UNIT-9 Oxidation-Reduction &

Electrochemistry
 An oxidation-reduction (redox)
reaction/electrochemical reaction involves
the transfer of electrons (e - ) from one
species to another.

Sodium transfers its electrons to chlorine

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 Redox rxns involve a change in oxidation number
of elements and can be written as two half-reactions:
Zn + S  ZnS
(undergoes oxidation) (undergoes Reduction)
Reducing Agent Oxidizing agent

Oxidation half-reaction.
Zn0 
Zn2+ + 2e-
In oxidation half reactions, electrons are written
on the right because electrons are lost

Reduction half-reaction.

S0 + 2e-  S 2-
In reduction half reactions, electrons are written
on the left because electrons are gained 3
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 Substance that is oxidized is the
Reducing agent •Substance that
is reduced is the Oxidizing agent

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 Oxidation: loss of e-; oxidation number increases

Reduction: gain of e-; oxidation number

decreases (“reduces”)

Oxidizing agent: causes another substance to be

oxidized; gains e-

Reducing agent: causes another substance to be

reduced; loses e-

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 LEO growls GER

Losing Gaining
Electrons Electrons
Oxidation Reduction 6
J Deutsch 2003
 Metal atoms lose electrons to become + ions
The oxidation numbers go up (increases)
Cr0  Cr3+ + 3e-

Nonmetals gain electrons to form – ions

The oxidation number goes down (reduces)

N20 + 6e-  2N3-

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Oxidation Numbers

In order to keep
track of what loses
electrons and what
gains them, we
assign oxidation
numbers.
Oxidation and Reduction

Zn loses two electrons to go from neutral zinc

metal to the Zn2+ ion, so zinc undergoes
oxidation.
 Oxidation and Reduction

Each of the H+ gains an electron given by Zn

and changes to H neutral and two of those
atoms combine to form H2. Thus, H+ is
reduced as it gains electrons.
Assigning Oxidation Numbers
1. Elements in their elemental form have an
oxidation number of 0. So, Na has an
oxidation number of zero.
2. The oxidation number of a monatomic ion
is the same as its charge.
– Group 1 Metals are always 1+
– Group 2 Metals are always 2+
Assigning Oxidation Numbers
3. Nonmetals tend to have negative
oxidation numbers, although some are
positive in certain compounds or ions.

Oxygen is always 2- except when combined with F or in

Peroxides
(In OF2 ,O is 2+ and in H2O2 ,O is 1- )
Hydrogen is −1 when bonded to a metal, +1 when bonded
to a nonmetal.
Fluorine always has an oxidation number of −1.
The other halogens have an oxidation number of −1 when
they are negative; they can have positive oxidation numbers,
however, most notably in oxyanions.
 Assigning Oxidation Numbers
4. The sum of the
oxidation numbers in a F -1
neutral compound is 0.
O -2
Oxidation state
of C in CO2? H +1
?–4=0 Cl -1
? = +4
 Assigning Oxidation Numbers
 The oxidation
numbers of atoms
in a compound add
F -1
up to zero.
O -2
Oxidation state
of Cu in CuCl2? H +1
? + (-2) = 0
Cl -1
Cu = +2
 Assigning Oxidation Numbers
 The oxidation
numbers of atoms F -1
in a compound
add up to zero.
O -2
Oxidation state
of N in NH3? H +1
?+3=0 Cl -1
-3
 Assigning Oxidation Numbers
The oxidation numbers of atoms in a compound
add up to zero.

 CuO  Na2SO4
– Na is +1 because it is a
Oxygen is -2
group 1 metal
The oxidation number of – O is -2
copper must be
– The oxidation number
calculated of Sulfur must be
X + -2 = 0 calculated
X = +2 2(+1) + X + 4(-2) = 0
(2 ) + X + (-8) =0
X = +6
J Deutsch 2003 16
 Assigning Oxidation Numbers
5. The sum of the oxidation
numbers in a polyatomic F -1
ion is the charge on the ion.

