1.

1) Atomic Radius.

Definition:

Is the distance of closest approach of one atom to another atom in a bonding situation.

Atomic radius is half the inter-nuclear distance between two identical atoms in a bonding
situation.

At such a distance, the repulsive forces between nucleus-nucleus, electron-electron and

the attractive forces between nucleus-electron just balance.

Trends in Atomic Radius I) Across the period.

Atomic radius decreases across the period. Explanation

• On traversing the period from one element to the next, the additional electron is
added to shells with the same energy ie no new energy level is formed.
• The nuclear charge progressively increases and yet the screening/ shielding effect
of the inner complete shells remains almost constant.
• As a result the effective nuclear charge increases and electrons in the outer most
shell are pulled more strongly leading to a decrease in atomic radius.

Elements At. Electronic

configuration
Num-

ber

Li 3 1S22S1

Be 4 1S22S2

B 5 1S22S22P1

C 6 1S22S22P2

1
 N 7 1S22S22P3

O 8 1S22S22P4

F 9 1S22S22P5

Ne 10 1S22S22P6

The diagram shows how the atomic radius changes as you go across Period 3.

The figures used to construct this diagram are based on:

metallic radii for Na, Mg and Al; covalent radii for Si, P, S and Cl; the van der
Waals radius for Ar because it doesn't form any strong bonds. ii) Down the group

Atomic radius increases down the group in the periodic Table.

Explanation

 On descending any group from one element to the next, electrons are being added
to shells with higher energies (i.e a new electron shell is formed)
 As a result both the nuclear charge and screening effect increase but the increase
in screening effect outweighs that due to nuclear charge.
 The effective nuclear charge therefore decreases , nuclear attraction for the outer
most electrons decreases hence increase in atomic radius.

Element Atomic Configuration

Num-

ber

Li 3 1S22S1

Na 11 1S22S22P63S1

2
 K 19 1S22S22P63S23P64S1

Rb 37 1S22S22P63S23P64S23d104P65S1

Cs 55 --------

Cation is (a positive ion) formed by the removal of one or more electrons from an atom. A
cation is smaller than the atom from which its formed.

Explanation

After the removal of one or more electrons, the number of protons in the nucleus become
greater than the number of remaining electrons, thus the proton-electron ratio increases.

As a result, the nuclear attraction for the remaining electrons increases leading to a
decrease in cationic radius.

An anion (a negatively charged ion) is formed by gain of one or more electrons by an

atom. The radius of an anion is bigger than that of the corresponding atom from which its
formed.

Explanation

After the gain of one or more electrons by an atom, the number of electrons present
becomes more than the number of protons present in the nucleus thus the proton-electron
ratio decreases.

The nuclear attraction for the many electrons now present decreases leading to increase in
anionic radius.

Isoelectronic ions are ions that have the same number of electrons and the same electronic
structure.

For example:

3
 Isoelectronic ions number of electrons

1. Al3+,Mg2+, Na+, F- 10 electrons

2. S2-, Cl-, K+, Ca2+ 18 electrons

isoelctronic ions, Al3+,Mg2+,Na+, F- (ions both have 10 electrons):

• Al3+ has 13 protons, a nuclear charge of +13.

• Mg2+ has 12 protons, a nuclear charge of +12.
• Na+ has 11 protons, a nuclear charge of +11.  F- has 9 protons, a nuclear charge of
+9.

Al3+, with the largest nuclear charge will be expected to have the greatest attraction of
its electrons .

Therefore Al3+ has the smallest ionic radius i.e radius is in the order Al3+ <Mg2+ <Na+ <F-

The radius decreases as the positive nuclear charge increases. Consequently charge
densities and polarizing powers of the ions increase.

Look at the second example of isoelctronic ions, S2-, Cl-, K+, Ca2+ (ions all have 18
electrons):

• S2- has 16 protons, a nuclear charge of +16.

• Cl- has 17 protons, a nuclear charge of +17.
• K+ has 19 protons, a nuclear charge of +19.
• Ca2+ has 20 protons, a nuclear charge of +20.

2. IONISATION ENERGY

The ionization energy of an atom measures how strongly an atom holds its electrons.

Definition:

Ionization energy( 1st ionization energy) of an element is the minimum amount of energy
required to remove an electron completely from the outer most shell of an isolated
gaseous atom to form a unipositively charged gaseous ion.

M(g) → M+(g) + e - H= 1st ionization energy.

Second ionization energy

4
 Is the minimum amount of energy required to remove an electron from the outer most
shell of a unipositively charged gaseous ion to form a dipositively charged gaseous ion.

M+(g) → M2+(g) + e- H= 2nd ionization energy.

The higher the value of the ionization energy, the more difficult it is to remove the
electron.

As electrons are removed, the positive charge from the nucleus remains unchanged,
however, the ionization energy is higher for each subsequent electron.

There is also a big increase in ionization energy for removal of an electron from an inner
shell (lower n value).

This is due to the fact that when you move to an orbital with a lower principle quantum
number, you are removing an electron which is much closer to the nucleus and is being
strongly held by the nucleus.

FACTORS AFFECTING 1ST IONIZATION ENERGY

1)Nuclear charge of an atom.

2)ShieldingScreening
/ effect of inner shells of
electrons.

3)Atomic radius.

Electronic configuration of the outer shell

Explanation

1. Nuclear charge.
 When the nuclear charge is high, the electrons present in the outer most shell are
attracted more strongly by the nucleus.
 Therefore removing an electron from this shell requires more energy leading to
high 1st ionization energy.
 When the nuclear charge is low, the electrons present in the outer shell are
attracted less strongly by the nucleus.

5
  Therefore removing an electron from it requires less energy leading to low 1 st

ionization energy.
2. Shielding effect of inner complete shells of electrons.
 This is the tendency of the inner electrons to screen the other outer electrons from
the nuclear attraction.
 When the screening effect is high, the effective nuclear charge for the outer most
electrons reduces.
 As such less energy is required to remove an electron from the outer most shell
leading to low 1st ionization energy.
 When the screening effect is low, the effective nuclear charge for the outer most
electrons increases.

As a result more energy is required to remove an electron from this outer shell against a
high nuclear attraction.

3. Atomic radius.
If the atomic radius is small, the outer most electrons are closer to the nucleus and
are attracted more strongly by it. Thus removing an electron from this outer shell
requires more energy leading to high 1st ionization energy.

If the atomic radius is large, the outer most electrons are more distant from the
nucleus. There is less attraction from the nucleus, and an electron can be removed
easily leading to a low 1st ionization energy.

4. Electronic configuration of the outer most shell.

 When the first electron is coming from an outer sub-shell which is half full (eg. N:
1S22S22P3), a lot of energy is needed since the unpaired electrons experience
minimum repulsion and the shell is thermodynamically stable.
 When the 1 st
electron is coming from an outer shell which is fully filled e.g Ne:
2 2 6
1S 2S 2P ,a lot more energy is needed to remove it because the shell is
thermodynamically more stable.
 When the 1 st
electron comes from a shell where electron pairing has begun e.g O:
2 2 4
( 1S 2S 2P ), less energy is required because of mutual repulsion between paired
electrons.

Periodic trends in ionization energies

First ionization energies as a function of atomic number

6
Within each period (row) the 1st ionization energy typically increases with atomic number

Within each group (column) the 1st ionization energy typically decreases with increasing
atomic number

The basis for these observations:

As the effective charge increases, or as the distance of the electron from the nucleus
decreases, the greater the attraction between the nucleus and the electron.

The effective charge increases across a period, in addition, the atomic radius decreases

As we move down a group the distance from the nucleus increases and the attraction of
the electrons for the nucleus decreases.

a) 1 st
ionization energy generally increases across the period in the periodic Table.

Explanation

On traversing any period in the periodic Table from one element to the next, electrons are
being added to shells with the same energy as such the nuclear charge progressively
increases while the screening effect of the inner shells remains almost constant.

Consequently, the effective nuclear charge increases leading to a high nuclear attraction
for the outer most electrons. Thus removing the 1st electron requires more energy.

b) 1 st
ionization energy generally decreases down any group in the periodic Table.

Explanation

7
On descending any group from one element to the next in the periodic table, electrons are
being added to shells with higher energy i.e an extra shell of electrons is added.

Thus both the nuclear charge and the screening effect increase but the increase in
screening effect out- weighs that due to nuclear charge.

The effective nuclear charge progressively decreases leading to a decreased nuclear

attraction for the outer most electrons hence 1st ionization energy decreases.

Explanation

 On traversing the short period, lithium to neon, the 1 st

ionization energy increases
in general but there is a break observed at boron and oxygen.
 Lithium, 1S 2S 2 1
has the lowest 1st ionization energy . This is because the single
electron in the outer most 2s shell is weakly held by the nucleus due to the
shielding effect of complete inner 1selectrons.
 Beryllium, 1S22S2 has a higher 1st I.E because the nuclear charge increases
whilst the electron is being added to the same 2s shell. Above all the outer most 2s
shell is full.
 Boron , 1S 2S2 2
2p1 loses the outer most p-electron easily despite an increase in
the nuclear charge because the shielding effect of the interposing complete inner
s-shells increases thus reducing the effective nuclear charge considerably. In
addition, the 2p sub-shell is further from the nucleus than the 2s electron that is
removed from Be (1st I.E of Be > for B).
8
  There after the nuclear charge increases from boron through carbon 1S22S22P2 to
2 2 3
nitrogen 1S 2S 2P , in line with an increase in nuclear charge while electrons are
being added to the same shell.
 At nitrogen, the 2p-subshell is half
full, the three electrons being unpaired
experience minimum repulsion thus thermodynamically stable.
 In the case of oxygen 1S 2S 2P
2 2 4
,electron is being paired in one of the 2p-orbitals
as such there is mutual repulsion between the two paired electrons. An electron
can easily be removed from this outer 2p-shell thus a decrease in 1st I.E is
observed.
 Further increase in ionization energy is observed on traversing the period from
oxygen to neon. This is in line with increase in nuclear charge as the 2p shell is
building up and reaches a maximum at neon, 1S22S22P6 , which has a complete
stable configuration.

A similar trend is observed on traversing the 2nd short period from sodium to argon.

NB:

In every period, noble gases have the highest 1st ionization energy. This is because noble
gases have fully filled outer most shell thus thermodynamically stable.

Helium : 1s2 has the highest 1st ionization energy of all atoms.

This is because Helium atom has the smallest atomic radius therefore electrons in its
outer most shell are closer to the nucleus and are attracted more strongly.

