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A2/A-level Chemistry: Standard Electrode Potential

Topic 3.1.11 -

January 24, 2022

Let's go over some specific terms about electrochemistry mentioned in A-level Chemistry!

Definition

  • Electromotive force (E.m.f.): the ‘push’ that a cell is able to provide to a current flowing through it (volts)
  • Standard electrode potentials (SEP): the potential difference of a half-cell relative to the standard hydrogen electrode (SHE)

Electrochemical cell

  • e.g. zinc-copper cell
  • Component: zinc and copper electrode, metal ion solution, salt bridge, high-resistance voltmeter
  • Oxidation: Zn electrode loses electron to form zn2+ ions
  • Reduction: Cu2+ ions in solution gain electrons to form Cu metal
  • Zinc electrode decreases in mass while copper electrode increases
  • Half-cell potential for copper = +0.34V
  • Half-cell potential for zinc = -0.76V
  • Overall reaction potential = Eoreduction – Eooxidation = 1.10V
  • E.m.f. calculated by reversing the least positive value then add up two half-cell potentials (if not familiar with the minus sign)
  • For a feasible reaction, cell potential MUST BE POSITIVE (usually over +0.6V)

Measurement of standard potential with SHE

Standard hydrogen electrode (SHE)

  • Reference half-cell (with standard potential 0.00V)
  • Used to measure other electrode potential
  • Condition: Hydrogen gas at 1 atm pressure, 298K, inert platinum electrode in 1.00 mol dm-3 H+(aq) ions
  • Anode: Metal electrode
  • Cathode: Standard Hydrogen Electrode (SHE)
  • other components include metal electrolyte, sald bridge, voltmeter
  • Oxidation half-cell: Metal(s)  ---> Metal ion(aq) + electrons
  • Reduction half-cell: H+(aq) + electron ---> 1/2 H2(g)
  • Overall reaction: Metal(s) + H+(aq) ---> Metal ion(aq) + H2(g)
  • In A-level Chemistry, the condition of standard potential is always at 1 atm pressure and 298K
  • Stronger oxidising agent with the more positive Ecell is on LHS of the equation.

  • Stronger reducing agent with the more negative Ecell is on RHS of the equation. 
  • **Strong oxidizing agent = weak reducing agent, vice versa

Remarks:

  • cell > +0.6V ---> reaction should go to completion
  • 0V < Eºcell < +0.6V ---> products predominate
  • -0.6V < Eºcell < 0V ---> reactants predominate
  • cell < -0.6V ---> NO reaction

Limitations

  • A reaction with a positive cell  may not actually take place – gives no indication of reaction rate
  • The reaction conditions may be very different from standard conditions
  • SEPs ONLY apply to aqueous equilibria, still there are many reactions that take place which are not in aqueous solutions

That's all~