Electrochemistry

 Electrochemistry is the study of electrochemical reactions.

 These are reactions that either produce electrical energy or require electrical
energy to proceed.

The electrochemical series of metals (Reactivity series)

 The electrochemical series of metals places metals in order of how easily they lose
electrons (ionise) and can be used to predict certain chemical reactions.

 The ability of metal atoms give away (donate) electrons to another reactant increases
going up the series. Therefore, the strength as a reducing agent increases going up the
series.

 Since metals lose electrons when they ionise, they act as reducing agents when they react
with other substances, i.e. they give electrons to the other reactant.

 The more easily they give electrons, the stronger their reducing power.
Displacement of metals
 A metal will displace a metal that is below it in the electrochemical series from a
compound containing the lower metal.

 This is because the higher metal is a stronger reducing agent, therefore, readily gives
electrons to the ions of the lower metal.

 As a result, the higher metal ionises and the ions of the lower metal are converted to
atoms, i.e. the ions are said to have been discharged.

Example 1:
Will a reaction occur if a strip of magnesium ribbon is placed in copper(II) sulphate
solution?

As the reaction proceeds the following are observed:

i. The magnesium ribbon gradually gets smaller as it ionises and the Mg2+ ions dissolve
in the solution.
ii. A pink solid builds up in the solution as copper is formed.
iii. The blue colour of the copper (II) sulphate solution gradually fades as the blue Cu2+
ions are discharged from the solution, forming copper.

This occurs because:

 Magnesium is higher than copper in the electrochemical series, therefore, magnesium can
displace the Cu2+ ions from the copper (II) sulphate.

 Magnesium is a stronger reducing agent, therefore, it gives electrons to the Cu2+ ions.

 The magnesium ionises forming Mg2+ ions and the Cu2+ions are discharged forming
copper atoms
Displacement of hydrogen
 Metals above hydrogen in the electrochemical series will displace the H+ ions in an acid,
forming hydrogen gas (H2).

 Metals below hydrogen will not displace the H+ ions.

 Metals above hydrogen are stronger reducing agents and will readily give electrons to the
H+ ions of the acid.

 Metals below hydrogen are weaker reducing agents, so will not reduce the H+ ions.

 Zinc is higher than hydrogen in the electrochemical series; therefore, zinc can displace
the H+ ions from the hydrochloric acid.
 Zinc is a stronger reducing agent; therefore, it gives electrons to the H+ ions.
 The zinc ionises forming Zn2+ ions and the H+ ions are discharged forming hydrogen
gas (H2)

Predicting reactions using the electrochemical series of non-metals

 The electrochemical series of non-metals places non-metals in order of how easily they
gain electrons, (ionise), and can be used to predict certain chemical reactions.

 The ability of non-metal atoms to ionise and take away electrons from another reactant
increases going up the series.

 Therefore, the strength as an oxidising agent increases going up the series.

The electrochemical series of certain non-metals
Non-metal Ease of ionization Ion
Fluorine F-
Sulphate SO42-
Nitrate NO3-
Chlorine Cl-
Bromine Br-
Iodine I-
Hydroxide OH-
 Example:
What will occur if chlorine gas is bubbled into sodium iodide solution?

Cl2 (g) + 2NaI(aq) -------- > 2NaCl(aq) + I2 (aq)

The ionic equation is:

Cl2 (g) + 2I(aq) -------- > 2Cl-(aq) + I2 (aq)

The transfer of electrons is shown in the ionic half equations:

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

2I-(aq) -------- > I2 (aq) + 2e-

 Chlorine is higher than iodine in the electrochemical series of non-metals, therefore,

chlorine can displace the I - ions from the sodium iodide.

 Chlorine is a stronger oxidising agent, therefore, it removes electrons from the I- ions.

 The chlorine ionises forming Cl- ions and the I- ions are discharged forming iodine (I2)

EXERCISE
1. For each of the following, predict whether or not a displacement reaction will occur:
a. aluminium + lead(II) nitrate solution -
b. silver + calcium nitrate solution -
c. iodine + sodium chloride solution -
d. bromine + potassium iodide solution -

2. A metal X was found to displace zinc from zinc nitrate solution but no displacement
occurred when it was added to magnesium nitrate solution. Arrange the three metals,
X, zinc and magnesium in decreasing order of ease of ionisation.

3. Metal X was found to displace metal Y from a solution containing the sulphate of Y.
However, X did not displace metal Z from a solution containing Z sulphate.

Which of the following is correct?

a. X is higher in the electrochemical series than Z.
b. Z is a stronger reducing agent than X
c. Y is higher in the electrochemical series than X.
d. Y is a stronger reducing agent than Z.
 4. Predict whether a displacement reaction will occur when EACH of the following are
mixed and write a balanced equation for EACH reaction that you predict will occur.
a. zinc and hydrochloric acid –
Zn (s) + 2 HCl (aq) ----- ZnCl2 (aq) + H2 (g)

b. aluminium and silver nitrate solution -

Al (s) + 3 AgNO2 (aq) ---- Al(NO2)3 (aq) + 3 Ag (s)
c. iron and zinc chloride solution -
d. copper and sulfuric acid -
e. iodine and potassium chloride solution
f bromine and sodium iodide solution

Br2 (aq) +2 NaI (aq) ----- 2 NaBr (aq) + I2 (aq)

Electrical Conduction
 In order for a substance to conduct an electric current, it must contain charged
particles which are able to move through the substance.

