NSSCAS Chemistry

Theme 2

Topic 2.2 Electrochemistry

 Topic 2.2 Electrochemistry

2.2.1 Redox processes: electron transfer and

changes in oxidation number (oxidation state)

2.2.2 Electrolysis
 2.2.1 Redox processes: electron transfer and
changes in oxidation number (oxidation state)

• calculate oxidation numbers of elements in compounds and ions

• describe and explain redox processes in terms of electron
transfer and changes in oxidation number
• use changes in oxidation numbers to help balance chemical
equations
• describe the use of aqueous potassium iodide in testing for
oxidising agents and acidified potassium manganate(VII) in
testing for reducing agents from the resulting colour changes
• use oxidation numbers to name oxyanions, including nitrate(III)
NO2-, nitrate(V) NO3-, chlorite(I) ClO-, chlorate(V) ClO3-
oxidation and reduction
• Electrons are transferred when
oxidation and reduction occurs. We
can use the acronym OILRIG to help
understand what is happening.
• Oxidation Is the Loss of electrons
and Reduction Is the Gain of
electrons.
• Oxidation and reduction always
occur simultaneously in a chemical
reaction. Such a r is called a redox
reaction.
• In a redox reaction, one substance
must be oxidised and another must
be reduced.
 oxidation and reduction
Oxidation is: Reduction is:
gain of hydrogen gain of oxygen

loss of oxygen loss of hydrogen

gain of electrons loss of electrons

decrease in oxidation increase in oxidation

number number
 oxidation and reduction

• It is important to understand that oxidation and reduction do not have to involve the
•  
loss or gain or gain of entire electrons.
• Oxidation and reduction can involve the loss or gain of partial electrons.
• The atoms do not necessarily need to gain and lose electrons to become anions and
cations to undergo oxidation and reduction.
• For example, in the reaction of H2 (g) + Cl2 (g) 2HCl (g), hydrogen and chlorine are
both non metals, they undergo covalent bonding and the electrons are being shared
between the two atoms.
• The electrons shared between hydrogen and chlorine are not shared equally because
chlorine is more electronegative than hydrogen therefore chlorine acquires a partial
negative charge () and hydrogen acquires a partial positive charge ().
• In this case we say chlorine has been reduced and hydrogen has been oxidised.
 oxidising agents and reducing agents

• Reducing agents lose electrons and are oxidised themselves.

• Reduction is a process and a reducing agent is a chemical.
• Oxidising agents gain electrons and are reduced themselves.
• Oxidation is a process and an oxidising agent is a chemical.
• An oxidising agent is a substance which oxidises another substance and itself is
reduced.
• A reducing agent is a substance which reduces another substance and itself is
oxidised.
• Thus, an oxidising agent undergoes reduction while a reducing agent undergoes
oxidation.
disproportionation – a special redox
• disproportionation is a redox reaction in which both
oxidation and reduction occurs on the same atom. The
atom is simultaneously oxidised and reduced.
oxidation state (oxidation
number) of a substance
• Oxidation state shows that total number of electrons
which have been removed from or added to an
element to get to its present state.
• When electrons have been removed, the oxidation
number increases (positive)
• When electrons have been added, the oxidation
number decreases (negative)
• Since removing electrons is an oxidation process,
therefore oxidation is the increase in oxidation
number
• Since adding electrons is a reduction process, therefore
reduction is the decrease in oxidation number.
• All atoms in an atom, molecule or ion can be given an
oxidation number.
• There are rules to determine the oxidation number of a
substance.
rules to determine the oxidation number of
a substance
• All free atoms in elements have an oxidation
number of zero.
 rules to determine the oxidation number of
a substance
• For simple ions, the oxidation number of the
simple ion is the same as the charge on the ion.
 rules to determine the oxidation number of
a substance
• For
  a polyatomic ion, the sum of all the oxidation
numbers of the atoms in the ion is equal to the
charge of the ion.