O -2
Oxidation state
of S in SO42- ? H +1
? – 8 = -2
Cl -1
? = +6
 Assigning Oxidation Numbers
The sum of the oxidation numbers of all the
atoms in a polyatomic ion is the charge of the
ion.
 NO3-  PO43-
Oxygen is 2- Oxygen is 2-
The oxidation number of The oxidation number of
nitrogen must be phosphorous must be
calculated calculated
X + 3(-2) = -1 X + 4(-2) = -3
X = 5+ X + (-8) = -3
X = +5

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 Assigning Oxidation Numbers
6.The oxidation
numbers of atoms in F -1
an ion add up to the
charge on the ion.
O -2
Oxidation state
of N in NH4+? H +1
? + 4 = +1
Cl -1
-3
Practice: Oxidation Numbers

KMnO4 potassium permanganate

K= ? Mn = ? O=?

NaClO3 sodium chlorate

Na = ? Cl = ? O=?

K2Cr2O7 potassium dichromate

K= ? Cr = ? O=?
 Naming of Binary Compounds
 Binary compounds have only two elements;
– electropositive element (cation) is named 1st while the
electronegative element (anion) comes last with a
modification of the name ends with –ide
– MgO – Magnesium oxide
– H2S – Hydrogen sulphide
– NH4Cl – Ammonium chloride
– NaH – Sodium hydride
 When 2 elements involved are non-metals, the
above rule is not followed:
– H2O – Water PH3 – Phosphine
– NH3 – Ammonia
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 Naming of Binary Compounds
 Name the following compounds
– NaCl; CaO; Al2O3; Li2S; H2O2

 For binary compounds that contains two non-metals, the

O.N of the 1st element is written in roman number. E.g.
– NO2 – Nitrogen (iv) oxide
– NO – Nitrogen (ii) oxide
– SO3 – Sulphur (vi) oxide
 For transition metals with variable O.N, roman number is
also used to indicate the oxidation number
– FeO – iron (ii) oxide
– Fe2O3 – Iron (iii) oxide
– Cu2S – copper (i) sulphide
– CoCl2 – Cobalt (ii) chloride 22
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 Naming Radicals and Compounds having
Elements with variable Oxidation number
 Radicals (group of atoms) are treated as a
single element when naming their
compounds
– NH4+ - Ammonium ion
– OH- - Hydroxyl ion
 For acid radicals, O.N is indicated by
Roman numbers in the bracket
– NO2- - Dioxonitrate (iii) ion
– NO3- - Trioxonitrate (v) ion
– CO32- - Trioxocarbonate (iv) ion
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 Naming Radicals and Compounds having
Elements with variable Oxidation number
 FeO – Iron (ii) oxide
 Cu2O – Copper (i) oxide
 MgCO3 – Magnesium trioxocarbonate (iv)

 Name the following compounds

– Fe2O3
– Na2SO4
– Cu(NO3)2
– Mg3(PO4)2
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 Naming Tertiary compounds and
Quaternary compounds
 Oxo-acids, normal salts, and acid salts e.g.
– HNO3 – Trioxonitrate (v) acid
– H2SO4 – Tetraoxosulphate (vi) acid
– H3PO4 – Tetraoxophosphate (v) acid
– KNO3 – Potassium trioxonitrate (v)
– Na2SO4 – Sodium tetraoxosulphate (vi)
– CuCO3 – Copper (ii) trioxocarbonate (iv)
– NaHSO3 – Sodium hydrogen trioxosulphate (iv)

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Practice: Oxidation Numbers

KMnO4 potassium permanganate

K = +1 Mn = +7 O = -2

NaClO3 sodium chlorate

Na = +1 Cl = +5 O = -2

K2Cr2O7 potassium dichromate

K = +1 Cr = +6 O = -2
 Practice: Oxidation Numbers
Find the oxidation numbers and see which
ones change during the chemical reaction

0 2+ 5+ 2- 2+ 5+ 2- 0
Zn + Cu(NO3)2 Zn(NO3)2 + Cu
Nitrate NO3 is -1
Since Nitrate ion is present before and after the reaction, it
is called a spectator ion

Zn0 Zn2+ + 2e- Oxidation

Cu2+ + 2e- Cu0 Reduction
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 IDENTIFYING REDOX REACTIONS
During redox, one atom is oxidized while another atom is
reduced. Reduction and oxidation happen together.

