Temperature dependence of Henry's law constant in an extended temperature range.
The Henry's law constants H for chloroform, 1,1-dichloroethane, 1,2-dichloropropane, trichloroethene, chlorobenzene, benzene and toluene were determined by the EPICS-SPME technique (equilibrium partitioning in closed systems--solid phase microextraction) in the temperature range 275-343 K. The curvature observed in the ln H vs. 1/T plot was due to the temperature dependence of the change in enthalpy delta H0 during the transfer of 1 mol solute from the aqueous solution to the gas phase. The nonlinearity of the plot was explained by means of a thermodynamic model which involves the temperature dependence of delta H0 of the compounds and the thermal expansion of water in the three-parameter equation ln (H rho TT) = A2/T + BTB + C2, where rho T is the density of water at temperature T, TB = ln(T/298) + (298-T)/T, A2 = -delta H298(0)/R, delta H298(0) is the delta H0 value at 298 K, B = delta Cp0/R, and C2 is a constant. delta Cp0 is the molar heat capacity change in volatilization from the aqueous solution. A statistical comparison of the two models demonstrates the superiority of the three-parameter equation over the two-parameter one ln H vs. 1/T). The new, three-parameter equation allows a more accurate description of the temperature dependence of H, and of the solubility of volatile organic compounds in water at higher temperatures.
Institute of Physical Chemistry, University of Szeged, P.O. Box 105, H-6701 Szeged, Hungary. gorgenyi@chem.u-szeged.hu
Miklós
M
Görgényi
Jo
J
Dewulf
Herman
H
Van Langenhove
D009930:Organic Chemicals / Q000737:chemistry*; D013696:Temperature; D013816:Thermodynamics
D009930:Organic Chemicals