INORGANIC CHEMISTRY

ADVANCED LEVEL

A: PERIODICITY.

Any phenomenon is said to be periodic if that phenomenon produce similar situations at similar
intervals.

The term periodicity in Chemistry refers to the recurrence of atomic properties at a regular
interval.

It may also refer to the similarity between the properties of chemical elements that are close to
each other in the periodic table.

The first attempt to classify elements was to classify elements as metals or non – metals. This
classification is still useful though it has several shortcomings. For example, there are elements
that cannot be classified as metals or non – metals. These are known as metalloids.

The periodic table of elements:

Periodic table, is the table of the chemical elements arranged to illustrate patterns of recurring
chemical and physical properties. Elements, such as oxygen, iron, and gold, are the most basic
chemical substances and cannot be broken down by chemical reactions. All other substances are
formed from combinations of elements. The periodic table provides a means of arranging all the
known elements and even those yet to be discovered.

NEWLAND’S PERIODIC TABLE

Newland put forward the law of octaves. According to the law of octaves, when the elements
are arranged in the order of their relative atomic masses, any element has properties similar to
those of the elements eight places in front it and eight places behind it. He called it the law of
octaves because they look like eight notes of music.
Since Newland’s octaves grouped the elements whose properties repeat periodically, his table
was called periodic table.

Weakness of Newland’s periodic table

(i) Some elements which are dissimilar were classified together.
(ii) Newland assumed that all the elements were discovered, so he didn’t leave gaps for
undiscovered elements.

MENDELEYEV PERIODIC TABLE.

According to Demitry Mendeleyev (who studied only 63 elements), the properties of elements
are periodic function of their relative atomic mass.
When the elements are arranged in order of their increasing relative atomic mass, almost all
elements with the same properties fell in the same vertical column. These vertical column are
known as groups and the horizontal rows were called periods.
Unlike Newland, Mendeleyev left gaps for some elements that were not yet discovered.
Shortcoming of Mendeleyev table

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The order of a few elements had to be reversed in order to fall nearly their respective groups. For
example, Tellurium has the a relative atomic mass of 127.6 and Iodine has a relative atomic
mass of 126.
Thus, in Mendeleyev periodic table, Iodine should come first (should be in group (vi)). However,
it doesn’t have the same properties as oxygen and sulphur.
The other pairs that were to be reversed are (Argon and Potassium), (Calcium and Nickel) and
(Thallium and Palladium).

The modern periodic law: (By Moseley)

The law states that, “ The properties of Chemical elements are periodic function of their atomic
number”
That is to say, the chemical and physical properties of elements will repeat periodically when the
elements are arranged in order of their increasing atomic numbers.
All modern classification, are based on modern periodic law.
Tellurium (atomic number 52) has the right of coming before Iodine ( Atomic number 53)
THE MODERN PERIODIC SYSTEM OF ELEMENTS
The modern periodic table consists of vertical columns known as groups and the horizontal
rows known as periods.
A group constitutes a chemical family of elements that posses similar chemical properties.
The periodic table of elements in columns and rows by shared chemical properties.
Elements appear in sequence according to their atomic number.

CAUSES OF PERIODICITY
The properties of elements depends on its electronic configuration particularly the outermost
configuration.
The elements with the same outermost configurations have similar properties. For example, the
alkali metals, have ns1 electronic configuration, and the halogens have ns2 np5 outer most
electronic configurations.

CLASSIFICATION OF ELEMENTS
Elements can be classified into two ways:
(i) Classification into blocks
(ii) Classification into metals and non – metals and metalloids.

(i) The classification into blocks

(a) The S- block elements: These include hydrogen, group (i) elements and group(ii) elements
because their outermost electrons are occupied on the S- orbital.

(b) The p – block elements: These include all elements whose outer electrons are occupied in the
p – orbital.
Their general configurations of the outermost shell are ns2np2, ns2np3 ….. ns2np6.
The properties of the p – block elements depend on the p – electrons.

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(c) The d – block el : These are elements with outermost electrons being filled in the d – orbital.
The properties of the d – block elements are due the d – sublevel.
Among the d – block elements, some are transition elements. Transition elements are those
elements with partially filled d – sublevels.
(d) The f – block elements: These are inner transition elements. This block won’t be discussed at
our level.
The classification of elements into metals and non – metals will be discussed later in their
respective groups.

PERIODIC VARIATIONS OF ATOMIC PROPERTIES

(i) Atomic radius.
The radius of any object is usually the distance from the centre to the boundary surface. If this
concept is applied to atoms, the atomic radius should therefore be defined as the distance from
the nucleus to the outermost shell.
However, it is not possible to apply this concept to atoms because:
(i) An atom is too small to be isolated hence difficult to measure the distance from the nucleus to
the outermost shell.
(ii) Formation of electron clouds by high speed spinning electrons around the nucleus. Bearing
these difficulties, we determine the atomic radius by considering the combining atoms of the
same element.
Atomic radius : Is defined as half the internuclear distance between two bonded atoms. If the
atoms combine to form a single covalent bond e. g. in non – metals, the atomic radius is known
as covalent radius.
If the atoms are joined together by a metallic bond, the atomic radius will be known as metallic
radius.

d
r = d/2 d

Where: r = atomic radius

d = internuclear distance

When ions are joined together by ionic bond, we define an ionic radius.

When an anion is formed, the atom receives an electron and the ionic radius is larger than the
atomic radius.

When the cation is formed, the ionic radius, will be smaller than the atomic radius.

Note: The anionic radius, is larger than the atomic radius, due to the re – distribution of the
nuclear force to hold extra electrons; and the cationic radius is smaller than the atomic radius due
to the re –distribution of the nuclear force to hold less electrons.

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The anionic radius increases as the number of electrons received increased, and the cationic
radius decreases as the number of electrons being lost increases.

TREND OF ATOMIC RADIUS ACROSS THE PERIOD AND DOWN THE GROUP.

(a) Across the period:

The atomic radius decreases across the period ( from left to right). This is due to the increase in
the number of electrons that causes the increase in the effective nuclear charge. by the valence
electrons from the nucleus.

As the effective nuclear charge increases, the electrons are pulled closer to the nucleus and
therefore the radius decreases.

(b) Down the group:

The atomic radius increases down the group due to:

(i) Increasing number of shells

(ii) Screening effect

Screening effect : Is the tendency of electrons in the penultimate shell to act as a shield and
reduce the nuclear force to the valence electrons. This results to an increase in atomic radius.

Down the group of the periodic table, the atomic number increases and therefore the nuclear
charge decreases.

At the same time, down the group of the periodic table, the number of electron shells increases.

The shells added will repel one another and reduce the effective nuclear charge. The outermost
electrons will therefore be pulled less to the nucleus and thus the atomic radius increases.

Note: The screening effect has the strongest impact on the group (i) elements which have only
one electron in their outermost shell. Hence they have the largest radii.

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 Summary

Atomic radius Decrease across the period due to an

increase in the number of electrons and

Increases down the group the effective nuclear charge

due to the increase in the

number of shells and screening

effect.

Decreases across the period

Screening effect

Increases down the

group.

Effective nuclear charge

Increases across the period

Decreases down

the group

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 IONIZATION ENERGY (I.E)

This is the energy required to remove an electrons (outer electrons) from a neutral gaseous atom
or a gaseous ion against the nuclear attractive force.

The energy required to remove an electron from a neutral gaseous atom to change it to a
monopositive gaseous ion is called the first ionization energy.

The energy required to remove the second electron from a monopositive gaseous ion to form a
dipositive gaseous ion is called the second ionization energy. The energy required to remove
the third electron is called the third ionization energy etc.

Usually, the second ionization energy is greater than the first ionization energy.

This is because; as electrons are removed, the effective nuclear charge increases.

Thus, the remaining outermost electrons are held with a great force. Since the third and fourth
ionization energies are very large, trivalent and tetravalent ions are rare.

The SI unit of I.E is Kjmol-1.

FACTORS AFFECTING IONIZATION ENERGY

(a) Atomic radius:

The ionization energy decreases with increase in atomic radius. This is because, as the radius
increases, the electrons become less strongly attracted to the nucleus.

Hence, the energy required to remove the loosely held bound electrons decreases.

VARIATION OF I.E WITH ATOMIC RADIUS.

Element Li Na K Rb
Atomic 0.134 0.157 0.203 0.216
radius(nm)
Ionization 522.06 497.10 420 404.50
energy(Kjmol-1)

(b) Screening effect

As the number of electron shells increases, the screening effect also increases. This will reduce
the attraction of the outermost electrons to the nucleus and hence the energy required to remove
electrons (I.E).

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(c) The magnitude of the effective nuclear charge.

As the effective nuclear charge increases, the electrons become strongly attracted to the nucleus.
Hence, the energy required to remove electrons will be higher.

(d) The type of orbital from which the electron is removed.

In the same principle energy level, the s – orbital is nearer to the nucleus than the p – orbital and
the p – orbital are nearer to the nucleus than the d – orbital. This implies that, electrons in the s –
orbital are more tightly held to the nucleus than the electrons in the p – orbital and the electrons
in the p – orbital are more tightly held to the nucleus than the electrons in the d – orbital etc.

Thus, the ionization energy decreases from s to p to d orbitals respectively.

(e) The electronic configuration:

Some electronic configurations are more stable than the others. The stable configurations are half
filled orbitals, full filled orbitals and noble gas configurations.

When an electron is removed from these stable configurations, higher energy is used.

GENERAL TREND OF IONIZATION ENERGY

Generally, the ionization energy increases across the period due to an increase in effective
nuclear charge and decreases down the group due to the increase in the number of shells and
screening effect down the group. Thus, the easy detaching an electron from an atom increases
down the group and decreases across the period.

Ionization energy Increases across the period due to an increase in effective

nuclear charge

Decreases down the group

due to an increase in atomic

radius and screening effect

The trend of Ionization energy across the period is not smooth; for example, Beryllium and
Nitrogen have abnormal high ionization first Ionization energy. This is due to extra stability of
the atoms due to their configurations.

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For paired electronic configurations, energy is required to separate those paired electrons. So,
pairing provides extra stability of the atoms and thus requires high ionization energy to remove
electrons.

Consider the graph below

Ionization

energy

( Kjmol-1)

He N

Be C

Li B

Atomic number

Explanation

There is a sharp rise in Ionization energy from H to He because He is more stable than H. The
stability of He is due to its configurations. He has a full filled 1S orbital and H has half filled 1S
orbital. Full filled orbital is more stable than half filled orbital and therefore more energy is
required to remove an electron from He than H.

The fall and rise of Ionization energy from Li to C is due pairing effect. In Li, an electron is
singly occupied and therefore less energy is required. For Be, electrons are paired and therefore
more energy is required etc.

There is abnormal trend of Ionization energy from C to N due to extra stability of N that
possesses half filled orbital which is a condition for extra stability. Thus, more energy is required
to remove an electron from nitrogen than from carbon.

IONIZATION ENERGY AND PROPERTIES OF ELEMENTS

The ionization energy can be used to explain qualitatively some of the properties of elements. It
determines whether the elements to be classified as metal or non – metal. The metallic character

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decreases as the ionization energy increases. The metallic character decreases across the period
and it increases down the group.

The tendency of forming ionic compounds decreases across the period and increases down the
group where as the tendency of forming covalent compounds increases across the period and
decreases down the group.

Ionization energy is also a measure of the reactivity of elements. Elements with low ionization
energy are very reactive and those with high Ionization energy are less reactive. Thus, reactivity
increases down the group and decreases across the period.

ELECTRON AFFINITY

Electron affinity is the energy change when a gaseous atom or ion of a non - metal gains an
extra electron.

Electron affinity is the measure of the electron attracting power of an atom. The more negative
the electron affinity, the more the power to attract electron.

The energy change when the first electron is added to a gaseous atom of a non – metal is called
the first electron affinity. The energy change when the second electron to a gaseous ion of a non
– metal is called the second electron affinity and the energy change when the third electron is
added to a gaseous ion is called the third electron affinity etc.

Thus, for ions that can receive more than one electrons, we have the second, third etc electron
affinities.

The second and further electron affinities are positive. This is because, when the second electron
is added to an ion, energy should be absorbed to overcome the strong repulsive force of the
already existing negative ion. For this reason, poly ions are rare.

FACTORS AFFECTING ELECTRON AFFINITIES

There are three factors affecting the electron affinities. These are:

(i) The size of the atom

(ii) The effective nuclear charge

(iii) Electronic configuration

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Atomic size

The larger the size of an atom the less the power of holding electrons, the less negative the
electron affinity( more positive electron affinity) and vice versa.

Effective nuclear charge.

The greater the effective nuclear charge, the greater the power of holding electrons and the more
the negative electron affinity and vice versa.

The electronic configuration

Full and half filled sublevels have extra stability. These do not favour receiving extra electrons.
Hence, atoms with half filled and full filled sublevels have low electron affinity ( less negative
electron affinity) due to their extra stability.

TRENDS OF ELECTRON AFFINITY IN THE PERIODIC TABLE

Across the period:

The electron affinity becomes more negative across the period due to the increase in effective
nuclear charge and decrease in atomic radius across the period. However, there are three
elements in each period which do not follow the general trend. These are:

(i) Group II elements

(ii) Group V elements

(iii) Noble gases.

The abnormality is due to their electronic configurations. The group II elements have full filled
nS sublevels (nS2). Thus the electron has to go to the nP – sublevel.

However, the screening by nS electrons lowers the effective nuclear charge making these
elements to have positive electron affinities.

Group V elements have half filled nP sublevel(nPx1 nPy1 nPz1). This configuration is very stable.

It doesn’t favor accepting an extra electron. Thus, these elements have positive or less negative
electron affinities.

The noble gases have full filled configurations (nS2 nP6) which also are very stable and do not
permit the addition of an extra electron. Hence, the noble gases have positive electron affinities.

In the periodic table, halogens have the most negative electron affinities due to their small size
and their highest effective nuclear charge.

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Down the group

Generally, the electron affinities become more positive down the group of the periodic table.

This is due to the reduction in effective nuclear charge as a result of increasing screening effect
down the group of the periodic table. This reduces the tendency of the atom to attract an extra
electron.

For halogens, contrary to our expectations, the electron affinity of Fluorine is lower than that of
Chlorine. This is because Fluorine has very small atomic radius. Thus, its 2P – sublevel is very
compact. The electron repulsion within the compact 2P – sublevel compensates for the high
effective nuclear charge, and consequently this reduces the electron affinity of Fluorine.

ELECTRONEGATIVITY

Electro negativity is the ability of an atom to attract electrons towards itself. The electro
negativity depends on the magnitude of the effective nuclear charge. The electro negativity
increases with an increase in effective nuclear charge.

Trend in the periodic table

The electro negativity increases across the period and decreases down the group. The increase
across the period is due to the increase in the effective nuclear charge and the decrease down the
group is due to the decrease in the effective nuclear charge.

ELECTROPOSITIVITY

Electro positivity simply refers to the ability of an atom to lose electrons. Less electro positive
atoms are highly electropositive and vice versa. The electro positivity, therefore, decreases
across the period and increases down the group of the modern periodic table.

DIAGONAL RELATIONSHIP

Diagonal relationship refers to the similarity in properties between the elements in the second
period and those in the third period which are just diagonally related.

