1.2.13

Redox Reactions of Transition Metals

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Oxidation of Transition Metals

Transition metal ions can undergo oxidation reactions. Remember that an "oxidation is a loss" of electrons.

Illustrative background for Oxidation of Fe<sup>2+</sup> to Fe<sup>3+</sup>Illustrative background for Oxidation of Fe<sup>2+</sup> to Fe<sup>3+</sup> ?? "content

Oxidation of Fe2+ to Fe3+

  • Iron (II) ions can be oxidised by potassium manganate (VII) solution in acidic conditions.
    • The observed colour change is from green to brown.
    • Iron is oxidised from oxidation state +2 to +3.
    • Manganese is reduced from oxidation state +7 to +2.
Illustrative background for Half-equation to equationIllustrative background for Half-equation to equation ?? "content

Half-equation to equation

  • You need to understand how to construct an equation from the half-equations. Consider these two half-equations:
    • Fe2+ → Fe3+ + e-
      MnO4- + 8H+ + 5e- → Mn2+ + 4H2O
  • One e- is produced with Fe3+ and five e- are in the reactants of the MnO4- half-equation.
    • You therefore need five times more of the first half-equation.
  • MnO4- + 8H+ + 5Fe2+ → Mn2+ + 4H2O + 5Fe3+
Illustrative background for Oxidation of Cr<sup>3+</sup> to Cr<sub>2</sub>O<sub>7</sub><sup>2-</sup>Illustrative background for Oxidation of Cr<sup>3+</sup> to Cr<sub>2</sub>O<sub>7</sub><sup>2-</sup> ?? "content

Oxidation of Cr3+ to Cr2O72-

  • Cr3+ in an excess of OH- ions (from NaOH) exists in the complex ion [Cr(OH)6]3-.
  • This complex ion and be oxidised with H2O2:
    • 2[ Cr(OH)6 ]3- + 3H2O2 → 2CrO42- + 2OH- + 8H2O
  • The colour changes observed are from purple to green when excess NaOH is added and from green to yellow when H2O2 is added.
Illustrative background for CrO<sub>4</sub><sup>2-</sup> to Cr<sub>2</sub>O<sub>7</sub><sup>2-</sup>Illustrative background for CrO<sub>4</sub><sup>2-</sup> to Cr<sub>2</sub>O<sub>7</sub><sup>2-</sup> ?? "content

CrO42- to Cr2O72-

  • A reversible reaction can be used to easily change between CrO42- and Cr2O72-:
    • CrO42-  add  OHadd  H+  \;\xrightleftharpoons[add\; OH^-]{add\;H^+}\;Cr2O72-
    • Use dilute sulphuric acid and sodium hydroxide to push the equlibrium to either side.
Illustrative background for Colour change and oxidation statesIllustrative background for Colour change and oxidation states ?? "content

Colour change and oxidation states

  • The colour change obeserved is from yellow (CrO42-) to orange (Cr2O72-).
  • Chromium is oxidised from oxidation state +3 to +6.
  • Oxygen is reduced from oxidation state -1 to -2.

Reduction of Transition Metals

Transition metal ions can undergo reduction reactions. Remember that a "reduction is a gain" of electrons.

Illustrative background for Reduction of iron (III) to iron (II)Illustrative background for Reduction of iron (III) to iron (II) ?? "content

Reduction of iron (III) to iron (II)

  • Iron (III) ions can be reduced by using aqueous iodide ions as the reducing agent.
    • The observed colour change is from brown to green.
Illustrative background for The equationIllustrative background for The equation ?? "content

The equation

  • Fe3+ + 2I- → 2Fe2+ + I2
    • Iron is reduced from oxidation state +3 to +2.
    • Iodine is oxidised from oxidation state -1 to 0.
Illustrative background for Reduction of chromium (VI) to chromium (III)Illustrative background for Reduction of chromium (VI) to chromium (III) ?? "content

Reduction of chromium (VI) to chromium (III)

  • Cr2O72- can be reducted with zinc in an acidic solution.
    • Cr2O72- + 14H+ + 3Zn → 2Cr3+ + 7H2O + 3Zn2+
  • A colour change from orange to green is observed.
    • Chromium is reduced from oxidation state +6 to +3.
    • Zinc is oxidised from oxidation state 0 to +2.
Illustrative background for Reduction of copper (II) to copper (I)Illustrative background for Reduction of copper (II) to copper (I) ?? "content

Reduction of copper (II) to copper (I)

  • Cu2+ can be reduced by iodide ions. In the process, the iodide ions are oxidised by the copper (II).
    • 2Cu2+(aq) + 4I- → 2CuI(s) + I2 (aq)
Illustrative background for Colour change and oxidation statesIllustrative background for Colour change and oxidation states ?? "content

Colour change and oxidation states

  • A colour change from orange to brown. An off-white precipitate of copper (I) iodide settles in the solution over time.
    • Copper is reduced from oxidation state +2 to +1.
    • Iodine is oxidised from oxidation state -1 to 0.

Disproportionation

Disproportionation occurs when an element both oxidises and reduces in a reaction.

Illustrative background for Disproportionation of copper (I)Illustrative background for Disproportionation of copper (I) ?? "content

Disproportionation of copper (I)

  • In solution, copper (I) ions (oxidation state +1) forms solid copper (oxidation state 0) and copper (II) ions (oxidation state +2).
    • It is therefore both reduced and oxidised in the solution.
  • 2Cu+(aq) → Cu(s) + Cu2+(aq)
Illustrative background for Example of disproportionationIllustrative background for Example of disproportionation ?? "content

Example of disproportionation

  • Copper (I) oxide can be dissolved in dilute sulphuric acid in a disproportionation reaction:
    • Cu2O(s) + H2SO4 (s) → Cu(s) + CuSO4 (aq) H2O(l)
  • Copper goes from oxidation state +1 in Cu2O(s) to oxidation state 0 in Cu(s) and oxidation state +2 in CuSO4 (aq).
    • The copper (I) has been both reduced and oxidised.

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1Principles of Science I

1.1Structure & Bonding

1.2Properties of Substances

1.3Cell Structure & Function

1.4Cell Specialisation

1.5Tissue Structure & Function

1.6Working with Waves

1.7Waves in Communication

2Practical Scientific Procedures and Techniques

3Science Investigation Skills

4Principles of Science II

4.1Extracting Elements

4.2Relating Properties to use of Substances

4.3Organic Chemistry

4.4Energy Changes in Industry

4.5The Circulatory System

4.6Ventilation & Gas Exchange

4.7Urinary System

4.8Cell Transport

4.9Thermal Physics

4.10Materials

4.11Fluids

5Contemporary Issues in Science

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