A-Level Chemistry OCR Notes

5.2.3 Redox and electrode potentials

Redox and electrode potentials
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Redox Equations
  • Redox reactions involve both oxidation and reduction
  • A redox reaction can be constructed from two half-equations; one representing an oxidation process, and the other a reduction process
  • To construct a full equation from half equations:
    • Balance the electrons
    • Combine the equations
    • Cancel the electrons
    • Check the charge balance and stoichiometry

​e.g.
Mg Mg2+ + 2e-
Cu2++ 2e-
Cu
1). Mg Mg2+ + 2e-
Cu2+ + 2e Cu

2). Mg + Cu2++ 2e- Mg2+ + 2e- + Cu

3). Mg + Cu2+ Mg2+ + Cu

Redox Reactions
  • Reduction: The gain of electrons and decrease in oxidation number of an element
  • Oxidation: The loss of electrons and increase in oxidation number of an element
  • Redox reactions involve both oxidation and reduction
  • Oxidising agents cause oxidation of other species, and so are themselves reduced
  • Reducing agents cause reduction of other species, and so are themselves oxidised
  • In the reaction below, H is reduced, Na is oxidised.
​2 HCl + 2 Na 2 NaCl + H2
+1 0 +1 0

Redox Titrations
  • Redox titrations can be carried out to show how much oxidising agent is needed to react exactly with a reducing agent.
  • Transition metals have variable oxidation states, so they are often present in either the oxidising or reducing agent
  • Manganate(VII) ions are readily reduced to Mn2+ ions under acidic conditions (purple to colourless). This can be used to find the amount of Fe2+ in a solution

Oxidation: Fe2+ Fe3+ + e-
Reduction: 8H+ + MnO4- + 5e- Mn2+ + 4H2O
Overall: 8H+ + MnO4- + 5Fe2+ Mn2+ + 4H2O + 5Fe3+
  • Fe2+ can also be oxidised by dichromate (VI) ions

Oxidation: Fe2+ Fe3+ + e-
Reduction: Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O
Overall: 6Fe2+ + Cr2O72- + 14H+ 2Cr3+ + 7H2O + Fe3

Electrode Potentials
  • Redox reactions can be used in electrochemical cells to generate electricity (a flow of charge)
  • Electrochemical cells consist of two half-cells. At one oxidation occurs, at the other reduction. Electrons flow between the two cells, driving the redox reaction
Zn → Zn2+ + 2e-
Cu2+ + 2e- → Cu
Picture
An equilibrium is reached: Cu2+ (aq) + 2e- ⇌ Cu (s)

  • Each one of these beakers is a half-cell. A solution in a standard half-cell will have a concentration of 1.00 mol dm-3
  • An electrode is a solid surface which allows the transfer of electrons to and from it.
  • The system above describes metal/metal ion half-cells. It is possible to make an ion/ion cell by using the same element with different oxidation states e.g. a mixture of Fe2+ and Fe3+ establishes an equilibrium: Fe3+ (aq) + e- ⇌ Fe2+ (aq)
  • In an ion/ion half cell there is no solid metal to transport electrons out of the cell so a platinum electrode is used
  • The standard electrode potential, E^θ is the voltage measured under standard conditions when the half-cell is connected to a standard hydrogen electrode.
  • Standard conditions includes 298K, 100kPa and 1.00 mol dm-3.
  • The voltage measured is also known as the electromotive force of the cell (EMF).
Picture
  • An electrochemical series is a list of standard electrode potentials of all the possible half-cells.
Picture
  • The more negative the electrode potential, the more the oxidation (backwards) reaction is favoured.
Picture

Electrochemical Cells
  • Electrochemical cells can be used as a commercial source of electrical energy
  • In a rechargeable battery, when the chemicals have reacted fully, a potential difference can be applied to the cell in the opposite direction, which will regenerate the original chemicals
  • Lithium-ion batteries are rechargeable:
At the positive electrode:
Li+ + CoO2 + e- Li+[CoO2]- Eθ=+0.56 V
At the negative electrode:
Li
Li+ + e- Eθ= -3.04 V
Eθ cell = +0.56 V (-3.04 V) = + 3.60 V
  • Some cells are non-rechargeable and disposed of when the chemicals have fully reacted.
  • In fuel cells the chemicals are stored externally and are fed into the cell when electricity is required.
  • An alkaline hydrogen fuel cell:
Picture
Positive electrode: O2 (g) + 2H2O (l) + 4e- 4OH- (aq) Eθ= +0.40 V

Negative electrode: 2H2 (g) + 4OH- (aq) 4H2O (l) + 4e- Eθ= ​- 0.83 V

Overall reaction: 2H2 (g) + O2 (g) 2H2O (g) Eθ cell = +1.23 V
Advantages
Disadvantages
They are more efficient than burning fossil fuels.
Energy is needed to build the fuel cells and produce hydrogen – this energy comes from fossil fuels.
They release water, which isn’t harmful.
Hydrogen is highly flammable so needs to be carefully handled.
They do not need to be recharged – they keep producing electricity for as long as they have fuel.
Highly toxic and can igniteLi is a very reactive metal.

Variable Oxidation States
  • Vanadium has 4 oxidation states II, III, IV & V
  • Vanadium species in oxidation states IV, III and II are formed by the reduction of vanadate(V) ions by zinc in acidic solution

Reduction from V(V) to V(IV)
​2VO2+ (aq) + 4H+ (aq) + Zn (s) → 2VO2+ (aq) + Zn2+ (aq) + 2H2O (l)

Reduction from V(IV) to V(III)
2VO2+ (aq) + 4H+ (aq) + Zn (s) → 2V3+ (aq) + Zn2+ (aq) + 2H2O (l)

Reduction from V(III) to V(II)
2V3+ (aq) + Zn (s) → Zn2+ (aq) + 2V2+ (aq)

  • Manganate (VII) ions are readily reduced to Mn2+ ions under acidic conditions (purple to colourless). This can be used to find the amount of Fe3+ in a solution

Oxidation: Fe2+ Fe3+ + e-
Reduction: 8H+ + MnO4- + 5e- Mn2+ + 4H2O
Overall: 8H+ + MnO4- + 5Fe2+ Mn2+ + 4H2O + 5Fe3+

  • When transition metals are oxidised, the 4s electrons are lost before the 3d electrons

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Redox and electrode potentials
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