Adsorption on iron oxide

Liu F, De Cristofaro A, Violante A (2001) Effect of pH phosphate and oxalate on the adsorption/desorption of arsenate on/from goethite. Soil Sci 166 197-208 Livesey NT, Huang PM (1981) Adsorption of arsenate by soils and its relation to selected properties and anions. Soil Sci 131 88-94 Manceau A (1995) The mechanism of anion adsorption on iron oxides Evidence for the bonding of arsenate tetrahedra on free Fe(0, OH)6 edges. Geochim Cosmochim Acta 59 3647-3653. 

Adsorption and desorption reactions of protons on iron oxides have been measured by the pressure jump relaxation method using conductimetric titration and found to be fast (Tab. 10.3). The desorption rate constant appears to be related to the acidity of the surface hydroxyl groups (Astumian et al., 1981). Proton adsorption on iron oxides is exothermic potentiometric calorimetric titration measurements indicated that the enthalpy of proton adsorption is -25 to -38 kj mol (Tab. 10.3). For hematite, the enthalpy of proton adsorption is -36.6 kJ mol and the free energy of adsorption, -48.8 kJ mol (Lyklema, 1987). 

The adsorption of ions on iron oxides regulates the mobility of species in various parts of the ecosystem (biota, soils, rivers, lakes, oceans) and thereby their transport betv een these parts. Examples are the uptake of plant nutrients from soil and the movement of pesticides and other pollutants from soils into aquatic systems. In such environments various ions often compete with each other for adsorption sites. Adsorption is the essential precursor of metal substitution (see Chap. 3), dissolution reactions (see Chap. 12) and many interconversions (see Chap. 14). It also has a role in the synthesis of iron oxides and in crystal growth. In industry, adsorption on iron oxides is of relevance to flotation processes, water pollution control and waste and anticorrosion treatments. 

Studies of adsorption on iron oxides have followed two main lines ... 

Anion adsorption on iron oxides is frequently described by this equation whereas cation adsorption data is often fitted to the Freundlich equation, i.e. 

Manceau, A. (1995) The mechanism of anion adsorption on iron oxides. Evidence for the bonding of arsenate tetrahedra at free Fe(0, OH) edges. Geochim. Cosmochim. Acta 59 3647-3653... 

Parfitt, R.L. Smart, R.S.C. (1977) Infrared spectra from binuclear bridging complexes of sulphate adsorbed on goethite (a-FeOOH). J. Chem. Soc. Faraday Trans. I. 73 796-802 Parfitt, R.L. Smart, R.S.C. (1978) The mechanism of sulfate adsorption on iron oxides. Soil Sci. Soc. Am. J. 42 48-50 Parfitt, R.L. (1980) Chemical properties of variable charge soils. In Theng, B.K. (ed.) Soils with variable charge. N. Z. Soc. Soil Sci., Lower Hutt. N. Z., 167-194 Parfitt, R.L. (1982) Competitive adsorption of phosphate and sulphate on goethite (a-FeOOH) A note. New Zealand J. Sci. 25 147-148... 

Peak, D. Sparks, D.L. (2002) Mechanisms of selenate adsorption on iron oxides and hydroxides. Envir. Sci. Techn. 36 1460-1466 Peak, D., Ford, R.G. Sparks, D.L. (1999)... 

Test of this proposal are under way, using bases of known Cb and Eg from Drago s tables, and measuring heats of adsorption on iron oxide and on silica from solutions in various hydrocarbons. 

The acidic sites on iron oxides are believed to be FeOH sites (32), much like the well-known SiOH sites on silica. Heats of adsorption on iron oxide of bases of known Cg and Eg, having appreciably different ratios of Cg to Eg ("hardness" or "softness"), allow estimation of the and for the acidic sites of iron oxide. Our initial studies were done by measuring adsorption isotherms at two or more temperatures (Figure 7) and from the temperature coefficient of the equilibrium constant K the enthalpy of adsorption was calculated. In Figure 7 the adsorption data is plotted as a Langmuir isotherm ... 

There is no particular a priori reason to suspect that oxygen production was any different from that in the modern ocean, except that there may have been constraints imposed by different availabilities of key nutrients such as phosphorus (Bjerrum Canfield 2002). Today, the availability of fixed nitrogen may constrain productivity on geological time scales (Falkowski 1997), but in the Archaean phosphorus removal by adsorption on iron oxides could have reduced P availability, significantly reducing productivity compared with today. 

Cowan, C. E., Zachara, J. M., and Resch, C. T. (1991). Cadmium adsorption on iron oxides in the presence of alkaline-earth elements. Environ. Sci. Technol. 25, 437-446. 

Cations and anions that adsorb by forming short directional bonds with the surface cannot be considered to be indifferent in character. These ions actually alter the surface charge by the very process of adsorption, and their bonding is classified as chemical adsorption (or chemisorption) in this text. Examples of chemisorption include copper and phosphate adsorption on iron oxides ... 

As iron oxides / oxyhydroxide have a very high affinity for the adsorption of anions as well as cations under natural conditions the early diagenetic reactivity of iron is often of great significance for the behavior of compounds such as trace metals, phosphate and organic acids. The adsorption on iron oxides is caused by the... 

The method developed here for the description of chemical equilibria including adsorption on charged surfaces was applied to interpret phosphate adsorption on iron oxide (9), and to study electrical double-layer properties in simple electrolytes (6), and adsorption of metal ions on iron oxide (10). The mathematical formulation was combined with a procedure for determining constants from experimental data in a comparison of four different models for the surface/solution interface a constant-capacitance double-layer model, a diffuse double-layer model, the triplelayer model described here, and the Stem model (11). The reader is referred to the Literature Cited for an elaboration on the applications. 

The objective of the present study is to examine the desorption kinetics of Cd following its adsorption on iron oxides. To simulate the effects of organic ligands in soil rhizosphere environment and chloride-bearing fertilizer, Cd desorption caused by citrate, acetate and chloride was investigated. 

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