Preferential Solvation in Alkan-1-ol/Alkylbenzoate Binary Mixtures by Solvatochromic Probes

Navarro, Ana M.; Garcı́a, Begoña; Álvaro, Francisco Javier Hoyuelos; Peñacoba, Indalecio A.; Leal, José M.

doi:10.1021/jp202019x

Cited by 30 publications

(25 citation statements)

References 59 publications

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“…One of the most commonly used models for studying the solute‐solvent and solvent‐solvent interactions and describing the synergism behaviour in solvent mixtures is the preferential model which is based on a simple change of solvent molecules in microsphere solvation of solute according to the following equations: [15–19]

true normalI (normalS 1)_{2} + 2 S 2 \overset{⇀}{↽} normalI (normalS 2)_{2} + 2 S 1

true normalI (normalS 1)_{2} + S 2 \overset{⇀}{↽} normalI (normalS 12)_{2} + S 1

…”

Section: Resultsmentioning

confidence: 99%

²³Na‐NMR Data Based Donor Number and Their Correlation with Solvatochromic Parameters in Binary Solvent Mixtures

2021

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Donor numbers (DNs) of binary mixtures of acetonitrile with methanol, ethanol, ethylene glycol, 1-butanol, and tert-butanol were calculated in the whole range of mole fractions based on 23 Na-NMR chemical shift of sodium perchlorate dissolved in solvent. Data showed positive deviation from hypothetical linear ideal behavior. Solvatochromic parameters including empirical polarity, dipolar/polarizability, hydrogen bond donor, and hydrogen bond acceptor of the solvent mixtures were spectrophotometrically measured in order to investigate the correlations among parameters. The trend of data showed the preferential solvation along with synergistic behavior in some of mixtures. Applying preferential solvation model confirmed the solvent-solvent interactions in the studied binary mixtures. Although no reasonable correlation was observed between DN with solvatochromic parameters, dual-parameters regressions showed that some of solvatochromic parameters have linear relationships with DN. The presence of solvent-solvent interactions in the media caused that the solvent mixtures didn't follow the known correlations as reported before.

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true normalI (normalS 1)_{2} + 2 S 2 \overset{⇀}{↽} normalI (normalS 2)_{2} + 2 S 1

true normalI (normalS 1)_{2} + S 2 \overset{⇀}{↽} normalI (normalS 12)_{2} + S 1

…”

Section: Resultsmentioning

confidence: 99%

²³Na‐NMR Data Based Donor Number and Their Correlation with Solvatochromic Parameters in Binary Solvent Mixtures

2021

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“…Deviations from this linear relationship can arise for two reasons. Often, the polar component, present in small amounts, aggregates within the nonpolar bulk, leading to microheterogeneity (Scheme , case B) . Such local nonideality can be also be induced by the pulsed photoexcitation of a solvation probe, which switches on a solute dipole moment.…”

Section: Introductionmentioning

confidence: 99%

The Role of Hydrogen Bonding in the Preferential Solvation of 5-Aminoquinoline in Binary Solvent Mixtures

et al. 2021

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5-Aminoquinoline (5AQ) has been used as a fluorescent probe of preferential solvation (PS) in binary solvent mixtures in which the nonpolar component is diethyl ether and the polar component is protic (methanol) or aprotic (acetonitrile). Hence, the roles of solvent polarity and solute−solvent hydrogen bonding have been delineated. Positive deviations of spectral shifts from a linear dependence on the concentration of the polar component, signifying PS, are markedly more pronounced in case of the protic solvent. Solvation dynamics on a nanosecond time scale mark the formation of the solvation shell around the fluorescent probe. Time-resolved area-normalized emission spectra indicate the occurrence of the continuous solvation of the excited state when the polar component is acetonitrile. In contrast, two distinct states were observed when the polar component was methanol, the second state being the hydrogen bonded one. Translational diffusion is the rate-determining step for formation of the solvation shell. The time constant associated with it has been estimated from rise times observed in fluorescence transients monitored at the red end of the fluorescence spectra and also from the time evolution of the spectral width of time-resolved emission spectra.

