Molecular-Microscopic Properties and Preferential Solvation in Protic Ionic Liquid Mixtures

Structural and molecular-microscopic properties of the solvatochromic probes 4-nitroaniline, 4-nitroanisole, and Reichardt’s dye were investigated in binary mixtures of ethylammonium propionate with methanol, ethanol, 1-propanol and 2-propanol. Solvatochromic parameters (α, hydrogen-bond donor acidity; β, hydrogen-bond acceptor basicity; π*, dipolarity/polarizability; $ E_{\text{T}}^{\text{N}} $ , normalized polarity parameter) in different binary mixtures of ionic liquid with molecular solvents were determined with UV–Vis spectroscopy. The $ E_{\text{T}}^{\text{N}} $ parameters show nearly ideal trends in all solvent mixtures, but the other parameters show different behavior in the mixtures. The π* parameters show a negative deviation from ideality in the ionic liquid/methanol system. In contrast, the α parameters have severe positive deviations from ideal behavior in ionic liquid/1-propanol and ionic liquid/2-propanol solvent mixtures. A synergistic solvation effect is observed for the π* parameters in IL/methanol mixtures. Specific solute–solvent interactions or solvent–solvent interactions, which cause non-ideal trends in some parameters, are justified and interpreted by the preferential solvation model.     

Solvatochromic parameters for binary mixtures of an ionic liquid with various protic molecular solvents

Abstract  Solvatochromic parameters (E _T ^N, normalized polarity parameter; π*, dipolarity/polarizability; β, hydrogen-bond acceptor basicity; α, hydrogen-bond donor acidity) have been determined for binary mixtures of propan-2-ol, propan-1-ol, ethanol, methanol and water with recently synthesized ionic liquid (IL; 2-hydroxyethylammonium formate) at 25 °C. In all solutions except aqueous solution, E _T ^N values of the media increase abruptly with the ILs mole fraction and then increase gradually to the value of pure IL. A synergistic behavior is observed for the α parameter in all solutions. The behavior of π* and β are nearly ideal for all solutions except for solutions of methanol with the IL. The applicability of nearly ideal combined binary solvent/Redlich–Kister equation was proved for the correlation of various solvatochromic parameters with solvent composition. The correlation between the calculated and the experimental values of various parameters was in accordance with this model. Solute–solvent and solvent–solvent interactions were applied to interpret the results. Graphical Abstract  Predicted values of solvatochromic parameters (SP) (E _T ^N, normalized polarity parameter; π*, dipolarity/polarizability; β, hydrogen-bond acceptor basicity; α, hydrogen-bond donor acidity) from the correlation equations versus its experimental values for binary mixtures of 2-hydroxyethylammonium formate with water, methanol, ethanol, propan-1-ol and propan-2-ol.      

Solvatochromic Probes Absorbance Behavior in Mixtures of 2-Hydroxy Ethylammonium Formate with Methanol,Ethylene Glycol and Glycerol

Solute-solvent and solvent-solvent interactions were investigated for binary mixtures of an ionic liquid (IL) 2-hydroxy ethylammonium formate as with methanol, ethylene glycol and glycerol. The physicochemical properties of the solvent mixtures at 25 °C, over the whole range of mole fractions, were determined using solvatochromic probes. High normal polarity (E_T^NE_{T}^{N}) in the alcohol-rich region confirms solute-solvent interactions in this medium. Dipolarity/polarizability (π ^∗) show a different trend to E_T^NE_{T}^{N} with a positive deviation from ideal behavior in IL-glycerol mixtures. However, these deviations for other solvent mixtures are insignificant. Contrary to what is observed for E_T^NE_{T}^{N} and π ^∗, hydrogen-bond donor (HBD) acidity and hydrogen-bond acceptor (HBA) basicity demonstrate similar trends. The applicability of the combined nearly-ideal binary solvent/Redlich-Kister (CNIBS/R-K) equation for the correlation of various parameters provides a simple computational model to correlate and/or predict various solvatochromic parameters for many binary solvent systems.     

