Factors

affecting
electrolysis
Prepared by Janadi
Gonzalez-Lord

Electrolysis summarized
A brief overview of what electrolysis is and how it
works

What is electrolysis?
Electrolysis

is the chemical separation of

an ionic compound using a direct
electrical current.

Key points in
electrolysis
Ionic
compou
nd in
molten
or
aqueou
s state

Key
points
in
Electrol
ysis

Ions
(instead
of
electron
s)
conduct
electric
al
current.

Needs
power
source

The electrolytic
cell
These are known as
electrodes. They are
usually a metallic (or in the
case of graphite a nonmetallic) conductor

The anode is
positively charged. It
attracts negatively
charged ions (anions)

The electrolyte is the

ionic compound in its
molten or aqueous
state. It provides mobile
electrons that allow
electrical conduction

The power
source provides
electrical current
that gives the
electrodes their
respective
charges
The cathode is
negatively charged. It
attracts positively
charged ions (cations)

How electrolysis works

These electrons then
provide the negative
charge for the negative
electrode (cathode)

The cations move

towards this
negatively charged
electrode (cathode).
In doing so, they gain
electrons to become
an electrically neutral
element.
Yn+ + ne- -> Y

The electrons
from the anions
then move along
the circuit
through the
power source to
the negative
electrode

Anions move towards

the positive electrode
(anode).
In doing so, they lose
electrons to become a
neutral element.
nXn- - ne- -> Xn

Factors affecting
electrolysis
What conditions affect what products are formed
during and after electrolysis?

Key factors affecting products

of electrolysis
Type

of electrolyte
The electrochemical series
Molarity/Concentration of Solution
Type of Electrodes

Type of electrolyte
A look at the role electrolytes play in determining
the products of electrolysis

Electrolytes can be either

o
Molten
Solution
r

Pure

Ionic

compound

Liquid form

Impure

Mixture

of ionic
compounds

Molten

Comparison of molten vs
solution electrolytes

Multiple products
possible based on
cations/anions
present in solution
Lower energy
consumption due to
impurities

Solution

Products limited to
cation and anion
present in binary
ionic compound only
High energy
consumption due to
high melting points
of pure ionic
compounds

So
So at
at the
the anode,
anode,
bromide
bromide ions
ions lose
lose
electrons
to
form
electrons to form
bromine
bromine gas:
gas:
--2Br
2Br -- 2e
2e ->
-> Br
Br22 (g)
(g)

Electrolysis of
molten lead (II)
bromide
The only ions here are Pb2+
and Br
While
at
While at the
the cathode,
cathode,
This
why
lead
lead
lead ions
ions gain
gain is deposited
and bromine
gassolid
is released
electrons
to
electrons
to form
form
solid
lead
lead metal:
metal:
2+
Pb
Pb2+ +
+ 2e
2e- ->
-> Pb
Pb (s)
(s)

At the anode, hydroxide

ions lose electrons to form
water and oxygen gas:
2OH- - 4e- -> 2H2O (l) + O2 (g)

Electrolysis of
aqueous
At
the
At
the cathode,
cathode, lead (II)
hydrogen
hydrogen is
is
bromide
displaced
displaced

(strangely
(strangely
enough!):
Water
is slightly ionised:
enough!):
+
2H
->
H
+ +
- H
2H+H+
+2O2e
2e
->
H OH
2
2 (g)
(g)

This means that in aqueous

solutions, there are two set of
cations and two sets of anions.
However, only one set gets off
at the electrodes. The ions that
do so are said to be displaced
from solution. Which ions get
displaced is discussed in later
parts of this presentation

The electrochemical
series
A look at how the electrochemical series affects
the products of electrolysis

What is the
electrochemical
series?
This is a list of elements in order
of their ability to be reduced.
For cations, the higher the
element in the series, the less
likely it is that this will gain
electrons (that is be reduced).
For anions, the higher it is on the
series the less likely will it lose
electrons (that is be oxidized)

Reduction potential
Why some ions have a greater ability to be
reduced than others

What affects the ability to be

reduced?
Group
Group to
to which
which
ion
belongs
ion belongs

Bond
Bond energies
energies

Ionic
Ionic radii
radii

Whether
Whether a
a
metal
or
nonmetal or nonmetal
metal

Reduction potential cations

An overview of the factors affecting the ability of
cations to be reduced.

For Group 1 elements

Group 1
elements
only need to
lose 1
electron in
order to
achieve a
stable octet
of electrons

The ionic
radii is
usually very
small and
therefore
Group 1 ions
tend to bond
very
strongly with
their anion
counterparts

The ionic
bond has a
low bond
energy
because it is
very strong
and would
be
energetically
preferred
that the
metal alone.

