IONIC THEORY

Ionic theory was used to explain the behaviour of electrolytes when electric current is
passed through their solution. A Swedish chemist, Swante Arrhenius (1884), was the first to
use the ionic theory to describe electrolysis. The theory proposed that when an electrolyte is
melted or dissolved in water, some if not all of the molecules of the substance dissociate
into freely-moving charged ions namely positive ions (called cations) and negative ions
(anions). The process of dissociation into ions is called ionization.

When an electric current is passed through an electrolyte, the free ions lose their random
movement. The positive ions become attracted to the negative electrode (cathode) while the
negative ions moves toward the positive electrode (anode). It is this movement of ions that
brings about the flow of current.

This Arrhenius version of the theory has been modified after X-ray diffraction studies show
that salts and strong alkalis is already consisted of oppositely charged ions even in their
solid states. The modern theory then proposes that the ions in such solid state are pulled
away from one another either as a result of heat energy applied when the solid melts or with
the help of the solvent molecules when the solid dissolves. Thus,

−¿ ¿
+¿+Cl( aq ) ¿
Arrheniustheory ; NaC l ( s ) → N a(aq )

−¿ ¿
+¿ +Cl ¿
(aq )
−¿→Na ( aq ) ¿

Moderntheory ; N a+¿C l ¿

EVIDENCES THAT SUPPORT IONIC THEORY

The following evidences are experimental observation which supports existence of ions.

(1) Ions present in solid electrolytes

X-ray diffraction studies have shown that electrolytes are composed of ions. For
example, a crystal of NaCl does not contain NaCl units but Na + and Cl- ions. With each
Na+ surrounded by six Cl- ions and each Cl- in turns surrounded by six Na +. Ionic
compounds behave as good conductors in the fused (molten) state. This can only be
possible if ions are already present in ionic solids.
(2) Ohms Law Applicability

Just like metallic conductors, electrolytic solutions obey ohm’s law. That is, the
strenght of the current flowing in a conductor is directly proportional to the potential
 difference applied across it and it is inversely proportion to the resistance of the
conductor. This can only be possible if ions are already present in the solution.
(3) Ionic Reactions:
Evidence for the existence of ions in aqueous solution of electrolytes is supported by
ionic reactions. A white precipitate of silver chloride is obtained whenever silver ions
come in contact with chloride ions.
e.g. Ag+ NO3- + K+ Cl-  AgCl(S) + Na+ + NO3- . But no precipitation is observed
when AgNO3 is added to CCl4, CHCl3 or C2H5Cl as these substances being non-
electrolytes do not produce Cl - ions in solution. An acid gives all test of H + ions when
dissolved in water (aqueous solution), but does not give the same test when dissolved
in organic solvent, because they don’t ionize in organic solvent.
(4)Heat of neutralization:
When one mole of a strong acid is neutralized by one mole of a strong base, the heat
evolved (-53.7kjmol-1) is always the same. This can be explained on the basis of
Arrhenius theory that an acid produces H + ions and a base produces OH - ions when
dissolved in water and the process of neutralization involves the common reaction
between H+ + OH-  H2O. Thus the heat of neutralization is actually the heat of
formation of water from H+ and OH-.
(5) Colour of Solution
The colour of electrolytes (if any) in solution is due to their ions. The CuSO 4 is blue in
solution due the presence of Cu2+ ions. Potassium tetraoxomanganate(vii) solution is
purple due to the presence of MnO4-.

LIMITATIONS OF THE ARHENIUS VERSION OF IONIC THEORY

(1)Strong electrolytes can conduct electricity in fused state (i.e. in the absence of
water). This is in contradiction to the Arrhenius theory in which the presence of
solvent is a must for ionization. This is one of the modifications made to Arrhenius
theory by the modern ionic theory, by stating that solid electrolytes already
contains ions which are made mobiles either by heat (in molten) or by the solvent
(in aqueous solution).
(2)Arrhenius theory also assumes independent existence of ions but fails to account
for the factors which influence their mobility.

FACTORS AFFECTING THE DEGREE OF IONISATION

The degree of ionization of electrolytes in solution depends upon the following factors
(1)Nature of Solute
 (2)Nature of Solvent
(3)Dilution
(4)Temperature
(1)Nature of Solute:
When the ionizable part of a molecule of a substance are held more by covalent bonding than
by ionic bonding, less ions are produced in solution. Such substance are known as weak
electrolytes. E.g. H2S, HCN, NH4OH, CH3COOH. But in strong electrolytes e.g. NaCl, Ba(NO 3)2,
KOH, NaOH e.t.c, the transfer of electrons seems to be more or less complete, therefore they
produce ions immediately when dissolved. Strong electrolytes are almost completely ionized in
solution.

(2)Nature of Solvent:
The main function of the solvent is to weaken the electrostatic forces of attraction between
the two ions and separate them. The force of attraction holding ions together in any medium is
usually expressed as
F= q1q2
Kr2
Where K is the dielectric constant of the medium. Thus, any solvent which has a high
value of dielectric constant has the capacity of separating ions. The dielectric constant
for water is 81, methyl alcohol is 35, ethyl alcohol is 27 and for acetone is 21. Water
is therefore considered to be the best solvent because it has the highest value of
dielectric constant.

(3) Dilution:
The extent of ionization of a substance in a solution is inversely proportional to the
concentration of its solution. Thus, degree of ionization increases with increase in
dilution of the solution (i.e. decrease in the concentration of the solution). Therefore, a
concentrated acid is less acidic in properties than a dilute acid because it contains
fewer number of hydrogen ions. Thus, the conductivity of an electrolyte increases with
increasing dilution or decreasing concentration.

