National Biochemicals Corp. 1780 Enterprise Parkway • P.O. Box 1986, Twinsburg, OH 44087, USA Phone: 330. 425. 2522 • Fax: 330. 425. 2583 www.nationalbiochem.com FERRIC CHLORIDE Product No.: MF7134 CAS No.: 7705-08-0 Storage Temperature: Ambient Synonyms: Iron(III) Chloride; Iron Trichloride; Molysite PRODUCT SPECIFICATIONS NOMENCLATURE Molecular Formula: FeCl3 Molecular Weight: 162.2 Appearance:Y e l l o w - B r o w n Deliquescent Crystals Solubility (3 g in 10 mL Water):Complete, Clear, B r o w n i s h - R e d , Haze-Free Assay (Min.):98.0% Ferrous Chloride (Max.): 1.0% Insoluble Matter (Max.): 2.0% IR Scan: Conforms to Reference The descriptor hydrated or anhydrous is used when referring to Ferric Chloride, to distinguish between the two common forms. The hexahydrate is usually given as the simplified empirical formula FeCl3 • 6H2O. It may also be given as trans-[Fe(H2O)4Cl2]Cl • 2H2O and the systematic name tetraaquadichloroiron(III) chloride dihydrate, which more clearly represents its structure. PRODUCT DESCRIPTION Ferric Chloride, also called Iron(III) Chloride, is an industrial scale commodity chemical compound. The color of Ferric Chloride crystals depends on the viewing angle; by reflected light, the crystals appear dark green, but by transmitted light they appear purple-red. Anhydrous Ferric 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, Ferric Chloride undergoes hydrolysis and gives off heat in an exothermic reaction. The resulting brown, acidic, and corrosive solution is used as a flocculant in sewage treatment and drinking water production, and as an etchant for copper-based metals in printed circuit boards. Anhydrous Ferric Chloride is a fairly strong Lewis acid, and it is used as a catalyst in organic synthesis. STRUCTURE & PROPERTIES Anhydrous Ferric Chloride adopts the Bil3 structure, which features octahedral Fe(III) centres interconnected by twocoordinate chloride ligands. Ferric Chloride hexahydrate consists of trans-[Fe(H2O)4Cl2]+ cationic complexes and chloride anions, with the remaining two H2O molecules embedded within the monoclinic crystal structure.5 Ferric Chloride has a relatively low melting point and boils at around 315°C. The vapor consists of the dimer Fe2Cl6 which increasingly dissociates into the monomeric FeCl3 at higher temperature, in completion with its reversible decomposition to give Ferric Chloride and chlorine gas.6 PREPARATION Anhydrous Ferric Chloride may be prepared by union of the elements:7 2Fe(s) + 3Cl2(g) → 2FeCl3(s) Solutions of Ferric Chloride are produced industrially both from iron and from ore, in a closed-loop process. 1. Dissolving pure iron in a solution of Ferric Chloride Fe(s) + 2FeCl3(aq) → 3FeCl2(aq) 2. Dissolving iron ore in hydrochloric acid Fe3O4(s) + 8HCl(aq) → FeCl2(aq) + 2FeCl3(aq) + 4H2O page 1 3. Oxidation 2FeCl2(aq) of + Ferric Chloride with chlorine Cl2(g) → 2FeCl3(aq) 4. Oxidation of Ferric Chloride with oxygen FeCl2(aq) + ¼O2 + HCl → FeCl3(aq) + ½H2O Like many other hydrated metal chlorides, Ferric Chloride can be converted to the anhydrous salt by refluxing with thionyl choride.8 Conversion of the hydrate to anhydrous Ferric Chloride is not accomplished by heating, as HCl and iron oxychlorides are produced. USES Industrial In industrial applications, Ferric Chloride is used in sewage treatment and drinking water production.13 In this application, FeCl3 in slightly basic water, reacts with the hydroxide ion to forma floc of iron(III) hydroxide, or more precisely formulated as FeO(OH)-, that can remove suspended materials. [Fe(H2O)6]3+ + 4HO- → [Fe(H2O)2(HO)4]- + 4H2O → [Fe(H2O)O(HO)2]- + 6H2O REACTIONS It is also used as a leaching agent in chloride hydrometallurgy,14 for example, in the production of Si from FeSi.15 Ferric Chloride undergoes hydrolysis to give an acidic solution. When heated with iron(III) oxide at 350°C, Ferric Chloride gives iron oxychloride, a layered solid intercalation host. Another important application of Ferric 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.16 FeCl3 + Fe2O3 → 3FeOCl FeCl3 + Cu → FeCl2 + CuCl FeCl3 + CuCl → FeCl2 + CuCl2 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 a 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.9 The compounds can be dimeric or trimeric.10 In the solid phase a variety of multinuclear complexes have been described for the nominal stoichiometric reaction between FeCl3 and sodium ethoxide:11,12 FeCl3 + 3[C2H5O]-Na+ → Fe(OC2H5)3 + 3NaCl Oxalates react rapidly with aqueous Ferric Chloride to give [Fe(C2O4)3]3-. Other carboxylate salts form complexes, e.g. citrate and tartrate. Ferric Chloride is used as catalyst for the reaction of ethylene with chlorine, forming ethylene dichloride, 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 In the laboratory, Ferric Chloride is commonly employed as a Lewis Acid for catalyzing reactions such as chlorination of aromatic compounds and Friedel-Crafts Reaction of aromatics. It is less powerful than aluminum chloride, but in some cases this mildness leads to higher yields, for example in the alkylation of benzene: FeCl3 Oxidation Ferric Chloride is a mild oxidizing agent, for