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Iron(III) chloride
Archivo:Iron(III) chloride hexahydrate.jpg
IUPAC name Iron(III) chloride
Iron trichloride
Other names Ferric chloride
Molysite
Flores martis
Identifiers
CAS number 7705-08-0
10025-77-1 (hexahydrate)
10025-77-1 (hexahydrate)
PubChem 24380
UN number 1773 (anhydrous)
2582 (aq. soln.)
RTECS number LJ9100000
Properties
Molecular formula FeCl3
Molar mass 162.2 g/mol (anhydrous)
270.3 g/mol (hexahydrate)
Appearance green-black by reflected light; purple-red by transmitted light
hexahydrate: yellow solid
aq. solutions: brown
Density 2.898 g/cm3 (anhydrous)
Melting point

306 °C (anhydrous)
37 °C (hexahydrate)

Boiling point

315 °C (anhydrous, decomp)
280 °C (hexahydrate, decomp) (partial decomposition to FeCl2 + Cl2)

Solubility in water 74.4 g/100 mL (0 °C) [1]
92 g/100 mL (hexahydrate, 20 °C)
Solubility in acetone
Methanol
Ethanol
Diethyl ether
63 g/100 ml (18 °C)
highly soluble
83 g/100 ml
highly soluble
Viscosity 40% solution: 12 cP
Structure
Crystal structure hexagonal
Coordination
geometry
octahedral
Hazards
MSDS ICSC 1499
EU Index Not listed
Main hazards Corrosive, especially in solution
NFPA 704
NFPA 704
0
3
2
 
Related compounds
Other anions Iron(III) fluoride
Iron(III) bromide
Other cations Iron(II) chloride
Manganese(II) chloride
Cobalt(II) chloride
Ruthenium(III) chloride
Related coagulants Iron(II) sulfate
Polyaluminium chloride
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Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references




Iron(III) chloride, also called ferric chloride, is an industrial scale commodity chemical compound, with the formula FeCl3. The colour of iron(III) chloride crystals depends on the viewing angle: by reflected light the crystals appear dark green, but by transmitted light they appear purple-red. Anhydrous iron(III) chloride is deliquescent, forming hydrated hydrogen chloride mists in moist air. It is rarely observed in its natural form, mineral molysite, known mainly from some fumaroles.

When dissolved in water, iron(III) chloride undergoes hydrolysis and gives off heat in an exothermic reaction. The resulting brown, acidic, and corrosive solution is used as a coagulant in sewage treatment and drinking water production, and as an etchant for copper-based metals in printed circuit boards. Anhydrous iron(III) chloride is a fairly strong Lewis acid, and it is used as a catalyst in organic synthesis.

Structure and propertiesEditar

Iron(III) chloride adopts the BiI3 structure, which features octahedral Fe(III) centres interconnected by two-coordinate chloride ligands.

Iron(III) chloride has a relatively low melting point and boils at around 315 °C. The vapour consists of the dimer Fe2Cl6 (c.f. aluminium chloride) which increasingly dissociates into the monomeric FeCl3 (D3h point group molecular symmetry) at higher temperature, in competition with its reversible decomposition to give iron(II) chloride and chlorine gas.[2]

Preparation Editar

Anhydrous iron(III) chloride may be prepared by union of the elements:[3]

2 Fe(s) + 3 Cl2(g) → 2 FeCl3(s)

Solutions of iron(III) chloride are produced industrially both from iron and from ore, in a closed-loop process.

  1. Dissolving pure iron in a solution of iron(III) chloride
    :Fe(s) + 2 FeCl3(aq) → 3 FeCl2(aq)
  2. Dissolving iron ore in hydrochloric acid
    :Fe3O4(s) + 8 HCl(aq) → FeCl2(aq) + 2 FeCl3(aq) + 4 H2O
  3. Upgrading the iron(II) chloride with chlorine
    :2 FeCl2(aq) + Cl2(g) → 2 FeCl3(aq)

Like many other hydrated metal chlorides, hydrated iron(III) chloride can be converted to the anhydrous salt by refluxing with thionyl chloride.[4] The hydrate cannot be converted to anhydrous iron(III) chloride by only heat, as instead HCl is evolved and iron oxychloride forms.