(4) Temperature:
The degree of ionization increases with the increase of temperature. This is due to the
fact that increase in temperature increases molecular speed which helps to overcome
the forces of attraction between the ions.

Quiz Me Please

(1) The process of splitting of molecules into ions of an electrolytes is called (a) ionization
(b) electrolysis (c) solvation (d) protonation
(2) The colour of CuSO4 solution is ___ (a) green (b) yellow (c) blue (d) red
(3) The colour of KMnO4 solution is ___ (a) green (b) yellow (c) purple (d) orange
(4) Which of the following is not an electrolyte? (a) silver trioxonitrate (V) solution (b)
sugar solution (c) copper (II) tetraoxo sulphate (VI) solution (d) acidulated water
(5) The colour of K2Cr2O7 solution is ___ (a) green (b) yellow (c) purple (d) orange
(6) Degree of ionization does not depends on ___ (a) temperature (b) pressure (c)
concentration (d) nature of solvent
(7) The colour of K2CrO4 solution is ___ (a) green (b) yellow (c) purple (d) orange
(8) Which of the following substances decomposes when an electric current is passed
through it? (a) glucose solution (b) zinc rod (c) tetrachloromethane (d) hydrochloric
acid
(9) The colour of FeCl3 Solution is ___ (a) green (b) white (c) brown (d) orange
(10) Electrolysis is not applied in ---- (a) tin plating (b) purification of copper (c) extraction
of aluminium (d) extraction of iron (e) manufacture of sodium hydroxide
(11) The element used as an electrode in car batteries is (a) sodium (b) potassium (c)
magnesium (d) lead
(12) Which of the following methods cannot be used to distinguish between a strong acid
and a weak acid? (a) conductivity measurement (b) action on starch iodide paper (c)
measurement of pH (d) measurement of heat of reaction
(13) The colour of [Cu(NH3)4]Cl2 Solution is ___ (a) green (b) blue (c) brown (d) orange
(14) The colour of electrolytes in solution is due to its ___ (a) ions (b) solvation (c)
electrolysis (d) dissolution
(15) In electrolysis, reduction takes place at the ---- (a) anode (b) cathode (c) electrodes (d)
cations
(16) Potassium chloride cannot conduct electricity in the solid state because it (a) does not
contain mobile ions (b) is very soluble in water (c) it is an electrovalent compound (d)
is a neutral salt
(17) An electrolyte is (a) aqueous solution of glucose (b) hydrogen chloride in methyl
benzene (c) molten sodium chloride (d) molten candle wax
(18) Which of the following is a good conductor of electricity (a) methyl benzene (b)
deionized water (c) mercury (d) sucrose solution
(19) What happens to the conductivity of an electrolyte as it concentration reduces? It (a)
increases (b) decreases (c) is unaffected (d) reduces to zero
(20) Which of the following liquid is a good conductor of an electric current (a) aqueous
solution of glucose (b) aqueous solution of potassium chloride (c) Mixture of water and
ethanol (d) mixture of kerosene and petrol
(21) 0.05moldm-3 of KCl conducts electricity better than 0.05moldm -3 NH3 because the
solution of KCl (a) is neutral (b) has a lower PH (c) is denser (d) contains more ions
In measuring cell potential, state one advantage of
(i) potentiometer over a traditional voltmeter.
(ii) digital voltmeter over a potentiometer
 (3) Dilution:
The extent of ionization of a substance in a solution is inversely proportional to the
concentration of its solution. Thus, degree of ionization increases with increase in
dilution of the solution (i.e. decrease in the concentration of the solution). Therefore, a
concentrated acid is less acidic in properties than a dilute acid because it contains
fewer number of hydrogen ions. Thus, the conductivity of an electrolyte increases with
increasing dilution or decreasing concentration.

(4) Temperature:
The degree of ionization increases with the increase of temperature. This is due to the
fact that increase in temperature increases molecular speed which helps to overcome
the forces of attraction between the ions.

ELECTROLYSIS
Electrolysis is the chemical decomposition of an electrolyte when a direct current is passed
through into its aqueous solution or molten form.

RELEVANT TERMINOLOGIES IN ELECTROLYSIS

1. Electrodes: Electrodes are conductors in the form of wires, rods or plates through
which electric current enters or leaves the electrolyte. The two types of electrodes are
the cathode (-ve electrode) and the anode (+ve electrodes).
[Link]: This is the positive electrode through which electrons leaves and convectional
current enters the electrolytes. It is the electrode which is usually joined to the positive
terminal of the external electric supply. During electrolysis, negative ions migrates to
the anode.
[Link]: This is the negative electrode through which electrons enter and convectional
current leaves the electrolytes. It is the electrode which is usually joined to the negative
terminal of the external electric supply. During electrolysis, positive ions migrates to the
cathode.
{Note: In an electrolytic cell, the negative electrode is known as the cathode while the positive electrode is
known as the anode but in an electrochemical cell, the negative electrode is the anode while the positive
electrode is the cathode}

2. Electrolytes
An electrolyte is a compound which conduct electricity in a molten or aqueous state and
become decomposed in the process.
Electrolytes conduct electric currents by movement of ions. Examples of electrolytes
include NaCl, CuCl2, CUSO4, HCl, H2SO4 etc.
There are two types of electrolytes:
(a) Strong electrolytes: These are electrolytes that ionize completely and can conduct
large electric current because they contain high concentration of free moving ions.
Examples are all strong acids (e.g. H 2SO4, HNO3, HCl), all strong bases (e.g. KOH, NaOH)
and salts (e.g. NaCl, AgNO3, KNO3, KBr)
(b) Weak electrolytes: These are those that partially ionize and conduct electricity poorly
because they contain low concentration of ions. Examples are weak acids (e.g.
CH3COOH, H3PO4, H2CO3) and weak bases [Ca(OH)2, NH3(aq).]

