Abstract
Two ionic clathrate hydrates with different structures are formed in the binary system tetrabutylammonium fluoride–water, namely tetragonal structure-I hydrate (TS-I) (n-С4H9)4NF · 32.8H2O, and cubic superstructure-I hydrate (CSS-I) (n-С4H9)4NF · 29.7H2O. The heats of fusion (ΔHf) of these polyhydrates were measured calorimetrically with differential scanning calorimeter. For TS-I polyhydrate ΔHf = (204.8 ± 2.3) kJ/mol hydrate, for CSS-I hydrate ΔHf = (177.5 ± 3.1) kJ/mol polyhydrate. The change of water molecules energy state in the water lattices of TS-I and CSS-I polyhydrates are discussed.
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Notes
Yet another hydrate (n-C4H9)4NF · 5.5H2O, monoclinic, was found in the low water content region [9]. In this compound tetrabutylammonium cations form the host channel framework, whereas the chains of small paired water-anion cavities are guests.
References
Jeffrey, G.A.: Hydrate inclusion compounds. In: MacNicol, D.D., Toda, F., Bishop, R. (eds.) Comprehensive Supramolecular Chemistry, vol. 6, chap. 23, pp. 757–788. Pergamon, Oxford (1996)
Aladko, L.S., Dyadin, Yu.A., Rodionova, T.V., Terekhova, I.S.: Effect of size and shape of cations and anions on clathrate formation in the system: halogenides of quaternary ammonium bases and water. J. Mol. Liq. 106(2–3), 229–238 (2003)
Feil, D., Jeffrey, G.A.: The polyhedral clathrate hydrates. Part 2. Structure of the hydrate of tetra iso-amyl ammonium fluoride. J. Chem. Phys. 35, 1863–1873 (1961)
Lipkowski, J., Suwinska, K., Rodionova, T.V., Udachin, K.A., Dyadin, Yu.A.: Phase and X-ray study of clathrate formation in the tetraisoamylammonium fluoride – water system. J. Incl. Phenom. Mol. Rec. Chem. 17, 137–148 (1994)
Dyadin, Yu.A., Terekhova, I.S., Polyanskaya, T.M., Aladko, L.S.: Clathrate hydrates of tetrabutylammonium fluoride and oxalate. J. Struct. Chem. 17, 566–571 (1977) (translated from Russian Zh. Struct. Khim. 17, 655 (1976))
Dyadin, Yu.A., Udachin, K.A.: Clathrate formation in water – peralkylonium salts system. J. Incl. Phen. 2, 61–72 (1984)
McMullan, R.K., Bonamico, M., Jeffrey, G.A.: Polyhedral clathrate hydrates. V. Structure of the tetra-n-butyl ammonium fluoride hydrate. J. Chem. Phys. 39, 3295–3310 (1963)
Komarov, V.Yu., Rodionova, T.V., Terekhova, I.S., Kuratieva, N.V.: The cubic superstructure-I of tetrabutylammonium fluoride (C4H9)4NF.29.7 H2O clathrate hydrate. J. Incl. Phenom. 59, 11–15 (2007)
Udachin, K.A., Lipkowski, J.: Water-fluorine chains in (n-Bu)4NF.5.5H2O hydrate. J. Supramol. Chem. 2, 449–451 (2002)
Nakayama, H.: Hydrates of organic compounds. VI. Heats of fusion and of solution of quaternary ammonium halide clathrate hydrates. Bull. Chem. Soc. Jpn. 55, 389–393 (1982)
Narten, A.H., Lindenbaum, S.: Diffraction pattern and structure of the system tetra-n-butylammonium fluoride – water at 25oC. J. Chem. Phys. 51, 1108–1114 (1969)
Nakayama, H.: Solid-liquid and liquid – liquid phase equilibria in the symmetrical tetraalkylammonium halide – water systems. Bull. Chem. Soc. Jpn. 54, 3717–3722 (1981)
Nakayama, H., Watanabe, K.: Hydrates of organic compounds. II. The effect of alkyl groups on the formation of quaternary ammonium fluoride hydrates. Bull. Chem. Soc. Jpn. 49, 1254–1256 (1976)
Lindenbaum, S.: Heats of dilution at 25o of aqueous solution of the bolaform electrolyte [Bu3N-(CH2)8-NBu3]X2. J. Chem. Phys. 73, 4334–4337 (1969)
Eisenberg, D., Kauzmann, W.: Structure and Properties of Water. Oxford Univ. Press, London (1969)
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Rodionova, T.V., Manakov, A.Y., Stenin, Y.G. et al. The heats of fusion of tetrabutylammonium fluoride ionic clathrate hydrates. J Incl Phenom Macrocycl Chem 61, 107–111 (2008). https://doi.org/10.1007/s10847-007-9401-5
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DOI: https://doi.org/10.1007/s10847-007-9401-5