Retention of toxic chromium from aqueous phase by H3PO4-activated lignin: Effect of salts and desorption studies

In this study, the feasibility of using H₃PO₄-activated lignin for hexavalent chromium adsorption has been investigated. The composite of activated lignin was characterized using FTIR, XRD and SEM with EDAX analysis. It was observed that the pH had a strong effect on the adsorption capacity; adsorption of Cr(VI) was more favorable at acidic pH with maximum uptake at pH 2. The adsorption equilibrium data were best represented by Koble-Corrigan isotherm. The monolayer sorption capacity obtained from the Langmuir model was found to be 77.85 mg/g. Adsorption showed pseudo-second order rate kinetics and the process involving the rate-controlling step is complex as it involves both film and intraparticle diffusion processes. The NaOH desorbing agent was able to release approximately 84% of metal ions. Thermodynamic parameters showed that the sorption process is exothermic and non-spontaneous. The overall Cr(VI) retention on the activated lignin surface perhaps includes both the physical adsorption of Cr(VI) and the consequent reduction of Cr(VI) to Cr(III). (C) 2011 Elsevier B.V. All rights reserved.

Desorption processes and the deuterium fractionation in molecular clouds

Several processes have been suggested as ways of returning accreted grain mantles to the gas, thus preventing the total removal of molecules from the gas phase in dark quiescent clouds. We attempt to distinguish between them by considering not only the calculated gas-phase abundances, but also the ratio of the abundances of deuterated species to non-deuterated species. We find that the D/H ratio in molecules is relatively model-independent, but that desorption due to the formation of H-2 on grains gives the best overall agreement with the observations.

IR laser desorption of oligonucleotides A novel gas phase target for radiation damage studies

The desorption of oligonucleotides by 3 mu m laser irradiation has been studied by laser induced fluorescence imaging of the resulting gas phase plumes. Fitting of the plume data has been achieved by using a modified Maxwell Boltzmann distribution which incorporates a range of stream velocities. Spatial density profiles, velocities and temperature variation have been determined from these fits indicating that the oligonucleotide plume only achieves a partial thermal relaxation. This laser desorption technique may provide a means of overcoming the limited mass range of gas phase biomolecules available from thermal evaporation techniques.

Hysteretic adsorption and desorption of hydrogen by nanoporous metal-organic frameworks

Adsorption and desorption of hydrogen from nanoporous materials, such as activated carbon, is usually fully reversible. We have prepared nanoporous metal-organic framework materials with flexible linkers in which the pore openings, as characterized in the static structures, appear to be too small to allow H-2 to pass. We observe hysteresis in their adsorption and desorption kinetics above the supercritical temperature of H-2 that reflects the dynamical opening of the "windows" between pores. This behavior would allow H-2 to be adsorbed at high pressures but stored at lower pressures.

Guest sorption and desorption in the metal-organic framework [Co(INA)(2)] (INA = isonicotinate) - evidence of intermediate phases during desorption

The metal-organic framework [Co(INA)(2)].0.5EtOH (INA = isonicotinate, NC5H4-4-CO2-), 1 was synthesised under solvothermal conditions. Its X-ray crystal structure shows channels containing ethanol guests which are hydrogen-bonded to carboxylate oxygens of the framework. The pyridyl rings of the framework alternate between `open' and `closed' positions along the channels resulting in large variation in the channel cross-sectional area from ca. 1.4 by 2.3 at the narrowest point to 4.9 by 5.3 at the widest. Despite the very small windows, the ethanol guests (of van der Waals diameter ca. 4.2-6.1 Angstrom) may be reversibly desorbed and sorbed into the structure quantitatively, as shown by in situ variable-temperture IR spectroscopy and XRPD. The single-crystal structure of the desolvated form [Co(INA)(2)]2 shows that there is no change in the overall connectivity on desolvation, but the rotational positions of the pyridine rings are altered. This suggests that pyridyl rotation may occur to allow guests to pass in and out. When the synthesis was conducted in 1-propanol solvent [Co(INA)(2)].0.5Pr(n)OH.H2O 3, was obtained, and a single-crystal X-ray structure revealed the same overall connectivity as in 1 but with pyridine rings disordered over closed and open positions. There was no evidence of included guests from X-ray crystallography, suggesting that they are also highly disordered. Variable-temperature XRPD performed on bulk samples showed peaks which were unsymmetrical and exhibited shoulders, suggesting that for each pattern obtained the material actually consisted of several closely-related phases. The movements of the peaks during desolvation showed the presence of intermediate phases before the final desolvated product was formed. The peak positions of the intermediate phases matched more closely with the calculated pattern for 3 than with 1 or 2, suggesting that they may have disordered structures similar to 3. The results also suggest that the intermediate phase represents an initial increase in volume before a larger decrease in volume occurs to give the final desolvated material.