PMID: 11604216Oct 18, 2001Paper

Thermodynamics of the hydrophobic effect. II. Calorimetric measurement of enthalpy, entropy, and heat capacity of aggregation of alkylamines and long aliphatic chains

Biophysical Chemistry
Daumantas Matulis, Victor A Bloomfield

Abstract

The thermodynamics of long aliphatic chain alkylamine aggregation in aqueous solution was studied by isothermal titration calorimetry (ITC). Protonated alkylammonium cations with linear aliphatic chains of 10-14 carbon atoms were fully soluble in aqueous solution at the beginning of titration, but practically insoluble after deprotonation by titrating with sodium hydroxide. The alkylamines aggregated and precipitated during the reaction, enabling direct measurement of the enthalpy of aggregation. The enthalpy of aggregation became increasingly exothermic upon increasing the chain length. Hydrophobic aggregation was enthalpy-driven and entropy-opposed for alkylamines with 12-14 carbon atoms at room temperature. Direct observation of hydrophobic aggregation by ITC at constant temperature and pressure provided more accurate thermodynamic parameters than obtainable from van't Hoff analysis. Aggregation into liquid or solid phases could be distinguished by ITC, but not by van't Hoff analysis of alkylamine solubility data.

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Citations

Jul 12, 2016·Journal of Hazardous Materials·Ling LengPo-Heng Lee
Oct 19, 2004·The Journal of Biological Chemistry·Madan KatragaddaJohn D Lambris
Mar 12, 2019·Pharmaceutical Nanotechnology·Uchechukwu OdunzeIjeoma Uchegbu
May 11, 2012·Angewandte Chemie·Daniel GörlFrank Würthner
Apr 13, 2010·The Journal of Physical Chemistry. B·Yael KatsirEshel Ben-Jacob
Jul 31, 2012·The Journal of Physical Chemistry. B·Prashant Kumar Gupta, Markus Meuwly
Apr 24, 2020·Journal of Chemical Theory and Computation·Evangelia Pantatosaki, George K Papadopoulos
Jan 25, 2012·The Journal of Physical Chemistry. B·Povilas NorvaišasDaumantas Matulis
Oct 29, 2013·Journal of the American Chemical Society·Dongcui Li, Norman J Wagner
Jul 11, 2013·The Journal of Physical Chemistry. B·Ioan Turcu, Mihaela Mic

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