and oxidation go together in these redox reactions.

of magnesium
Compounds, Formulae
Table 3.1 The charges & Redox 1
on common ions.

Positive ions (cations) Negative ions (anions)

Charge Cation Symbol Charge Anion Symbol
1+ Sodium Na+ 1− Chloride Cl−
Potassium K + Bromide Br −

Silver Ag + Iodide I− Tip

Copper(i) Cu + Hydroxide OH −
You may fin
Hydrogen H+ Nitrite NO2−
Ammonium NH4+ Nitrate NO3−
helpful whe
terms of th
2+ Magnesium Mg2+ 2− Oxide O2−

Calcium Ca2+ Sulfide S2− Oxidation

Zinc Zn2+ Sulfite SO32−
1
Is
Copper(ii) Cu2+ Sulfate SO42−
Iron(ii) Fe 2+ Carbonate CO3 2− Loss

3+ Aluminium Al3+ 3− Nitride N3−

Iron(iii) Fe3+ Phosphate PO43−

Notice from
Skill Check 1 Table 3.1 that:
Key term
metal
1●Write theions are always
symbols for thepositive
following elements including state symbols.
non-metal + + A redox rea
a)
● solid sodiumions are negative b) except
liquidhydrogen,
mercury H , and ammonium, NH4
c) some metals
● gaseous can form mored)
helium than one ion
chlorine – this
water is characteristic
(aqueous chlorine) of metals involves re
in the d block such as copper and iron An oxoanio
● some non-metal ions are compound ions containing more than one kind of
2 Write the formula for the following compounds including state symbols. formula is X
atom, including oxoanions such as the sulfate, nitrate and phosphate ions. any elemen
a) liquid water b) gaseous carbon dioxide
an oxygen a
c) ice d) sodium chloride solution
Ionic half-equations metal elem
A half-equation is used to describe either the gain or the loss of electrons oxoanions o
3 Write formulae for the following compounds: Table 3.1 a
during a redox process. Half-equations help to show what is happening
a) sodium fluoride b) magnesium oxide
during a reaction. Two half-equations combine to give the overall balanced A half-equa
c) potassium
equation. oxide d) barium chloride used to des
the loss, of
Zinc metal can reduce copper ions to copper. This happens when pieces
4 Name the following ions: reaction.
of zinc are added to a solution of copper(ii) sulfate (Figure 3.4). In this
a) OH — b) O 2— c) Cl— d) Al3+ e) SO 2—
example of a displacement reaction the more reactive metal, zinc,
4 Displaceme
displaces the less reactive metal, copper. The reaction can be shown as two reactions w
5half-equations:
Write formulae for the following transition metal compounds: compare th
metals as r
a) copper(II) chloride b)
2+zinc oxide
electron gain (reduction): Cu (aq) + 2e → Cu(s)
−
metals as o
c) copper sulfate d) iron(III)2+
hydroxide −
electron loss (oxidation): Zn(s) → Zn (aq) + 2e reactive me
metal from
6 Name the following compounds:
a) CO2 b) KNO3 c) CuCO3 d) HF e) MgSO4

3.2 Equations to explain oxidation and

7 Write formulae for the following compounds:
a) ammonium sulfate b) sulfur dioxide
c) calcium carbonate d) aluminium sulfate
e) silver iodide
469983_03_Chem_Y1-2_083-096.indd 85
f) zinc bromide
g) potassium oxide h) sodium sulfide
i) calcium hydroxide j) iron(iii) chloride
Compounds, Formulae & Redox 2
Skill Check 2
1 Balance the following equations:

a) Zn + O2 → ZnO

b) Na + Cl2 → NaCl

c) CaO + HCl → CaCl2 + H2O

d) Zn + AgNO3 → Zn(NO3)2 + Ag

e) Fe + Cl2 → FeCl3 1
2 For each of the following reactions, first write an unbalanced equation and
then amend it to produce a balanced equation. Include state symbols in your
balanced equations

a) sodium + oxygen → sodium oxide

b) zinc + hydrochloric acid → zinc chloride(solution) + hydrogen

c) magnesium carbonate(solid) + hydrochloric acid → magnesium

chloride(solution) + carbon dioxide + water

d) silver nitrate(solution) + copper chloride(solution) → silver

chloride(solid) + copper nitrate(solution)

e) copper(ii)oxide(solid)+nitricacid→copper(ii)nitrate(solution)+water

f) iron(iii) chloride(solution) + sodium hydroxide(solution) → iron(iii)

hydroxide(solid) + sodium chloride(solution)
Compounds, Formulae & Redox 3
Ionic equations
Some chemical reactions which involve ionic compounds are actually
reactions between only some of the ions involved in the reaction. The
balanced equation can be rewritten as an ionic equation leaving out the ions
which do not take part in the reaction. Ions which do not take part in the
reaction are known as spectator ions.

For each ionic substance in the reaction write the ions present below it and
how many of each ion are present. Covalent substances should be left as they

1
are. If an ion appears on both sides of the equation (in the same state), it
should not be included in the ionic equation.

Sometimes state symbols need to be included to show exactly what ions have
changed and which have not changed.

Aqueous sodium hydroxide reacts with hydrochloric acid to produce aqueous

sodium chloride and water. This can be represented by the equation:

NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)

Water is covalent and is, therefore, present as intact covalent molecules.

Sodium hydroxide and sodium chloride are ionic and so is the hydrochloric
acid. Their ions can behave independently.

The sodium ions and chloride ions are not changed by the reaction – they
remain in solution as free, independent ions. It is the hydroxide ions and the
hydrogen ions that react. They combine to form covalent water molecules.

This is shown by the ionic equation:

+ –
H (aq) + OH (aq) → H2O(l)

Skill Check 3
1 Write an ionic equation for the reaction between copper(II) sulfate solution
and sodium hydroxide solution.