3. Non-Electrolytes These are substances which do not conduct electricity because they
do not ionize. Examples are urea, ethane, benzene, trichloromethane, cane sugar,
ether, tetrachloromethane, glucose solution, sucrose solution e.t.c
 DIFFERENCES BETWEEN AN ELECTROLYTE AND A CONDUCTOR
S/ ELECTROLYTES CONDUCTOR

1. Conducts electricity by free Conduct electricity by free

mobile ions mobile electrons
2. Conduct electricity in molten Conduct electricity in solid
or aqueous form form
3. Get decomposed in the Does not get decomposed in
process the process
4. It is a compound It is an element

4. An Electrolytic Cell: This is a device that uses electricity to bring about chemical
change. It is an assemblage of two electrodes in an electrolyte and used for the
electrolysis of the substance. This simple set-up used during electrolysis is called a
voltameter. In an electrolytic cell, oxidation occurs at the anode and reduction occur at
the cathode.

DIFFERENCES BETWEEN ELECTROLYTIC CELLS AND ELECTROCHEMICAL CELLS

 ELETROLYTIC CELL ELETROCHEMICAL CELL
1 Convert electrical energy to chemical Convert chemical energy to electrical
. energy energy.
2 The process is non-spontaneous. The process is spontaneous.
.
3 Electrodes are in the same compartment Electrodes are in separate compartments
.
4 Salt bridge is not needed Salt bridge is required
.
5 Ions are discharged at both cathode and Ions are discharged only at the cathode
. anode
5 Only one electrolyte is used Two electrolytes are used
.
6 Cathode is the negative electrode while Cathode is the positive electrode while
. anode is the positive electrode anode is the negative electrode
DIFFERENCES BETWEEN ELECTROLYTIC AND ELECTROCHEMICAL CELL

THE MECHANISM OF ELECTROLYSIS

An electrolyte is composed of positive and negative ions. Before the passage of current,
these ions move about randomly in the electrolyte.
When electrolysis begins, the battery pumps electrons through its own anode into the
cathode of the electrolytic cell. This makes the cathode to become electron-rich and
negatively charged. Hence, positive ions migrate to the cathode, and are therefore called
cathode ions (cations). At the same time, the cathode of the battery draws electrons
away from the anode of the electrolytic cell. This makes the anode to become electron
deficient and positively charged. Hence, negatively charged ions migrate to the anode,
and are therefore called anode ions (anions).
Thus, at the cathode (negative and electron rich electrode), the cations accepts
electrons to become discharged as electrically neutral atoms. Simultaneously at the
anode (positive and electron-deficient electrode), the anions give up their electrons to
become discharged as electrically neutral atoms.
Since, cations gain electrons at the cathode, reduction is said to occur there. This
reaction at the cathode is known as cathodic half-reaction. Anions lose their electrons at
the anode, oxidation is therefore said to occur there. The reaction taking place at this
anode is known as anodic half reaction. As a result of this chemical reaction that occur at
 these electrodes, metals and hydrogen gas are usually discharged at the cathode, while
non-metals are discharged at the anode with the exception of hydrogen.
When molten electrolytes are used during electrolysis, only one cation and one anion will
be present. This cation will get discharged at the cathode while the anion will
simultaneously get discharged at the anode. But if the electrolyte used is an aqueous
solution, two cations (one from the electrolyte and hydrogen ions from water) are present
and two anions (one from the electrolyte and hydroxide ion) are present. The two cations
will both migrate to the cathode, while the two anions will simultaneously migrate to the
anode. Now, there will be two – two ions at each electrode and only one ion can get
discharged, the other ion must remain in solution. What will now happen, which ones will
get discharged at both electrodes, which ones would remain in the solution?

PREFERENTIAL DISCHARGE OF IONS

What is meant by preferential discharge of ions in electrolysis?
Preferential discharge of ions is defined as the selective discharge of ions in
preference to others at the electrode due to certain factors. This implies that there are
some factors that determines which ion is to be discharged in preference to another
during electrolysis.
FACTORS AFFECTING THE DISCHARGE OF IONS / PRODUCT OF ELECTROLYSIS
Three major factors determine the discharge of ions at the electrodes. They are
(1)The relative position of ions in the electrochemical series
(2)The concentration of the ions in the electrolyte
(3)The nature of electrode

1. THE RELATIVE POSITION OF IONS IN THE ELECTROCHEMICAL SERIES

Generally, cations that are lower in the electrochemical series will get discharged in
preference to those above them. This is because metals that are lower in the series
have greater tendency of accepting electrons than those above them. Thus, these
metals will accept electrons from the cathode more easily and readily than those above
them.
Likewise, anions that are higher in the series will be preferentially discharged to those
that are below them in the series. This is because they are less electronegative and
therefore give out electrons more readily to the anode than those below them.

The relative position of ions in the electrochemical series.

 CATIONS ANIONS
K+ If two cations are If two anions are OH-
Na +
present in an present in electrolyte, I-
Ca2+ electrolyte the the anions that is Br-
Mg2+ cation below the above the other one Cl-
Al3+ other one in the in the electrochemical
Zn2+ electrochemical series will be
Fe2+ series will be preferentiallydischa NO3
Sn2+ preferentially rged
SO42-
discharged.
Pb 2+