 These charged particles can be either electrons or ions.

 Materials can be classified into two groups based on their ability to conduct an electric
current:

i. Conductors
 These are substances which allow electricity to pass through.
 They can be solids, liquids or solutions.
 Examples of conductors include metals, graphite, molten ionic compounds,
solutions of ionic compounds and aqueous acids and alkalis.
ii. Non-conductors/Insulators
 These are substances which do not allow an electric current to pass through.
 Non-conductors can be solids, liquids, solutions and gases.
 Examples of non-conductors include non-metals (except graphite), plastics,
covalent substances and solid ionic compounds.

Metallic and electrolytic conduction

 When ionic compounds melt or dissolve in water, the liquid or solution created contains
ions and is known as an electrolyte.

 Electrolytes are conductors.

 There are certain differences between conduction in a metal, known as metallic
conduction, and conduction in an electrolyte, known as electrolytic conduction.

 Electrolytes are conductors because the ionic bonds have broken and the ions are free to
move.

 When an electric current passes through an electrolyte it decomposes.

Electrolytic conduction
When an ionic compound melts, the ions are no longer held together by ionic bonds and they
become free to move throughout the liquid:

heat
NaCl(s) ----- > Na+(l) + Cl-(l)

Similarly, when an ionic compound dissolves in water, the ionic bonds break and the ions are
free to move throughout the solution:

water
NaCl(s) ----- > Na+(aq) + Cl-(aq)

These electrolytes conduct an electric current because of the presence of mobile ions which
are able to move throughout the liquid or aqueous solution.

During electrolytic conduction, the electrolyte is decomposed, i.e. it is chemically changed

Pure Water
 Pure water is an extremely weak electrolyte.
 Approximately one in every 5.56 x 108 water molecules is ionised into H+ and OH- ions at
any one time:

H2O(l) H+(aq) + OH-(aq)

 The presence of these ions is important when an electric current passes through an
aqueous electrolyte.
ELECTROLYSIS

 Electrolysis is the chemical change occurring when an electric current passes through an
electrolyte.

 Electrolysis is carried out in an electrolytic cell, which has three main components:

i. A battery or other DC power supply. This supplies the electric current.

ii. Two electrodes - These are connected to the power supply by wires and are placed in
the electrolyte so that they can carry the current into and out of the electrolyte. They
are usually made of an inert material, e.g. graphite (carbon) or platinum, which can
conduct electricity:

 The anode – this is positive electrode which is connected to the positive

terminal of the power supply.

 The cathode – this is negative electrode which is connected to the negative

terminal of the power supply.

iii. The electrolyte - This is a molten ionic compound or solution which contains mobile
ions.

The Mechanism of Electrolysis

 During electrolysis both anions and cations are discharged i.e. they lose or gain
electrons to form neutral atoms. This occurs as follows:

i. The anions (negative ions) are attracted to the anode (positive electrode). The anions
lose electrons to the anode and form atoms, i.e. they are discharged:

An- -------- > A + ne-

Oxidation occurs at the anode (OIL). The anode acts as the oxidising agent.

ii. The electrons, lost by the anions at the anode, travel through the circuit to the positive
terminal of the battery. They then re-enter the circuit from the negative terminal of the
battery and travel to the cathode.

iii. The cations (positive ions) are attracted to the cathode (negative electrode). The
cations gain the electrons from the cathode forming atoms, i.e. they are discharged:

Cn- + ne- -------- > C

Reduction occurs at the cathode (RIG). The cathode acts as the reducing agent
Electrolysis of aqueous electrolytes
 An aqueous solution contains at least two different cations and two different anions
because it contains ions from the solute and H+ ions and OH- ions from the ionisation
of water molecules.

 During electrolysis, one type of cation and one type of anion are discharged in
preference to any others present. This is called preferential discharge.

Preferential discharge of anions

There are three main factors which influence the preferential discharge of the anions that you
will be studying:

1. The position of the ion in the electrochemical series

 The lower the ion in the electrochemical series of anions, the more likely it is to be
preferentially discharged.
 Ions at the top of series are the hardest to discharge because they are the most
stable.
 Ions at the bottom are the easiest to discharge because they are the least stable.
 Table: The electrochemical series of anions
Anion Name
-
F fluoride
2-
SO4 sulphate
-
NO3 Nitrate
-
Cl Chloride
-
Br bromide
-
I Iodide
-
OH hydroxide
2. The type of anode
 An anode which is not inert, e.g. copper, can take part in the electrolysis process
and this affects what happens at the anode.
 If an active anode is used, the reaction occurring is the one which requires the least
energy.
 This usually involves the anode ionising instead of an anion being discharged.

3. The concentration of the electrolyte

 The greater the concentration of an ion, the more likely it is to be preferentially
discharged.
 This rule applies mainly to solutions containing halide ions (Cl-, Br- and I- ions).

Preferential discharge of cations

There is one main factor which influences the preferential discharge of the cations:

1. The position of the ion in the electrochemical series

 The lower the ion in the electrochemical series of cations, the more likely it is to be
preferentially discharged.
 Ions at the top of the series are the hardest to discharge because they are the most
stable.
 Ions at the bottom are the easiest to discharge because they are the least stable.

Table: The electrochemical series of cations

Cations
K+
Ca2+
Na+
Mg2+
Al3+
Zn2+
Fe2+
Pb2+
H+
Cu2+
Ag+
Examples of reactions in aqueous electrolytes: