Revisiting the Effect of the Resistance to Gas Accumulation in Constant Volume Systems on the Membrane Time Lag.

The time-lag method is commonly used to determine membrane permeability, diffusivity and solubility in a single gas permeation experiment in a constant volume system. An unwritten assumption on which this method relies is that there is no resistance to gas accumulation in the downstream receiver of the system. However, this is not the case, even with the specially designed receiver used in this study when, in addition to tubing, the receiver utilizes an additional accumulation tank. The resistance to gas accumulation originates from a finite diffusivity (Knudsen diffusion) of gases in tubing, which are magnified by "resistance-free" accumulation tank(s). As a result of the resistance to gas accumulation, the time lag of the membrane is underestimated, which leads to an overestimation of gas diffusivity in the membrane. The experimentally predicted resistances in different configurations of the receiver, expressed by the difference in the time lag at two different receiver locations, were several times greater than the theoretically predicted values. A high molecular PPO membrane was used to demonstrate this effect. The time lags measured at different locations differed by as much as 30%. The diffusivity of nitrogen in a PPO of 4.04 × 10^-12 m²/s determined at the optimum configuration of the receiver is at least 50% lower than the literature-reported values.