By Kamal Ahmad (LGS, BSS, CBS)

Electrochemistry-Notes-OL
Electrolysis:
“When current flows through a molten or aqueous solution of ions then redox reactions occur to form neutral
products”.

What is current?
“It is the movement of electrons in one direction in a wire”. Similarly, in a liquid, the movement of positive &
negative ions in a specific direction is also called current.

Electrolyte:
“A liquid that contains freely moveable positive & negative ions is called electrolyte”. So the current can flow
through an electrolyte due to the presence of these free ions.
There are two types of electrolytes,
(i) Molten (liquid) Salts:
Solid salt can be converted into the liquid by heating. For example, if we heat the table salt (NaCl) up to 801 0C,
it melts and converts into liquid. So, positive & negative ions become free (or separated). Now it is called a
molten salt which is an electrolyte.
Diagram:

(ii) Aqueous Solution of Salt:

When a soluble salt is dissolved in water then its positive & negative ions become free. Now this aqueous
solution of the salt is an electrolyte.
Diagram:

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 By Kamal Ahmad (LGS, BSS, CBS)
Electrolysis of molten (or liquid) NaCl
In this electrolysis, molten NaCl is an electrolyte than contains free Na+1 and Cl-1 ions.
Diagram:

Do practice
to make all
diagrams of
this chapter

Reactions occurring at Anode & Cathode Or Ionic half-equations:

A reaction that occurs at electrode is called electrode reaction. It could be oxidation (lose of electrons) or
reduction (gain of electrons). Oxidation occurs at anode while reduction occurs at cathode.
At anode: (oxidation: Loss of electrons)

2Cl-1 (l) → Cl2(g) + 2e-

At cathode: (Reduction: Gain of electrons)

Na+1(l) + 1e- → Na(s)

Chemical equation of reaction that is occurring at anode or cathode is known as “ionic half equation”.

Important points of electrolysis of molten NaCl:

 Always mention the physical states of substances in an electrode reaction.
 Diatomic elements are H2, O2, N2, F2, Cl2, Br2, I2, At2 (8 non-metals) while most of the other elements
exist as monatomic form e.g. Na, Mg, Fe, Cu, Pb etc.
 We can predict products easily when we perform electrolysis of molten salts or ionic compounds
 Metal and hydrogen ions, due to attraction, go to cathode and non-metal ions go to anode so we get
metals at cathode while non-metals at anode.
 Ions go to their respective electrodes and convert into neutral substances, this is called discharging of
ions because ions lose their charges during electrode reactions.

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 By Kamal Ahmad (LGS, BSS, CBS)
What is an electrode?
An electrode is made up of a metal or graphite that can conduct the current. Electrode that is connected with
the positive terminal of battery is called anode (carries positive charge) and the electrode that is connected
with the negative terminal of battery is called cathode (carries negative charge).
Best electrode is graphite due to the following reasons,
1. conducts electricity
2. unreactive or inert
3. insoluble
4. high melting point conducts electricity
Note: Alternative of graphite is platinum (Pt) that is another inert electrode.

Role of battery:
It is a power source of electricity. Battery acts as an electron pump. It takes up the electrons from anode and
sends the electrons to cathode. Remember that the charge on anode is positive while on cathode is negative.

Separation of ions of an ionic compounds when it melts

Subscript (lower number) of an ion becomes coefficient on other side of arrow

NaCl (S) Na+1 (l) + Cl-1(l)

PbBr2(S) Pb+2 (l) + 2Br-1(l)
Li2O (S) 2Li+1 (l) + O-2(l)
Al2O3 (S) 2Al+3 (l) + 3O-2(l)
Predicting the products of some important molten ionic compounds at cathode
and anode during electrolysis
Salt or Ionic compound Ions At cathode At anode
NaCl Na+1, Cl-1 Na Cl2
PbBr2 Pb+2, Br-1 Pb Br2
CaCl2 Ca+2, Cl-1 Ca Cl2
Li2O Li+1, O-2 Li O2

