Analysis of CO2 kinetics in Na,Cs-Rho crystals using the zero length column: a case study for slow systems

Experimental measurements of systems with slow gas transport kinetics are generally considered a relatively easier task when compared to the challenges of measurements of very fast systems. On the other hand, when the transport process goes towards time constants of the order of several hours, not only the measurements, but also the analysis and interpretation of the data offer challenges which make the assessment of the correct time constant of the process non trivial. In this work we used the measurements of CO2 diffusion in Na,Cs-Rho crystals, carried out using the zero length column (ZLC) technique, as a case study for the use of the technique for very slow adsorption processes. The system, which has a time constant of the order of 8 h, shows the importance of using the partial loading approach for the determination of an unambiguous time constant from the analysis of the ZLC desorption curves. The traditional analysis is refined by using the nonlinear ZLC model to take into account the isotherm nonlinearity that results in a concentration dependent diffusivity. Finally, the method proposed by Cavalcante is used to confirm the 3-D diffusion path of the system.