The purpose of this paper is to study the surface energetics of the polymer excipient cellulose acetate propionate (CAP) in the solid form. The net retention volumes, VN, for n-alkanes and polar solutes have been measured in the temperature range 353.15–403.15 K by inverse gas chromatography. The dispersive surface free energy, γSd\documentclass[12pt]{minimal}
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\begin{document}$$ \gamma_{\text{S}}^{\text{d}} $$\end{document}, and Lewis acid–base parameters Ka\documentclass[12pt]{minimal}
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\begin{document}$$ K_{\text{a}} $$\end{document} and Kb\documentclass[12pt]{minimal}
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\begin{document}$$ K_{\text{b}} $$\end{document}, have been determined using VN values. The γSd\documentclass[12pt]{minimal}
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\begin{document}$$ \gamma_{\text{S}}^{\text{d}} $$\end{document} values are decreased linearly with increase of temperature. The γSd\documentclass[12pt]{minimal}
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\begin{document}$$ \gamma_{\text{S}}^{\text{d}} $$\end{document} value at 353.15 K is 24.50 ± 1.54 mJ/m2, and the temperature gradient was found to be −0.287 mJ/m2/K1. The Ka\documentclass[12pt]{minimal}
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\begin{document}$$ K_{\text{b}} $$\end{document} values are 0.410 ± 0.021 and 1.708 ± 0.388, respectively, which suggest that the CAP solid surface contain relatively more basic sites. The Ka and Kb values of CAP are compared with the similar values obtained on the cellulose acetate butyrate solid surface.