The oxidation numbers of the atoms will

change…. one goes up (0 to +1) and one
goes down (0 to -2)

Oxidation

0 0 + 2-
2H + O2 2 2H O2
Reduction

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 IDENTIFYING REDOX REACTIONS

2Mg(s) + O2(g)  2MgO(s)

Must be a redox!

Oxidised – loss of e-

Mg  Mg2+ +2e-
Reduced – gain of e-

O +2e-  O2-
IDENTIFYING REDOX REACTIONS

Cu(s) + 2AgNO3(aq)  Cu(NO3 )2(aq) + 2Ag(s)

Must be a redox!

Oxidised – loss of e- Cu  Cu2+ +2e-

Reduced – gain of e- Ag+ +e-  Ag

 IDENTIFYING REDOX REACTION

Cr2O72- (aq) + Cl1- (aq) → Cr3+ (aq) + Cl2 (g)

+6 -2 -1 +3 0

Reduction half-reaction:
Cr2O72- (aq) + 3 e- → Cr3+ (aq)

Oxidation half-reaction:
2Cl1- (aq) → Cl2 (g) + 2e-

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 Table J tells us if a
redox reaction can
occur between
given reactants.

 Zn + CuSO4  Cu + ZnSO4
Zinc replaces copper because zinc is
more active than copper.

 Cu + ZnSO4  No Reaction
Copper cannot replace zinc
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 Table J tells us if a redox reaction can
occur between given reactants.
 A more active metal(high on table J) will replace a
less active metal (below it on Table J) from a
compound.
MgCl2 + 2Na  2NaCl + Mg
 A more active nonmetal (high on table J) will
replace a less active non metal(below it on Table J)
from a compound.
MgCl2 + F2  Mg F2 + Cl2
 Any metal above H is more active than H and will
react with an acid to produce H2(g)
– The higher up t table, the more readily the replacement
will take place.
J Deutsch 2003 Zn + 2 HCl  ZnCl2 + H2 33
Redox Half-Reactions
 A half-reaction shows either the oxidation or
reduction portion of a redox reaction, including
the electrons gained or lost.

 A reduction half-reaction shows an atom or an

ion gaining one or more electrons while its
oxidation number decreases
 Ex. Na+1 + 1e-  Na0

 An oxidation half-reaction shows an atom or an

ion losing one or more electrons while its
oxidation number increases.
 Ex. Na0  Na+1 + 1e-
 Balancing Redox Reactions
Redox Reaction
__Na + ___HCl  ___NaCl + ___H2
For every redox reaction we can write out two half reactions.
They are designed to show electrons being gained or lost
as oxidation numbers change

Oxidation Half Reaction

Na0  Na+1 + e-
Reduction Half Reaction
e- + H+1  H0
2e- + 2H+1  H2
Half-reactions must show conservation of mass and charge, so
they must be balanced, and have the same charge on both
sides of the reaction arrow
2Na + 2HCl  2NaCl + ___H2
 Balancing Redox Reactions
In a redox reaction the number of electrons lost must
be equal to the number of electrons gained.
0 0 3+ 2-
Al + O2  Al2O3
Al0  Al3+ + 3e- oxidation - 3 electrons lost
O20 + 4e-  2O2- reduction - 4 electrons gained

4(Al0  Al3+ + 3e-) multiply by 4

3(O20 + 4e-  2O2- ) multiply by 3
12 electrons are transferred in this reaction
4Al + 3O2  2Al2O3
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Writing Half-Reactions
 To write the half-reactions for an equation such as
MgCl2 + 2Na  2NaCl + Mg
 Make sure the equation is balanced
 Next assign oxidation numbers to each atom, then write a partial
half-reaction to show the change in oxidation number including the
coefficients from the balanced equation.
Oxidation: 2Na0  2Na+1
Reduction Mg+2  Mg0
 Then place the correct number of electrons on one side of the
equation to make the net charge equal on both sides. (remember
electrons will always be a product in oxidation and a reactant in
reduction)
Oxidation: 2Na0  2Na+1 + 2e-
Reduction: 2e- + Mg+2  Mg0
 When you have written a correct oxidation and reduction half-reaction
the electrons lost (oxidation) should be equal to the electrons gained
(reduction)
 Practice Half Reactions
 Try writing the two half reactions for each example:

Ex 1) ___H2 + ___O2  ___H2O

Ex 2) ___AgCl + ___Ca  ___CaCl2 + ___Ag

Answers: Ex 1) 4H0  4H+1 + 4e- (oxidation)

2O0 + 2e-2  2O-2 (reduction)

Ex 2) 2Ag+1 + 2e-  2Ag0 (reduction)

Ca0  Ca+2 + 2e- (oxidation)
 Balancing Redox Reactions

___Mg + ___Al 3+  ___Al + ___ Mg 2+

___Cr 3+ + ___ Na  ___Cr + ____Na +

___Pb 4+ + ___ Sr  ____Sr2+ + ___Pb

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 Introduction to Electrochemistry
 An electric cell converts chemical
energy into electrical energy
 Alessandro Volta invented the first
electric cell but got his inspiration from
Luigi Galvani. Galvani’s crucial
observation was that two different Alessandro Volta
metals could make the muscles of a (1745–1827)
frog’s legs twitch. Unfortunately,
Galvani thought this was due to some
mysterious “animal electricity”. It was
Volta who recognized this experiment’s
potential.
Luigi Galvani
(1737–1798)
 An electric cell produces very little electricity, so Volta came
up with a better design:
A battery is defined as two or more electric cells connected
in series to produce a steady flow of current
Volta’s first battery consisted of several bowls of brine
(NaCl(aq)) connected by metals that dipped from one bowl to
another.
His revised design, consisted of a sandwich of two metals
separated by paper soaked in salt water.

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 An electrochemical cell can be
either a voltaic or electrolytic
cell

Voltaic Cell/ Galvanic Cell:

A Device that generates electric current from
a spontaneous electrochemical reaction.

Electrolytic Cell:
A device that uses external power source to
make a non-spontaneous reaction happen.
J Deutsch 2003 42
 VOLTAIC/GALVANIC CELL

e- flow

(-) (+)
anode Zn NO 3
1-
Na 1+
Cu cathode

salt bridge, saturated

with NaNO3 (aq)

Zn2+ (aq) Cu2+ (aq)

Oxidation half-cell: Zn (s) → Zn2+ (aq) + 2 e-

Reduction half-cell: Cu2+ (aq) + 2 e- → Cu (s)

43
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
 Voltaic Cells/Galvanic Cell)
The electrons flow from the anode to the cathode (“a before c”)
through an electrical circuit rather than passing directly from one
substance to another.
A porous boundary separates the two electrolytes while still
allowing ions to flow to maintain cell neutrality. Often the porous
boundary is a salt bridge, containing an inert aqueous electrolyte
(such as Na2SO4(aq) or KNO3(aq)), Or you can use a porous cup
containing one electrolyte which sits in a container of a second
electrolyte.
 VOLTAIC/GALVANIC CELL
Electrodes: metals connected by an external
circuit to allow the flow ofv electrons
Anode: Electrode where where oxidation
occurs
Cathode: Electrode where reduction occurs
An Ox Red Cat

Oxidation at the Anode Reduction at the Cathode

45
 WORKING O
F A VOLTAIC
CELL

Ex: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Cell Notation for Voltaic Cells
Voltaic cells can be represented using cell notation:

The single line represents a phase boundary (electrode

to electrolyte) and the double line represents a
physical boundary (porous boundary)
For a redox reaction to be spontaneous, the metal
with higher reduction potential should be made
cathode. Notation:
Anode| Anode product|Salt |Cathode|
Write cell notation for Cathode product
Zn-Cu cell Zn(s)|Zn2+(aq, 1 M)|NaNO3 (saturated)|
Cu2+(aq, 1 M)|Cu(s)
 A voltaic cell spontaneously converts
chemical energy to electrical energy.
Batteries are voltaic cells

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 Electrons flow from the anode (- electrode)
to the cathode (+ electrode) through the
wire in a voltaic cell.
An Ox -oxidation Red Cat -reduction
takes place…electrons takes place…electrons
are lost. are gained.

