Electrolysis

Electrolysis The 3 Questions

** Preliminary Qn: Is there a Battery?
YES: it is an electrolysis question.
NO: it is a simple cell question.

e
Cathode

2. **What will take place at the Cathode?

Anode

+
+
+
+

1. **What will take place at the Anode?

Any Observations?

Battery
+

+
+
+
+
+

Table 15-A

+
+
+
+
+
+
-

Any Observations?

3. **What will happen to the Electrolyte?

-

Electrolyte contains IONs:

- Cations are attracted to the Cathode,
- Anions are attracted to the Anode.

Any Observations?

Electrolyte:
A. Solution (aq) - Also contains H+ and OH ions.
B. Molten Ionic Compound (l)

Electrolysis Set-up:
1 **Reaction at the Anode?
Observations?
Battery
+

e
Cathode

+
+
+
+
+

2 **Reaction at the Cathode?

Observations?

Anode

+
+
+
+

+
+
+
+
+
+
-

3 **Changes to Electrolyte?
Observations?
-

Electrolyte:
H2O H+ + OHA. Solution (aq) - Also contains H+ and OH ions.
B. Molten Ionic Compound (l)
Electrolyte contains IONs:
- Cations are attracted to the Cathode,
- Anions are attracted to the Anode.

Demonstration:
Electrolysis of CuSO4 (aq) Using Graphite Anode
and a Coin as Cathode(Electroplating)
Battery
+

Anode

Cathode

+
+
+
+
+

What are the observations?

+
+
+
+

+
+
+
+
+
+
-

1. Anode:

2. Cathode:

3. Electrolyte:

Demonstration:
Electrolysis of CuSO4 (aq) Using Graphite Anode
and a Coin as Cathode(Electroplating)
Battery
+

Anode

Cathode

+
+
+

What are the observations?

+
+

+
+
+
+

+
+
+
+
+
+
-

1. Anode:
Bubbles are seen!!!

2. Cathode:
Reddish brown solid deposited
on the cathode (coin)!!!
3. Electrolyte:
The blue colour fades.

Demonstration:
Electrolysis of CuSO4 (aq) Using Graphite Anode
and a Coin as Cathode(Electroplating)
Battery
+

Anode

Cathode

+
+
+

What are the observations?

+
+

+
+
+
+

+
+
+
+
+
+
-

1. Anode:
Bubbles are seen!!!
4OH- (aq)
O2(g) + 2H2O(l) + 4eElectrons goes into the
external circuit into the
battery.

2. Cathode:
Reddish brown solid deposited
on the cathode (coin)!!!!!!
Cu2+ (aq) + 2e-
Cu (s)
3. Electrolyte:
The blue colour fades.
Bec Cu2+ ions have discharged.

Demonstration:
Electrolysis of CuSO4 (aq) Using Graphite Anode
and a Coin as Cathode(Electroplating)
Electrolyte: CuSO4(aq)

Anode: C

Cations , Anions

Ions Present:
attracted to
the cathode

Cu2+

SO42-

H+

OH-

**Reaction at the Anode:

Observation:

**Reaction at the Cathode:

Observation:

**Changes to the electrolyte:

attracted to the anode

Demonstration:
Electrolysis of CuSO4 (aq) Using Graphite Anode
and a Coin as Cathode(Electroplating)
Battery
+

Anode (Graphite)

Cathode

Cu2+ ions
H+ ions

+ +
+
+ +
+
+
+
+ ++ +
+

+
+
+
+
+
+
-

SO42- ions
OH- ions

The 2 ions attracted to the electrode competes to discharge.

So who will discharge???
Anode: OH- ions were preferentially discharged over SO42- ions.
Cathode: Cu2+ ions were preferentially discharged over H+ ions.

Factors affecting Selective Discharge of ions:

1. Nature of the ions.
Eg. At the Anode & Cathode:
The more stable ions will remain in the solution and will not
discharge.

2. Concentration of the ions.

Eg. At the Anode:
Halide ions will discharge before OH ions when the solution
contains higher concentration of the halide ions than OH- ions.
(This is usually the case.)

3.Nature of the electrodes.

Eg: If the Anode is a reactive electrode, it will dissolve into the
solution.

Selective Discharge of ions:

Table 15-B/C

Anions

Cations

Note:
NO3-, SO42-, CO32- ions
will never discharge.

K+
Na+
Ca2+
Mg2+
Al3+
Zn2+
Fe2+
Sn2+
Pb2+
H+

Halide ions
eg. Cl , Br , I
However, Halide ions will
discharge before OH- ions
in a concentrated solution.

