Chemistry 30: Electrolytic Cells
Section 13.3 (pgs 502-513)
Electrolytic Cell
• A cell that uses an external source of electrical
energy to drive a non-spontaneous redox
reaction
• Converts electrical energy into chemical
energy
Pg. 503
Voltaic Cell Electrolytic Cell
Spontaneous reaction Non-spontaneous reaction
Chemical energy electrical energy Electrical energy chemical energy
Anode (negatively charged) : Anode (positively charged):
Cathode (positively charged) : electrode Cathode (negatively charged):
Oxidation (at anode): Oxidation (at anode):
Reduction (at cathode): Reduction (at cathode):
Anions to anode, cations to cathode Anions to anode cations to cathode
Electrons travel from anode to cathode Electrons travel from anode to cathode
Electrolytic Cell
• All definitions are the same as for voltaic cells,
except the signs on the electrodes change
Cell Potentials
• A negative cell potential means a non-
spontaneous reaction
• We interpret this voltage as the voltage needed
in order to drive the non-spontaneous reaction
Electrolysis of Water
• Locate the two half reactions that contain pure
water
• Oxidation (anode) 2H2O (l) O2 (g) + 4H+ (aq) + 4e-
• Reduction (cathode) 2H2O (l) + 2e- H2 (g) + 2OH- (aq)
Electrolysis of Water
• When water is subjected to electrolysis:
– Some water molecules are oxidized at the anode
while other water molecules are reduced at the
cathode
• Oxidation (anode) 2H2O (l) O2 (g) + 4H+ (aq) + 4e- -E = -0.82 V
• Reduction (cathode) 2H2O (l) + 2e- H2 (g) + 2OH- (aq) E= -0.42 V
– Note that values reported here are different from those in table, as species in water are
not present in 1.0 mol/L
Electrolysis of Aqueous Solutions
• Sir Humphry Davy (1778-1829) used a large
voltaic cell with which to conduct electrolysis
experiments
• Wanted to isolate pure metals from aqueous
solutions
Electrolysis of Aqueous Solutions
• Oxidation: 2Cl- (aq) Cl2 (g) + 2e-
• Reduction: Na+ (aq) + e- Na (s)
• Instead, hydrogen gas was produced
• The only source of hydrogen was the water in
which the sodium chloride was dissolved
• Water was being reduced at the cathode
instead of sodium ions
Chlor-Alkali Process
• Chlorine and sodium hydroxide are two of the most
extensively produced commercial chemicals
• Chlorine
– Laundry bleach
– Bleach paper pulp
– Disinfectant
– Water treatment
– Polyvinyl chloride (plastic)
• Sodium hydroxide
– Paper industry
– Soaps, detergents
– Aluminum
Chlor-alkali Process
• 2Cl- (aq) Cl2 (g) + 2e-
• (Anode (+))
• 2H2O (l) + 2e- 2OH- (aq) + H2 (g)
• (Cathode (-))
Chlor-Alkali Process
Predicting Products of Electrolysis of
Aqueous Solution
• Choose the half-reactions that contain the
strongest oxidizing agent and strongest
reducing agent
Electroplating
• Process by which metal ions in solution are
reduced, coating the electrode with metal
• Predict the products of the electrolysis of 1.0
M copper (II) sulfate
Predicting Products of the Electrolysis of
Molten Salts
• Since water is not present, the only two half-
reactions that can occur are the reduction of
the cation and oxidation of the anion
• Eg. the electrolysis of molten sodium chloride
• Na+ (l) + e- Na (l)
• 2Cl- (l) Cl2 (g) + 2e-
• Rechargeable batteries function as both voltaic
and electrolytic cells
– When they are discharging (being used to provide
electricity), they are functioning as voltaic cells
– When they are recharging (an external source of
electricity is used to drive the reverse
nonspontaneous reaction), they are functioning as
electrolytic cells
Lead Storage Battery (Rechargeable
Battery)
Lead Storage Battery
• 3, 5, 2, 3
• Pg 508 #5-8
• Pg. 513 #1-3, 5-7