Examples:
• : 1 (+7) + 4 (2) = 1
• : 2 (+6) + 7 (2) =
• : 1 (+5) + 4 (2) = 1
 rules to determine the oxidation number of
a substance
• For a neutral molecule or formula, the sum of all the oxidation numbers of the
atoms in the molecule is equal to zero.
• For a neutral covalent molecule, the more electronegative atom is always given
a negative oxidation
• number while the less electronegative atom is given a positive one.
 rules to determine the oxidation number of
a substance
• For
  Group I and Group II elements, their oxidation
number are always +1 and +2 respectively. For
aluminium, it is always +3.
• For hydrogen, its oxidation number is always +1 except
in metal hydrides. For example, NaH, where its
oxidation number is -1.
• For oxygen, its oxidation number is always -2 except in
peroxides and fluorine compounds. For example, in
H2O, O = 2; in H2O2, O = 1; in OF2, O = +2
• For fluorine, its oxidation number is always -1, with no
exceptions.
Element Oxidation state in compounds Example
Uncombined elements Always = 0. All elements on the periodic table

Group 1 Always +1 All group 1 elements

Group 2 Always +2 All group 2 elements
Aluminium Always +3 All Al compounds
Fluorine Always 1 (it is the most All F compounds
electronegative element)
Oxygen 2 EXCEPT in peroxides where O = In H2O, O = 2
1 and in OF2 where O = +2 In H2O2, O = 1
In OF2, O = +2
Hydrogen +1 EXCEPT in hydrides (H bonded In HF, H = +1
to metals), H= 1 In NaH (hydride), H = 1
Chlorine 1 EXCEPT when bonded to F and In KCl, Cl = 1
O, Cl would have a + value. In ClF3, Cl = +3
Monoatomic ions The oxidation number = charge = 1; = +2
on the ion
Sum of oxidation state of Always = 0 In H2O; H = +1 2 = +2; O = 2 so +2 2 = 0
atoms in a neutral In NaCl; Na = +1; Cl = so +1 1 = 0
molecule or formula

The sum of oxidation Is equal to the charge on the ion. In ; O = 2 4 = so + S = 2 thus S = +6

state of the atoms in a
polyatomic ion
• To work out the oxidation number of a particular
atom in a molecule/ ion, find the sum of all the
oxidation number of the atoms present and
equate it to zero/ charge of the ion.
 balancing redox equations
There are two methods to balance complicated
redox equations:
• Using electron half-equations.
• Using changes in oxidation number.
 using electron half-equations to balance redox equations in acidic conditions

•• In  this method, the redox equation is divided into two half-equations.
One for oxidation and another for reduction.
• Steps(in acidic condition):
1. Divide the equation or information given into two half-equations.
2. Balance all other elements other than oxygen and hydrogen.
3. Balance the oxygen by adding O to the appropriate side of the
equation.
4. Balance the hydrogen by adding to the appropriate side of the
equation.
5. Balance the charge by adding electrons to the appropriate side of the
equation.
6. Combine two half-equations such that the electrons cancel out each
other.
 using electron half-equations to balance redox equations in alkaline conditions

• Balance
  the equation as it happens in an acidic
condition first.
• Add to both sides of the equation to react
with all the to form O .
• Cancel the excess O on either side of the
equation.
• Note: If it is obvious enough that OH⁻ must
be added in order to balance the equation,
then add OH⁻ instead.
 using electron half-equations to balance
redox equations
•   equations show reduction and oxidation stages in 2
Half
equations. All half equations must have electrons in. There
are some rules for balancing half equations.
1. Write down the species before and after a reaction
2. Balance any atoms apart from oxygen and hydrogen
(these will be dealt with later in rules 3 and 4).
3. Balance any oxygen with H2O.
4. Balance any hydrogen with or ions.
5. Balance any charges with electrons ().
6. Step 3 and 4 does not need to be done always if there are
no H and O in the equation.
 using changes in oxidation number to
balance redox equations
• This method utilises the fact that an increase
in certain amount of oxidation number in a
substance must be accompanied by a
decrease in same amount of oxidation number
in another substance.
 Testing for the presence of an oxidising agent

