Iron(II,III) oxide is the chemical compound with formula Fe3O4. It occurs in nature as the mineral magnetite. It is one of a number of iron oxides, the others being iron(II) oxide (FeO), which is rare, and iron(III) oxide (Fe2O3) also known as hematite. It contains both Fe2+ and Fe3+ ions and is sometimes formulated as FeO ∙ Fe2O3. This iron oxide is encountered in the laboratory as a black powder. It exhibits permanent magnetism and is ferrimagnetic, but is sometimes incorrectly described as ferromagnetic.[2] Its most extensive use is as a black pigment which is synthesised rather than being extracted from the naturally occurring mineral as the particle size and shape can be varied by the method of production.[3]
Contents [hide]
1 Preparation
2 Reactions
3 Structure
4 Properties
5 Uses
6 Biological Occurrence
7 See also
8 References
Preparation[edit]
Under anaerobic conditions, ferrous hydroxide (Fe(OH)2) can be oxidized by water to form magnetite and molecular hydrogen. This process is described by the Schikorr reaction:
3 Fe(OH)2 → Fe3O4 + H2 + 2 H2O
ferrous hydroxide → magnetite + hydrogen + water
The well-crystallized magnetite (Fe3O4) is thermodynamically more stable than the ferrous hydroxide (Fe(OH)2 ).[4]
Magnetite can be prepared in the laboratory as a ferrofluid in the Massart method by mixing iron(II) chloride and iron(III) chloride in the presence of sodium hydroxide.[5] Magnetite can also be prepared by the chemical co-precipitation in presence of ammonia, which consist in a mixture of a solution 0.1 M of FeCl3·6H2O and FeCl2·4H2O with mechanic agitation of about 2000 rpm. The molar ratio of FeCl3:FeCl2 can be 2:1; heating this solution at 70 °C, and immediately the speed is elevated to 7500 rpm and adding quickly a solution of NH4OH (10 volume %), immediately a dark precipitate will be formed, which consists of nanoparticles of magnetite.[6] In both cases, the precipitation reaction rely on a quick transformation of acidic hydrolyzed iron ions into the spinel iron oxide structure, by hydrolysis at elevated pH values (above ca. 10).
Considerable efforts has been devoted towards controlling the particle formation process of magnetite nanoparticles due to the challenging and complex chemistry reactions involved in the phase transformations prior to the formation of the magnetite spinel structure.[7] Magnetite particles are of interests in bioscience applications such as in magnetic resonance imaging (MRI) since iron oxide magnetite nanoparticles represent a non-toxic alternative to currently employed gadolinium-based contrast agents. However, due to lack of control over the specific transformations involved in the formation of the particles, truly superparamagnetic particles have not yet been prepared from magnetite, i.e. magnetite nanoparticles that completely lose their permanent magnetic characteristic in the absence of an external magnetic field (which by definition show a coercivity of 0 A/m). The smallest values currently reported for nanosized magnetite particles is Hc = 8.5 A m−1,[8] whereas the largest reported magnetization value is 87 Am2 kg−1 for synthetic magnetite.[9][10]
Pigment quality Fe3O4, so called synthetic magnetite, can be prepared using processes that utilise industrial wastes, scrap iron or solutions containing iron salts (e.g. those produced as by-products in industrial processes such as the acid vat treatment (pickling) of steel):