2 Write an ionic equation for the reaction between potassium chloride solution
and silver nitrate solution.

3 Write an ionic equation for the reaction between zinc(II) ions and hydroxide
ions to produce zinc(II) hydroxide.

4 Convert the following balanced symbol equations into ionic equations by

removing spectator ions:

a) Mg(s) + CuSO4(aq) → MgSO4(aq) + Cu(s)

b) Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g)
Compounds, Formulae & Redox 4
5 Write ionic equations for each of the reactions below. Include state symbols.

a) reacting aqueous silver nitrate and aqueous sodium bromide to produce

a precipitate of silver bromide and a solution of sodium nitrate

b) reacting aqueous barium chloride and aqueous sodium sulfate to produce

a precipitate of barium sulfate and a solution of sodium chloride

c) reacting sulfuric acid and aqueous sodium hydroxide

d) reacting hydrochloric acid and aqueous potassium carbonate

1
e) reacting magnesium and aqueous zinc chloride

f) reacting solid zinc oxide and sulfuric acid

Redox Reactions
Oxidation occurs when a species loses one or more electrons. Reduction
occurs when a species gains one or more electrons.

Redox reactions are reactions in which oxidation and reduction occur

simultaneously.

Electron transfer
Magnesium burns brightly in air. The product is a white solid: the ionic
compound magnesium oxide, Mg2+O2—.

Mg(s) + ½O2(g) → Mg2+O2–(s)

Electron transfer in redox reactions
Electron transfer in redox reactions
During the reaction,
Theeach magnesium
combustion atom givesin
of magnesium upoxygen
two electrons and turnsreaction:
is an oxidation
The combustion of magnesium in oxygen is an oxidation reaction:
into a magnesium ion: Mg 1 → Mg2+ + 2e–
Mg + 21O2 → MgO
Mg + 2 O2 → MgO
Oxygen takes upThis the involves the
electrons fromaddition
the of oxygen.
magnesium
This involves the addition of oxygen. to produce oxide ions:
½O2 + 2e– → MagnesiumO2– 2
has the electron configuration [Ne] 3s 2. In this reaction, each ma
Magnesium has the electron configuration [Ne] 3s . In0 this reaction, each m
atom loses its two outer electrons, becoming [Ne] 3s .0 The electrons are ga
atom loses its two outer electrons, becoming [Ne] 3s .
2+ The electrons are
2− g
In this way, electrons transferatom.
an oxygen from magnesium
The result isatoms to oxygen
the formation ofatoms
an Mgand 2+
ion and an O 2−
ion
an oxygen atom. The result is the formation of an Mg ion and an O io
form ions from atoms.
2e−
2e−
1_
Mg(s) + 21_O2(g) → Mg O (s)
2+ 2−
Mg(s) + 2O2(g) → Mg2+O2−(s)
What happens to the magnesium in this reaction is identical to what happ
What happens to the magnesium
in the reaction with chlorine: in this reaction is identical to what hap
This is identical toinwhat happenswith
the reaction to magnesium
chlorine: when it reacts with chlorine:
2e−
2e −
−
Mg(s) + Cl2(g) → Mg 2Cl (s)
2+
Mg(s) + Cl2(g) → Mg2+2Cl−(s)
The magnesium is oxidised because it has lost electrons. Oxygen in the first e
Thechlorine
and magnesium is oxidised
in the second, because it hasbecause
are reduced lost electrons. Oxygen
they have gainedinelectrons
the first
and chlorine in the second, are reduced because they have gained electron
 electrons by the Fe 3+ ions in the oxide:
Compounds,
+
Fe 3+→Formulae
3e
Fe −
& Redox 5
Whenone
When onesubstance
substance is reduced by gaining electrons,the
gaining electrons, theelectrons
electronshave
havebeen
been supplied
by another
supplied species, species,
by another which lost them
which lostand soand
them became oxidised.
so became WhenWhen
oxidised. chlorine gas is
passed through a solution of potassium bromide, the bromide ions
chlorine gas is passed through a solution of potassium bromide, the bromide lose electrons
(are oxidised) and become bromine. The chlorine molecule gains the electrons (is
ions lose electrons (are oxidised) and become bromine. The chlorine molecule
reduced) and becomes chloride ions:
gains the electrons (is reduced) and becomes chloride ions:
2e−

− −
2Br + Cl2 → Br2 + 2Cl

Bromide
Bromideions
ionsare
areoxidised to to
oxidised bromine andand
bromine chlorine is reduced
chlorine to chloride
is reduced ions. ions.
to chloride

Oxidation States1
Oxidation numbers
Many reactions involve a complete transfer of electrons from one substance to
Redox and
another reactions cantoalso
it is easy seebe described
that in terms
they involve redox.of the oxidation
These numbers of the
processes usually
mber of elements concerned. The oxidation number of the species in a simple
have ions as either the reactants or the products. In some cases, both the ionic compound
ompound is the charge on the ion. For example, in magnesium chloride, the magnesium ions
reactants and the products are ions.
ge that the are 2+, so the oxidation number of magnesium is +2. The charge on each chloride
ave if the ion is 1−, so the oxidation number of each chlorine in MgCl is
There are, however, some reactions in which it is difficult to appreciate the
2 −1. This concept
can be extended to covalent substances and to polyatomic ions such as sulfate, SO4 . 2−
ully ionic. redox processes involved because there is no obvious transfer of electrons
The one
from oxidation
substancenumber is calculated on the basis that the bonding electrons are
to another.
assigned to the more electronegative atom in a covalent bond. Consider hydrogen
sulfide,
In 2 S. The bonding
Hovercome
order to is covalent
this problem, and the
the concept of sulfur atom
oxidation shares(or
number a pair of electrons
with each hydrogen atom. However, sulfur is more electronegative
oxidation state) was introduced. This provided a similar, but alternative, than hydrogen,
so the bond pair is assigned to the sulfur in both H−S bonds. In this way, the sulfur
definition of redox to that involving electron transfer. An oxidation number is a
number assigned to an atom or an ion to describe its relative state of oxidation
tion and reduction: redox
or reduction.(Topic 3)

