Thermodynamic properties of aqueous organic solutes in relation to their structure. Part III. Apparent molal volumes and heat capacities of low molecular weight alcohols and polyols at 25 °C

1976 ◽  
Vol 54 (4) ◽  
pp. 624-631 ◽  
Author(s):  
Carmel Jolicoeur ◽  
Ghyslain Lacroix
Keyword(s):  
Butyl Alcohol ◽  
Heat Capacities ◽  
Apparent Molal Volume ◽  
Molal Volume ◽  
Specific Effects ◽  
Alkyl Groups ◽  
Tert Butyl Alcohol ◽  
Dilute Aqueous Solutions ◽  
Solute Interactions ◽  
Molal Volumes

The density and specific heat of dilute aqueous solutions of various alcohols and polyols have been measured at 25 °C. Such measurements have been carried out for the following solutes: methanol, ethanol, n-propanol, n-butanol, isobutanol, s-butanol, tert-butyl alcohol, n-pentanol. 3-pentanol, neo-pentanol, ethyleneglycol, 1,4-butanediol, 1,6-hexanediol, dimethyl-2,2-propanediol, 1,1,1-tris(hydroxymethyl)ethane, and pentaerythritol.The limiting apparent molal volume [Formula: see text] and heat capacities [Formula: see text] derived from these data exhibit some variations among the properties of isomers (e.g. branched vs. normal alkyl groups), but these variations cannot be conclusively attributed to specific effects in the hydration of the alkyl groups. On the other hand, the data allows one to derive group contributions to [Formula: see text] and [Formula: see text] namely [Formula: see text] for the methylene group, [Formula: see text] for the OH functional group and [Formula: see text] for the C—H of a terminal methyl group.The concentration dependence of [Formula: see text] brings out some interesting new features. With most of the alcohols, [Formula: see text] decreases with concentration, in a way related to the degree of hydrophobicity of the alcohol. Solute–solute interactions contribute to reduce [Formula: see text] of the hydrophilic solutes, but the opposite effect is observed with the most hydrophobic alcohols.

Volumes and Heat Capacities of Dimethylsulfoxide, Acetone, and Acetamide in Water and of some Electrolytes in these Mixed Aqueous Solvents

1975 ◽  
Vol 53 (21) ◽  
pp. 3263-3268 ◽  
Author(s):  
Osamu Kiyohara ◽  
Gèrald Perron ◽  
Jacques E. Desnoyers
Keyword(s):  
Binary Mixtures ◽  
Transfer Functions ◽  
Mixed Solvents ◽  
Water Structure ◽  
Heat Capacities ◽  
Ternary Mixtures ◽  
Specific Heats ◽  
Solute Interactions ◽  
Molal Volumes ◽  
Mixed Aqueous Solvents

The densities and volumetric specific heats of binary mixtures of dimethylsulfoxide (DMSO), acetone (ACT), and acetamide (ACM) in water were measured at 25 °C with a flow densimeter and a flow microcalorimeter. The same properties were also determined for ternary mixtures of 0.1 m LiCl, NaCl, Me4NBr, and Bu4NBr in ACT–water and DMSO–water mixtures, and volumes for 0.1 m Bu4NBr in ACM–water and urea–water mixtures. The derived apparent molal volumes and heat capacities of nonelectrolytes in water and the transfer functions of the electrolytes from water to the mixed solvents suggest that, contrary to urea, the present non-electrolytes are slightly hydrophobic but, with the possible exception of ACT, their overall influence on water structure has practically no influence on the various solute–solute interactions.

Heat capacities and volumes of dilute aqueous solutions of 1,3-dioxane and trioxane

1981 ◽  
Vol 59 (17) ◽  
pp. 2599-2600 ◽  
Author(s):  
Gérald Perron ◽  
Jacques E. Desnoyers
Keyword(s):  
Aqueous Solutions ◽  
Concentration Dependence ◽  
Infinite Dilution ◽  
Unit Volume ◽  
Heat Capacities ◽  
Cyclic Ethers ◽  
Group Additivity ◽  
Simple Correlation ◽  
Dilute Aqueous Solutions ◽  
Molal Volumes

The densities and heat capacities per unit volume of 1,3-dioxane and trioxane were measured in water at 25 °C in the concentration range 0.1 to 1 mol kg−1. Apparent molal volumes [Formula: see text] and [Formula: see text] heat capacities were derived. The infinite dilution [Formula: see text] shows excellent group additivity with other cyclic ethers in water but the additivity is less satisfactory for[Formula: see text]. No simple correlation can be made for the concentration dependence of these functions.

Enthalpies, heat capacities, and volumes of transfer of the tetrabutylammonium ion from water to aqueous mixed solvents from the point of view of the scaled-particle theory

1976 ◽  
Vol 54 (23) ◽  
pp. 3800-3808 ◽  
Author(s):  
Nicole Desrosiers ◽  
Jacques E. Desnoyers
Keyword(s):  
Mixed Solvents ◽  
Butyl Alcohol ◽  
Heat Capacities ◽  
Point Of View ◽  
Scaled Particle Theory ◽  
Particle Theory ◽  
Tert Butyl ◽  
Tetrabutylammonium Ion ◽  
Tert Butyl Alcohol ◽  
Alcohol Water

The enthalpies, heat capacities, and volumes of transfer of the tetrabutylammonium ion from water to urea–water, tert-butyl alcohol–water, and sodium chloride–water mixtures have been calculated at 25 °C using the scaled-particle theory. In general, the signs, magnitudes, and overall trends in the cosolvent concentration dependence of the properties are predicted from the cavity contributions only. These calculations are found to be very sensitive to the diameters chosen for the various species.For these calculations it was necessary to measure with a dilatometer the coefficients of thermal expansion of tert-butyl alcohol–water mixtures as a function of concentration and temperature.

