Volume-related properties of thiophene and furan-2-carboxaldehyde phenylhydrazone derivatives in DMSO: A discussion about non-intrinsic contribution

• Published in: The Journal of chemical thermodynamics Vol. 85; pp. 210 - 215
• Main Authors: Alvarado, Ysaías J., Ballestas-Barrientos, Alfonso, Restrepo, Jelem, Vera-Villalobos, Joan, Ferrer-Amado, Gladys, Rodríguez-Lugo, Patricia, Ferrebuz, Atilio, Infante, Miguel, Cubillán, Néstor
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 01.06.2015
• Subjects: Constraining; Densitometry; Derivatives; Limiting partial molar volume; Mathematical analysis; Mathematical models; Non-intrinsic contribution; Particle theory; Refractometry; Scaled-particle theory; Solvents; Specific and non-specific interactions; Thiophenes; Scaled-particle theory; Specific and non-specific interactions; Densitometry; Limiting partial molar volume; Non-intrinsic contribution; Refractometry
• ISSN: 0021-9614; 1096-3626
• DOI: 10.1016/j.jct.2015.01.016

[Display omitted] •The non-intrinsic contribution to the limiting partial molar volume 〈θ〉 is analyzed.•A new refractometric method for determining 〈θ〉 was proposed.•The refractometric 〈θ〉 was comparable to the densitometric 〈θ〉.•The attractive interactions play an important role in 〈θ〉 by the Lee–Graziano. An analysis of the experimental and theoretical non-intrinsic contribution to the limiting partial molar volume, θ, of thiophene- and furan-2-carboxaldehyde phenylhydrazone, 4-nitrophenylhydrazone and 2,4-dinitrophenylhydrazone derivatives – henceforth referred as PHT, NHT, DHT, PHF, NHF and DHF, respectively – in dimethylsulfoxide is presented. A refractometric method to determine θ was proposed, which was able to successfully reproduce the method based on high-precision densitometry measurements at T=293.15K. No general trend of θ with the molecular size was observed. The theoretical values were calculated within the Scaled Particle Theory framework using both the Kharakoz equation and the Lee–Graziano model with a volumetric contribution from attractive interactions. The values of θ of the more rigid systems, were better represented by the Lee–Graziano model. The attractive term was examined considering the (solute+solvent) separation distance suggesting a possible contribution of specific interactions.