We use oxidation numbers to keep track of the electrons transferred or shared

during chemical changes. Oxidation numbers make it much easier to
2.indd 78
recognise redox reactions. Oxidation numbers also provide a useful way of 27/02/
organising the chemistry of elements such as chlorine, which can be oxidised
or reduced to varying degrees. Chemists have also chosen to base the names
of inorganic compounds on oxidation numbers.
Compounds, Formulae & Redox 6
Oxidation number rules
1. The oxidation number of uncombined elements is zero.
Thus, the oxidation number of Mg is 0, as is the oxidation number of
chlorine atoms in Cl2.

2. In simple ions the oxidation number of the element is equal to the

charge on the ion.
Thus, the oxidation numbers of Cl–, Fe2+ and Fe3+ are –1, +2 and +3,
respectively.

1
3. In neutral compounds, the sum of the oxidation numbers is zero.
E.g. in MgCl2 the sum of the oxidation numbers [+2 and 2(−1)] is 0.

4. In polyatomic ions, the sum of the oxidation numbers of the

elements is equal to the charge on the ion.
E.g. in the sulfate ion, SO42−, the sum of the oxidation numbers is:
[+6 + (−2 × 4)] = −2
S O x4

5. Some elements have fixed oxidation numbers in all their compounds.

(a) The oxidation number of fluorine in all compounds is -1.

(b) The oxidation number of hydrogen is +1

(except where it is combined with a reactive metal, for example in
sodium hydride, NaH [Na+H−], where it is −1).

(c) The oxidation number of oxygen is −2 (except in peroxides, like

H2O2, where it is −1 and oxygen difluoride, OF2, where it is +2).

(d) The oxidation number of chlorine is −1 (except in compounds with

oxygen and fluorine).

6. In a covalent bond in a molecule, the more electronegative element

is given a negative oxidation number and the less electronegative
element, a positive oxidation number. E.g., in chlorine fluoride, ClF, the
chlorine atom is less electronegative than the fluorine atom (the most
electronegative element). Therefore chlorine is assigned an oxidation
number of +1 and fluorine that of −1.
Compounds, Formulae & Redox 7
Skill Check 4
Deduce the oxidation states of vanadium in the following ions and
compounds:
a VO2+ bV 2+ c [V(H2O)6]3+

d V2O5 e NH4VO3 f VO 2+

Skill Check 5
1. What is the oxidation number of:
a) aluminium in Al2O3
1
b) nitrogen in magnesium nitride, Mg3N2
c) nitrogen in barium nitrate, Ba(NO3)2
d) nitrogen in the ammonium ion, NH4+?

2. What are the oxidation numbers of each element in the following?

MgCl2, SO2, CO, NaOH, PCl3, SO4 2–, MnO4 —

3. What are the oxidation numbers of sulfur in the following compounds?

NaHSO4, CS2, SO2Cl2, Na2S, S2Cl2

4. Deduce the oxidation number of iodine in:

I2O7, KIO4, IO3− , Ba(IO2)2

5. Work out the oxidation number of the species in bold in each of the
following compounds:
Na2O KBrO3 Na2SO3 K2CrO4 NH4NO3

6. State the oxidation numbers of chlorine in these ions:

Cl−, ClO−, ClO2−, ClO3−, ClO4−

7. State the oxidation numbers of nitrogen in these molecules:

N2, NH3, N2H4, HNO3, HNO2, NH2OH, NF3
 9.1 Oxidation and reduction 28
Compounds, Formulae & Redox 8
Oxidation
■ Namingnumbers
inorganicand the names of compounds
compounds
The following
concept oflist
oxidation number
gives some is used
of the in the
basic modern
rules chemical
for naming naminginorganic
common of ionic inorganic
substances.
compounds: This system of nomenclature, or naming, is called the Stock notation. In this system
the oxidation number is inserted immediately after the name of an ion. Roman numerals are
inserted after the name or symbol of the element. For example:
1. The ending ‘-ide’ shows that a compound contains just two elements
FeCl2 2+ −
mentioned in[Fethe 2Cl ] The more
name. iron(ii) chloride
electronegative element comes second
3+ −
–FeCl
as in3 sodium[Fe sulfide,
3Cl ] Na2S, carbon
iron(iii) chloride
dioxide, CO2, and magnesium nitride,
Mg 3N 2.
This notation is only used for the transition metals, and tin and lead from group 14 (iv) of the
periodic table where variable or multiple oxidation states are exhibited. For the metals from
2. The1 Roman
groups (i), 2 (ii)numbers initnames
and 13 (iii) indicatenecessary
is not usually the oxidation numbers
to indicate of the state of the
the oxidation
metal, for example
elements – forcalcium chloride
example, 1
iron(II)rather than
sulfate,
two cations, for example the ‘mixed oxide’ of lead:
calcium(ii)
FeSO chloride.
4, and iron(III) Some compounds contain
sulfate,
Fe2(SO4)3.
Pb3O4 [2Pb2+ Pb 4+ 2−
4O ] dilead(ii) lead(iv) oxide
3. The more systematic names for oxoacids and oxo salts use oxidation 3–,
The Stock system is also used to name complex 2– ions (Chapter 13). For example, [Fe(CN) 6 ]
numbers, as in sulfate(VI) for sulfate, SO , and sulfate(IV) for sulfite,
3+ SO 2–
–
which consists of an iron(iii) ion surrounded by six cyanide ions, that is, [Fe 6CN ], is named
4 3

as the hexacyanoferrate(iii) ion. Stock names are used for the following oxoanions:

Chromate(vi) CrO4 2− Dichromate(vi) Cr2O7 2−

Manganate(vii) MnO4 − Manganate(vi) MnO4 2−

Chlorate(i) ClO− Chlorate(iii) ClO2−

Chlorate(v) ClO3− Chlorate(vii) ClO4 −

9.10 This is because, for example, the names ‘chlorate’ (Figure 9.10) and ‘manganate’ are not precise
ph of crystals enough and potentially refer to more than one species. For compounds between non-metals
chlorate(v), the Stock notation is generally not used and the actual numbers of the atoms in the molecular
l oxidizing formula are
Skill Check 6shown in the name. For example, dinitrogen oxide, N 2O, rather than nitrogen(i)
oxide and sulfur hexafluoride, SF6, rather than sulfur(vi) fluoride.
1. Write the formulae of the following compounds:
2a) Deduce
tin(II) oxide
Stock names for the following transition compounds:
a Na2Cr2O7 c V2O5 e CuSO4.H2O g Zn(NO3)2
b) tin(IV) oxide
b K 2CrO4 d NH4VO3 f Cu2SO4 h ScCl3
c) iron(III) nitrate(V)
d) potassium chromate(VI).
ToK Link
Oxidation states are useful when explaining redox reactions. Are artificial conversions a useful or valid way
of clarifying knowledge?
2. Give the systematic name for these
−
ions:
Manganese in the manganate(VII) ion, MnO4 , has an oxidation number of +7. This implies the presence
ofa)
Mnnitrate, NO
7+ —
. It must be3remembered that the oxidation state of an atom does not represent the ‘real’ charge
on that atom. This is— particularly true of high oxidation states, where the ionization energy required to
b) nitrite, NO 2
produce a highly charged positive ion is far greater than the energies available in chemical reactions.
The manganese–oxygen bonds in the manganate(VII) ion are polar covalent bonds. The assignment of
electrons between atoms in calculating an oxidation state is purely a set of useful but artificial beliefs for
the understanding of many chemical reactions. Oxidation numbers are not ‘real’ – they are simply useful
3.mathematical
Write the constructs
formulaeused of the following
to keep track ofcompounds:
electrons during redox reactions.

a) dinitrogen trioxide
b) phosphorus
ToK Link pentachloride
c) aluminium
Chemistry nitride
has developed a systematic language that has resulted in older names becoming obsolete. What
has been lost and gained in this process?
d) iron(iii) nitrate
The alchemists gave names to many inorganic compounds which were often related to their method of
e) silverorsulfite
preparation appearance. Examples include ‘spirit of salt’ (hydrochloric acid) because it was made from
salt, ‘the green lion’ (iron(II) sulfate), ‘spirit of hartshorn’ (aqueous ammonia) which was distilled from harts’
horns, and aqua regia (King’s water), a mixture of hydrochloric and nitric acids, which could dissolve gold.
 Compounds, Formulae & Redox 9
Redox in terms of oxidation numbers
Redox reactions or redox equations are easily recognized by:

• deducing all of the oxidation numbers of the atoms in the chemical species
present in the molecular, ionic or half-equation. Note that the equation
does not have to be balanced in order to do this.

• examining the numbers to see if the oxidation number of any atom has
changed. If it has, the reaction is a redox reaction.

1
• An increase in oxidation number is oxidation and a decrease in oxidation
number is reduction.

• If there are no changes in oxidation numbers during the chemical reaction,

then the reaction is not a redox reaction.

Oxidation is an increase in oxidation number.

Reduction is a decrease in oxidation number.

+3 3+
Fe

+2 2+ 2+
Mg Fe
Oxidation number

+
+1 Na
reduction
oxidation

0 Mg Fe Na O2 Cl 2

–
–1 Cl

2–
–2 O

Figure 4.3 !
Considernumbers
Oxidation the following reactions.
of atoms and ions.

2FeCl2(s) + Cl2(g) → 2FeCl3(s)

Oxidation number rules
The1oxidation
The oxidation number
numbers of are
of iron uncombined elements
+2 and +3, is zero.
respectively and the oxidation
2 In simple ions the oxidation number of the element is the charge
numbers for chlorine are 0 and −1, respectively. The iron has undergone
on the ion.
oxidation and the chlorine has undergone reduction.
3 The sum of the oxidation numbers in a neutral compound is zero.
4 The sum of the oxidation numbers for an ion is the charge on the
ion. Mn(NO3)2(s) → MnO2(s) + 2NO2(g)
5 Some elements have fixed oxidation numbers in all their
compounds.
±
The oxidation numbers of manganese are +2 and +4, respectively, and the
2 oxidation
Metals
numbers for nitrogen are +5 and
Non-metals
+4, respectively. The manganese
hasgroup
undergone oxidation
1 metals +1 and the nitrogen has undergone reduction.
hydrogen +1
2±
(e.g. Li, Na, K) (except in metal hydrides, H–)
2 group 2 metals +2 fluorine –1
Compounds, Formulae & Redox 10
(NH4)2Cr2O7(s) → Cr2O3(s) + 4H2O(g) + N2(g)

The oxidation numbers of chromium are respectively +6 and +3, and the
oxidation numbers for nitrogen are –3 and 0, respectively. The chromium has
undergone reduction and the nitrogen has undergone oxidation.

MgO(s) + 2HCl(aq) → MgCl2(aq) + H2O(l)

The oxidation numbers of magnesium, chlorine, hydrogen and oxygen remain

1
unchanged at +2, −1, +1 and −2. Acid–base reactions are therefore not redox
reactions.

