Kakali Mukherjee

Chromium removal technologies

Chromium can exist in different oxidation states (e.g. 0, III, VI). Chromium can be both beneficial and toxic to animals and humans depending on its oxidation state and concentration. At low concentration, Cr(III) is essential for animal and human health. Chromium(VI) compounds are highly soluble, mobile and bioavailable compared to trivalent chromium. Chromium(VI) is dangerous for humans due to its toxicity and carcinogenic properties. The presence of hexavalent chromium in waste water is a potential hazard to aquatic animals and humans. Various methods are adopted for the removal of hexavalent chromium from industrial effluents. Among these different techniques, biosorption is the most promising one. In this process, the various components present in biomaterial reduce the toxic hexavalent chromium to non-toxic trivalent chromium. Algae, fungi and bacteria have biosorption properties, and cell walls are responsible for biosorption of dead biomaterial. But this process removes chromium from waste water very slowly. So for chemical modification of biosorbents, optimization of biosorption parameters is required to increase the effectiveness of this process.

Micellar catalysis on picolinic acid promoted hexavalent chromium oxidation of glycerol

Under pseudo-first-order conditions, monomeric Cr(VI) was found to be kinetically active in the absence of picolinic acid (PA), whereas in the PA-promoted path, the Cr(VI)–PA complex undergoes nucleophilic attack by the substrate to form a ternary complex which subsequently experiences redox decomposition, leading to glyceraldehydes and Cr(IV)–PA complex. The uncatalyzed path shows a second-order dependence on [H+], whereas the PA-catalyzed path shows zero-order dependence on [H+]. Both the uncatalyzed and PA-catalyzed path show a first-order dependence on [glycerol]T and [Cr(VI)]T. The PA-catalyzed path is first order in [PA]T. All these observations remain unaltered in the presence of externally added surfactants. The effect of the cationic surfactant cetyl pyridinium chloride (CPC) and anionic surfactant sodium dodecyl sulfate (SDS) on the PA-catalyzed path have been studied. CPC inhibits, whereas SDS accelerates the reaction. Here, SDS is a catalyst for glyceraldehydes production and at the same time reduction of carcinogenic hexavalent chromium to nontoxic trivalent chromium. The reaction proceeds simultaneously in both aqueous and micellar phase. Micellar effects have been explained by considering the preferential partitioning of reactants between the micellar and aqueous phase. The Menger–Portnoy model, Piszkiewicz cooperative model, and pseudo-phase ion exchange model have been tested to explain the observed micellar effect.

Efficient combination of promoter and catalyst for chromic acid oxidation of propan-2-ol to acetone in aqueous acid media at room temperature.

Oxidation of propan-2-ol to acetone was carried out in aqueous media at room temperature. The effect of promoter (PA, bpy, phen), micellar catalyst (SDS, CPC, TX-100) and their combination has been studied. The reactions were performed under the condition [Propan-2-ol]T≫[Cr(VI)]T at 30°C. Then kobs and half life of all the reaction were determined to identify which promoter and which combination are the most effective for this oxidation. Among the promoters phen accelerates the reaction most in aqueous media. In absence of promoters anionic surfactant SDS increases the rate more effectively than neutral surfactant TX-100. CPC retards the rate in comparison to aqueous media. The rate of the oxidation is highest in presence of the combination of bpy and SDS.

Micellar Catalysis on 1,10-Phenanthroline Promoted Chromic Acid Oxidation of Glycerol in Aqueous Media

Abstract On pseudo-first order conditions, the monomeric species of Cr(VI) was found to be kinetically active in the absence of phenanthroline (phen) whereas in the phen-promoted path, the Cr(VI)-phen complex undergoes a nucleophilic attack by glycerol to form a ternary complex which subsequently experience a redox decomposition leading to glyceraldehydes and Cr(III)-phen complex. The effect of the cationic surfactant, cetyl pyridinium chloride (CPC); anionic surfactant, sodium dodecyl sulphate (SDS) and nonionic surfactant, triton X-100 (TX-100) on the unpromoted and phen-promoted path have been studied. Micellar effects have been explained by considering the preferential partitioning of reactants between the micellar and aqueous phase.