Diagonal similarities arise from the fact that electro negativity increases across the period from
left to right and decreases as the group is descended.

This leads to comparable electro negativities for diagonal elements as well as comparable
properties between them.

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The most prominent diagonal similarities exist between:

(i) Lithium and Magnesium

(ii) Beryllium and Aluminium

(iii) Boron and Silicon

Diagonal relationship can also be explained in terms of polarizing power of diagonal elements.

Along the period from left to right, the polarizing power increases; and decreases down the
group. The increase and decrease in polarizing power across the period and down the group
respectively, leads to similarities for diagonally related elements.

Diagonal relationship

Li Be B C N O F ( Period 2 elements)

Na Mg Al Si P S Cl ( Period 3 elements)

Therefore, diagonally related elements have:

(i) Similar electro negativity.

(ii) Similar polarizing power.

VARIATION OF PROPERTIES ACROSS THE PERIOD 3 (Na to Ar)

(i) Variation of physical properties

(a) Melting point

Melting point is the temperature at which a solid substance is converted into a liquid form. The
melting point of the element is the measure of the amount of energy that must be supplied to
break the regular arrangement of atoms or molecules in a crystal.

The melting point of period three elements do not follow a regular trend. The melting point
increases sharply from Na to Mg. This is because Na atom contributes only one electron in the
electron clouds of the metallic crystal but Mg contributes two electrons. The two electrons
contributed by Mg results into a stable crystal with high melting point. This accounts for low
melting points of Sodium compared to Magnesium.

Aluminium has three electrons in the outer valence shell but contributes only two of them to the
electron clouds of the metallic crystal. This makes the melting point of Aluminium to be very
close to that of Magnesium because they contribute the same number of electrons in the electron
clouds of the metallic crystal. The slight difference in melting point between Aluminium and

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Magnesium is attributed to their sizes. Aluminium is very small as compared to Magnesium;
therefore it forms s relatively stable metallic crystal.

Silicon is a non – metal though it has some metallic character. In period 3, Silicon has the highest
melting point due its ability of forming a giant structure. The strong giant structure results into a
strong covalent bond and therefore high melting point.

Phosphorus and Sulphur have relatively low melting points because their molecules are held
together by weak Van der waal forces.

Sulphur has higher melting point than phosphorus due to the difference in size of their
molecules. Sulphur exists as S8 and Phosphorus exists as P4. Thus, Sulphur has stronger van der
waal forces because of its larger molecular size compared to Phosphorus and hence associated
with higher melting point than Phosphorus.

Chlorine which is a diatomic gas at room temperature has a very low melting point because the
molecules are far apart.

ELECTRO NEGATIVITY

This property increases across the period due to the increase in the effective nuclear charge
across the period. Thus, along the same period , atomic size and consequently the metallic
character decreases.

FIRST IONIZATION ENERGY

The first Ionization energy increases from Na to Mg and falls at Aluminium and then rises again
to Phosphorus and falls at Sulphur and finally rises at Chlorine and Argon as shown below:

I.E

Ar

P Cl

Mg Si S

Na Al

Atomic number

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 Assignment: Give an explanation for the variation of ionization energy shown in the
graph above.

VARIATION OF CHEMICAL PROPERTIES

(a) The hydrides

Hydrides are binary compounds of atoms and hydrogen. The hydrides of period three are
NaH, MgH2, AlH3, SiH4, PH3, H2S and HCl.

Sodium hydride is strongly ionic because the electro negativity difference between Na and H is
very large.

Magnesium hydride is largely ionic in character but the bonds are covalent

Aluminium hydride is covalent. This is caused by high polarizing power of Aluminium.

Reaction with water

The hydrides of Sodium, Magnesium, Aluminium and Silicon react with water yielding
hydrogen gas and metal hydroxide
NaH + H2O NaOH + H2

MgH2 + H2O Mg(OH)2 + H2

AlH3 + H2O Al(OH)3 + H2

SiH4 + H2O Si(OH)4 + H2

Phosphine (PH3), does not react with water. This is because PH3 is non – polar. It is non – polar
because the electro negativity difference between Phosphorus and Hydrogen is very small.

PH3 + H2O No reaction

The hydrides of Sulphur and Chlorine ( H2S and HCl) are polar covalent and therefore react with
water to form acids.

H2S + H2O H3O+ Hܵ ି

HCl + H2O H3O+ + ‫ି ݈ܥ‬

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(b) Chlorides

These are binary compounds of elements and Chlorine. The Chlorides of period three elements
are:

NaCl , MgCl2, Al2Cl6, SiCl4, PCl5 and S2Cl2.

Sodium and Magnesium Chloride are strongly ionic salts. The rest of the chlorides are covalent
in nature.

The progressive decrease in melting point from sodium to Aluminium reflects the increasing
weakness of the bonding in the crystals.

Reaction with water

NaCl and MgCl2 are not hydrolysed in water because they are strongly ionic and therefore in
aqueous solution they are converted to free ions.

NaCl + H2O Na+ + C݈ ି

MgCl2 + H2O Mg2+ + 2C݈ ି

Magnesium Chloride is not hydrolysed but its hydrated crystals undergo partial hydrolysis when
heated to give hydrogen chloride and basic Magnesium Chloride.

MgCl2. 6H2O Mg(OH)Cl + HCl + 5H2O

For this reason, Magnesium Chloride cannot be prepared by heating its hydrated crystals to
remove water.

Aluminium Chloride is easily hydrolysed by water to produce an acidic solution.

Al2Cl6 + 12H2O 2[Al(H2O)6]3+

[Al(H20)6]3+ + H2O [Al(H2O)5OH]2+ + H3ܱା

[Al(H2O)5OH]2+ + H2O [Al( H2O)4(OH)2]+ + H3ܱା

The H3O+ released during hydrolysis determines the acidity of the solution and the acidity
increases with increasing hydrolysis.

The Chlorides of Silicon, Phosphorus and Sulphur hydrolyses completely in water.

SiCl4 + 3H2O H2SiO3 + 4HCl

PCl3 + 3H2O H3PO3 + 3HCl

S2Cl2 + H2O 2HCl + H2S + H2SO3

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 (c) Hydroxides

These are compounds of the elements with OH groups . The hydroxide of period 3 are:

NaOH, Mg(OH)2, Al(OH)3, OSi(OH)2, OP(OH)3 O2S(OH)2 and O3Cl(OH)

Sodium and Magnesium hydroxides have strong tendency of releasing the hydroxyl group in the
form of OH- ions. These, therefore, are true hydroxides.

Aluminium hydroxide ( Al(OH)3) is amphoteric; that is, it has both acidic and basic properties.

From Silicon onwards, the compounds are not hydroxides but they are oxy – acids of the non –
metals. The acidic character of the oxy – acids is due to their ability of losing H+ ions from the
hydroxyl group. This is because, Si, P, S and Cl are highly electro negative and therefore
withdraw electrons by negative inductive effect from the OH bond and thus facilitate the release
of a proton, H+.

The structures of these oxy – acids are shown below:

OH

HO Si OH Silicic (iv) acid

OH

HO P OH Phosphoric (v) acid

OH

HO S OH Sulphuric (vi) acid

O Cl OH Chloric (vii) acid

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Silicic acid is not known to release either OH or H+ ions. It has the tendency to polymerize
releasing water molecules.

OH OH OH OH

HO Si OH HO Si OH HO Si O Si OH + H2O

OH OH OH OH

The remaining oxy – acids have acidities that vary in the following order:

H3PO4 ∠ H2SO4 ∠ HClO4

This arrangement is determined by the arrangement of the central atom to withdraw electrons
from the OH group. The order of withdrawing electrons depends on the electro negativity of the
central atom.

The more the electronegative the element the higher the withdrawing power. The order of
electro negativity follow the following trend:

P ∠ S ∠ Cl

(d) Oxides

Sodium and Magnesium are strongly metallic, and their oxides are ionic. Aluminium oxide is
also ionic although Aluminium is not as strong metal as Sodium and Magnesium. The oxides of
these metals have high melting points because the ionic bonding in their crystal structures are
very strong.

Sodium and Magnesium oxides are strong bases, Aluminium oxide is amphoteric and the
remaining oxides are acidic oxides as shown below:

Oxides Na2O MgO Al2O3 SiO2 P4O10 SO2, SO3 Cl2O7

Nature Basic Basic Amphoteric Acidic Acidic Acidic Acidic

SOME REACTIONS OF THE ELEMENTS ACROSS PERIOD THREE

1. Reaction with water:

Sodium floats on water violently liberating hydrogen gas and forming sodium hydroxide.

2Na + 2H2O 2NaOH + H2

Magnesium reacts with boiling water or with steam to give Magnesium oxide and hydrogen.

Mg(s) + H2O(g) MgO(s) + H2(g)

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Magnesium reacts very slowly with cold water due to the formation of a protective layer of
Mg(OH)2 on the surface of the metal.

Mg(s) + H2O(l) Mg(OH)2

Aluminium does not react with water. This is due to the formation of a thin film of insoluble
protective layer of oxide when exposed to air.

The formation of a protective oxide layer (Al2O3) on the metal surface prevents any further
reaction with water.

Silicon reacts with steam only at red heat

Si(s) + 2H2O(g) SiO2 + 2H2

Phosphorus does not react with cold water. Of the two common allotropes of Phosphorus, red
and white Phosphorus, the white Phosphorus is only very slightly soluble in water.

Sulphur does not react with water.

Chlorine dissolves in water to form hypochlorous acid and hydrochloric acid by the following
reversible reaction:

H2O(l) + Cl2 HClO + HCl(aq)

The resulting solution is called Chlorine water.

On exposure to bright sunlight, Chlorine water evolves oxygen.

2HClO Sunlight 2HCl + O2

Generally in the presence of bright sunlight,

2Cl2(g) + 2H2O Sunlight 4HCl + O2

2 .Reaction with acids.

The reaction of Sodium metal with acids is dangerous. They are very vigorous and explosive.

Dilute hydrochloric acid and sulphuric acid react with Magnesium metal to form soluble salts
liberating hydrogen gas.

Mg + 2 HCl MgCl2 + H2

Mg + H2SO4 MgSO4 + H2

Magnesium is among very few metals known to liberate hydrogen from very dilute nitric acid

Mg + HNO3 Mg(NO3)2 + H2

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Nitric acid is an oxidizing agent that it can’t liberate hydrogen gas with most metals. Any
hydrogen produced is immediately oxidized to water. Concentrated nitric acid is so oxidizing
that it produces nitrogen oxide and water when reacted with Magnesium.

3Mg(s) + 8HNO3 3Mg(NO3)2 + 4H2O + 2NO

Hot concentrated Sulphuric acid also strong oxidizing properties and therefore oxidizes
Magnesium to produce Sulphur dioxide gas and water.

Mg + 2H2SO4 MgSO4 + 2H2O + SO2

Aluminium reacts with hydrochloric acid. The reaction gets more vigorous as the acid becomes
hotter and more concentrated.

The reaction produces Aluminium chloride and Hydrogen gas.

2Al(s) + 6HCl 2AlCl3 + H2

Dilute Sulphuric acid does not react with Aluminium. This is due to the formation of a protevtive
oxide on the metal surface.

Silicon does not react with mineral acids.

Sulphur is attacked by oxidizing acids. Hot and concentrated Sulphuric acid oxidizes Sulphur to
Sulphur dioxide.

S(s) + 2H2SO4 2H2O + 3SO2

Concentrated nitric acid Oxidizes Sulphur to sulphuric acid and itself get reduced to nitrogen
dioxide.

S(s) + 6HNO3 H2SO4 + 6H2O + 6NO2

Dilute or concentrated hydrochloric acid has no action on Sulphur.

Chlorine reacts only with reducing acids such as sulphorus acid and nitrous acid.

Cl2 + H2SO3 + H2O H2SO4 +2HCl

Cl2 + HNO2 + H2O HNO3 + 2HCl

3. Reaction with alkalis

Sodium dissolves in liquid ammonia to produce a deep blue solution containing sodium amide.

On standing, the colour disappears and sodium amide is precipitated with the evolution of
hydrogen gas.

2Na + 2NH3 2NaNH2(s) + H2

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The reaction between sodium metal and sodium hydroxide forms sodium oxide and hydrogen
gas is liberated.

2Na + 2NaOH 2Na2O(s) + H2

Magnesium does not react with the alkalis

With ammonia gas, Magnesium forms Magnesium nitride.

3Mg(s) + 2NH3(g) Mg3N2 + 3H2

Aluminium powder reacts violently with hot and concentrated sodium hydroxide forming
sodium aluminate and hydrogen gas.

2Al(s) + NaOH + 6H2O 2NaAl(OH)4 + 3H2

Silicon reacts with very dilute solution of caustic alkalis hydrogen gas and forming the
corresponding silicate.

Si(s) + 2OH- +H2O SiO32- + 2H2

White Phosphorus reacts with strong alkali to give Phosphine.

P4 + 3NaOH(aq) +3H2O 3NaH2PO2 + PH3(g)

Sodium hypophosphate

Sulphur reacts hot and concentrated sodium hydroxide to produce sulphide and thiosulphate.

6OH-(aq) + 4S(s) S2O32- (aq) + 2S-(aq) + 3H2O

Chlorine gas reacts with aqueous solution of the caustic alkalis to produce different products
depending on the reaction conditions.

In the reaction between Chlorine gas and alkalis, Chlorine gas becomes oxidized and reduced at
the same time.

The reaction in which a single species becomes oxidized and reduced at the same time is called
disproportionation reaction.

We can simply say, therefore that, Chlorine undergoes a disproportionation reaction with alkalis.

When the alkali is cold and dilute, a mixture of Chloride and hypochlorite is produced.

Cl2(g) + NaOH(aq) NaCl(aq) + NaClO(aq) + H2O(l)

Oxidation Oxidation Oxidation

state = 0 state = -1 state = +1

In NaCl, Cl has been reduced from 0 to -1, in NaClO, Cl has been oxidized from 0 to +1

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Ionically:

2OH- + Cl2(g) Cl-(aq) + ClO- + H2O

When excess Chlorine is passed through hot and concentrated alkali, a chloride and a chlorate
are obtained.

Example.

6NaOH(aq) + 3Cl2(g) 5NaCl(aq) + NaClO3(aq) + 3H2O

Ionically:

6OH-(aq) + 3Cl2(aq) 5Cl- + ClO3- + 3H2O

HYDROGEN AND ITS POSITION IN THE PERIODIC TABLE

It brings some difficulties in placing hydrogen in the periodic table because it has both,
hydrogen like properties and alkali metal like properties.

Resemblance of hydrogen with alkali metals

1. Like all alkali metals, hydrogen can lose one to form a unipositive ion.

H H+ +e- ( Hdrogen)

Na Na+ + e- ( Alkali metal)

2. Like all alkali metals, hydrogen can combine with highly electronegative elements.

H2 + Cl2 2HCl

2Na + Cl2 2NaCl

3. Like all alkali metals, hydrogen has only one electron in the outermost shell.

4. Like all alkali metals, the outermost electron in hydrogen is occupied in the S- orbital.

Resemblance of hydrogen with halogens.