Skill Check 7
Are these elements oxidised or reduced when they react to form these
compounds?
a) calcium to calcium bromide
b) chlorine to lithium chloride
c) chlorine to chlorine dioxide
d) sulfur to hydrogen sulfide
e) sulfur to sulfuric acid

Skill Check 8
1. Write equations for the following reactions and use oxidation numbers to
show that they are redox reactions.
a) Magnesium with dilute sulfuric acid
b) Zinc with dilute hydrochloric acid
c) Lithium with dilute hydrochloric acid

2. Classify these reactions of calcium and its compounds as redox, acid–base,

precipitation or thermal decomposition.
a) CaCl2(aq) + K2SO4(aq) → CaSO4(s) + 2KCl(aq)
b) CaCO3(s) → CaO(s) + CO2(g)
c) Ca(s) + 2H2O(l) → Ca(OH)2(aq) + H2(g)
d) Ca(OH)2(s) + 2HCl(aq) → CaCl2(aq) + 2H2O(l)
e) Ca(s) + 2HCl(aq) → CaCl2(aq) + H2(g)
 [Cu(H22O) 2+2+
O)66] ] (aq)
(aq)++4NH
4NH
[Cu(H 3
Compounds, Formulae & Redox 11
Disproportionation The oxidation
oxidationnumber
numberofofcop
co
oxidation
oxidation number
number
Disproportionation occurs when a single species is both oxidized and reduced and
and this
this re
not a redox
redox
simultaneously. An example of disproportionation is the catalytic reaction.
reaction.
decomposition of hydrogen peroxide.

H O (aq) → H O(l) +
1
1 O (g)
Disproportionatio
■ Disproportionat
■
H O2 (aq)
2 → H O(l)
2 + 2O 2(g) 2
2 2 2 2
Disproportionation occurs
Disproportionation occurs w
(Figure
(Figure 9.13).
9.13). An
Anexample
example of
o
1
0 12 O2(g) peroxide (Chapter 6).
0 O
2 2 (g) peroxide (Chapter 6).
oxidation number of oxygen One of the oxygen atoms
1 One of the oxygen atom
oxidation number of oxygen

molecule and during this cha

molecule and during this ch
oxidation. The other oxygen
oxidation.
molecule The
and other
during oxygen
this cha
–1 H2O2 molecule and during this ch
–1 H2O2 reduction.
reduction.
Another example of dispr
Another example of disp
(Chapter 3) to form a mixtur
(Chapter 3) to form a mixtu
2 H2O Cl2(g) + H2O(l) → H
2
■ Figure 9.13 H2O 0 2(g) + H2O(l) →
Cl
One of the oxygen atoms inFigure
■The thedisproportionation
hydrogen 0
9.13 peroxide molecule becomes part of
an oxygen molecule andThe during this change the
One
oxidation
of
number
the chlorine
increases
atoms in
of hydrogen peroxide
disproportionation
from −1 to zero. Hence, this is oxidation. The other oxygenchange
One
atomof
in the
the
the oxidation
chlorine number
atoms i
of hydrogen peroxide chlorine atom in the chlorine
change
hydrogen peroxide molecule becomes part of a water molecule and duringthe oxidation numb
this change the oxidation number decreases from −1 to −2. change
chlorine the oxidation
atom
Hence, this number
is in the chlori
reduction. Other examples of
change the oxidation numb disprop
■ the reaction
Other between
examples chlo
of dispr
Another example of disproportionation is the reaction between chlorine and
■
■
water to form a mixture of hydrochloric and chloric(i) acids: the
the reaction
reaction between
betweensolu
ch
(Chapter 13)
■ the reaction between so
Cl2(g) + H2O(l) → HOCl(aq) + ■
HCl(aq)
the overall cell reaction t
(Chapter 13)
Skill Check 9 on the accompanying web
■ the overall cell reaction
1. Which of the following reactions involve redox?
on the accompanying w
a) Cl2 + 2OH— → Cl— + ClO— + H2O ■ Redox equations
b) Cu2+ + 2OH— → Cu(OH)2
c) H2O + SO3 → H2SO4 ■ Redox equation
Constructing half-equa
d) 2CrO42— + 2H+ → Cr2O72— + H2O Many of the oxidizing and re
Constructing half-equ
and reduction in an acidified
2. Use oxidation numbers to show that these are disproportionation
Many of the
molecules andoxidizing
hydrogenand
ionsr
reactions.
a) 2CO → C + CO
(g) (s) 2(g)
and reduction
constructed. in an acidifie
b) 3K2MnO4(aq) + 2H2O(l) → MnO2(s) + 2KMnO4(aq) +1 molecules
Write
4KOH (aq)
and hydrogen ion
down the formulas
c) 2Ca(OH)2(s) + 2Cl2(aq) → CaCl2(aq) + Ca(ClO)2(aq) +constructed.
2H2O(l)
Cr2O72− → Cr3+
1 Write down the formula
2 Balance with respect to th
Compounds, Formulae & Redox 12
Skill Check 10
1. In the reaction: CuO + Mg ➝ Cu + MgO
What are the oxidation states of oxygen before and after the reaction?

2. Which one of the following represents an oxidation–reduction reaction?

(a) I2(s) + 2OH−(aq) → I−(aq) + OI−(aq) + H2O(l)

(b) PO43−(aq) + H2O(l) → HPO42−(aq) + OH−(aq)

(c) SO3(g) + 2H2O(l) → HSO4−(aq) + H3O+(aq)

(d) Cu2+(aq) + H2S(aq) → CuS(s)

1
+ 2H +(aq)

3. State which of the following reactions are redox reactions and, for each
redox reaction, identify the element that has been oxidised and the element
that has been reduced.