Solvatochromic parameters for binary mixtures of an ionic liquid with various protic molecular solvents

Abstract  

Solvatochromic parameters (E _T ^N, normalized polarity parameter; π*, dipolarity/polarizability; β, hydrogen-bond acceptor basicity; α, hydrogen-bond donor acidity) have been determined for binary mixtures of propan-2-ol, propan-1-ol, ethanol, methanol and water with recently synthesized ionic liquid (IL; 2-hydroxyethylammonium formate) at 25 °C. In all solutions except aqueous solution, E _T ^N values of the media increase abruptly with the ILs mole fraction and then increase gradually to the value of pure IL. A synergistic behavior is observed for the α parameter in all solutions. The behavior of π* and β are nearly ideal for all solutions except for solutions of methanol with the IL. The applicability of nearly ideal combined binary solvent/Redlich–Kister equation was proved for the correlation of various solvatochromic parameters with solvent composition. The correlation between the calculated and the experimental values of various parameters was in accordance with this model. Solute–solvent and solvent–solvent interactions were applied to interpret the results.     

Solvatochromism in Binary Solvent Mixtures by Means of a Penta‐tert‐butyl Pyridinium N‐Phenolate Betaine Dye

The solvatochromic behavior of a penta‐tert‐butyl prydinium N‐phenolate betaine dye was studied using UV‐visible spectrophotometry in several binary mixture solvents. The solvent polarity parameter, E_T (1) (kcal. mol^?1) was calculated from the position of the longest‐wavelength intramolecular charge transfer absorption band of this penta‐tert‐butyl betaine dye. For binary solvent mixtures, all plots of E_T (1) versus the mole fraction of a more polar component are nonlinear owing to preferential solvation of the probe by one component of the binary solvent mixture. In the computation of E_T (1) it was assumed that the two solvents mixed interact to form a common structure with an E_T (1) value not always intermediate between those of the two solvents mixed. The results obtained are explained by the strong synergism observed for some of the binary mixtures with strong hydrogen bond donors (HBD) solvents such as alcohols.     

Variation of some microscopic properties with composition in 2-methoxyethanol and 1,2-ethanediol mixtures

Selected microscopic properties, namely E_T(30) polarity, Kamlet-Taft solvatochromic parameters and dissociation constant of picric acid, have been correlated with solvent composition in 2-methoxyethanol/1,2-ethanediol mixtures. Theoretical and semi-empirical equations which embody preferential solvation of the solute and show standard deviations lower than 0.01 for solvatochromic parameters and 0.03 for pK values have been proposed.     

Study of molecular interaction in binary liquid mixtures of ethyl acetoacetate with chloroform and dimethylsulphoxide using excess acoustic parameters and spectroscopic methods

Densities and ultrasonic velocities were measured for binary liquid mixtures of ethyl acetoacetate (EAA) with chloroform (CHCl₃) and dimethylsulphoxide (DMSO) over the entire composition range. These experimental values were used to calculate the adiabatic compressibility (βs), intermolecular free length (L_f), excess molar volume (V^E), excess adiabatic compressibility (β_s^E) and excess intermolecular free length (L_f^E) for the liquid mixtures under consideration. In all the excess parameters, a positive deviation was observed in CHCl₃–EAA binary mixture, whereas a slight negative deviation was found for EAA–DMSO binary liquid mixture. These deviations were explained in terms of molecular interactions between like and unlike molecules and further affirmed by UV–Vis spectroscopic measurements in terms of polar and non-polar environment in the close proximity of solvatochromic dye. Fourier transform infrared spectroscopy (FT-IR) and proton-nuclear magnetic resonance (H¹ NMR) measurements have also been done to explain the molecular interaction in the binary liquid mixtures.     

Study of Solvent Effects on the Protonation of Functional Group of Disubstituted Anilines: Factor Analysis Applied to the Correlation between Protonation Constants and Solvatochromic Parameters in Ethanol–Water Mixtures

Summary. The stoichiometric protonation constants (log β) of some disubstituted aniline derivatives in ethanol–water mixtures (0–90% ethanol by volume) at 25.0 ± 0.1°C were firstly submitted to factor analysis in order to obtain the number factors which affect the variation of the whole data sets and, afterwards, submitted to target factor analysis to identify these factors. The influence of solvatochromic parameters in the interactions between aniline derivatives and the solvent studied was identified and quantified. The general equation of Kamlet and Taft was reduced for these mixtures to two terms using combined factor analysis (FA) and target factor analysis (TFA): the independent term and the hydrogen-bond donating ability, α (HBD), solvatochromic parameters. Further, the quasi-lattice quasi-chemical (QLQC) theory of preferential solvation has been applied to quantify the preferential solvation by water of electrolytes in ethanol–water mixtures. The effects of the substituents on the protonation constants, the additivities of these effects, and the applicability of the Hammett equation to the behavior of substituents are also discussed. Further, Hammett’s reaction constant for the protonation of disubstituted anilines has been obtained for all the solvent mixtures and correlates well with α (HBD) of the solvent.     