Also it has a stable outer most shell 1s2 .

IMPORTANCE OF IONIZATION ENERGY

Ionization energy provides a basis for understanding the chemistry of an element. The
following information is provided:

1. Atomic number of the element .

This is given by the number of successive ionization energies an atom has got e.g sodium
with 11 successive ionization energies has atomic number 11.

9
 2. The arrangement of electrons in the shells.

A plot of successive ionization energies of calcium shows distinct portions.

Qn.

Element 1st I.E 2nd I.E 3rd I.E 4th I.E

A 800 2400 3700 25000

B 900 1800 14800 21000

C 500 4600 6900 9500

D 1090 2400 4600 6200

E 1310 3400 5300 7500

The table below shows the 1st four ionization energies of elements A-E.

a) Which group in the periodic table does each of the following elements belong:

i) A ii) B iii) C

Give a reason for your answer in each case.

Qn.

Elemen A B C D E F

10
 1st I.E 101 100 125 151 418 590

3 0 5 9

2nd 190 225 229 266 306 114

I.E 4 5 7 5 7 6

3rd 291 338 385 393 439 491

I.E 6 9 3 3 3 6

The table below shows the successive ionization energies of elements A-F.

a) Which element is a noble gas? Give reason for your answer.

b) Which element belongs to :
i) group(i) ii) group(ii).

Give reason for your answer in each case.

Qn.

The table below shows the 1st five ionization energies in K/J per mole for elements W-Z.

Element 1st 2nd 3rd 4th 5th

W 577 1816 2745 11575 13251

X 738 1450 7730 10550 12756

Y 495 4563 6912 9540 11936

11
 Z 1255 2297 3849 5163 13989

a) Identify the group to which each of the elements belong and give a reason for your
answer in each case.
b) Which pair of elements will form :
i) an ionic bond between them?
ii) a covalent bond?
Qn.

The first 8 ionization energies in K/J per mole of an element Y are shown below:

1s 2nd 3rd 4th 5th 6th 7th 8th

7 15 80 32 30 43 60 160 200 236 291

8 00 00 00 00

Which group in the periodic table does element Y belong? Give a reason for your answer.

3. ELECTRON AFFINITY

Non-metallic electronegative elements accept electrons to form anions with a noble gas
like structure as such the concept of electron affinity is more useful or important than
ionization energy.

Electron affinity is defined as the enthalpy change that occurs when a gaseous atom gains
an extra electron to form a univalently charged gaseous anion.

M(g) + e → M-(g) H= 1st Electron Affinity.

12
The electron affinity is a measure of the attraction between the incoming electron and the
nucleus. The higher the attraction, the higher the electron affinity.

First electron affinity:

of an element is defined as the energy released when a gaseous atom gains an extra
electron to form a univalently charged gaseous anion.

X(g) + e → X-(g) H= 1st electron affinity

After the gain of an electron by a gaseous atom, the negatively charged gaseous ion
formed repels any further electron.

Second electron affinity is defined as the amount of energy absorbed/ required when
a univalently charged gaseous anion gains an electron to form a divalently charged
gaseous anion.

X-(g) + e → X2-(g) H=2nd electron affinity

First electron affinity is an exothermic process .

Explanation:

This is because the incoming electron experiences a greater attraction from the nucleus
than repulsion from the electrons already present .

Second electron affinity is an endothermic process.

Explanation:

This is attributed to greater repulsive force which the electron being added experiences
from electrons already present than the attraction from the nucleus, thus work must be
done to over come the effect of repulsion. This work involves input of heat energy.

Note:
13
Because of the same reason, the 3rd ,4th ,5th etc elec- tron affinity will have a positive H sign.

FACTORS THAT DETERMINE THE VALUE

OF 1st E.A
1. Nuclear charge.

2. Atomic radius.

3. Shielding
/ screeningeffect of the inner complete
shells of electrons.

4. Electronic configurati
on of theouter shell of an
atom
Explanation

1. Nuclear charge
If the nuclear charge is high, the nuclear attraction for the incoming electron will be high.
As the atoms gains the electron, a lot of energy is released.

If the nuclear charge is low, the attraction for the incoming electron will be low leading to
a low electron affinity.

2. Atomic radius
If the radius of an atom is small, the incoming electron experiences a high attraction from
the nucleus of the atom. As such a lot of energy is given out as the atom gains the electron
giving rise to a high electron affinity.

If the radius of an atom is large, the incoming electron experiences a weak attraction
from the nucleus of the atom. As such a lot of energy is given out as the atom gains the
electron giving rise to a high electron affinity.

3. Shielding effect of the electrons in the inner shells.

If the screening effect of the electrons in the inner shells is high, electron being added
experiences a low attraction from the nucleus leading to a low value of electron affinity.
14
However, if the screening effect is low, the incoming electron experiences a high
attraction from the nucleus leading to a large value of electron affinity.

4. Electronic configuration of the outer shell.

If an electron is being added to an atom with a stable outer electronic configuration (i.e
half full or fully filled sub shell), the addition will not occur easily leading to a low value
of electron affinity. Variation of electron affinity

i) Across the period.

First electron affinity generally increases on traversing any period in the periodic table.

Explanation:

In moving across from one element to the next, electrons are being added to the shells
with the same energy as a result the nuclear charge progressively increases while the
screening effect of the electrons in the inner shells remains almost constant.

The effective nuclear charge increases leading to increased nuclear attraction for the
electron being added and hence an increase in 1st E.A.

ii) Down the group.

On descending any group in the periodic table, the electron affinity decreases.

Explanation.

15
In moving down the group from one element to the next, electrons are being added to
shells with higher energy levels i.e an extra shell is created.

Both the nuclear charge and shielding effect increase but the increase in shielding effect is
more rapid and outweighs that due to nuclear charge as such effective nuclear charge
decreases.

Thus electron being added experiences a weaker attraction from the nucleus leading to a
decrease in 1st

E.A

1st ELECTRON AFFINITY OF HALOGENS

Element 1st E.A

Fluorine -328

Chlorine -349

Bromine -325

Iodine -295

Trend

The E.A decreases numerically from Chlorine to Iodine.

As the atomic radius increases down the group, the screening effect of the inner complete
shells of electrons increases too.

As such the electron being added experiences a weaker attraction from the nucleus
leading to a decrease in 1st E.A.

Fluorine ,however, has a low value for its electron affinity, numerically less than that for
chlorine.

This is due to very small atomic radius of fluorine atom, the 7 electrons in the outermost
shell are much closer to each other that they repel each other strongly hence the electron
being added experiences a great repulsive force from the electrons already present.

16
Electronegativity:

is the tendency of an atom in a covalent bond to attract/pull the bonding electrons more
towards itself thereby creating partial charges.

17
FACTORS THAT DETERMINE ELECTRONEGATIVITY VALUES

1. Nuclear charge.
2. Atomic radius.
3. Screening effect of inner electrons.
Explanation

1. Nuclear charge.
If the nuclear charge of an atom covalently bonded to another atom is high, the nuclear
attraction for the bonding electrons will be greater leading to a high electronegativity
value.

If the nuclear charge is low, the attraction for the bonding electrons will be weaker
leading to a low electronegativity value.

2. Atomic radius.
If the radius of an atom is small, the bonding electrons are nearer to the nucleus and as
such experience a high nuclear attraction from the electronegative atom leading to a
high electronegativity value.

If the atomic radius is large, the bonding electrons are far from the nucleus and as such
experience a weak attraction from the nucleus leading to a low electronegativity value.

3. Shielding effect of the electrons in the inner shells.

If the screening effect of the electrons in the inner shells is high, the electrons in the
covalent bond experience a low attraction from the nucleus leading to a low value of
electronegativity.

However, if the screening effect is low, the electrons in the covalent bond experience a
high attraction from the nucleus leading to a large value of electronegativity .

VARIATION IN ELECTRONEGATIVITY

Period 3:

18
 Element Na Mg Al Si P S Cl

Electronegativity 0.9 1.2 1.5 1.8 2.1 2.5 3.0

a) Across the period, electronegativity increases from one element to the next.

Explanation:

As one traverses a period from one element to the next , additional electron is added to
shells with the same energy.

As such the nuclear charge increases progressively while the screening effect of the inner
complete shells of electrons remains almost unchanged.

As a result, the effective nuclear charge increases leading to increased nuclear attraction
for the electrons in the covalent bond and hence increase in the electronegativity.

b) Down the group electronegativity generally decreases .

19
Group7

Element Electronegativity

F 4.0

Cl 3.0

Br 2.8

I 2.5

On descending any group in the periodic table from one element to the next, the screening
effect of the inner complete shells of electrons out-weighs the increase in the nuclear
charge due to an extra shell added.

The effective nuclear charge decreases as such the attraction for the electrons in the
covalent bond decreases leading to a decrease in electronegativity.

ELECTROPOSITIVITY

20
This is the tendency of an atom to lose one or more electron(s) from its outer most shell to
form a positively charged ion.

Electropositive elements are those which easily lose one or more electrons to become
positively charged ions. E.g Na, Mg, Ca, K, Rb, Ba etc.

FACTORS THAT AFFECT ELECTROPO-

SITIVITY
1. Atomic Radius

2.Nuclear Charge

3.Shielding effect of the inner complete shells.

4.Electronic configuration.

Explanation:

1. Atomic radius

If the radius of an atom is small, the outer most electrons are nearer to the nucleus and
experience a high nuclear attraction. Its then not easy for an atom to lose electrons leading
to a decrease in electro positivity.

If the radius of an atom is large, the outer most electrons are far from the nucleus and
experience a weak nuclear attraction and as a result they can easily be lost leading to an
increase in electro positivity.

2. Nuclear charge

When the nuclear charge is high, the electrons in the outer shell are attracted more
strongly as such removing an electron is difficult leading to a decrease in electro
positivity.

When the nuclear charge is low, the electrons in the outer most shell are attracted less
strongly as such removing an electron is relatively easy leading to an increase in electro
positivity.

21
3. Shielding effect of inner complete shells

When the shielding effect of the inner complete shells is high, the effective nuclear charge
decreases as such electrons in the outer most shell are less attracted to the nucleus.
Removal of these electrons is easy leading to increase in electro- positivity.

When the screening effect is low, the effective nuclear charge increases as such electrons
in the outer most shell are attracted more strongly to the nucleus. Removal of these
electrons is difficult leading to a decrease in electro positivity.

