Electrochemistry & Electrolysis

ELECTROLYSIS
ELECTROLYSIS
CONTENTS
• What is electrolysis?
• Electrolysis of ionic compounds
• Electrolysis of molten sodium chloride
• Electrolysis of aqueous sodium chloride (brine)
ELECTROLYSIS
Passing an electric current through ionic substances that are molten

or in aqueous solution, breaks them down into elements.
ELECTROLYSIS

The process is known as ELECTROLYSIS

ELECTROLYSIS

During electrolysis…
Positively charged ions move to the negative electrode - CATHODE
Negatively charged ions move to the positive electrode - ANODE
ELECTROLYSIS

During electrolysis…
Positively charged ions move to the negative electrode - CATHODE
Negatively charged ions move to the positive electrode - ANODE
CATHODE +ive ions gain electrons REDUCTION

ANODE - ive ions give up (lose) electrons OXIDATION
ELECTROLYSIS OF
IONIC COMPOUNDS
CONDUCTING ELECTRICITY
For a substance to conduct electricity it must have either…


electrons which are free to move about (metals / graphite)

or ions which are free to move about

or ions which are free to move about
When an ionic substance is melted or dissolved in water,

the ions are free to move about within the liquid or solution.
ELECTROLYSIS OF IONIC COMPOUNDS
SOLID
Cl- Na+ Cl- Na+
Na+ Cl- Na+ Cl-
Cl- Na+ Cl- Na+
WHEN SOLID, THE IONS

ARE NOT FREE TO MOVE
NO CONDUCTION
OF ELECTRICITY
SOLID IONIC COMPOUNDS DON’T CONDUCT ELECTRICITY

SOLID MOLTEN
Cl- Na+ Cl- Na+

Na+ Cl-
Na+ Cl- Na+ Cl- Na+
Cl-
Cl-
Cl- Na+ Cl- Na+
Cl-
Na+ Na+
WHEN SOLID, THE IONS WHEN MOLTEN, THE IONS

ARE NOT FREE TO MOVE ARE FREE TO MOVE
NO CONDUCTION ELECTRICITY IS
OF ELECTRICITY CONDUCTED
MOLTEN IONIC COMPOUNDS DO CONDUCT ELECTRICITY

SOLID
Cl- Na+ Cl- Na+
Na+ Cl- Na+ Cl-
Cl- Na+ Cl- Na+

NO CONDUCTION
OF ELECTRICITY
SOLID IONIC COMPOUNDS DON’T CONDUCT ELECTRICITY

SOLID
Cl- Na+ Cl- Na+
Na+ Cl- Na+ Cl-

Add to water
Cl- Na+ Cl- Na+

NO CONDUCTION
OF ELECTRICITY
AQUEOUS SOLUTIONS OF IONIC COMPOUNDS DO CONDUCT ELECTRICITY

SOLID IN AQUEOUS SOLUTION
Cl- Na+ Cl- Na+

Na+ Cl-
Na+ Cl- Na+ Cl- Na+
Cl-
Cl-
Cl- Na+ Cl- Na+
Cl-
Na+ Na+
WHEN SOLID, THE IONS WHEN DISSOLVED IN

ARE NOT FREE TO MOVE WATER, THE IONS ARE
FREE TO MOVE
NO CONDUCTION
OF ELECTRICITY ELECTRICITY IS
CONDUCTED
AQUEOUS SOLUTIONS OF IONIC COMPOUNDS DO CONDUCT ELECTRICITY

