Water-acetonitrile mixtures

Venables D S and Schmuttenmaer C A 1998 Far-infrared spectra and associated dynamics in acetonitrile-water mixtures measured with femtosecond THz pulse spectroscopy J. Ohem. Rhys. 108 4935-44... 

Silica gel, per se, is not so frequently used in LC as the reversed phases or the bonded phases, because silica separates substances largely by polar interactions with the silanol groups on the silica surface. In contrast, the reversed and bonded phases separate material largely by interactions with the dispersive components of the solute. As the dispersive character of substances, in general, vary more subtly than does their polar character, the reversed and bonded phases are usually preferred. In addition, silica has a significant solubility in many solvents, particularly aqueous solvents and, thus, silica columns can be less stable than those packed with bonded phases. The analytical procedure can be a little more complex and costly with silica gel columns as, in general, a wider variety of more expensive solvents are required. Reversed and bonded phases utilize blended solvents such as hexane/ethanol, methanol/water or acetonitrile/water mixtures as the mobile phase and, consequently, are considerably more economical. Nevertheless, silica gel has certain areas of application for which it is particularly useful and is very effective for separating polarizable substances such as the polynuclear aromatic hydrocarbons and substances... 

Katz, Lochmuller and Scott also examined acetonitrile/water, and tetrahydrofuran (THF)/water mixtures in the same way and showed that there was significant association between the water and both solvents but not nearly to the same extent as methanol/water. At the point of maximum association for methanol, the solvent mixture contained nearly 60% of the methanol/water associate. In contrast the maximum amount of THF associate that was formed amounted to only about 17%, and for acetonitrile the maximum amount of associate that was formed was as little as 8%. It follows that acetonitrile/water mixtures would be expected to behave more nearly as binary mixtures than methanol/water or THF/water mixtures. 

Reverse-phase Squalane Zipax-HCP Cyanoethylsilicone Water and alcohol-water mixtures acetonitrile and acetonitrile-water mixtures... 

To retain solutes selectively by dispersive interactions, the stationary phase must contain no polar or ionic substances, but only hydrocarbon-type materials such as the reverse-bonded phases, now so popular in LC. Reiterating the previous argument, to ensure that dispersive selectivity dominates in the stationary phase, and dispersive interactions in the mobile phase are minimized, the mobile phase must now be strongly polar. Hence the use of methanol-water and acetonitrile-water mixtures as mobile phases in reverse-phase chromatography systems. An example of the separation of some antimicrobial agents on Partisil ODS 3, particle diameter 5p is shown in figure 5. 

The most popular bonded phases are, without doubt, the reverse phases which consist solely of aliphatic hydrocarbon chains bonded to the silica. Reverse phases interact dispersively with solvent and solute molecules and, as a consequence, are employed with very polar solvents or aqueous solvent mixtures such as methanol/water and acetonitrile/water mixtures. The most commonly used reverse phase appears to be the brush type phase with aliphatic chains having four, eight or eighteen carbon atom chains attached. These types of reverse phase have been termed C4, C8 and Cl8 phases respectively. The C8... 

The newcomer to chromatography, faced with a hitherto unknown sample, would do well to start with a C8 silica based reverse phase and an acetonitrile water mixture as a mobile phase and carry out a gradient elution from 100% water to 100% acetonitrile. From the results, the nature and the complexity of the sample can be evaluated and a more optimum phase system can be inferred. 

Sample unloading and product extraction by an acetonitrile-water mixture with its further NMR and chromatographic analysis. 

Ruthenium tetroxide can also be used in the oxidation of alkenes. Conditions that are selective for formation of ketols have been developed.36 Use of 1 mol % of RuC13 and five equivalents of KHS05 (Oxone ) in an ethyl acetate-acetonitrile-water mixture gives mainly hydroxymethyl ketones from terminal alkenes. 

Eberson and Olofsson, 4> observed exactly the same effect, and advanced the same rationale, in their study of the electrochemical oxidation of 5 in acetonitrile-water mixtures, to afford mixtures of pentamethylbenzyl alcohol (10) and the amide 9. 

Tetraazamacrocyclic complexes131 of cobalt and nickel were found110 to be effective in facilitating the reduction of C02 at -1.3 to -1.6 V versus SCE (Table 8). An acetonitrile-water mixture and water were used as solvents, while in dry dimethylsulfoxide no catalytic reduction of C02 took place. Using an Hg electrode, both CO and H2 were produced, where total current efficiencies were greater than 90%. The turnover numbers of the catalysts were 2-9 h 1. The catalytic activity lasted for more than 24 h and the turnover numbers of the catalysts exceeded 100. A protic source was required to produce both CO and H2, and the authors suggested that both products may arise from a common intermediate, which is most likely a metal hydride. The applied potential for C02 reduction was further reduced by using illuminated p- Si in the presence of the above catalysts.111... 

Tinnemans et al.132 have examined the photo(electro)chemical and electrochemical reduction of C02 using some tetraazamacrocyclic Co(II) and Ni(II) complexes as catalysts. CO and H2 were the products. Pearce and Pletcher133 have investigated the mechanism of the reduction of C02 in acetonitrile-water mixtures by using square planar complexes of nickel and cobalt with macrocyclic ligands in solution as catalysts. CO was the reduction product with no significant amounts of either formic or oxalic acids... 

Hufford et al. [13] determined the dissociation constants of primaquine by titration with 0.1 N hydrochloric acid in acetonitrile-water mixture and values were extrapolated to water by using linear regression analysis. 