Study of Solvent Effects on the Protonation of Functional Group of Disubstituted Anilines: Factor Analysis Applied to the Correlation between Protonation Constants and Solvatochromic Parameters in Ethanol–Water Mixtures

The stoichiometric protonation constants (log β) of some disubstituted aniline derivatives in ethanol–water mixtures (0–90% ethanol by volume) at 25.0 ± 0.1°C were firstly submitted to factor analysis in order to obtain the number factors which affect the variation of the whole data sets and, afterwards, submitted to target factor analysis to identify these factors. The influence of solvatochromic parameters in the interactions between aniline derivatives and the solvent studied was identified and quantified. The general equation of Kamlet and Taft was reduced for these mixtures to two terms using combined factor analysis (FA) and target factor analysis (TFA): the independent term and the hydrogen-bond donating ability, α (HBD), solvatochromic parameters. Further, the quasi-lattice quasi-chemical (QLQC) theory of preferential solvation has been applied to quantify the preferential solvation by water of electrolytes in ethanol–water mixtures. The effects of the substituents on the protonation constants, the additivities of these effects, and the applicability of the Hammett equation to the behavior of substituents are also discussed. Further, Hammett’s reaction constant for the protonation of disubstituted anilines has been obtained for all the solvent mixtures and correlates well with α (HBD) of the solvent.     

Solvent effects on the rate of reaction of Cl2˙− and SO4˙− radicals with unsaturated alcohols

Rate constants have been measured in several aqueous/organic solvent mixtures for the addition reaction of Cl₂^˙? radicals with 2-propen-1-o1 and 2-buten-1-o1 as a function of temperature and with 2, 3-dimethyl-2-butene at room temperature. The rate constants were in the range of 10⁶–10⁹ L mol^?1 s^?1, the activation energies were relatively low (1–10 kJ mol^?1), and the pre-exponential factors varied over the range log A = 7.9 to 9.4. The rate constants (k) decreased (by up to a factor of 30) upon increasing the fraction of organic solvent and log k correlated linearly with the dielectric constant for a given water/organic solvent system, but the lines for the different solvent systems had different slopes. A better correlation of log k was found with a combination of the solvatochromic factor, E_T(30), and the hydrogen-bond donor acidity factor, α. This suggests that the rate of reaction is influenced by the solvent polarity and also by specific solvation of the ionic reactant and product. Solvent effect on the reaction of SO₄^˙? with 2-propen-1-o1 was studied for comparison. © 1993 John Wiley & Sons, Inc.     

Solvent effects and correlation with Reichardt'sE T values on charge transfer spectra of bis(2,2′-bipyridyl)biscyanoiron(II)

The solvatochromic behaviour of biscyano-bis(2,2′-bipyridyl)iron(II) in a variety of solvents is described. The frequencies are correlated with Reichardt's solvent parameterE _T . Various trends are indicated, solvatochromic shifts of the title complex in various aqueous mixtures ofDMF and 2-butoxy ethanol are also reported.     

Solvatochromism and piezochromism of pentacyanoferrate(II) complexes in binary aqueous solvent media

Summary The solvatochromic behaviour of a number of pentacyano-ferrates (II), [Fe^II(CN)₅L] ^n-, is described, for solutions in H₂O-alcohol, -Me₂CO and -DMSO mixtures. The strong dependence of solvent sensitivity on the nature of the ligand L is particularly fully documented for H₂OMeOH mixtures (0–100% MeOH). The piezochromic behaviour of seven pentacyanoferrates(II) has been established, in aqueous solution. The connection between piezochromism and solvatochromism is detailed, and the solvatochromic results discussed in terms of (preferential) solvation.     