Thermodynamic and Transport Properties of Sodium Benzoate and Hydroxy Benzoates in Water at 25 °C

1973 ◽  
Vol 51 (13) ◽  
pp. 2129-2137 ◽  
Author(s):  
Jacques E. Desnoyers ◽  
Robert Pagé ◽  
Gérald Perron ◽  
Jean-Luc Fortier ◽  
Paul-André Leduc ◽  
...  
Keyword(s):  
Heat Capacity ◽  
Hydrogen Bonding ◽  
Sodium Benzoate ◽  
Specific Interaction ◽  
Osmotic Coefficients ◽  
Heat Capacities ◽  
Excess Properties ◽  
Apparent Molal Volume ◽  
Molal Volume ◽  
Ortho Isomer

The densities, heat capacities, heats of dilution, osmotic coefficients, viscosities, and conductivities of sodium benzoate and the ortho, meta, and para isomers of sodium hydroxybenzoate have been measured in water at 25 °C. The densities and heat capacities of phenol solutions and the osmotic coefficients of aqueous potassium benzoate have also been determined. The addition of an —OH or a —COONa group on a benzene ring has little effect on the properties related to the effective size of the solute (apparent molal volume, Bη viscosity coefficient, and ionic conductivity) but decreases significantly the apparent molal heat capacity. The addition of an —OH group in the meta or para position of sodium benzoate has a similar effect. The large negative contribution to the heat capacity probably reflects the solute–solvent hydrogen bonding. The ortho isomer, which can form an internal hydrogen bond, has a significantly different behavior from that of the other isomers.The excess properties show no evidence of association at low concentrations although some specific interaction is apparent for the ortho isomer at high concentration. There seems to be some cation–anion structural attraction with the meta and para isomers which again may be related to the hydrogen-bonding ability of these solutes. Sodium and potassium benzoates show signs of association above 1 m.

The heat capacities, volumes, and expansibilities of tert-butyl alcohol – water mixtures from 6 to 65 °C

1977 ◽  
Vol 55 (5) ◽  
pp. 856-862 ◽  
Author(s):  
Cees de Visser ◽  
Gerald Perron ◽  
Jacques E. Desnoyers
Keyword(s):  
Microphase Separation ◽  
Butyl Alcohol ◽  
Heat Capacities ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Alcohol Water ◽  
Order Of Magnitude ◽  
Hydrophobic Solutes ◽  
High Concentrations ◽  
Specific Heat Capacities

The densities and specific heat capacities of mixtures of tert-butyl alcohol (TBA) and water (W) have been measured at 6, 10, 25, 40, 55, and 65 °C. From these data the apparent molal volumes[Formula: see text], heat capacities[Formula: see text], and expansibilities [Formula: see text] were evaluated. Generally, the temperature dependence of these quantities is rather characteristic of hydrophobic solutes in water. At high concentrations [Formula: see text]and [Formula: see text] resemble those of surfactants, suggesting the existence of some microphase separation. At low temperatures [Formula: see text] show a significant hump as a function of concentration, which is probably not due to the presence of the —OH group on the TBA molecule. A similar behaviour is observed for[Formula: see text]. The [Formula: see text] and [Formula: see text] of water in TBA have also been calculated; [Formula: see text] is in theTBA-rich region 2 to 2.5 cm3 mol−1 smaller than the molar volume of water, but [Formula: see text] is of the same order of magnitude as the molar heat capacity of water.

scholarly journals Volumetric Properties of Secondary Butanol and Tertiary Butanol in Water and Aqueous Micellar Systems of Sodium Dodecyl Sulphate

2020 ◽  
Vol 12 (3) ◽  
pp. 419-429
Author(s):  
J. Alauddin ◽  
S. Pande ◽  
S. C. Mohanta ◽  
M. Alauddin
Keyword(s):  
Sodium Dodecyl Sulphate ◽  
Sodium Dodecyl ◽  
Water System ◽  
Apparent Molal Volume ◽  
Micellar System ◽  
Volume Data ◽  
Molal Volume ◽  
Apparent Molal Volumes ◽  
Aqueous Solvent ◽  
Molal Volumes

The apparent molal volumes of sec-butanol and t-butanol in water and in aqueous micellar system of sodium dodecyl sulphate have been determined from density measurements at different surfactant concentrations and temperatures. The partial molal volumes of the alcohols in aqueous micellar system at infinite dilution, V20 (mean, mic) were obtained from apparent molal volume data and compared with the corresponding values in aqueous solvent, V20  (mean, aq). The standard partial molal expansibilities, E20 (mean) of the alcohols were evaluated from V20 (mean) data at various temperatures. The transfer apparent molal volumes, ∆φtr0 for the alcohols from water to surfactant-water system are determined from apparent molal volume data. The sign and magnitude of these parameters are used to analyze the location of the solubilizate (alcohols) in the micellar system and the nature of interactions between alcohols and the micellar aggregates.

Sign in / Sign up

Export Citation Format

Share Document