1. It lacks only one electron to be stable.

2. It exists as a diatomic gas at room temperature.

3. Can combine with a highly electropositive element

H2 + 2Na 2NaH

Cl2 + 2Na 2NaCl

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4. Hydrogen can be replaced by halogens in organic substitution reactions of alkanes

CH4 + Cl2 U.V CH3Cl + HCl

The best position of hydrogen in the periodic table

The best position of Hydrogen in the Periodic table is group I. This is because the atomic
number of hydrogen is one. According to the modern periodic law, the properties of chemical
elements are periodic function of their atomic number.

Hydrogen with atomic number equals to one should therefore belong to group I.

Isotopes of Hydrogen

Three Isotopes of hydrogen exist

(i) Hydrogen protium denoted by ଵଵ‫ܪ‬

(ii) Hydrogen deuterium denoted by ଶଵ‫ܪ‬

ଷ
(iii) Hydrogen tritium denoted by ଵ‫ܪ‬

Allotropes of hydrogen.

Only three allotropes of Hydrogen exist, Ortho and Para hydrogen.

In ordinary mixture of two allotropic hydrogen, ortho hydrogen is 75% and para hydrogen is
only 25%. In ortho hydrogen, the nuclei of the atoms in hydrogen molecule are spinning in the
same direction.

ORTHO HYDROGEN

H H

H . H .
INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 22
The nuclei spins in the molecule of para hydrogen are in the opposite directions.

PARA HYDROGEN

H H

H . H .
Ortho hydrogen is very stable at high temperature where as para hydrogen is stable at low
temperature.

GROUP ( I) ELEMENTS

( THE ALKALI METALS)

This group consists of the elements Lithium (Li), Sodium (Na), Potassium (K) ,
Rubidium(Rb),

Caesium (Cs) and Francium (Fr).

Group I elements are very reactive metals because they can easily lose electron and participate in
chemical reaction due to their large size.

Group I elements are known as alkali metal because their oxides dissolve very easily in water to
form alkalis.

Francium is a radioactive element with a very short half life hence a little information is known
about the Chemistry of Francium.

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 Physical properties of Alkali metals.

All group I elements have only one electron in the outermost orbital. The electronic
configuration of group I elements are

Element Symbol Electronic configuration

Lithium Li [He] 2S1
Sodium Na [Ne] 3S1
Potassium K [Ar] 4S1
Rubidium Rb [Kr] 5S1
Caesium Cs [Xe] 6S1

Atomic and ionic size

The atoms of group I are the largest in their corresponding periods. On descending the group
(down the group) from Li to Cs, the atomic and ionic sizes increase. This is due to the increase in
the number of shells and screening effect.

First ionization energy

Atoms of alkali metals are larger such that the outer orbital electrons are far away from the
nucleus and therefore they are very easy to remove.

Their first ionization energies are very low and decrease down the group as the radius increases.

Flame test

Due to their large size, when alkali metals or their salts are subjected to flame test, their elements
absorb energy and become excited to higher energy levels.

When these electrons return to the ground state, the extra energy is released in the form of light
in the visible region of the electromagnetic spectrum.

Thus, alkali metals or their salts impart colours to flame.

Na - Golden yellow

K – Lilac

Rb – Violet etc

Note: Flame test offers a sensitive and reliable test for alkali metals.

Electro positivity

Due to low first ionization energy, alkali metals have great tendency of losing electrons forming
positively charged ions.

M M+ + e-

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Group I elements are therefore highly electropositive and their electro positivity increase down
the group.

Caesium and Potassium are so electropositive that they emit electrons when exposed to light
(Photo electric effect). These elements are therefore found in photo electric cells.

Chemical properties of alkali metals

Alkali metals are highly electro positive and their reactivity increases down the group. Because
of this , the alkali metals are stored under oil or kerosene because they will react with oxygen
when exposed to it or water when stored under it.

Reaction with water:

Alkali metals react with water forming hydroxides and liberate hydrogen gas.

2Na + H2O 2NaOH + H2

2K + H2O 2KOH + H2

2Rb + H2O 2RbOH + H2

Hydrides

Group I elements combine directly with hydrogen forming white crystalline hydrides. These
hydrides are hydrolysed by water forming metal hydroxide and hydrogen gas.

NaH + H2O NaOH + H2

KH + H2O KOH + H2

RbH + H2O RbOH + H2

CsH + H2O CsOH + H2

Reaction with non – metals

Alkali metals react with non – metals to form stable compounds.

Examples:

2K(s) + Cl2(g) 2KCl(s)

2Na(g) + Br2(g) 2NaBr(s)

2K(s) + S(s) K2(s)

Reaction with oxygen of the air

Lithium burns in air to give Lithium monoxide (Li2O), Sodium forms peroxide (Na2O2) and
Potassium and others form the peroxide of the type MO2.

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Reducing properties

Alkali metals are good reducing agents because they are good electron donors.

Good reducing agents are substances which have a great tendency of releasing electrons due to
their large size, and therefore alkali metals are good reducing agents.

Thermal stability of the compounds of alkali metals

Group I compounds are thermally very stable. This is due to low polarizing power of group I
elements. Thermal stability of alkali metal compounds increase down the group. The increases
of thermal stability of the compounds down the group is due to the increase in atomic size down
the group that result to efficient package of the crystals.

Because of its small size, Lithium which is the first member in group I is thermally unstable.

(a) Carbonates

Li2CO3 Li2O + CO2

Na2CO3 No reaction

Upon strong heating, Na2CO3 changes to liquid state.

Na2CO3(s) Strong heat Na2CO3 (l)

(b) Hydroxides

The hydroxides of alkali metals are also thermally very stable except Lithium hydroxide that
gives Lithium oxide and water.

NaOH(s) Heat No reaction

LiOH Heat Li2O + H2O

(c) NitrateS

Lithium nitrate being an exceptional, it gives Li2O, NO2 and O2

The remaining nitrates give nitrite and Oxygen.

Example:

NaNO3 Heat NaNO2 + O2

LiNO3 Heat Li2O +NO2 + O2

The anomalous behavior of Lithium

Lithium, being the first member of group I, differs from other members of the group.

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The differences may be due to the following reasons:

(i) Small size and high polarizing power

(ii) High electro negativity value

The differences between Lithium and other alkali metals include:

1 . Lithium hydroxide decomposes when heated giving Lithium oxide and water. The hydroxide
of others remain unchanged.

2. Lithium carbonate is not stable to heat. It produces carbon dioxide when heated. The
carbonates of other alkali metals are thermally stable.

3. Lithium nitrate will evolve nitrogen dioxide and oxygen when heated

4LiNO3 2LiO + 4NO2 + O2

Sodium and Potassium nitrate will evolve only Oxygen.

2NaNO3(s) 2NaNO2 + O2

4. Lithium hydride is stable at 8000C. The stability of these hydrides decrease down the group.

5. Lithium can combine directly with nitrogen to give nitride while others cannot.

Li + N2 Li3N

Solubility of alkali metals

Compounds of alkali metals are highly soluble in polar solvent. The solubility vary depending on
the nature of the cations and anions that make up a compound.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 27

 GROUP (II) ELEMENTS

(The alkaline earth metals)

Group II elements include the following:

1. Beryllium (Be)

2. Magnesium (Mg)

3. Calcium ( Ca)

4. Strontium (Sr)

5. Barium ( Ba)

6. Radium (Ra)

Group II elements are called alkaline earth metals because most of their oxides existed in the
earth’s crust and were alkaline in nature.

All group II elements have the outer shell electronic configuration of nS2 and therefore they are

S – block elements.

Group II elements are electropositive but less electropositive than alkali metals.

The first member of the group, Beryllium, is anomalous. This is because Beryllium is smaller,
less electropositive and has higher polarizing power than the rest of the members.

Diagonal similarities between Lithium and Magnesium.

1.The carbonates of both, Lithium and Magnesium are thermally unstable. They decompose
upon heating giving oxides and carbon dioxide.

Li2CO3 Li2O + CO2

MgCO3 MgO + CO2

2. When the hydroxides of both Lithium and Magnesium are heated, decompose giving oxides
and water.

LiOH Li2O + H2O

Mg(OH)2 MgO + H2O

3. Both, LiNO3 and Mg(NO3)2 decompose when heated forming normal oxides, nitrogen dioxide
and Oxygen gas.

LiNO3 Li2O + NO2 + O2

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 Mg(NO3)2 MgO + NO2 + O2

4. Both Lithium and Magnesium burn in Oxygen forming normal Oxides.

4Li + O2 2Li2O

2Mg + O2 2MgO

5. Both Lithium and Magnesium burn in nitrogen forming nitrides.

6Li + N2 3Li3N

3Mg + N2 Mg3N2

SIMILARITIES IN PHYSICAL PROPERTIES

(i) Atomic and ionic size

Group II atoms are large but smaller than group I atoms. Their atomic sizes increase down the
group. Their ions are also large but smaller than group I ions and the size of the ions also
increase down the group.

(ii) Electro negativity and electro positivity

The electro negativity values decrease down the group from Be to Ba where as their electro
positivity increases.

(iii) Ionization energy

The ionization energy decreases down the group from Be to Ba as the atomic radius increases.
The first ionization energy of alkaline earth metals is relatively low but not as low as alkali
metals. Their second ionization energy is higher than their first ionization energy.

(iv) Valency

The larger value of the second ionization energy as compared to the first ionization energy
suggests that alkaline earth metals would prefer to form monovalent positive ions rather than
divalent positive ions.

In actual practice, only the +2 ions exist, example Ca2+, Mg2+ etc .

This is because the +2 ions are easily hydrated. The large amount of hydration energy released
during hydration counterbalance the higher value of the second ionization energy.

Because of being excessively hydrated, most compounds of group II elements are hydrates. For
example, MgCl2.6H2O, CaCl2.6H2O, BaCl2.6H2O etc.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 29

(v) Flame test

Beryllium and Magnesium do not impart any colour to Bunsen burner flame (give negative flame
test). This is because Beryllium and Magnesium are relatively small in size and therefore their
electrons are firmly hold by the nucleus and are not excited by the heat of flame. The rest of the
elements have characteristic flame colours.

SIMIRALITIES IN CHEMICAL PROPERTIES

Group II elements are highly reactive and thus never found in the free state.

Their reactivity increases down the group due to the increase in atomic radius down the group.

(i) Reaction with Oxygen

Alkaline earth metals burn in oxygen forming oxides.

2Ca + O2 2CaO

2Mg + O2 2MgO

(ii) Action with Nitrogen

When heated in nitrogen, alkaline earth metals form nitrides.

3Ca(s) + N2 Ca3N2

These nitrides are colourless, crystalline solids which react with water to liberate ammonia.

Ca3N2(s) + 6H2O(l) Ca(OH)2(s) + 2NH3 (g)

(iii) Carbonates

Their carbonates decompose when heated giving the corresponding oxides and carbon dioxide.

The stability of the carbonates increases down the group.

BeCO3 BeO + CO2

MgCO3 MgO + CO2

CaCO3 CaO + CO2

(iv) Carbides

All alkaline earth metals react with carbon forming carbides except Beryllium that gives
methanide, BeC.

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e.g CaC2(l) + 2H2O(l) Ca(OH)2 + C2H2.

MAGNESIUM

Action of water on Magnesium.

Magnesium react with boiling water or steam and form Magnesium oxide and hydrogen gas.

Mg(s) + H2O(g) heat MgO(s) + H2

Action of dilute acid on Magnesium.

Magnesium liberates hydrogen from dilute acids including nitric acid.

Remember: other metals do not liberate hydrogen with nitric acid.

Magnesium Chloride

Magnesium Chloride exists as MgCl2.6H2O.

Anhydrous Magnesium Chloride, MgCl2 cannot be prepared by heating the hydrated crystal to
eliminate water.

When the hydrated crystal of Magnesium Chloride is heated, it undergoes partial hydrolysis to
form basic Magnesium Chloride. ( Mg(OH)Cl.

Stronger heating will leave Magnesium oxide.

MgCl2.6H2O(s) heat Mg(OH)Cl(s) + HCl + 5H2O

Mg(OH)Cl(s) heat MgO + HCl

CALCIUM ( Ca)

Reaction with air

(a) With nitrogen it forms a nitride.

3Ca + N2 Ca3N2

(b) With Oxygen it forms an Oxide.

2Ca + O2 2CaO

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(c) With hydrogen, Calcium rapidly forms Calcium hydride.

Ca + H2 heat CaH2

The hydride dissolves in water to liberate hydrogen.

CaH2 + 2H2O Ca(OH)2(s) + 2H2

Calcium react with water forming Calcium hydroxide and hydrogen gas.

Ca(s) + 2H2O Ca(OH)2(s) + H2(g)

CALCIUM CARBONATE (CaCO3)

Calcium carbonate decomposes reversibly on heating forming Calcium oxide and carbon
dioxide.

CaCO3 heat CaO + CO2

Quick lime

When excess water is added to the solid CaO, lime water is formed.

CaO + H2O Ca(OH)2

Lime water

A solution of Calcium hydroxide in water is called lime water.

The carbon dioxide gas turns lime water milky.

Ca(OH )2(aq) + CO2 (g) CaCO3(s) + H2O(l)

Solubility of Calcium carbonate.

Calcium carbonate is almost insoluble in water. However, it dissolves in water containing carbon
dioxide.

CaCO3(s) + CO2 + H2O Ca(HCO3)2

When heated, Calcium hydrogen carbonate decomposes to calcium carbonate, carbon dioxide
and water.

2Ca(HCO3)2 heat CaCO3 + CO2 + H2O

Anomalous behavior of Beryllium

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1. Beryllium is the smallest and highly electronegative in the group

2.Where as other alkaline earth metals react with water or steam, Beryllium does not react with
any.

3. Unlike other alkaline earth metals, Beryllium does not liberate hydrogen from dilute acids.

4. While the oxides of other alkaline earth metals are basic, the oxides and hydroxides of
Beryllium are amphoteric. They can react with both acids and bases.

For example,

BeO + H2SO4 BeSO4 + H2O

BeO + NaOH Na2BeO2 + H2O

5. Beryllium has the ability of forming complexes while other alkaline earth metals very few
complexes.

DIOGONAL RELATIONSHIP BETWEEN BERYLLIUM AND ALUMINIUM

1. Their acidic salts dimerize under vapour phase.

For example, Beryllium Chloride exist as Be2Cl4 and Aluminium Chloride exist as Al2Cl6

2. They both do not impart any colour to the Bunsen burner flame.

3. They are both rendered passive with nitric acid by forming an insoluble cover of their oxides.

4. The oxides and hydroxides of both Beryllium and hydroxide are amphoteric.

5. When their carbides are treated with water, they both evolve methane.

Be2C (s) + 2H2O(l) CH4(g) + 2BeO(s)

Al4C3 + 6H2O CH4(g) + 2BeO(s)

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 33

 GROUP (III) ELEMENTS.

The elements that constitute group III are Boron (B), Aluminium(Al), Gallium (Ga), Indium(In)
and Thallium(Tl).

Group III elements belong to the P – block of the periodic table and have three electrons in their
valence shell.