•• To
  test for an oxidising agent, you need to make use of a reducing
agent. The most common reducing agent in school laboratories is
aqueous potassium iodide (KI) which is colourless. Aqueous potassium
iodide is a salt solution and it dissociates into ions as KI (aq) (a) +
(aq). You need to be able to describe the test for an oxidising agent.
• Test: Add aqueous potassium iodide to the oxidising agent. Shake the
mixture.
• Result: A brown solution of iodine is produced. The presence of iodine
can be confirmed by adding starch solution. A dark blue coloration is
obtained.
• The brown solution of iodine is formed because the iodine ions lose
electrons (becomes oxidised, increase in oxidation state) and become
iodine atoms as follow:2(aq) I2 (l) + 2. The brown colour results from
the formation of iodine.
 Testing for the presence of a reducing agent

•• To
  test for a reducing agent, you need to make use an oxidising agent.
The most common oxidising agent in school laboratories is acidified
potassium manganate (VII), KMN, which is purple in colour. Acidified
potassium manganate (VII), KMN dissociates as KMN(aq) (aq) + (aq).
You need to be able to describe the test for a reducing agent.
• Test: Add acidified potassium manganate (VII) to the reducing agent.
Shake the mixture.
• Result: The acidified potassium manganate (VII) becomes
decolourised (becomes colourless). Aqueous potassium manganate
(VII) is an oxidising agent.
• The formation of the colourless solution results because of the
reaction between the manganite(VII) ions and the acid as (aq) + 8(aq)
+ 5 (aq) + 4H2O(l) which is colourless. The (aq) is reduced because it
gains electrons and there is an increase in the oxidation number to
form (aq).
 naming oxyanions
•• Oxyanions are polyatomic ions involving one or more oxygen atoms plus
 
another non-metal atom. Oxyanions commonly have negative charges of 1,
2 and 3. Examples of oxyanions include: (carbonate), (nitrite), (sulfate).
• General rules for naming oxyanions.
• Write the root of the name of the non-oxygen element.
• Add the –ate or –ite suffix to the end of the name, according the rules.
• Example: For , nitrogen is the non-oxygen element, remove the –ogen and
add –ate to form nitrate. For , sulfur is the non-oxygen element, remove
the –fur and add –ate to form sulfate.
• There will often be more than one oxyanion involving a given element. The
difference is the number of oxygen atoms bonded. For example: (nitrite)
and (nitrate); (sulfite) and (sulfate); hypochlorite (), (chlorite), (chlorate)
and (perchlorate). Notice that the charge on the polyatomic ion is the
same for both anions in the pair. The species with fewer oxygen atoms ends
with –ite and the species with more oxygen atoms end with –ate. Also
notice the prefixes of hypo- and per- used in the chlorite/chlorate ions.
 2.2.2 Electrolysis
• describe electrolysis as the conduction of electricity by an ionic compound
(an electrolyte), when molten or dissolved in water, leading to the
decomposition of the electrolyte
• use the concept of selective discharge to identify the electrode products of
aqueous solutions to include:
• hydrogen ions and metal cations: silver, copper, (hydrogen), iron, zinc, sodium
• non-metal anions hydroxide and chloride in dilute and concentrated solutions
• describe in outline the use of electrolysis in the extraction of metals from
acidic leached solutions, for example copper and manganese
• construct ionic half-equations for reactions at the cathode and anode
• describe the transfer of charge during electrolysis to include:
• the movement of electrons in the metallic conductor
• the removal or addition of electrons from the external circuit at the
electrodes
• the movement of ions in the electrolyte
Electrolysis
 electrolysis
• electrolysis is the conduction of electricity by an ionic compound (an
electrolyte), when molten or dissolved in water, leading to the
decomposition of the electrolyte.
• Uses of electrolysis:
– to extract useful metals from their ores.
– to produce useful by-products such as chlorine gas.
– to purify metals.
• Electrolysis is carried out in an electrolytic cell.
• An electrolytic cell consists of:
– the electrolyte which is the compound being decomposed. It is either a molten ionic
compound or a concentrated aqueous solution of ions. Solid ionic compounds and
covalent compounds cannot be used because they do not conduct electricity.
– the electrodes which are rods made from graphite or a metal which conducts electricity
to and from the electrolyte.
• anode is the positive electrode.
• cathode is the negative electrode.
– external power supply of direct current and a complete d.c. circuit.
 redox reactions in electrolysis
• During electrolysis, the cations (+) are attracted to the cathode () while the
• anions
  () are attracted to the anode (+).
• At the cathode, cations gain electrons and are reduced. Reduction occurs at
the cathode.
• At the anode, anions lose electrons and are oxidised. Oxidation occurs at the
anode.
• A simple example is the electrolysis of molten sodium chloride:
– At the cathode: Na⁺ + e⁻ → Na...........gain electrons, reduction.
– At the anode: 2Cl⁻ → + 2e⁻...........lose electrons, oxidation.
– Sodium metal and chlorine gas are produced.
• For electrolysis of aqueous sodium chloride:
– In an aqueous solution of sodium chloride, four types of ions are present (Na⁺, Cl⁻, H⁺
and OH⁻).
– However, only one type of ion can be discharged at each electrode. This is called
selective discharge of ions.
 electrochemical series
Metals reactivity Cations Anions