ELECTROLYSIS OF
MOLTEN SODIUM
CHLORIDE
ELECTROLYSIS OF SODIUM CHLORIDE
DOWNS CELL
SOLID SODIUM CHLORIDE DOES NOT

CONDUCT ELECTRICITY BECAUSE
THE IONS ARE NOT FREE TO MOVE
TO THE ELECTRODES

TO THE ELECTRODES
WHEN MOLTEN, THE IONS HAVE

MORE FREEDOM AND CAN MOVE

TO THE ELECTRODES

SODIUM IONS GO TO THE CATHODE

AND EACH PICK UP AN ELECTRON
Na+ + e- Na

TO THE ELECTRODES


Na+ + e- Na

TO THE ELECTRODES


Na+ + e- Na
CHLORIDE IONS GO TO THE ANODE

AND EACH GIVE UP AN ELECTRON
Cl- Cl + e-
2Cl- Cl2 + 2e-

TO THE ELECTRODES


Na+ + e- Na

Cl- Cl + e-
2Cl- Cl2 + 2e-
SUMMARY
TO THE ELECTRODES


Na+ + e- Na

Cl- Cl + e-
2Cl- Cl2 + 2e-
ELECTROLYSIS OF
AQUEOUS SODIUM
CHLORIDE (BRINE)
ELECTROLYSIS OF BRINE
WHEN SODIUM CHLORIDE DISSOLVES

IN WATER, THE IONS SEPARATE

WATER CONTAINS A FEW IONS


POSITIVE IONS ARE ATTRACTED TO

THE NEGATIVE CATHODE...


OF THE TWO, HYDROGEN IONS ARE
PREFERRED


PREFERRED
NEGATIVE IONS ARE ATTRACTED TO

THE POSITIVE ANODE...


PREFERRED
NEGATIVE IONS ARE ATTRACTED TO

THE POSITIVE ANODE...
OF THE TWO, CHLORIDE IONS ARE
PREFERRED
AT THE NEGATIVE CATHODE

HYDROGEN IONS PICK UP AN
ELECTRON AND BECOME ATOMS
H+ + e- H

H+ + e- H
2H+ + 2e- H2
The atoms form molecules and

hydrogen gas H2 is produced

H+ + e- H
2H+ + 2e- H2
AT THE POSITIVE ANODE

CHLORIDE IONS GIVE UP AN
Cl- Cl + e-

H+ + e- H
2H+ + 2e- H2

Cl- Cl + e-
2Cl- Cl2 + 2e-
The atoms form molecules and

chlorine gas Cl2 is produced

H+ + e- H
2H+ + 2e- H2

Cl- Cl + e-
2Cl- Cl2 + 2e-

SODIUM HYDROXIDE
SOLUTION REMAINS

H+ + e- H
2H+ + 2e- H2

Cl- Cl + e-
2Cl- Cl2 + 2e-

SODIUM HYDROXIDE
SOLUTION REMAINS
SUMMARY
H+ + e- H
2H+ + 2e- H2

Cl- Cl + e-
2Cl- Cl2 + 2e-

SODIUM HYDROXIDE
SOLUTION REMAINS
ELECTROLYSIS PRODUCT USING INERT
ELECTRODES
ELECTROLYTE IONS IN PRODUCT AT PRODUCT AT

SOLUTION CATHODE ANODE
Conc. HCl H+(aq) Cl-(aq) Hydrogen gas Chlorine gas
Conc. NaCl sol. Na+(aq) Cl-(aq) Hydrogen gas from Chlorine gas
water
Dilute H2SO4 H+(aq) SO42-(aq) Hydrogen gas Oxygen from

water
CuSO4 sol. Cu2+ (aq) SO42- Copper metal Oxygen from

(aq) water
41
INTRODUCTION TO ELECTROLYSIS 8/27/2019
ELECTRODE PRODUCT IN DIFFERENT
SOLUTIONS
CATIONS PRODUCT AT CATHODE ANIONS `PRODUCT AT ANODE
K+ Cl- Chlorine
Hydrogen gas from
Na+
Ca2+ water Br- Bromine
Mg2+ I- Iodine
Al3+
Ni2+ Nickle Oxygen from water