H+
F-
Cu 2+

Hg2+
Ag+
Au3+
Pt2+B

EXAMPLES
(1) ELECTROLYSIS OF SODIUM CHLORIDE SOLUTION USING INERT ELECTRODES
Note: Inert electrodes are the electrodes that will not influence the product of electrolysis.
Examples are carbon (graphite) and platinum
Compound Present: NaCl, H2O
Ions Present: NaCl  Na+ + Cl-
H2O(l) ⇌ H+(aq) + OH-(aq)
At the anode: Both OH- and Cl- will migrate to the anode where OH - ions will be
preferentially discharged because they are above Cl - in the electrochemical series.
Anodic half reaction: 4OH-(aq) → 2H2O(l) + O2(g) + 4e-
At the cathode: Both Na+ ions and H+ ions migrate to the cathode where H + ions are
preferentially discharged because they are below Na + ions in the electrochemical series.
Cathodic half reaction: 4H+(aq) + 4e- → 2H2(g)
Overall reaction: 4OH-(aq) + 4H+(aq) → 2H2O(l) + O2(g) + 2H2(g).
Products of electrolysis: Hydrogen gas is produced at the cathode and oxygen gas is
produced at the anode.
Effect of electrolysis on the electrolyte: At the end of the electrolysis, the electrolyte
will more concentrated since OH- and H+ have been removed from the electrolyte.

(2) ELECTROLYSIS OF CUSO4 SOLUTION USING COPPER – CARBON ELECTRODE

(Copper as Cathode)
The electrolyte ionizes as follows

CuSO4 (aq) →
Cu2+ + SO42-(aq)
 H2O(l) ⇌ H+(aq) + OH-(aq)
When electric current is passed through the electrolyte Cu 2+ and H+ ion migrate to the
cathode, and SO42-(aq) and OH- ions migrate to the anode.
At cathode: The Cu2+ is discharged in preference to H + being lower in the
electrochemical series

Cu2+(aq) + 2e- →
Cu(s)

At anode: The OH- ions is discharged preferentially because it is lower in the

electrochemical series. Hence, oxygen is liberated at the anode.

4OH- →
2H2O (l) + O2 ( g) + 4e-

Overall Reaction: 2Cu2+ + 4OH-(aq)  2Cu(s) + 2H2O(l) + O2(g)

Product of the electrolysis: Copper metal is produced at the cathode, while oxygen is
liberated at the anode.
Effect of electrolysis on the electrolyte: The solution gradually becomes acidic due to
the presence of H+ and SO42- ions left behind in the solution. This is evident from the
gradual fading away of the blue colour of the electrolyte because the Cu 2+ which is
responsible for the blue colour has been discharged.

(3) ELECTROLYSIS OF ACIDIFIED WATER (DILUTE H2SO4) using platinum

electrodes.
The equation of the reaction that is involved in this process is given as shown below:

H2SO4 2H+ + SO42 - (1)

⇌
→

H2O H+ + OH- (2)

At the cathode: H+ ions migrate to the cathode and are reduced by gaining electrons to
become neutral hydrogen atoms.

H+(aq) + e- →
H(g)

The hydrogen atoms then combine in pairs to form diatomic hydrogen gas molecules

H(g) + H(g) →
H2(g).

At the Anode: SO42- and OH- ions migrate to the anode. The OH - ions being lower than
SO42- in the electrochemical series are preferentially discharged.

Anodic half equation: OH-(aq) →

OH (g) + e-.

The OH groups interact to form water and oxygen molecules;

OH + OH →
H2O + O

O+O →
O2
 Overall Anodic half-equation: 4OH- →
O2 + 2H2O + 4e-

Product of the electrolysis: The net result of the electrolysis is that two volumes of
hydrogen are produced at the cathode and one volume of oxygen is produced at the
anode.
Effect of electrolysis on the electrolyte: The percentage of ionized water is very low.
So, the discharge of OH- during electrolysis disturbs the ionic equilibrium of water. To
restore the equilibrium, more water molecules will ionize.
H2O(l) ⇌ H+ + OH-(aq).
At the end of the electrolysis the total amounts of the acid in the solution remain
unchanged. But its concentration increases due to the removal of water molecules.

Exercise 10:
1. Briefly discuss the electrolysis of the following compound using graphite (or platinum)
electrodes
(a) Molten Sodium Chloride (b) Molten alumina (Al2O3) (c) molten
lead (ii) iodide
(d) Aqueous lead(ii) iodide (e) Dilute solution of Potassium Bromide (KBr)
2. Discuss briefly and list three observable changes that takes place when a dilute
solution of copper(ii) chloride is electrolyzed using platinum electrodes.

2. THE CONCENTRATION OF COMPETING IONS

All other conditions being equal, increasing the concentration of a given ion tends to
promote the discharge of that ion from the solution. However, the effect of concentration
is only effective when the position of the two competing ions are very close in the
electrochemical series. Thus, if the position of the two competing ions are very far apart,
the effect of concentration becomes insignificant.

EXAMPLE
(1) ELECTROLYSIS OF BRINE (CONCENTRATED SODIUM CHLORIDE)
In the electrolysis of concentrated NaCl (aq) using inert electrodes. Note that in this
electrolysis, the cathode can be either platinum or carbon but the anode must be carbon
to resist attack by chloride because platinum is easily attacked by chlorine.
The electrolytic cell is given as
 The electrolyte ionizes thus:
NaCl (aq) Na+(aq) + Cl-(aq)
⇌
→
H2O (l) H+(aq) + OH-(aq)

Ions in the electrolyte:

CATIONS ANIONS
Na+ (Conc) Cl- (Conc)
H+ OH-

At the anode: Both, Cl- and OH- will migrate to the anode where Cl- ions will be
preferentially discharged because they are more concentrated. (i.e they are more in
concentration inside the electrolyte).
Anodic half reaction: 2Cl-(aq) → Cl2(g) + 2e-
At the cathode: Both the Na+ and H+ will migrate to the cathode where H+ will be
preferentially discharged. This is because even though Na + ions are more in concentration
in the electrolyte, the distance between Na + and H+ in the electrochemical series is very
far thus making the effect of concentration to be negligible.
Cathodic half reaction: 2H+(aq) + 2e- → H2(g)
Overall reaction of electrolysis: 2Cl- + 2H+  Cl2(g) + H2(g)
Product of electrolysis: Chlorine gas is produced at the anode and hydrogen gas at the
cathode.
Effect of electrolysis on the electrolyte: At the end of the electrolysis, the electrolyte
will become alkaline because H+ and Cl- have been removed from the electrolyte leaving
behind Na+ and OH- which forms NaOH solution.

