Partial molal volume behavior of tetraalkylammonium chlorides in aqueous acetone and aqueous dimethylsulfoxide

1970 ◽  
Vol 48 (15) ◽  
pp. 2416-2422 ◽  
Author(s):  
Digby D. Macdonald ◽  
J. B. Hyne
Keyword(s):  
Molecular Weight ◽  
Aqueous Acetone ◽  
Solvent Composition ◽  
Partial Molal Volume ◽  
Volume Data ◽  
Molal Volume ◽  
Partial Molal Volumes ◽  
Molal Volumes ◽  
Aqueous Dimethylsulfoxide ◽  
Linear Expression

The partial molal volumes of a series of tetraalkylammonium chlorides in aqueous acetone and aqueous dimethylsulfoxide at 25.000 °C are reported as a function of solvent composition. It is shown that for each solvent composition the partial molal volume data are better represented by a quadratic in solute molecular weight than by the linear expression previously employed in similar studies. Extrapolation of molecular partial molal volumes to zero cation molecular weight has permitted evaluation of the partial molal volumes of the ions R4N+ and Cl−. The variation of molecular and ionic partial molal volume as a function of solvent composition is discussed.

scholarly journals The partial molal volume of two nickel chelate complexes

1980 ◽  
Vol 58 (17) ◽  
pp. 1795-1798 ◽  
Author(s):  
Y. K. Sze ◽  
W. A. E. McBryde
Keyword(s):  
Ethylenediaminetetraacetic Acid ◽  
Structural Features ◽  
Partial Molal Volume ◽  
Spectral Measurements ◽  
Chelate Complexes ◽  
Molal Volume ◽  
Nickel Chelate ◽  
Partial Molal Volumes ◽  
Molal Volumes ◽  
Methyliminodiacetic Acid

Partial molal volumes have been determined for the nickel(II) complexes of ethylenediaminetetraacetic acid (mono complex) and methyliminodiacetic acid (bis complex). The formation of these is accompanied by appreciable increases in volume, greater in the case of the second ligand. The observations are discussed in terms of reduced electrostriction of water by the complexes, and the different volume increases are accounted for by structural features of the complexes which are partially confirmed by spectral measurements.

Partial molal volumes of amines in benzene. Specific interactions

1986 ◽  
Vol 64 (2) ◽  
pp. 387-393 ◽  
Author(s):  
Ester F. G. Barbosa ◽  
Isabel M. S. Lampreia
Keyword(s):  
Specific Interaction ◽  
Secondary Amines ◽  
Partial Molal Volume ◽  
Tertiary Amines ◽  
Molal Volume ◽  
Conformational Effects ◽  
Partial Molal Volumes ◽  
Amine Groups ◽  
Vibrating Tube Densimeter ◽  
Molal Volumes

Apparent molal volumes, [Formula: see text], of secondary and tertiary amines and linear hydrocarbons were determined in benzene at 25 °C, using a vibrating tube densimeter. These quantities have been extrapolated to infinite dilution to obtain partial molal volumes. The contribution to partial molal volume of the amine groups, calculated using a simple additive scheme, [Formula: see text], were interpreted in terms of conformational effects present in these molecules. A first attempt to find a measure of the contribution to the partial molal volume of the specific interaction amine–benzene in tertiary and secondary amines was made. The results agree well in the two different approaches used.

Effect of Pressure on the Solvolysis of Dimethyl-t-butyl Sulfonium Iodide in Ethanol–Water Mixtures

1972 ◽  
Vol 50 (14) ◽  
pp. 2270-2275 ◽  
Author(s):  
Claude S. Davis ◽  
J. B. Hyne
Keyword(s):  
Reaction Mechanism ◽  
Transition State ◽  
Pressure Dependence ◽  
Composition Dependence ◽  
Partial Molal Volume ◽  
Molal Volume ◽  
Effect Of Pressure ◽  
Partial Molal Volumes ◽  
Molal Volumes

The pressure dependence of the rate of solvolysis of dimethyl-t-butyl sulfonium iodide has been studied in ethanol–water mixtures at 60.00 °C. Determination of the partial molal volume of the substrate ions has enabled the volumes of activation to be dissected into initial and transition state components. The solvent composition dependence of the partial molal volumes of the two states provides further details of the nature of the reaction mechanism.

