0000000000427026
AUTHOR
R. Horst
(Vapour + liquid) equilibria of (water + dimethylformamide): application of the headspace-gas chromatography for the determination of thermodynamic interactions
Abstract Isothermal measurements of the partial vapour pressures have been carried out on {water + dimethylformamide (DMF)} at temperatures betweenT=305.15 K andT=323.15 K using an apparatus composed of a headspace sampler and a normal gas chromatograph. These data were simultaneously evaluated in one step with respect to the (composition dependent, integral) Flory-Huggins interaction parametergby means of a new method which minimizes the Gibbs energy of mixing and does not require chemical potentials. The expression forggiven by Koningsveld and Kleintjens, originally designed for polymer solutions, describes the present results best.
Computation of Unstable Binodals Not Requiring Concentration Derivatives of the Gibbs Energy
The equilibrium of three liquid phases in a binary mixture implies the existence of tie lines and binodals that are different from the normal experimentally observable ones. First of all, there are the metastable extensions of the binodal built up by S/S tie lines. These S/S tie lines fulfill the equilibrium condition of the minimum of the Gibbs energy of the entire two-phase system. Both coexisting phases are located within the meta(stable) region. There are two additional types of tie lines: U/U (maximum of the Gibbs energy; both end points within the unstable area) and U/S tie lines (saddle point; one end point within the (meta)stable, the other within the unstable region). All types of…