ABSTRACT

The enthalpies of solution of 12-crown-4 ether have been measured in chloroform, ethyl acetate, acetone, pyridine, acetonitrile and methanol at 298.15 K. The values of enthalpy of solvation and solute-solvent interaction were determined from the obtained results and similar literature data for 12-crown-4 in solvents of various polarities. It was shown that the certain correlation is observed between the enthalpy of solute-solvent interaction and the squared dipole moment of the solvent molecule for solutions in tetraclormethane, ethyl acetate, pyridine, acetonitrile, DMF, DMSO and propylene carbonate. This means that the electrostatic interaction of 12-crown-4 with polar solvent molecules contributes significantly to the exothermic effect of solvation. The understated negative value is observed for the enthalpy of interaction of 12-crown-4 with acetone that can be connected with domination of low polar conformer of the crown ether in acetone medium. The most negative values of enthalpy of solvation are exhibited in chloroform and water because of hydrogen bonding between O-atoms of crown ether and molecules of the indicated solvents. This effect is not observed in methanol. The negative coefficient of pairwise solute-solute interaction in methanol suggests that the effects of solvophobic solute-solute interaction and H-bonding of the ether molecule with chain associates of methanol are not evinced in the thermochemical behavior of 12-crown-4.

Compounds

#	Formula	Name
1	CHCl3	trichloromethane
2	C4H8O2	ethyl acetate
3	C8H16O4	1,4,7,10-tetraoxacyclododecane
4	C5H5N	pyridine
5	C3H6O	acetone
6	C2H3N	acetonitrile
7	CH4O	methanol

Datasets

The table above is generated from the ThermoML associated json file (link above). POMD and RXND refer to PureOrMixture and Reaction Datasets. The compound numbers are included in properties, variables, and phases, if specificied; the numbers refer to the table of compounds on the left.
Type	Compound-#	Property	Variable	Constraint	Phase	Method	#Points
POMD	1 3	Molar enthalpy of solution, kJ/mol ; Liquid	Molality, mol/kg - 3; Liquid	Temperature, K; Liquid Pressure, kPa; Liquid	Liquid	ISOPERIBOL	5
POMD	2 3	Molar enthalpy of solution, kJ/mol ; Liquid	Molality, mol/kg - 3; Liquid	Temperature, K; Liquid Pressure, kPa; Liquid	Liquid	ISOPERIBOL	5
POMD	4 3	Molar enthalpy of solution, kJ/mol ; Liquid	Molality, mol/kg - 3; Liquid	Temperature, K; Liquid Pressure, kPa; Liquid	Liquid	ISOPERIBOL	5
POMD	5 3	Molar enthalpy of solution, kJ/mol ; Liquid	Molality, mol/kg - 3; Liquid	Temperature, K; Liquid Pressure, kPa; Liquid	Liquid	ISOPERIBOL	5
POMD	6 3	Molar enthalpy of solution, kJ/mol ; Liquid	Molality, mol/kg - 3; Liquid	Temperature, K; Liquid Pressure, kPa; Liquid	Liquid	ISOPERIBOL	5
POMD	7 3	Molar enthalpy of solution, kJ/mol ; Liquid	Molality, mol/kg - 3; Liquid	Temperature, K; Liquid Pressure, kPa; Liquid	Liquid	ISOPERIBOL	7

Thermodynamics Research Center / ThermoML | Thermochimica Acta

Effect of electrostatic interaction on thermochemical behavior of 12-crown-4 ether in various polar solvents

Barannikov, V. P.[Vladimir P.], Guseynov, S. S.[Sabir S.], Vyugin, A. I.[Anatoliy I.]

ABSTRACT