Browsing by Author "Farrell, Patrick G."

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Partial Molar Volumes of Organic Compounds in Water Part 5. Betaines of a/o-Aminocarboxylic Acids
(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1978, 74 (05), 1978) Shahidi, Fereidoon; Farrell, Patrick G.
The partial molar volumes of a number of ω-(N,N,N-trimethyl-amino)-α-carboxylic acids in water at 25°C have been measured, and related to their van der Waals volumes. The effects of progressive methylation of the nitrogen atom are examined and volume changes arising from electrostriction of the solvent or hydrophobic hydration effects are deduced. It is shown that the interaction of the trimethylalkylammonium group in the betaines with the solvent is identical to that of the alkylammonium group with the solvent in the corresponding aminoacids.
Partial molar volumes of organic compounds in water. Part 1.—Ethers, ketones, esters and alcohols
(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1977, 73 (05), 1977) Edward, John T.; Farrell, Patrick G.; Shahidi, Fereidoon
The partial molar volumes of a number of ethers, ketones, esters and alcohols in water at 25.0°C have been determined and related to their van der Waals volumes by one of two equations, depending on whether the molecules are spherical or cylindrical in shape. Allowance has been made for the void volume associated with each molecule and the results imply that calculated volumes must be reduced by a constant amount for each carbonyl or hydroxyl group present, owing to hydrogen bonding to water. No such reduction in the calculated volume is required for the oxygen atom of an ether. It is shown for diols that the amount of void volume per additional —CH2— group remains constant for straight-chain compounds (i.e., cylinders), whereas for spherical molecules the amount of void volume decreases with increase in the number of carbon atoms, as predicted.
Partial molar volumes of organic compounds in water. Part 2.—Amines and Amides
(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1977, 73 (05), 1977) Shahidi, Fereidoon; Farrell, Patrick G.; Edward, John T.
The partial molar volumes of a variety of aliphatic amines and amides in water at 25°C have been determined, and related to their van der Waals volumes. In accordance with earlier studies the relationship between partial molar and van der Waals volumes is shown to depend upon molecular geometry. Hydrogen bonding to the solvent causes a volume reduction and group contributions (decrements) for such interactions of amines have been obtained. Additivity of group contributions is shown to allow the prediction of partial molar volumes for nitrogen-containing compounds.
Partial Molar Volumes of Organic Compounds in Water: Part 4.—Aminocarboxylic Acids
(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1978, 74 (04), 1978) Shahidi, Fereidoon; Farrell, Patrick G.
The partial molar volumes of the a,a>-aminocarboxylic acids up to 11-aminoundecanoic acid, together with those of a number of cyciopentane and cyclohexane analogues, have been measured in water at 25'C, and related to their van der Waals volumes. Similar studies of the isomeric <■;- hydroxyalkyl amides have allowed an estimation of the electrostriction arising from the interaction of the charges with the solvent, and the individual contributions due to the carboxylate and alkylammonium ions have been deduced. The application of these values to the calculation of partial molar volumes for aminocarboxyiic acids, assuming the spherical model previously described, is illustrated.