Element Atomic number Electronic configuration

Boron (B) 5 [He] 2S2 2P1
Aluminium (Al) 13 [Ne] 3S2 3P1
Gallium (Ga 31 [Ar] 4S2 4P1
Indium (In) 49 [Kr] 5S2 5P1
Thallium (Tl) 81 [Xe] 6S2 6P1

Group III elements exhibit a group valence of 3, but the three valence ions (+3 ions) are difficult
to form due to the large sum of the first three ionization energy.

Boron which is the first member in the group is small in size and highly electronegative.
Boron is therefore non – metallic .

Aluminium is a metal though it has non – metallic tendencies.

The metallic character like in any other group increases down the group due to increasing ability
of loosing electrons as the size of the atoms increases down the group.

Group III elements show the oxidation state of +3. The oxidation state of +1 becomes more
stable as the group is descended (down the group)

Because of its small size, the first three ionization energies for Boron is also so large that the ion
B3+ does not exist.

The Chemistry of Boron is therefore of covalent compounds. Simple aluminium ions are rare.
They exist in compounds like AlF3 and Aluminium complex ions like [Al(H2O)6]3+.

Due to their small sizes, High polarizing power and large sum of the first three ionization
energies, group three elements show covalency.

The Chlorides of all group III elements are covalent. The hydrated cations of the type
[M(H2O)6]3+ are known for all elements except Boron.

Al3+, with its high charge and small size has high polarizing power. The ion therefore polarizes
water molecules and becomes hydrated. In the hydration process, the hydration energy
compensate for the large sum of the first three ionization energies and thus stabilizes the Al3+.

Al3+ + 6H2O [Al(H2O)6]3+

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B3+ does not exist either in the free state or in hydrated state. The ion is too small to
accommodate water molecules around itself to enable the heat of hydration compensate the
energy of ionization.

As the group is descended, the +1 oxidation state becomes more stable than the +3 oxidation
state due to inert pair effect.

Inert pair effect : This refers to the resistance of the electron pair in the S- orbital to get lost or
participate in covalent bond formation due to poor shielding effect caused by the inner electrons.

ALUMINIUM

Occurance and extraction of Aluminium.

The following are forms in which Aluminium occurs in nature.

(i) The free oxide, corundum (Al2O3)

(ii) The hydrated oxide, bauxite, (Al2O3.2H2O)

(iii) The fluoride, cryolite, ( Na3AlF6)

Bauxite is the most economic ore from which aluminium is extracted.

Extraction of Aluminium from Bauxite.

Aluminium is obtained by electrolysis of Bauxite dissolved in molten cryolite.

The extraction process occur in two stages

(i) Purification of bauxite to remove impurities

(ii) Electrolysis of Aluminium oxide

1. Purification

(i) The ore is powdered and roasted at low temperature to convert all iron present to iron (iii)
state. The main impurities in bauxite are Fe2O3, SiO2 and TiO2.

(ii) The powder is therefore heated with aqueous sodium hydroxide. In this, only Al2O3
should dissolve.

Al2O3(s) + 6OH-(aq) + 3H2O(l) 2[Al(OH)6]3-(aq)

(iii) Filtration: The undissolved impurities are filtered off.

(iv) The aluminate is precipitated as the hydroxide by passing in CO2 or ‘ seeding’ with
freshly prepared aluminium hydroxide.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 35

2[Al(OH)6]3-(aq) + CO2(g) Al(OH)3(s) + CO32-(aq) + H2O(l)

Or

[Al(OH)6]3- Seeding Al(OH)3(s) + OH-(aq)

(v) The hydroxide is filtered off, washed, dried and heated strongly to leave pure aluminium
oxide.

2Al(OH)3(s) heat Al2O3(s) + 3H2O(l)

2. Electrolysis of Aluminium Oxide

The Aluminium oxide is dissolved in molten cryolite (Na3AlF6) and electrolyzed at 9000C.

During electrolysis, aluminium is discharged at the cathode and collected at the bottom of the
molten cryolite as a liquid.

Oxygen is evolved at the anode and is responsible for the slow burning of the anode.

At the cathode:

2Al3+ + 6e- 2Al(s)

The cathode reaction is the reduction of Aluminium.

The anode reaction is the oxidation of the oxide ion, O2-

2O2- O2 + 4e-

CHEMICAL PROPERTIES OF ALUMINIUM

Reaction with dilute acids.

(i) Dilute hydrochloric acid reacts with Aluminium to give hydrogen and aluminium chloride.

(ii) Dilute sulphuric acid does not react with Aluminium. This is due to the formation of an
oxide layer on the Aluminium surface which prevents further reaction.

(iii) Dilute nitric acid has no action on aluminium. This is because aluminium is oxidized by
nitric acid to form a protective layer of oxide which prevent further reaction.

Reaction with concentrated acids

(i) Aluminium reacts with concentrated hydrochloric acid in the same way as dilute hydrochloric
acid. This reaction becomes faster as the acid becomes hotter and more concentrated.

(ii) Hot, concentrated sulphuric acid react with aluminium to liberate sulphur dioxide and form
aluminium sulphate.

2Al + 6H2SO4 Al2(SO4)3 + 6H2O + 3SO2

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(iii) Concentrated nitric acid renders aluminium passive. This passivity is caused by the
formation of a protective layer of oxide which is insoluble in acid.

Reaction with aqueous caustic alkali

Aluminium reacts with sodium hydroxide solution producing sodium aluminate (iii) and evolve
hydrogen.

2Al + 2OH- + 10H2O 2[Al(OH)4(H2O)2]-(aq) + 3H2(g)

COMPOUNDS OF ALUMINIUM

(i) Aluminium oxide

It is prepared by decomposing aluminium hydroxide or heating aluminium in pure oxygen.

2Al(OH)3(s) heat Al2O3 + 3H2O.

4Al(s) + 3O2(g) 2Al2O3(s)

Aluminium oxide is amphoteric. It reacts with acids as well as alkalis.

With acids

Al2O3 + 6HCl 2AlCl3 + 3H2O

With alkalis

Al2O3 + 2NaOH + 3H2O 2NaAl(OH)4(aq)

(ii) Aluminium hydroxide.

This is formed when ammonium hydroxide solution is added to a solution containing aluminium
ions. Aluminium hydroxide is amphoteric. It reacts with both acids and alkalis.

With acids:

Al(OH)3(s) + 3HCl AlCl3 + 3H2O

With alkalis:

Al(OH)3 + 3OH- [Al(OH)6]3-

(iii)Aluminium Chloride (Al2Cl6)

Anhydrous Aluminium Chloride is prepared by passing dry hydrogen or dry Chlorine (Cl2) over
heated aluminium.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 37

 2Al + 6HCl heat Al2Cl6 + 3H2

2Al + 3Cl2 heat Al2Cl6

The preparation must be done in the absence of moisture to avoid rapid hydrolysis of the
Chloride.

In the vapour phase and in organic solvents, the molecular weight of Aluminium Chloride is
twice as much. This is because under such conditions, Aluminium Chloride exist as a dimer.

Cl Cl Cl

Al Al

Cl Cl Cl

(iv) Aluminium carbide. ( Al4C3)

Aluminium carbide is hydrolysed by water, with evolution of methane.

Al4C3 + 12H2O 4Al(OH)3 + 3CH4

HYDROLYSIS OF ALUMINIUM SALTS.

Aqueous solution of aluminium salts are acidic. The acidity of these salts is explained as follows:

The Aluminium ion, Al3+, has high polarizing power due to its small size and high charge.

The ion polarizes the O – H bond of the water molecules and abstract protons from the polarized
water molecules in the [Al(H2O)6]3+ to form the acidic hydroxonium ions, H3O+.

[Al(H2O)6]3+ + H2O [Al(H2O)5OH]2+ + H3O+

[Al(H2O)5OH]2+ +H2O [Al(H2O)4(OH)2]+ + H3O+
The acidity of the aluminium salts increases with increasing hydrolysis.

USES OF ALUMINIUM

(i) Because of the resistance to chemical reaction during cooking, many cooking utensils are
made up of Aluminium..

(ii) Used in electroplating to prevent rusting of iron.

(iii) Used in construction of ships and aero plane because Aluminium is very light.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 38

(iv) Used in the distribution of electricity because Aluminium is a good conductor of electricity.

EXPANSION OF VALENCE SHELL.

This is the ability of an atom to accept electrons in its empty d – orbital apart from its SP- hybrid
orbital.

Boron does not expand its valence shell due to the lack of an empty d – orbital. Other atoms can
expand their valence shell.

Anomalous behaviours of Boron

1. Boron is a non – metal while other elements are metals.

2. Boron does not displace hydrogen from acids while aluminium does.

3.The compounds of Boron are covalent while other elements form few covalent compounds in
anhydrous state.

Diagonal relationship between Boron and Silicon.

(i) Both are non- metals.

(ii) Both have high melting points

(iii) They both burn in halogen to form halides.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 39

 GROUP IV ELEMENTS

This group is also known as the carbon family. The group consists of the following elements:

(i) Carbon (C)

(ii) Silicon (Si)

(iii) Germanium (Ge)

(iv) Tin (Sn)

(v) Lead (Pb)

Metallic and non- metallic character.

Carbon and Silicon are non – metals ,Germanium is a metalloid while tin and lead are metals.

The metallic character increases down the group.

Electronegativity.

Carbon is the most electronegative element in the group and the electro negativity decreases
down the group.

Valence, Oxidation state and inert pair effect.

All group IV elements are tetravalent. The sum of the first four ionization energies being very
large, the existence of M4+ ions is unlikely.

Because the electron affinity values for group IV elements being low, M4- ions do not normally
exist.

Inert pair effect

This is more prominent with heavier members of the group.

As the group is descended, the stability of the +4 oxidation state decreases and that of +2
oxidation state increases.

Lead and Tin, though are not transition elements, they exhibit variable oxidation states( variable
valencies)

They can exist as Sn2+ and Pb2+ or Sn4+ and Pb4+.

The lower valence (M2+) is largely ionic, and the M4+ is covalent.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 40

The formation of either +2 or +4 oxidation states are energy dependent. If the energy supplied to
remove the outermost electrons is too high, then the +4 oxidation state is formed and if the
energy supplied is low, then the +2 oxidation state is formed.

CATENATION

Catenation refers to the tendency to form chains of self linked identical atoms. This is the
prominent feature of group IV elements and this tendency decreases down the group.

Why other groups apart from group IV do not show the catenation tendency?

Group I, II and III do not catenate do to their large size that results to the formation of weaker
inter atomic bonds.

Group V, VI and VII do not catenate due to the effect of lone pairs of electrons present in their
hybrid structures. The lone pairs provide the repulsive force when the atoms approach each
other to catenate.

Tendency of complex formation.

The tendency of an atom to form complexes is fovoured by three factors:

(i) High charge

(ii) Small size of the atoms

(iii) The availability of empty orbitals of right enrgy on it.

Carbon atom doesn’t form complex at all. This is because carbon atom can not expand its
valency shell. The remaining elements in the group can form complexes due to their ability to
expand their valency shell.

COMPOUNDS OF GROUP IV ELEMENTS

(i) Hydrides

The elements form covalent hydrides of the formula MH4.

CH4, SiH4, GeH4, SnH4 and PbH4.

The thermal stability of these hydrides decreases down the group.

(ii) Halides.

Group IV elements form tetra halides that are covalent. The halides of carbon are much more
stable and are not hydrolysed. The halides of other elements are easily hydrolysed.

CCl4 and CF4 not hydrolysed

SiCl4 easily hdrolysed.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 41

 Anomalous properties of carbon.

(i) Carbon cannot expand its valency shell while other members of the group can.

(ii) Carbon has a unique ability of forming multiple bonds while other members of the group do
not.

(iii) Its extent of catenation is extreme, it can form branches as well as cyclic chains.

OXIDES

Group IV elements form dioxides of the fomular MO2. CO2 and SiO2 are acidic, GeO2 is less
acidic and SnO2 and PbO2 are amphoteric.

Carbon dioxide is a gas at room temperature while SiO2 is solid at room temperature.

Silicon dioxide has the ability of associating together to form giant molecules. This results to
strong bond that makes the oxide solid. Carbon dioxide molecules have no ability of forming
giant molecules due to the inability of carbon to accept lone pair of electrons.

LEAD

Occurrence and extraction

Lead occurs naturally as Galena, PbS and is extracted by chemical reduction method.

Stages of extraction.

The first stage involves burning of Galena in air, to form either Lead oxide or lead sulphate.

2PbS + 3O2 PbO + 2SO2

PbS + 2O2 PbSO4

Then, the PbSO4 is mixed with sand (SiO2) and limestone (CaCO3) and roasted in the furnance,
where coke is added.

PbSiO4 + SiO2 PbSiO3 + SO3

CaCO3 heat CaO + CO2

CO2 + C 2CO

Autoreduction stage:

PbO + CO Pb + CO2

PbSiO3 + CaO + CO Pb + CaSiO3 + CO2

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 42

Reaction of Lead with acids.

Dilute nitric acids dissolves lead readily

3Pb(s) + 8HNO3(aq) 3Pb(NO3)2. + 4H2O + 2NO

Concentrated nitric acid has little action on lead due to the formation of a protective layer of
oxide on the metal.

Dilute sulphuric acid has no action on lead because any lead (ii) sulphate formed protects the
metal from further attack by the acid.

Concentrated sulphuric acid dissolves because the sulphate formed is soluble in the acid.

Pb(s) + 2H2SO4 PbSO4 + 2H2O + SO2

Concentrated hydrochloric acid attacks lead very slowly liberating hydrogen.

Pb + 2H+ Pb2+ + H2

This displacement is facilitated by the conversion of Lead (ii) ions into soluble complex ions.

Pb2+ (aq) + 4Cl- (aq) [PbCl4]2-(aq)

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 43

 GROUP V ELEMENTS

This group is also known as the Nitrogen family. The group consists of the following elements:

• Nitrogen (N)
• Phosphorus (P)
• Arsenic (As)
• Antimony (Sb)
• Bismuth (Bi)

Group V elements are P – block elements having the outer electronic configuration nS2 nP3.

Nitrogen as the first member of the group differ from the other elements of the group.

This is due to:

(i) The small atomic radius of Nitrogen

(ii) Inability of nitrogen to expand its valence shell

(iii) The great stability of nitrogen as a free element.

The stability of nitrogen is due to the strong triple bond between nitrogen atoms in nitrogen
molecules (N N) in N2.

VARIATION OF PHYSICAL PROPERTIES.

(i) Valency.

All elements in the group except nitrogen contain d – orbitals. In other words, all group V
elements except nitrogen have the ability of expanding their valency shell. Due to this ability of
expanding the valency shell, phosphorus, Arsenic and antimony can form five covalent bonds.

Nitrogen cannot form five covalent bonds due to the inability of nitrogen to expand its valence
shell.

(ii) Inert pair effect.

Inert pair effect is the resistance of the nS electrons to get lost or to participate in covalent
bonding due to poor screening effect caused by inner electrons.

Nitrogen cannot form pentavalent compounds like NCl5 due to the absence of d – orbitals.
Nitrogen is therefore unable to expand its valence shell.

Phosphorus, Arsenic and antimony form pentavalent compounds e.g. PCl5, SbCl5 and AsCl5
because the d – orbitals are available and there is no inert pair effect.

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Although d – orbitals are present in bismuth, it cannot form pentavalent compounds due to inert
pair effect.

(iii) Metallic and nom – metallic character.