Zn Zn + 2e
2+ - e- e- e- e- Cu2+ + 2e -
Cu0

e-
- e-
+
e-
e-
Electrons
Electrons
e- needed
released e- here for
here by e- reduction
oxidation

J Deutsch 2003 49
 The salt bridge completes the circuit
allows ions to flow from one ½ cell to
the other ½ cell to maintain neutrality.

Zn Zn + 2e
2+ - Cu2+ + 2e -
Cu0

- +

J Deutsch 2003 50
Voltaic Cells & Table J
 Oxidation and reduction occur at the electrodes.
 To identify which electrode is your anode or the
site of oxidation and which is your cathode or
the sight of reduction you must compare the
reactivity of the metals on Table J in your
reference table.
 The more reactive metal will always lose
electrons (oxidation) which makes it your
Anode.
 The less reactive metal will always gain electrons
(reduction) it is always your cathode.
 Remember “Red Cat An Ox”
 Table J
 So in summary the metal higher up on Table J is your Anode (oxidation) the metal lower on Table J is your cathode (reduction).

 Once you identify your anode and cathode you can identify the flow of electrons they flow from the Anode to the Cathode.

 Try the practice questions on the next page !!!

 Voltaic Cell Summary
 A voltaic cell consists of two-half cells
separated by a porous boundary with
solid electrodes connected by an external
circuit

 Oxidizing agent undergoes reduction at

the cathode (+ electrode) – cathode
increases in mass

 Reducing agent undergoes oxidation at

the anode (- electrode) – anode
decreases in mass

 Electrons always travel in the external

circuit from anode to cathode

 Internally, cations move toward the

cathode, anions move toward the anode,
keeping the solution neutral
 Electrolytic Cell

An electrolytic cell requires

electrical energy to produce
chemical change. This process is
known as electrolysis.

J Deutsch 2003 54
 Electrolytic Cells
 Electrolytic Cell – a cell in
which a nonspontaneous
redox reaction is forced to
occur; a combination of two
electrodes, an electrolyte
and an external power
source.
 Electrolysis – the process
of supplying electrical
energy to force a
nonspontaneous redox
reaction to occur Electrons are pulled from the
anode and pushed to the
cathode by the battery or
power supply
Electroplating
 The most common use of electrolytic cells is an
electroplating cell.
 Electroplating involves plating a small layer of
usually a precious metal on another metal.
 The material to be plated for example a spoon or a
piece of jewelry, would be the cathode were
reduction occurs.
 The metal being used to plate for example gold or
silver would be the anode were oxidation occurs.
 Electrolytic Cell

Cu2+ ions
are reduced
to Cu0
metal at the
negative
electrode.

The cathode is negative and is the site of

reduction in an electrolytic cell.
J Deutsch 2003 57
Electrolytic Cell For Electroplating
Power Source

Anode
Cathode

•Anode-Oxidation •Cathode-Reduction

•Ag0 Ag+1 +1e- •Ag+1 + 1e- Ag0

Electrolysis
 Electrolysis can be used to break up compounds
to reform the elements it is made up of.
 For instance if you wanted to break up water
molecules into hydrogen and oxygen gas you
could use an Electrolytic Cell.
 Since the reaction will be non-spontaneous a
power source must be used to force the reaction
to occur.
 The power source is usually a battery.

