High-Accuracy Vapor Pressure Data of the Extended [C(n)C(1)im][Ntf(2)] Ionic Liquid Series: Trend Changes and Structural Shifts
authors Rocha, MAA; Lima, CFRAC; Gomes, LR; Schroder, B; Coutinho, JAP; Marrucho, IM; Esperanca, JMSS; Rebelo, LPN; Shimizu, K; Lopes, JNC; Santos, LMNBF
nationality International
journal JOURNAL OF PHYSICAL CHEMISTRY B
keywords THERMODYNAMIC PROPERTIES; VAPORIZATION ENTHALPIES; N-ALKANES; CONFORMATIONS
abstract For the first time, two distinct trends are clearly evidenced for the enthalpies and entropies of vaporization along the [C(n)mim][Ntf(2)] ILs series. The trend shifts observed for Delta H-g(1)m degrees and Delta S-g(1)m degrees, which occur at [C(6)mim] [Ntf(2)], are related to structural modifications. The thermodynamic results reported in the present article constitute the first quantitative experimental evidence of the structural percolation phenomenon and make a significant contribution to better understanding of the relationship among cohesive energies, volatilities, and liquid structures of ionic liquids. A new Knudsen effusion apparatus, combined with a quartz crystal microbalance, was used for the high-accuracy volatility study of the 1-alkyl-3-methylirnidazolium bis(trifluoromethylsulfonyl)imide series ([C(n)mim][Ntf(2)], where n = 2, 3, 4, 5, 6, 7, 8, 10, 12). Vapor pressures in the (450-500) K temperature range were measured, and the molar standard enthalpies, entropies, and Gibbs energies of vaporization were derived. The thermodynamic parameters of vaporization were reported, along with molecular dynamic simulations of the liquid phase structure, allowing the establishment of a link between the thermodynamic properties and the percolation phenomenon in ILs.
publisher AMER CHEMICAL SOC
issn 1520-6106
year published 2011
volume 115
issue 37
beginning page 10919
ending page 10926
digital object identifier (doi) 10.1021/jp2049316
web of science category Chemistry, Physical
subject category Chemistry
unique article identifier WOS:000294875100015
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