As in other groups, the metallic character of group V elements increases down the group. Thus,
Nitrogen, and Phosphorus are non – metals, Arsenic and Antimony are metalloids and
Bismuth is a true metal.

HYDRIDES.

The hydrides of group V elements are NH3, (ammonia), Phosphine (PH3), Arsenic hydride,
(Arsene) (AsH3), Stibine (SbH3) and BiH3.

The stability of these hydrides decreases down the group from NH3 to BiH3. Ammonia has basic
character and its molecules are associated in the liquid state. The lone pair in ammonia gives it
its basic character. Its high electro negativity accounts for the association of liquid ammonia
molecules by hydrogen bonding.

Phosphine (PH3) is a weaker base than ammonia and the basic character decreases down the
group due to increasing difficulty in making nS2 lone pairs available for donation.

THE STABILITY OF THE HYDRIDES.

Group V hydrides are very stable. Their stability is caused by association of the molecules by
hydrogen bonding. The stability of these hydrides decreases gradually from NH3 to BiH3.
This is due to the decrease in the strength of hydrogen bonding as a result of increasing electro
positivity of the group V elements down the group and the lone pairs also becomes less reactive
down the group due to inert pair effect.

The association of group V elements with hydrogen bonding affects the properties of their
hydrides like boiling points and melting points. The boiling points of the hydrides of group V are
as tabulated below:

Hydrides Molecular mass Boiling points (0C)

NH3 17 -33
PH3 34 -85
AsH3 78 -55
BiH3 125 -17

When a graph of Boiling point against molecular mass is plotted, it appears as shown below:

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 45

THE GRAPH OF BOILING POINT AGAINST MOLECULAR MASS FOR GROUP V
HYDRIDES.

B.P

10 20 30 40 50 60 70 80 90 100 110 120 130 140 150

-10 M. weight

-20 BiH3

-30

-40 NH3

-50

-60 AsH3

-70

-80

-90 PH3

-100

-110

-120

From the graph, NH3 has the highest boiling point due to the association of the molecule with
hydrogen bonding caused by highly electro negative nitrogen.

When compared with water, the boiling point of water is higher than that of ammonia. This is
because oxygen produces stronger electro negativity effect than nitrogen that results into stronger
hydrogen bonding ( about two times) than that of ammonia.

From the graph, if NH3 has to behave like other group V hydrides, the melting point of ammonia
would be about -1030C.

HALIDES.

Group V elements form tri halides of the formula MX3 but some members of the group can form
pentahalides.

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Nitrogen does not form pentahalides which are formed by subsequent elements e.g. PCl5 or
SbCl5. The inability of nitrogen to form pentavalent compounds is due to the inability of
nitrogen to expand its valence shell.

OXIDES.

Nitrogen forms a number of oxides of the e.g. dinitrogen oxide (N2O), dinitrogen
pentoxide(N2O5), nitrogen oxide (NO) and nitrogen dioxide (NO2). All other oxides of nitrogen
are acidic except N2O and NO which are neutral.

Phosphorus gives the trioxide (P4O6 and not P2O3), the dioxide (PO2) and the pentoxide (P4O10
and not P2O5). Phosphorus oxides are acidic in nature.

P4O6 + 6H2O 4H3PO3

2PO2 + 3H2O H3PO3 + H3PO4

P4O10 + 6H2O 4H3PO4

DIFFERENCES BETWEEN NITROGEN AND OTHER GROUP V ELEMENTS.

1. Nitrogen is a gas at room temperature while other group V elements are solid at room
temperature.

2. Nitrogen is diatomic while others are tetra – atomic e.g. P4, As4 and Sb4.

3. Oxides of nitrogen are monomeric while the tetra oxides and pentoxide of other elements of
the group are dimeric.

4. Nitrogen cannot form complexes by accepting electron pairs. The other elements form such
complexes due to the presence of available d – orbital.

5. The hydride of nitrogen (NH3), is usually associated with hydrogen bonding but those of the
other elements are not.

THE UNIQUE FEATURES OF NITROGEN THAT MAKE IT DIFFER FROM OTHER

GROUP ELEMENTS ARE:

1. It is small in size

2. It has high electro negativity

3. It has a tendency towards multiple bond formation.

4. Lack the available d – orbital to increase its coordination number above four.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 47

 PHOSPHORUS.

Allotropes.

There are three allotropic forms of phosphorus, white phosphorus, red phosphorus and black
phosphorus.

The black phosphorus is the most stable form of phosphorus. The white phosphorus is a white –
yellow, waxy, poisonous solid which melts 44.20C and boils at 2810C in the absence of air.
White phosphorus is kept under water in which it does not dissolve. White phosphorus may
dissolve in organic solvents like benzene. White phosphorus exists as P4 as shown below:

The P4 molecule.

Red phosphorus is a violet – red powder and it is non – poisonous. It is neither soluble in water
nor in common solvents. When heated without air to about 5000C, it sublimes. On cooling these
vapours, white phosphorus is obtained. Red phosphorus consists of cross – linked chains of P4
units.

The chain of P4 units in a red phosphorus crystals.

Differences between white and red phosphorus.

White Phosphorus Red phosphorus

1. Yellow – white solid Red powder
2. Very toxic Not toxic
3. Ignites in air when dry at 350C. Ignite in air only above 2500C.
4. Soluble in organic solvents Insoluble in common solvent
5. Kept under water Kept under ordinary conditions
6. Reacts with alkali Has no reaction with alkali.

Black phosphorus is obtained by applying high pressure to white phosphorus. At 5500C, black
phosphorus converts to red phosphorus.

CHEMICAL REACTIONS OF PHOSPHORUS.

White phosphorus has no reaction with water, and for this reason it is kept under water.

White phosphorus reacts with air to form a white smoke of phosphorus pentoxide.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 48

P4(s) + 5O2(g) P4O10(s). This reaction is accompanied with the emission of
light instead of heat.

This glow of phosphorus is called phosphorescence. The light emitted is green in colour.

With halogens: White phosphorus reacts spontaneously with chlorine gas to produce
phosphorus trichloride. If Chlorine is in excess, the pentachloride will be formed.

P4(g) + 6Cl2(g) 4PCl3(s). OR

P4(s) + 10Cl2 4PCl5(s).

Red phosphorus will react with chlorine only when heated.

With alkalis: White phosphorus will undergo disproportionation reaction when warmed with a
solution of strong alkali.

P4(s) + 3KOH(aq) + 3H2O PH3 + 3KH2PO2(aq)

By forming potassium hypophosphite (KH2PO2), phosphorus has undergone oxidation and by

forming Phosphine (PH3), it has undergone reduction.

USES OF PHOSPHORUS.

1. Used in the manufacture of large amount of phosphoric acid.

2. Red phosphorus is used in the manufacture of safety matches. The match head contains a
mixture of sulphur and an oxidizing agent like potassium chlorate (KClO3). The match box
surface contains a mixture of red phosphorus and glass powder for causing friction when striken.

3. Used in the manufacture of phosphate fertilizers.

GROUP VI ELEMENTS.
(THE OXYGEN FAMILY)

The members of group VI include the following:

(i) Oxygen (O)

(ii) Sulphur (S)

(iii) Selenium (Se)

(iv) Tellurium (Te)

(v) Polonium (Po)

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Of the group members, Polonium is radioactive. Group VI elements are p – block elements
having the general electronic configuration nS2 nP4.

GENERAL GROUP TREND.

Metallic and non – metallic character.

Oxygen and sulphur are non – metals, Selenium and Tellurium are semi – metals where as
Polonium is a typical radioactive short lived metal. The metallic character decreases down the
group.

Electro negativity.

The electro negativity decreases down the group from oxygen to polonium.

Electronic configuration.

Group VI elements have the outer electronic configuration nS2 nP4. This outer electronic
configuration suggests that, in many of their compounds, the elements complete their octet by the
following ways:

(i) By gaining two electrons to form divalent anion, X2-. This property is shown by all the
members except Polonium which is a metal thus has no tendency of gaining electrons.

(ii) By electron sharing to form covalent single bond or double bond.

Oxidation state.

All the group members except Polonium exhibit the -2 oxidation state. The stability of the -2
oxidation state decreases down the group as the electro negativity of the elements decreases.

The high electro negativity value of oxygen suggests that most of the metal oxides will be ionic
and the oxidation state of oxygen is -2. Oxygen is divalent since it has only two unpaired
electrons and it cannot expand its valence shell. It has no d – orbital available.

1S 2S 2P

In the remaining elements, the d – orbitals are available for bonding and they can form four or
six bonds by unpairing electrons.

Take sulphur as an example.

Ground state Sulphur atom

1S 2S 2P 3d

SP3 hybridization.

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The two unpaired electrons can form two equivalent covalent bonds. Due to SP3 hybridization,
the atom assumes a tetrahedral structure with two positions occupied by lone pairs. Example in
H2S and SCl2.

First excited state sulphur atom:

3S 3P 3d

SP3d hybridization

Four unpaired electrons can form four covalent bonds. Due to SP3d hybridization, the atom has a
trigonal bipyramidal structure with one position occupied by lone pair.

Second excited state sulphur atom.

3S 3P 3d

SP3d2 hybridization

Six unpaired electrons can form six equivalent covalent bonds and form an octahedral structure.

Sulphur is made up of S8 molecules.

S
S

S
S S

S
S

USES OF SULPHUR.

1. Much sulphur is used in the manufacture of sulphuric acid and the related salt, e.g sulphates.

2. Sulphur is needed in the vulcanization of rubber. The soft pliable natural rubber products are
converted into tough ones by heating them with sulphur, the process known as vulcanization of
rubber.

3. It is used in pharmaceutical industries, for example, in the manufacture of sulphur drugs.

4. It is used in the manufacture of matches and gun powder.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 51

CHEMICAL REACTIONS OF SULPHUR.

(a) Sulphur reacts with most metals directly to form sulphides. However, with less reactive
metals, heating is necessary.

Fe(s) + S(s) heat FeS(s)

The more reactive metals may explode in their reactions with sulphur. Sulphur also burns in
Oxygen or air to form sulphur dioxide.

O2(g) + S(s) SO2(g)

Carbon combines with sulphur when heated to produce the liquid carbon disulphide, (CS2).

2S(s) + C(s) CS2(l)

Sulphur combines with chlorine to form sulphur monochloride (S2Cl2) which is a liquid.

2S(s) + Cl2(g) S2Cl2(l)

Sulphur also reacts with oxidizing acids. The most common oxidizing acids are hot concentrated
sulphuric acid and nitric acid.

Hydrochloric acid does not have an oxidizing property at any proportion.

2H2SO4(l) + S(s) heat 2H2O(l) + 3S02(g)

6HNO3 + S(s) heat 2H2O(l) + 6NO2 + H2SO4.

COMPOUNDS OF SULPHUR.

(a) Hydrogen sulphide.

This is the hydride of that can be prepared in the laboratory by reacting an acid with the metal
sulphide. The common reagents for its preparation are Iron (II) sulphide and dilute hydrochloric
acid. Sulphuric acid may also be used.

2HCl + FeS(s) H2S(s) + FeCl2(s)

The gas is slightly soluble in water but may be collected over hot water and can be dried by
phosphorus (V) oxide, P4O10.

Hydrogen sulphide is a colourless poisonous gas with a characteristic of nauseating smell of

rotten egg. It’s bad smell helps people to keep away from it but in high concentration, it may
paralyze the ability to smell it. This property makes it even more dangerous.

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REACTIONS OF HYDROGEN SULPHIDE.

(i) With Chlorine gas:

Hydrogen sulphide will reduce Chlorine gas to hydrogen chloride

H2S(g) + Cl2(g) 2HCl(g) + S(s)

(ii) With nitric acid:

When hydrogen sulphide gas is bubbled through hot nitric acid, sulphur is precipitated and
nitrogen dioxide gas is produced.

H2S(g) + 2HNO3(aq) 2NO2(g) + 2H2O(l) + S(s)

(iii) With aqueous Fe3+ ions:

When hydrogen sulphide gas is bubbled through an aqueous solution of iron (II) chloride, the
colour changes from yellow to pale green. The Iron (III) is thus reduced to iron (II) ions.

H2S(g) + 2FeCl3(aq) 2FeCl2(aq) + 2HCl(aq) + S(s)

(iv) With concentrated sulphuric acid:

Concentrated nitric acid is a drying agent but cannot be used to dry hydrogen sulphide gas
because the two react together.

Sulphuric acid is reduced to sulphur dioxide while hydrogen sulphide is oxidized to sulphur.

H2S(g) + H2SO4(l) 2H2O(l) + SO2 + S(g)

SULPHURIC ACID.

This is normally prepared in the laboratory. When its required, the commercial acid is usually
diluted with water to the required concentration.

When diluting, the concentrated acid is added into water slowly and carefully (almost drop –
wise) with stirring.

Water should never be added into the commercial concentrated sulphuric acid. The dilution
process evolves a lot of heat and this could be dangerous.

Physical properties of sulphuric acid.

Pure sulphuric acid is a viscous liquid which is colourless and odorless. It has a density of
1.84g/cm3 at 150C. The concentrated acid used in the laboratory has a strength of 98%.

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In the complete absence of water, the pure acid will not show any acidic properties, that is it
won’t turn blue litmus paper to red. This is because, the sulphuric acid molecule is covalently
bonded. What water does to the acid is to hydrolyse it and dissociate into ions.

Chemical properties of sulphuric acid.

(a) As a dehydrating agent.

Concentrated sulphuric acid has a very strong affinity for water. A large amount of heat is set
free when the pure concentrated acid is mixed with water. For this reason, it is used to dry gases
which do not react with it like SO2, Cl2, N2 and O2.

The affinity for water is so high that the concentrated acid will take the elements of water from
many organic compounds. For example, sucrose and glucose will give carbon.

C12H22O11(s) conc. H2SO4 12C(s) + 6H2O(l)

Sucrose (brown) Black

C6H12O6 conc. H2SO4 6C(s) + 6H2O.

Glucose (white) Black

The concentrated acid may remove the water of crystallization from hydrated compounds.

For example,

CuSO4.5H2O conc. H2SO4 CuSO4 + 5H2O

Blue White

GROUP VII ELEMENTS (THE HALOGENS).

Group VII elements include the following :

(i) Fluorine ( F )

(ii) Chlorine ( Cl)

(iii) Bromine ( Br )

( iv) Iodine (I)

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(v) Astatine (At).

The elements of this group are called halogens. The name is derived from the Greek words
meaning salt producers.

Electronic configuration.

All halogens atoms have seven electrons in the outermost shell. The general electronic
configuration of the valence shell is nS2nP5.

Oxidation state and valencies.

In all its compounds, Fluorine exists in the oxidation state of -1. The other elements exist in
several as shown in the table below:

Element Symbol Oxidation states

Fluorine F -1
Chlorine Cl -1, +1, +3, +4, +5, +6
Bromine Br -1, +1, +3, +4, +5, +6
Iodine I -1, +1, +3, +5, +6, +7
Astatine At Not known
The oxidation state of fluorine is restricted to one because there is no d – orbital immediately
available to allow the expansion of Valence by excitation. In other halogens, d – orbitals are
available and expansion of valence by excitation is possible.