The pressure dependence of benzyl chloride solvolysis in aqueous acetone and aqueous dimethylsulfoxide

1970 ◽  
Vol 48 (16) ◽  
pp. 2494-2499 ◽  
Author(s):  
Digby D. Macdonald ◽  
J. B. Hyne
Keyword(s):  
Transition State ◽  
Benzyl Chloride ◽  
Activation Volume ◽  
Aqueous Acetone ◽  
Solvent Composition ◽  
Pressure Data ◽  
Initial State ◽  
First Order ◽  
Solvent Systems ◽  
Aqueous Dimethylsulfoxide

First-order rate constants for the solvolysis of benzyl chloride in a series of aqueous acetone and aqueous dimethylsulfoxide (DMSO) mixtures at 50.100 °C and at various pressures in the range 1–4083 atm are reported. Volume of activation, calculated from the rate/pressure data, is found to exhibit extremum behavior with varying solvent composition in both solvent systems. The activation volumes are dissected into their initial state and transition state contributions by determining the "instantaneous" volumes of solution of benzyl chloride in the solvent systems. The contributions of both the initial state and the transition state to the behavior of the activation volume as a function of solvent composition are discussed.

Transition state volumes and solvolysis mechanisms

1970 ◽  
Vol 48 (13) ◽  
pp. 2025-2030 ◽  
Author(s):  
MOYRA J. Mackinnon ◽  
A. B. Lateef ◽  
J. B. Hyne
Keyword(s):  
Transition State ◽  
Benzyl Chloride ◽  
Activation Volume ◽  
Solvent Composition ◽  
Binary Solvent ◽  
Partial Molal Volume ◽  
Butyl Chloride ◽  
Molal Volume ◽  
Reaction Type

The transition state partial molal volume behavior, [Formula: see text] as a function of binary solvent composition was obtained for three reactions by dissection of the activation volume, ΔV*, into initial and transition state components: [Formula: see text] The solvolyses of t-butyl chloride, benzyl chloride, and p-chlorobenzyl chloride represented a gradation of reaction type between SN1 and SN2 and the transition state partial molal volume behavior was found to be distinctly different in each case and in agreement with the mechanistic classification of these reactions.

Solvation of ions. XXXI. Partial molal volumes of sodium, silver(I) and copper(I) ions in acetonitrile/water mixtures

1983 ◽  
Vol 36 (9) ◽  
pp. 1675 ◽  
Author(s):  
P Singh ◽  
ID MacLeod ◽  
AJ Parker
Keyword(s):  
Solvent Composition ◽  
Solvent Interactions ◽  
Aqueous Acetonitrile ◽  
Partial Molal Volumes ◽  
Complex Dependence ◽  
Solvation Of Ions ◽  
Acetonitrile Solutions ◽  
Molal Volumes ◽  
Solvent Solvent

The partial molal volumes of Na+, Ag+, Cu+, Ph4As+, BPh4-, Cl- and NO3- are reported for transfer from water to various acetonitrile/water (MeCN/H2O) mixtures by using the tatb assumption that ΔVt(Ph4As+) = ΔVt(BPh4-). The results, which show a complex dependence of ionic partial molal volumes on MeCN/H2O solvent composition, are discussed in terms of ion-solvent and solvent-solvent interactions. This study complements earlier work on the energetics of transfer (tatb assumption) of these ions from water to aqueous acetonitrile solutions.

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.

Partial molal volumes of calcium-montmorillonite

Clay Minerals ◽  
1971 ◽  
Vol 9 (2) ◽  
pp. 177-184 ◽  
Author(s):  
E. A. Ferreiro ◽  
A. K. Helmy
Keyword(s):  
Silica Gel ◽  
Alcohol Concentration ◽  
Apparent Molal Volume ◽  
Surface Charges ◽  
Molal Volume ◽  
Density Measurements ◽  
Partial Molal Volumes ◽  
Molal Volumes ◽  
Low Alcohol

AbstractPartial molal voltmae of Ca-montmorillonite, apparent molal volume of silica gel in water and of Ca-montmorillonite in ethanol-water mixtures, were determined using pycnometer density measurements. No electrostriction of water was observed with silica gel but took place in Ca-montmorillonite thus indicating the principle role of surface charges in stricting water. In ethanol-water mixtures alcohol molecules were salted out at low alcohol concentration, but they started reaching inner zones near the clay surfaces when their mole fraction in solution was increased beyond the value of 0·55.

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