(2) ELECTROLYSIS OF CONCENTRATED COPPER (II) CHLORIDE SOLUTION USING

COPPER – CARBON (or Platinum) ELECTRODE
A copper rod is used as the cathode and carbon rod as the anode. The equations of the
reaction involved were given as shown below:
 CuCl2 (aq →
Cu2+ (aq) + 2Cl-(aq)

H2O(l) →
H+(aq) + OH-(aq)

When electric current is passed through the electrolytic solution, Cu 2+ and H+ ions
migrate to the cathode, and Cl- with OH- migrate to the anode.
At the cathode: Cu2+ being lower than H+ in the electrochemical series is preferentially
discharged. The Cu2+ gains two electrons from the cathode; which are in turn deposited
as neutral metallic copper at the cathode.

Cathodic half equation: Cu2+(aq) + 2e- →

Cu(s)

At the Anode: Cl- for its higher concentration than OH - is preferentially discharged as it
loses an electron to the anode and becoming chlorine atoms.

Anodic half equation: 2Cl- (aq)

→
Cl2(g) + e-

The chlorine atoms then combine to form chlorine molecules.

Product of the electrolysis: Copper is produced at the cathode and Chlorine is
liberated at the anode
Effect of electrolysis on the electrolyte: The discharge of copper and chlorine causes
the solution to become progressively dilute as evidenced by the fading away of the light
green colour of the electrolyte. If electric current is passed continuously without adding
more electrolyte, at a stage, the hydroxyl ions begin to discharge, because at this stage,
the influence of concentration of Cl - ion is no longer the overall controlling factor. In the
end, a mixture of chlorine and oxygen is obtained at the anode.
Exercise 11:
Using platinum electrodes, briefly discuss the electrolysis of
(a) Zinc bromide solution (b) Tin(ii)iodide solution (c) concentrated hydrochloric acid

[Link] OF THE NATURE OF ELECTRODE

Some electrode which have strong affinity for certain ions may influence the discharge of
such ions. For example, mercury have strong affinity for sodium and if used as a cathode,
the mercury will tend to associate with sodium to form sodium amalgam (Na/Hg) and in
turns influence its discharge. This is because the formation of amalgam will make the
discharge of Na+ requires less energy than that of H + and so Na+ will be preferentially
discharged.
Na+(aq) + Hg(l) + e-  Na/Hg
Furthermore, electrodes which have similar characteristics to those of the ions in the
electrolytes may influence the discharge of such ions. For example, if a copper anode is
used in the electrolysis of a solution of CuSO 4, neither the SO42- or OH- will be discharged.
 Instead, the copper atoms from the anode will go into solution as Cu 2+ ions because this
atoms will give up their electrons more readily than SO 42- or OH- since the anode (Cu) has
similar nature as the metallic ions (Cu2+) that is present in the solution.

EXAMPLES
ELECTROLYSIS OF COPPER(II) TETRAOXOSULPHATE(VI), CUSO4 (USING ANY
CATHODE AND COPPER ANODE)
Electrolysis of CuSO4 solution using copper anode. The cathode can be any electrode e.g.
platinum, graphite.
The electrolytic cell is the same as above but the anode is copper and cathode is graphite
The equation of the reaction of the electrolysis is given as shown below.

CuSO4 aq) →
Cu2+ + SO42-(aq)

H2O (l)
→
H+ (aq) + OH-(aq)

In this case, because both the cathode and anode are made up of copper metal, at the
anode three possible mechanisms occurs.
At the cathode: Both the Cu2+ ions and H+ ions will migrate to the cathode where Cu 2+
ions will be preferentially discharged.
Cathode half reaction: Cu2+ (aq) + 2e- → Cu (s)

1. Discharge of SO42- ion by loss of electrons

SO42-(aq) →
SO4 (g) + 2e- (i.e sulphation of the anode)

2. Discharge of OH- ions by loss of electrons

OH-(aq) →
OH(g) + e-

3. Copper metal loses electrons become Cu2+ (aq)

Anode : Cu(s) →
Cu2+(aq) + 2e-

Out of these possibilities, reaction (3) occurs most readily because it requires the least
energy. As a result, no ions are discharge at the anode. Instead, for each copper atom
deposited at the cathode, one atom of copper is dissolved from the anode to form Cu 2+
ion in solution.

At the anode: Both SO42- and OH- will migrate to the anode but none of them will be
discharged. The reason is that, the anode (which is a copper metal) has the nature as the
metallic ions (copper (II) ions) in the electrolyte.
Anodic half reaction: Cu(s) → Cu2+ (aq) + 2e-
Overall equation: Cu(s) + Cu2+(aq) → Cu2+ (aq) + Cu(s)
Product of electrolysis: Copper is deposited at the cathode, and nothing is produced at
the anode except that the copper anode dissolves into solution for every copper ions that is
deposited at the cathode.

Effect of Electrolysis on the electrolyte: The amount of copper lost at the anode is
gained at the cathode, hence the concentration of Cu 2+ ions present in solution remains
constant. Therefore, there is no change in the concentration of the electrolyte. Thus, the
bluish colour of the solution will not change. The cathode will getter bigger in size and mass,
and the anode will get smaller by the same proportion.