Fluorine is the most electronegative element and may exist in the ground state only. The other
elements may be in the ground state as well as the first, second and third excited state.

The oxidation state of a halogen atom in a compound depends on the electro negativity of the
other elements bonded to it.

The ground state and excited states of halogens are as shown below:

Ground state

First excited state

Second excited state

Third excited state

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The main tendency of ground state halogen atom is to complete its octet by either formation of a
negative ion or formation of a covalent bond.

The oxidation states exhibited will either be -1 or +1 depending on whether the element
combining with the halogen is less or more electro negative than the halogen.

By gaining one electron, the halogen form the monovalent ions, e.g. F-, Cl-, Br- and I-. This is
possible when the halogens combine with highly electro positive metals.

By sharing electrons, the halogens make covalent bonds either with themselves e.g. F2, Cl2, Br2,
I2 or with hydrogen e.g. HF, HCl, HBr, and HI.

IONIZATION ENERGY.

The ionization energies of halogens are very high indicating that these atoms have very little
tendency to lose electrons. The ionization energy decreases down the group as the atomic size
decreases.

DISSOCIATION ENERGY.

All halogens exist as diatomic gases (X2) at room temperature. i.e. F2, Cl2, Br2 and I2. During
their chemical reactions, halogens must dissociate to gaseous atoms. The energy required for
their dissociation is called dissociation energy. This energy depends on the bond length between
the halogen molecules.

The dissociation energy is inversely proportional to the bond length.

Dissociation energy α 1/ bond length.

The shorter the bond length the larger the amount of dissociation energy and vice versa.
Therefore, it is expected that, the dissociation energy for halogens will be decreasing as moving
down the group due to an increase in atomic radius that results to an increase in bond length.

The dissociation energies for the halogens are as shown below:

Molecule F2 Cl2 Br2 I2

Dissociation energy (Kjmol-1) 142 290 180 161
Fluorine which is expected to have the highest dissociation energy has unexpected low
dissociation energy. This is due to strong repulsive effect of the lone pair. The two repelling
atoms give very weak and unstable bond that require a little amount of dissociation energy.

ELECTRON AFFINITIES.

Electron affinities decrease gradually down the group from Chlorine to Iodine. The electron
affinity of Fluorine is unexpectedly low, even lower than Chlorine. This is due to the fact that
fluorine molecule (F2) has unusual heat of dissociation.

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ELECTRO NEGATIVITY.

Group VII has elements whose electro negativities are higher than those of any other group.
Fluorine is the most electro negative element known. The electro negativity decreases down the
group from fluorine to iodine.

CHEMICAL REACTIONS OF THE HALOGENS.

1. Oxidizing power.

The halogens in general have oxidizing properties. Fluorine is an extremely powerful oxidizing
agent and the oxidizing power decreases down the group as the metallic character increases.

2. Reactivity.

The halogens are so reactive that they will react with nearly all metals and many of non – metals.
Fluorine is the most reactive halogen. The reactivity decreases down the group as the atomic
number increases. Fluorine oxidizes elements to their highest oxidation state.

Reactions of Chlorine.

(i) With water.

When Chlorine is dissolved in water, hypochlorous and hydrochloric acid are formed by
reversible reaction.

Cl2(g) + H2O(l) HClO(aq) + HCl(aq)

If this mixture is exposed to bright sunlight, the hypochlorous acid decomposes to release
oxygen.

2HClO(aq) Strong sunlight 2HCl(aq) + O2(g).

(ii) With Caustic Alkalis (NaOH and KOH).

Chlorine undergoes disproportionation reaction with caustic alkalis. Chlorine reacts with excess
of cold dilute caustic alkali to give a mixture of chloride and hypochlorite.

Cl2(g) + 2OH-(aq) OCl-(aq) + H2O(l) + Cl-

Excess Chlorine reacts differently with hot and concentrated caustic alkalis. It forms a mixture of
Chlorides and Chlorates.

3Cl2 + 6OH-(aq) ClO3-(aq) + 5Cl-(aq) + 3H2O.

(iii) With metals: Chlorine react with metals to produce chloride salts.

2Na + Cl2 2NaCl

Zn + Cl2 heat ZnCl2

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 2 Fe + 3Cl2 heat 2FeCl3

Acidity of the halogens acids.

The halogens acids are HF, HCl, HBr and HI. The acidity of these down the group in the order
HI > HBr > HCl > HF. This acidity trend depends on the ability of an acid to release proton.

Inter – halogens compounds.

Halogens can form compounds among themselves. These are called inter – halogens compounds.
In such compounds, the elements found at the bottom act as metals and those at the top as non –
metals. This is because the metallic character increases down the group.

Examples of inter – halogens compounds include IF, ICl, IF5 etc.

TRANSITION ELEMENTS.

Transition elements are d block elements with partially filled d orbitals. They are called d block
elements because their outermost electrons are occupied in the d orbitals. A transition metal is
one which forms one or more stable ions which have incompletely filled d orbitals. The first
row of these is shown in the shortened form of the Periodic Table below.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 58

The electronic structures of the d block elements shown are:

2 2 6 2 6 1 2 [Ar]3d 4s
21 Scandium, Sc 1s 2s 2p 3s 3p 3d 4s

2 2 6 2 6 2 2 [Ar]3d 4s
22 Titanium, Ti 1s 2s 2p 3s 3p 3d 4s

2 2 6 2 6 3 2 [Ar]3d 4s
23 Vanadium, V 1s 2s 2p 3s 3p 3d 4s

24 Chromium, Cr
2 2 6 2 6
1s 2s 2p 3s 3p 3d 4s
5 1 [Ar]3d 4s

25 Manganese, Mn
2 2 6 2 6
1s 2s 2p 3s 3p 3d 4s
5 2 [Ar]3d 4s

2 2 6 2 6 6 2 [Ar]3d 4s
26 Iron, Fe 1s 2s 2p 3s 3p 3d 4s

2 2 6 2 6 7 2 [Ar]3d 4s
27 Cobalt, Co 1s 2s 2p 3s 3p 3d 4s

28 Nickel, Ni
2 2 6 2 6
1s 2s 2p 3s 3p 3d 4s
8 2 [Ar]3d 4s

1s 2s 2p 3s 3p 3d 4s [Ar]3d 4s
2 2 6 2 6 10 1
29 Copper, Cu

1s 2s 2p 3s 3p 3d 4s [Ar]3d 4s
2 2 6 2 6 10 2
30 Zinc, Zn

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 59

On the basis of the definition outlined above, scandium and zinc don't count as
transition metals - even though they are members of the d block.

On the basis of the definition outlined above, scandium and zinc don't count as
transition metals - even though they are members of the d block.

Scandium has the electronic structure [Ar] 3d14s2. When it forms ions, it always
loses the 3 outer electrons and ends up with an argon structure. The Sc3+ ion has no
d electrons and so doesn't meet the definition.

Zinc has the electronic structure [Ar] 3d104s2. When it forms ions, it always loses
the two 4s electrons to give a 2+ ion with the electronic structure [Ar] 3d10. The
zinc ion has full d levels and doesn't meet the definition either.

By contrast, copper, [Ar] 3d104s1, forms two ions. In the Cu+ ion the electronic
structure is [Ar] 3d10. However, the more common Cu2+ ion has the structure [Ar]
3d9.

Copper is definitely a transition metal because the Cu2+ ion has an incomplete d
level.

When you work out the electronic structures of the first transition series (from
scandium to zinc) using the Aufbau Principle, you do it on the basis that the 3d
orbitals have a higher energy than the 4s orbital.

That means that you work on the assumption that the 3d electrons are added after
the 4s ones.

However, in all the chemistry of the transition elements, the 4s orbital behaves as
the outermost, highest energy orbital. When these metals form ions, the 4s
electrons are always lost first.

You must remember this:

When d-block elements form ions, the 4s electrons are lost first.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 60

To write the electronic structure for Co2+:

Co [Ar] 3d74s2

Co2+ [Ar] 3d7

The 2+ ion is formed by the loss of the two 4s electrons.

To write the electronic structure for V3+:

V [Ar] 3d34s2

V3+ [Ar] 3d2

Scandium has the electronic structure [Ar] 3d14s2. When it forms ions always loses
the 3 outer electrons and ends up with an argon structure.

The Sc3+ ion has no d electrons and so doesn't meet the definition.

Zinc has the electronic structure [Ar] 3d104s2. When it forms ions, it always loses the
two 4s electrons to give a 2+ ion with the electronic structure [Ar] 3d10. The zinc ion
has full d levels and doesn't meet the definition either.

By contrast, copper, [Ar] 3d104s1, forms two ions. In the Cu+ ion the electronic
structure is [Ar] 3d10. However, the more common Cu2+ ion has the structure [Ar]
3d9.

Copper is definitely a transition metal because the Cu2+ ion has an incomplete d
level.

To qualify as a transition element, an element must have partially filled with

electrons in the d – orbital and its ions must have 1 to 9 electrons in the d – orbital.

General characteristics of transition elements:

Because they possess the properties of metals, the transition elements are also
known as the transition metals. These elements are very hard, with high melting
points and boiling points. Moving from left to right across the periodic table, the

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 61

five d orbitals become more filled. The d electrons are loosely bound, which
contributes to the high electrical conductivity and malleability of the transition
elements. The transition elements have low ionization energies. They exhibit a
wide range of oxidation states or positively charged forms. The positive oxidation
states allow transition elements to form many different ionic and partially ionic
compounds. The formation of complexes causes the d orbitals to split into two
energy sublevels, which enables many of the complexes to absorb specific
frequencies of light. Thus, the complexes form characteristic colored solutions
and compounds. Complexation reactions sometimes enhance the relatively low
solubility of some compounds.

Summary of Common Properties

• Low ionization energies

• Variable positive oxidation states
• Very hard
• High melting points
• High boiling points
• High electrical conductivity
• Malleable
• Five d orbitals become more filled, from left to right on periodic table
• form complexes
• form ions which result in a coloured solution
• show catalytic activity

(a) Metallic properties.

All transition elements are metals of high melting point and boiling points. They
have high densities due to their relatively small atomic radii.

The high melting and boiling points are due to strong metallic bond. Electrons are
withdrawn from both 4S and 3d – orbitals to the common cloud of metallic bond.

(b) Variable oxidation state. The interesting thing about transition metals is that
their valence electrons, or the electrons they use to combine with other elements, are
present in more than one shell. This is the reason why they often exhibit several
common oxidation states.
The variable valence is due to the ability of transition elements to lose electrons
from both, the outer quantum shell and the penultimate shell to form ions. The
4s and 3d orbitals have very little energy differences and thus they can both be used
for valence purposes. The most common oxidation state is +2 which is acquired by
losing the two 4s electrons.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 62

The maximum oxidation state of transition elements depends on the number of
unpaired electrons available in the d – orbital.
Examples of variable oxidation states in the transition metals

Iron

Iron has two common oxidation states (+2 and +3) in, for example, Fe2+ and Fe3+. It
also has a less common +6 oxidation state in the ferrate(VI) ion, FeO42-.

Manganese

Manganese has a very wide range of oxidation states in its compounds. For example:

+2 in Mn2+

+3 in Mn2O3

+4 in MnO2

+6 in MnO42-

+7 in MnO4-

(c) Catalytic activity

Transition metals and their compounds are often good catalysts. Transition metals
and their compounds function as catalysts either because of their ability to change
oxidation state or, in the case of the metals, to adsorb other substances on to their

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 63

surface and activate them in the process.

The catalytic activity of transition metals and their compounds is associated with
their variable oxidation state and their ability to accept and donate electrons in
chemical reactions.

Transition metals as catalysts

Iron in the Haber Process

The Haber Process combines hydrogen and nitrogen to make ammonia using an iron
catalyst.

Nickel in the hydrogenation of C=C bonds

This reaction is at the heart of the manufacture of margarine from vegetable oils.

However, the simplest example is the reaction between ethene and hydrogen in the
presence of a nickel catalyst.

Transition metal compounds as catalysts

Vanadium(V) oxide in the Contact Process

At the heart of the Contact Process is a reaction which converts sulphur dioxide into
sulphur trioxide. Sulphur dioxide gas is passed together with air (as a source of
oxygen) over a solid vanadium(V) oxide catalyst.

Iron ions in the reaction between persulphate ions and iodide ions

Persulphate ions (peroxodisulphate ions), S2O82-, are very powerful oxidising agents.
Iodide ions are very easily oxidised to iodine. And yet the reaction between them in
solution in water is very slow.

The reaction is catalysed by the presence of either iron(II) or iron(III) ions.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 64

(d) Magnetic properties.

The magnetic properties of an element or ion are due to the presence of unpaired
electrons. If unpaired electrons are present in an atom or ion or molecules, the
material will be classified as paramagnetic. As the number of unpaired electrons
increases, the material becomes strongly attracted by magnet and it is classified as
ferromagnetic. If unpaired electrons are absent, the material will not respond to
magnetism and it is classified as diamagnetic.

When unpaired electrons are spinning about their own axis, they create small
magnetism that will be attracted by external magnets.
Paired electrons spin in opposite directions and their small magnets cancel each
other. Materials with paired electrons do not respond to external magnetism.

(e) Formation of coloured ions.

Compounds of transition elements are often recognized by their characteristic

colours. The colours are characteristics of the hydrated ions and not of the simple
ions. Transition metal ions exist in aqueous solution as complex ions, where the
metal ion is surrounded by chemical species called ligands. The colour of the
complex ions or complex compounds depend on the type of ligands which are
involved. The following are examples of ligands, and their names arranged
according to their strengths, the strongest at the top.

Ligand Name Type

CN- Cyano Negative
CO Carbonyl Neutral
NO2- Nitro Negative
NH3 Ammine Neutral
H2O Aqua Neutral
OH- Hydroxo Negative
F- Fluoro Negative
Cl- Chloro Negative
Br- Bromo Negative
I- Iodo Negative

Complex compounds of transition metals ions that do not have electrons in the d –
orbitals e.g. Sc3+ or those with d – orbital completely filled with electrons e.g. Cu+
and Zn2+ are colourless. Only those transition metal complexes having partially

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 65

filled d – orbitals exhibit colour.

The table below include some coloured ions and the compounds in which they may
be found.

Ion Colour Compound

[Co(H2O)6]2+ Pinkish – red Cobalt (II) chloride
[Fe(CN)]4- Greenish – yellow Potassium
hexacyanoferrate (II)
[Fe(H2O)6]2+ Pale green Iron (II) sulphate
[Fe(H2O)6]3+ Brownish yellow Iron (III) chloride
[Cu(NH3)4]2+ Deep – blue Tetraamminecopper(II)
sulphate
[Cu(H2O)4]2+ Pale blue Hydrated CuSO4
Cu2+ White Anhydrous CuSO4
Cu+ White Copper (I) chloride

The explanation to why transition elements form coloured complexes is given by the
crystal field theory.

According to this theory, the approach of ligands to the central metal atom causes
the splitting of the five equivalent d – orbitals into two degenerates.