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 By Kamal Ahmad (LGS, BSS, CBS)
Electrolysis of dil. Aqueous NaCl
When a salt is dissolved in water then its positive & negative ions become free.
As water is also there so few molecules of water, out of total water molecules, are present in the form of ions
(H+1 & OH-1). Water is broken down into its ions as,

H2 O H+1 + OH-1
So, when water breaks up into its ions, we get one hydrogen ion (H+1) and one hydroxide ion (OH-1).
When NaCl is dissolved in water then it gets separated into its ions as,

So now, due to presence of water, we have two positive ions (Na+1 & H+1) and two negative ions (Cl-1 & OH-1)
in the solution or electrolyte
Diagram:

Due to attraction, both positive ions go to cathode and both negative ions go to anode.
One positive ion has more tendency to discharge than the other one which is according to discharging series
of positive ions. Similarly, discharging of the negative ions is also as per their discharging series,

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 By Kamal Ahmad (LGS, BSS, CBS)

Remember that SO4-2

and NO3-1 never ever
discharged during the
electrolysis

Important:
From Na+1 & H+1, H+1 will discharge, in dilute as well as concentrated salt solutions, because it is lower in the
series. Similarly, from Cl-1 & OH-1, OH-1 will be discharged when solution is dilute but if the salt solution is
concentrated then Cl-1 will be discharged because now concentration of chloride ions is greater than OH-1
ions.
Remember that metals and hydrogen ions go to cathode while non-metals go to anode.

Reactions occurring at Anode & Cathode:

At anode: (oxidation: Loss of electrons)

4OH-1 (aq) → 2H2O (l) + O2 (g) + 4e-

At cathode: (Reduction: Gain of electrons)

2H+1(aq) + 2e- → H2 (g)

Electrolysis of Concentrated aq. NaCl
Now at anode, we get Cl2 gas instead of O2. Rest of things are same as above topic.
Rule: For concentrated solution, negative ion other than OH-1 will discharge.
Reason: Concentration of Cl-1 ions is greater than OH-1 ions.

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 By Kamal Ahmad (LGS, BSS, CBS)
Therefore, only the reaction occurring at anode will be changed as,
At anode: (oxidation: Loss of electrons)

2Cl-1 (aq) → Cl2(g) + 2e-

Note: Metals or hydrogen are formed at the cathode and that non-metals (other than hydrogen) are formed
at the anode

Extraction of Al by electrolysis
 Aluminium is extracted (separated) commercially from “bauxite” by electrolysis.
 Bauxite is a mixture of different substances that mainly contains Aluminium oxide, Al2O3 therefore
bauxite is an “ore” of Al (An ore is a natural rock from which a metal can be extracted commercially)
 To increase electrical conductivity of Al2O3 and to decrease melting point of bauxite, another
substance cryolite is added.
 Now heat up to 1000 0C to get “molten Al2O3 + Cryolite” mixture
 In this electrolysis, both electrodes (anode and cathode) are made up of graphite (Carbon)
 When Al2O3 melts then it separates into its ions as,

Al2O3 (S) 2Al+3 (l) + 3O-2(l)

Diagram:

Reactions occurring at Cathode & Anode:

At cathode: (Reduction: Gain of electrons)

Al+3(l) + 3e- → Al (s)

At anode: (oxidation: Loss of electrons)

2O-2 (l) → O2 (g) + 4e-

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 By Kamal Ahmad (LGS, BSS, CBS)
As the temperature is very high during electrolysis, O2 (which is formed at anode) reacts with graphite (C)
anode to form CO2 gas. So, the final product at anode is CO2 instead of O2. Reaction is,

C + O2 → CO2
Inert & reactive electrodes
During electrolysis, if an electrode does not take part in a chemical reaction then it is called inert electrode
but if an electrode takes part in a chemical reaction then it is called reactive electrode. Size of the reactive
electrode may be decreases or increased depending upon the situation.
Remember that in extraction of Al2O3, anode is a reactive electrode while cathode is an inert electrode.