The Solvent-Like Nature of Silica Particles in Organic Solvents

Summary.   Kamlet-Taft’s α (hydrogen bond donor acidity) and π^* (dipolarity/polarizability) values of various silica batches measured in various solvents are presented. The α and π^* parameters for the various solid acids are analyzed by means of Fe(phen)₂(CN)₂ (cis-dicyano-bis-(1,10)-phenanthroline-iron(II), 1), Michler’s ketone (4,4′-bis-(dimethylamino)-benzophenone, 2), and two hydrophilic derivatives of 2, (4-(dimethylamino)-4′-(di-2-hydroxyethyl)-amino-benzophenone (3a) and 4,4′-bis-(di-(2-hydroxyethyl)-amino)-benzophenone (3b) as well as coumarin 153 (4) as solvatochromic surface polarity indicators. Apparent β (hydrogen bond acceptor basicity) parameters for bare silica have been evaluated by means of an aminobenzodifuranone dye (5) as solvatochromic probe. The chemical interpretation of the α and π^* parameters and the nature of the solvent/surface interaction which they reflect are discussed. It can be shown that an increase of the HBA (hydrogen bond accepting) capacity of the solvent significantly decreases the HBD (hydrogen bond donating) capacity of the surface environment, whereas the dipolarity/polarizability value of the silica/solvent interface is a composite of many effects. The classification of the polarity of silica particles in organic solvents compared to pure liquids is outlined. Theoretical E _T(30) values of the solid/solvent interfaces are calculated by applying linear solvation energy (LSE) relationships using the independently measured α and π^* values of the solid acids according to Received February 2, 2001. Accepted (revised) March 3, 2001     

A Correlation Between Solvatochromic Solvent Polarity Parameters and the Ionization Constants of Various Phenols in 1,4-Dioxane–Water Mixtures

Precise thermodynamic ionization constants K for 3-nitrophenol, 3,4-dichlorophenol, and 4-cyanophenol have been obtained in 1,4-dioxane-water mixtures (0–70% volume fraction in dioxane) at 25°C using a potentiometric method. The same information for another twelve cationic, neutral, and anionic phenols were taken from the literature. Three different methods were used to study the effects of the solvents on the ionization constants: one involves a single polarity parameter, E _T(30); the next involves the Kamlet–Taft multiparametric method; and the last involves the preferential solvation model. The pK values follow the preferential solvation model, but the parameters obtained are highly correlated. Using the data for the phenol molecule as reference, a linear correlation between ΔpK and E _T(30) has been used to develop a new method of obtaining pK values for any binary solvent composition, with only the pK in water known. The pK(s) values correlate with the molecular parameters for the dipolarity/polarizability of the solvent π* and its hydrogen-bond donor ability α. The preferential solvation parameter, f _12/1, correlates with the parameter for the hydrogen-bond donor ability of the solvent. All the phenols follow Hammett's equation and the reaction constants have been calculated for the different water–dioxane mixtures.     

Determination of the Dissociation Constants of Some Macrolide Antibiotics in Methanol–Water Binary Mixtures by UV-Spectroscopy and Correlations with the Kamlet and Taft Solvatochromic Parameters

The dissociation constants of six common human and veterinary antibiotics, namely, erythromycin, roxithromycin, tilmicosin, oleandomycin, josamycin, and spiramycin in 15?%, 25?%, 40?% and 50?% (v/v) methanol?Cwater solvent mixtures were determined by UV/pH titration and correlated with the Kamlet and Taft solvatochromic parameters, ?? ^?, ?? and ??. Kamlet and Taft??s general equation was reduced to two terms by combined factor analysis and target factor analysis in these mixtures: the independent term and polarity/polarizability ?? ^?, which are solvatochromic parameters. The influence of methanol on the dissociation constants was investigated. Further, the quasi-lattice quasi-chemical (QLQC) model of preferential solvation has been applied to quantify the preferential solvation by water of electrolytes in methanol?Cwater mixtures.     

Structure-retention and mobile phase-retention relationships for reversed-phase high-performance liquid chromatography of several hydroxythioxanthone derivatives in binary acetonitrile-water mixtures

The reversed-phase high-performance liquid chromatographic (RP-HPLC) behavior of some newly synthesized hydroxythioxanthone derivatives using binary acetonitrile-water mixtures as mobile phase has been examined. First, the variation in the retention time of each molecule as a function of mobile phase properties was studied by Kamlet-Taft solvatochromic equations. Then, the influences of molecular structure of the hydroxythioxanthone derivatives on their retention time in various mobile phase mixtures were investigated by quantitative structure-property relationship (QSPR) analysis. Finally, a unified model containing both the molecular structure parameters and mobile phase properties was developed to describe the chromatographic behavior of the systems studied. Among the solvent properties, polarity/polarizability parameter (π^*) and hydrogen-bond basicity (β), and among the solute properties, the most positive local charge (MPC), the sum of positive charges on hydrogen atoms contributing in hydrogen bonding (SPCH) and lipophilicity index (log P) were identified as controlling factors in the RP-HPLC behavior of hydroxythioxanthone derivatives in actonitrile-water binary solvents.     