2H2O + electrical energy  2H2 + O2

Electrolytic Cell for Electrolysis

Power Source
•Write the half-reactions:
•Reduction: 4H+1 + 4e- 2H2 (Cathode)
•Oxidation: 2O-2 O2 + 4e- (Anode)
 Electrolysis of table salt
Na+ (l) + Cl- (l) → Na (l) + Cl2 (g)
Oxidation half-cell: 2 Cl- (l) → Cl2 (g) + 2 e-
Reduction half-cell: Na+ (l) + e- → Na (l)

(+) (-) e- flow

Pt Pt

Cl2 (g) Na (l)

anode NaCl (l)cathode

• In a voltaic cell: anode is (-), cathode is (+)

• In an electrolytic cell: anode is (+), cathode is (-)

61
 Comparing Voltaic and
Electrolytic Cells
Similarities Differences
1. Both use redox 1. Voltaic cells use spontaneous
reactions reactions to produce energy
(voltmeter)
2. The anode is the site of
oxidation 2. Electrolytic use non-spontaneous
reactions that requires energy
3. The cathode is the site (power source)
of reduction 3. Voltaic cells the anode is negative
4. The electron flow and the cathode is positive
through the wire is 4. Electrolytic cells the anode is
from anode to cathode positive and the cathode is negative.
 Regents Question: 06/02 #22

Which process requires an external power source?

(1) neutralization

(2) synthesis
(3) fermentation
(4) electrolysis

J Deutsch 2003 63
 Regents Question: 08/02 #29

As a Ca atom undergoes oxidation to Ca2+ , the number of

neutrons in its nucleus
(1) decreases
(2) increases
(3) remains the same

J Deutsch 2003 64
 Regents Question: 06/02 #20

Which particles are gained and lost during a redox

reaction?
(1) electrons
(2) Protons
(3) Neutrons
(4) positrons

J Deutsch 2003 65
 Regents Question: 06/03 #27

Which statement is true for any electrochemical cell?

(1) Oxidation occurs at the anode, only.
(2) Reduction occurs at the anode, only.
(3) Oxidation occurs at both the anode and the cathode.
(4) Reduction occurs at both the anode and the cathode.

J Deutsch 2003 66
 Regents Question: 06/03 #26

In which substance does chlorine have an

oxidation number of +1?
(1) Cl2
(2) HCl
(3) HClO
(4) HClO2

J Deutsch 2003 67
 Regents Question: 01/03 #46

According to Reference Table J, which of these metals

will react most readily with 1.0 M HCl to produce
H2(g)?
(1) Ca
(2) K
(3) Mg
(4) Zn

J Deutsch 2003 68
 Regents Question: 08/02 #22
In any redox reaction, the substance that undergoes
reduction will
(1) lose electrons and have a decrease in oxidation number
(2) lose electrons and have an increase in oxidation number
(3) gain electrons and have a decrease in oxidation number
(4) gain electrons and have an increase in oxidation number

J Deutsch 2003 69
 Regents Question: 06/02 #21

What is the oxidation number of chromium in

K2Cr2O7 ?
(1) +12

(2) +2
(3) +3
(4) +6

J Deutsch 2003 70
 Regents Question: 06/02 #18

Given the equation:

C(s) + H2O(g) CO(g) + H2 (g)
Which species undergoes reduction?
(1) C(s)
(2) H + LEO growls GER
(3) C2+
(4) H2 (g)

J Deutsch 2003 71
 Regents Question: 06/02 #18

Given the reaction:

Mg(s) + 2H+(aq) + 2Cl–(aq) Mg2+(aq) + 2Cl–(aq) + H2(g)

Which species undergoes oxidation?

(1) Mg(s)
(2) H+(aq)
LEO growls GER
(3) Cl– (aq)
(4) H2 (g)

J Deutsch 2003 72
 Regents Question: 06/03 #28

Given the equation:

2 Al + 3 Cu2+ 2 Al3+ + 3Cu
The reduction half-reaction is
(1) Al Al 3+ + 3e –
(2) Cu 2+ + 2e – Cu
(3) Al + 3e – Al 3+
(4) Cu 2+ Cu + 2e –

J Deutsch 2003 73
 Regents Question: 06/03 #46
A diagram of a chemical cell and an equation are shown
below.

When the switch is closed, electrons will flow from

(1) the Pb(s) to the Cu(s) (3) the Pb2+ (aq) to the Pb(s)

J Deutsch 2003 (2) the Cu(s) to the Pb(s) (4) the Cu2+ (aq) to the Cu(s) 74
 Regents Question: 06/02 #70-75
Base your answers to the next six questions on the following redox
reaction, which occurs spontaneously in an electrochemical cell.