Purification of Cu by electrolysis
Or
Electrolysis of aq. CuSO4 using copper electrodes
Copper, which is produced in the factories, is not 100% pure. So Cu is impure that means there are some
impurities in copper. This impure copper can be purified by the help of electrolysis.
During the electrolysis the impure Cu is connected with the positive terminal of battery (so impure Cu
becomes anode) while a thin rod of pure Cu is connected with the negative terminal of battery (so pure Cu
becomes cathode).
Electrolyte is aq. CuSO4 (copper sulfate solution)
Diagram:

Process explanation (to develop a good understanding):

Let’s focus on a single atom of Cu which is present in impure Cu anode. This Cu atom loses two electrons,
becomes Cu+2 ion and dissolves in solution of aq. CuSO4

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 By Kamal Ahmad (LGS, BSS, CBS)
Now this Cu+2 ion or another Cu+2 ion from solution goes to cathode, gains two electrons, becomes Cu atom
and deposits on cathode
So, by time size of pure Cu cathode increases while size of impure Cu anode decreases. In this way, Cu from
impure anode is transferred to pure cathode. This is called purification of Cu. Both the electrodes taking part
in the chemical reaction therefore these are referred as reactive electrodes.
Remember, there are two positive ions Cu+2 & H+1. Cu+2 will discharge as it is lower than H+1 in the series. All
other ions like H+1, OH-1 and SO4-2 are left unchanged in solution.

Reactions occurring at Anode & Cathode:

At anode: (oxidation: Loss of electrons)

Cu (s) → Cu+2 (aq) + 2e-

At cathode: (Reduction: Gain of electrons)

Cu+2 (aq) + 2e- → Cu (s)

(Remember that second equation is a reverse of the first equation)
Use of copper: In electrical wiring because of its good electrical conductivity and ductility
Color of electrolyte: In the purification of copper, Cu is being transferred from anode to cathode so number of
Cu+2 ions stay constant in the solution. Blue color of solution is due to Cu+2 ions so the color remains
unchanged with the time.

Electroplating by electrolysis
“To deposit layer of one metal on another metal by using current is called electroplating”
Recall above topic (purification of copper), if we connect a metal iron spoon with negative terminal of battery
(instead of pure Cu piece) then a layer of Cu will be deposited on iron spoon. In this way iron spoon is
electroplated by copper. This is called copper plating.
Diagram:

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 By Kamal Ahmad (LGS, BSS, CBS)
Important points

 Metal which is to be deposited is made anode (connected with positive terminal of battery)
 Electrolyte is aq. solution of a salt of depositing metal e.g. to deposit Cu, electrolyte is aq. CuSO4
 Second metal, which is electroplated, is made cathode (connected with negative terminal of battery)

Reactions occurring at Anode & Cathode:

At anode: (oxidation: Loss of electrons)

Cu (s) → Cu+2 (aq) + 2e-

At cathode: (Reduction: Gain of electrons)

Cu+2 (aq) + 2e- → Cu (s)

(Remember that second equation is the reverse of first equation)

Use of electroplating:
 To make objects that are more resistant to corrosion
 To improve the appearance
 To make harder objects
Remember that in the purification of Cu and electroplating, both the electrodes are reactive.

Electrolysis of dil. aq. CuSO4 using inert electrode

Ions = Cu+2, SO4-2, H+1, OH-1
According to reactivity series, Cu+2 and OH-1 will be discharged.

Reactions occurring at Anode & Cathode:

At anode: (oxidation: Loss of electrons)

4OH-1 (aq) → 2H2O (l) + O2 (g) + 4e-

At cathode: (Reduction: Gain of electrons)

Cu+2 (aq) + 2e- → Cu (s)

Products: Copper and oxygen (O2) gas
Color of electrolyte: Cu+2 ions are discharged here so the number of Cu+2 ions is decreasing in the solution. As
blue color of solution is due to Cu+2 ions so the color fades with time.