This means
This is why
they tend to be at the
that they
not
top of thewould
electrochemical
series
easily gain
easily gain
back the
electrons
lost

For Group 2 elements

The ionic
radii is
usually very
small but
larger than
that of Group
1 elements in
the same
period.
Therefore
Group 2 ions
tend to bond
very strongly
with their
anion
counterparts
but not as
strongly
when
compared to
Group 1 ions

This is why they tend to be at

the top of the
electrochemical series but
under Group 1 elements
generally

Group 2
elements
need to lose
2 electron in
order to
achieve a
stable octet
of electrons

However, it is
more difficult
to lose the
nd electron
2nd
st
than the 1st
electron as
you will be
trying to
remove an
electron from
an already
positive ion

The bond
energy would
be lower than
that of the
metal alone
but higher
than that of
Group 1
elements

They would
be more
likely to gain
electrons
than Group 1
metals

For Group 3 elements

The ionic
radii is
usually small
but larger
than that of
Group 1& 2
elements in
the same
period.
Therefore
Group 3 ions
tend to bond
strongly with
their anion
counterparts
but not as
strongly
when
compared to
Group 1 &
Group 2 ions

This is why they tend to be at

the top of the
electrochemical series but
under Group 2 elements
generally

Group 3
elements
need to lose
3 electron3 in
order to
achieve a
stable octet
of electrons

However, it is
more difficult
to lose the
3rdd electron
nd
than the 2nd
st
and 1st
electrons as
you will be
trying to
remove an
electron from
an already
positive ion

The bond
energy would
be lower than
that of the
metal alone
but higher
than that of
Group 1 &
Group 2
elements

They will be
more likely to
gain
electrons
than Group 1
or 2 metals

For Transition elements

The ionic
radii is
usually
larger than
that of other
elements in
the same
period.
Therefore
transition
element ions
tend to not
bond
strongly with
their anion
counterparts

This is why they tend to be at

bond
the bottomThe
of
the
They will be
energy
more likely
would
be
electrochemical
series for
to gain
higher than
electrons
that of
than other
cations
metallic
metals.

Transition
elements
need to lose
a varying
number of
electrons in
order to
achieve a
stable octet
as they are
in the 4th
period.

elements

Reduction potential anions

An overview of the factors affecting the ability of
anions to be reduced.

For polyatomic anions

This is why they tend to be at
The ionic
radiitop
for
the
of
the
The larger the
polyatomic anions
anion, the less
is usually larger
strongly the
The bond energy
They will be more
than that of other
electrochemical
series
for
electrons are held
would be higher
likely to lose
anions. Therefore
by the nucleus and
than that of
electrons than
polyatomic anion
the more likely
monatomic anions
other anions.
anions
tend to not bond
electrons will be
strongly with their
easily lost.

strongly with their

cation counterparts

For halide anions

This is why chloride ions (Cl-)
Ionic radii for Group
Those elements
is
The larger
thehigher in the series than
7 anions increases
lower down the
anion, the less
as you go down the
The bond
energy
group will be more
strongly the
group. Therefore
would
be
likely
to lose
bromide
ions
(Br
)
which
is
electrons are
held
elements lower
increasingly higher
electrons than
by the nucleus and
down in the group as you go down the other anions.
That
the more likely
higher
than
iodide
ions
(I
)
tend to not bond
group
is,in order of
electrons will be
strongly with their
oxidizing power, Cl
easily lost.

strongly with their

cation counterparts

oxidizing power, Cl-> Br--> I--

Displacement
How an ions position in the electrochemical
series affects its displacement from solution

CATIONS
For cations,

The lower the IN

ion is THE
in the
LOWER
electrochemical series, the more likely it
will
want to gain electrons
(that
is be
SERIES
WILL
BE
reduced)
The cathode
DISPLACED
supplies electrons
to cations in
MOREsolution
READILY
Ions lower in the series would
therefore
be moreOTHER
strongly attracted
THAN
to the cathode than other cations in
solution. AT
CATIONS
THE CATHODE

For ANIONS
cations, LOWER

The lower
the anion
is in the
IN
THE
SERIES
electrochemical series, the more likely it
will want to
lose electrons
(that is be
WILL
BE
oxidised)
The anode accepts
DISPLACED
electrons from
anions READILY
in solution
MORE
Ions lower in the series would
therefore
be moreOTHER
strongly attracted
THAN
to the anode than other anions in
solution.
ANIONS
AT THE
ANODE

In solution, the cations are Cu2+

and H+.
Since Cu2+ is lower in the series
than H+, it would preferentially
be displaced at the cathode

At the anode, hydroxide

ions lose electrons to form
water and oxygen gas:
2OH- - 4e- -> 2H2O (l) + O2
(g)

At the cathode,
Cu2+ ions then
Electrolysis
of
gain 2 electrons to form solid
copper
copper: (II)
Cu2+sulphate
+ 2e- -> Cu(s) solution
At the cathode, pink copper
metal is deposited.

In solution, the anions are

So42- and OH-. Since OH- is
lower in the electrochemical
series than SO42-, it will be
preferentially displaced

At the anode, oxygen gas is

produced.