Note: This method is frequently employed in the purification of copper. If an impure copper
is made the anode, it will dissolve into solution, and get the deposited at the cathode leaving
the impurities behind and get the deposited at the cathode. Thus, the cathode will get
bigger and the anode will get smaller due to the transfer of copper atoms from the anode to
the cathode.

Exercise 12 (N):
(1)Briefly discuss the electrolysis of
(a) aqueous sodium chloride using mercury cathode and graphite anode
(b)Copper (ii) chloride solution using platinum cathode and copper anode
(c) Copper(ii)tetraoxosulphate(vi) solution using copper electrodes
(d)Copper(ii)tetraoxosulphate(vi) solution using platinum cathode and carbon
anode
2. Copy and complete the table
Electrolyte Catho Product Anod Produc Effect on the electrolyte
de discharg e t
ed at the dischar
cathode ged at
the
anode
Acidified Platin Plati
water um num
Conc. CuCl2 Coppe Carb
soln r on
Dilute CuCl2 Coppe Carb
Soln r on
Conc. Coppe Copp
CuSO4 soln r er
 Concentrat Carbo
ed HCl n
Conc. NaCl Platin
(Brine) um
Molten Carbo
NaCl n
Conc. NaOH Platin Copp
Soln um er
Conc. NaCl Mercu Carb
Soln ry on
Dilute NaCl Platin Plati
Soln um num
Molten Platin Carb
Alumina um on
Molten KBr Platin Plati
um num

3. Mass of copper anode before experiment = 14.40g

Mass of copper anode after experiment = 8.00g
Mass of copper cathode before experiment = 11.50g
(a) What was the mass of the cathode after the experiment?
(b)Explain what happened to the concentration of the solution during the electrolysis
(c) Explain why a crystal of sodium chloride is a poor conductor of electricity but its
solution in water readily conducts electricity.
(d)Write the equation which represent the dissociation in solution of the salt formed from
a trivalent cation X and a bivalent anions Y

QUIZICAL
1. In the electrolysis of aqueous solution of Na 2SO4, which species migrate to the anode
(a) Na+ and SO42 (b) Na+ and H+ (c) H3O+ and OH- (d) SO42- and OH-
2. During the electrolysis of caustic potash solution using platinum electrodes (a)
alkalinity at the cathode increases (b) potassium metal is deposited at the anode (c)
potassium metal is deposited at the cathode (d) oxygen gas is given off at the anode
3. During electrolysis, (a) negative ions are discharged at the anode by gaining sufficient
electrons to become neutral (b) positive ions are discharged at the anode by gaining
sufficient electrons to become neutral (c) negative ions are discharged at the anode
by loosing sufficient electrons to become neutral (d) positive ions are discharged at
the anode by loosing sufficient electrons to become neutral
4. The reaction that takes place at the cathode compartment during the electrolysis of
CuSO4 solution is (a) Cu2+ + 2e-  Cu(s) (b) 2H+ + 2e-  H2(g) (c) Cu(s)  Cu2+(aq) + 2e- (d)
Cu2+(aq) + SO42-(aq)  CuSO4(aq)
5. In the electrolysis of CuSO4 using carbon electrodes, the products at the anode and
cathode respectively are (a) hydrogen and copper (b) copper and hydrogen (c)
oxygen and copper (d) copper and oxygen
6. The reaction that takes place at the anode during the electrolysis of very dilute
aqueous solution of sodium chloride is (a) Na + + e- + Hg  Na/Hg amalgam (b) 4OH-
(aq)  2H2O(l) + O2(g) + 4e-(aq) (c) 2Cl-(aq)  Cl2(g) + 2e- (d) OH-(aq) + Cl-(aq)  HCl(g) + O2-(aq)
7. The electrolysis of CuSO4 can be used to purify crude copper if the crude copper is (a)
dissolved in the solution (b) made both anode and the cathode (c) made the anode
(d) made the cathode
8. Hydrogen and oxygen will be produced using platinum electrodes during the
electrolysis of (a) dilute copper(ii) chloride (b) dilute sodium chloride solution (c)
concentrated hydrochloric acid (d) glucose solution
9. In the electrolysis of CuSO 4 using platinum electrodes, the solution gets progressively
(a) amphoteric (b) acidic (c) basic (d) neutral
10. A Substance that decomposes when electric current is passed through it is (a)
sucrose solution (b) copper rod (c) tetraoxosulphate(vi) acid solution (d) methylated
spirit
11. Which of the reactions takes place at the anode during the electrolysis of CuSO 4(aq)
using copper electrodes (a) discharge of Cu 2+ (b) Dissolution of copper electrode (c)
discharge of OH- (d) Discharge of SO42-
12. Which of the following ions is discharged at the anode during the electrolysis of a
concentrated solution containing H+ , Cu2+, OH- and Cl- using carbon electrodes? (a) Cl-
(b) OH- (c) Cu2+ (d) H+
13. Which of the following ions would migrate to the cathode during electrolysis (a)
sodium ions (b) hydroxide ions (c) sulphide ions (d) chloride ions
14. The common feature of reactions at the cathode is that (a) electrons are produced
(b) ions are oxidized (c) reduction is involved (d) the electrolyte is diluted
15. In electrolysis, reduction takes place at the ---- (a) anode (b) cathode (c) electrodes
(d) cations
16. Which of the following will conduct the least amount of electricity (a) 1.00moldm -3
aqueous solution of KCl (b) 0.01moldm -3 aqeous solution of KCl (c) 0.01moldm -3
aqueous solution of ethanoic acid (d) 0.01moldm -3 aqueous solution of glucose
17. What happens to the conductivity of an electrolyte as it concentration reduces? It (a)
increases (b) decreases (c) is unaffected (d) reduces to zero
18. Which of the following methods cannot be used to distinguish between a strong acid
and a weak acid? (a) conductivity measurement (b) action on starch iodide paper (c)
measurement of pH (d) measurement of heat of reaction
19. Which of the following substances decomposes when an electric current is passed
through it? (a) glucose solution (b) zinc rod (c) tetrachloromethane (d) hydrochloric
acid
20. In electrolysis, reduction takes place at the ---- (a) anode (b) cathode (c) electrodes
(d) cations
 FARADAY’S LAWS OF ELECTROLYSIS
Faraday’s first law of electrolysis states that the mass (m) of a substance liberated or
deposited at an electrode during electrolysis is directly proportional to the quantity (q) of
electricity passing through the electrolyte.
Mathematically;
M α Q -------------- (1)
The unit of quantity is coulombs (c). It is the product of current in Amperes and time in
seconds
Q = It --------------------- (2)
M α It
.: M = k It --------------------- (3)

