Thermodynamics of aqueous mixtures of nonelectrolytes. I. Excess volumes of water-n-alcohol mixtures at several temperatures

Benson, George C.; Kiyohara, Osamu

doi:10.1007/bf00646798

Cited by 244 publications

(117 citation statements)

References 18 publications

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“…Addition of a small amount of alcohol to water leads at first to enhancement of water structure. This is confirmed bv such experimental facts as the composition dependence of thermodynamic functions of mixing (1, 2 , 4 , 6 ) , partial molar volumes and expansibilities (5,(7)(8)(9)32), structural contribution to the temperature of maximum density (TMD) of alcohol-water mixtures (33,34), mutual diffusion coefficients (35)(36)(37), and sound absorption and velocity (13).…”

Section: A Yields O F Solvated Electrorzssupporting

confidence: 55%

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Effects of solvent structure on electron reactivity and radiolysis yields: 2-propanol/water mixed solvents

Cygler¹,

Freeman²

1984

Can. J. Chem.

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. Can. J. Chem. 62, 1265Chem. 62, (1984.Reaction of solvated electrons with nitrobenzene, N, is nearly diffusion controlled in both pure solvents; kN -10"'dm3/mol s. The value of kN is approximately proportional to the inverse viscosity -r-' in the pure solvents, and in the mixed solvents at different temperatures. However, on going from zero to 74 mol% water at the same temperature kN is independent of the 40% increase of -q. Electron diffusion in the mixed solvents is not a simple function of fluidity.Reaction with the inefficient scavengers tryptophane (ks -10" dm3/mol s) and phenol (ks -lo7-10' dm3/mol s) correlates inversely with the electron optical absorption energy. The latter is related to the trap depth in the solvent; electrons in deeper traps have less tendency to react with molecules of low electron affinity.Addition of 3 mol% 2-PrOH to water at 296 K increases the value of GE,,,.,, by 16%. although the value in pure 2-PrOH is three-fold smaller than that in pure water. The increase is attributed to an increase in the free ion yield, caused by an increase in the product of the electron thermalization range and the microscopic dielectric constant of the fluid between the ion and electron, averaged over the time that they exist as a correlated pair. Addition of a small amount of alcohol to water increases the orderliness of the water structure.JOANNA CYCLER et GORDON R. FREEMAN. Can. J . Chem. 62, 1265 (1984). La reaction des Clectrons solvatCs avec le nitrobenzkne, N, est une rCaction qui est a toutes fins pratiques contr61Ce par la diffusion dans les deux solvants a I'Ctat pur; kN -10"' dm2/mol s. La valeur de kN est approximativement proportionnelle I'inverse de la viscositC -r-' dans les solvants purs et dans les solvants mixtes a diffkrentes tempkratures. Cependant, si on opkre a une temptrature constante et que I'on fait varier la quantitC d'eau de zCro jusqu'i 74 mol% d'eau, la valeur de kN ne varie pas malgrC une augmentation de 40% de la valeur de T. La diffusion des Clectrons dans les solvants mixtes n'est pas une fonction simple de la fluiditC.

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Section: A Yields O F Solvated Electrorzssupporting

confidence: 55%

“…Partial molar volumes display a sharp minimum and partial molar expansibilities a maximum in the low concentration range (2-7 mol%) of alcohol (5,(7)(8)(9)32).…”

Section: A Yields O F Solvated Electrorzsmentioning

confidence: 99%

Effects of solvent structure on electron reactivity and radiolysis yields: 2-propanol/water mixed solvents

Cygler¹,

Freeman²

1984

Can. J. Chem.