SO42-
Pb2+ Lead
H+ Hydrogen NO3- Oxygen from water
Cu2+ Copper
Ag+ Silver
42
INDUSTRIAL
ELECTROLYSIS
OF BRINE
SODIUM CHLORIDE
THE DIAPHRAGM CELL
CHLORINE GAS HYDROGEN GAS
BRINE
IONS
IONS
SODIUM
HYDROXIDE
DIAPHRAGM SOLUTION
(CAUSTIC SODA)
STOPS CHLORINE MIXING
WITH SODIUM HYDROXIDE
THE DIAPHRAGM CELL
IMPORTANT ASPECTS
CHLORINE HYDROGEN
BRINE
IONS
IONS SODIUM
HYDROXIDE
(CAUSTIC SODA)
DIAPHRAGM
WHAT IS AN ADVANTAGE OF
ELECTROLYSING BRINE
RATHER THAN MOLTEN SODIUM
CHLORIDE?
THE DIAPHRAGM CELL
IMPORTANT ASPECTS
CHLORINE HYDROGEN
BRINE
IONS
IONS SODIUM
HYDROXIDE
(CAUSTIC SODA)
DIAPHRAGM
WHAT IS AN ADVANTAGE OF LESS ENERGY IS NEEDED

ELECTROLYSING BRINE BECAUSE YOU DON’T HAVE TO
RATHER THAN MOLTEN SODIUM MELT THE SODIUM CHLORIDE;
CHLORIDE? IT HAS A HIGH MELTING POINT
THE DIAPHRAGM CELL
IMPORTANT ASPECTS
CHLORINE HYDROGEN
BRINE
IONS
IONS SODIUM
HYDROXIDE
(CAUSTIC SODA)
DIAPHRAGM
WHAT HAPPENS AT THE

POSITIVE ANODE?
THE DIAPHRAGM CELL
IMPORTANT ASPECTS
CHLORINE HYDROGEN
BRINE
IONS
IONS SODIUM
HYDROXIDE
(CAUSTIC SODA)
DIAPHRAGM
WHAT HAPPENS AT THE CHLORIDE IONS ARE OXIDISED

POSITIVE ANODE?
Cl¯ – e¯ Cl
2Cl¯ – 2e¯ Cl2
THE DIAPHRAGM CELL
IMPORTANT ASPECTS
CHLORINE HYDROGEN
BRINE
IONS
IONS SODIUM
HYDROXIDE
(CAUSTIC SODA)
DIAPHRAGM
WHAT HAPPENS AT THE

NEGATIVE CATHODE?
THE DIAPHRAGM CELL
IMPORTANT ASPECTS
CHLORINE HYDROGEN
BRINE
IONS
IONS SODIUM
HYDROXIDE
(CAUSTIC SODA)
DIAPHRAGM
WHAT HAPPENS AT THE HYDROGEN IONS ARE REDUCED

NEGATIVE CATHODE?
H+ + e¯ H
2H+ + 2e¯ H2
THE DIAPHRAGM CELL
IMPORTANT ASPECTS
CHLORINE HYDROGEN
BRINE
IONS
IONS SODIUM
HYDROXIDE
(CAUSTIC SODA)
DIAPHRAGM
WHAT IS THE
DIAPHRAGM FOR?
THE DIAPHRAGM CELL
IMPORTANT ASPECTS
CHLORINE HYDROGEN
BRINE
IONS
IONS SODIUM
HYDROXIDE
(CAUSTIC SODA)
DIAPHRAGM
WHAT IS THE PREVENTS CHLORINE COMING INTO

DIAPHRAGM FOR? CONTACT WITH ANY SODIUM
HYDROXIDE
THE DIAPHRAGM CELL
IMPORTANT ASPECTS
CHLORINE HYDROGEN
BRINE
IONS
IONS SODIUM
HYDROXIDE
(CAUSTIC SODA)
DIAPHRAGM
WHAT IS ALSO
PRODUCED?
THE DIAPHRAGM CELL
IMPORTANT ASPECTS
CHLORINE HYDROGEN
BRINE
IONS
IONS SODIUM
HYDROXIDE
(CAUSTIC SODA)
DIAPHRAGM
WHAT IS ALSO THE SOLUTION CONTAINS SODIUM