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 By Kamal Ahmad (LGS, BSS, CBS)
Electrolysis of Water (containing a little H2SO4, using inert electrodes)
Or
Electrolysis of dil. H2SO4
To conduct electrolysis of water, we need to add a little amount of H2SO4 into the water.
Water dissociates into its ions as,

H2O → H+1 + OH-1

Sulfuric acid dissociates into its ions as,

H2SO4 → 2H+1 + SO4-2

So, ions in aqueous solution of sulfuric acid are H+1, OH-1 and SO4-2. When electrolysis is carried out then we
get H2 gas at cathode and O2 at anode while sulfate ions (SO4-2) stay in solution. So, ions of water convert into
products. As the amount of water decreases in the solution so concentration of H2SO4 increases. At
electrodes, we get double volume of hydrogen as compared to oxygen because hydrogen is double than
oxygen in the formula of water (H2O) Or we can say that mole ratio of H to O in water is 2:1

Reactions occurring at Anode & Cathode:

At anode: (oxidation: Loss of electrons)

4OH-1 (aq) → 2H2O (l) + O2 (g) + 4e-

At cathode: (Reduction: Gain of electrons)

2H+1(aq) + 2e- → H2 (g)

Very important:

Remember that during the

electrolysis of dil. H2SO4,
ions of water (H+1 & OH-1)
are actually electrolyzed. So,
we get two gases hydrogen
and oxygen. Vol. of
hydrogen is double than vol.
of oxygen because in the
water, ratio of H:O is 2:1.

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 By Kamal Ahmad (LGS, BSS, CBS)
A same type of electrolysis occurs of dilute aq. solution of HCl, NaOH or KOH that gives the same products,
hydrogen & oxygen in molar ratio 2:1.
This whole process is also known as “decomposition of water” into hydrogen and oxygen by electrolysis and it
is an endothermic process because it needs energy in the form of current.

Important observations in electrochemistry

 Hydrogen = bubbles of colorless gas
 Oxygen = bubbles of colorless gas
 Chlorine = bubbles of green gas
 Bromine = bubbles of orange gas or orange liquid
 Pb= Grey solid
 Cu= Pink solid

Hydrogen–oxygen fuel cell

“A hydrogen–oxygen fuel cell uses hydrogen and oxygen to produce electricity with water as the only chemical
product”.
Overall reaction that occurs in the fuel cell is,

Water is the only product of this reaction.

Let’s observe the oxidation states of H and O in the water molecule, on the right side of above reaction. It is
obvious that H has been oxidized while O has been reduced, so electrons have been transferred from H to O.
Let’s allow this transfer of electrons through a wire, for which, we have following apparatus,

Since hydrogen & oxygen are

continuously supplied as fuel
of the cell therefore this is
called fuel cell.

H2 is continuously supplied at anode where it is oxidized (loose electrons).

O2 is continuously supplied at cathode where it reduces (gain electrons).

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 By Kamal Ahmad (LGS, BSS, CBS)
Electrolyte is aq. KOH so ions in solution are K +1, H+1 and OH-1. Only H+1 and OH-1 ions are used up in reactions
at electrodes while K+1 ions stay in solution.

Reactions occurring at Anode & Cathode:

At hydrogen anode: (oxidation: Loss of electrons)

Memorize eq.1 and eq.2

for exams.
At oxygen cathode: (Reduction: Gain of electrons)

Use of fuel cell:

It is used in spaceships & some buses to produce electrical energy.

Advantages of fuel cell as compared to petrol or gasoline engines:

 Fuel cells are more energy efficient than petrol engines.
 The product of fuel cell is water only that is environment friendly, so it causes no pollution.
 Fuel cells use H2 and O2 that are renewable sources. These can be re-obtained as given below,
 electrolysis of water gives hydrogen & oxygen Reaction: 2H 2O → 2H2 + O2
 cracking of methane gives hydrogen Reaction: CH4 → C + 2H2

Disadvantages of fuel cell:

 Storage problem with hydrogen or oxygen.
 Hydrogen is explosive so its handling could be a risk.

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