Abstract
The thermal properties and conductivity of quaternary ammonium compound Bu4NHSO4 were firstly investigated. Tetrabutylammonium hydrogen sulfate is thermally stable up to 260 °C, followed by slow decomposition. It was shown that the enthalpy of Bu4NHSO4 melting is −48.4 J/g. The conductivity of Bu4NHSO4 changes in a wide range: from 10−8 S/cm at 60 °C to 10−2 S/cm in the melt. The conductivity of the melt (165–180 °C) is higher than 10−2 S/cm with activation energy of conductivity 0.5 eV, while activation energy at lower temperatures (50–125 °C) is equal to 0.8 eV. The most important factors affecting the conductivity of the compound are structural characteristics, the nature of the bonding of sulfate tetrahedra, and the energy of hydrogen bonds. The crystal structure of Bu4NHSO4 consists of sulfate tetrahedra pairwise linked into isolated dimers by strong hydrogen bonds with significant distances for proton transfer. It hinders the formation of conductivity pathways.
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References
Dockx J (1973) Quaternary ammonium compounds in organic synthesis. Synthesis-Stuttgart 14:441–456
Starks CM, Liotta CL, Halpern ME (1994) Phase-transfer catalysis: fundamentals, applications, and industrial perspectives. Springer, Dordrecht
Watanabe M, Thomas ML, Zhang S, Ueno K, YasudaT DK (2017) Application of ionic liquids to energy storage and conversion materials and devices. Chem Rev 117:7190–7239
Bureš F (2019) Quaternary ammonium compounds: simple in structure, complex in application. Top Curr Chem 377:14
Chen L, Hu M, Wu P, Feng J (2019) Thermal expansion performance and intrinsic lattice thermal conductivity of ferroelastic RETaO4 ceramics. J Am Ceram Soc 102:4809–4821
Chen L, Guo J, Zhu Y, Hu M, Feng J (2021) Features of crystal structures and thermo-mechanical properties of weberites RE3NbO7 (RE=La, Nd, Sm, Eu, Gd) ceramics. J Am Ceram Soc 104:404–412
Das C (2014) Electrical conductance of some tetraalkylammonium bromide salts in 2-butoxyethanol (1) + water (2) mixtures at (298.15, 303.15, 308.15, and 313.15) K. J Chem Eng Data 59:168–175
Salamanca YP, Blanco LH, Buchner R, Vargas EF (2012) Electrical conductivity studies of tetraalkylammonium bromides in aqueous solutions at several temperatures. J Chem Eng Data 57:2203–2210
MacFarlane DR, Forsyth M (2001) Plastic crystal electrolyte materials: new perspectives on solid state ionics. Adv Mater 13:957–966
Pringle JM, Howlett PC, MacFarlane DR, Forsyth M (2010) Organic ionic plastic crystals: recent advances. J Mater Chem 20:2056–2062
Miran MS, Hoque M, Yasuda T, Tsuzuki S, Ueno K, Watanabe M (2019) Key factor governing the physicochemical properties and extent of proton transfer in protic ionic liquids: ΔpKa or chemical structure? Phys Chem Chem Phys 21:418–426
Greaves TL, Calum J, Drummond CJ (2008) Protic ionic liquids: properties and applications. Chem Rev 108:206–237
Timperman L, Beguin F, Frackowiak E, Anouti M (2014) Comparative study of two protic ionic liquids as electrolyte for electrical double-layer capacitors. J Electrochem Soc 161:A228–A238
Wei D, Ng TW (2009) Application of novel room temperature ionic liquids in flexible supercapacitors. Electrochem Commun 11:1996–1999
Lee SY, Ogawa A, Kanno M, Nakamoto H, Yasuda T, Watanabe M (2010) Nonhumidified intermediate temperature fuel cells using protic ionic liquids. J Am Chem Soc 132:9764–9773
Fedorova IV, Krestyaninov MA, Safonova LP (2021) Structure and ion-ion interactions in trifluoroacetate-based ionic liquids: quantum chemical and molecular dynamics simulation studies. J Mol Liq 328:115449
Das S, Mondal A, Reddy CM (2020) Harnessing molecular rotations in plastic crystals: a holistic view for crystal engineering of adaptive soft materials. Chem Soc Rev 49:8878–8896
Siddique TA, Balamurugan S, Said SM, Sairi NA, Normazlan WMDW (2016) Synthesis and characterization of protic ionic liquids as thermoelectrochemical materials. RSC Adv 6:18266–18278
Shmukler LE, Fedorova IV, Fadeeva YA, Safonova LP (2021) The physicochemical properties and structure of alkylammonium protic ionic liquids of RnH4-nNX (n = 1–3) family. J Mol Liq 321:114350
Fedorova IV, Safonova LP (2020) Ion pair structures and hydrogen bonding in RnNH4−n alkylammonium ionic liquids with hydrogen sulfate and mesylate anions by DFT computations. J Phys Chem A 124:3170–3179
Speziali NL, Chapius G (1991) Phase transitions in N(CH3)4HSO4: a novel compound with an incommensurate phase. Acta Cryst B47:757–766
Kossev K, Sbirkova H, Petrova N, Shivachev B, Nikolova R (2013) Crystal structure and properties of urea and thiourea adducts of tetraalkyl ammonium hydrogen sulphate. Bulg Chem Commun 45:446–454
Light ME, Gale HMB (2001) Anion–anion dimerization in tetrabutylammonium hydrogensulfate. Acta Cryst E57:o705–o706
Pardey AJ, Rivas AB, Longo C, Funaioli T, Fachinetti G (2004) New media in homogeneous catalysis: wet sodium or tetrabutylammonium hydrogensulfate salts for reppe syntheses catalyzed by a Ru (II) carbonyl complex. J Coord Chem 57:871–882
Stashenko EE, Martinez RJ (2004) Derivatization and solid-phase microextraction. Trends Anal Chem 23:553–561
Brandenburg K, Putz H (1999) DIAMOND. Crystal Impact GbR, Bonn
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This work was supported by Russian Science Foundation grant №20-13-00302.
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Ponomareva, V.G., Bagryantseva, I.N. & Uvarov, N.F. Electrotransport and thermal properties of tetrabutylammonium hydrogen sulfate. Ionics 27, 2067–2071 (2021). https://doi.org/10.1007/s11581-021-03979-1
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DOI: https://doi.org/10.1007/s11581-021-03979-1