ELECTROCHEMISTRY - Electrolytic Cells
ELECTROCHEMISTRY - Electrolytic Cells
ELECTROCHEMISTRY - Electrolytic Cells
An electrolytic cell is an electrochemical cell wherein a non-spontaneous redox reaction is made to occur by pumping
electrical energy into the system. It is composed of a voltage source (battery) connected by wires to two electrodes
dipped in an electrolyte.
• The battery pulls the electrons from the anode, making it positively charged, and
pushes it to the cathode, making it negatively charged.
• The two electrodes is dipped in an electrolyte which is either molten or dissolved
in a suitable solvent.
To maintain electrical neutrality,
• the anions in the electrolyte will go to the positively-charged anode to give up
electrons, undergo oxidation, to produce a neutral substance. On the other hand,
• the cations in the electrolyte will go to the negatively-charged cathode to receive
electrons, undergo reduction, to produce a neutral substance.
This process taking place in an electrolytic cell wherein electricity is used to pass through an electrolyte causing the
separation of materials is called electrolysis.
*Ionic compounds are chemical compounds composed of a cation and an anion held together by electrostatic forces
called ionic bonding.
*An electrolyte is a substance that acquires the capacity to conduct electricity when it is molten or dissolved in water as
it dissociates into ions. All ionic compounds are strong electrolytes.
CHEM131:Electrochemistry 1 of 5
OXIDATION REDUCTION
CHEM131:Electrochemistry 2 of 5
Water will undergo oxidation at the anode to produce oxygen gas since it will need lesser voltage for the reaction to
occur.
The overall reaction for the reaction is
2H2O(l) + 2e − → H2(g) + 2OH(aq)
−
E ∘ = − 0.83V
+
2H2O(l) → O2(g) + 4H(aq) + 4e − E ∘ = − 1.23V
2H2O(l) → 2H2(g) + O2(g) E ∘ = − 2.06V
Water is a weak electrolyte, it does not undergo electrolysis easily. In this case, water is converted to hydrogen gas and
oxygen gas and the Na+(aq) and the F-(aq) stay in solution. The sodium fluoride undergoes no chemical change - it simply
provides ions to carry the current.
Decomposition of Aqueous KI
• The aqueous solution is an electrolyte which is a mixture of two electrolytes - the compound and the water.
- The water ionizes to give H+ and OH- ions
- KI dissolves in water to form K+ and I-
• Possible cathode reduction reactions
2H2O(l) + 2e − → H2(g) + 2OH(aq)
−
E ∘ = − 0.83V
K(aq) + e − → K(s) E ∘ = − 2.936V
Water will undergo reduction at the cathode to produce hydrogen gas since it will need lesser voltage for the reaction to
occur.
• Possible anode oxidation reactions
+
2H2O(l) → O2(g) + 4H(aq) + 4e − E ∘ = − 1.23V
−
2I(aq) → I2(g) + 2e − E ∘ = − 0.534V
Iodide ion will undergo oxidation at the anode to produce iodine gas since it will need lesser voltage for the reaction to
occur.
The overall reaction for the reaction is
2H2O(l) + 2e − → H2(g) + 2OH(aq)
−
E ∘ = − 0.83V
−
2I(aq) → I2(g) + 2e − E ∘ = − 0.534V
− −
2H2O(l) + 2I(aq) → H2(g) + I2(g) + 2OH(aq) E ∘ = − 1.334V
The hydrogen ion in water undergoes reduction producing hydrogen gas at the cathode and the iodide ion in KI
undergoes oxidation producing iodine gas at the anode. The hydroxide ion and the potassium ion remains in solution
forming potassium hydroxide.
CHEM131:Electrochemistry 3 of 5
Electrolysis of Aqueous NaCl
• The aqueous solution is an electrolyte which is a mixture of two electrolytes - the compound and the water.
- The water ionizes to give H+ and OH- ions
- NaCl dissolves in water to form Na+ and Cl-
• Possible cathode reduction reactions
2H2O(l) + 2e − → H2(g) + 2OH(aq)
−
E ∘ = − 0.83V
Na(aq) + e − → Na(l) E ∘ = − 2.71V
Water will undergo reduction at the cathode to produce hydrogen gas since it will need lesser voltage for the reaction to
occur.
• Possible anode oxidation reactions
+
2H2O(l) → O2(g) + 4H(aq) + 4e − E ∘ = − 1.23V
−
2Cl(aq) → Cl2(g) + 2e − E ∘ = − 1.36V
Ideally, water will undergo oxidation to produce O2 since it will need lesser voltage for the reaction to occur.
In actual electrolysis of aqueous NaCl, Cl2 is formed at the anode instead of O2. This is because the formation of O2
involves higher activation energy(overvoltage), thus kinetically less favorable.
The overall reaction for the reaction is
2H2O(l) + 2e − → H2(g) + 2OH(aq)
−
E ∘ = − 0.83V
−
2Cl(aq) → Cl2(g) + 2e − E ∘ = − 1.36V
− −
2H2O(l) + 2Cl(aq) → 2OH(aq) + H2(g) + Cl2(g) E ∘ = − 2.19V
The hydrogen ion in water undergoes reduction producing hydrogen gas at the cathode and the chloride ion in NaCl
undergoes oxidation producing chlorine gas at the anode. The hydroxide ion and the sodium ion remains in solution
forming sodium hydroxide.
Sodium hydroxide is commercially produced by electrolysis of a brine solution – saturated solution in a chlor-alkali
process.
Chlorine is used to
purify drinking water
and large quantities
are consumed in Hydrogen is used
making plastics such chiefly in the synthesis
as PVC of ammonia
Sodium hydroxide is
used in processing
pulp and paper, in
the purification of
aluminum ore, in the
manufacture of glass
and textiles
CHEM131:Electrochemistry 4 of 5
Applications of Electrolysis
• Production of Chemicals
Many chemicals, such as caustic soda, chlorine, potassium permanganate, ammonium per-sulphate, hydrogen and
oxygen etc. are produced by electrolysis on a large scale. The most important is production of caustic soda by
electrolysis of brine. During the process of electrolysis of brine, chlorine is given off at one electrode (at anode) and
hydrogen at the other (at cathode) leaving caustic soda in the cell. The brine solution becomes more and more rich in
caustic soda. The by-products of hydrogen and chlorine in no way are less important. These by-products are further
used to produce hydrochloric acid (HCI). If chlorine and hydrogen are not separated, hydrochloride, chlorate or peri
CHEM131:Electrochemistry 5 of 5
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