PRODUCED? IONS AND HYDROXIDE IONS SO
SODIUM HYDROXIDE IS PRODUCED
THE DIAPHRAGM CELL
INDUSTRIAL IMPORTANCE
The products of the electrolysis of brine are of great

industrial importance…
CHLORINE making bleach

making plastics such as pvc
HYDROGEN used as fuel

used in margarine production
SODIUM production of soaps and detergents

HYDROXIDE used in the paper industry
ELECTROLYSIS OF…
MOLTEN LEAD BROMIDE

ELECTROLYSIS OF…
MOLTEN LEAD BROMIDE
Pb2+
Br- Br-
ANODE
CATHODE
ELECTROLYSIS OF…
MOLTEN LEAD BROMIDE
Pb Br Br
Pb2+
Br- Br-
ANODE 2Br- Br2 + 2e- OXIDATION
CATHODE Pb2+ + 2e- Pb REDUCTION

ELECTROLYSIS OF…
DILUTE SULPHURIC ACID

ELECTROLYSIS OF…
SO42-
ANODE
CATHODE
ELECTROLYSIS OF…
O O
H H
H H
SO42-
ANODE 4OH- 2H2O + O2 + 4e- OXIDATION
CATHODE 4H+ + 4e- 2H2 REDUCTION

ELECTROLYSIS OF…
This electrolysis
can be used to
deduce the
formula of water
O O
H H
H H
SO42-
ANODE 4OH- 2H2O + O2 + 4e- OXIDATION
CATHODE 4H+ + 4e- 2H2 REDUCTION

 During electrolysis the product formed depends
on the nature of electrolyte.
 If electrolyte is a solution, the product formed at
the electrodes may vary because the solvent
which is water will also ionize.
 The product which is formed at the electrode will
depend on wheather it is the ion from the
electrolyte or solvent which is being discharged
at the electrode.
 This depends on the
 Position of the ion in the electrochemical
series
 Concentration of the ion in the
electrolyte
 Nature of the electrode.
FACTORS EFFECTING SELECTIVE/

PREFERENTIAL DISCHARGE OF IONS
63
POSITION OF IONS IN THE ELECTROCHEMICAL SERIES
 If all the other factors are constant, a cation which is

lower in the series( less electropositive) will show a
greater tendency to discharge then the ion which is
higher up in the series because less electropositive can
gain electrons more readily from the cathode to
become neutral while more electropositive tend to
persist in solution as a positive ion.
 Thus K+, Na+, Ca2+, Mg2+, Al3+ may never be discharged
at all from aqueous solution since H+ will discharge first.
 An anion which is higher in the series (less
electronegative) is discharged in preference to anion
which is lower down in series ( more electronegative).
Less electronegative loses electrons more readily
 Thus SO42-, NO3- are never discharged from the
aqueous solution due to preferential discharge of OH-
64
65
RELATIVE CONCENTRATION OF THE IONS IN THE SERIES
 Some times the order of discharge as indicated by

electrochemical series may be reversed by the
concentration effect because increasing the concentration
of a given ion tends to promote its discharge from the
solution where other conditions are kept constant.
 It is effective only if the two rival ions are closely positioned in
the series. The further apart they are the less important is the
effect of concentration.
 Example: In electrolysis of NaCl solution, at cathode Cl- ions is
preferentially discharged although OH- ions are high up the
series. The effect of concentration is predominant due to
closeness of the position of Cl- & OH- in series
66
NATURE OF ELECTRODES
 Inelectroysis of brine if platinum or graphite
cathode is used the H2 gas is displaced but if
mercury cathode is used then sodium will associate
with mercury cathode to form sodium amalgum
and discharged. This method is used in industrial
manufacturing of NaOH.
 Na+(aq) + Hg(l) + e -------- Na/Hg (l)
 If Cu anode is used in solution of CuSO4 then neither