A review of biphasic hydroformylation for long chain substrates

The regioselective hydroformylation reactions of long chain olefins catalyzed by different unmodified and modified Co-based, Rh-based catalysts are summarized. The mechanism of homogeneous hydroformylation reactions using Co-based/Rh-based catalysts (unmodified) showed inhibition of reaction rate due to higher partial pressure of CO and also caused difficulty in separating catalysts from the product mixture. Hydroformylation reactions in biphasic medium using water soluble catalysts (Rh, Co, Ru/TPPTS) with an effective surfactant, cetyltrimethylammonium bromide (CTAB), are discussed. The homogeneous biphasic systems are not applicable for long chain olefins due to their low solubility in aqueous phase.

Surfactant-assisted bioremediation of hexavalent chromium by use of an aqueous extract of sugarcane bagasse

Agricultural products and by-products are now widely used for removal of hexavalent chromium from waste water. This option is more efficient and less expensive than conventional physicochemical treatments. The purpose of this study was reduction of carcinogenic hexavalent chromium to non-toxic trivalent chromium by use of aqueous extracts of sugar cane bagasse, which contains a variety of reducing components, for example sugar. The rate of this process is accelerated by use of surfactant as catalyst.

Micellar Catalysis on Pentavalent Vanadium Ion Oxidation of Ethanol in Aqueous Acid Media

Abstract Vanadium(V) oxidation of ethanol follows a first order dependency on the concentration of ethanol, vanadium(V), H+ and HSO4–. These observations remain unaltered in the presence of externally added surfactants. The effect of the cationic surfactant (i.e., N-cetylpyridinium chloride [CPC]), anionic surfactant (i.e., sodium dodecyl sulphate [SDS]) and neutral surfactant (i.e., Triton X-100 [TX-100]) has been studied. CPC inhibits the reactions, whereas SDS and TX-100 accelerate the reaction to different extents. Observed effects have been justified by considering the hydrophobic and electrostatic interaction between the surfactants and reactants. SDS and TX-100 can be used as catalysts in the production of acetaldehyde from ethanol.

Surfactant-assisted bioremediation of hexavalent chromium from contaminated water

AbstractBioremediation is an efficient and cheap process for the removal of heavy metals. Solid agricultural wastes are frequently used as biosorbent for the removal of Cr(VI). In this study, water extract of Azadiracta indica sawdust is used to reduce Cr(VI) to Cr(III) and thereby lowering the toxicity. Water extract of A. indica sawdust effectively reduces hexavalent chromium at acidic pH (pH = 2). The reaction is irreversible. Trivalent chromium produced after reduction of Cr(VI) forms soluble organo-Cr(III) complex. Coordination of Cr(III) in the water extract occurs via the chelating coordination of –OH, –NH, etc, functional groups. The presence of these functional groups were confirmed from the IR spectra of the freeze-dried water extract, and the formation of Cr(III) is proved from the UV–vis spectra of the reaction mixture after the completion of reaction. But the rate of this reduction is very slow. Addition of nonfunctional surfactants increases the rate of reduction. Anionic surfactant sodium d...

Combination of Best Promoter and Micellar Catalyst for Cr(VI) Oxidation of Lactose to Lactobionic Acid in Aqueous Medium at Room Temperature

Abstract In aqueous acidic media, picolinic acid, 2,3-dipicolinic acid, and 2,6-dipicolinic acid promoted Cr(VI) oxidation of lactose to lactobionic acid has been carried out at room temperature. A possible reaction mechanism, which is based on the kinetic results and the product analysis, has been proposed. The anionic surfactant sodium dodecyl sulphate (SDS) and nonionic surfactant Triton-X-100 (TX-100) accelerate the process while the cationic surfactant N-cetylpyridinium chloride (CPC) retards the reaction.

Best combination of promoter and micellar catalyst for the rapid conversion of sorbitol to glucose

Kinetic data for oxidation of D-sorbitol to glucose by hexavalent chromium in aqueous medium and aqueous surfactant medium (SDS, TX-100) have been reported. Effect of promoter such as PA, bipy and phenanthroline on the reaction has been investigated. The reaction is performed under pseudo first order condition with an excess of substrate over the oxidant. The reaction is first order with respect to substrate and oxidant. The micelles have a catalytic effect on the reaction. Combination of phen and TX-100 produces almost twelve times increase in rate of oxidation.