Ferroin

Ferroin
The structure of the [Fe(o-phen)3]2+ complex cation in ferroin
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.035.145
UNII
  • InChI=1S/3C12H8N2.Fe.H2O4S/c3*1-3-9-5-6-10-4-2-8-14-12(10)11(9)13-7-1;;1-5(2,3)4/h3*1-8H;;(H2,1,2,3,4)/q;;;+2;/p-2 Y
    Key: CIWXFRVOSDNDJZ-UHFFFAOYSA-L Y
  • InChI=1/3C12H8N2.Fe.H2O4S/c3*1-3-9-5-6-10-4-2-8-14-12(10)11(9)13-7-1;;1-5(2,3)4/h3*1-8H;;(H2,1,2,3,4)/q;;;+2;/p-2
    Key: CIWXFRVOSDNDJZ-NUQVWONBAU
  • [Fe+2].[O-]S([O-])(=O)=O.n3c2c1ncccc1ccc2ccc3.n3c2c1ncccc1ccc2ccc3.n1c3c(ccc1)ccc2cccnc23
Properties
C36H24FeN62+
Molar mass 596.27 g/mol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Ferroin is the chemical compound with the formula [Fe(o-phen)3]SO4, where o-phen is an abbreviation for 1,10-phenanthroline, a bidentate ligand. The term "ferroin" is used loosely and includes salts of other anions such as chloride. Ferroin is one of many transition metal complexes of 1,10-phenanthroline.

Structure

Many salts of [Fe(o-phen)3]2+ have been characterized by X-ray crystallography. The structures of [Fe(o-phen)3]2+ and [Fe(o-phen)3]3+ are almost identical, consistent with both being low-spin. These cations are octahedral with D3 symmetry group. The Fe-N distances are 197.3 pm.

Preparation and reactions

Ferroin sulfate may be prepared by combining phenanthroline to ferrous sulfate in water.

3 phen + Fe2+ → [Fe(phen)3]2+

The main reaction is 1-electron oxidation. [Fe(phen)3]2+ → [Fe(phen)3]3+ + 1 e− Addition of sulfuric acid to an aqueous solution of [Fe(phen)3]2+ causes hydrolysis:

[Fe(phen)3]2+ + 3 H2SO4 + 6 H2O → [Fe(OH2)6]2+ + 3 [phenH]HSO4−

Redox indicator

Phenanthroline Fe(II) (Redox indicator)
E0= 1.06 V
Reduced. ↔ Oxidized
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This complex is used as an indicator in analytical chemistry. The active ingredient is the [Fe(o-phen)3]2+ ion, which is a chromophore that can be oxidized to the ferric derivative [Fe(o-phen)3]3+. The potential for this redox change is +1.06 volts in 1 M H2SO4. It is a popular redox indicator for visualizing oscillatory Belousov–Zhabotinsky reactions.

Ferroin is suitable as a redox indicator, as the color change is reversible, very pronounced and rapid, and the ferroin solution is stable up to 60 °C. It is the main indicator used in cerimetry.

Nitroferroin, the complex of iron(II) with 5-nitro-1,10-phenanthroline, has transition potential of +1.25 volts. It is more stable than ferroin, but in sulfuric acid with Ce4+ ion it requires significant excess of the titrant. It is however useful for titration in perchloric acid or nitric acid solution, where cerium redox potential is higher.

The redox potential of the iron-phenanthroline complex can be varied between +0.84 V and +1.10 V by adjusting the position and number of methyl groups on the phenanthroline core.

References

  1. ^ Sattar, Simeen (2011). "A Unified Kinetics and Equilibrium Experiment: Rate Law, Activation Energy, and Equilibrium Constant for the Dissociation of Ferroin". Journal of Chemical Education. 88 (4): 457–460. Bibcode:2011JChEd..88..457S. doi:10.1021/ed100797s.
  2. ^ Baker, Joe; Engelhardt, Lutz M.; Figgis, Brian N.; White, Allan H. (1975). "Crystal Structure, Electron Spin Resonance, and Magnetism of Tris(o-Phenanthroline)Iron(III) Perchlorate Hydrate". Journal of the Chemical Society, Dalton Transactions (6): 530. doi:10.1039/DT9750000530.
  3. ^ Harris, D. C. (1995). Quantitative Chemical Analysis (4th ed.). New York, NY: W. H. Freeman. ISBN 978-0-7167-2508-4.
  4. ^ a b c Handbook on the Physics and Chemistry of Rare Earths. Elsevier. 2006. pp. 289–. ISBN 978-0-08-046672-9.