ReactionsEditar

Archivo:Iron(III) chloride.JPG

Iron(III) chloride under goes hydrolysis to give a an acidic solution. When heated with iron(III) oxide at 350 °C, iron(III) chloride gives iron oxychloride, a layered solid and intercalation host.[citation needed]

FeCl3 + Fe2O3 → 3 FeOCl

It is a moderately strong Lewis acid, forming adducts with Lewis bases such as triphenylphosphine oxide, e.g. FeCl3(OPPh3)2 where Ph = phenyl. It also reacts with other chloride salts to give the yellow tetrahedral FeCl4 ion. Salts of FeCl4 in hydrochloric acid can be extracted into diethyl ether.

Alkali metal alkoxides react to give the metal alkoxide complexes of varying complexity[5]. The compounds can be dimeric or trimeric[6]. In the solid phase a variety of multinuclear complexes have been described for the nominal stoichiometric reaction between FeCl3 and Sodium ethoxide:[7][8]

FeCl3 + 3 [C2H5O]-Na+ → Fe(OC2H5)3 + 3 NaCl

Oxalates react rapidly with aqueous iron(III) chloride to give [Fe(C2O4)3]3−. Other carboxylate salts form complexes, e.g. citrate and tartrate.

OxidizationEditar

Iron(III) chloride is a mild oxidising agent, for example capable of oxidising copper(I) chloride to copper(II) chloride.

FeCl3 + CuCl → FeCl2 + CuCl2

It also reacts with iron to form iron(II) chloride:

2 FeCl3 + Fe → 3 FeCl2

Reducing agents such as hydrazine convert iron(III) chloride to complexes of iron(II).

Uses Editar

IndustrialEditar

In industrial application, iron(III) chloride is used in sewage treatment and drinking water production.[9] In this application, FeCl3 in slightly basic water reacts with the hydroxide ion to form a floc of iron(III) hydroxide, or more precisely formulated as FeO(OH)-, that can remove suspended materials.

Fe3+ + 4 OH → Fe(OH)4 → FeO(OH)2·H2O

It is also used as a leaching agent in chloride hydrometallurgy,[10] for example in the production of Si from FeSi. (Silgrain process)[11]

Another important application of iron(III) chloride is etching copper in two-step redox reaction to copper(I) chloride and then to copper(II) chloride in the production of printed circuit boards.[12]

FeCl3 + Cu → FeCl2 + CuCl
FeCl3 + CuCl → FeCl2 + CuCl2

Iron(III) chloride is used as catalyst for the reaction of ethylene with chlorine, forming ethylene dichloride (1,2-dichloroethane), an important commodity chemical, which is mainly used for the industrial production of vinyl chloride, the monomer for making PVC.

H2C=CH2 + Cl2 → ClCH2CH2Cl

Laboratory useEditar

In the laboratory iron(III) chloride is commonly employed as a Lewis acid for catalysing reactions such as chlorination of aromatic compounds and Friedel-Crafts reaction of aromatics. It is less powerful than aluminium chloride, but in some cases this mildness leads to higher yields, for example in the alkylation of benzene:

Iron(III) chloride as a catalyst

The ferric chloride test is a traditional colorimetric test for phenols, which uses a 1% iron(III) chloride solution that has been neutralised with sodium hydroxide until a slight precipitate of FeO(OH) is formed.[13] The mixture is filtered before use. The organic substance is dissolved in water, methanol or ethanol, then the neutralised iron(III) chloride solution is added—a transient or permanent coloration (usually purple, green or blue) indicates the presence of a phenol or enol.

This reaction is exploited in the Trinder spot test, which is used to indicate the presence of salicylates, particularly salicylic acid and acetylsalicylic acid (aspirin). Both these compounds contain phenolic OH groups.

Other usesEditar

  • Used in anhydrous form as a drying reagent in certain reactions.
  • Used by American coin collectors to identify the dates of Buffalo nickels that are so badly worn that the date is no longer visible.
  • Used by knife craftsmen and sword smiths to stain blades, as to give a contrasting effect to the metal, and to view metal layering or imperfections.
  • Used to etch the widmanstatten pattern in iron meteorites .
  • Necessary for the etching of photogravure plates for printing photographic and fine art images in intaglio and for etching rotogravure cylinders used in the printing industry.
  • Used in veterinary practice to treat overcropping of an animal's claws, particularly when the overcropping results in bleeding.
  • Reacts with cyclopentadienylmagnesium bromide in one preparation of ferrocene, a metal-sandwich complex.[14]
  • Sometimes used in the technique of Raku firing as an additive during the reduction process, turning a pottery piece a burnt orange color due to the iron content present in the reducing atmosphere.
  • Used to test the pitting and crevice corrosion resistance of stainless steels and other alloys.
  • Used in conjunction with NaI in acetonitrile to mildly reduce organic azides to primary amines.[15]
  • Used in an animal thrombosis model [16]

SafetyEditar

Iron(III) chloride is toxic, highly corrosive and acidic. The anhydrous material is a powerful dehydrating agent.