K
Na
Mg
Al
Zn
Fe
Sn  
Pb  
(H)  
Cu
Ag
Au
 The effect of the position of the ion in the
electrochemical series on the selective discharge of ions
• The order of selectivity of the ions happen in the order of reactivity of the
•  
elements.
• Looking at the cations, potassium is the most reactive metal and gold is the least
elective. Since potassium is the most reactive, it prefers to exist in the ionic state,
it prefers to exist as an ion instead of an atom because it is very reactive.
• On the other hand, less reactive elements prefer to exist as atoms. Therefore, if
both potassium and gold ions are present in an electrolyte, gold ions will be
selectively discharged instead on potassium ions.
• Cations of less reactive elements are said to have a higher ease of discharge
compared to cations of more reactive elements.
• Therefore if there is and ions present in an electrolyte, the will be selectively
discharged.
• For electrolysis of aqueous sodium chloride:
– At the cathode: 2H⁺ + 2e⁻ → ............because H⁺ is lower in the electrochemical series.
– At the anode: 4OH⁻ → + 2H2O + 4e⁻.............because OH⁻ is lower in the electrochemical
series.
 The effect of the position of the ion in the
electrochemical series on the selective discharge of ions
•• For
  the anions, the ions have the highest ease of discharge.
The and will not be discharged at all.
• Therefore if and ions are present in the electrolyte, the
ions will be selectively discharged.
• When the electrolyte is an aqueous solution for example
NaCl (aq), the and should be considered.
• In the case of NaCl (aq), the ions present in the electrolyte
are (aq), (aq), (aq) and (aq).
• For the cations, the (aq) will be selectively discharged.
 The effect of the concentration of the ions on the
selective discharge of ions
• The
  higher the concentration of the ion, the higher
the possibility for it to be discharged.
• For the anions, the concentration affects which ions
will be selectively discharged.
• If the solution is dilute, the (aq) ions will be
selectively discharged because in a dilute solution,
the (aq) ions are in a higher concentration.
• If the solution is concentrated, the other anions
such as (aq) will be selectively discharged because
when the solution is concentrated, the (aq) ions
are in a lower concentration.
 Extraction of aluminium from bauxite ore

• Bauxite is impure aluminium oxide, . The impurities are iron oxides, silicon
•  dioxide and titanium dioxide. Bauxite is the major aluminium ore.
• The first step is to purify the bauxite to get pure aluminium oxide, .
• Molten aluminium oxide is electrolysed in a solution of cryolite, to give out
the required aluminium metal.
 Extraction of aluminium from bauxite ore
•• The function of dissolving aluminium oxide in large amount of cryolite is
 
to:
– lower the melting point of the electrolyte from about 2140 °C to 970 °C.
– improve the electrical conductivity of the electrolyte.
– At the cathode: Al³⁺ + 3e⁻ → Al...........reduction
– At the anode: 2O²⁻ → O + 4e⁻............oxidation
2