SO42- nor OH- will be discharged instead the atoms
from the anode will go into solution as Cu2+ because
these atoms will give up their electrons more readily
then SO42- or OH-. This principle is made use in the
extraction and purification of some metals.
67
ELECTROLYSIS
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Electrochemistry & Electrolysis

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ELECTROLYSIS

Passing an electric current through ionic substances that are molten

Passing an electric current through ionic substances that are molten

The process is known as ELECTROLYSIS

Passing an electric current through ionic substances that are molten

The process is known as ELECTROLYSIS

Passing an electric current through ionic substances that are molten

The process is known as ELECTROLYSIS

CATHODE +ive ions gain electrons REDUCTION

For a substance to conduct electricity it must have either…

For a substance to conduct electricity it must have either…

For a substance to conduct electricity it must have either…

For a substance to conduct electricity it must have either…

When an ionic substance is melted or dissolved in water,

Cl- Na+ Cl- Na+

Na+ Cl- Na+ Cl-

Cl- Na+ Cl- Na+

WHEN SOLID, THE IONS

SOLID IONIC COMPOUNDS DON’T CONDUCT ELECTRICITY

Cl- Na+ Cl- Na+

WHEN SOLID, THE IONS WHEN MOLTEN, THE IONS

MOLTEN IONIC COMPOUNDS DO CONDUCT ELECTRICITY

Cl- Na+ Cl- Na+

Na+ Cl- Na+ Cl-

Cl- Na+ Cl- Na+

WHEN SOLID, THE IONS

SOLID IONIC COMPOUNDS DON’T CONDUCT ELECTRICITY

Cl- Na+ Cl- Na+

Na+ Cl- Na+ Cl-

WHEN SOLID, THE IONS

AQUEOUS SOLUTIONS OF IONIC COMPOUNDS DO CONDUCT ELECTRICITY

SOLID IN AQUEOUS SOLUTION

Cl- Na+ Cl- Na+

WHEN SOLID, THE IONS WHEN DISSOLVED IN

AQUEOUS SOLUTIONS OF IONIC COMPOUNDS DO CONDUCT ELECTRICITY

SOLID SODIUM CHLORIDE DOES NOT

SOLID SODIUM CHLORIDE DOES NOT

WHEN MOLTEN, THE IONS HAVE

SOLID SODIUM CHLORIDE DOES NOT

WHEN MOLTEN, THE IONS HAVE

SODIUM IONS GO TO THE CATHODE

SOLID SODIUM CHLORIDE DOES NOT

WHEN MOLTEN, THE IONS HAVE

SODIUM IONS GO TO THE CATHODE

SOLID SODIUM CHLORIDE DOES NOT

WHEN MOLTEN, THE IONS HAVE

SODIUM IONS GO TO THE CATHODE

CHLORIDE IONS GO TO THE ANODE

SOLID SODIUM CHLORIDE DOES NOT

WHEN MOLTEN, THE IONS HAVE

SODIUM IONS GO TO THE CATHODE

CHLORIDE IONS GO TO THE ANODE

WHEN MOLTEN, THE IONS HAVE

SODIUM IONS GO TO THE CATHODE

CHLORIDE IONS GO TO THE ANODE

WHEN SODIUM CHLORIDE DISSOLVES

WHEN SODIUM CHLORIDE DISSOLVES

WATER CONTAINS A FEW IONS

WHEN SODIUM CHLORIDE DISSOLVES

WATER CONTAINS A FEW IONS

POSITIVE IONS ARE ATTRACTED TO

WHEN SODIUM CHLORIDE DISSOLVES

WATER CONTAINS A FEW IONS