OH- ions

Difficult

Ease
of
Discharge

Easiest

Cu2+
Ag+

Very stable
ions will not
discharge.
Very Reactive
Metals form Very
Stable Ions which
are more difficult
to discharge!

Less stable
ions discharge
more easily;
Accepts emore readily.

Demonstration:
Electrolysis of CuSO4 (aq) Using Graphite Anode
and a Coin as Cathode(Electroplating)
Anode: C

Electrolyte: CuSO4(aq)
discharge more easily than H+
Cations , Anions

Ions Present:
attracted to
the cathode

Cu2+

SO42-

H+

OH-

**Reaction at the Anode:

will never discharge.

attracted to the anode
Electrons goes into the

external circuit into the

4 OH- (aq)
O2 (g) + 2 H2O (l) + 4e- battery.

Observation: Effervescence is seen at the anode.

**Reaction at the Cathode:

Cu2+ (aq) + 2e-

Cu (s)

Observation: Reddish brown solid is deposited at the

cathode.

**Changes to the electrolyte: The blue solution fades until it becomes

colourless. The pH decreases as the
solution turns into sulfuric acid.

3. What will happen to the Electrolyte?

Table 15-D

Consider the ions left behind at the end of the electrolysis expt.
Will there be any changes in the electrolytes
- Colour,
- Acidity,
- Concentration?
Colour is affected if a metal cation with its characteristic
colour is discharged from the solution.
Acidity is affected if EITHER H+ OR OH- ions is
discharged from the solution.
Concentration is affected if BOTH H+ AND OH- ions are
discharged, resulting in water molecules being lost.

Electrolysis of Aqueous Solutions

**IMPT > Aqueous Solutions also contains H+ and OH ions!!!
Selective Discharge takes place at the electrodes.
Example 1: Electrolysis of silver nitrate solution using
platinum electrodes.
Electrolyte: AgNO3 (aq)
Ions Present:

Anode: Pt

Cations , Anions
Ag+ , NO3H+

**Reaction at the Anode:

Observation:

**Reaction at the Cathode:

OH-

Note:
NO3-, SO42-, CO32- ions
will never discharge.

4 OH- (aq)

Electrons goes into the

external circuit into the
O2 (g) + 2 H2O (l) + 4e- battery.

Effervescence is seen at the anode.

Ag+ (aq)

+ e

Ag (s)

Observation: A silvery solid is coated onto the Pt cathode.

**Changes to the electrolyte: Electrolyte turns into nitric acid.

Hence, pH decreases.

Example 2: Electrolysis of concentrated copper(II)

chloride solution using graphite electrodes.
Electrolyte: Conc. CuCl2 (aq)
Ions Present:

Anode: C

Cations , Anions
Cu2+ , ClH+

**Reaction at the Anode:

Observation:

**Reaction at the Cathode:

Observation:

OH-

Electrons goes into the

external circuit into the
Cl2 (g) + 2ebattery.

2 Cl (aq)

Effervescence is seen at the anode.
Greenish-yellow gas evolved.
Cu2+ (aq) + 2e-

Cu (s)

Reddish brown solid coats over the

graphite cathode.

**Changes to the electrolyte: Blue solution fades as copper (II) ions

are discharged. The solution also
becomes less concentrated.

Example 3: Electrolysis of dilute sulphuric acid using

carbon electrodes.
Electrolyte: H2SO4 (aq)
Ions Present:

Cations , Anions
H+
, SO42H+
, OH-

**Reaction at the Anode:

Observation:

**Reaction at the Cathode:

Observation:

Experimental Setup:
refer to page 267

Anode: C

Electrons goes into the

external circuit into the
O2 (g) + 2 H2O (l) + 4e- battery.

4 OH- (aq)

Effervescence is seen at the anode.
2H+ (aq) + 2e-

H2 (g)

Effervescence is seen at the cathode.

+
**Changes to the electrolyte: Since both H and OH ions are

discharged, effectively, water is being

lost. The solution thus becomes more
concentrated.

**Overall Equation:

2H2O
O2

+ 2H2

Anode:
Cathode:
x2 :

4 OH-

O2

+ 2 H2O + 4e-

2H+ + 2e-

H2

4H+ + 4e-

2H2

Combining Anode & Cathode Eqns:

Eqn 1

Eqn 2

Eqn 1 + Eqn 2

4OH- + 4H+ + 4e-
O2 + 2H2O + 2H2 + 4e4OH- + 4H+
O2 + 2H2O + 2H2

4H2O

O2 + 2H2O + 2H2

Overall Equation:
2H2O
O2

+ 2H2

25

**Example 4: Electrolysis of concentrated potassium iodide

solution using platinum electrodes.

