Add time:08/12/2019         Source:sciencedirect.com

In the temperature range of 388–506 K in saturated vapor over 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMImTfO) ionic liquid along with the monomer neutral ionic pairs (NIP) C+A–, where C+ is EMIm+ (cation) and A– is TfO– (anion), the dimers (C+A–)2 were registered with a fraction of 0.5% for the first time. The corresponding associative ions C2A+ and C3A2+ formed as a result of attachment of the cation C+ to the monomer and dimer NIPs were also found. The evaporation enthalpies ΔvH°(298.15 K) = 128 ± 5 kJ mol–1 (monomer) and ΔvH°(298.15 K) = 161 ± 9 kJ mol–1 (dimer) were determined. The enthalpy of formation of the monomer and dimer NIP of EMImTfO at 298.15 K in the state of ideal gas were derived from the evaporation enthalpies: –1033 ± 50 kJ mol–1 and –2160 ± 50 kJ mol–1, respectively. The desorption enthalpies ΔdesH°(T) of the C+, C2A+, and C3A2+ cations were found to be 164 ± 5 kJ mol–1 (435 K), 159 ± 7 kJ mol–1 (435 K), and 152 ± 21 kJ mol–1(457 K), respectively. The equilibrium constants of the heterophase ion-molecular reactions were measured and the formation enthalpies of associative ions were calculated: ΔfH°(C2A+, 298.15 K) = –493 ± 50 kJ mol–1 and ΔfH°(C3A2+, 298.15 K) = –1631 ± 50 kJ mol–1.

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