• Overall equation: 4Al³⁺ + 6O²⁻ → 4Al + 3 or → 4Al + 3

• Aluminium is denser than the electrolyte. It drops to the bottom of the
electrolytic cell and is removed using a suction tube or through a tap hole.
• The oxygen gas released will oxidise the hot carbon electrodes to carbon
dioxide and carbon monoxide. So the electrodes have to be replaced from
time to time.
• Some environmental issues related:
– The carbon monoxide gas produced is poisonous.
– Large amount of energy is needed because the current needed to electrolyse the
electrolyte is very high.
 electrolysis of brine - concentrated aqueous
solution of sodium chloride
• Brine is concentrated aqueous
solution of sodium chloride.
• It is obtained from sea water or by
dissolving rock salt in water.
• Electrolysis of brine is used to
produce chlorine, hydrogen and
sodium hydroxide.
• The electrolyte level in the anode
compartment is kept higher than in
the cathode compartment. This
ensures the flow of the solution is
always towards the cathode
compartment. This reduces the
possibility of sodium hydroxide
solution formed moving back as they
are to be collected.
 electrolysis of brine
•• The
  ions present in the aqueous solution of sodium chloride are Na⁺,
Cl⁻, H⁺ and OH⁻. H⁺ and OH⁻ comes from the slight ionisation of
water.
• O H⁺ + OH⁻
• At the cathode: 2H⁺ + 2e⁻ → .........because H⁺ is lower in the
electrochemical series.
• At the anode: 2Cl⁻ → + 2e⁻...........because Cl⁻ is in a far more greater
concentration than OH⁻.
• Overall: 2NaCl + 2 O → 2NaOH + +
• As more and more H⁺ are removed, more are formed from the
ionisation of water because the position of equilibrium shifts to the
right. The H⁺ formed are being removed again until none is left.
• At the same time, more and more OH⁻ are being produced. When all
the H⁺ are removed, only OH⁻ and Na⁺ are left in the electrolyte and
NaOH is formed.
Electrolytic purification of copper
 Electrolytic purification of copper
• Copper is extracted from its ore in a smelter through reduction with carbon/ roasting
in air. However, the copper obtained is impure.
• Most of the copper uses such as electrical wires require the use of pure copper
(99.99% pure) for efficient transmission of electrical energy. Even small amounts of
impurity reduces its conductivity greatly.
• Electrolytic purification of copper is carried out in cells using:
– an electrolyte of copper(II) sulfate solution acidified with sulfuric acid (acidic
leaching, forming acidic leached solutions).
– an anode of impure copper.
– a cathode of pure copper.
• At the anode: Cu → Cu²⁺ + 2e⁻
• At the cathode: Cu²⁺ + 2e⁻ → Cu
• The result is the transfer of copper from the anode to the cathode. As a result, the cathode
gets thicker and the anode get thinner. The impurities in the anode settle down as anode
'sludge'.
• The concentration of copper(II) sulfate solution does not change because the number of
moles of Cu²⁺ ions formed at the anode is exactly the same as the number of moles of Cu²⁺
ions discharged at the cathode.
 Electrolytic purification of manganese
•• In nature, manganese is found commonly in a manganese dioxide ore
 
which is combined with iron and other minerals.
• Manganese is extracted in two steps.
• Firstly, the impure manganese dioxide is washed in water and filtered
to remove the soluble contaminants.
• The impure manganese ore is dissolved in sulfuric acid and oxalic acid
to form manganese sulfate, carbon dioxide and water. The equation is
MnO2 (s) + H2O (aq) + C2O4H2 (aq) MnSO4 (aq) + 2H2O (l) + 2CO2 (g).
• The solution is filtered to remove an excess impurities.
• The filtrate is heated to concentrate it.
• The manganese sulfate electrolyte is then separated using electrolysis.
• Two graphite cathodes and a single titanium anode are placed in this
aqueous bath at an elevated temperature ranging between 120 and
155 .
End of topic activity