Where k = proportionality constant

I = current in ampere (A)
T = time in seconds (S)
It can be shown that the reciprocal of k, which is called charge –to-mass ratio, is Cf/M. It is
constant for a particular element
MIt
i.e. m =
cF
m ¿
Re-arranging =
M cF
Where m= mass f element deposited in grams
M = molar mass of the element in g/mol
I = current, in ampere
t = time, in seconds
c = charge on the element (number of Faradays)
F = Faraday (96500Cmol-1)
The quantity of electricity required for the passage of one mole of electrons is
[Link] is called one Faraday. i.e. Faraday, F=96500C = 1 mole of electrons

FARADAY’S SECOND LAW OF ELECTROLYSIS

This states that when the same quantity of electricity is passed through different
electrolytes, the relative amounts in moles of the element deposited are inversely
proportional to the charge on the ion of respective element.
 I
Mathematically, n α
c
i.e. n C = constant
Where n is the amount, in moles, of the element liberated, and c is the charge on its ion.
For two different elements: n1 c 1=n2 c 2

CALCULATIONS
Example 1
During the electrolysis of silver trioxonitrate (v) solution, 9650 coulombs of electricity was
passed. Calculate (i) the amount of silver deposited in moles (ii) the mass of silver deposited
in grains (Faraday = 9650 coulombs, Ag = 108g mol -1)
Solutions
The equation of reaction is given as
Ag+ (aq) + e- → Ag(s)
(i) From the above equation, 1 mole of electron is required to deposited 1 mol of Ag but, 1
mol of electron = 1 Faraday 96500C.
i.e. 96500C will deposit 1 mol of Ag
.. 1/96500 X 9650/1 = 0.1 mol
. : Amount of silver deposited = 0.100 mol
(i) Since 1 mol of silver, (Ag) is 108g
.: 0.1mol of Ag will be 108/1 X 0.1 =10.8g
.: Mass of silver deposited = 10.8g

Example 2
When a solution of copper (II) salt was electrolyzed 3.20g of copper was deposited. Calculate
the quantity of electricity required for electrolysis. (Cu=6; 1 F = 96500C).
Solutions
Equation of the reaction is: Cu2+ (aq) + 2e- → Cu(s)
2F → 64(1 mol)
mass(g)
Amount in mole copper deposited is n =
Molar mass
3.20 mol
n= = 0.050 mol
64
From the equation, 2 moles of electrons will deposit 1 mol of Cu. But 1 mol of electrons =
Faraday = 96500C .: 2 mol of electrons will require 2 X 96500C to deposit 1 mol of Cu.
1 mol of Cu requires 2 X 96500C
.: 0.05mol of Cu will require 2 X 96500 X 0.05C
Quantity of electricity required = 9650coulombs.

Exercise 13:
(1)By passing an electric current for 1 hour through a copper and a silver coulometer
connected in series, 1.28g of copper was deposited at the cathode of the copper
coulometer calculate (a)the strength of the current used and (b) the mass of silver
deposited on the cathode of the coulometer (faraday = 96500C mol -1, Cu =63.5; Ag =
108).
(2)Calculate the volume of gas that would be produced at the electrodes when 0.005 mole
of electrons are passed through a dilute solution of tetraoxosulphate (VI) acid (gaseous
molar volume = 22.4dm3 at stp.)

