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( Introduction )

( Molten electrolyte )

( Aqueous electrolyte )

( Summary )

We have learnt that ionic compounds conduct electricity when molten or aqueous.

When an electric current passes through such compounds, the compounds are decomposed in a chemical reaction. This is known as electrolysis.

The ionic compound is called an electrolyte.

We will learn about the electrolysis of:

Molten ionic compounds Aqueous ionic compounds

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Let us look at the electrolysis of molten lead (II) bromide. The experimental setup is shown below.

Heat
Heat

Carbon electrodes

Porcelain crucible Clay triangle

Molten lead(II) bromide

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ELECTRODES

Anode

The electrode attached to the positive terminal of the cell.

Anions are attracted to it.

Cathode

The electrode attached to the negative terminal of the cell.

Cations are attracted to it.

Electrodes are usually made of carbon or platinum, as they are unreactive or inert. They do not react with the compounds in electrolysis.

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At the cathode

The lead ions take electrons from the cathode to become lead atoms (reduction).

 
Pb 2+
Pb 2+

+

e -
e -
e -
e -
Pb 2+ + e - e - Pb
Pb
Pb

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Pb 2+

+

2e -

( Exit ) Pb + 2e Pb

Pb

Lead forms molten globules at the bottom of the crucible. We say the lead ions have been discharged.

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At the anode

The bromide ions donate electrons to the anode to become bromide molecules (oxidation).

Br - Br - 2Br -
Br -
Br -
2Br -
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Br Br Br 2
Br
Br
Br 2

+

e - e -
e -
e -

+

2e -

The bromine is seen as a reddish-brown gas around the anode during the electrolysis.

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( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary ) The overall

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The overall chemical reaction is PbBr 2 Pb + Br 2 cathode anode Lead ions are
The overall chemical reaction is
PbBr 2
Pb
+
Br 2
cathode
anode
Lead ions are
Bromide ions are
attracted to the
Pb 2+
Br -
attracted to the
cathode
anode
Pb 2+
Br -
Molten lead (II) bromide
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Lead ions move

near to cathode

cathode anode Pb 2+ Br - Pb 2+ Br - Molten lead (II) bromide
cathode
anode
Pb
2+
Br -
Pb
2+
Br -
Molten lead (II) bromide

Bromide ions

move near to

anode

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  • Bromide ions
    donate electrons

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from anode to

Electrons flow

battery

Bromide ions

donate electrons

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Battery pumps electrons

  • Bromide ions
    donate electrons

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Electrons flow

from battery to

cathode

  • Bromide ions
    donate electrons

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Electrons flow

from battery to

cathode

Lead ions accept

electrons

e - e - cathode e - anode e - e - e - e -
e
-
e -
cathode
e
-
anode
e -
e -
e
-
e
-
e
-
e -
Pb
2+
Br -
e
-
e -
Pb
2+
Br -
Molten lead (II) bromide

Bromide ions

donate electrons

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Lead atoms are

produced

cathode anode Br Mg Pb Cl Br Br Mg Pb Cl Br Molten lead (II) bromide
cathode
anode
Br
Mg
Pb
Cl
Br
Br
Mg
Pb
Cl
Br
Molten lead (II) bromide

Bromine atoms

combine to form

bromine gas

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QUIZ 1

1. The electrolysis of molten iron (III) chloride yields iron metal and a gas. What is the colour of this gas produced?

  • A. Reddish-brown.

    • B. Colourless.

    • C. Yellowish-green.

Click on the correct answer

Next question

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QUIZ 1

2. With reference to the previous question, at which electrode is the gas formed?

A.

Anode.

B.

Cathode.

Click on the correct answer

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Solutions can be electrolysed using the apparatus shown below.

carbon electrodes

test-tubes - + to battery
test-tubes
-
+
to battery

electrolyte (solution)

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Let us look at the electrolysis of dilute sulfuric acid. The experimental setup is shown below.

carbon electrodes

test-tubes - + to battery
test-tubes
-
+
to battery

dilute sulfuric acid

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At the cathode

The hydrogen ions take electrons from the electrode to become hydrogen atoms (reduction).

H + H +
H +
H +
+ e - + e -
+
e
-
+
e -
H
H
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H

When two of the newly formed atoms combine, hydrogen gas is produced.

H
H

+

H
H

H

+

H

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H H H 2
H
H
H 2

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At the anode

There are two anions in the electrolyte: hydroxide and sulfate ions. Since hydroxide ions are easier to discharge, oxygen gas is produced at the anode.

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O O
O
O
H H O + +
H
H
O
+
+
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e - e - e - e -
e -
e -
e -
e -
OH - OH - OH - OH - ( Exit )
OH -
OH -
OH -
OH -
( Exit )

4OH -

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O 2

+

2H 2 O

+

4e -

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The electrolysis of dilute sulfuric acid is will result in the production of

hydrogen gas and oxygen at the cathode and anode respectively.

- +
-
+
oxygen
oxygen

hydrogen

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carbon electrodes

dilute sulphuric acid

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What gas do you think will be found at the anode when aqueous copper(II) sulphate is electrolysed?

Sulphur dioxide?

No, not quite. Oxygen gas is evolved at the anode instead and copper metal is deposited at the cathode.

How do you explain this phenomenon?

The products can come from the electrolyte or from the water present. The product that is discharged depends on the nature

of the ions.

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Negative ions from the electrolyte are discharged if they are chloride, bromide or iodide ions. For sulphates and nitrates, oxygen from water is discharged.

Positive ions from the electrolyte that are below H + (aq) in the electrochemical (or reactivity) series are discharged at the

negative cathode.

If the positive ions are those of reactive metals above H + (aq)

(e.g ..

Na + , K + and Ca 2+ ), hydrogen gas from water is

discharged.

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Cations

Anions

K + (aq)

SO 4 2- (aq)

Na + (aq)

NO 3 - (aq)

Ca 2+ (aq)

Cl - (aq)

Mg 2+ (aq)

Br - (aq)

Zn 2+ (aq)

I - (aq)

Fe 2+ (aq)

OH - (aq)

Pb 2+ (aq)

H + (aq)

Cu 2+ (aq)

Ag + (aq)

Difficulty of

discharge

decreases

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QUIZ 2

1. When we electrolyse a solution, what takes place at the cathode?

A.

Oxidation.

B.

Reduction.

Click on the correct answer

Next question

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QUIZ 2

2. During the electrolysis of sulphuric acid, hydrogen gas and another gas are produced. What is the other gas?

A.

Oxygen.

  • B. Sulphur dioxide.

Click on the correct answer

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The decomposition of a substance by electricity is called electrolysis.

An electrolyte is an ionic compound, in the molten or aqueous state, that conducts electricity and is decomposed by the current.

The rods through which the direct current enters and leaves the cell are known as electrodes. Electrodes are usually inert.

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The anode is the electrode which is connected to the positive terminal of a cell. Anions are attracted to it. Oxidation occurs at the anode.

The cathode is the electrode connected to the negative terminal of the cell. Cations are attracted to the cathode. Reduction occurs at this electrode.

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When a molten electrolyte is electrolysed,

a metal (from the positive ions) is discharged at the cathode.

a non-metal (from the negative ions) is discharged at the anode.

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When a aqueous electrolyte is electrolysed,

the products come from either the electrolyte or water present.

The product at the cathode is a metal or hydrogen gas.

The product at the anode is a non-metal.

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Reactive metals are not discharged at the cathode. Instead, hydrogen from water is evolved.

Sulfate and nitrate ions are not discharged at the anode. Instead, oxygen from water is produced.

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