The Kinetics of Uptake of Cu++ Ions in Ionac SR-5 Cation Exchange Resin

The kinetics of sorption of Cu⁺⁺ ions in a typical cation exchange resin (IONAC SR-5) have been studied by two methods; the traditional batch method which involves following the change in Cu⁺⁺ concentration in a solution of finite volume in contact with the resin, and by removing and sectioning individual resin particles to follow the progress of the adsorption front. The results obtained by both methods are consistent. The equilibrium isotherm for this system is of highly favorable (Langmuir) form and the uptake kinetics show a clear transition from linear Fickian behavior at low concentrations to irreversible (shrinking core) behavior at high concentrations. The addition of ammonia to the system has little effect on the equilibrium isotherm but the intraparticle diffusivity is increased by a factor of about four. This may be due to reduction in the degree of hydration of the cuprammonium ion in comparison with uncomplexed Cu⁺⁺.     

Combining macroscopic and microscopic diffusion studies in zeolites using NMR techniques

In this study the zero length column (ZLC) technique is extended to the case where the decay of the adsorbed phase concentration is observed directly by nuclear magnetic resonance (NMR). An adsorption-desorption apparatus compatible with a 400-MHz NMR spectrometer was developed. It operates with nitrogen or helium as the inert purge gas. The column of the adsorbent material is placed in the sensitive region of the superconducting magnet and the rf coil of the NMR spectrometer. The time scales of the adsorption and desorption processes depend on concentration, temperature and crystal shape and are found to be in the range of 1-10 min. From the desorption branch, the non-equilibrium ZLC-NMR measurements yield intracrystalline diffusion coefficients in the range of 10(-13) to 10(-11) m2/s for different alkanes in silicalite-1. These values are always found to be smaller than the values measured by pulsed field gradient NMR under equilibrium condition indicating that there must be additional transport resistance at the external surface of these silicalite-1 zeolite crystals.     

Monitoring molecular mass transfer in cation-free nanoporous host crystals of type AlPO-LTA

Micro-imaging is employed to monitor the evolution of intra-crystalline guest profiles during molecular adsorption and desorption in cation-free zeolites AlPO-LTA. The measurements are shown to provide direct evidence on the rate of intra-crystalline diffusion and surface permeation and their inter-relation. Complemented by PFG NMR and integral IR measurements, a comprehensive overview of the diffusivities of light hydrocarbons in this important type of host materials is provided.