Solubility of gases in a hydroformylation solvent

The solubility of reactants used in homogeneously catalyzed hydroformylation of alkene was studied in a pressurized, semi-batch autoclave. The solubilities of alkene, carbon monoxide and hydrogen in the 2,2,4-trimethyl-1,3-pentanediol mono(2-methylpropanoate) solvent (NX 795) were determined by precise pressure and weight measurements. The measured solubilities were tested against empirical and theoretical models. Logarithmic empirical models gave a very good fit to experimental solubility data. To obtain nonempirical equations for the gas solubility, thermodynamic models based on activity coefficients and equations of state were used. The activity coefficient models based on regular solution theory (RST) predicted the solubilities well, but the selection of the model is the critical issue. For 1-butene, the best prediction was provided by the Yen and McKetta modification of the RST, whereas for carbon monoxide and hydrogen it was necessary to include a mixing entropy term in the RST. The Soave–Redlich–Kwong equation of state gave a fairly good prediction of the solubilities, but not as good as the RST-based models.