outer sphere complexes
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Author(s):  
Tatyana Rakitskaya ◽  
Tatyana Kiose ◽  
Lyudmila Raskola

The effect of the nature and concentration of d-metal salts attached to synthetic zeolites NaA and KA on the kinetic and stoichiometric parameters of the chemisorption-catalytic oxidation of sulphur dioxide with air oxygen at ambient temperature was studied. It was found that the adsorption capacity of NaA zeolite relative to SO2 is 100 times higher than that of KA zeolite; the time of protective action of NaA and KA zeolites increases upon modification with transition metal salts and with an increase of their content in the compositions. It was shown that the formation of inner and outer sphere complexes and the relationship between them is determined by the nature and concentration of metal ions and by the nature of the carrier. It was proven that the chemisorption-catalytic process ends with the oxidation of SO2 to H2SO4.


Minerals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 195
Author(s):  
Eloise C. Lewis ◽  
Nelson Y. Dzade

The mobility of arsenic in aqueous systems can be controlled by its adsorption onto the surfaces of iron oxide minerals such as cobalt ferrite (Fe2CoO4). In this work, the adsorption energies, geometries, and vibrational properties of the most common form of As(III), arsenous acid (H3AsO3), onto the low-index (001), (110), and (111) surfaces of Fe2CoO4 have been investigated under dry and aqueous conditions using periodic density functional theory (DFT) calculations. The dry and hydroxylated surfaces of Fe2CoO4 steadily followed an order of increasing surface energy, and thus decreasing stability, of (001) < (111) < (110). Consequently, the favourability of H3AsO3 adsorption increased in the same order, favouring the least stable (110) surface. However, by analysis of the equilibrium crystal morphologies, this surface is unlikely to occur naturally. The surfaces were demonstrated to be further stabilised by the introduction of H2O/OH species, which coordinate the surface cations, providing a closer match to the bulk coordination of the surface species. The adsorption complexes of H3AsO3 on the hydroxylated Fe2CoO4 surfaces with the inclusion of explicit solvation molecules are found to be generally more stable than on the dry surfaces, demonstrating the importance of hydrogen-bonded interactions. Inner-sphere complexes involving bonds between the surface cations and molecular O atoms were strongly favoured over outer-sphere complexes. On the dry surfaces, deprotonated bidentate binuclear configurations were most thermodynamically favoured, whereas monodentate mononuclear configurations were typically more prevalent on the hydroxylated surfaces. Vibrational frequencies were analysed to ascertain the stabilities of the different adsorption complexes and to assign the As-O and O-H stretching modes of the adsorbed arsenic species. Our results highlight the importance of cobalt as a potential adsorbent for arsenic contaminated water treatment.


2019 ◽  
Vol 64 (10) ◽  
pp. 1091-1104
Author(s):  
O. N. Karaseva ◽  
L. I. Ivanova ◽  
L. Z. Lakshtanov

Strontium adsorption has been studied by the method of acid-base potentiometric titrations at three different temperatures: 25, 50, 75C. The effect of pH, ionic strength, sorbate/sorbent ratio, and temperature on adsorption was investigated. Experimental data were simulated using two various surface complexation models, with two different electrostatic descriptions of the interface: the constant capacitance model (CCM) and the triple-layer model (TLM). Although the both models used are able to account for the acid-base reactions and surface complexation of strontium on birnessite, we consider that the TLM is more applicable for a description of heterophaseous system H+ MnOH Sr2+. Under conditions of low ionic strength and negatively charged surface, Sr2+ ions compete with the electrolyte ions and form outer-sphere complexes along with inner-sphere complexes. Consequently, using the CCM for description of strontium adsorption data could be mathematically satisfactory, but physically senseless. The equilibrium model proposed here consists of the complexes of inner (MnOHSr2+, MnOSr+, MnOSrOH0) and outer types ([MnO Sr2+]+). The corresponding intrinsic equilibrium constants of the formation of these surface complexes were calculated for 25,50, and 75C.


2011 ◽  
Vol 63 (4) ◽  
pp. 818-824 ◽  
Author(s):  
Antri Demetriou ◽  
Ioannis Pashalidis

The paper presents and discusses the effect of various physicochemical parameters (e.g. pH, ionic strength, Cr(VI) initial concentration, amount of the adsorbent, temperature and contact time between metal ion and adsorbent) on the adsorption efficiency of Cr(VI) on dunite in aqueous solutions under atmospheric conditions. Evaluation of the experimental data shows that dunite presents increased affinity for Cr(VI) over a wide pH range and Cr(VI) concentration, and the experimental data are well fitted by the Kd adsorption model. The relative adsorption is pH dependent and decreases slightly (about 10%) with increasing pH, because of changes in the surface charge of the solid. The effect of the ionic strength is significant (particularly at low pH), indicating the predominance of outer-sphere complexes. Moreover, adsorption experiments at various temperatures, two different pH values (pH 3 and pH 8) and three different ionic strengths (0.0, 0.1 and 1.0 M NaClO4), indicate an endothermic but spontaneous entropy-driven processes.


2009 ◽  
pp. 7342 ◽  
Author(s):  
William J. Evans ◽  
Justin R. Walensky ◽  
Joseph W. Ziller

2008 ◽  
Vol 42 (20) ◽  
pp. 7601-7606 ◽  
Author(s):  
Eva Hartmann ◽  
Bart Baeyens ◽  
Michael H. Bradbury ◽  
Horst Geckeis ◽  
Thorsten Stumpf

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