| Abstract: | This article evaluates the influence of temperature on the sorption of gases in two isomers of polynorbornene. The subject polymers were stereoisomers with nearly identical bulk density and total free volume. Because of differences in the mobility of the polymer backbone, the isomers packed differently resulting in differences in the average free‐volume element size within the matrix. The influence of these differences on free‐volume element size was characterized by the heat of sorption of gases in the matrix. The most pronounced differences were observed in the isosteric heats of sorption of condensable carbon dioxide and methane in the polymer isomers. This analysis suggests that the relative space available for sorption into free‐volume elements is higher in the methyl II isomer relative to methyl III. These conclusions support the physical characterizations reported in Part I of this series suggesting that the methyl II isomer has larger average free‐volume elements but fewer of them than the methyl III isomer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1939–1946, 2003 |