4. Electronic configuration

If the outer most shell is fully or half filled, it is thermodynamically stable and an electron
can not easily be lost leading to a decrease in electro positivity.

However, when electron pairing begins in one of the orbitals, the paired electrons
experience mutual repulsion between them thus can easily be lost leading to an increase in
electro positivity.

Variation of electro positivity

a) Electro positivity increases in moving down the group in the periodic table.
Explanation:

Down any group in the periodic table ,the increase in the screening effect out-weighs that
due to nuclear charge due to an extra shell of electrons added from one element to the
next.

This decreases the effective nuclear charge as a result the attraction for the outer most
electrons reduces hence they can easily be lost leading to an increase in electro positivity.

b) Electro positivity decreases in moving across the period

Explanation

Across the period, the nuclear charge progressively increases while the screening effect of
the inner complete shells remains almost unaltered from one element to the next as
additional electron is added to shells with the same energy .

This increases the effective nuclear charge as such electrons in the outer most shell are
attracted more strongly leading to increase in electro positivity.

Melting point is the constant temperature at which the pure solid and liquid phases of a
substance co- exist in equilibrium at a given pressure.
22
FACTORS THAT DETERMINE MELTING

POINT

a) metals

The melting points of metals depend on the following factors:

1. The number of electrons available for metallic bonding(delocalized electrons).

The greater the number of electrons contributed for metallic bonding the stronger the
bond and the higher is the melting point.

2. The atomic radius.

When the radius of a metallic atom is small, the bonding electrons are attracted more
strongly by the nucleus making the inter-atomic (element-element) bond length to be
shorter and stronger thus high melting point.

When the radius of a metallic atom is large, the metallic bonding electrons are weakly
attracted by the nucleus as a result the element-element bond becomes longer and weaker
leading to a low melting point.

3. The crystal structure of the element.

b) Non-metals(molecular substances)

Melting points of non-metals depend on:

• Molecular mass
• Shape of molecules
• Type of intermolecular forces of attraction.

Trends in melting points/boiling points across period 2

(Li, Be, B, C, N, O, F, Ne) Observation:

23
The Melting point of elements in period 2 increases from lithium to carbon and then
decreases abruptly for the non metals nitrogen to neon.

Explanation

The increase in melting point or boiling point from Li to C is attributed to:

 Increase in number of electrons available for metallic bonding.

(1 for Li, 2 for Be, 3 for B & 4 for C)

The greater the electrons available, the stronger the bond and the higher the melting
point.

 Decrease in atomic radius from Li to C.

The smaller the atomic radius, the closer are the bonding electrons to the nucleus and thus
the shorter and stronger are the metallic bonds.

Change in the crystal structure of the elements across the period.

Li has a body centred cubic (b.c.c) structure which has its atoms less efficiently packed
than Be with hexagonal closed packed (h.c.p).

Boron and carbon have giant (macro-) molecular structure composed of large number of
covalently bonded atoms with carbon atoms more strongly bonded than boron.

However, the non metallic elements form simple molecular structures held by weak van
der Waals forces of attractions as such have very low melting points.
24
 TRENDS IN MELTING POINTS ACROSS PERIOD 3

The chart shows how the melting and boiling points of the elements change as you go
across the period. The figures are plotted in Kelvin rather than °C to avoid having negative
values.

The melting points increase from Na to Si and drops abruptly for the non metallic elements
phosphorus to argon.

Melting and boiling points rise across the three metals because of the increasing strength of
the metallic bonds.

The number of electrons which each atom can contribute to the metallic bonding increases.

The atoms also get smaller(atomic radius decreases) as you go from sodium through magnesium
to aluminium.

The nuclei of the atoms are getting more positively charged and the bonding electrons are
getting progressively nearer to the nuclei and so more strongly attracted.

Silicon has the highest melting and boiling points because it has a giant covalent structure.

Here strong covalent bonds have to be broken before it

25
melts or boils.

Phosphorus, sulphur, chlorine and argon have simple molecular structures held by weak
van der Waals forces of attractions . Thus their melting points are much lower.

The melting and boiling points of non metals are governed entirely by the sizes of the
molecules.

Phosphorus

Phosphorus contains a smaller P4 molecules. To melt phosphorus you don't have to break
any covalent bonds - just the much weaker van der Waals forces between the molecules.

Sulphur

Sulphur consists of a larger S8 rings of atoms. The molecules are bigger than phosphorus
molecules, and so the van der Waals forces of attractions will be stronger, leading to a higher
melting and boiling point.

Chlorine

Chlorine, Cl2, is a much smaller molecule with comparatively weak van der Waals forces of
attractions, and so chlorine will have a lower melting and boiling point than sulphur or
phosphorus.

26
Trend in melting points of Group 2 elements

The melting and boiling points of g it’s roup 2 metals are higher than those of
corresponding group 1 elements.

Graph of physical data

Explanation of this trend

Melting points generally decrease going down Group

2.

 The Group 2 elements are all metals with metallic bonding. In metallic bonding,
metal cations in a metal lattice are attracted to delocalized electron.
 Therefore going down Group 2:
 the number of delocalized electrons remains the same .
 the charge on each metal cation stays the same at +2, but..
 the atoms become larger so that the positive nucleus gets further away from the
delocalized electrons...

so the force of attraction between the delocalized electrons and the metal cations
decreases.

Although in general the melting point decreases going down the group, the melting point
for magnesium is anomalously low.

27
 This is because magnesium has a different metallic structure from the other elements
in the group apart from Be:

beryllium and magnesium have a hexagonal closepacked structure (h.c.p) calcium and
strontium have a face-centred cubic structure (f.c.c) and barium has a body-centred
cubic structure (b.c.c).

2.

Solubility of ionic salts in water is governed by two energy terms:

I. Lattice energy,
II. Hydration ( solvation) energy. Lattice energy is the amount of energy required to
break 1 mole of an ionic salt into its constituent gaseous ions at standard conditions.

NaCl(s) → Na+(g) + Cl-(g) H = Lattice

energy

Or

Lattice energy is the amount of energy released when 1 mole of an ionic salt is formed
from its constituent gaseous ions at standard conditions.

Na+(g) + Cl-(g) → NaCl(s) H = Lattice energy.

Hydration energy is the amount of energy released when 1 mole of gaseous

ions is fully dissolved in water at a given temperature.

Na+(g) + aq → Na+(aq) H = Hydration energy.

Hydration energy has a negative sign because it involves attraction between a charge and
water molecule which releases energy.

NB:

1. Each ion has its own hydration energy.

Mg2+(g) + aq → Mg2+(aq) HθHyd(298k) = -696kj/mol.

Na+(g) + aq → Na+(aq) HθHyd(298k) = -406kj/mol.

Cl-(g) + aq → Cl-(aq)

HθHyd(298k) = -377kj/mol.

28
 Therefore the HθHyd(298k) of NaCl = (-406 + -377) = 783kj/mol and that of MgCl2 = (-696
+ 2x-377)= 1450.

The smaller the ionic radius the higher the charge density and so the greater(more
negative) the hydration energy.

2. Water is a suitable solvent for dissolving ionic salts because:

• it is a polar solvent,
• has a high dielectric constant.
• has a large dipole moment, so that ion-dipole interaction is high.

If the solvation energy of a substance is greater than its lattice energy, the substance will
dissolve exothermically in the solvent.

If the solvation energy is less than the lattice energy then the substance dissolves
endothermically.

However, if lattice energy is much larger than hydration energy then the salt does not
dissolve in water.

H solution is defined as the heat change that occurs when 1 mole of an ionic salt is fully
dissolved in water at a given pressure.

NaCl(s) + aq → Na+(aq) + Cl-(aq) H = Enthalpy of solution.

Na+(g) +Cl-(g)

H lattice H hydration

29
NaCl(s)

H solution

Na+(aq) + Cl-(aq)

Figure shows Born-Haber cycle for solubility of NaCl.

H solution = H lattice + H hydration

NB:

Whenever this formula is being applied in calculation, the value of H lattice must be
positive. This is because the formula is only valid when the salt is being decomposed as
shown in the cycle above.

Qn1.

The lattice and hydration energies of MgCl2 are -2644 kj/mole and -2653 kj/mole
respectively.

i) Draw an energy diagram/ Born-Haber cycle for the solubility of MgCl2 and
indicate the energy changes that occur. ii) Calculate the enthalpy of solution of the
salt.

Qn2.

i) Using potassium iodide, draw an energy diagram/ Born Haber Cycle to show the
energy changes during solubility of an ionic salt in water.
ii) The enthalpy of solution and lattice energy of po-tassium iodide are +21kj/mol and -
642kj/mol respectively. Calculate the hydration energy for potassium iodide.

Factors that affect lattice energy

• Ionic charge ( charge on the ion e.g Na+, Mg2+, Al3+)

• Ionic radius ( distance between the ions)  Crystal structure of a compound.

Explanation

Lattice energy is directly proportional to the ionic charge.

30
  If ionic charge is large, the electrostatic forces of attraction between the opposite
charges is stronger leading to a high lattice energy.
 If ionic charge is small, the electrostatic forces of attraction between the opposite
charges is weaker leading to a low lattice energy.

Lattice energy is inversely proportional to ionic radius.

 If ionic radius is large, the electrostatic forces of attraction between the opposite
charges is weaker leading to a low lattice energy.
 On the other hand if the distance between the ions is small, the electrostatic forces
of attraction between the opposite charges is greater leading to a high lattice
energy.

Variation in Lattice & Hydration energies

a) Both lattice and hydration energies increase across the period.

Explanation

Across the period, the radius of ions become increasingly smaller and as such the charge
density increases.

This implies that an ion is easily hydrated and also exerts a stronger electrostatic forces of
attraction.

b) Both lattice and hydration energies decrease on de-scending the group.

Explanation.

Down the group, the radius of ions become increasingly larger. As such the charge
density decreases and the ion is less hydrated and also exerts a weaker electrostatic forces
of attraction.

A relationship within the periodic table by which certain elements in the second period
have a close chemical similarity to their diagonal neighbours in the next group of the third
period.

31
 This is particularly noticeable with the following pairs. o Lithium and
Magnesium: o Beryllium and Aluminium:

o Boron and Silicon

Causes of diagonal relationship:

I. Similar electro negativities,

II. Similar atomic & ionic radius ,
III. Similar hydration energies,
IV. Similar electrode potentials,
V. Similar charge densities & similar polarizing pow-

ers,

VI. Similar electropositivities.

Resemblance between Li & Mg

(1) Both react directly with nitrogen to form nitrides on heating.