See also Editar

ReferencesEditar

  1. Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN 0070494398
  2. Holleman, A.F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN 0-12-352651-5. 
  3. Tarr, B.R. (1950). "Anhydrous Iron(III) Chloride". Inorganic Syntheses 3: 191–194. DOI:10.1002/9780470132340.ch51.
  4. Pray, Alfred R.; Richard F. Heitmiller, Stanley Strycker (1990). "Anhydrous Metal Chlorides". Inorganic Syntheses 28: 321–323. DOI:10.1002/9780470132593.ch80.
  5. The chemistry of metal alkoxides, Nataliya Ya Turova , 12.22.1 'Synthesis' , p.481 google books link
  6. Alkoxo and aryloxo derivatives of metals By D. C. Bradley , 3.2.10 , Alkoxides of later 3d metals , p69 google books links
  7. Fe9O3(OC2H5)21·C2H5OH - A New Structure Type of an Uncharged Iron(III) Oxide-Alkoxide Cluster , Michael Veith, Frank Grätz, Volker Huch , European Journal of Inorganic Chemistry , Vol 2001, Issue 2, pp.367-368 online link
  8. The synthesis of iron (III) ethoxide revisited: Characterization of the metathesis products of iron (III) halides and sodium ethoxide , Gulaim A. Seisenbaevaa, Suresh Gohila, Evgeniya V. Suslovab, Tatiana V. Rogovab, Nataliya Ya. Turovab, Vadim G. Kesslera , Inorganica Chimica Acta , Volume 358, Issue 12, 1/8/2005, pp.3506-3512 , online link
  9. (PDF) Water Treatment Chemicals. Akzo Nobel Base Chemicals. 2007. http://www.akzonobel.com/ic/system/images/AkzoNobel_WTCBrochureENG_tcm18-9982.pdf. Retrieved 2007-10-26. 
  10. Separation and Purification Technology 51 (2006) pp 332-337
  11. Chem. Eng. Sci. 61 (2006) pp 229-245
  12. Greenwood, N.N.; A. Earnshaw (1997). Chemistry of the Elements (2nd ed.). Oxford: Butterworth-Heinemann. 
  13. Furnell, B.S.; et al. (1989). Vogel's Textbook of Practical Organic Chemistry (5th ed.). New York: Longman/Wiley. 
  14. Kealy, T.J. (1951). "A New Type of Organo-Iron Compound". Nature 168: 1040. DOI:10.1038/1681039b0.
  15. Kamal, Ahmed (2002). "Mild and efficient reduction of azides to amines: synthesis of fused [2,1-b]quinazolines". Tetrahedron Letters 43: 6961. DOI:10.1016/S0040-4039(02)01454-5.
  16. Tseng, Michael (2006). "Transendothelial migration of ferric ion in FeCl3 injured murine common carotid artery". Thrombosis Research 118 (2): 275–280. DOI:10.1016/j.thromres.2005.09.004. PMID 16243382.

Further reading Editar

  1. Handbook of Chemistry and Physics, 71st edition, CRC Press, Ann Arbor, Michigan, 1990.
  2. The Merck Index, 7th edition, Merck & Co, Rahway, New Jersey, USA, 1960.
  3. D. Nicholls, Complexes and First-Row Transition Elements, Macmillan Press, London, 1973.
  4. A.F. Wells, 'Structural Inorganic Chemistry, 5th ed., Oxford University Press, Oxford, UK, 1984.
  5. J. March, Advanced Organic Chemistry, 4th ed., p. 723, Wiley, New York, 1992.
  6. Handbook of Reagents for Organic Synthesis: Acidic and Basic Reagents, (H. J. Reich, J. H. Rigby, eds.), Wiley, New York, 1999.

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