Abstract
Excess molar volumes V E for 40 mixtures of heptane with a liquid alkane and apparent molar volumes in heptane for eight solid alkanes have been obtained at 298.15 K. They include five linear, 30 branched-chain, and 13 cyclic alkanes. Almost all systems exhibit negative V E values. For mixtures with open chain alkanes, V E increases from C5 to C7 and then decreases. A similar trend is shown by mixtures with cycloalkanes. V E values are compared with known H E data for mixtures with heptane and tetrachloromethane. Signs and trends of V E and H E are correlated with the free volume and interactional terms of the Flory theory. The partial molar volumes at infinite dilution in heptane, V°, have also been obtained and discussed together with literature data on other hydrocarbons and polar compounds. The calculated contributions to V° by CH3, CH2, CH and C groups are compared with previously determined contributions of polar groups. The lower contributions of the latter groups are explained with the volume contraction caused by dipole-induced dipole interaction. The volume effects associated with branching and cyclization have been evaluated and compared with the corresponding effects on solvation enthalpy. The branching effect, in the order of magnitude of few cm3·mol−1, and the larger negative values of cyclization volumes, down to −24 cm3·mol−1, are discussed in terms of packing and solute–solvent interactions, in analogy to polar organic solutes either in heptane and tetrachloromethane. A negative cyclization effect is also exhibited by the solvation enthalpies.
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Abbreviations
- Bu:
-
Butyl group
- Cn:
-
Alkane with n carbon atoms
- Et:
-
Ethyl group
- Me:
-
Methyl group
- OHMI:
-
Octahydro-4,7-methano-1H-indene
- Pe:
-
Pentyl group
- Pr:
-
Propyl group
- R:
-
Generic alkyl group
- TCM:
-
Tetrachloromethane
References
Lepori, L., Gianni, P.: Partial molar volumes of ionic and nonionic organic solutes in water: A simple additivity scheme based on the intrinsic volume approach. J. Solution Chem. 29, 405–447 (2000)
Van, H.T., Patterson, D.: Volumes of mixing and the P* effect: part I. Hexane isomers with normal and branched hexadecane. J. Solution Chem. 11, 793–805 (1982)
Pierotti, R.A.: A scaled particle theory of aqueous and nonaqueous solutions. Chem. Rev. 76, 717–726 (1976)
Kirkwood, J.G., Buff, F.P.: The statistical mechanical theory of solutions I. J. Chem. Phys. 19, 774–777 (1951)
Marongiu, B., Porcedda, S., Lepori, L., Matteoli, E.: The effect of the molecular shape on the enthalpic behaviour of liquid mixtures: cyclic hydrocarbons in heptane and tetrachloromethane. Fluid Phase Equilib. 108, 167–183 (1995)
Lepori, L., Matteoli, E.: Excess volumes of (tetrachloromethane + an alkanol or + a cyclic ether) at 298.15 K. J. Chem. Thermodyn. 18, 13–19 (1986)
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. Thermodyn. 33, 629–641 (2001)
Matteoli, E., Lepori, L., Spanedda, A.: Volumetric properties of cyclic hydrocarbons in tetrachloromethane at 25 °C. J. Solution Chem. 23, 619–638 (1994)
Berti, P., Lepori, L., Matteoli, E.: Excess volumes of cyclohexane + a linear ether. Fluid Phase Equilib. 44, 285–294 (1989)
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)
Lepori, L., Gianni, P., Spanedda, A., Matteoli, E.: Thermodynamic study of (heptane + amine) mixtures. II. Excess and partial molar volumes at 298.15 K. J. Chem. Thermodyn. 43, 805–813 (2011)
Kimura, F., Benson, G.C.: Excess volumes of binary mixtures of n-heptane with hexane isomers. J. Chem. Eng. Data 28, 387–390 (1983)
Steiger, M., Boisonnas, Ch.G., Fernández-Garcia, J.G., Stoeckli, H.F.: Thermodinamique des mélanges liquids binaries. Volume de mélange d’alcanes normaux et ramifies. Helv. Chim. Acta 55, 1329–1333 (1972)
Apam-Martínez, D., Trejo, A.: Excess heat capacities and excess volumes of n-alkane mixtures. J. Chem. Soc. Faraday Trans. I. 84, 4073–4086 (1988)
