Abstract
The spectroscopic properties and liquid structure of pure tri-n-butyl phosphate (TBP) and FeCl3/TBP solutions have been investigated by Uv–Vis and Raman spectroscopies, X-ray diffraction and conductometry. Uv–Vis and Raman spectra, supported by conductometric measurements, consistently indicate that the solubilized salt is present mostly as TBP n [FeCl3 − n ]n+ and FeCl4 − complex ions due to specific interaction with the TBP phosphate group. Thanks to this interaction, a high amount of salt (up to 13 % w/w) can be dissolved despite the relatively low dielectric constant of TBP. The X-ray diffractogram of pure TBP has been interpreted in terms of three main contributions which can be attributed to spatial pair correlations between atoms of interacting TBP molecules. In the presence of increasing FeCl3 amounts, it has been observed a progressive structuring effect, exerted by the dissolved salt, on the layers of opportunely oriented TBP molecules due to the formation of the complex ionic species. By simple treatment with NaBH4, the synthesis of Fe nanoparticles has been achieved. The absence of water, the easiness of preparation, the high amount of salt which can be suspended and the peculiar physico-chemical properties of such systems are all elements worth of note for the fields of nanoparticle synthesis and for specialized technological applications.
References
Dudowicz J, Douglas JF, Freed KF (2008) Self-assembly by mutual association: basic thermodynamic properties. J Phys Chem B 112:16193–16204
Calandra P, Ruggirello A, Mele A, Turco Liveri V (2010) Self-assembly in surfactant-based liquid mixtures: bis(2-ethylhexyl)phosphoric acid/bis(2-ethylhexyl)amine systems. J Colloid Interface Sci 348:183–188
Gordon CM, Holbrey JD, Kennedy AR, Seddon KR (1998) Ionic liquid crystals: hexafluorophosphate salts. J Mater Chem 8:2627–2636
Chiarizia R, Jensen MP, Rickert PG, Kolarik, Borkowski M, Thiyagarajan P (2004) Extraction of zirconium nitrate by TBP in n-octane: influence of cation type on third phase formation according to the “sticky spheres” model. Langumir 20:10798–10808
Cui S, de Almeida VF, Hay BP, Ye X, Khomami B (2012) Molecular dynamics simulation of Tri-n-butyl-phosphate liquid: a force field comparative study. J Phys Chem B 116:305–313
Estok FK, Wendlandt WW (1955) Electric moments of some phosphates and thiophosphates. J Am Chem Soc 77:4767–4769
Ceraulo L, Fanara S, Ruggirello A, Turco Liveri V (2007) FT-IR investigation of the state of iron(III) chloride clusters confined in AOT reverse micelles dispersed in carbon tetrachloride. J Clust Sci 18:883–895
Calandra P, Ruggirello A, Turco Liveri V (2009) Complex permittivity of FeCl3/AOT/CCl4 microemulsions probed by AC impedance spectroscopy. J Colloids Interface Sci 337:285–288
Zhou Y, Liu W-J, Zhang W, Cao X-Y, Zhou Q-F, Ma Y, Pei J (2006) Selective oxidative cyclization by FeCl3 in the construction of 10H-indeno[1,2-b]triphenylene skeletons in polycyclic aromatic hydrocarbons. J Org Chem 71:6822–6828
Ai Z, Lu L, Li J, Zhang L, Qiu J, Wu M (2007) Fe@Fe2O3 core − shell nanowires as iron reagent. 1. Efficient degradation of rhodamine B by a novel sono-fenton process. J Phys Chem C 111:4087–4093
Arcoleo V, Goffredi M, TurcoLiveri V (1995) Electrical conductivity and permittivity of water-AOT-n-heptane microemulsions. J Solution Chem 24:1135–1142
Brealey GJ, Uri N (1952) Photochemical oxidation-reduction and photocatalysis. The photochemical activity of FeCl4 − in alcohol as oxidizing agent and as catalyst. J Chem Phys 20:257–262
Balzani V, Carassiti V (1970) Photochemistry of coordination compounds. Academic Press, London and New York
Gamlen GA, Jordan DO (1953) A spectrophotometric study of the iron(III) chloro-complexes. J Chem Soc 1435–1443
Owen ED, Brooks SR (1985) A reversible photoreaction of iron(III) chloride in poly(vinyl chloride) film. Polym Photochem 6:21–30
Rabek JF, Lucki J, Qu BJ, Shi WF (1991) Coordination complexes between iron(III) chloride and polyether, polyester, and poly(ether ester). Macromolecules 24:836–843
Mano V, Felisberti MI, De Paoli MA (1997) Influence of FeCl3 on the mechanical, thermal, and dynamic mechanical behavior of PVC. Macromolecules 30:3026–3030
Meek DW, Drago RS (1961) A coördination model as an alternative to the solvent system concept in some oxychloride solvents I. Similarity in the behavior of phosphorus oxychloride and triethyl phosphate as Non-aqueous solvents. J Am Chem Soc 8:4322–4325
Burger LL (1984) Physical properties. In: Schulz WW, Navratil JD, Talbot AE (eds) Science and technology of tributyl phosphate, vol 1. CRC Press, Inc, Boca Raton, pp 25–68
Voyiatzis GA, Kalampounias AG, Papatheodorou GN (1999) The structure of molten mixtures of iron(III) chloride with caesium chloride. Phys Chem Chem Phys 1:4797–4803
Murata K, Irish DE (1988) Raman studies of the hydrated melt of FeCl36H2O. Spectrochim Acta A 44:739–743
Papatheodorou GN, Voyiatzis GA (1999) Vibrational modes and structure of molten iron(III) chloride. Chem Phys Lett 303:151–156
Klatt LN (1980) A dielectric constant detector for the determination of tri-n-butylphosphate in mixtures with hydrocarbons. Anal Chim Acta 116:289–396
Born M, Wolf E (1993) Principles of optics, 6th edn. Pergamon Press, Oxford
RRUFF database, http://rruff.info/iron/display=default/. Accessed Jul 2014
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The authors gratefully acknowledge financial support from the University of Palermo.
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In part from Doctor in Chemistry thesis of L. Todaro, University of Palermo
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Calandra, P., de Caro, T., Caschera, D. et al. Spectroscopic and structural characterization of pure and FeCl3-containing tri-n-butyl phosphate. Colloid Polym Sci 293, 597–603 (2015). https://doi.org/10.1007/s00396-014-3439-x
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DOI: https://doi.org/10.1007/s00396-014-3439-x