Hufford et al [13] used a 13C NMR spectroscopic method for the assignments of dissociation constants of primaquine. The first and second dissociation constants of primaquine were determined by titration with 0.1 N hydrochloric acid in acetonitrile-water mixtures and values were extrapolated to water by using linear regression analysis. The assignments of the dissociation constants were unambiguously achieved by studying the 13C NMR spectral data obtained with monohydrochloride, dihydrochloride, and trihydrochloride salts. 

The products resulting from acid-catalysed solvolysis of A-acetoxy-A-butoxy-benzamides 26 in acetonitrile-water mixtures, as illustrated in Scheme 7, are... 

The van der Waals volume can be related to the hydrophobicity of the solutes, and retention of molecular compounds can be predicted from their van der Waals volumes, 7r-energy, and hydrogen-bonding energy effects [72-74], It should be noted that the isomeric effect of substituents cannot be predicted with good precision because this is not simply related to Hammett s a or Taft s other hand, the hydrophobicity is related to enthalpy [75], Retention times of non-ionizable compounds were measured in 70 and 80% acetonitrile/water mixtures on an octadecyl-bonded silica gel at 25-60°C and the enthalpy values obtained from these measurements. 

The polarity values of binary acetonitrile/water and methanol/water mobile phases used in RPLC were measured and compared with methylene selectivity (acH2) for both traditional siliceous bonded phases and for a polystyrene-divinylbenzene resin reversed-phase material [82], The variation in methylene selectivity for both was found to correlate best with percent organic solvent in methanol/water mixtures, whereas the polarity value provided the best correlation in acetonitrile/water mixtures. The polymeric resin column was found to provide higher methylene selectivity than the siliceous-bonded phase at all concentrations of organic solvent. 

The absorption spectrum of each resolved component of TIN in the methanol/DMSO mixtures can be calculated by virtue of the isosbestic point at 290 nm because at this wavelength the extinction coefficients of the two forms are equal (Figure 6). At 300 nm the extinction coefficient of the planar and non-planar forms is 1.5 x 104 M 1 cm 1 and 1.0 x 104 M 1 cm 1 respectively. These values are very similar to those calculated for TINS in acetonitrile/water mixtures (1.8 x 104 M 1 cm 1 and 1.0 x 104 M 1 cm 1 for the planar and non-planar forms respectively) (12). 

On this basis the cyclic voltammetric responses of the [tcnq]0/ process using superconducting electrodes have been studied in acetonitrile-water mixtures. Figure 15 shows the results obtained, at room temperature, at a YBa2Cu307 x electrode, also in comparison with the analogous responses obtained at a platinum electrode. 

From the theoretical viewpoint, acetonitrile is the most suitable solvent to study the correlation of retention times and log P values of analytes, since the dipole moment (2.44) is nearly equal to that of water (2.55) (Figure 4.4). The electron donor effect can therefore be eliminated, and the elution order is not changed on modification of the acetonitrile-water mixture ratio. The first choice of an eluent should therefore be an acetonitrile-water mixture for non-ionic compounds in reversed-phase liquid chromatography. Methanol, acetone, THF, or DMF can then be added to improve the resolution. 

A good correlation was obtained in 20-80% acetonitrile-water mixtures. The standard non-ionic compounds used to evaluate the columns were 2-hydroxy-acetophenone, coumarin, acetophenone, indole, propiophenone, butyro-phenone, isopropyl benzoate, butyl benzoate, and isopentyl benzoate. The plotted lines for the linear relationship measured in five different proportions... 

Solvent effects have been investigated in isatin (193) hydrolysis. Results from ethanol-water and acetonitrile-water mixtures revealed that for alkaline hydrolysis log k was correlated with the reciprocal of the dielectric constant. A tetrahedral intermediate (194) is involved, which breaks down to yield the ring-opened amino acid (195). A comparison has been made of the lability of isatin (193) towards diethyl-amine and hydroxide ion, the latter showing the greater effect. ... 

Choudhry, G.G. and Hutzinger, 0. Acetone-sensitized andnonsensitizedphotolysesoftetra-, penta-, and hexachlorobenzenes in acetonitrile-water mixtures photoisomerization and formation of several products including polychlorobiphenyls, Environ. Sci. Technol, 18(4) 235-241, 1984. 

Solvatochromism and piezochromism of a range of pentacyanoferrates(II) have been examined in binary aq ueous solvent mixtures, " and their solvatochromism in micelles and reversed micelles. The solvatochromism of [Fe(CN)5(nicotinamide)] has been established in several ranges of water-rich binary solvent mixtures, " of [Fe (CN)5(2,6-dimethylpyrazine)] in acetonitrile-water mixtures.The solvatochromism of [Fe(CN)5(4Phpy)] and [Fe(CN)5(4Bu py)] has been proposed as an indicator of selective solvation in binary aqueous solvent mixtures. ... 

Redox potentials of pentacyanoferrates are often determined in association with kinetic and stability constant determinations. They are also available for 4-methyl- and 4-amino-pyri-dine pentacyanoferrates, and for [Fe(CS )5(2,6-dimethylpyrazine)] in acetonitrile-water mixtures.Oxidation potentials of [Fe(CN)5L] complexes correlate with the electron-withdrawing or -releasing properties of the ligands... 

AU the products resulting from acid-catalysed solvolysis of A-acetoxy-A-butoxybenz-amides in acetonitrile-water mixtures were derived from the A-butoxy-A-hydroxybenz-amide intermediate (103), which is itself an anomeric amide and is the amide equivalent of a hemi-acetal . Decomposition reactions of 103 under acidic conditions are presented in Scheme 20. 

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