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.

Biosorption of toxic chromium from aqueous phase by lignin: mechanism, effect of other metal ions and salts

Surface reaction methodology was implicated in the optimization of hexavalent chromium removal onto lignin with respect to the process parameters. The influence of altering the conditions for removal of chromium(VI), for instance; solution pH, ionic strength, initial concentration, the dose of biosorbent, presence of other metals (Zn and Cu), presence of salts and biosorption-desorption studies, were investigated. It was found that the biosorption capacity of lignin depends on solution pH, with a maximum biosorption capacity for chromium at pH 2. Experimental equilibrium data were fitted to five different isotherm models by non-linear regression method, however, the biosorption equilibrium data were well interpreted by the Freundlich isotherm. The maximum biosorption capacities (q(max)) obtained using Dubinin-Radushkevich and Khan isotherms for Cr(VI) biosorption are 31.6 and 29.1 mg/g. respectively. Biosorption showed pseudo second order rate kinetics at different initial concentrations of Cr(VI). The intraparticle diffusion study indicated that film diffusion may be involved in the current study. The percentage removal of chromium on lignin decreased significantly in the presence of NaHCO3 and K2P2O7 salts. Desorption data revealed that nearly 70% of the Cr(VI) adsorbed on lignin could be desorbed using 0.1 M NaOH. It was evident that the biosorption mechanism involves the attraction of both hexavalent chromium (anionic) and trivalent chromium (cationic) onto the surface of lignin. (C) 2011 Elsevier B.V. All rights reserved.

An Introduction to the Special issue - Housing in Hard Times: Marginality, Inequality and Class, with Kim McKee

‘Housing in Hard Times’ was the theme of the Housing Studies Association annual conference in April 2011. The papers featured in this special issue are drawn from that conference. They examine the uneven impact of economic change on housing policy and related areas, with reference to conceptual ideas pertaining to urban marginality, inequality and class. Whilst the empirical focus of the papers is the UK, their intellectual contribution represents an attempt to ‘bring class back in’ to the housing studies literature and encourage more critical, theoretically informed scholarship.

Reactivity difference between protolytic forms of some macrocyclic chromium(III) complexes in ligand substitution and electron transfer processes

The review provides insight into the mechanism of ligand substitution and electron transfer (from chromium(III) to iron(III)) by comparison of the reactivity of some tetraazamacrocyclic chromium(III) complexes in the conjugate acid-base forms. Use of two geometrical isomers made possible to estimate the influence of geometry and protolytic reactions in trans and cis position towards the leaving group on the rate enhancement. Studies on the reaction rates in different media demonstrated the role played by outer sphere interactions in a monodentate ligand substitution. (C) 2009 Published by Elsevier B.V.

Kinetics and mechanism of a macrocyclic chromium(III) complex oxidation to chromium(IV) by hexacyanoferrate(III) in strongly alkaline media

Oxidation of the macrocyclic Cr(III) complex cis-[Cr(cycb)(OH)(2)](+), where cycb = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, by an excess of the hexacyanoferrate( III) in basic solution, slowly produces Cr(V) species. These species, detected using e.p.r. spectroscopy, are stable under ambient conditions for many hours, and the hyperfine structure of the e.p.r. spectrum is consistent with the interaction of the d-electron with four equivalent nitrogen nuclei. Electro-spray ionization mass spectrometry suggests a concomitant oxidation of the macrocyclic ligand, in which double bonds and double bonded oxygen atoms have been introduced. By comparison basic chromate(III) solutions are oxidized rapidly to chromate(VI) by hexacyanoferrate(III) without any detectable generation of stable Cr(V) intermediates.

OXIDATIVE DISSOLUTION OF CHROMIUM(III) OXIDES BY METAPERIODATE IONS IN PERCHLORIC-ACID

The kinetics of oxidative dissolution of a number of different samples of chromium(III) oxide by periodate ions in 1 mol dm-3 HClO4 solution have been studied and the results interpreted using the inverse-cubic rate law. The metaperiodate acts as a two-electron oxidant and the overall reaction stoichiometry involves the reaction of 3 mol of periodate with 1 mol of Cr(III) oxide. From a detailed study of the kinetics of dissolution the rate-determining step appears to be the reaction between an adsorbed periodate ion and its associated Cr(III) oxide surface site, with inhibition by one of the reaction products, iodate, through competitive adsorption. Analysis of the kinetic data generates values for the Langmuir adsorption coefficients for periodate and iodate ions on highly hydrated Cr(III) oxide of 84 +/- 8 and 2600 +/- 370 dm3 mol-1, respectively. The Cr(III) oxide-periodate reaction has a high overall activation energy, 82 +/- 6 kJ mol-1. The kinetics of dissolution of highly hydrated Cr(III) oxide under conditions in which the simple inverse-cubic rate law function does not apply can be successfully predicted using a simple kinetic model.