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“…Therefore, this dye measures the solvent HBD acidity in addition to the nonspecific dye−solvent interactions. This betaine dye was used to define the E T (30) parameter and the normalized one (E T N ) to give a dimensionless value of 1 for water and 0 for tetramethylsilane, TMS. 4-Aminonitrobenzene (probe 2) is a hydrogen-bond donor molecule (HBD) and an electron pair-acceptor (EPA) as well.…”

Section: ■ Introductionmentioning

confidence: 99%

Polarity of Some [NR₁R₂R₃R₄]⁺[Tf₂N]⁻ Ionic Liquids in Ethanol: Preferential Solvation versus Solvent–Solvent Interactions

et al. 2012

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The polarity of the ionic liquids [N 4111 ][Tf 2 N], [N 4441 ][Tf 2 N], and [choline][Tf 2 N], as well as their binary mixtures with ethanol has been investigated using solvatochromic dyes and expressed in terms of the Reichardt parameter, E T N , and the Kamlet−Taft parameters (π*, α, and β), at 298.15 K. The synergetic behavior revealed essentially by the ethanol + [N 4441 ][Tf 2 N] system for the acidity of the solvent shows the potential importance of this solvent media for some chemical applications. Even though the preferential solvation model of Bosch and co-workers has been applied with some statistical success to the whole composition range of EtOH + [N 4111 ]-[Tf 2 N] and EtOH + [N 4441 ][Tf 2 N] binary mixtures, the interpretation of the results is somehow difficult due to the competition of molecular interactions in the evaluation of transition energies for the pairs: dye−solvent (dye−cation and/or dye−anion, dye− EtOH, dye−complex entity) and cation−anion, depending on the composition range. Different patterns of solvent polarity behavior are shown along the entire ionic liquid (IL) composition. ■ INTRODUCTIONAlthough molecular solvents have been the usual media for physical and chemical processes in solution, 1 in the past decade, room temperature ionic liquids (RTILs) have shown to be very useful because of their very particular properties, such as nonflammability, thermal stability, very low volatility at ambient conditions, and high solubility in organic and inorganic compounds with a wide range of polarity. These characteristics make ionic liquids (ILs) promising compounds for use in industry and with a recent emphasis in the pharmaceutical industry. 2−8 When compared with molecular solvents, ILs often present higher dipolarity/polarizability characteristics which make them valuable "effective polarity" solvents. 9−11 In this perspective it will be crucial to obtain information regarding the relative polarity of ILs and to study the change in physicochemical properties produced by their addition to molecular solvents. It has been already identified that, when an IL is mixed with an other solvent such as water or an alcohol, the polarity properties of the system can be tunable depending on the combination of the cation and anion and on the careful choice of the cosolvent. 12−17 The solvent polarity is defined as "its overall solvation capability" depending on the action of all possible, specific (hydrogen bonds, electron pair donor/electron pair acceptor), and nonspecific (van-der-Waals and Coulombic interactions) intermolecular solute−solvent forces. 1,18 The inadequate way of characterizing the solvent polarity, merely based on macroscopic physical parameters, gave rise to the appearance of solvatochromic parameters. These parameters are based on molecular probes, the spectroscopic properties of which are strongly solvent-dependent and serve as appropriate model processes for the study of other solvent effects. 19−24 The purpose of this work is to measure the polarity of the ILs, butyl-trim...

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Preferential Solvation in Alkan-1-ol/Alkylbenzoate Binary Mixtures by Solvatochromic Probes

Cited by 30 publications

References 59 publications

²³Na‐NMR Data Based Donor Number and Their Correlation with Solvatochromic Parameters in Binary Solvent Mixtures

²³Na‐NMR Data Based Donor Number and Their Correlation with Solvatochromic Parameters in Binary Solvent Mixtures

The Role of Hydrogen Bonding in the Preferential Solvation of 5-Aminoquinoline in Binary Solvent Mixtures

Polarity of Some [NR₁R₂R₃R₄]⁺[Tf₂N]⁻ Ionic Liquids in Ethanol: Preferential Solvation versus Solvent–Solvent Interactions

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Preferential Solvation in Alkan-1-ol/Alkylbenzoate Binary Mixtures by Solvatochromic Probes

Cited by 30 publications

References 59 publications

23Na‐NMR Data Based Donor Number and Their Correlation with Solvatochromic Parameters in Binary Solvent Mixtures

23Na‐NMR Data Based Donor Number and Their Correlation with Solvatochromic Parameters in Binary Solvent Mixtures

The Role of Hydrogen Bonding in the Preferential Solvation of 5-Aminoquinoline in Binary Solvent Mixtures

Polarity of Some [NR1R2R3R4]+[Tf2N]− Ionic Liquids in Ethanol: Preferential Solvation versus Solvent–Solvent Interactions

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²³Na‐NMR Data Based Donor Number and Their Correlation with Solvatochromic Parameters in Binary Solvent Mixtures

²³Na‐NMR Data Based Donor Number and Their Correlation with Solvatochromic Parameters in Binary Solvent Mixtures

Polarity of Some [NR₁R₂R₃R₄]⁺[Tf₂N]⁻ Ionic Liquids in Ethanol: Preferential Solvation versus Solvent–Solvent Interactions