Iron oxide, precipitation hydrolysis reactions

The most important synthetic routes to iron oxide pigments involve either thermal decomposition or aqueous precipitation processes. A method of major importance for the manufacture of a-Fe203, for example, involves the thermal decomposition in air of FeS04-7H20 (copperas) at temperatures between 500 °C and 750 °C. The principal method of manufacture of the yellow a-FeO(OH) involves the oxidative hydrolysis of Fe(n) solutions, for example in the process represented by reaction (1). 

In aqueous solutions, in which the most probable ligand is the water molecule, most of the lower oxid ation states (i.e. + 2, + 3 and some of the + 4 states) of transition metal ions are best regarded as hexaaqua complex ions, e.g. [Feu(H20)6]2 +. In these ions the six coordinated water molecules are those that constitute the first hydration sphere, and it is normally accepted that such ions would have a secondary hydration sphere of water molecules that would be electrostatically attracted to the positive central ion. The following discussion includes only the aqua cations that do not, at pH = 0, undergo hydrolysis. For example, the iron(III) ion is considered quite correctly as [Fe(H20)6]3 +, but at pH values higher than 1.8 the ion participates in several hydrolysis reactions, which lead to the formation of polymers and the eventual precipitation of the iron(III) as an insoluble compound as the pH value increases, e.g. ... 

Fe(OH)2 is prepared from Fe° solutions by precipitation with alkali. When freshly precipitated under an inert atmosphere (in a Schlenck apparatus for example) Fe(OH)2 is white (Bernal et al., 1959). It is, however, readily oxidized by air or even water upon which it darkens. Fe(OH)2 has the CdL type structure with hep anions and half of the octahedral interstices being filled with Fe ions. The crystals form hexagonal platelets. In solution Fe(OH)2 transforms by a combination of oxida-tion/de-hydration/hydrolysis reactions to other iron oxides and hydroxides. The end product depends both upon the order in which these processes occur and upon their rates. 

The diversity of reactions that are considered to be surface mediated has also increased over the past decade. It is not only strict sorption/desorption and precipitation/dissolution processes that are important but also the surface mediation of reactions such as electron transfer (eg. 14-17), hydrolysis 18) and various photochemical transformations. In addition certain solid phases, in particular metallic iron, iron oxides and smectitic clays, are capable of transferring electrons in and out of their bulk structure (eg. 19-23), When viewed in this context, minerals should not be considered as passive solids, or even as simple sources of a reactive surface but must be considered as bulk reactants. 

A trivalent iron solution is placed into a bowl flask and heated up to 80 °C under refluxing conditions for a period of time of 2 hours. A precipitate is formed and separated from supernatant. Trivalent iron cation is hydrolyzed due to an increment of temperature promoting the hydrolysis and forming a trivalent iron oxide-hydroxide (FeOOH). After the 2 hours of hydrolysis reaction, a yellowish precipitate is obtained. 

Sol-gel and precipitation methods are simple and commonly used wet-chemical synthesis methods of ceramic nanoparticles such as calcium phosphates, iron oxides, silica, titanium oxides, and zinc oxides. Basically, the sol-gel method uses inorganic precursors (i.e., meal salts or organometalhc molecules) that react in aqueous environment and subsequently form integrated network (gel). For example, metal oxide nanoparticles are often synthesized via the hydrolysis and condensation reactions of metal alkoxides ... 

A review of iron(III) in aqueous solution covers hydrolysis and polymerization, the formation and dissociation of binuclear species, and kinetics and mechanisms of water exchange and complex formation. " Kinetic and equilibrium data for hydrolytic reactions of iron(III) have been conveniently assembled. Reviews of hydrolysis of Fe aq, and subsequent precipitation of hydrated oxide-hydroxide species, cover a very wide range of media, from geochemistry to biology to human metabolism. Added anions or pH variation can affect which form... 

The type and quality of the pigment are determined not only by the nature and concentration of the additives, but also by the reaction rate. The rate depends on the grades of iron used, their particle size, the rates of addition of the iron and nitrobenzene (or another nitro compound), and the pH value. No bases are required to precipitate the iron compounds. Only ca. 3 % of the theoretical amount of acid is required to dissolve all of the iron. The aromatic nitro compound oxidizes the Fe2 + to Fe3 + ions, acid is liberated during hydrolysis and pigment formation, and more metallic iron is dissolved by the liberated acid to form iron(II) salts consequently, no additional acid is necessary. 

The exposure of sulfide minerals contained in mine wastes to atmospheric oxygen results in the oxidation of these minerals. The oxidation reactions are accelerated by the catalytic effects of iron hydrolysis and sulfide-oxidizing bacteria. The oxidation of sulfide minerals results in the depletion of minerals in the mine waste, and the release of H, SO4, Fe(II), and other metals to the water flowing through the wastes. The most abundant solid-phase products of the reactions are typically ferric oxyhydroxide or hydroxysulfate minerals. Other secondary metal sulfate, hydroxide, hydroxy sulfate, carbonate, arsenate, and phosphate precipitates also form. These secondary phases limit the concentrations of dissolved metals released from mine wastes. 

We now consider Fe hydrolysis. The hexaaquaflFerric cation[Fe(H20)e] is more acid than hexaaquaferrous cation [Fe(H20)g]. The equilibrium constant of hydrolysis is approximately one order lower than that in phosphoric acid, whereas the equilibrium constant of the hydrolysis of Fe " is approximately one order higher than that in boric add. During the hydrolysis the following essentially mononuclear complexes are produced [FeOH] ", [Fe(OH)2]" , [Fe(OH)3(aq)]° and [Fe(OH)4]. By other reactions a series of polynuclear complexes is formed, for example, [Fe2(OH)2], [Fe3(OH)4] , [Fe4(OH)g] , etc. (for simplicity, the coordinated water molecules are omitted). First, colloid hydroxo complexes are formed and finally there is a precipitate of hydrated ferric oxide which is in fact a mixture of different polynuclear complexes. The distribution of polynudear complexes depends not only on pH, but also on the initial concentration of iron. In diluted solutions of ferric salts a precipitate of hydrated Fe203 is separated only at a higher pH. The equilibrium between particular polynuclear complexes is established only very slowly. 

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