partial least squares (NIPALS) algorithm for faster computation. Iterative target transform factor analysis (ITTFA) was applied to convert the initial estimation of score matrix to true concentration profile and loading matrix to pure spectra of pure components of the mixtures. In case of methanol-water the number of principal components was found to be 4 and those initial guess of factors were converted to the pure spectra of water methanol and two kinds of complexes. In case of acetonitrile-water the number of pure components of the mixtures was found to be 3 and the pure spectrum of acetonitrile-water complex was found. The nonlinear characteristics of concentration profiles of complexes in the solvent mixtures may give a good criteria in understanding their elution characteristics in reverse-phase liquid chromatogrsphy.

• Bulletin of the Korean Chemical Society
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• v.23 no.1
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• pp.65-70
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• 2002

We have evaluated the specific hydroxyl group-solvent and carbonyl group-solvent interactions by using an Alltima C18 stationary phase and by measuring the retention data of carefully selected solutes in 60/40, 70/30, and 80/20(v/v%) acetonitrile/water eluents at 25, 30, 35, 40, 45, and 50 oC. The selected solutes are phenol, acetophenone, alkylbenznes(benzene to hexylbenznene), 4 positional isomers of phenylbutanol, 5-phenyl-1-pentanol, 3 positional isomers of alkylarylketone derived from butylbenzene, and 1-phenyl-2-hexanone. The magnitudes of hydroxyl group-acetonitrile/water specific interaction enthalpies are larger than those of carbonyl group-acetonitrile/water specific interaction enthalpies in general while the magnitudes of carbonyl group-methanol/water specific interaction enthalpies are larger than those of hydroxyl group-methanol/water specific interactions. We observed clear discrepancies in functional group-solvent specific interaction among positional isomers. The variation trends of solute transfer enthalpies and entropies with mobile phase composition in the acetonitrile/water system are much different from those in the methanol/water system. The well-known pocket formation of acetonitrile in aqueous acetonitrile mixtures has proven to be useful to explain such phenomena.

• Journal of the Korean Chemical Society
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• v.18 no.1
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• pp.8-11
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• 1974

The solvolysis of p-substituted benzenesulfonyl chlorides $(substituents:p-H, p-Br, p-NO_2, p-OCH_3)$ in acetonitrile-water mixtures below 50 % of water content has been studied kinetically. Results show that Hammett plots give concaved curves but the mechanism is predominantly $S_N2$ and water acts both as nucleophile and general-base.

• Journal of the Korean Chemical Society
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• v.34 no.2
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• pp.123-129
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• 1990

The rate constants for the solvolysis of $trans-[Cr(en)_2Br_2]^+$ ion were determined by the spectrophotometric method in methanol-, ethanol-, acetone-, and acetonitrile-water mixtures, at 20, 25, 30, and 35$^{\circ}C$, respectively. The rate constants increased with increasing co-solvent compositions. The rate constant did not show any relation with the reciprocal of dielectric constant of the solvent-mixtures. The m values of Grunwald-Winstein equation for methanol-, ethanol-, acetonitrile-, and acetone-water mixtures are 0.109, 0.103, 0.101, and 0.095, respectively. A free energy cycle for the process from the initial state to the transition state in water and water + co-solvent mixtures shows that the change in solvation at the transition state has a dominant effect on the rate. From the above results, it is believed that the mechanism for the aquation of this complex is the Id mechanism.

• 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.27 no.2
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• pp.208-210
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• 2006

The enthalpies of transfer, $\Delta H_t^\theta$, of urea from water to aqueous ethanol, EtOH, propan-1-ol, PrOH, and acetonitrile, MeCN, are reported and analysed in terms of the new solvation theory. The analyses show that the solvation of urea is random in the considered solvent mixtures. It is also found that urea interact more strongly with EtOH or PrOH than water.

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2377-2381
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• 2007

Solvolyses of 3,4-dimethoxybenzenesulfonyl chloride (DSC) in water, D2O, CH3OD, and in aqueous binary mixtures of acetone, acetonitrile, 1,4-dioxane, ethanol, methanol, and 2,2,2-trifluoroethanol (TFE) have been investigated at 25.0 oC. Kinetic solvent isotope effects (KSIE) in water and in methanol and product selectivities in alcohol-water mixtures are also reported. The Grunwald-Winstein plot of first-order rate constants for the solvolyic reaction of DSC with YCl shows marked dispersions into separated lines for various aqueous mixtures. With use of the extended Grunwald-Winstein equation, the l and m values obtained are 1.12 and 0.58 respectively for the solvolyses of DSC. The relatively large magnitude of l is consistent with substantial nucleophilic solvent assistance. From Grunwald-Winstein plots the rate data are dissected approximately into contributions from two competing reaction channels. This interpretation is supported for alcohol-water mixtures by the trends of product selectivities, which show a maximum for ethanol-water mixtures. From the KSIE of 1.45 in methanol, it is proposed that the reaction channel favored in methanolwater mixtures and in all less polar media is general-base catalysed and/or is possibly (but less likely) an addition-elimination pathway. Also, the KISE value of 1.35 for DSC in water is expected for SN2-SN1 processes, with minimal general base catalysis, and this mechanism is proposed for solvolyses in the most polar media.

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2683-2688
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• 2012

The position of the thermodynamic equilibrium for reverse thermochromic spiropyran 6-carboxylates (SP-COOHs) was easily determined in aqueous binary mixtures, such as water-methanol, water-acetonitrile and water-dimethyl sulfoxide. The existence of more than one type of interconvertible species of the ring-opened form of SP-COOH in aqueous binary solvents enables us to evaluate the molar extinction coefficients of the ring-opened species of SP-COOH and to obtain the thermodynamic parameters.

• Bulletin of the Korean Chemical Society
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• v.3 no.3
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• pp.92-98
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• 1982

Solvolysis reactions of some substituted benzoyl chlorides were studied in ethanol-water, ethanol-trifluoroethanol and methanol-acetonitrile mixtures. Results showed that the reaction proceeds via an $S_N2$ process in which bond formation is more advanced than bond cleavage. Comparison of the two models for predicting transition state variation indicated superior nature of the quantum mechanical model relative to the potential energy surface model.