example, it is capable of oxidizing copper(I) chloride to copper(II) chloride. FeCl3 + CuCl → FeCl2 + CuCl2 It also reacts with iron to form iron(II) chloride: 2FeCl3 + Fe → 3FeCl2 Reducing agents such as hydrazine convert Ferric Chloride to complezes of iron(II). Cl excess 83% yield The Ferric Chloride test is a traditional colorimetric test for phenols, which uses a 1% iron(III)chloride solution that has been neutralized with sodium hydroxide until a sight precipitate of FeO(OH) is formed.17 The mixture is filtered before use. The organic substance is dissolved in water, methanol or ethanol, then the neutralized Ferric Chloride solution is added - a transient or permanent coloration 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, which contains a phenolic OH group. page 2 Other Uses • Used drying in anhydrous reagent in form certain as a reactions. • Used to detect compounds in examining purity the presence of phenol organic synthesis, e.g. of synthesized Aspirin. • Used in water and wastewater treatment to precipitate phosphate as iron(III) phosphate. • 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 plates for images in cylinders to for the etching of photogravure printing photographic and fine art intaglio and for etching rotogravure used in the printing industry. • Used make printed circuit boards. • Used in veterinary practice to treat overcropping of an animal’s claws, particularly when the overcropping results in bleeding. PRECAUTIONS & DISCLAIMER This product is solely for Research and Development use. It is not for drug, household, or any other uses. Please review the Safety Data Sheet for information regarding risks and safe handling practices. REFERENCES 1. Pradyot, P., Handbook of Inorganic Chemicals, (2002). 2. w w w . e r m a n z . g o v t . n z / C h e m i c a l s / C h e m i c a l D i s p l a y. a s p x ? S u b s t a n c e I D = 1 0 7 6 4 . 3. Various Suppliers, Collated by the Baylor College of Dentistry, Texas A&M University, (2010). 4. GHS Classification, Japanese Inter-ministerial Committee, GHS (2006). 5. Lind, M.D., Crystal Structure of Ferric Chloride Hexahydrate, J. Chem. Phys., 47: 990, (1967). 6. Holleman, A.F., Wiberg, E., Inorganic Chemistry, (2001). 7. Tarr, B.R., Booth, H.S., Dolance, A., Anhydrous Iron (III) Chloride, Inorganic Synthesis, Inorganic Synthesis, 3: 191 - 194, (1950). 8. Pray, A.R., Heitmiller, R.F., Strycker, S., Anhydrous Metal Chlorides, Inorganic Synthesis, 28: 321 - 323, (1990). • Reacts with cyclopentidienylmagnesium bromide in one preparation of ferrocene, a metal-sandwich complex.18 9. The Ya • Sometimes used in a technique of Raku ware firing, the iron coloring a pottery piece shades of pink, brown and orange. 10. Alkoxo and Aryloxo Derivatives of Metals by D.C. Bradley, Alkoxides of later 3D metals, p. 69. • Used to test the pitting and crevice corrosion resistance of stainless steels and other alloys. • Used in conjunction with Nal in acetonitrile to mildly reduce organic azides to primary amines.19 11. Veith, M., Grätz, F., Huch, V., Fe9O3(OC2H5)21 • C2H5OH - A new structure Type of an Uncharged Iron(III) Oxide-Alkoxide Cluster, European J. of Inorg. Chem., Vol. 2001, Issue 2, p. 367 - 368. • Used in an animal thrombosis model.20 SAFETY Ferric Chloride is toxic, highly corrosive and acidic. The anhydrous material is a powerful dehydrating agent. Although reports of poisoning in humans are rare, ingestion of Ferric Chloride can result in serious morbidity and mortality. Inappropriate labeling and storage lead to accidental swallowing or misdiagnosis. Early diagnosis is important, especially in seriously poisoned patients. chemistry of metal Turova, N., Synthesis, alkoxides, p. 481. 12. Seisenbaevaa, G.A., Gohila, S., Suslovab, E.V., Rogovab, T.V., Turovab, N.Y., Kesslera, V.G., The synthesis of iron(III) ethoxide revisted: Characterization of the metathesis products of iron(III) halides and sodium ethoxide, Inorganica Chimica Acta, Volume 358, Issue 12, p. 3506 - 3512, (2005). 13. w w w . a k z o n o b e l . c o m / i c / s y s t e m / i m a g e s / AkzoNobel_WTCBrochureENG_tcm18-9982.pdf. 14. Separation Technology, 51: and 332 15. Chem. Sci., 61: page 3 Eng. 229 337, - Purification (2006). 245, (2006). 16. Greenwood, Chemistry of N.N., Earnshaw, the Elements, 2nd ed., 17. Furnell, B.S., et al., Vogel’s Practical Organic Chemistry, 5th A., (1997). Textbook of ed., (1989). 18. Kealy, T.J., Pauson, P.L., A new type of Organoiron compound, Nature, 168(4285): 1040, (1951). 19. Kamal, A., Ramana, K., Ankati, H., Ramana, A., Mild and efficient reduction of azides to amines: synthesis of fused [2,1-b]quinazolines, Tetrahedron Letters, 43(38): 6961, (2002). 20. Tseng, M., Dozier, A., Haribabu, B., Graham, U.M.,Transendothelial migration of ferric ion in FeCl3 injured murine common carotid artery, Thrombosis Research, 118(2): 275 - 280, (2006). NBC warrants that its products will conform with the information provided in this information sheet, though the Purchaser must determine the suitability of the products for their particular usage needs. Additional terms and conditions may apply. page 4 MF7134 • 08/08/13 • Rev. 1