Abstract
Excess molar volumes, V m E, over the whole composition range for binary mixtures of 1-butanol, 2-butanol, and 2-methyl-2-propanol + 1-octanol, or 2-octanol, or di-n-butyl ether, or n-hexylacetate were determined at 298.15 K from density measurements carried out with a vibrating-tube densimeter. Small V m E values, both positive and negative, are displayed by mixtures containing 1- or 2-octanol, whereas positive and larger values are always found for mixtures containing dibutyl ether and hexylacetate. These results can be justified in terms of H-bonding interactions and/or steric hindrance due to the branched alkyl chains. Partial molar volumes at infinite dilution of the isomeric butanols in the C8 compounds were also calculated from the apparent molar volumes in dilute solution. The solute-solvent interactions and the effects of the local organisation of the solvent around the butanol molecules were discussed using the void and cavity volumes as different estimates of the intrinsic volume of the molecules. The volumetric behavior of butanols seems to be determined by the solute-solvent interactions rather than packaging effects.
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Bernazzani, L., Cabani, S., Conti, G., Mollica, V.: Thermodynamic study of the partitioning of organic compounds between water and Octan-1-ol, J. Chem. Soc., Faraday Trans. I, 91, 649–655 (1995).
Bernazzani, L., Carosi, M.R., Ceccanti, N., Conti, G., Gianni, P., Lepori, L., Matteoli, E., Mollica, V., Tinè, M.R.: Thermodynamic study of organic compounds in di-n-Butyl Ether. Enthalpy and Gibbs energy of solvation. Phys. Chem. Chem. Phys. 2, 4829–4836 (2000).
See, F.I., Roberts, M.S., Pugh, W.J., Hadgraft, J., Watkinson, A.C.: Epidermal permeability- penetrant structure relationships: 1. An analysis of methods of predicting penetration of monofunctional solutes from aqueous solutions. Int. J. Pharm. 126, 219–233 (1995); Roberts, M.S., Pugh, W.J., Hadgraft, J.: Epidermal permeability: penetrant structure relationships. 2. The effect of H-bonding groups in penetrants on their diffusion through the stratum corneum. Int. J. Pharm. 132, 23–32 (1996); Pugh, W.J., Roberts, M.S., Hadgraft, J.: Epidermal permeability-penetrant structure relationships. 3. The effect of hydrogen bonding interactions and molecular size on diffusion across the stratum corneum. Int. J. Pharm. 138, 149–165 (1996).
Bernazzani, L., Bertolucci, M., Conti, G., Mollica, V., Tiné, M.R.: Thermodynamics of the solvation of non-electrolytes in C8 monofunctional organic solvents. Thermochim. Acta 366, 97–103 (2001).
Bernazzani, L., Mollica, V., Tiné, M.R.: Partial Molar Volumes of Organic Compounds in C8 Solvents at 298.15 K. Fluid Phase Equil. 203, 15–29 (2002).
See, F.I., Bhardwaj, U., Maken, S., Singh, K.C.: Excess volumes of 1-Butanol, 2-Butanol, 2-Methylpropan-1-Ol, and 2-Methylpropan-2-Ol with Xylenes at 308.15 K. J. Chem. Eng. Data 41, 1043–1045 (1996); Troncoso, J., Carballo, E., Cerdeiriña, C.A., Gonzáles, D., Romaní, L.: Systematic determination of densities and speeds of sound of nitroethane + isomers of butanol in the range (283.15–308.15) K. J. Chem. Eng. Data 45, 594–599 (2000); Gascón, I., Martín, S., Cea, P., López, M.C., Royo, F.M.: Density and speed of sound for binary mixtures of a cyclic ether with a butanol isomer. J. Solution Chem. 31, 905–915 (2002); Ali, A., Abida, Nain, A.K., Hyder, S.: Molecular interactions in formamide + isomeric butanols: an ultrasonic and volumetric study. J. Solution Chem. 32, 865–877 (2003); Fenclová, D., Perez Casas, S., Costas, M., Dohnal, V.: Partial molar heat capacities and partial molar volumes of all of the 23 isomeric (C3 to C5) alkanols at infinite dilution an water at 298.15 K. J. Chem. Eng. Data 49, 1833–1838 (2004); Ansón, A., Garriga, R., Martínez, S., Pérez, P., Gracia, M.: Densities and viscosities of binary mixtures of 1-chlorobutane with butanol isomers at several temperatures. J. Chem. Eng. Data 50, 677–682 (2005).
Awwad, A.M., Pethrick, R.A.: Ultrasonic investigations of mixtures of n-Octane with isomeric octanols: isoentropic compressibility and excess volumes of mixing. J. Chem. Soc., Faraday Trans. I, 78, 3203–3212 (1982).
Edward, J.T., Farrell, P.G., Shahidi, F.: Partial molal volumes of organic compounds in carbon tetrachloride. IV. Ketones, alcohols, and ethers. Can. J. Chem. 57, 2585–2592 (1979); French, R.N., Criss, C.M.: Effect of solvent on the partial molal volumes and heat capacities of non-electrolytes. J. Solution Chem. 10, 713–740 (1981); Cabani, S., Gianni, P., Mollica, V., Lepori, L.: Group contributions to the thermodynamic properties of non-ionic organic solutes in dilute aqueous solution. J. Solution Chem. 10, 563–595 (1981).
Bondi, A.: van der Waals Volumes and Radii. J. Phys. Chem. 68, 441–445 (1964); 1; Bondi, A.: Physical Properties of Molecular Crystals, Liquids, and Gases, Wiley, New York, 1968.
Lepori, L., Gianni, P.: Partial molar volumes of ionic and non-ionic organic solutes in water: a simple additivity scheme based on the intrinsic volume approach. J. Solution Chem. 29, 405–447 (2000).
Terasawa, S., Itsuki, H., Arakawa, S.: Contribution of hydrogen bonds to the partial molar volumes of nonionic solutes in water. J. Phys. Chem. 79, 2345–2351 (1975).
Pierotti, R.A.: A scaled particle theory of aqueous and nonaqueous solutions. Chem. Rev. 76, 717–726 (1976).
Bernazzani, L., Ceccanti, N., Conti, G., Gianni, P., Mollica, V., Tiné, M.R., Lepori, L., Matteoli, E., Spanedda, A.: Volumetric properties of (an organic compound + di-n-Butyl ether) at T = 298.15 K. J. Chem. Thermodynamics 33, 629–641 (2001).
Lepori, L., Matteoli, E.: Excess volumes of (Tetrachloromethane + an alkanol or + a cyclic ether) at 298.15 K. J. Chem. Thermodynamics. 18, 13–19 (1986); Malatesta, F., Zamboni, R., Lepori, L.: Apparent molar volumes of alkaline earth hexacyanocobaltates (III) in aqueous solution at 25∘C. J. Solution Chem. 16, 699–714 (1987).
Press, W.H., Teukolski, S.A., Vetterling, W.T., Flannery, B.P.: Numerical recipes in fortran. the art of the scientific computing, 2nd ed., Cambridge Univ. Press, Cambridge, 1992. 24
Pflug, H.D., Benson, G.C.: Molar excess volumes of binary n-alcohol systems at 25∘C. Can. J. Chem. 46, 287–294 (1968).
Camacho, A.G., Postino, M.A., Pedrosa, G.C., Acevedo, I.L., Katz, M.: Densities, refractive indices and excess properties of mixing of the n-octanol + 1,4-dioxane + 2-butanol ternary system at 298.15 K. Can. J. Chem. 78, 1121–1127 (2000).
Kammerer, K., Lichtenthaler, R. N.: Excess properties of binary alkanol-ether mixtures and the application of the ERAS model. Thermochim. Acta 310, 61–67 (1998).
Marcus, Y.: Introduction to Liquid State Chemistry, Wiley (Interscience), New York, 1977.
Patterson, D.: Structure and the thermodynamics of non-electrolyte mixtures. J. Solution Chem. 23, 105–120 (1994).
Ben-Naim, A.: Solvation thermodynamics. Plenum Press, New York, 1987.
Majer, V., Svoboda, V.: Enthalpies of vaporisation of organic compounds: a critical review and data compilation. IUPAC Chemical Data Series, Blackwell, Oxford, 1985.
Franks, N.P., Abraham, M.H., Lieb, W.R.: Molecular organization of liquid n-octanol: an X-Ray diffraction analysis. J. Pharm. Sci. 82, 466–470 (1993).
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Bernazzani, L., Carosi, M.R., Duce, C. et al. Volumetric Properties of Binary Mixtures of Isomeric Butanols and C8 Solvents at 298.15 K. J Solution Chem 35, 1567–1585 (2006). https://doi.org/10.1007/s10953-006-9079-0
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DOI: https://doi.org/10.1007/s10953-006-9079-0