LET’S QUIZ TOGETHER

(1) The first law of electrolysis is expressed mathematically as (a) m α 1/Q (b) m α Q (c) m
α Q2 (d) m α Q1/2
(2) One faraday of electricity will produce one mole of (a) chlorine molecules (b) oxygen
molecules (c) hydrogen atoms (c) oxygen atoms
(3) One faraday is equal to (a) 9650 coulombs (b) 96500 coulombs (c) two moles of
element (d) half a mole of electron
(4) In the electrolysis of brine, the anode must be carbon because (a) carbon is a
reducing agent (b) chlorine is a reducing agent (c) carbon induces the discharge of
chlorine (d) chlorine attacks other elements but not carbon
(5) Which of the electrodes does oxidation occur? (a) at the cathode (b) at the anode (c)
at the electrolyte (d) at the half electrode.
(6) How many moles of copper would be produced by passing one faraday of electricity
through an aqueous solution of copper (ii) tetraoxosulphate (vi)? (a) 2 (b) 0.5 (c) 3
(d) 4
(7) How many electrons in mole will discharge 2.0g of copper (II) ions, Cu 2+(Cu=64) (a)
0.03125mol (b) 0.0625mol (c) 0.0938mol (d) 32.00mol
(8) What current in amperes will deposit 5.4g of aluminum in 2hours (Al=27,
F=96500Cmol-1) (a) 2.0 (b) 4.0 (c) 6.0 (d) 8.0
(9) What is the quantity of electricity required to deposit 128g of copper from molten
copper(ii)chloride (Cu = 64, F=96500Cmol-1)
(a) 1.93 x 105c (b) 3.86 x 105c (c) 1.93 x 106c (d) 3.86 x 106c
(10) Calculate the maximum weight of copper deposited on the cathode if 0.2F of
electricity was passed through a solution of CuSO 4 (Cu=64) a) 32.0g (b) 16.0g (c)
6.4g (d) 3.2g
(11) If 24,000 coulombs of electricity are required to discharge 0.25mole of potassium
from a molten potassium chloride mass, then ten number of coulombs required to
discharge 3 moles of lead from molten lead(ii)bromide is (a) 384,000 (b) 576,000 (c)
192,000 (d) 288,000
(12) A current of 15.0A was passed for 30 minutes through a solution of silver
trioxonitrate (v) between silver electrodes. Which of the following observations would
be correct? (1F=96500Cmol-1) (i) The original Ag+ ion concentration of the solution
remains unchanged (ii) The original Ag+ ion concentration of the solution decreases
(iii) the original Ag+ ion concentration of the solution increases (iv) 0.280 mole of
silver is dissolved from the anode (v) 0.280mole of silver of silver is deposited at the
cathode (a) (i) only (b) (i) and (iv) only (c) (i), (iv) and (v) only (d) (ii), (iv) and (v)
only
(13) Two electrolytic cell one containing a solution of AgNO 3 (silver electrodes) and the
other a solution of CuSO4 (copper electrodes) were connected together through a
wire. A current was passed through for 15minutes and 4.32g of silver was deposited
on the cathode of AgNO3 cell. What is the mass of copper deposited on the cathode
of CuSO4 cell during the same period (Ag+108, Cu=64) (a) 0.32g (b) 0.48g (c) 0.64g
(d) 1.28g
(14) If the cost of electricity required to deposit 1g of aluminium is N4.00, How much (in
naira) would it cost to deposit 24g of copper? (Al=27g, Cu=64) (a) 27.02 (b) 37.02 (c)
47.02 (d) 57.02
(15) What is the mass of copper deposited at the cathode by the passage of 3200
coulombs of electricity through CuSO4 solution using copper electrodes? (Cu=64g) (a)
21.12g (b) 10.56g (c) 5.28g (d) 2.64g
(16) Copper(ii) tetraoxosulphate (vi) is electrolyzed using platinum electrodes. How many
grams of copper are deposited when when a current of 0.386A is passed for 50
minutes? (Cu=64, 1F=96500c) (a) 0.924g (b) 0.880g (c) 0.768g (d) 0.384g
(17) A quantity of electricity liberates 1.50g of aluminum from its ions. The mass of silver
that will be liberated from its ions by the same quantity of electricity is (a) 10.80g (b)
5.40g (c) 6.05g (d) 3.03g
(18) If 6.4g of copper is deposited in a copper coulometer connected in series with a
Hofman voltameter, the volume of oxygen liberated at s.t.p is (a) 0.22dm 3 (b)
11.2dm3 (c) 1.12dm3 (d) 22.4dm3
(19) If 0.1farady of electricity deposited 3.2g of copper during the electrolysis of an
aqueous solution, then the number of moles of copper that will be deposited by 0.6F
is (a) 0.10 (b) 0.15 (c) 0.20 (d) 0.30 (Cu=64)
(20) How many kilograms of aluminum will be produced by the electrolysis of aluminum
trioxonitrate(v) in a cell operating for 24 hours at 400amperes (Al=27, 1F=96500c)
(a) 3.2 (b) 6.4 (c) 9.6 (d) 12.8
(21) A current of 0.50A flows for 16minutes 5seconds and deposits 0.163g of a metal X
during the electrolysis of an aqueous solution of a salt of the metals. What is the
charge on the metal ion? (a) 4 (b) 3 (c) 2 (d) 1 (X=65, IF=96500c)
(22) What volume of oxygen measured at s.t.p would be liberated by passing a current of
10A through acidified water for 965seconds (a) 5.60dm 3 (b) 0.560dm3 (c) 11.2dm3 (d)
1.12dm3 (G.M.V = 22.4dm3, F=96500c)
(23) How many mole of zinc would be deposited by passing 5F of electricity through a
solution of zinc tetraoxosulphate(vi) (a) 1.0 (b) 1.5 (c) 2.0 (c) 2.5 (1F = 96500c)
(24) 1.5F of electricity are passed through electrolytic cells containing K +, Zn2+, Au3+,
connected in series. How many moles of each metal would be formed at the cathode
of each cell? (a) 1.5moles of K, 3.0moles of Zn and 4,5moles of Au (b) 1.5moles of K,
1.5moles of Zn and 1.5moles of Au (c) 1.5moles of K, 0.75moles of Zn and 0.5moles
of Au (d) 0.5moles of K, 1.0moles of Zn and 1.5moles of Au
(25) A current of 20A is passed for 30 minutes during the electrolysis of
gold(iii)tetraoxosulphate(vi). The mass of gold deposited at the cathode is (a) 24.4g
(b) 26.5g (c) 28.9g (d) 32.6g (Au=197, F=96500Cmol-1)
(26) What quantity of electricity will liberate 0.200mole of oxygen molecules during the
electrolysis of water (a) 96500C (b) 77200C (c) 51467C (d) 25733C
(27) What is the quantity of chlorine in moles liberated when a current of 15A is passed
through molten potassium chloride in 1930seconds (a) 0.05 (b) 0.10 (c) 0.15 (d) 0.20
[1F =96500C)
(28) What mass of bromine would be produced during the electrolysis of molten lead(ii)
bromide in which 10.35g of lead was deposited. [Pb=207, Br=80] (a) 4.00g (b) 7.00g
(c) 4.50g (d) 8.00g