6Li(s) + N2(g) → 2Li3N(s)

3Mg(s) + N2(g) → Mg3N2(s)

(2) Both react with oxygen gas to form normal oxides only.

4Li(s) + O2(g) → 2Li2O(s)

2Mg(s) + O2(g) → 2MgO(s)

(3) Both their nitrates decompose on heating to form normal oxide, nitrogen dioxide
and oxygen gas.

4LiNO3(g) → 2Li2O(s) + 4NO2(g) + O2(g)

2Mg(NO3)2(g) → 2MgO(s) + 4NO2(g) + O2(g)

32
(4) both form carbonates that decompose on heating.

Li2CO3(s) → Li2O(s) + CO2(g)

MgCO3(s) → MgO(s) + CO2(g)

(5) Both react with carbon when heated to form ionic carbide.

4Li(s) + C(s) → Li4C(s)

2Mg(s) + C → Mg2C(s)

(6) Both form chlorides and bromides that hydrolyze slowly and are soluble in
ethanol;

MgCl2(s) + 2H2O(l) Mg(OH)Cl(l) +

H3O+(aq) + Cl-(aq)

The oxonium ions produced makes the resultant solution acidic.

Resemblance between Beryllium and aluminium:

(1) Both elements are passive to concentrated nitric acid.

(2) Both react with conc. alkalis (to form complex )and mineral acids .(amphoteric
metals)

Be(s) + 2OH-(aq) + 2H2O(l) → Be(OH)42-(aq) + H2(g)

2Al(s) + 2OH-(aq) + 6H2O(l) → 2 Al(OH)4-(aq) + 3H2(g)

Be(s) + 2H+(aq) → Be2+(aq) + H2(g)

2Al(s) + 6H+(aq) → 2Al3+(aq) + 3H2(g)

(3) Both elements form chlorides which are partly covalent and exist as dimmers.

Cl Cl Cl

Cl
33
Cl Be Be Cl Al

Al

Cl Cl Cl

Cl

(4) Their oxides are amphoteric as are their hydroxides.

Oxides

BeO(s) + 2OH-(aq) + H2O(l) → Be(OH)42-(aq)

Al2O3(s) + 2OH-(aq) + 3H2O(l) → 2 Al(OH)4-(aq)

BeO(s) + 2H+(aq) → Be2+(aq) + H2(g)

Al2O3(s) + 6H+ (aq) → 2Al3+(aq) + 3H2O(l)

Hydroxides

Be(OH)2(s) + 2OH- (aq) → Be(OH)42-(aq)

Al(OH)3(s) + OH- (aq) → Al(OH)4-(aq)

Be(OH)2(s) + 2H+(aq) → Be2+(aq) + 2H2O(l)

Al(OH)3(s) + 3H+(aq) → Al3+(aq) + 3H2O(l)

(5) Both their carbides hydrolyze in water to form methane gas.

Be2C(s) + 4H2O(l) → 2Be(OH)2(s) + CH4(g)

Al4C3(s) + 12H2O(l) → 4Al(OH)3(s) + 3CH4(g) Explanation as to why the two

elements (Li & Mg, Be & Al, B & Si) show resemblance in chemical properties:

Similar electro negativities, similar electrode

potentials, similar hydration energies, similar
ionization energies.

34
 their ions have similar charge densities and polarizing powers

The alkali metals are solids with body centred cubic (b.c.c) arrangement.

They have one valence electron with outer most shell electronic configuration of ns1.

They have low melting and boiling point (only one electron available for bond formation).

They have the largest atomic radius and lowest ionization energy in any period.

They are highly electropositive and the most reactive metals.

The alkaline earth metals are electropositive metals with 2 valence electrons (i.e. two
electrons in their outer most shell).

The general electronic configuration of their outer shell is ns2

They have a smaller atomic radii than corresponding group 1 metals.

They have higher melting and boiling points than corresponding group 1 metals.

They have a higher 1st ionization energies than corresponding elements in group 1.

They are less electropositive, less reactive and form more covalent compounds than group
1.

35
1. Reaction with Hydrogen.
The more electropositive metals of group 1 & 2 react with hydrogen to form ionic hydride
except Be and Mg which form covalent hydride.

2Na(s) + H2(g) → 2NaH(s)

Ca(s) + H2(g) → CaH2(s)

The ionic hydrides are hydrolyzed by water to form hydroxide and hydrogen gas.

NaH(s) + H2O(l) → NaOH(aq) + H2(g)

2. Reaction with Water.

All group 1 metals react with water more vigorously than their group II counterparts to
form corresponding hydroxide and hydrogen gas. The vigor of reaction increases down
the group.

Explanation

These metals form positive ions in the course of their reaction. Group I lose one electron
while group II lose two electrons. Therefore less energy is required to remove one
electron than two from the outer most shell as such group I metals react faster with water
than corresponding metals of group II.

As the atomic radius increases down the group, ionization energy decreases thereby
increasing reactivity in each group. The lower the ionization energy, the lower the
activation energy for reaction and thus the faster the reaction.

 2X(s) + H O(l) → 2XOH(aq) + H (g).

2 2 X = Li, Na, K, Rb, Cs.
 Be does not react with water.
 Magnesium has a very slight reaction with cold water, but burns in steam to form
white MgO and hydrogen gas.

Mg(s) + H2O(l) → Mg(OH)2(aq) + H2(g)

(with cold water)

36
Mg(s) + H2O(g) → MgO(s) + H2(g) . ( with steam)

 Ca, Sr, and Ba react with increasing vigor with cold water to form corresponding
hydroxide and hydrogen gas.

X(s) + 2H2O(l) → X(OH)2(aq) + H2(g)

X= Ca, Sr,& Ba.

NB

The hydroxides of Be & Mg have low solubility in water. However the solubility of
hydroxides increase from Ca(OH)2 through Sr(OH)2 to Ba(OH)2 .

Explanation

Down the group, the radius of the cations increase while the charge on them remains the
same. This leads to a decrease in both the lattice and hydration energies.

Therefore the increase in solubility of the hydroxides down the group is attributed to the
fact that the lattice energy of the hydroxides decrease more rapidly than the hydration
energy.

As such the lattice energy is easily superseded by the hydration energy thus facilitating
solubility of the hydroxides.

See table below.

Hydrox- Solubility per 100g of water at 250c

ide

Be(OH)2 0.00

Mg(OH)2 0.01

Ca(OH)2 0.15

Sr(OH)2 0.89

Ba(OH)2 3.32

37
3. Reaction with Acid.

i) Dilute and concentrated hydrochloric acid

They react similarly with group 2 metals to form corresponding salt and liberating
hydrogen gas.

M(s) + 2H+(aq) → M2+(aq) + H2(g) M= Be, Mg, Ca, Sr, Ba.

ii)Dilute sulphuric acid.

Be reacts with hot dilute sulphuric acid to form salt and hydrogen gas.

Be(s) + 2H+(aq) → Be2+(aq) + H2(g)

Mg reacts with cold dilute to form salt and hydrogen gas.

Mg(s) + 2H+(aq) → Mg2+(aq) + H2(g)

Ca, Sr & Ba react to form a sparingly soluble sulphate which renders the reaction passive.

iii) Conc. sulphuric acid

Be reacts in the same way as with dilute sulphuric acid.

However other members of the group react with conc. sulphuric acid to form salt, sulphur
dioxide and water.

M(s) + 2H2SO4(l) → MSO4(aq) + SO2(g) +

2H2O(l) M = Mg, Ca, Sr, Ba. iv) Nitric acid.

Be does not react with nitric acid at all conditions.

Mg reacts with dilute nitric acid to form salt and hydrogen gas.

Mg(s) + 2HNO3(aq) → Mg(NO3)2(aq) + H2(g)

Mg reacts with conc. nitric acid to form salt, nitrogen dioxide and water.

Mg(s) + 4HNO3(aq) → Mg(NO3)2(aq) + 2NO2(g) + 2H2O(l)

Ca, Sr & Ba react with nitric acid to form salt, nitrogen dioxide and water.

Ba(s) + 4HNO3(aq) → Ba(NO3)2(aq) + 2NO2(g) + 2H2O(l)

38
4. Reaction with Oxygen.

The s-block elements react with oxygen to form 3 types of oxides namely 
Normal oxide (O2-)

 Peroxide (O22-)
 Superoxide (O2-)

All group 1 metals form normal oxide with oxygen.

4X(s) + O2(g) → 2X2O(s) X= Li, Na, K, Rb, Cs.

Elements Na to Cs in addition form peroxides of the type X2O2

2X (s) + O2(g) → X2O2(s) X= Na, K, Rb, Cs.

Elements K to Cs in addition form superoxide.

X(s) + O2(g) → XO2(s) X= K, Rb ,Cs NB:

Li can not form higher oxides due to the fact that Li+ is very small, with high charge
density & high polarizing power. Thus the larger oxides can not be accommodated around
it otherwise the compound would be highly covalent & unstable.

All group 2 metals when heated form normal oxide in oxygen.

2M(s) + O2(g) → 2MO(s) M= Be, Mg, Ca, Sr, Ba

The more electropositive metals form peroxides e.g Sr & Ba.

M(s) + O2(g) → MO2(s) M = Sr, Ba NB:

The tendency to form peroxide increases down the group. This is because the radii of the
cations increase down the group, as such their charge densities and polarizing powers
decrease. Therefore the larger peroxide can easily be accommodated around the cation
with least polarization forming stable lattice.

Beryllium oxide is amphoteric, shows both basic and acidic properties.

The other oxides are ionic and basic in nature.

39
(5) Reaction with halogens.

All the metals of group 1 & 2 combine directly under heat to form chlorides.

2Li(s) + Cl2(g) →2LiCl(s)

Mg(s) + Cl2(g) → MgCl2(s)

1) Compounds of group(ii) tend to be less ionic than those of group(i).

Explanation:

 The cations of group 2 have smaller ionic radius than corresponding group 1.
 Group 2 cations are doubly charged while those of group 1 are singly charged.
 Therefore cations of group 2 have higher charge density and more polarizing
power than corresponding group 1. As such compounds of group 2 are less ionic
than corresponding group1 compounds. e.g. MgCl2 and NaCl.
2) Salts of group 2 elements are less soluble in water than the corresponding group 1
salts.

Explanation

 The cations of group 2 have smaller ionic radius than corresponding group 1.
 Group 2 cations are doubly charged while those of group 1 are singly charged.
 Therefore the lattice energy of group 2 salts are much higher than those of
corresponding group 1 salts.

