Andrey G. Kabo

Thermodynamic properties of adamantane and the energy states of molecules in plastic crystals for some cage hydrocarbons

Thermodynamic properties of adamantane (I) were investigated in this paper. Heat capacities of I in the condensed state between 340 and 600 K were measured by a scanning calorimeter of triple heat bridge type, and characteristics of the fusion of I were determined. The measurements of the enthalpy of sublimation and the saturated vapor pressure for I were made. Thermodynamic functions of I in the ideal gas state were calculated by the statistical thermodynamics methods. The energy states of molecules in the plastic crystals for some cage hydrocarbons (adamantane, bicyclo[2.2.2]octane, pentacycloundecane, heptacyclotetradecane and diamantane) are discussed.

Calorimetric determination of the enthalpy of 1-butyl-3-methylimidazolium bromide synthesis: a key quantity in thermodynamics of ionic liquids.

The enthalpy of the 1-butyl-3-methylimidazolium bromide [C(4)mim]Br ionic liquid synthesis reaction 1-methylimidazole (liq) + 1-bromobutane (liq) --> [C(4)mim]Br (liq) was determined in a homemade small-volume isoperibol calorimeter to be Delta(r)H degrees (298) = -87.7 +/- 1.6 kJ x mol(-1). The activation energy for this reaction in a homogeneous system E(A) = 73 +/- 4 kJ x mol(-1) was found from the results of calorimetric measurements. The formation enthalpies for the crystalline and liquid [C(4)mim]Br were determined from the calorimetric data: Delta(f)H degrees (298)(cr) = -178 +/- 5 kJ x mol(-1) and Delta(f)H degrees (298)(liq) = -158 +/- 5 kJ x mol(-1). The ideal-gas formation enthalpy of this compound Delta(f)H degrees (298)(g) = 16 +/- 7 kJ x mol(-1) was calculated using the methods of quantum chemistry and statistical thermodynamics. The vaporization enthalpy of [C(4)mim]Br, Delta(vap)H degrees (298) = 174 +/- 9 kJ x mol(-1), was estimated from the experimental and calculated formation enthalpies. It was demonstrated that vapor pressure of this ionic liquid cannot be experimentally determined.