(a) Cu2+(aq) + 2OH—(aq) → Cu(OH)2(s)

(b) 2ZnS + 3O2 → 2ZnO + SO2

(c) 2Na + 2H2O → 2NaOH + H2

(d) SO3 + H2O → H2SO4

(e) Na2CO3 + 2HCl → 2NaCl + H2O + CO2

(f) 2FeSO4 + H2SO4 + H2O2 → Fe2(SO4)3 + 2H2O

(g) 3HgSO4 → Hg2SO4 + Hg + 2SO2 + 2O2

(h) 2I− + H+ + HOCl → I2 + H2O + Cl−

4. Write the equation for the disproportionation reaction of copper(I) ions to

copper metal and copper(II) ions.

5. Chlorine reacts with hot aqueous potassium hydroxide:

3Cl2 + 6KOH → 5KCl + KClO3 + 3H2O

Explain why this is a disproportionation reaction.

Compounds, Formulae & Redox 13
Ionic half-equations
A half equation is an ionic equation used to describe either the gain or loss of
electrons during a redox process. Half equations help to show what is
happening during a reaction. Two half equations combine to give the overall
balanced equation.

Zinc metal can reduce copper ions to copper. This can be shown as two half
equations:

electron gain (reduction): Cu (aq)

2+ + 2e– → Cu(s)
1
electron loss (oxidation): Zn(s) → Zn 2+ (aq) + 2e–

When these two half equations are added together, they produce the full ionic
equation. The electrons on each side must cancel out so. The electrons gained
on one side of the equation equal the electrons lost on the other side.

Cu (aq)
2+ + 2e– → Cu(s)

Zn(s) → Zn2+ (aq) + 2e–

Cu (aq) + Zn(s)
2+ → Cu(s) + Zn (aq)
2+

As already mentioned above, a redox equation may be broken down into two
half equations.These half equations show the oxidation and reduction
processes separately.

For instance, in the equation 2Br—(aq) + Cl2(aq) → 2Cl−(aq) + Br2(aq)

we can separate the two processes as:

2Br—(aq) → Br2(aq) + 2e— Oxidation

Cl2(aq) + 2e— → 2Cl—(aq) Reduction

2—
Cr2O7 (aq) + 2+ 3+ 3+
+ 14H (aq) + 6Fe (aq) → 6Fe (aq) + 2Cr (aq) + 7H2O(l)

This reaction can be separated as:

2—
Cr2O7 (aq) + 3+
+ 14H (aq) + 6e → 2Cr (aq) + 7H2O(l)
— Reduction
2+ 3+
6Fe (aq) → 6Fe (aq) + 6e— Oxidation
Compounds, Formulae & Redox 14
Br2 + SO2 + 2H2O → SO4 2— + 2H + 2HBr
+

This reaction can be separated as:

+
Br2 + 2H + 2e— → 2HBr Reduction
+
SO2 + 2H2O → SO4 2— + 4H + 2e— Oxidation

dd

Constructing half equations

1
Half equations must balanced in terms of the number of atoms on both sides
and in terms of the total charge on both sides. In some cases it is very
straightforward to balance half equations, and electrons must simply be added
to one side or the other.

For example, consider the half equation:

Ni2+ → Ni

Although the number of nickel atoms on each side is the same, the total
charge on the left-hand side is 2+ but the total charge on the right-hand side
is 0. In order to balance the charges, we must simply add 2e− to the left-hand
side:

Ni2+ + 2e— → Ni

Now the number of atoms and the charges balance on each side.

Now, let’s look at the following half-equation:

Br2 → Br—

In this example, neither the number of atoms nor the total charge balance.

First of all we balance the atoms to get:

Br2 → 2Br—

The total charge on the left-hand side is zero, but that on the right-hand side is
2−. In order to balance the charges we need to add 2e— to the left- hand side
so that the charge is equal on both sides:

Br2 + 2e— → 2Br—

This is now balanced. These were both fairly straightforward examples, but the
process becomes a bit more difficult in some cases, and we will now consider
balancing more complex half equations in acidic solution.
Compounds, Formulae & Redox 15
Skill Check 11
1 These are incomplete half-equations for changes involving reduction in
solution. Complete and balance the half-equations.

(a) H+(aq) → H2(g)

(b) Fe3+(aq) → Fe2+(aq)

(c) H2O2(aq) + 2H+(aq) → 2H2O(l)

(d) Mg(s) → Mg2+(aq)

(e) Sn2+(aq) → Sn4+(aq)

1
(f) I−(aq) → I2(aq)

2 Write half-equations for:

(a) the reduction of Sn4+ to Sn2+

(b) the oxidation of iodide ions, I−, to iodine, I2

3 These are incomplete half-equations for changes involving reduction. Copy

and complete and balance the half-equations. You need to add the electrons.

(a) H+(aq) → H2 (g)

(b) Fe3+(aq) → Fe2+(aq)

(c) Br2 (aq) → 2Br— (aq)

4 Balance the following half equations:

(a) S2O32— → S4O662—

(b) C2O42— → CO2

Compounds, Formulae & Redox 16
Constructing half equations in acidic solution
Consider the following reaction:

2— 3+
Cr2O7 → Cr

1 Balance all atoms except H and O – the Cr atoms must be balanced:

2— 3+
Cr2O7 → 2Cr

2 Add H2O to side deficient in O to balance O – there are 7 O atoms on the

1
left-hand side and none on the right-hand side, so 7H2O must be added to
the right-hand side:

2— 3+
Cr2O7 → 2Cr + 7H2O

3 Add H+ to side deficient in H to balance H – there are 14 H atoms on the

right-hand side but none on the left-hand side, so 14H+ must be added to the
left-hand side:

2— 3+
Cr2O7 + 14H+ → 2Cr + 7H2O

4 Add e— to side deficient in negative charge to balance charge – the total

charge on the left-hand side is 2− + 14+ = 12+, and the total charge on the
right-hand side is 2 × 3+ = 6+, so 6e— must be added to the left-hand side to
balance the charges:

2— 3+
Cr2O7 + 14H+ + 6e— → 2Cr + 7H2O

Skill Check 12
Balance the following half equations in acidic solution:

(a) VO2+ → V3+

(b) Xe → XeO3

(c) NO3— → NO

(d) NO3— → N2O

(e) VO2+ → VO2+

Compounds, Formulae & Redox 17
Skill Check 13
1 Balance the following half equations in acidic solution:

(a) I2 + H2O → IO— + H+ + e—

(b) MnO4— + H+ + e— → MnO2 + H2O

(c) IO3— + H+ + e— → I2. + H2O

(d) N2 + H2O → NO3— + H+ + e—

(e) SO42— + H+ + e— → H2SO3 + H2O

1
2 Write half-equations for these changes in solution and in each case state
whether the process is an example of oxidation or of reduction:

(a) cobalt(ii) ions turning into cobalt(iii) ions

(b) sulfur dioxide molecules in acid solution turning into hydrogen sulfide
molecules

(c) hydroxide ions turning into oxygen and water molecules

(d) hydrogen molecules turning into hydrogen ions

Compounds, Formulae & Redox 18
Forming redox equations
Redox equations are written by combining two half-equations: one describing
the action of an oxidizing agent and the other describing the action of a
reducing agent. Often one or both of the two half-equations must be
multiplied by suitable coefficients so that the number of electrons gained by
the oxidizing agent equals the number of electrons lost by the reducing agent.
The electrons can then be cancelled from both sides of the equations and, if
necessary, the numbers of water molecules and hydrogen ions (if present)
simplified.

1
Write a redox equation for the reduction of acidified manganate(vii) ions and
the oxidation of iron(ii) using the balanced half-equations below:

Fe2+(aq) → Fe3+(aq) + e—

MnO4—(aq) + 8H+(aq) + 5e— → Mn2+(aq) + 4H2O(l)

1. Multiply the top equation by 5 to balance electrons

2. Add the two half equations together and cancel the electrons

3. Simply the number of water molecules and H+ ions if needed.

Compounds, Formulae & Redox 19
Write a redox equation for the reduction of acidified manganate(vii) ions and
the oxidation of methanol using the balanced half-equations below:

2H2O(l) + CH3OH(l) → CO2(g) + H2O(l) + 6H+(aq) + 6e—

MnO4—(aq) + 8H+(aq) + 5e— → Mn2+(aq) + 4H2O(l)

1. Multiply the top equation by 5 and the bottom equation by 6 to balance

electrons

2. Add the two half equations together and cancel the electrons

3. Simply the number of water molecules and H+ ions if needed.

Compounds, Formulae & Redox 20
Skill Check 14
1 Zinc metal reacts with IO3- ions in acidic solution. Construct a balanced
ionic equation for this reaction, using the two half-equations below:

2IO3— + 12H+ + 10e— → I2 + 6H2O

Zn → Zn2+ + 2e—

2 Use half-equations to write balanced ionic equations for these redox

reactions.
1
(a) H2O2 with Fe2+ to give H2O and Fe3+

(b) SO32− and Cl2 to give SO42− and Cl−

(c) the disproportionation of IO− into I− and IO3−

3. In industry, iodine is produced from the NaIO3 that remains after sodium
nitrate has been crystallised from the mineral Chile saltpetre. The final stage
involves the reaction between NaIO3 and NaI in acidic solution.
Half equations for the redox processes are given below.

IO3— + 5e— + 6H+ ➝ 3H2O + ½I2

I— ➝ I2 + e—

Use these half equations to deduce an overall ionic equation for the
production of iodine by this process.

4. a) Balance the following half equations by inserting the correct balancing

numbers.

i) SO2 + ___ H2O → SO42— + ___ H+ + ___ e—

ii) MnO42— + ___ H+ + ___ e— → Mn2+ + ___ H2O

b) Write an ionic equation for the reaction between sulfur dioxide and
manganate(VI) ions
Compounds, Formulae & Redox 21
Balancing redox reactions using oxidation numbers
Method 1
You can use the idea of oxidation states to help balance equations for redox
reactions.

For an equation to be balanced:

• the numbers of atoms of each element on each side of the equation must
be the same and

1
• the total charge on each side of the equation must be the same.
Example 1
This is a strongly exothermic reaction in which aluminium reacts with iron(III)
oxide to produce molten iron. It was used to weld railway lines.
The unbalanced equation is:

Fe2O3(s) + Al(s) ➝ Fe(l) + Al2O3(s)

Write the oxidation states below each element:

Fe2O3(s) + Al(s) ➝ Fe(l) + Al2O3(s)

+3 —2 0 0 +3 —2

You can see that only the iron and aluminium have changed their oxidation
state. The oxygen is unchanged.

Each iron atom has been reduced by gaining three electrons so you can write
the half equation:

Fe3+ + 3e ➝ Fe
–

Each aluminium atom has been oxidised by losing three electrons:

Al ➝ Al3+ + 3e–

In the reaction, the number of electrons gained must equal the number of
electrons lost. This means that there must be the same number of aluminium
atoms as iron atoms. (The oxygen is a spectator ion.) You started with two iron
atoms, so you must also have two aluminium atoms. The balanced equation is
therefore:

Fe2O3(s) + 2Al(s) ➝ 2Fe(l) + Al2O3(s)

Compounds, Formulae & Redox 22
Example 2
Sometimes in aqueous solutions, species take part in redox reactions but are
neither oxidised nor reduced. You must balance them separately. These
include water molecules, H ions
+ (in acid solution), and OH ions
(in alkaline
—

solution). Oxidation states only help us to balance the species that are oxidised
or reduced.