The higher lattice energy of group 2 salts make them less soluble than their corresponding
group 1 salts.

SULPHATES OF GROUP 1 & 2

Sulphates of group 1 are white solids which are stable to heat and are readily soluble in
water.

40
Sulphates of group 2 are white solids and sparingly soluble in water. Their solubility
decrease down the group.

Sulphate Solubility per 100g of water at 250c

BeSO4 43

MgSO4 36

CaSO4 0.20

SrSO4 0.011

BaSO4 0.0024

Explanation.

Down the group, the radius of the cations increase while the charge on them remains the
same. This leads to a decrease in both the lattice and hydration energies.

Therefore the decrease in solubility of the sulphates down the group is attributed to the
fact that the hydration energy of the suphates decreases more rapidly than the lattice
energy down the group.

NB

Solubility of the nitrates , carbonates and chromates are similar to those of the sulphates.

CARBONATES OF GROUP 1 & 2

The carbonates of group1 metals are white solids ,readily dissolve in water and are stable
to heat except lithium carbonate which decomposes on heating.

Li2CO3(s) → Li2O(s) + CO2(g)

Explanation

41
Li+ ion has a very small radius giving it a high charged density and a high polarizing
power. As such the smaller oxide ion (O2-) with a similar charged density approaches the
Li+ ion with least polarization thus forming a stable oxide.

However, as the group is descended the radii of the cations increase and their charged
densities decrease. Thus they can not easily be accommodated around the smaller oxide
ion due to its high polarizing effect.

Carbonates of group 2 decompose on heating to form the metal oxide and carbondioxide
gas.

XCO3(s) → XO(s) + CO2(g) X= Be, Mg, Ca, Sr, Ba.

The thermal stability of the carbonates increases as the group is descended.

Carbonate Decomposition temp. 0C

BeCO3 100

MgCO3 350

CaCO3 900

SrCO3 1290

BaCO3 1350

Explanation

On descending the group, the charged densities of the metal cations progressively
decrease due to increase in cationic radius.

Since an oxide is smaller than a carbonate, the decomposition of metal carbonates become
less energetically favourable down the group.

NITRATES OF GROUP 1 & 2

Group 1 nitrates (except lithium nitrate) decompose to form nitrites and oxygen.

42
 2XNO3(s) → 2XNO2(s) + O2(g) X= Na, K, Rb, Cs.

However lithium nitrate decomposes to form metal oxide, nitrogen dioxide and oxygen.

4LiNO3(s) → 2Li2O(s) + 4NO2(g) + O2(g)

Explanation

The oxide(O2-)ion is much smaller than the NO3- ion. Li+ ion has a very small radius
giving it a high charge density and a high polarizing power.

As such the smaller oxide ion (O2-) with a similar charged density approaches the Li+ ion
more closely with least polarization thus forming a stable oxide.

However, as the group is descended the radii of the cations increase and their charge
densities decrease. Their nitrates decompose to a relatively smaller nitrites. The decrease
from nitrate to nitrite stabilizes the compound.

COMPLEX FORMATION BY GROUP 2 CATIONS

Complex ion formation is favoured by:

 Presence of empty orbitals on the cations to accommodate the lone pairs of

electrons donated by ligands.
 Small radius of cation.
 High charge on the cation.

E.g Be(OH)4-, Be(H2O)42+

Beryllium cation forms complex easily due to its very small ionic radius & high charge
density.

The tendency to form complex ions decreases rapidly down the group with increasing
cationic radius & decrease in the charge density of cations. This is because the attraction
for the lone pairs of electrons on the ligands decrease.

Reactions in which Be resembles other group 2 elements include:

 All burn in air to form normal oxide.

 All react with chlorine gas when heated to form chloride.
 All react with dilute hydrochloric acid liberating hydrogen gas.

43
Reactions in which Be differs from other group 2 metals include:

• Be reacts with conc. alkalis but others don’t.

• BeO oxide is amphoteric, reacts with both acid and alkalis. Other oxides of the
group are basic in nature.
• Be carbide reacts with water to form methane.

Other members of the group don’t.

• Be forms chloride which is partly covalent and exist as dimmers. Other members
form ionic chlorides.
• Be forms only one type of oxide, the monoxide . Other members form more than
one type of oxide.

Qn.

A chloride of beryllium Z, contains 11.25% beryllium and 88.75% of chlorine.

i) Calculate the empirical formula of Z.

ii) Determine the molecular formula of Z(vapor den-sity of Z=80). iii) Write the
structural formula of Z.

Qn.

A chloride of aluminium X, contains 20% aluminium and 80% chlorine.

i) Calculate the empirical formula of X.

ii) Determine the molecular formula of X(vapor den-sity of X= 133.5). iii) Write the
structural formula of X.

Qn.

When 0.13g of a chloride of iron was vaporized at 600k and 1 atmosphere pressure,
20cm3 of vapor was formed.

i) Calculate the relative mass of iron chloride.

ii) Determine the molecular formula of the iron chlo-ride.
iii) Write the structural formula of the iron chloride.
Qn.

44
i) Compare the reaction of beryllium and barium with sulphuric acid under various
conditions.
ii) Explain how the solubility and basicity of the hy-droxides of the elements of group 2
in the Periodic Table vary down the group.

Qn.

Describe the reactions, if any, between each of the following elements, Be, Mg and
Ca with: i) warm dilute sulphuric acid. ii) warm conc. sodium hydroxide.

Ore of aluminium is called Bauxite, Al2O3.xH2O Impurities found in the ore are:

• Silica, SiO2
• iron(iii) oxide,Fe2O3

In order to obtain pure aluminium, the ore must first be refined to eliminate the impurities
stated above.

Purification of bauxite

The ore is roasted and then crushed to powder.

Conc. sodium hydroxide is added to dissolve the amphoteric oxide, Al2O3 and the acidic
oxide SiO2

The impurity, Fe2O3 , is eliminated by filtering off.

Aluminium is then re-precipitated as Al(OH)3.xH2O by either:

i) by adding a little prepared aluminium hydroxide to the filtrate.

Al(OH)4-(aq) → Al(OH)3(s) + OH-(aq) ii) by bubbling CO2 gas through the

filtrate to remove the excess OH- ions.

45
2Al(OH)4-(aq) + CO2(g) → 2Al(OH)3(s) + CO32-

(aq)

The hydroxide, Al(OH)3 is heated to form aluminium (III)oxide.

2Al(OH)3 → Al2O3(s) + 3H2O(g)

Extraction of Aluminium ( By electrolysis of the fused ore)

The pure oxide is 1st dissolved in molten cryolite (sodium aluminium fluoride - Na3AlF6)
to lower its melting point.

The melt is then electrolyzed at a temperature between 800-900 0c at a high current

density between graphite electrodes.

Molten aluminium sinks to the bottom at the cathode where it is tapped off while oxygen
is liberated at the carbon anode.

Cathode: Al3+(l) + 3e- → Al(l)

Anode: 2O2-(l) → O2(g) + 4e-

The electrolysis cell

Reactions of aluminium a) Reaction with

water.

46
Aluminium reacts slowly with steam to form the oxide and hydrogen gas.

2Al(s) + 3H2O(g) → Al2O3(s) + 3H2(g) b) Reaction with chlorine.

Aluminium when heated reacts with dry chlorine to form a chloride which sublimes. The
chloride is predominantly covalent.

2Al(s) + 3Cl2(g) → 2AlCl3(s)

Explanation

Aluminium forms a smaller cation with high charge density & high polarizing power. It
distorts the electron cloud of surrounding anions. The larger the anion, the greater the
extent of polarization. Therefore the large chloride ion is polarized greatly and as such a
covalent character is induced.

The chloride forms dimer , Al2Cl6 , at high temperature with a chloride bridge structure.
Aluminium bromide & iodide have similar structures.

c) Reaction with solution of alkalis (NaOH & KOH).

Aluminium is an amphoteric metal. It reacts with concentrated alkalis to form aluminates

complex and hydrogen gas.

2Al(s) + 2OH-(aq) + 6H2O(l) → 2 Al(OH)4-(aq) + 3H2(g) d) Reaction with acids.

With dilute mineral acids except nitric acid, aluminium forms salt and hydrogen gas.

2Al(s) + 6H+(aq) → 2Al3+(aq) + 3H2(g)

With hot conc. H2SO4, aluminium forms salt, sulphurdioxide gas and water.

2Al(s) + 6H2SO4(aq) → Al2(SO4)3(aq) + 3SO2(g) + 6H2O(l).

Aluminium does not react with dilute nitric acid . The metal is rendered passive due to the
formation of an impervious layer of oxide.

The acidity of the hexa-aqua ions

In aqueous solution, soluble salts of aluminium i.e. AlCl3, Al2(SO4)3 etc exist as
[Al(H2O)6]3+.

The resultant solution is acidic due to hydrolysis reactions:

47
white ppt

The hydroxonium ions produced make the resultant solution acidic with PH less than 7
and a white solid is formed.

If sodium carbonate solution is bubbled through aqueous solution of aluminium salts,

bubbles of a colorless gas that turns lime water milky is formed.

The oxide and hydroxide of aluminium are amphoteric. They react with both conc. alkalis
and dilute acids.

Some uses of aluminium include:

48
 Aluminium is used for: Because

1. Aircraft light, strong, resists corrosion

2. other transport such as ships' light, strong, resists corrosion

superstructures, container vehicle bodies, tube
trains

3. overhead power cables . light, resists corrosion, good

conductor of electricity

4. Saucepans light, resists corrosion, good

appearance, good conductor of heat

(Carbon, Silicon, Germanium, Tin, and Lead)

49
  All group(iv) elements have four electrons in their outermost shell with a general
2 2
outer configuration of ns np

n=2 for C, n=3 for Si, n=4 for Ge, n=5 for Sn n=6 for Pb etc

 Metallic character increases down the group as the radius of the atoms become larger.
Carbon and Silicon are non metals , Germanium is a metalloid ie it exhibits properties
characteristics of metals and non metals. While Tin & Lead are weak metals.eg they
form amphoteric oxides
 All elements show an oxidation states of +2 and +4. The +2 oxidation state arise due
to the inability

of the outer most paired ‘s’ electrons to take part in bond formation. This is called the
inert pair effect.