The splitting rises two of the d – orbitals to a higher energy level while the
remaining orbitals occupy the lower energy level as shown below:

Higher energy degenerates

Five equivalent d – orbitals E

Lower energy degenerates

o In each of the four box diagrams (1)-(4) below, the five raised 3d
'degenerate' (meaning equal) orbitals are shown on the left, and the
'splitting' effect of the ligands is shown on the right.
o The lower three 3d orbitals represent the 'new' ground state.
o The upper two 3d orbitals represent either an upper ground state if the
lower 3d levels are fully occupied, or more pertinent to colour theory,

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 66

 a potentially upper excited state if they are not fully occupied.
o We can now consider what possible electronic 'transitions' can take
place for four different ions - coloured and colourless.

The electronic ground states of scandium(III), titanium(III), copper(II) and

zinc(II) are illustrated below.

Note: The splitting effect of the d – orbital depends on the strength of the ligands.
Stronger ligands have stronger splitting effects and vice versa.

THE SPLITTING OF THE d – ORBITALS.

Stronger splitting results into a greater energy difference between the two
degenerates. The larger the energy difference the more electrons will absorb energy
and emit radiations of shorter wavelength and higher frequencies.

Recall this sequence:

V I B G Y O R

Increasing frequencies and decreasing wavelength

V - Violet
I – Indigo
B – Blue
G - Green
Y – Yellow
O – Orange
R – Red

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 67

Electron Movement between the two groups of d – orbitals absorb energy and emit radiadions of
specific wavelengths corresponding for specific colour that we observe.

• The colour arises from electronic transitions from the ground state to excited states, the
energy needed can be calculated using
o Planck's Equation, ΔE = hv , E = energy of a single photon (J), h = Planck's
Constant (6.63 x 10-34 JHz-1), v = frequency (Hz).
o Therefore if the photo energy/frequency is equal to ΔE then energy is absorbed
and an electron can be promoted from the lower 3d level to the higher 3d level.
o If ΔE is in the visible light frequency range the complex will be 'coloured'.
o In the case of coloured transition metal complexes, the colour arises from
visible light energy absorption on promoting electrons from the lower 3d
levels to the higher 3d levels.
• However, this can only occur if there is at least one electron in the 'lower' 3d orbitals and
at least one half-filled 'higher' 3d quantum level, i.e. the minimum pre-conditions for an
electronic transition or 'excitation'.
• Consequently because there a lack of such possible transitions in Sc(III) and Zn(II) their
compounds are usually colourless i.e. no light absorbed in the visible region of the
spectrum
• In the true transition metals from Ti to Cu, it is possible for the electromagnetic radiation
energy to produce this excitation from the lower to the higher 3d sub-levels and it is
usually in the visible region.
• Certain frequencies-frequency ranges of visible radiation are absorbed and the perceived
colour arises from the frequencies not absorbed i.e. the transmitted visible light.
+
o copper(I) cannot form a stable simple Cu (aq) ion, but copper(I) compounds tend
to be colourless when pure e.g CuCl, copper(I) chloride,
2+
o but copper(II) forms the blue square planar [Cu(H2O)4] ion.

(f) Complex formation by transition metals.

A complex is a molecule or ion composed of a central metal atom surrounded by a negative or

neutral ligands.

Neutral complexes or compounds containing complex ions are known as coordination

compound. Most transition metals are known to have the ability to form complexes. This
ability of transition metals to form complexes is attributed to the high polarizing power of their
ions. The ions have small size and have relatively high charge.

Conditions for complex formation.

(i) Every ligand must contain at least one lone pair of electrons. This lone pair is used to form the
coordination bond with the central metal atom.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 68

(ii) The central metal atom must have empty d – orbital into which the ligands will supply the
lone pairs so as to establish a coordination bond.
In other words, The transition metal ion acts as a Lewis Acid and the ligand acts as a Lewis base.
The number of co-ordinate bonds in the complex is the co-ordination number of that
complex. Example of complexes are the tetrachlorocobaltate(II) ion, [CoCl4]2- and the hexaqaua-
iron(III) ion, [Fe(H2O)6]3+.

Ligands can be divided into three categories: unidentate, bidentate and multidentate.
Unidentate ligands can form one co-ordinate bond with a central metal ion. Bidentate ligands can
form two co-ordinate bonds with a central metal ion and so on.

NAMING INORGANIC COMPLEXES.

Rules for naming inorganic complexes.

(i) The anions are always named before the cations. The oxidation state of the central metal atom
or ion is shown by roman numerals in brackets immediately after its name.

(ii) Within a complex, the ligands are named first followed by the central metal ion.
If both, negative and neutral ligands are present, negative ligands are named first followed by
neutral ligands. Within each category, if there are more than one type of ligand, they must be
named in alphabetical order.

(iii) Greek prefixes are used to designate the number of each type of ligand in the complex ion,
e.g. di-, tri- and tetra-. If the ligand already contains a Greek prefix (e.g. ethylenediamine) or if it
is polydentate ligands (ie. can attach at more than one binding site) the prefixes bis-, tris-,
tetrakis-, pentakis-, are used instead.

Number Prefix Number Prefix Number Prefix

1 mono 5 penta 9 nona (ennea)

(pentakis)

2 di (bis) 6 hexa (hexakis) 10 deca

3 tri (tris) 7 hepta 11 undeca

4 tetra (tetrakis) 8 octa 12 dodeca

Note: If the ligang is present only alone, there is no need of using the prefix mono, instead
the ligand is named directly.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 69

Some of the common ligands, both, charged and neutral ligands are as tabulated below:

Anionic Names Neutral Ligands Names

Ligands

Br- bromo NH3 ammine

F- fluoro H2O aqua

O2- oxo NO Nitrosyl

OH- Hydroxo CO Carbonyl

CN- cyano O2 dioxygen

C2O42- oxalato N2 dinitrogen

CO32- carbonato C5H5N pyridine

CH3COO- acetato H2NCH2CH2NH2 ethylenediamine

(en)

(iv). After naming the ligands, name the central metal. If the complex ion is a cation (Cationic
complex), the metal is named same as the element. For example, Co in a complex cation is call
cobalt and Pt is called platinum. If the complex ion is an anion (Anionic complex), the name of
the metal ends with the suffix –ate. For example, Co in a complex anion is called cobaltate and
Pt is called platinate. For some metals, the Latin names are used in the complex anions e.g. Fe is
called ferrate (not ironate).

Examples Give the systematic names for the following coordination compounds:

1. [Cr(NH3)3(H2O)3]Cl3

Answer: triamminetriaquachromium(III) chloride

Solution: The complex ion is inside the parentheses, which is a cation.

The ammine ligands are named before the aqua ligands according to alphabetical order.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 70

Since there are three chlorides binding with the complex ion, the charge on the complex ion
must be +3 ( since the compound is electrically neutral).

From the charge on the complex ion and the charge on the ligands, we can calculate the
oxidation number of the metal. In this example, all the ligands are neutral molecules.
Therefore, the oxidation number of chromium must be same as the charge of the complex ion,
+3.

2. [Pt(NH3)5Cl]Br3

Answer:Choropentaammineplatinum(IV) bromide

Solution: The complex ion is a cation, the counter anion is the 3 bromides.

The charge of the complex ion must be +3 since it bonds with 3 bromides.

The NH3 are neutral molecules while the chloride carries - 1 charge. Therefore, the oxidation
number of platinum must be +4.

3. [Pt(H2NCH2CH2NH2)2Cl2]Cl2

Answer: dichlorobis(ethylenediamine)platinum(IV) chloride

Solution: ethylenediamine is a bidentate ligand, the bis- prefix is used instead of di-

4. [Co(H2NCH2CH2NH2)3]2(SO4)3

Answer: tris(ethylenediamine)cobalt(III) sulfate

Solution: The sulfate is the counter anion in this molecule. Since it takes 3 sulfates to bond
with two complex cations, the charge on each complex cation must be +3.

Since ethylenediamine is a neutral molecule, the oxidation number of cobalt in the complex
ion must be +3.

Again, remember that you never have to indicate the number of cations and anions in the
name of an ionic compound.

5. K4[Fe(CN)6]

Answer: potassium hexacyanoferrate(II)

Solution: potassium is the cation and the complex ion is the anion.

Since there are 4 K+ binding with a complex ion, the charge on the complex ion must be - 4.

Since each ligand carries –1 charge, the oxidation number of Fe must be +2.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 71

The common name of this compound is potassium ferrocyanide.

6. Na2[NiCl4]

Answer: sodium tetrachloronickelate(II)

Solution: The complex ion is the anion so we have to add the suffix –ate in the name of the
metal.

7.[ Pt(NH3)2Cl4]

Answer:tetrachlorodiammineplatinum(IV)

Solution: This is a neutral molecule because the charge on Pt+4 equals the negative charges
on the four chloro ligands.

If the compound is [Pt(NH3)2Cl2]Cl2, eventhough the number of ions and atoms in the
molecule are identical to the example, it should be named: diamminedichloroplatinum(II)
chloride, a big difference.

8. Fe(CO)5

Answer: pentacarbonyliron(0)

Solution: Since it is a neutral complex, it is named in the same way as a complex cation. The
common name of this compound, iron carbonyl, is used more often.

9. (NH4)2[Ni(C2O4)2(H2O)2]

Answer: ammonium bis(oxalato)diaquanickelate(II)

Solution: The oxalate ion is a bidentate ligand.

10. [Ag(NH3)2][Ag(CN)2]

Answer: diamminesilver(I) dicyanoargentate(I)

You can have a compound where both the cation and the anion are complex ions. Notice how
the name of the metal differs even though they are the same metal ions.

EXERCISE.

Write the structure of the following coordination compounds:

1. hexaammineiron(III) nitrate

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 72

2. ammonium tetrachlorocuprate(II)

3. sodium monochloropentacyanoferrate(III)

4. potassium hexafluorocobaltate(III)

Can you give the name of the following coordination compounds?

5. [CoBr(NH3)5]SO4

6. [Fe(NH3)6][Cr(CN)6]

7. [Co(SO4)(NH3)5]+

8. [Fe(OH)(H2O)5]2+

Answers:

1. [Fe(NH3)6](NO3)3

2. (NH4)2[CuCl4]

3. Na3[FeCl1(CN)5]

4. K3[CoF6]

5. Bromopentaamminecobalt(III) sulfate

6. hexaammineiron(III) hexacyanochromate (III)

7.Sulfatopentaamminecobalt(III) ion

8.Hydoxopentaaquairon(III) ion

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 73

Name of Metals in Anionic Complexes

Name of Metal Name in an Anionic Complex

Iron Ferrate

Copper Cuprate

Lead Plumbate

Silver Argenate

Gold Aurate

Tin Stannate

COORDINATION NUMBER AND SHAPES OF COMPLEXES

Coordination number refers to the number of dative bonds that the ligands link with the central
metal atom. Those ligands which link to the central metal atom by only a single dative bond
are called unidentate ligands; for example: H2O, CN-, NH3 etc. Those ligands that link to the
central metal by two dative bonds are called bidentate ligands; for example: Oxalato (C2O42-)
and ethylenediammine (NH2 – CH2CH2 – NH2) or simply (en).

Coordination number two.

Complexes with coordination number two are linear in structure. This coordination number is
predominant with oxidation state +1 metal cation. Examples are:

(i) [Cu(NH3)2]+

(ii) [AgCl2]-

(iii) [Ag(NH3)2]+

(iv) [Au(CN)2]-

(v) [HgCl2]-

The ligand – metal bond angle for these complexes is 1800. Example:

[H3N Ag NH3]+

Coordination number three.

These complexes are trigonal planar in structure with Ligand – Central metal – Ligand bond
angle 1200.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 74

 L

L L

L stands for ligands and M stands for central metal atom.

Complexes with coordination number three are not common.

Note: The direction of arrows are pointing towards the central metal atom because in
complex formation, ligands are normally donating electrons to the central metal.

Coordination number four.

This coordination number assumes two possible structures;

(i) Tetrahedral structures

(ii) Square planar structures

The most common complexes with this coordination number have square planar structures.
Tetrahedral complexes which occur in molecules like methane (CH4) are less common.

The L – M – L bond angle in square planar complexes is 900.

Example:

H3N NH3 2+

Cu

H3N NH3 Square planar complex of [Cu(NH3)4]2+

Coordination number five.

Two structures are possible for coordination number five. These are trigonal bipyramid and
square pyramidal.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 75

Trigonal bipyramid is a common structure for complexes with coordination number five.

Example: [Ni(CN)5]3-

CN NC 3-

Ni

CN NC

NC

The trigonal bipyramidal structure of [Ni(CN)5]3-.

Coordination number six.

Complexes belonging to this coordination number have octahedral structures. For example, the
complex [Fe(CN)6]4- has an octahedral structure.

CN 4-

CN CN

Fe

CN CN

CN

Isomerism of complexes.

The term isomerism refers to the existence of a compound into different structures but of the
same molecular formular.

Complex compounds exhibit different types of isomerism as explained below:

(i) Ionisation isomerism.

In this type of isomerism, the complexes produce different ions in solution .

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 76

For example, [Co(NH3)5SO4]Br and , [Co(NH3)5 Br] SO4 are ionization isomers.

[Co(NH3)5SO4]Br produces [Co(NH3)5SO4]+ and Br- ions in aqueous solution while

[Co(NH3)5 Br] SO4 produces [Co(NH3)4Br]2+ and SO42- ions in aqueous solution.

(ii) Solvate isomerism.

In this type of isomerism, the complexes differ in the amount of water linked to the central atom.

For example, [Cr(H2O)6]Cl3, [Cr(H2O)5Cl]Cl2.H2O and [Cr(H2O)4Cl2]Cl . 2H2O are solvate

isomers.

(iii) Coordinate isomerism.

In this type of isomerism, the complexes differ in the type of ligand linked to each metal. There
is an interchange of ligands.

Examples:

(i) [Co(NH3)6][Cr(CN)6] and [Co(CN)6][Cr(NH3)6]

(ii) [Pt(NH3)4][CuCl4] and [Pt Cl4][Cu(NH3)4]

Hybrid orbitals for metal complexes.

The metal ions accommodate electron pairs from ligands in suitably hybridized metal valence
orbitals. The hybridization decides the geometry of the complex.

The metal should have available number of empty valence hybrid orbitals equals to its
coordination number value.

Consider the following examples:

(i) Tetrahedral [Be(H2O)4]2+ ion.

Be2+ has the electronic configuration 1s22s02p0. This gives rise to sp3 valence hybridization and
four empty hybrids receive electron pairs from H2O ligands.

2S 2P

SP3 hybridization

H2O H2O H2O H2O

The complex is diamagnetic because it is lacking unpaired electrons.

INORGANIC CHEMISTRY NOTES FOR A – LEVEL (IJM) Page 77

(ii) In [Ti(H2O)6]3+.

Electronic configurations:

Ti = [Ar]3d24s24p0

Ti3+ = [Ar] 3d14s04p0.

[Ti(H2O)6]3+ =

3d 4s 4p

H2O H2O H2O H2O H2O H2O

The type of hybridization is d2sp3

The geometrical structure is octahedral

The magnetic property : Paramagnetic due to the presence of one unpaired electrons.

In [Co(NH3)6]3+

3d 4s 4p

[Co(NH3)6]3+ =

N H3 NH3 NH3 NH3 NH3 NH3

The type of hybridization : d2sp3.

Geometrical structure : Octahedral

Magnetic property : Diamagnetic due to the absence of unpaired electron.

Inner and outer orbital complexes.

