Binary mixtures of dimethyl sulfoxide with methanol, ethylene glycol, and glycerol as solvent: Solvatochromism and chemical kinetics study

Harifi‐Mood, Ali Reza; Khorshahi, Hasan

doi:10.1016/j.molliq.2018.03.039

Cited by 12 publications

(7 citation statements)

References 26 publications

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“…The solvatochromic parameters of pure ACN, Met, Et, EG, But, t‐But, and Their binary mixtures with ACN ( α , β, π *,

E_{T}^{N}

) over the entire composition range have been determined based on the procedure reported elsewhere according to Equations 2–6: [15]

true E_{T} ((), 30) / normalk normalc normala normall . {normalm normalo normall}^{- 1} = 2.8592 ϑ_{normalR normalD}

true E_{T}^{N} = \frac{E_{T} ((), s, o, l, v, e, n, t) - E_{T} ((), T, M, S)}{E_{T} ((), w, a, t, e, r) - E_{T} ((), T, M, S)}

true π^{^{*}} = 0.427 (() 34.12 - ϑ_{A N S})

true β = \frac{31.10 - 3.14 π^{^{*}} - ϑ_{normalA normalN normalI}}{2.79}

true α = - 0.186 (() 10.91 - ϑ_{R D}) - 0.72 π^{^{*}}

…”

Section: Resultsmentioning

confidence: 99%

“…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%

“…The solvatochromic parameters of pure ACN, Met, Et, EG, But, t-But, and Their binary mixtures with ACN (α, β, π*, E N T ) over the entire composition range have been determined based on the procedure reported elsewhere according to Equations 2-6: [15] E T 30 ð Þ=kcal:…”

Section: Reichardt and Kamlet-taft Parameters In The Binary Mixtures mentioning

confidence: 99%

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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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“…The solvatochromic parameters of pure ACN, Met, Et, EG, But, t‐But, and Their binary mixtures with ACN ( α , β, π *,

E_{T}^{N}

) over the entire composition range have been determined based on the procedure reported elsewhere according to Equations 2–6: [15]

true E_{T} ((), 30) / normalk normalc normala normall . {normalm normalo normall}^{- 1} = 2.8592 ϑ_{normalR normalD}

true E_{T}^{N} = \frac{E_{T} ((), s, o, l, v, e, n, t) - E_{T} ((), T, M, S)}{E_{T} ((), w, a, t, e, r) - E_{T} ((), T, M, S)}

true π^{^{*}} = 0.427 (() 34.12 - ϑ_{A N S})

true β = \frac{31.10 - 3.14 π^{^{*}} - ϑ_{normalA normalN normalI}}{2.79}

true α = - 0.186 (() 10.91 - ϑ_{R D}) - 0.72 π^{^{*}}

…”

Section: Resultsmentioning

confidence: 99%

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%

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

2021

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“…Preferential solvation (PS) theory as proposed by Rosés et al , is commonly applied with UV–vis spectroscopy that uses Kamlet–Taft (KT) solvatochromic indicators to estimate local compositions and polarity of the solutions. The PS theory has been applied to binary aqueous systems, , nonaqueous systems, − and ionic liquid–molecular solvent systems. , The PS theory is based on a solvent-exchange mechanism that occurs in the cybotactic region of a solvatochromic dye such that it allows one to estimate the local composition of (1–2) complex molecules formed between a molecule of solvent type 1 and a molecule of solvent type 2 due to specific mutual interactions that change in bulk concentration. − , In this work, local compositions determined by UV–vis spectroscopy with solvatochromic indicators (dyes) are denoted.…”

Section: Introductionmentioning

confidence: 99%

Correspondence between Spectral-Derived and Viscosity-Derived Local Composition in Binary Liquid Mixtures Having Specific Interactions with Preferential Solvation Theory

et al. 2018

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Local interactions between unlike molecules (1–2) in solution are commonly measured with spectroscopy and used to estimate local composition. Herein, a viscosity model based on preferential solvation (PS) theory is developed for aqueous and nonaqueous binary liquid mixtures containing a dipolar aprotic solvent that provides local composition considering the hydration or solvation shell around complex (1–2) molecules. Spectral-derived and viscosity-derived local composition distributions showed similar trends with bulk composition, and their correspondence is attributed to characteristics of the hydration or solvation shell. Viscosity-derived local compositions were consistent with literature molecular simulations, whereas spectral-derived local composition distributions contained artifacts. The PS viscosity model is also applicable to nonpolar–polar mixtures for which self-association occurs, and it can be used to estimate solvent mixture dipolarity/polarizability. Since the PS viscosity model only requires bulk viscosity, it may provide a means to estimate microviscosity or the solvent environment around biomolecules.

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“…However, the solute-solvent interactions have been widely investigated by using the physical property Y as a solvatochromic parameter, 27,[31][32][33] the use of this model as a nonlinear relationship between activation free energy of chemical reactions and solvent composition (non-LFER) has demonstrated interesting results. 20,33,34 Equation 6 was applied for log k A , and the results are summarized in Table 4. Statistical parameters and good agreement shown in Figure 3 confirm the ability of Equation 6 in reproducing the reaction rate coefficients.…”

Section: Preferential Solvationmentioning

confidence: 99%

Deep eutectic solvent as an operative media on structure‐reactivity relationships

Harifi‐Mood

Khorshahi

2019

Int J of Chemical Kinetics

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Deep eutectic solvents seem to be environmentally friendly solvents, particularly because they are prepared easily and have very low‐vapor pressures under ambient conditions. They are suitable candidates as green solvents for reaction media with special properties. To present this behavior, substitution reactions of some para‐ and meta‐substituted anilines with 1‐fluoro‐2,4‐dinitrobenzene have been spectrophotometrically investigated in varying mole fractions of ethaline as a deep eutectic solvent in dimethyl sulfoxide (DMSO). The measured rate coefficients of the reaction demonstrated a noticeable variation with the increasing mole fraction of ethaline in ethaline‐DMSO mixtures. The linear free energy relationship (LFER) of second‐order rate coefficients based on Hammett's substituent constants demonstrates a reasonably linear straight line with a negative slope in different mole fractions of ethaline‐DMSO mixtures. Another LFER investigation based on the polarity parameters of the media showed a good agreement with hydrogen bond donor and acceptor abilities of the solvent. Non‐LFER assay according to the preferential solvation model confirmed differences between the microsphere solvation of the solute molecules and the bulk composition of the solvents.

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Binary mixtures of dimethyl sulfoxide with methanol, ethylene glycol, and glycerol as solvent: Solvatochromism and chemical kinetics study

Cited by 12 publications

References 26 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

Correspondence between Spectral-Derived and Viscosity-Derived Local Composition in Binary Liquid Mixtures Having Specific Interactions with Preferential Solvation Theory

Deep eutectic solvent as an operative media on structure‐reactivity relationships

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Binary mixtures of dimethyl sulfoxide with methanol, ethylene glycol, and glycerol as solvent: Solvatochromism and chemical kinetics study

Cited by 12 publications

References 26 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

Correspondence between Spectral-Derived and Viscosity-Derived Local Composition in Binary Liquid Mixtures Having Specific Interactions with Preferential Solvation Theory

Deep eutectic solvent as an operative media on structure‐reactivity relationships

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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