 The stability of the +2 oxidation state increases down the group from carbon to lead.
This is due to increasing metallic character and increasing inert pair effect as the
group is descended.eg Carbon and Silicon form extremely unstable compounds in +2
oxidation state.
 Germanium and tin compounds in +2 oxidation state are predominantly covalent and
are readily oxidized ie they are powerful reducing agent.
 Lead invariably forms more stable compounds in +2 oxidation state than +4 oxidation
state. Also compounds of lead in +2 oxidation state are ionic in nature. Therefore lead
(iv) compounds are unstable, and readily decompose to +2 oxidation state.eg

2 PbO2(s) → 2PbO(s) +O2(g)

PbCl4(l) → PbCl2(s) + Cl2(g)

 The stability of +4 oxidation state decreases down the group. Carbon , silicon and
germanium form more stable compounds in +4 oxidation state than in +2. This could
explain why their compounds in +2 oxidation states are good reducing agents.
 Carbon is the only member of the group whose covalency is restricted to a maximum
of +4.This is

due to absence of the vacant ‘d’ orbitals. Other elements have a maximum of +6 due
to the availability of vacant d-orbitals which allows them to expand their octet.

 Hoverer, all the elements exhibit a covalency of

4 but compounds of the type M4+ or M4- are rare.

This is because the sum of the first four ionization energies or first four electron
affinities would be highly endothermic. An ion of the type M4+ would be very

50
 small with high charged density as such would exert high polarizing effect on the
surrounding anion thus making the compound formed highly covalent & unstable.

NB:

Carbon, however, being the most electronegative with the smallest atomic radius
and least number of electrons is most likely to form compounds of the type M4+ or
M4-

 Carbon exhibit a unique property of catenation. This is the ability of an element to

form covalent bonds with its own atoms so as to produce long chains and rings.
 Carbon therefore form limitless hydrides, alkanes, alkenes, alkynes etc due to
catenation. This unique property of carbon is attributed to the small atomic radius of
carbon. The electrons involved in bond formation between two carbon atoms are
closer to the nuclei and are strongly

held by it thus making bonds very strong and stable. However as you descend the
group, atomic radius increases. Therefore electrons between the atoms become
more distant from the nuclei making the bond weaker and unstable.

 The melting points of group(iv) elements decrease as the group is descended. Carbon,
however, has a much higher melting point than others. This is because carbon has a
giant molecular (Macro-molecular) structure composed of many atoms due to its
ability to catenate. It has abnormally high melting point because large number of short
and strong carbon –carbon bonds have to be broken before it melts.

Melting point then decreases gradually from silicon to lead in line with increase in atomic
radius down the group. The inter-atomic bond length (element-element bonds) become
longer and weaker thus melting point decreases.

CHEMICAL PROPERTIES OF GROUP (IV) ELEMENTS.

1.Reaction with water.

Carbon reacts with steam when heated to form carbon monoxide and hydrogen gas.

C(s) + H2O(g) → CO(g) + H2(g)

Silicon reacts with steam when heated to form silicon dioxide and hydrogen gas.

Si(s) +2H2O(g) → SiO2(s) + 2H2(g)

Germanium and Tin do not react with water at any condition.

Lead reacts slowly with soft water forming lead(ii) hydroxide.

51
2Pb(s) + 2H2O(l) + O2(g) → 2Pb(OH)2(s)

NB

The above reaction leads to lead poisoning and explains why lead pipes are not used for
transporting water for drinking.

2. Reaction with Oxygen (air).

a) Carbon.
When carbon is heated in limited air, carbon monoxide is formed and in excess air,
carbondioxide is formed.

2C(s) + O2(g) → 2CO(g)

C(s) + O2(g) → CO2(g)

b) When the rest of the elements are heated with oxy-gen , they form dioxides except
lead which forms lead(ii) oxide.

Si(s) + O2(g) → SiO2(s) Ge(s) + O2(g)

→ GeO2(s) Sn(s) + O2(g) → SnO2(s)

2Pb(s) + O2(g) → 2PbO(s)

3. Reaction with acids.

a) Carbon is attacked by all oxidizing acids eg hot conc. Sulphuric acid and hot conc.
Nitric acids.

C(s) + 4HNO3(aq) → CO2(g) + 4NO2(g) + 2H2O(l) C(s) + 2H2SO4(aq) →

CO2(g) + 2SO2(g) +2H2O(l)

b) Silicon is resistant to all acids except hydrofluoric acid (HF)

Si(s) + 6HF(aq) → H2SiF6(aq) + 2H2(g)

c) Germanium, Tin and Lead are oxidized by hot conc. nitric acid
3Ge(s) + 4HNO3(aq) → 3GeO2(s) + 2H2O(l) +4NO(g)

52
3Sn(s) + 4HNO3(aq) → 3SnO2(s) + 2H2O(l) +4NO(g) Pb(s) +4HNO3(aq) →
Pb(NO3)2(aq) + 2H2O(l) +

2NO2(g)

Lead is rendered passive in both cold dilute hydrochloric and sulphuric acids due to
formation of insoluble salt of lead(ii) chloride & lead(ii) sulphate respectively.

However, lead reacts with hot dilute hydrochloric acid to form lead(ii) chloride and
hydrogen gas.

Pb(s) + 2HCl(aq) → PbCl2(aq) + H2(g)

Tin reacts with hot conc. Sulphuric acid to form tin(iv) sulphate.

Sn(s) + 4H2SO4(aq) → Sn(SO4)2(aq) + 2SO2(g) +

4H2O(l)

Lead reacts with hot conc. Sulphuric acid to form lead(ii) sulphate, sulphur dioxide and
water.

Pb(s) + 2H2SO4(aq) → PbSO4(s) + SO2(g) +

2H2O(l)

This reaction is similar to Al & Chromium

4. Reaction with Alkalis

Carbon is resistant to alkalis but silicon dissolves in conc. Solution to form silicate.

Si(s) + 2NaOH(aq) + H2O(l) → Na2SiO3(aq) +

2H2(g)

( 2KOH(aq))

Germanium dissolves in conc. Alkalis to form hexahydroxo-germanate (iv)

Ge(s) +2KOH(aq) +4H2O(l) → K2Ge(OH)6(aq) +

2H2(g)

Ionically:

Ge(s) + 2 OH-(aq) + 4H2O(l) → Ge(OH)62-(aq)

53
 + 2H2(g)

Tin and Lead dissolve slowly in hot conc. Solution of alkalis to form
hexahydroxystannate(ii) and plumbate(ii) respectively.

Sn(s) +4KOH(aq) +2H2O(l) → K4Sn(OH)6(aq) +

H2(g)

Pb(s) +4KOH(aq) +2H2O(l) → K4Pb(OH)6(aq) +

H2(g)

COMPOUNDS OF GROUP(IV) ELEMENTS

Group(iv) elements form compounds in +2 and +4 oxidation states. The +2 oxidation state
becomes more stable while the stability of +4 decreases as the group is descended.

THE OXIDES OF GROUP 4

These elements form oxides of the type XO, wherein the element shows an oxidation
state of +2 and also of the type XO2, wherein the element shows an oxidation state of +4.

The oxides of the elements at the top of Group 4 are acidic, but acidity of the oxides falls
as you go down the Group. Towards the bottom of the Group, the oxides become more
basic - although without ever losing their acidic character completely.

The trend is therefore from acidic oxides at the top of the Group towards amphoteric ones
at the bottom.

An oxide which can show both acidic and basic properties is said to be amphoteric.

MONOXIDES

The monoxide of carbon and silicon are usually treated as neutral oxides, but in fact
carbon monoxide is very, very slightly acidic. It doesn't react with water, but it will react
with hot concentrated sodium hydroxide solution to give a solution of sodium methanoate.

The fact that the carbon monoxide reacts with the basic hydroxide ion shows that it must
be acidic

54
 Those of germanium, tin and lead are amphoteric. The amphoteric monoxides ( GeO,
SnO and PbO) react with acids to give corresponding salts and alkalis to give
germanate(ii), stannate(ii) and plumbate(ii) complex ions.

SnO(s) + 2H+(aq) →Sn2+(aq) + H2O(l) SnO(s) + 2OH-(aq) + H2O(l)

→Sn(OH)42-(aq) Similar reactions are undergone by GeO & PbO
Alternatively:

XO(s) + 2OH-(aq) → XO22-(aq) + H2O(l)

GeO(s) + 2OH-(aq) → GeO22-(aq) + H2O(l)

SnO(s) + 2OH-(aq) →SnO22-(aq) + H2O(l)

PbO(s) + 2OH-(aq) → PbO22-(aq) + H2O(l)

They all react with concentrated hydrochloric acid.

. . . where X can be Ge and Sn, but unfortunately needs modifying a bit for lead.

Lead(II) chloride is fairly insoluble salt in water and, , it would form an insoluble layer
over the lead(II) oxide if dilute hydrochloric acid is used - stopping the reaction from
going on.

However, using concentrated hydrochloric acid the large excess of chloride ions in
the concentrated acid react with the lead(II) chloride to produce a yellow soluble
complex PbCl42-.

DIOXIDES

The first four dioxide are prepared by heating the elements in oxygen but a similar
process with lead gives lead(ii) oxide.

C(s) + O2(g) → CO2(g)

Si(s) + O2(g) → SiO2(s)

Ge(s) + O2(g) → GeO2(s)

55
 Sn(s) + O2(g) → SnO2(s)

2 Pb(s) + O2(g) → 2PbO(s)

NB

Lead(iv) oxide is made by action of hot dilute nitric acid on red lead, Pb3O4.

Pb3O4(s) + 4HNO3(aq) → PbO2(s) + 2Pb(NO3)2(aq) + 2H2O(l)

Brown solid

With warm conc. HCl, red lead reacts according to the equation:

Pb3O4(s) + 14HCl(aq) → 3H2PbCl4(aq) + Cl2(g) + 4H2O(l)

Yellow solution

Red lead is used in paints to prevent the corrosion of iron

In the case of lead(IV) oxide, the reaction has to be done with ice-cold
hydrochloric acid. If the reaction is done any warmer, the lead(IV)
chloride decomposes to give lead(II) chloride and chlorine gas. This is an
effect of the preferred oxidation state of lead being +2 rather than +4.

Here the acid should be cold and conc.

PbO2(s) + 4HCl(aq) → PbCl4(l) + 2

H2O(l)

If the reaction is carried out at elevated temperature, lead(iv) oxide oxidizes hot conc.
hydrochloric acid to chlorine gas.

PbO2(s) + 4HCl(aq) → PbCl2(aq) + 2 H2O(l) + Cl2(g

The dioxides will react with hot concentrated sodium hydroxide solution to give soluble
complexes of the form [X(OH)6]2-.