Electrolyte: Conc. KI (aq)

Ions Present:

Anode: Pt

Cations , Anions
K+
,
IH+
, OH-

**Reaction at the Anode: 2 l (aq)
I2 (aq) + 2eObservation:

**Reaction at the Cathode:

Observation:

Colourless solution around the

anode turns yellowish/reddish brown.
2H+ (aq) + 2e-

H2 (g)

Effervescence is seen at the cathode.

**Changes to the electrolyte: The pH increases as hydrogen ions are

less than hydroxide ions. Iodine
solution also formed.

Electrolysis of Molten Compounds

High temp!!! Above m.p. of Pb!!!

Example 5: Electrolysis of molten lead(II) bromide using

graphite electrodes.
Electrolyte: PbBr2 (l)
Ions Present:

Anode: C

Cations , Anions
Pb2+ , Br -

**Reaction at the Anode: 2 Br (l)

Br2 (g) + 2e-

Observation: Effervescence is seen at the anode.

Reddish brown gas evolved.
**Reaction at the Cathode: Pb2+ (l) + 2e
Pb (l)
Observation: Silvery-grey liquid formed at the cathode
sinks to the bottom of the crucible/container.

**Changes to the electrolyte:

The amount/volume of molten lead(II) bromide decreases as it
decomposes to form lead and bromine.
**Overall Equation:

PbBr2

Pb

Br2

High temp!!! Above the m.p. of Na!!!

Example 6: Electrolysis of molten sodium chloride using

carbon rods.
Electrolyte: NaCl (l)
Ions Present:

Anode: C

Cations , Anions
Na+ , Cl -

**Reaction at the Anode: 2 Cl - (l)

Cl2 (g) + 2e-

Observation: Effervescence is seen at the anode.

Greenish-yellow gas evolved.
**Reaction at the Cathode: Na+ (l) + e
Na (l)
Observation: Silvery-grey liquid formed at the cathode
float to the surface and burns in air with
flashes of yellow light.

**Changes to the electrolyte:

The amount/volume of molten sodium chloride decreases as it
decomposes to form sodium and chlorine.
**Overall Equation:

2 NaCl

2 Na + Cl2

**(Application: Extraction of Sodium)

Industrial Manufacture of Sodium by Electrolysis

29

PART 2:
The

REACTIVE Anode
INERT Anode : Graphite (C) & Platinum (Pt)
REACTIVE Anode : Any other Metal anode
The reactive anode will change the reaction at the anode.

Scenario A: Anode is INERT

I want
electrons!!!

Where will the positive end of the

battery get electrons from?
Usually from the ANIONS in the

Battery
+

electrolyte if the anode is INERT.

Anode

+
+
+
+ +

+
+
+
+
+
+
-

I will give you

electrons!!!

However, there is another way..!!!

The REACTIVE Anode

Scenario B: Anode is REACTIVE
I want
electrons!!!
Battery
+

Reactive Metals can give away

electrons by turning into ions:

Anode

+
+
+
+ +

Where will the positive end of the

battery get electrons from?

+
++
++
++
++
++ + - -

No!!! I will
give you
instead!!!
I will give you
electrons!!!

M (s)
M+ (aq) + eThe anode dissolves!

Since the anode now supplies the

electrons instead of the anions, the
anions cannot discharge.

The REACTIVE Anode

Example 7: Electrolysis of silver nitrate solution
using a silver anode and an iron cathode.
Electrolyte: AgNO3 (aq)

Anode: Ag

Cations , Anions

Ions Present:

Ag+

NO3-

H+

OH-

**Reaction at the Anode:

Ag (s)

The reactive silver anode will

prevent the anions from
discharging.
Electrons goes into the external
circuit into the battery.
Ag+ (aq) + e-

Observation: The silver anode dissolves into the solution.

**Reaction at the Cathode:

Ag+ (aq)

+ e

Ag (s)

Observation: A silvery solid is coated onto the iron cathode.

**Changes to the electrolyte: No changes.

**(Application: Silver Plating)

Example 8: Electrolysis of aqueous copper(II) sulphate

using copper electrodes.
**
**(Application: Purification of Impure Copper)
- Put the impure copper at the Anode and
pure copper at the Cathode.
As the anode dissolves, the impurities sinks to the bottom
of the container.
Electrolyte:
Anode: Cu
CuSO4 (aq)

Ions Present:

Cations , Anions
Cu2+ , SO42H+
, OH-

**Reaction at the Anode:

Observation:

**Reaction at the Cathode:

Observation:

The reactive copper anode will

prevent the anions from
discharging.