Thermodynamics of liquid mixtures containing a very strongly polar compound: Part 6. DISQUAC characterization of N,N-dialkylamides

Systems of N,N di(n-alkylamides) (hereafter, N,N-dialkylamides) with alkane, benzene, toluene, 1-alkanol or 1-alkyne have been investigated in the framework of the DISQUAC model. The corresponding interaction parameters are reported. They change regularly with the molecular structure of the mixture components. This variation is similar to those encountered when treating other systems in terms of DISQUAC. The model describes consistently a whole set of thermodynamic properties: liquid–liquid equilibria (LLE), vapor–liquid equilibria (VLE), solid–liquid equilibria (SLE), molar excess Gibbs energies (G^E), molar excess enthalpies (H^E), molar excess heat capacities at constant pressure (C_P^E), partial molar excess properties at infinite dilution, enthalpies and heat capacities. The model also provides good results for the Kirkwood–Buff integrals and for the linear coefficients of preferential solvation. For ternary systems, DISQUAC predictions on VLE and H^E, obtained using binary parameters only, are in good agreement with the experimental data. A short comparison between DISQUAC and Dortmund UNIFAC results is shown. DISQUAC improves UNIFAC results on H^E and C_P^E, magnitudes which strongly depend on the molecular structure. The investigated mixtures behave similarly to those characterized by thermodynamic properties which arise from dipolar interactions. Association/solvation effects do not play, as a whole, an important role in the studied systems. This may explain that the ERAS model fails when representing the thermodynamic properties of dimethylformamide + 1-alkanol mixtures.     

Preferential solvation of Fe(phen)2(CN)2 in binary aqueous acetone and 2-methoxyethanol mixtures

Summary Preferential solvation ofbis-1,10-phenanthroline-bis-cyanoiron(II) was investigated in aqueous acetone and 2-methoxyethanol binary mixtures. The solvatochromic behaviour is discussed in terms of donor and acceptor numbers. The thermodynamic model ofFrankel was used to treat preferential solvation in the binary aqueous 2-methoxyethanol mixtures and reveals that preferential solvation by the organic solvent occurs. The preferential solvation constant at 298.15K was found to be equal to 3.30±0.039, and the free energy of preferential solvation amounts to 2.96kJ·mole^–1.

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Bevorzugte Solvatation von Fe(phen)₂(CN)₂ in binären Mischungen aus Wasser und Aceton bzw. 2-Methoxyethanol

Zusammenfassung Die bevorzugte Solvatation vonbis-1,10-Phenanthrolin-bis-cyanoeisen(II) wurde in binären wäßrigen Mischungen mit Aceton bzw. 2-Methoxyethanol als organischer Komponente untersucht. Das solvatochrome Verhalten wird in Zusammenhang mit Donor- und Akzeptorzahlen diskutiert. Die theoretische Behandlung erfolgte mit Hilfe des thermodynamischen Modells vonFrankel und zeigt, daß das organische Lösungsmittel bevorzugt solvatisiert. Die entsprechende Konstante bei 298.15K wurde zu 3.30±0.039 ermmittelt. Die freie Energie der bevorzugten Solvatation beträgt 2.96kJ·mol^–1.

     

Solvent effects on kinetics of an aromatic nucleophilic substitution reaction in mixtures of an ionic liquid with molecular solvents and prediction using artificial neural networks

Kinetics of the reaction between 1‐chloro‐2,4‐dinitrobenzene and aniline was studied in mixtures of 1‐ethyl‐3‐methylimidazolium ethylsulfate ([EMIM][EtSO₄]) with methanol, chloroform, and dimethylsulfoxide at 25°C. Single‐parameter correlations of log k_A versus normalized polarity parameter (E^N_T), hydrogen‐bond acceptor basicity (β), hydrogen‐bond donor acidity (α), and dipolarity/polarizability (π*) of media do not give acceptable results. Multiparameter linear regression (MLR) of log k_A versus the solvatochromic parameters demonstrates that the reaction rate constant increases with E^N_T, π*, and β and decreases with α parameter. To predict accurately solvent effects on the rate constant, optimized artificial neural network with three inputs (including α, π*, and β parameters) was applied for prediction of the log k_A values in the prediction set. It was found that properly selected and trained neural network could fairly represent the dependence of the reaction rate constant on solvatochromic parameters. Mean percent deviation of 5.023 for the prediction set by the MLR model should be compared with the value of 0.343 by the artificial neural network model. These improvements are due to the fact that the reaction rate constant shows nonlinear correlations with the solvatochromic parameters. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 153–159, 2009