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“…In fact, the local density of the water and its molecular dynamics seems to be strongly related. 15 The findings for alcohol-water mixtures further imply that it is mainly the dynamics of water that exhibits an anomalous nonmonotonic concentration dependence, in contrast to what was observed for the 2PGME-water system. 16 Further insights about how hydrogen bonds affect the structure and dynamics of liquids, and the possible formation of larger structural entities of hydrogen bonded molecules, can be gained by imposing geometrical constraints.…”

Section: Introductioncontrasting

confidence: 41%

Anomalous dynamics of aqueous solutions of di-propylene glycol methylether confined in MCM-41 by quasielastic neutron scattering

Swenson

Elamin

Chen

et al. 2014

The Journal of Chemical Physics

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The molecular dynamics of solutions of di-propylene glycol methylether (2PGME) and H 2 O (or D 2 O) confined in 28 Å pores of MCM-41 have been studied by quasielastic neutron scattering and differential scanning calorimetry over the concentration range 0-90 wt.% water. This system is of particular interest due to its pronounced non-monotonic concentration dependent dynamics of 2PGME in the corresponding bulk system, showing the important role of hydrogen bonding for the dynamics. In this study we have elucidated how this non-monotonic concentration dependence is affected by the confined geometry. The results show that this behaviour is maintained in the confinement, but the slowest diffusive dynamics of 2PGME is now observed at a considerably higher water concentration; at 75 wt.% water in MCM-41 compared to 30 wt.% water in the corresponding bulk system. This difference can be explained by an improper mixing of the two confined liquids. The results suggest that water up to a concentration of about 20 wt.% is used to hydrate the hydrophilic hydroxyl surface groups of the silica pores, and that it is only at higher water contents the water becomes partly mixed with 2PGME. Hence, due to this partial micro-phase separation of the two liquids larger, and thereby slower relaxing, structural entities of hydrogen bonded water and 2PGME molecules can only be formed at higher water contents than in the bulk system. However, the Q-dependence is unchanged with confinement, showing that the nature of the molecular motions is preserved. Thus, there is no indication of localization of the dynamics at length scales of less than 20 Å. The dynamics of both water and 2PGME is strongly dominated by translational diffusion at a temperature of 280 K.

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“…They are interesting also because of the many anomalous properties they show such as a maximum in heat capacity and a minimum in partial molar volume. [1][2][3][4] Alcohols are also the simplest form of amphiphilic molecules having both hydrophobic and hydrophilic segments. Solvation of polar and non-polar segments in water is of importance in biomolecular systems.…”

Section: Introductionmentioning

confidence: 99%

Hydrophobic and hydrophilic interactions in aqueous mixtures of alcohols at a hydrophobic surface

Ballal

Chapman

2013

The Journal of Chemical Physics

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Aqueous solutions of alcohols are interesting because of their anomalous behavior that is believed to be due to the molecular structuring of water and alcohol around each other in solution. The interfacial structuring and properties are significant for application in alcohol purification processes and biomolecular structure. Here we study aqueous mixtures of short alcohols (methanol, ethanol, 1-propanol, and 2-propanol) at a hydrophobic surface using interfacial statistical associating fluid theory which is a perturbation density functional theory. The addition of a small amount of alcohol decreases the interfacial tension of water drastically. This trend in interfacial tension can be explained by the structure of water and alcohol next to the surface. The hydrophobic group of an added alcohol preferentially goes to the surface preserving the structure of water in the bulk. For a given bulk alcohol concentration, water mixed with the different alcohols has different interfacial tensions with propanol having a lower interfacial tension than methanol and ethanol. 2-propanol is not as effective in decreasing the interfacial tension as 1-propanol because it partitions poorly to the surface due to its larger excluded volume. But for a given surface alcohol mole fraction, all the alcohol mixtures give similar values for interfacial tension. For separation of alcohol from water, methods that take advantage of the high surface mole fraction of alcohol have advantages compared to separation using the vapor in equilibrium with a water-alcohol liquid. © 2013 AIP Publishing LLC.

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Thermodynamics of aqueous mixtures of nonelectrolytes. I. Excess volumes of water-n-alcohol mixtures at several temperatures

Cited by 244 publications

References 18 publications

Effects of solvent structure on electron reactivity and radiolysis yields: 2-propanol/water mixed solvents

Effects of solvent structure on electron reactivity and radiolysis yields: 2-propanol/water mixed solvents

Anomalous dynamics of aqueous solutions of di-propylene glycol methylether confined in MCM-41 by quasielastic neutron scattering

Hydrophobic and hydrophilic interactions in aqueous mixtures of alcohols at a hydrophobic surface

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