Solution concentration
How a solutions molarity can affect the products
of electrolysis

Concentration defined
In chemistry,
concentration
deals with the
amount of
solute in a
given volume
of solvent

Higher concentration means

that the given solute: solvent
ratio is high, that is, there is a
high level of solute to a given
volume of solvent

Low concentration means

that the given solute: solvent
ratio is low, that is, there is a
low level of solute to a given
volume of solvent

What happens during electrolysis

of concentrated solutions?
Although

the electrochemical series can

still predict which ions will be displaced,
in concentrated solution, sheer numbers
means that other ions slightly higher in
the series can be preferentially
displaced
However, if the ions are very far apart in
the electrochemical series, then the
lower ion will be discharged
preferentially

Oxidation half-equation at anode:

2Cl- - 2e- -> Cl2(g)

The anions in solution are

OH- and Cl-. Since the
concentration of Cl- ions is
high and there is Cl- is not
much higher on the
electrochemical series as
compared to OH-, it
requires a almost the
same amount of energy to
displace Cl- ions compared
to OH- ions. This is why Clions are preferentially
displaced at the anode

Reduction half-equation at cathode:

2H+ + 2e- -> H2(g)

The cations in solution are H+

and Na+. Although the
concentration of Na+ ions is
high, Na+ is very high on the
electrochemical series as
Electrolysis
of
compared to H+. This great
difference between the
brine
reduction potentials of the
Brine is concentrated sodium
two cations means that it
chloride solution.
requires a great deal less
+
energy
displace H
ions
At
the endto
of electrolysis,
hydrogen
+
is produced at
compared
tothe
Nacathode
ions.while
This is
chlorine
is
produced
at
the
anode.
why H+ ions are preferentially
displaced at the cathode

Types of electrodes
How inert and active electrodes affect the
products of electrolysis

Types of electrodes

Inert
Inert
Inert electrodes
electrodes do
do not
not actually
actually
participate
participate in
in electrolysis
electrolysis but
but just
just
provide
provide electrical
electrical current
current

Active
Active
Active electrodes
electrodes actually
actually
participate
participate in
in electrolysis
electrolysis while
while
providing
providing electrical
electrical current
current

Example of inert
electrodes

Graphit
e

Platinu
m

Mercury

How inert electrodes work

The word inert

means
unreactive

This means that

inert electrodes
do not actively
participate in the
reaction

They just behave

as electrodes
should behave
accepting and
providing
electrons to the
ions in the
electrolyte

Active electrodes
Usually

made of the metal that

corresponds to the metallic ion in the
electrolyte
Actively donates electrons and ions to
the electrolytic circuit

The cathode is
If the metal of the electrode is
negatively charged in
very close or the same that of
order to attract
the ions in solution, it is easier
cations.
to lose or gain electrons from
With an inert cathode,
the electrode itself compared
the ice-cream
electrons are cone
It isfor
really
like
getting an
to waiting
electron
loss
given to one
the cations,
from
the
right on
and/or
gainacross
from ions
in street versus
reducing the cation to
solution.
the corner from where
you are.
the corresponding
metal.
It is easier to use the store
closest to you,

How active electrodes work

just like it is easier to use the region (in

this case the electrode) closest to the
circuit. With active electrodes, it
really depends on how
close the ions in solution
are to the metal in the
electrode in the
electrochemical series

Lets compare electrolysis of

Copper (II) sulphate solution
using graphite electrode

Copper (II) sulphate

using copper electrodes

Electrolysis using
inert
electrodes
Once the power
supply
is
turned on, the Cu2+ ions
gravitate towards the
cathode as Cu2+ ions are
lower in the
electrochemical
series
the
Cu2+ +ions
than H ions.

Cop
per
(II)
sulp
At the cathode,
hat
e
gain 2e to form solid Cu metal:
solu
Cu2+(aq) + 2e- -> Cu(s)
tion
usin
The OH- ions go towards the
g
anode as OH is much lower in
gra
phit
series than
-At the
theelectrochemical
anode,
the
OH
ions
lose
e
SO42-.
4e-- to form oxygen gas and elec
trod
water:
e
-2OH--(aq)
4e
-> 2H22O(l)
+ O2(g)
(aq)
(l)
2(g)

Electrolysis using
active
electrodes
Once the power supply
is turned
on, the Cu2+ ions gravitate
towards the cathode as Cu2+ ions
are lower in the electrochemical
series than H+ ions.

Cop
per
(II)
sul
At the cathode, the Cu2+ ions
pha
gain 2e to form solid Cu metal:
te
sol
Cu2+(aq) + 2e- -> Cu(s)
utio
n
The OH- ions go towards the
usi
anode as OH- is much lower in
ng
the electrochemical series than
-cop
At the anode,
the OH ions lose
SO42-.
4e-- to form oxygen gas and per
ele
ctro
water:
de
-

2OH-(aq)
- 4e- -> 2H22O(l)
+ O2(g)
(aq)
(l)
2(g)