AbstractA new method of interpreting gas‐chromatographic (GC) data for determining solvents for thermally stable polymers has been developed. An equation is derived for molar Gibbs energy of sorption in terms of chromatographically measured parameters. The polymer used in this study is poly(5,5′‐bibenzimidazole‐2,2′‐diyl‐1,3‐phenylene), or PBI. A battery of 40 compounds, including solvents and nonsolvents for PBI, was studied. This method involves determining molar heats of sorption and molar Gibbs energies of sorption at infinitely dilute surface coverage. Mathematical correlations between the measured thermodynamic quantities and the solvent polarizabilities and dipole moments were developed. From these correlations it was possible to explain the behavior of known solvents of PBI and predict new solvents for this polymer. The results of the interpretation of GC data were supported by quantitative solubil
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