Zn + Cr3+ Zn2+ + Cr
 Write the half-reaction for the reduction that occurs.
Cr3+ + 3e- Cr0

 Write the half-reaction for the oxidation that occurs.

Zn0 Zn2+ + 2e-

 Balance the equation using the smallest whole-number

coefficients.
The number of e-s gained = the number of e-s lost
3Zn + 2Cr3+ 3Zn2+ + 2Cr

J Deutsch 2003 75
 Regents Question: 06/02 #70-75
Base your answers to the next five questions on the following
redox reaction, which occurs spontaneously in an
electrochemical cell. Zn + Cr3+ Zn2+ + Cr
 Which species loses electrons and which species gains
electrons?
Zn0 loses electrons, Cr3+ gains electrons

 Which half-reaction occurs at the cathode?

Hint: Red Cat
Cr + 3e-
3+
Cr 0

 State what happens to the number of protons in a Zn atom

when it changes to Zn2+ as the redox reaction occurs.
The number of protons remains the same.
J Deutsch 2003 76
 Regents Question: 01/03 #53-55
• Indicate with one or more arrows the direction of electron
flow through the wire.
Hint: Zinc is above copper on table J so Zn is oxidized
• Write an equation for the half-reaction that occurs at the
zinc electrode.
Zn Zn 2+ + 2e-
• Explain the function of the salt bridge.
e-
The salt bridge completes the
circuit and allows ions to
flow from one ½ cell to the
other. This keeps the ½ cells
neutral.

J Deutsch 2003 77
 FARADAY’S LAWS OF ELECTROLYSIS
 First Law: The law states that the mass (m)
of a substance liberated at an electrode
during electrolysis is proportional to the
quantity (Q) of electricity passed.
– The quantity of electricity (Q) is measured in
coulombs;
– one coulomb is the quantity of electricity
passing when one ampere (current) flows for
one second, that is
– No. of coulombs = No. of amperes x No. of
seconds
J Deutsch 2003
• Q= I x t 78
 FARADAY’S LAWS OF ELECTROLYSIS
 Second Law: The law states that when the
same quantity of electricity is passed
through solutions of different electrolytes
the masses of the substances liberated at the
electrodes are in the ratio of their
equivalents. That is
Mass of A deposited = Equivalent of A
Mass of B deposited Equivalent of B


J Deutsch 2003 79
 FARADAY’S LAWS OF ELECTROLYSIS
 1 Faraday = 96500 coulomb = one mole
of electron
 It follows that:
Cu2+ + 2e  Cu(s)
1 moles 2moles
of Cu2+ of
electron
 Therefore 63.5g of copper is liberated by
2 x 96500 C = 2 Faradays.
J Deutsch 2003 80
 FARADAY’S LAWS OF ELECTROLYSIS
 Example 1: 0.222g of a divalent metal is
deposited at the electrode when a current
of 0.45 ampere is passed through a
solution of its salt for 25 minutes using
appropriate electrodes; calculate the
relative atomic mass of the metal. [F =
96500 Cmol-1] (SSCE)

J Deutsch 2003 81
 FARADAY’S LAWS OF ELECTROLYSIS
 Quantity of electricity, Q = current x time in seconds
= 0.45 x 60 x 25 C
M2+ + 2e - M(s)
1 mole 2 moles
of of
M2+ electron
2 Faradays = 2 x 96500C
0.45 x 60 x 25 C liberated 0.222g of Metal (M)
2 x 96500 C will liberate 0.222 x 2 x 96500
0.45 x 60 x 25
= 63.5g
Therefore, relative atomic mass of M = 63.5g
J Deutsch 2003 82
 FARADAY’S LAWS OF ELECTROLYSIS
 When a current of 4A was passed through an
electrolyte solution for 20 minutes, a mass
1.5917g of a divalent metal was deposited at the
cathode. What mass of the metal will be
deposited when a current of 10A is passed
through the solution for 40 minutes?

J Deutsch 2003 83