56
+2 halides

Carbon and Silicon do not form +2 halides. Those of Ge, Sn and Pb can be prepared by heating
the tetra-chlorides with the free metal.

GeCl4(l) + Ge(s) → 2GeCl2(s)

SnCl4(l) + Sn(s) → 2SnCl2(s)

PbCl4(l) + Pb(s) → 2PbCl2(s)

57
 passing dry HCl gas over heated tin. a purp

Sn(s) + 2HCl(g) → SnCl2(s) + H2(g) exist a

eleme mo
Lead(ii) chloride can also be prepared either by action of hot conc. HCl over lead(iv) oxide or by s
passing dry hydrogen chloride gas or chlorine over heated metal.
an ele
PbO2(s) + 4HCl(aq) → PbCl2(s) + 2H2O(l) + Cl2(g) covale are
low
Conditions: hot/ conc. acid,
weak wei
NB: Lead(ii) chloride is more soluble in concentrated hydrochloric acid than in water. Explain this enoug
observation.

Lead(ii) chloride has a high lattice energy which is not over-come on addition of cold water.
However on heating, the high lattice energy is overcome and therefore lead(ii) chloride dissolves in
hot water.

r
Tin(ii) chloride may be prepared in anhydrous form by

chlori

Lead(ii) chloride dissolves in conc. Hydrochloric acid due to formation of a soluble complex tetra-
chloroplumbate(ii) ions.

PbCl2(s) + 2Cl-(aq) → PbCl42-(aq)

Yellow solution.

+4 halides

All the elements form tetra chlorides of the type XCl4, which are covalently bonded and are
volatile liquids.

the element is surrounded by 4 chlorine atoms. bond b

betwe
58
 molec low
Preparation of the tetra chlorides bo

CCl4

By reacting chlorine with carbon disulphide .

All the tetra chlorides have a tetrahedral shape in which

CS2(l) + 3Cl2(g) AlCl3/heat CCl4(l) + S2Cl2(l) The two liquids are separated by
fractional distillation.

SiCl4 , GeCl4 & SnCl4

lead(iv) oxide. atom, @

oth
PbO2(s) + 4HCl(aq) → PbCl4(l) + 2 H2O(l)
to incr
haloge

Are prepared by passing a stream of dry chlorine over the heated metal.

Si(s) + 2Cl2(g) → SiCl4(l)

Ge(s) + 2Cl2(g) → GeCl4(l)

Sn(s) + 2Cl2(g) → SnCl4(l)

If a stream of chlorine is passed over heated lead, only lead(ii) chloride is formed.

Pb(s) + Cl2(g) → PbCl2(s)

To prepare lead(iv) chloride, use ice cold conc. HCl on

screen

CCl4 does not under go hydrolysis in water. This is attributed to absence of the empty/ vacant d-
orbitals.

However, other tetrachlorides under go hydrolysis in water. This is attributed to availability of

the empty d-orbitals thereby allowing the elements to expand their octet and show a covalency
59
 of more than +4. This empty d-orbitals accept lone pairs of electrons from the oxygen atom of
water molecule thus facilitating the hydrolysis of the tetra chlorides.

SiCl4(l) + 2H2O(l) → SiO2(s) + 4HCl(g)

SiCl4(l) + 2H2O(l) → SiO2(s) + 4HCl(g)

White solid.

GeCl4(l) + 2H2O(l) → GeO2(s) + 4HCl(g)

SnCl4(l) + 2H2O(l) → SnO2(s) + 4HCl(g)

its low

PbCl4(l) + 2H2O(l) → PbO2(s) + 4HCl(g)

Brown solid

NB: In each case white fumes of hydrogen chloride gas is is add formed.

Stability of the tetrachloride the ha

The tetrachlorides of carbon, silicon, and germanium are structu

stable to heat, but those of tin and lead decompose on heating to form di-chlorides.

SnCl4(l) → SnCl2(s) + Cl2(g)

PbCl4(l) → PbCl2(s) + Cl2(g)

HYDRIDES OF GROUP 4

from t
affinit
The boiling points of the hydrides increase from methane down to stannane. This is due to increase
in relative molecular mass. Thus the Van der Waals forces of attraction which bind the molecules atom,
n together become progressively stronger as the relative molecular mass increases. being
attract
n Methane, germane and stannane do not react with sodium hydroxide, but silane reacts with dilute betwe
60
 sodium hydroxide to form sodium silicate and hydrogen gas. affinit

CH4 Methane

SiH4 Silane

GeH4 Germane

SnH4 Stannane

Iodine greate
PbH4 Plumbane

SiH4(l) + 2NaOH(aq) + H2O(l) → Na2SiO3(aq) + 4H2(g)

Ionically:SiH4(l) + 2OH- (aq) + H2O(l) → SiO32- (aq) + 4H2(g)

Hydrolytic behavior of hydrides of group 4

Methane does not under go hydrolysis due to absence of vacant d-orbitals.

61
 trons from the water molecules. fluorin
electro
SiH4(l) + 4 H2O(l) → Si(OH)4(s) + 4H2(g) water

GeH4(l) + 4 H2O(l) → Ge(OH)4(s) + 4H2(g) positiv

SnH4(l) + 4 H2O(l) → Sn(OH)4(s) + 4H2(g)

s
 Its covalency is limited to 4 but others can have a

n maximum of 6. Due to absence of a vacant d-orbitals in carbon but others have. extra e
vacan

Other hydrides are able to hydrolyse in water due to the availability of vacant d-orbitals which
can accept elec-

due to availability of vacant 'd'-orbitals which allows them to expand their

62
c
g  Its unique ability to catenate. Due to its small atomic radius, the bonding electrons between agents
two carbon atoms are closer to the nuclei and are attracted more strongly.
reactio
 Its unique ability to form multiple bonds such as: C=C-, -C=C-, -C=N, etc.
 Its tetrachloride does not hydrolyze in water but tetra chlorides of other elements hydrolyze.
which
Due to absence of vacant d-orbitals. solubl
 Carbon is the only element in group 4 which forms only gaseous oxides.

 Very small atomic radius of carbon atom.

 High electro- negativity of carbon atom.

 Absence of vacant d-orbitals.
 Unable to show the inert pair effect Qn.

energy and
th betwe

solven
When dilute hydrochloric acid is added to a solution of lead(ii) nitrate, a white precipitate is
formed ,but if the concentrated acid is used, a much less precipitate is formed. Explain this
behavior and write ionic equation for the reaction.

63
 The Hydrides of period 3

Hydride Formula

Sodium hydride NaH

Magnesium hydride MgH2

Aluminium hydride AlH3

t
Silane SiH4

Phosphine PH3

Hydrogen sulphide H2S

Hydrogen chloride HCl

<H-Cl< H-Br< H-I. s very strong as a result of small atomic radius and high electronegativity o

ween HF molecules and water molecules inhibits the ionization of HF in a ivity decreases whereas atomic radius increases.
As such the H- halide bon

64
re hydrogen ions.

lly decreases in moving from HF to HI i e

r gets more and more distant from the nucleus. The attraction is less, and t

e smallest atomic radius thus the H-F bond is the most polar. Iodine is the

The greater the extent of polarity, the greater the ionic character in the bond

om other members of its group are:

er oxidation state. This because fluorine lacks empty d-orbitals but others h

gases at room temperature. This is due to the strong hydrogen bonds betwee he hydrides of other members are fairly more
acidic in aqueous solution. Th

ow bond dissociation energy and high electronegativity.

cter due to its high electronegativity and charge density of the small F- ion oint in aqueous solution due to extensive
ydrogen bonds .

l. ge density, high polarising

power, and high enthalpy of
hydration. es with increase in the
number of oxygen atoms attached
o chlorine atom. O d more towards
tself.

greater the number of oxygen atoms attached the stronger the effect and th

h of oxyacids above .

ine with the following substances( in each case illustrate your answer with

65
d-block elements:

A d-block element is one in which the inner ‘d’ sub-shell (which has a higher energy) is in the process of filling up after
the outermost ‘s’ subshell(which has a lower energy) has been filled first.

In the periodic table, they are found between the very reactive s-block elements and the less reactive p-block elements.

Transition elements:

A transition element is one that has a partially filled d-orbitals either in the free atom in its ground state or in one
or more chemically important ions.

66
The sub shells are filled up in order of increasing energy and so the 4s- orbitals are filled 1 st before the 3d-orbitals.

NB:

For chromium, the electronic configuration of [Ar]3d54s1 is a more stabl arrangement than[Ar] 3d44s2.

This is because the former configuration has more unpaired electrons than the latter and therefore more stable owing
to half filled 3d-orbitals. Unpaired electrons experience minimum repulsion between each other .

Sc3+
Cr3+
Mn2+
Mn3+
Fe2+
Fe3+
Cu+

Cu2+
Zn2+

For copper, the configuration 3d104s1 is a more stable arrangement than 3d94s2. The explanation is because the 3d-
subshell is full therefore its energetically stable.

CONFIGURATION OF SELECTED IONS

When a transition metal atom loses electrons to form ions, the 4s-electrons are lost first
before 3d-electrons.

This is because the 3d sub -shell is situated closer to the nucleus than the 4s sub shell.

67
 Thus when the 3d sub shell is occupied, the electrons in it repel the 4s-electrons further
from the nucleus thereby increasing their energies than 3d-electrons and they are lost
first.

GENERAL CHARACTERISTICS OF TRANSITION ELEMENTS

1. High melting and boiling points.

Melting points of metals depend on the number of electrons available for metallic bond formation.

Transition elements use both the 4s and 3d-electrons on. in the metallic bond formation. The greater the
number of electrons contributed to the metallic bonds , the higher the melting point. Hence they have
high melting and boiling points.

The melting points of these metals rise to a maximum value and then decrease with increase in atomic number.

A dip in the melting point is observed at manganese [Ar]4S23d5. This is attributed to the stability of a half-filled 3d-
orbitals, electrons therefore being less available for bond formation.

Zinc [Ar]4S23d10 with a full 3d-orbitals uses only the outer most 4s-electrons in metallic bond formation as such has
the lowest melting point.

2. Variable oxidation states.

68
The variable oxidation states exhibited by transition elements is attributed to the fact that both the 4s and 3d-electrons
are energetically similar and they can both be used in bond formation.

