Enthalpies of mixing of tetrahydrofuran + .gamma.-butyrolactone and water + .gamma.-butyrolactone systems at 299.15 K

Ramkumar, D. H. S.; Kudchadker, Arvind P.; Deshpande, D. D.

doi:10.1021/je00042a037

Cited by 11 publications

(16 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Additional papers reported excess enthalpy or excess volume data for the (GBL + water) system; they however dealt with concentrated mixtures rather than dilute solutions. Meaningful, but qualitative only comparisons can be done with H E measurements of Ramkumar et al and V E measurements of Abdullah et al which include data points below x 1 < 0.05. Graphically, these comparisons are presented in Figures S3 and S4.…”

Section: Resultsmentioning

confidence: 99%

Thermal and Volumetric Properties of Five Lactones at Infinite Dilution in Water

2019

View full text Add to dashboard Cite

Mixing enthalpies and densities of highly dilute aqueous solutions of five lactones (namely γ-butyrolactone (GBL), γ-valerolactone (GVL), αangelica lactone (AAL), γ-hexalactone (GHL), and δ-hexalactone (DHL)) were measured as a function of solution composition at several temperatures in the range from (288.15 to 318.15) K using a tandem flow arrangement of isothermal mixing microcalorimeter and vibrating-tube densimeter. The densities of the neat lactones were measured, also. The dissolution of the lactones in water was found to be exothermic (except for AAL at higher temperatures) and accompanied by volume contraction. On the basis of these systematic measurements, reliable values of partial molar excess enthalpy, partial molar volume, and partial molar excess volume of the studied solutes at infinite dilution in water were determined. Precision of our measurements allowed us to evaluate with a good accuracy also respective temperature derivative properties, that is, infinite dilution partial molar excess heat capacity, expansion, and excess expansion. The observed thermodynamic behavior was shown to be governed by hydrogen bonding of water molecules to the oxygen atoms of the lactone group. Several structural effects like those of the alkylation of lactone ring, its enlargement, the introduction of the double bond, and the lactone molecular volume on the determined properties were identified and rationalized on the molecular level.

show abstract

Section: Resultsmentioning

confidence: 99%

Thermal and Volumetric Properties of Five Lactones at Infinite Dilution in Water

2019

View full text Add to dashboard Cite

show abstract

“…To explore the effect of changing electrolytic conditions on the electrochemical properties of Xerogel-V 2 O 5 , we consider three different regimes (separated by dashed lines in Figure ): (i) “wet” or aqueous electrolyte, where the water activity, a H 2 O , is set to ∼1, (ii) “dry” with 10 –2 < a H 2 O < 10 –6 , and (iii) “superdry” with a H 2 O < 10 –7 . An activity a H 2 O = 10 –4 would correspond to ∼10 ppm by weight of water under the ideal solution approximation in solvents such as glymes. , Each colored region in Figure corresponds to a single stable phase, whose composition is indicated with a Mg x (H 2 O) n V 2 O 5 notation. While the lines separating the single phase regions indicate the coexistence of two phases, the triple points correspond to a three-phase coexistence.…”

Section: Methodsmentioning

confidence: 99%

“…An activity a H 2 O = 10 −4 would correspond to ∼10 ppm by weight of water under the ideal solution approximation in solvents such as glymes. 61,62 Each colored region in Figure 2 corresponds to a single stable phase, whose composition is indicated with a Mg x (H 2 O) n V 2 O 5 notation. While the lines separating the single phase regions indicate the coexistence of two phases, the triple points correspond to a three-phase coexistence.…”

mentioning

confidence: 99%

Role of Structural H₂O in Intercalation Electrodes: The Case of Mg in Nanocrystalline Xerogel-V₂O₅

et al. 2016

View full text Add to dashboard Cite

Co-intercalation is a potential approach to influence the voltage and mobility with which cations insert in electrodes for energy storage devices. Combining a robust thermodynamic model with firstprinciples calculations, we present a detailed investigation revealing the important role of H2O during ion intercalation in nano-materials. We examine the scenario of Mg 2+ and H2O co-intercalation in nano-crystalline Xerogel-V2O5, a potential cathode material to achieve energy density greater than Li-ion batteries. Water co-intercalation in cathode materials could broadly impact an electrochemical system by influencing its voltages or causing passivation at the anode. The analysis of the stable phases of Mg-Xerogel V2O5 and voltages at different electrolytic conditions reveals a range of concentrations for Mg in the Xerogel and H2O in the electrolyte where there is no thermodynamic driving force for H2O to shuttle with Mg during electrochemical cycling. Also, we demonstrate that H2O shuttling with the Mg 2+ ions in wet electrolytes yields higher voltages than in dry electrolytes. The thermodynamic framework used to study water and Mg 2+ co-intercalation in this work opens the door for studying the general phenomenon of solvent co-intercalation observed in other complex solvent-electrode pairs used in the Li-and Na-ion chemical spaces.