Cu (s)

Cu2+

Electrons goes into the external

(aq) + 2e- circuit into the battery.

Anode dissolves.
Cu2+ (aq) + 2e-

Cu (s)

Reddish brown solid coats over /

deposits onto the cathode.

**Changes to the electrolyte: No change.

Applications of Electrolysis
1. Purification of Copper.
- Put the impure copper at the ____________ .
- Pure copper is formed at the ____________ .
* Other precious metals present in the impurities can also
be collected.
2. Electroplating. (Eg. To Silver-plate a Spoon)
- Put the Silver at the _____________ .
- Put the Spoon at the _____________ .
3. Extraction of Aluminium. (and other reactive metals)
- Refer to Table 12.

The REAL Definition of Anode & Cathode

Anode : is the electrode where
Oxidation takes place.
Cathode : is the electrode where
Reduction takes place.
Memory Aid:

An Ox chasing a Red Cat

Table 15A

The 3 Questions
1. What will take place at the

Anode?
A. Will Anode
Dissolve?
(If YES, No Selective
Discharge)

B. (If NO, Anode

does not dissolve)

Selective
Discharge
of anions takes place.

2. What will take place at the

3. What will happen to the

Cathode?

Electrolyte?

Selective Discharge
of cations will take place!

Will there be any

changes in the
electrolytes
- Colour,

- Acidity,
- Concentration?

Electrolysis The 3 Questions

** Preliminary Qn: Is there a Battery?
YES: it is an electrolysis question.
NO: it is a simple cell question.

Any Observations?

Battery
+

2. **What will take place at the Cathode?

e
Cathode

+
+
+
+
+

Anode

+
+
+
+

1. **What will take place at the Anode?

+
+
+
+
+
+
-

Any Observations?

3. **What will happen to the Electrolyte?

-

Electrolyte contains IONs:

- Cations are attracted to the Cathode,
- Anions are attracted to the Anode.

Any Observations?

Electrolyte:
A. Solution (aq) - Also contains H+ and OH ions.
B. Molten Ionic Compound (l)

Selective Discharge of ions:

Table 15-B/C

Anions

Cations

Note:
NO3-, SO42-, CO32- ions
will never discharge.

K+
Na+
Ca2+
Mg2+
Al3+
Zn2+
Fe2+
Sn2+
Pb2+
H+

Halide ions
eg. Cl , Br , I
However, Halide ions will
discharge before OH- ions
in a concentrated solution.

OH-

ions

Difficult

Ease
of
Discharge

Easiest

Cu2+
Ag+

Very stable
ions will not
discharge.
Very Reactive
Metals form Very
Stable Ions which
are more difficult
to discharge!

Less stable
ions discharge
more easily.

1. What will take place at the Anode?

Table 15-B

A. If the anode is reactive, it will dissolve into the

solution to form ions.
Note:
Only anodes made of Graphite (C)
- the anode is reactive if
and Platinum (Pt) will not dissolve
it is any Metal other than C or Pt !! because they are INERT.
At Anode: M
M+ + e
Observation: Anode dissolves into the solution.
(Note: Anions cannot discharge at the anode when the anode is dissolving!!!)

of
B. If the anode is inert (C or Pt), selective dischargeNote:
anions will take place at the anode.
NO , SO , CO
will never
Anion, X- Vs OH- Competition to discharge.ions
discharge.
-

2-

2-

IMPT > Halide ions will discharge before OH ions in a conc. solution!
At Anode: 2X 2e
X2
(where X is a halide)
(or) 4OH 4e
2H2O + O2

(if halide ion not present

or soln is dilute)
Observation: Eg. Effervescence produced at the anode.

2. What will take place at the Cathode?

Table 15-C

Since the Cathode will never dissolve into the solution even if it is
a reactive electrode, only selective discharge of cations will
take place at the cathode.
Cation, M+ Vs H+ Competition to discharge.
IMPT > Ions of the less reactive metal will discharge before H+ ions!
At Cathode:

M+ + e
M (if M is less reactive than H)

Observation: Eg. A silvery solid is coated onto the cathode.

(or)

2H+ + 2e
H2 (if H is less reactive than M)

Observation: Effervescence produced at the cathode.

3. What will happen to the Electrolyte?

Table 15-D

Consider the ions left behind at the end of the electrolysis expt.
Will there be any changes in the electrolytes
- Colour,
- Acidity,
- Concentration?
Colour is affected if a metal cation with its characteristic
colour is discharged from the solution.
Acidity is affected if EITHER H+ OR OH- ions is
discharged from the solution.
Concentration is affected if BOTH H+ AND OH- ions are
discharged, resulting in water molecules being lost.

--- End ---