ELECTROCHEMISTRY - Electrolytic Cells

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CHEM 131: CHEMISTRY FOR ENGINEERS

ELECTROCHEMISTRY: Electrolytic Cells


Prepared by: Engr. Karla Jane N. Puracan

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.

Electrolysis of Molten Electrolyte


When a molten electrolyte is made to undergo electrolysis:
• There is reduction of a cation at the cathode to a corresponding metal, and
• Oxidation of an anion at the anion to a corresponding nonmetal
Example:
The industrial production of sodium metal is done through the electrolysis of molten NaCl. IT is carried out in Downs
cells at a 600C temperature with chlorine as a by-product. The anode and cathode chambers are separated by a steel
screen to prevent contact between molten sodium metal and chlorine gas to prevent an explosive reaction between the
two reactive elements. The molten sodium metal forms at the cathode and chlorine gas is formed at the anode.
Sodium ions migrate to the cathode, where electrons enter the melt and are reduced to sodium metal:
+
2Na(l) + 2e − → 2Na(l)
Chloride ions migrate the other way, toward the anode. They give up their electrons to the anode and are oxidized to
chlorine gas:

2Cl(l) → Cl2(g) + 2e −
The overall reaction is: 2NaCl(l) → 2Na(l) + Cl2(g)

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OXIDATION REDUCTION

anions move to cations move to


the anode to give the cathode to
up their electrons consume the
electrons
Cl- move to Na+ move to
the anode the cathode
anions loses Cations combine with
electrons and are the electrons and are
transformed to transformed to
neutral elements neutral elements or
molecules
or molecules
Cl2 gas is Metallic Na is
formed
formd

Electrolysis of Aqueous Electrolyte


The electrolysis of an aqueous electrolyte is more complicated because of the presence of water which can also
undergo electrolysis to produce hydrogen gas and oxygen gas.
* The electrolysis of water is the decomposition of water into oxygen gas and
hydrogen gas due to the passage of an electric current.
- at the cathode, hydrogen ions combine with electrons from the external circuit to
form hydrogen gas
- at the anode, hydroxide ions give up electrons to form oxygen gas
Because of this, there are two possible reactions that would take place at the anode and
the cathode
• at the cathode
- The reduction of a cation to a corresponding metal
- The reduction of a water molecule to hydrogen gas
• At the anode
- The oxidation of an anion to the corresponding nonmetal
- The oxidation of a water molecule to oxygen gas
The material produced in each electrode would depend on the half reaction that would require the least amount of
voltage for the reaction to take place.
Decomposition of Aqueous NaF
• 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
- NaF dissolves in water to form Na+ and F-
• 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

2F(aq) → F2(g) + 2e − E ∘ = − 2.889V

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

2Cl−(aq) + 2H2O(l) → Cl2(g) + H2(g) + 2OH−(aq)

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

chlorates are produced. 


• Electrolytic Reduction of Metals from their Compounds
• Extraction and Refining of Metals
Electrolytic refining is the process of the refining of metal from their ores or compounds in which an impure metal is
made the anode and a thin strip of pure metal is made the cathode. A solution of metal salt is used as an electrolyte.
Electrolytic Refining of Copper
- Impure copper from the chemical reduction of copper ore is
cast into large slabs that serve as the anodes for electrolytic
cells.
- The cells use thin sheets of ultra pure copper as cathodes and
aqueous copper (II) sulfate as the electrolyte.
- The impure copper slabs contain impurities which are also
oxidized at the anode.
- By maintaining a low voltage supply, only copper is deposited
at the cathode, which is made of pure copper metal sheet and
the ionic impurities remain in the solution.
• Electroplating
Electroplating is the coating of one metal on the surface by means of electrolysis. The object to be plated serves as the
cathode and the plating metal serves as the anode. The metals which are most commonly used in electroplating include
gold, silver, copper, nickel and chromium. The thin coating protects metals from corrosion, serves as decoration, help in
conduction of electricity, reduce friction and even protect from radiation. Plating a thin coating of a metal that resists
corrosion can protect other metals that readily corrode. The electrolyte used usually contains a low concentration of
electroplating metal.

CHEM131:Electrochemistry 5 of 5

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