Reactions at electrodes

Galvanic cell: Electrolytic cell:

Red1 → Ox2 + νe- Red1 → Ox2 + νe-

Ox1 + νe- → Red2 Ox1 + νe- → Red2
Half-reactions Nils Walter: Chem 260
 Types of electrodes I
Gas electrode: Insoluble-salt electrode:
Porous, insoluble
Gas (e.g., H2)
salt (e.g., AgCl)

solution metal solution metal

(e.g., H+) (e.g., Pt) (e.g., Cl-) (e.g., Ag)
Ag(s)|| AgCl(s)|| Cl-(aq) Q = aCl −
Pt(s)|| H2(g)|| H+(aq)
1 AgCl(s) + e- Ag(s) + Cl-(aq)
2H+ + 2e- H2(g) Q = 2
aH + Nils Walter: Chem 260
 Types of electrodes and how to put them
together in a galvanic cell
Redox electrode: Daniell cell:

Left:
Zn2+(aq) + 2e-
→ Zn(s)

Right:
Cu2+(aq) + 2e-
→ Cu(s)
Pt(s)|| Fe2+(aq),Fe3+(aq)
Zn(s)|| ZnSO4(aq) | | CuSO4(aq)|| Cu(s)
Fe3+ + e- Fe2+ Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq)
aRe d aFe 2+ aZn 2+
Q= = Q=
aOx aFe3+ aCuNils
2+
Walter: Chem 260
 Cell reaction and potential
Cathode (Right): Cu2+(aq) + 2e- → Cu(s)
Anode (Left): Zn2+(aq) + 2e- → Zn(s) } this way the reaction
becomes spontaneous

Overall (R-L): Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq) e- disappear

Cell reaction: Difference of electrode half-reactions

(Reduction at Cathode - Oxidation at Anode)

Cell potential E: Potential difference between

the electrodes
Ox + νe- → Red ⇒ νNA e- transferred per mole of
reaction Faraday constant = eNA
= 96,485 Cmol-1
⇒ νNA × (-e) = -ν
νF charge transferred
Maximum electrical work done in
a galvanic cell: w’ = - νNils
F ×Walter:
E = ∆Chem
rG 260
 The cell potential and the Gibbs energy
∆rG
- νFE = ∆rG ⇒ E = − @ equilibrium: ∆rG = 0 ⇒ E = 0
νF
if ∆rG < 0 ⇒ E > 0 for a spontaneous reaction
if ∆rG > 0 ⇒ E < 0 for a non-spontaneous reaction
and ∆ r G = ∆ r G + RT ln Q
O

@ 25oC: 25.7 mV

∆rG
O
⇒ E=−
RT RT
− ln Q = E − ln Q @ equilibrium:
O

νF νF νF
νFE
O

standard cell potential ln K =

Nernst equation RT

Standard cell potentials are measured relative to the

O
standard hydrogen electrode: Pt(s)|| H2(g)|| H (aq) with E = 0 V
+

Nils Walter: Chem 260

 The electrochemical series

reduced E O = E RO − E LO

⇒ a cell reaction
is spontaneous
if ERO > ELO

O
Cathode (Right): Cu2+(aq) + 2e- → Cu(s); ER
O
Anode (Left): Zn2+(aq) + 2e- → Zn(s); EL
Overall (R-L): Cu2+(aq) + Zn(s)
oxidized Cu(s) + Zn2+(aq)

Low reduces high;

high oxidizes low
Nils Walter: Chem 260