Electrode Systems

Electrochemical cells
Two electrodes are separated by at least one
electrolyte system
Zn/Zn2+ , Cl-/AgCl/Ag

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Another electrochemical cells

Pt/H2/H+ , Cl-/AgCl/Ag

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Two electrode system

Most of the time one is interested in only one of
these reactions, and the electrode at which it
occurs is called Working (indicator) electrode
To focus on it, one standardizes the other half of
the cell by using an electrode, called reference
electrode, which made up of phases having
essentially constant composition
We can control the potential of working electrode
wrt to the reference electrode
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Example of reference electrode

Primary ref electrode is Standard Hydrogen Electrode

(SHE) or Normal Hydrogen Electrode (NHE)

Potential is 0.00 V
Both anode or cathode
Pt is inactive in any reaction
Difficult to operate
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More reference electrode

Saturated Calomel Electrode (SCE)
Hg/Hg2Cl2/KCl
Hg2Cl2(s) + 2e- 2Cl- + 2Hg(l)
Ecell = + 0.242 V vs. NHE
Silver-Silver Chloride electrode
Ag/AgCl/KCl
AgCl(s) + e- Cl- + Ag(s)
Ecell = +0.197 V vs. NHE
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Another electrochemical cell

An electrochemical cell is a device in which the

free energy of a physical or chemical process is
converted into electrical energy

Construction of a cell

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Reduction process
A + e

A-

Finally, a flow of electron from

electrode to solution, a reduction
current occur

The critical potentials at which the

processes occur are related to E0 A/AReduction process of species A in solution: highest
occupied MO and lowest vacant MO
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Oxidation process
A - e

A+

Finally, a flow of electron from

solution to electrode, an oxidation
current occur

related to E0 A+/A

Oxidation process of species A in solution: highest

occupied MO and lowest vacant MO
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More reference electrode

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Types of electrode

1. Metal-metal ion electrode

Anode: Zn (s)/Zn2+ (aq.)
Cathode: Zn2+ (aq)/Zn (s)

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Types of electrode

2. Gas electrode
Cathode: H+ (aq) + e-

H2 (g)

H+ (aq) / 1/2H2 (g) , Pt

Anode: 1/2H2 (g)

H+ (aq) + e-

Pt , 1/2H2 (g) / H+ (aq)

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Types of electrode

3. Metal insoluble salt of metal electrode

Calomel electrode
Anode: Hg (l) / Hg2Cl2 (s) , KCl (aq)

Cathode: KCl (aq) , Hg2Cl2 (s) / Hg (l)

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Types of electrode

4. Oxidation-reduction electrode

Quinhydrone electrode

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Conclusions

Different electrode systems

Electrchemical cells

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