Suppose you want to balance the following equation, where dark purple
manganate(VII) ions react in acid solution with Fe2+ ions to produce pale pink
Mn2+ ions and Fe3+ ions.
1
The unbalanced equation is:
MnO4— + Fe2+ + H + ➝ Mn2+ + Fe3+ + H2O

Write the oxidation state above each element.

MnO4— + Fe2+ + H + ➝ Mn2+ + Fe3+ + H2O
+7 —2 +2 +1 +2 +3 +1 —2

Identify the species that has been oxidised and the species that has been
reduced and create two half equations.

+7 +2
MnO4— ➝ MnManganese has been reduced from +7 to +2 therefore five
2+

electrons must be gained.

MnO4— + 5e— ➝ Mn2+ (this equation is not chemically balanced)

Balance the remaining atoms, those that are neither oxidised nor reduced. In
order to ‘use up’ the four oxygen atoms on the left-hand side, you need 4H2O
on the right-hand side, which will in turn require 8H+ on the left-hand side.
MnO4— + 5e— + 8H+ ➝ Mn2+ + 4H2O

+2 +3
Fe2+ ➝ Fe3+ Fe has been oxidised from +2 to +3 so one electron must be
lost.
Fe2+ ➝ Fe3+ + e—

In order to balance the number of electrons that are transferred, this step must
be multiplied by 5:
5Fe2+ ➝ 5Fe3+ + 5e—
There are 5Fe2+ ions to every MnO4— ion.

Add the two half equations and cancel the e— and any species that are both
sides of the equation.

MnO4— + 5Fe2+ + 8H+ ➝ 5Fe3+ + Mn2+ + 4H2O

 precipitation or thermal decomposition.
a) CaCl2(aq) + K2SO4(aq) → CaSO4(s) + 2KCl(aq)
Compounds,
b) CaCOFormulae
3(s) → CaO(s)& + Redox
CO2(g) 23
c) Ca(s) + 2H2O(l) → Ca(OH)2(aq) + H2(g)
Methodd)#2Ca(OH)2(s) + 2HCl(aq) → CaCl2(aq) + 2H2O(l)
Oxidatione)numbers
Ca(s) + help
2HCl(aq) → CaCl2(aq)
in balancing + Hequations,
redox 2(g) because the total
decrease in oxidation number for the element reduced must equal the total
4.4 Balancing redox equations
increase in oxidation number for the element oxidised. This is illustrated below
through the oxidation of hydrogen bromide by concentrated sulfuric
Oxidation numbers help in balancing redox equations, because the total acid. The
Tutorialmain products
decrease inare bromine,
oxidation sulfur dioxide
number for the and water.reduced must equal the total
element
increase in oxidation number for the element oxidised. This is illustrated
below
1. Write through
down the oxidation
the formulae for theof hydrogen
atoms, bromide
molecules andbyions
concentrated
involved in sulfuric
the
acid.
reaction The main products are bromine, sulfur dioxide and water.
Step 1: Write down the formulae for the atoms, molecules and ions involved
HBrreaction
in the 1
+ H2SO4 → Br2 + SO2 + H2O
HBr + H2SO4 → Br2 + SO2 + H2O
2. Identify the elements that change in oxidation number and the extent of
Step
change. 2: Identify the elements that change in oxidation number and the
extent of change.
In this example, only bromine and sulfur show changes of
In this example, only bromine and sulfur show changes of oxidation state. oxidation
state.
change of +1
HBr + H2SO4 → Br2 + SO2 + H2O
change of –2
Step 3: Balance so that the total increase in oxidation number of one
3. Balance soelement
that theequals the totalindecrease
total increase oxidationofnumber
the other element.
of one element
In this example, the increase
equals the total decrease of the other element. of +1 in the oxidation number of two
bromine atoms balances the −2 decrease of one sulfur atom.
In this example,
2HBrthe+increase
H2SO4 →of +1
Br2in+the
SOoxidation
2
+ H 2
O number of two bromine
atoms balances the −2 decrease of one sulfur
Step 4: Balance for oxygen and hydrogen. atom.
In this example, the four hydrogen atoms on the left of the
2HBr join
equation + Hwith
2SO4the→ two Br + SOoxygen
remaining
2 2 + atoms
H2O to form two
water molecules.
4. Balance for oxygen and hydrogen. In this example, the four hydrogen atoms
2HBr + H2SO4 → Br2 + SO2 + 2H2O
on the left of the equation join with the two remaining oxygen atoms to form
Step 5: Add state symbols.
two water molecules.
2HBr(g) + H2SO4(l) → Br2(l) + SO2(g) + 2H2O(l)
2HBr + H2SO4 → Br2 + SO2 + 2H2O
Test yourself
11 Write balanced equations for these redox reactions. State which element is
oxidised and which is reduced in each example.
Skill Check 15
a) Fe reacts with Br2 to give iron(III) bromide
Use oxidation
b) Festates
reactstowith
balance
H2SO4the
(aq)following equations
to give iron( and hydrogen
II) sulfate and write the half
equationsc)forFeach
2 reacts with
reaction.H2O to give HF and oxygen
d) Ba reacts with HCl(aq) to form BaCl2(aq) and hydrogen
(a) Cl2 + NaOH ➝ NaClO3 + NaCl + H2O

(b) Sn + HNO3 ➝ SnO2 + NO2 + H2O

 Compounds, Formulae & Redox 24
Skill Check 16
Use half-equations to write balanced ionic equations for these redox reactions.

a) An acidic solution of chloric(i) acid, HOCl, is reduced to chloride ions as it

oxidises iodide ions to iodine.

b) H2O2 with Fe2+ to give H2O and Fe3+

c) SO32— and Cl2 to give SO42— and Cl—

1
d) the disproportionation of IO— into I— and IO3—

Skill Check 17

TIONS AND OXIDATION NUMBERS

Skill Check 18