Mechanism of iodine vapor sorption in polyacetylene

Simultaneous measurements of weight uptake and conductivity variation during iodine vapor sorption of polyacetylenes (PA) at 20–25°C show that the sorption is a two-stages process. For the first stage, iodine diffusion to the fibrilar surface of the cis-rich and trans-rich PA is of Knudsen type pore diffusion as supported by the sorption measurements of hexane for the cis-rich PA, and has a diffusion coefficient in the order of 10⁷ cm²/sec. Conductivity of the PA rises rapidly and reaches a maximum at end of the stage. For the second stage, the diffusion is more restrictive and has a diffusion coefficient lower than the first stage by a factor of about 10 due to multilayer sorption of iodine, which leads to a decrease in the pore diameter and therefor the diffusion rate. In addition to the restricted diffusion in the second stage, diffusion of the iodine molecules adsorped on the fibrilar surface into the interior of the fibrils is appreciable for cis-rich PA (leading to a conductivity drop) and is negliglible for tran-rich PA (leading to insignificant variation in conductivity).