This work examined the effect of sulfate ions on the rate of decomposition of H2O2 by Fe(III) in homogeneous aqueous solutions. Experiments were carried out at 25 degrees C, pH < or = 3 and the concentrations of sulfate ranged from 0 to 200 mM ([Fe(III)]0 = 0.2 or 1 mM, [H2O2]0 = 10 or 50 mM). The spectrophometric study shows that addition of sulfate decreased the formation of iron(III)-peroxo complexes and that H2O2 does not form complexes with iron(III)-sulfato complexes. The rates of decomposition of H2O2 markedly decreased in the presence of sulfate. The measured rates were accurately predicted by a kinetic model based on reactions previously validated in NaClO4/HClO4 solutions and on additional reactions involving sulfate ions and sulfate radicals. At a fixed pH, the pseudo-first-order rate constants were found to decrease linearly with the molar fraction of Fe(II) complexed with sulfate. The model was also able to predict the rate of oxidation of a probe compound (atrazine) by Fe(III)/H2O2. Computer simulations indicate that the decrease of the rate of oxidation of organic solutes by Fe(III)/H2O2 can be mainly attributed to the complexation of Fe(III) by sulfate ions, while sulfate radicals play a minor role on the overall reaction rates.
An attempt has been made in this review to provide some insights into the possible adsorption mechanisms of hexavalent chromium onto layered double hydroxides-based adsorbents by critically examining the past and present literature. Layered double hydroxides (LDH) nanomaterials are typical dual-electronic adsorbents because they exhibit positively charged external surfaces and abundant interlayer anions. A high positive zeta potential value indicates that LDH has a high affinity to Cr(VI) anions in solution through electrostatic attraction. The host interlayer anions (i.e., Cl -, NO3 -, SO4 2-, and CO3 2-) provide a high anion exchange capacity (53-520 meq/100g) which is expected to have an excellent exchangeable capacity to Cr(VI) oxyanions in water. Regarding the adsorptioncoupled reduction mechanism, when Cr(VI) anions make contact with the electron-donor groups in the LDH, they are partly reduced to Cr(III) cations. The reduced Cr(III) cations are then adsorbed by LDH via numerous interactions, such as isomorphic substitution and complexation. Nonetheless, the adsorption-coupled reduction mechanism is greatly dependent on: (1) the nature of divalent and trivalent salts utilized in LDH preparation, and (2) the types of interlayer anions (i.e., guest intercalated organic anions). The low Brunauer-Emmett-Teller specific surface area of LDH (1.80-179 m 2 /g) suggests that pore filling played an insignificant role in Cr(VI) adsorption. The Langmuir maximum adsorption capacity of LDH (Q o max) toward Cr(VI) was significantly affected by the used inorganic salt natures and synthetic methods of LDH. The Q o max values range from 16.3 mg/g to 726 mg/g. Almost all adsorption processes of Cr(VI) by LDH-based adsorbent occur spontaneously (∆G° <0) and endothermically (∆H° >0) and increase the randomness (∆S° >0) in the system. Thus LDH has much potential as a material that can effectively remove anion pollutants, especially Cr(VI) anions in industrial wastewater.
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