Somoza, J.A., Garcia, M., Rey, C., Rodriguez, J.R., Perez Villar, V.: Excess volumes of (n-heptane + n-nonane + cyclohexane) and (n-heptane + n-decane + cyclohexane) at 298.15 K. J. Chem. Thermodyn. 16, 1053–1058 (1984)
Aucejo, A., Burguet, M.C., Muñoz, R., Marques, J.L.: Densities, viscosities, and refractive indices of some n-alkane binary liquid systems at 298.15 K. J. Chem. Eng. Data 40, 141–147 (1995)
Chevalier, J.L.E., Petrino, P.J., Gaston-Bonhomme, Y.H.: Viscosity and density of some aliphatic, cyclic, and aromatic hydrocarbons binary liquid mixtures. J. Chem. Eng. Data 35, 206–212 (1990)
Ilic, P.V., Jiménez, E., Legido, J.L., Fernández, J., Paz Andrade, M.J.: Excess molar volumes of (methyl butanoate + n-heptane + n-decane) and of (butyl butanoate + n-heptane + n-decane) at 298.15 K. J. Chem. Thermodyn. 22, 865–871 (1990)
Siddiqi, M.A., Götze, G., Kohler, F.: Excess volumes of mixtures of cycloalkanes and methylcycloalkanes. Ber. Bunsenges. Phys. Chem. 84, 529–536 (1980)
Fujihara, I., Ogawa, H., Murakami, S.: Excess volumes of cis-decalin + benzene, + toluene, + isooctane and + n-heptane at 298.15 K. J. Chem. Thermodyn. 17, 761–764 (1985)
Dixon, J.A.: Phase equilibria molecular transport thermodynamics. Binary solutions of saturated hydrocarbons. J. Chem. Eng. Data 4, 289–294 (1959)
Malhotra, R., Woolf, L.A.: Thermodynamic properties and excess volumes of 2,2,4-trimethylpentane + n-heptane mixtures from 298 to 338 K for pressures up to 400 MPa. Int. J. Thermophys. 12, 163–170 (1991)
Dohnal, V., Patterson, D.: Excess volumes of (cyclopentane + an isomeric hexane or heptane) at 298.15 K. J. Chem. Thermodyn. 16, 1007–1012 (1984)
Martin, M.L., Symons, L.: Excess volumes of an n-alkane + cycloheptane, + cyclooctane, and + cyclodecane at 298.15 K by continuous-dilution dilatometry. J. Chem. Thermodyn. 13, 81–88 (1981)
Letcher, T.M., Spiteri, W.L.: The excess volumes of some mixtures of a cycloalkane and an n-alkane. J. Chem. Thermodyn. 11, 435–440 (1979)
Treszczanowicz, A.J., Benson, G.C.: Excess volumes for n-alkanols + n-alkanes II. Binary mixtures of n-pentanol, n-hexanol, n-octanol, and n-decanol + n-heptane. J. Chem. Thermodyn. 10, 967–974 (1978)
Costas, M., Patterson, D.: Order destruction and order creation in binary mixtures of non-electrolytes. Thermochim. Acta 120, 161–181 (1987)
Costas, M., Patterson, D.: Volumes of mixing and the P* effect: part II. Mixtures of alkanes with liquids of different internal pressures. J. Solution Chem. 11, 807–821 (1982)
Bondi, A.: van der Waals volumes and radii. J. Phys. Chem. 68, 441–451 (1964)
Lepori, L., Gianni, P., Spanedda, A., Matteoli, E.: Thermodynamic study of (heptane + amine) mixtures. III: Excess and partial molar volumes in mixtures with secondary, tertiary, and cyclic amines at 298.15 K. J. Chem. Thermodyn. 43, 1453–1462 (2011)
Edward, J.T., Farrell, P.G., Shahidi, F.: Partial molar volumes of organic compounds in carbon tetrachloride. 1. Alkanes. Conformational effects. J. Phys. Chem. 82, 2310–2313 (1978)
Edward, J.T., Farrell, P.G., Shahidi, F.: Partial molar volumes of organic compounds in carbon tetrachloride. IV. Ketones, alcohols, and ethers. Can. J. Chem. 57, 2585–2592 (1979)
Bernazzani, L., Carosi, M.R., Ceccanti, N., Conti, G., Gianni, P., Mollica, V., Tiné, M.R., Lepori, L., Matteoli, E.: Thermodynamic study of organic compounds in di-n-butyl ether. Enthalpy and Gibbs energy of solvation. Phys. Chem. Chem. Phys. 2, 4829–4836 (2000)
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)
French, R.N., Criss, C.M.: Effect of solvent on the partial volumes and heat capacities of nonelectrolytes. J. Solution Chem. 10, 713–740 (1981)
Mann, G., Mühlstädt, M., Braband, J., Düring, E.: Konformation und physikalische Daten von Alkanen und Cyclanen—II: Einfach und zweifach verzweigte Alkane. Tetrahedron 23, 3393–3401 (1967)
Rossini, F.D., Pitzer, K.S., Arnett, R.L., Braun, R.H., Pimentel, G.C.: API Research Project 44. Carnegie Press, Pittsburgh (1953)
Majer, V., Svoboda, V.: Enthalpies of Vaporization of Organic Compounds. Blackwell, Oxford (1985)
Edward, J.T., Farrell, P.G., Shahidi, F.: Partial molar volumes of organic compounds in carbon tetrachloride. V. Cyclic alkanes, ethers, alcohols, ketones, and bromides. Can. J. Chem. 57, 2892–2894 (1979)
Matteoli, E., Lepori, L., Spanedda, A.: Thermodynamic study of heptane + amine mixtures I. Excess and solvation enthalpies at 298.15 K. Fluid Phase Equilib. 212, 41–52 (2003)
Meyer, A.Y.: Molecular mechanics and molecular shape. Part 1. van der Waals descriptors of simple molecules. J. Chem. Soc. Perkin Trans. II 2, 1161–1169 (1985)
Boublik, T., Fried, V., Hala, E.: The Vapour Pressures of Pure Substances. Elsevier, New York (1973)
Garcia, M., Rey, C., Perez Villar, V., Rodriguez, J.R.: Excess volumes of (n-heptane + n-octane + cyclohexane) at 298.15 K. J. Chem. Thermodyn. 16, 603–607 (1984)
NIST Webbook. http://webbook.nist.gov/chemistry/form-ser.html.en-us.en. Accessed 1 June 2013
Itsuki, H., Terasawa, S., Shinohara, K., Ikezawa, H.: Partial molar volumes at infinite dilution for C m H2m+2 as solute in C n H2n+2 as solvent for m, n = 6–16 at 298.15 K. J. Chem. Thermodyn. 19, 555–559 (1987)
Fandiño, O., Pensado, A.S., Luga, L., Comuñas, M.J.P., Fernández, J.: Compressed liquid densities of squalane and pentaerythritol tetra(2-ethylhexanoate). J. Chem. Eng. Data 50, 939–946 (2005)
Cox, J.D., Pilcher, G.: Thermochemistry of Organic and Organometallic Compounds. Academic Press, New York (1970)
TRC, Thermodynamic Tables, Thermodynamic Research Center, Texas A&M University System (1968)
Riddick, J.A., Bunger, W.B., Sakano, T.K. In: Weissberger, A. (ed.) Organic Solvents, Techniques of Chemistry, vol. II. Wiley, New York (1986)
Verevkin, S.P., Emel’yanenko, V.M.: Enthalpy of formation and strain of norbornane from thermochemical measurements and from ab initio calculations. J. Phys. Chem. A 108, 6575–6580 (2004)
Gomez-Ibanez, J.D., Wang, T.C.: The excess volumes of binary mixtures of trans-decalin with cyclohexane and with n-alkanes. J. Phys. Chem. 70, 391–395 (1966)
Letcher, T.M.: The excess volumes of bicyclohexyl + n-heptane, + n-octane, + n-nonane, + n-decane, + n-dodecane, and + n-hexadecane at temperatures between 283.15 and 313.15 K. J. Chem. Thermodyn. 13, 27–29 (1981)
Handa, Y.P., Reeder, J., Knobler, C.M., Scott, R.L.: Volume changes on mixing normal alkanes with branched alkanes. J. Chem. Eng. Data 22, 218–219 (1977)
Landolt-Börnstein, Thermodynamic Properties of Organic Compounds and Mixtures. Densities of Aliphatic Hydrocarbons. Alkanes vol. 8B. Springer, Berlin (1996)
Gmehling, J., Holderbaum, T.: Heats of Mixing Data Collection, Vol. III, part 3, DECHEMA, Frankfurt/Main (1989)
Young Jr., J.C., Binford Jr., J.S., Campbell, S.W.: Excess enthalpies of five pentanol isomer + n-heptane systems measured at 303.15 K and a model describing the behavior. Fluid Phase Equil 209, 255–264 (2003)
Lide, D.R. (ed.): CRC Handbook of Chemistry and Physics, 81st edn. CRC, Boca Raton, (2001)
Matteoli, E., Gianni, P., Lepori, L.: Thermodynamic study of heptane + secondary, tertiary and cyclic amine mixtures Part IV. Excess and solvation enthalpies at 298.15 K. Fluid Phase Equilib. 306, 234–241 (2011)
Handa, Y.P., Benson, G.C.: Volume changes on mixing two liquids: A review of the experimental techniques and the literature data. Fluid Phase Equil. 3, 185–249 (1979)
Treszczanowicz, A.J., Benson, G.C.: Excess volumes for (2-methylbutan-2-ol + n-heptane) and (cyclopentanol + n-heptane). J. Chem. Thermodyn. 17, 123–129 (1985)
Fuchs, R., Stephenson, W.K.: Enthalpies of transfer of alkane solutes from the vapor state to organic solvents. Can. J. Chem. 63, 349–352 (1985)
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The authors thank CNR for granting associate researcher positions at IPCF.
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Lepori, L., Gianni, P. & Matteoli, E. The Effect of the Molecular Size and Shape on the Volume Behavior of Binary Liquid Mixtures. Branched and Cyclic Alkanes in Heptane at 298.15 K. J Solution Chem 42, 1263–1304 (2013). https://doi.org/10.1007/s10953-013-0023-9
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DOI: https://doi.org/10.1007/s10953-013-0023-9