Iron oxide acid-base adsorption

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 ... 

Iron oxides have been known to adsorb either acids or bases (25). The ratio of acidic to basic sites can be estimated by a method developed by Manson and Straume (31), based on the adsorption of... 

The phenomena presented in this book were discussed in many reviews. For example, Schwarz [13] discussed methods used to characterize the acid base properties of catalysts. The review on sorption on solid - aqueous solution interface by Parks [14] includes also principles of surface science. The book Environmental Chemistry of Aluminum edited by Sposito reviews the solution and surface chemistry of aluminum compounds. Chapter 3 [15] provides thermochemical data for aluminum compounds. Chapter 5 [16] lists the points of zero charge of aluminum oxides, oxohydroxides and hydroxides with many references on adsorption of metal cations and various anions on these materials. Unlike the present book, which is confined to sorption from solution at room temperature, publications on coprecipitation and adsorption from gas phase or at elevated temperatures are also cited there. Brown et al. [17] reviewed on dry and wet surface chemistry of metal oxides. Stumm [18] reviewed sorption of ions on iron and aluminum oxides. The review by Schindler and Stumm [19] is devoted to surface charging and specific adsorption on oxides. Schindler [19] published a review on similar topic in German. Many other reviews related to specific topics are cited in respective chapters. 

Systems such as iron on an acid-base-type support follow Mechanism 2 or 3 (both are two-step pathways). Mechanism 2 proposes the occurrence of RWGS reaction coupled with dehydrogenation of EB in the presence of CO2. In this mechanistic pathway, the acid-base bifunctionality of the catalyst plays an important role in C02-mediated oxidative dehydrogenation reactions [49]. The acid properties of the catalyst are important in the activation of EB, whereas the basic sites are for CO2 adsorption to form carbonates for hydrogen blockage. The cooperative action of acid sites and basic sites is fundamental [49]. 

Silica gel and aluminium oxide layers are highly active stationary phases with large surface areas which can, for example, — on heating — directly dehydrate, degrade and, in the presence of oxygen, oxidize substances in the layer This effect is brought about by acidic silanol groups [93] or is based on the adsorption forces (proton acceptor or donor effects, dipole interactions etc) The traces of iron in the adsorbent can also catalyze some reactions In the case of testosterone and other d -3-ketosteroids stable and quantifiable fluorescent products are formed on layers of basic aluminium oxide [176,195]... 

Metal oxides have surface sites which are acidic, basic, or both and these characteristics control important properties such as lubrication, adhesion, and corrosion. Some of the newer infrared techniques such as lazer-Raman and Fourier transform infrared reflection spectroscopy are important tools for assessing just how organic acids and bases interact with the oxide films on metal surfaces. Illustrations are given for the adsorption of acidic organic species onto aluminum or iron surfaces, using Fourier transform infrared reflection spectroscopy. 

Carbon monoxide, a soft base, is expected to interact with a soft acidic surface site (19), The octahedral iron cations (+2.5 average oxidation state) are the softer of the acid sites on magnetite and may be expected to provide CO adsorption sites. The initial interaction should result in a carbonyl surface species, and such species have been observed by infrared spectroscopy (20-22)t... 

Faulkner, Hopkinson, and Cundy, 2005). Because of the adverse effect of OH on soil remediation, due to the immobilization of many metal ions by precipitation in alkalinized soils, and the reduced efficiency of electrokinetic remediation when sacrificial iron-rich electrodes are employed (e.g. Leinz, Hoover, and Meier, 1998), noncorrosive electrodes and techniques to minimize soil alkalinization are generally employed for electrokinetic remediation (e.g. Rohrs, Ludwig, and Rahner, 2002 Virkutyte, Sillanpaa, and Latostenmaa, 2002). However, low adsorption of Cr(VI) in soils occurs in alkaline conditions, whereas high adsorption of Cr(VI) is favored in acidic conditions (Reddy et al, 1997). Furthermore, the reduction of Cr(VI) to Cr(III) by the delivery of iron (Fe°, Fe " ) is fairly well documented (Rai, Sass, and Moore, 1987 Eary and Rai, 1991 Haran et aL, 1995 Powell et aL, 1995 Pamukcu, Weeks, and Wittle, 1997 Batchelor et al., 1998 Reddy et /., 2003). Accordingly,under an applied direct current (DC) electric field, stabilization of Cr(VI)-contaminated soils may potentially be achieved where oxidative dissolution of iron-rich anodic electrodes provides Fe(j,q) to react with the anode-bound migration of Cr(VI). Hence, the use of iron-rich sacrificial electrodes and soil alkalinization may find application in the electrokinetic stabilization of Cr(VI)-contaminated soils. This concept is explained in this chapter based on the results of laboratory stabilization experiments on three Cr(VI)-impacted soils taken from three sites within the UK. 

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