show abstract

“…Figure S2 (Supporting Information) shows molar excess enthalpy ( H E ) data for 11 H 2 O–HBA mixtures obtained from the literature. − , The 11 H 2 O–HBA mixtures had minima in H E values in water-rich compositions (Figure S2). Minimum H E values of the H 2 O–HBA mixtures (− H max E -, Figure S2) are tabulated in Table .…”

Section: Results and Discussionmentioning

confidence: 99%

“…Figure S2 (Supporting Information) shows molar excess enthalpy (H E ) data for 11 H 2 O−HBA mixtures obtained from the literature. [52][53][54][55][56][57][58][59][60]65 The 11 H 2 O−HBA mixtures had minima in H E values in water-rich compositions (Figure S2). Minimum H E values of the H 2 O−HBA mixtures (−H max E -, Figure S2) are tabulated in Table 1 S3) show positive V̅ 1 E values, indicating formation of a hydration shell of water according to Marcus' criterion.…”

Section: Extrema In Thermodynamicmentioning

confidence: 99%

Does Synergism in Microscopic Polarity Correlate with Extrema in Macroscopic Properties for Aqueous Mixtures of Dipolar Aprotic Solvents?

et al. 2017

View full text Add to dashboard Cite

Aqueous mixtures of dipolar aprotic solvents (acetonitrile, γ-valerolactone, γ-butyrolactone, tetrahydrofuran, 1,4-dioxane, acetone, pyridine, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide) show synergism in microscopic polarity and extrema in macroscopic viscosity (η) and molar excess enthalpy (H) in water-rich compositions that correlate with solvent functional group electrostatic basicity (β). Microscopic polarities of aqueous solvent mixtures were estimated by measuring the spectral shift (λ) of 4-nitroaniline with UV-vis spectroscopy at 25 °C. Dynamic viscosities (η) and densities were measured for eight aqueous dipolar aprotic mixtures over the full range of compositions at (25 to 45) °C. The λ, η, and H values of the aqueous mixtures showed a linear trend with increasing electrostatic basicity of the solvent functional groups that is attributed to the size and strength of the hydration shell of water. Density functional theory (DFT) calculations were performed for 1:3 complexes (solvent: (HO)) and it was found that aqueous mixtures with high basicity have high binding energies and short hydrogen bonding distances implying that the size and strength of the hydration shell of water is proportional to functional group basicity. Consideration of functional group basicity of dipolar aprotic solvents allows one to relate synergism in microscopic polarity to extrema in macroscopic properties for a wide range of aqueous dipolar aprotic solvent mixtures.

show abstract

Enthalpies of mixing of tetrahydrofuran + .gamma.-butyrolactone and water + .gamma.-butyrolactone systems at 299.15 K

Cited by 11 publications

References 3 publications

Thermal and Volumetric Properties of Five Lactones at Infinite Dilution in Water

Thermal and Volumetric Properties of Five Lactones at Infinite Dilution in Water

Role of Structural H₂O in Intercalation Electrodes: The Case of Mg in Nanocrystalline Xerogel-V₂O₅

Does Synergism in Microscopic Polarity Correlate with Extrema in Macroscopic Properties for Aqueous Mixtures of Dipolar Aprotic Solvents?

Contact Info

Product

Resources

About

Enthalpies of mixing of tetrahydrofuran + .gamma.-butyrolactone and water + .gamma.-butyrolactone systems at 299.15 K

Cited by 11 publications

References 3 publications

Thermal and Volumetric Properties of Five Lactones at Infinite Dilution in Water

Thermal and Volumetric Properties of Five Lactones at Infinite Dilution in Water

Role of Structural H2O in Intercalation Electrodes: The Case of Mg in Nanocrystalline Xerogel-V2O5

Does Synergism in Microscopic Polarity Correlate with Extrema in Macroscopic Properties for Aqueous Mixtures of Dipolar Aprotic Solvents?

Contact Info

Product

Resources

About

Role of Structural H₂O in Intercalation Electrodes: The Case of Mg in Nanocrystalline Xerogel-V₂O₅