Complexes can be classified as inner orbital complexes or outer orbital complexes depending on
the nature of ligand linked to the central metal.

Strong ligands like cyano ligand push unpaired electrons inwards and force them to pair up. This
will result to the formation of inner orbital complex.

For example; the complex [Fe(CN)6]4- is an inner orbital complex.

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The electronic configuration of Fe at ground state is:

3d 4s 4p

The electronic configuration of Fe2+ is :

The coming of CN- ligand forces the pairing of the inner electrons.

Fe2+ ion in the complex [Fe(CN)6]4-

3d 4s 4p

CN CN CN CN CN CN

The type of hybridization : d2sp3 hybridization.

The geometrical structure : Octahedral

The magnetic property : Diamagnetic.

[CoF6]3- – hexafluorocobaltate(iii) ion.

This is an outer orbital complex because the fluoro ligands are weak. They cannot force the
pairing of electrons inwards. The six fluoro ligands manage to occupy orbitals in the 4th quantum
shell, 4s,4p and 4d – orbitals.

The resulting hybridization is described as sp3d2.

Co at ground state:

3d 4s 4p 4d

Co3+ =

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[CoF6]3- =

4s 4p 4d

F F F F F F

Sp3d2 hybridization.

The type of hybridization: sp3d2.

Geometrical structure: Octahedral.

Magnetic property : Paramagnetic.

The number and arrangement of ligands of around the central metal ion determines the type of
coordination and the structure of the complex crystals.

The relationship is summarized on the table below:

State of hybridization Shape of complex Number of ligands Bond angle

SP Linear 2 1800
SP2 Trigonal planar 3 1200
SP3 Tetrahedral 4 900
dsp3 Trigonal bipyramidal 4 108028’
Sp3d2 Octahedral 5 1200 and 90o
d2sp3 Octahedral 6 900
6 900

The Chemistry of some transition elements.

SCANDIUM:

Atomic number = 21

Electronic configuration: [Ar] 3d14s2.

Important oxidation state = +3

The Sc3+ is colourless since no 3d – electrons are present.

TITANIUM.

Atomic number = 22

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Electronic configuration : : [Ar] 3d24s2

Important oxidation states: +2, +3 and +4.

Titanium is a strong corrosion resistant metal with a density of about 60% that of iron. Because
of its high corrosion resistant ability, Titanium is useful in aircraft industry where it is used often
in place of steel and aluminium.

VANADIUM.

Atomic number : 23

Electronic configuration: [Ar] 3d34s2

Important oxidation states: +4 and +5.

Atomic number : 24

Electronic configuration: [Ar] 3d54s1

Important oxidation states: +2, +3,+6.

Chromium is a hard and brittle metal that is also very resistant to corrosion.

The most important ore of chromium is chromite, FeCr2O4. This ore may be changed directly
into an alloy by heating with coke.

FeCr2O4 + 4C heat Fe(l) + 2Cr(l) + 4CO

Alloy

The alloy is called ferrochrome and it is used in the manufacture of stainless steel. This is the
type of steel which is very resistant to corrosion.

Of the three oxidation states of chromium, +2, +3 and +6, the +2 oxidation state is characterized
by the blue Cr2+ ion in aqueous solution which is very easily oxidized to +3 state which is the
most stable oxidation state.

Chromium (iii) ion forms many stable complex ions in aqueous solution and it actually exist as
the violet complex ion [Cr(H2O)6]3+

This ion is what gives many chromium (iii) salts their violet colour.

Like, [Al(H2O)6]3+ ion, [Cr(H2O)6]3+ ion is slightly acidic and the acidic strength increases as
the ion becomes progressively hydrolysed.

[Cr(H2O)6]3+ + H2O [Cr(H2O)5OH]3+ + H3O+

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The H3O+ ion liberated is the one that determines acidity.

When a base is added to the solution of the ions, protons are extracted from the water molecules
attached to the chromium and pale blue precipitate is formed.

[Cr(H2O)6]3+ + 3OH- [Cr(H2O)3(OH)3] + 3H2O

Pale – blue precipitate.

The precipitates re – dissolve in additional base or in acid. So, Chromium (iii) ion is amphoteric.

[Cr(H2O)3(OH)3](s) + OH- [Cr(H2O)3(OH)4]-(aq) + H2O.

In acid:

[Cr(H2O)3(OH)3] + 3H+ [Cr(H2O)6]3+ + 3H2O

In the +6 oxidation state, Chromium forms a red oxide, CrO3.

Chromium (vi) oxide is a strong oxidizing agent . When the oxide is heated, it decomposes, to
chromium (iii) oxide and oxygen.

4CrO3(s) + heat 2Cr2O3 + 3O2.

The oxide (CrO3) is called Chromic anhydride because it is soluble in water to form chromic
acid (H2CrO4).

Two species of Chromate ions exist:

One is a yellow Chromate ion (CrO42-) and the other is a red – orange dichromate ion (Cr2O72-).

Both are strong oxidizing agents and exist in equilibrium with each other as:

2CrO42- + 2H+ Cr2O72- + H2O

Yellow Orange

Cr2O72- + OH- CrO42-

COMPOUNDS OF CHROMIUM.

(a) Sodium Chromate (vi), Na2CrO4.10H2O.

It is prepared by heating a mixture of Calcium oxide, anhydrous sodium carbonate and powdered
chromate. Air must be in plentiful supply.

4FeCr2O4(s) + Na2CO3 + 7O2 2Fe2O3(s) +8Na2CrO4 + 8CO2(g).

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The product is further mixed with hot water where the chromate dissolves but the oxide of iron
does not. The salt forms ten water hydrated crystals, Na2CrO4.10H2O.

(b) Potassium chromate (vi), K2CrO4.

Potassium chromate (vi) is prepared in a similar method as that for preparing sodium chromate
(vi) except that during the process, potassium carbonate is used instead of sodium carbonate.

It is very soluble in water and therefore used to precipitate other chromates which are insoluble.

The following are examples of precipitation reactions involving CrO42-:

CrO42-(aq) + Pb2+(aq) PbCrO4(s)

CrO42-(aq) + Ba2+(aq) BaCrO4(s)

CrO42-(aq) + 2Ag+(aq) Ag2CrO4(s)

(c) Sodium dichromate (vi), Na2Cr2O7.2H2O.

Sodium dichromate (vi) is obtained by adding concentrated sulphuric acid in a saturated solution
of sodium chromate. The sulphate formed crystallizes out first and filtered off. The filtrate is
concentrated by evaporation while sodium dichromate (vi) crystallizes out on cooling. The
reddish crystals formed are deliquescent and very soluble in water.

Na2CrO4(aq) +H2SO4(l) Na2SO4 + Na2Cr2O7 + H2O.

(d) Potassium dichromate (vi), K2Cr2O7.

Potassium dichromate (vi) is prepared by mixing saturated solutions of potassium chloride and
sodium dichromate(vi) while hot.

Sodium chloride which is not very soluble in the mixture, crystallizes out, and it is filtered off.
The crystals of K2Cr2O7 form on cooloing.

NaCr2O7(aq) + 2KCl(aq) 2NaCl + K2Cr2O7(aq)

Oxidizing properties of dichromate (vi) ions.

Dichromate (vi) ion acts as powerful oxidant in acidic media. Dilute sulphuric acid is the
commonly used reagent with these ions. In the process of oxidation, the dichromate ion accept
electrons from reductants and get reduced from +6 oxidation state to +3 oxidation state.

The reduction equation is essentially as follows:

Cr2O72-(aq) + 14H+(aq) +6e- 2Cr3+(aq) +7H2O.

Orange Green

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During the process, the orange colour of the dichromate (vi) ion is replaced by the green colour
of the hydrated chromium (iii) ion [Cr(H2O)6]3+ produced.

Examples of reactions:

(i) Conversion of iron (ii) to iron (iii) in acidic medium.

6Fe2+(aq) + Cr2O72-(aq) + 14H+ 6Fe3+(aq) + 2Cr3+(aq) + 7H2O(l).

The color changes in this reactions are not sharp. If the reaction is to be used in titrations, a
suitable redox indicator e.g. diphenylammines must be used for a sharper end point.

(ii) Liberation of Iodine from acidified potassium iodide.

6I-(aq) + 14H+(aq) + Cr2O72-(aq) 3I2(s) + 7H2O + 2Cr3+(aq)

Yellow Brown

The yellow colour due to Cr2O72- is changed to brown as iodine is liberated. The iodine remains
dissolved and masks the green colour of Cr3+.

(iii) Oxidation of hydrogen sulphide to sulphur.

In aqueous solution, hydrogen sulphide dissociates reversibly to release sulphide ions.

H2S(aq) 2H+(aq) + S2-(aq).

The sulphide ions are oxidized by the dichromate (vi) to sulphur which precipitates out.

Cr2O72-(aq) + 14H+ + 3S2-(aq) 2Cr3+ (aq) + 7H2O + 3S(s)

Chromium (iii) hydroxide, Cr(OH)3.

It is sometimes represented as the hydrated oxide of chromium (iii) (Cr2O3. xH2O).

The hydroxide is amphoteric and dissolve in excess base to form soluble complex chromates.

Cr3+(aq) + 3OH-(aq) Cr(OH)3(s).

Cr(OH)3(s) + 3OH-(aq) [Cr(OH)6]3- (aq)

Chromium (iii) hydroxide dissolves in dilute acids to form salt and water.

Cr(OH)3(s) + 3HCl CrCl3aq) + 3H2O.

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Chromium (iii) Chloride.

When dry Chlorine gas is passed over heated chromium metal, anhydrous chromium (iii)
chloride is formed.

3Cl2(g) + 2Cr(s) 2CrCl3(s).

The reddish – violet solid is insoluble in water suggesting some degree of covalency in its bond.

When chromium (iii) chloride is prepared and crystallized from aqueous solutions, dark – green
hexahydrate crystals are obtained.

This compound is known to exhibit hydrate isomerism.

For example;

(i) [Cr(H2O)6]Cl3 which is violet coloured, when is reacted with aqueous silver nitrate, three
moles of silver chloride are precipitated. All the three chloride ions outside the bracket
participate in the reaction.

[Cr(H2O)6]Cl3(aq) + 3Ag+(aq) [Cr(H2O)6]3+(aq) + 3AgCl(s)

(ii) [Cr(H2O)5Cl]Cl2.H2O. This is light green in colour. This isomer reacts with silver nitrate to
precipitate two moles of silver chloride.

Only two chloride ions outside the bracket are precipitated. The Chloro ligand inside the
bracket is the part of the complex ion and therefore is not precipitated.

[Cr(H2O)6]Cl2.H2O(aq) + 2Ag+(aq) [Cr(H2O)5Cl]2+(aq) + 2AgCl(s)

(iii) [Cr(H2O)4Cl2]Cl.2H2O. This is green coloured. Only one mole of silver chloride is
precipitated when this isomer reacts with an aqueous solution of silver nitrate. The two chloro
ligands inside the bracket remain complexed and are not precipitated.

Chromium (iii) sulphate, Cr2(SO4)3.XH2O.

There are several known hydrates of Chromium (iii) sulphate. These hydrates have colours
ranging from violet to green.

The hydrate [Cr(H2O)4(SO4)2]-(aq) gives no precipitates when treated with a solution of Barium
Chloride.

The hydrate [Cr(H2O)6]2(SO4)3 precipitates BaCl2 according to the equation:

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[Cr(H2O)6]2(SO4)3 + Ba2+ BaSO4 + 2[Cr(H2O)6]3+(aq).

MANGANESE.

Atomic number: 25

Electronic configuration: [Ar]3d54s2.

Important oxidation states: +7, +6, +4 and +2.

Compounds of Manganese:

(i) Manganese (vii) Oxide, Mn2O7.

This is prepared by adding potassium permanganate into very cold concentrated sulphuric acid.

2MnO4- (aq) + 2H+(aq) Mn2O7 + H2O .

The oxide separates out as a reddish – brown oil.

Note: No attempt should be made to prepare this oxide in junior laboratories because it is
extremely unstable and may decompose explosively.

Mn2O7 4MnO2 + 3O2

(ii) Potassium manganate (vii), KMnO4.

This compound is commonly known as potassium permanganate. It may be prepared by fusing

manganese (iv) oxide and potassium hydroxide in the presence of an oxidizing agent such as
potassium chlorate.

The product of the above reaction is potassium manganate (vi), K2MnO4.

MnO2(s) + 6OH-(aq) + ClO3-(aq) 3MnO42-(s) + 3H2O + Cl-

Potassium manganate (vi) is extracted from the mixture with water and the resulting solution is
converted to potassium permanganate by oxidation.

In the laboratory, Chlorine may be used to carry out the oxidation.

2MnO42-(aq) + Cl2(g) 2MnO4-(aq) + 2Cl-(aq)

When potassium permanganate is heated, it decomposes to liberate oxygen and form potassium
manganate (vi) as well as manganese (iv) oxide.

2KMnO4(s) heat K2MnO4 + MnO2 + O2(g)

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Oxidizing action of potassium permanganate.

Permanganate ions, MnO4-, are strong oxidizing agents in aqueous solutions. They get reduced in
acidic conditions (normally sulphuric acid) according to the following half ionic equation:

MnO4- + 8H+ +5e- Mn2+ + 4H2O.

During titration involving potassium permanganate, the following should be noted:

(i) The end point is marked by the appearance of a purple colour of the potassium
permanganate.

(ii) The permanganate solution should be added slowly and not rapidly to allow full reaction.

(iii) Only sulphuric acid should be used to acidify the solution. Nitric acid is unsuitable
because itself is an oxidizing agent like the permanganate, and therefore can interfere with the
product of the reaction. Hydrochloric acid is also unsuitable because itself is a reducing
agent and therefore it is oxidized by KMnO4 to Chlorine. The redox reactions involving
potassium permanganate are never carried in basic medium because in basic medium, the
permanganate is converted to a black residue of MnO2 which obscures the end point of the
reaction. If permanganate solution is standardized using oxalate ions, C2O42-, the titration is
conducted using hot oxalate solution of the temperature ranging from 500C to 800C to enhance
the formation of more C2O42- ions in the solution. But this temperature should not exceed this
range so as to avoid the decomposition of oxalate into carbon dioxide and carbon monoxide.

When potassium permanganate is standardized using iron (ii) salts, the Fe2+ ions are to be
derived from FeSO4(NH4)2SO4 and mixed with dilute sulphuric acid so as to avoid the
hydrolysis and air oxidation of Fe2+ to Fe3+ before titration starts. FeSO4 is not used in most
cases, unless prepared by using acidic aqueous solution in which the acid can prevent hydrolysis
and oxidation of Fe2+ ions to Fe3+ ions.
Also the titration of between iron (ii) salts and permanganate must be done in cold conditions
( using cold solution) to avoid the oxidation of some Fe2+ to Fe3+ by heat.

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Note: Potassium permanganate cannot be used as a primary standard because its solution leaves
behind brown deposits of Manganese dioxide. To avoid this precipitation of brown solid of
Manganese dioxide, sufficiently excess of sulphuric acid should be added.

A primary standard is a compound of known concentration, which is used for preparing a

standard solution. A primary standard has the following properties:

(i) Must always be available in a pure form

(ii) Must be stable in air

(iii) Must be readily soluble in a given solvent.

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