All elements with exception of scandium and zinc show variable oxidation states. For an oxidation state of +2, only
the outer most 4s-electrons are used in bond formation. For an oxidation state greater than +2, both the 4s and 3d-
electrons are involved in bond formation.

The maximum oxidation state is achieved when all the 4s and 3delectrons are involved in bonding.

Workout the oxidation state of the transition metal in each of the following compounds or ions: i) MnO4- ii)
MnO42- iii) MnO2 iv) Cr2O72- v) K2CrO4 vi) Fe(CN)63- 3. Catalytic activity.

Transition metals and their compounds behave as catalysts due to the presence of partially filled d-orbitals .

The reacting gases are adsorbed onto the surface of the catalyst where they form weak bonds by either
donating or accepting electrons. This weakens the internal bonding of the reactant molecules thereby
reducing the activation energy.

Also there is a higher concentration of the reactants at the surface of the catalyst as a result the rate of reaction
increases.

Some common examples include:

Haber process in the manufacture of ammonia, finely divided iron is used.

Contact process in the manufacture of sulphuric acid, vanadium pent oxide is used.

Decomposition of hydrogen peroxide , manganese(iv) oxide is used.

69
Hydrogenation of alkenes and alkynes, nickel metal is used.

4.Complex ion formation.

A complex ion basically consists of a central metal atom or ion surrounded by

electron donating groups called ligands capable of forming dative covalent bonds
with the metal atom or ion.

Complex ion formation in transition metals is affected by the following

factors:

 presence of vacant d-orbitals.  the high charge on the metal

cation.)  the small radius of the cation.

Example of a complex ion is [Ni(H2O)6]2+, and is said to have a coordination number of 6.

Coordination number is the number of ligands directly bonded to the central metal ion. A complex species can
be cationic, anionic or neutral.

Cationic complexes are those that carry an over all positive charge

Anionic complexes are those that carry a negative charge.

Neutral complexes are those that carry no charge.

70
 Ni(CO)4, Tetracarbonylnickel(O)

Fe(CO)5, Pentacarbonyliron(O)

Qn. Give the name, coordination number, and the oxidation state of the metal ions in the following complexes:

i) Cr(H2O)6Br3 ii) [ Cr(H2O)6]Cl3 iii)[Cr(H2O)5Cl]2+ iv) [Co (NH3)5Br] 2+SO42- v) [Cr (H2O)4Cl2]+.

5. Form colored compounds.

Transition metal ions are colored because they have partially filled ‘d’ sub shell.

A transition metal ion exhibits color when it absorbs light from the visible region.

Light in the visible region has sufficient energy to promote delectrons from a lower energy level to a
higher energy level.

6. Magnetic Properties

Molecules with one or more unpaired electrons are attracted into a magnetic field. The more unpaired electrons
in the molecule the stronger the attraction. This type of behavior is called paramagnetism.

Substances with no unpaired electrons are weakly repelled by a magnetic field. This property is called
diamagnetism.

Many transition metal complexes exhibit simple paramagnetism. In such compounds the individual metal ions
possess some number of unpaired electrons.

CHROMIUM

a) Write the electronic configuration of the following species (atomic i)Cr ii)Cr 2+ iii)Cr3+ iv) Cr6+
b) State the common oxidation states of chromium.
c) Aqueous sodium hydroxide was added drop wise to a solution containing Cr3+ ,state what was
observed and write equation for the reaction that took place.
d) Discuss using equation where applicable the reactions of chromium with:
71
 i) air ii) water iii) nitric acid ,hydrochloric acid and sulphuric acid .

ANSWERS

a) i) Cr: 1S22S22P63S23P63d54S1 ii) Cr2+:1S22S22P63S23P63d4 iii) Cr3+: 1S22S22P63S23P63d3 iv)

Cr6+:1S22S22P63S23P6

NB

Chromium adopts the above electronic configuration rather than the expected 1S22S22P63S23P63d44S2 because
the 3d is half filled unlike in the expected configuration therefore it’s more energetically stable.

b) +2, +3, +6
c) Observation

Green precipitate, soluble in excess to form deep green solution.

Equations

Cr3+ (aq) + 3 OH- (aq) → Cr(OH)3 (s)

Cr(OH)3 (s) + 3 OH-(aq) → Cr(OH)63-(aq) d)

i) With Air (oxygen)

Chromium does not react with oxygen at room temperature, when heated it forms green chromium (iii) oxide.

4Cr(s) + 3O2(g) → 2Cr2O3(s)

green ii) With water.

Chromium reacts with steam to form green chromium (iii) oxide and hydrogen gas.

2Cr(s) + 3 H2O(g) → Cr2O3(s) + 3H2(g) iii) With acids.

Chromium reacts with dilute hydrochloric acid forming  green

chromium(iii) chloride solution and,  Liberating hydrogen gas.

2Cr(s) +6HCl(aq) → 2CrCl3(aq)+ 3H2(g)

 Chromium reacts with dilute sulphuric acid forming blue solution of chromium(ii) sulphate and
liberating hydrogen gas.
 The blue solution turns to green when exposed to air. This is due to aerial oxidation of Cr 2+
to Cr3+
ions.

72
Cr(s) + H2SO4(aq) → CrSO4(aq) + H2(g)

4CrSO4(aq) + O2(g) + 2H2SO4(aq) → 2Cr2(SO4)3(aq) + H2O(l) Ionically:

Cr(s) + 2H+(aq) → Cr2+(aq) + H2(g)

4Cr2+(aq) + 4H+(aq) + O2(g) → 4Cr3+(aq) +2H2O(l)

 Chromium reacts with dilute sulphuric acid on heating to form chromium(iii) sulphate and hydrogen
gas

2Cr(s) + 3H2SO4(aq) → Cr2(SO4)3(aq) + 3H2(g)

 Chromium reacts with hot conc. sulphuric acid to form chromium (iii) sulphate, sulphur dioxide and
water.

2Cr(s) + 6H2SO4(aq) → Cr2(SO4)3(aq) + 6H2 O (aq) + 3SO2(g)

NB: Chromium does not react with nitric acid due to the formation of a thin layer of chromium (vi)
oxide which renders it passive towards nitric acid.

iv) With chlorine

If chlorine gas is passed over heated chromium, green solid of chromium (iii) chloride is formed.

2Cr(s) + 3Cl2(g) → 2CrCl3(s)

NB: If hydrogen chloride is used instead, chromium (ii) chloride is for

Cr(s) + 2HCl(g) → CrCl2(s) + H2(g)

V) With sodium hydroxide solution.

Chromium dissolves to give:

 effervescence of a colorless gas that burns with a pop sound and  a green solution is formed.

2Cr(s) + 2OH-(aq) + 6H2O(l) → 2Cr(OH)4-(aq) + 3H2(g)

73
 Cr(OH)63-(aq)

Compounds of Chromium

Chromium shows a principle oxidation states of +2, +3, & +6.

The most stable oxidation state of chromium is +3.

The acidity of the hex aqua ions

In aqueous solution, soluble salts of chromium in +3 oxidation state i.e. CrCl3, Cr(SO4)3 etc exist as
[Cr(H2O)6]3+. The resultant solution is acidic due to hydrolysis reaction.

[Cr(H2O)6]3+(aq)+H2O(l) ↔ [Cr(H2O)5OH]2+(aq)

+H3O+(aq)

[Cr(H2O)5OH]2+(aq)+H2O(l) ↔ [Cr(H2O)4 2OH]+(aq) +

H3O+(aq)

[Cr(H2O)4 2OH]+(aq)+ H2O(l) ↔ [Cr(H2O)33OH](s) +

H3O+(aq)

Over all equation:

[Cr(H2O)6]3+(aq)+3H2O(l) ↔ [Cr(H2O)33OH](s) + 3H3O+(aq)

(Green ppt).

The hydroxonium ions produced make the resultant solution acidic with PH less than 7 and a green solid
is formed.

If sodium carbonate solution is bubbled through aqueous solution of chromium (iii) salts, bubbles of a colorless
gas that turns lime water milky is formed.

74
 If magnesium ribbon is added to aqueous chromium (iii) salt, a colorless gas that burns with a pop sound
is liberated.

Mg(s) + 2H3O+(aq) → Mg2+(aq) + H2(g) + 2H2O(l) or

Mg(s) + 2H+(aq) → Mg2+(aq) + H2(g)

Similar reactions occur with aqueous solution of Aluminium salts & iron (iii) salts.

Chromium(iii) oxide, Cr2O3:

It’s a green solid which can be obtained by heating chromium (iii) hydroxide.

2Cr(OH)3(s) → Cr2O3(s) + 3H2O(l)

Its amphoteric, reacts with dilute mineral acids to form corresponding Cr3+ salt and with sodium hydroxide to form
complex.ie

Cr2O3(s) + 6H+(aq) → 2Cr3+(aq) + 3H2O(l)

Cr2O3(s) + 6OH-(aq) + 3H2O(l) → 2Cr(OH)63-(aq)

(Green solution).

75
Chromium(iii) hydroxide

It’s a green solid formed when little sodium hydroxide is added to a solution of Cr3+ ions. It’s an amphoteric
hydroxide, reacts with dilute acids forming corresponding Cr3+ salts and with aqueous alkalis forming a complex
species.

Cr(OH)3(s) + 3H+(aq) → Cr3+(aq) + 3H2O(l)

Cr(OH)3(s) + 3OH-(aq) → Cr(OH)63-(aq) Chromite ion NB:

Chromium (iii) hydroxide is oxidized by hydrogen peroxide solution in an alkaline medium to form
chromate ion. i.e.

Addition of sodium hydroxide drop-wise till excess to a solution containing Cr3+ ions followed by a little H2O2 and
boiling the resultant solution.

Observation:

A green precipitate soluble in excess, forming green solution. The solution turns yellow on addition of hydrogen
peroxide.

Equation:

76
The presence of the chromate ions produced can be confirmed by:

 Addition of Lead (ii) ethanoate or Lead (ii) nitrate solution.

Observation

A yellow precipitate is formed. Equation

 Addition of Barium nitrate or Barium chloride solution.

Observation

A yellow precipitate is formed Equation

77
 Addition of silver nitrate solution.
Observation

A brick red precipitate is formed. Equation

 Addition of a little amyl alcohol (eg Butan-1-ol) followed by dilute sulphuric acid.
Observation

A blue color is observed in the organic layer.

Hydrated Chromium(iii) Chloride.CrCl3.6H2O

This salt of chromium exhibits hydration isomerism i e existence of compounds with the same molecular
formula but different structural formulae.

The following are the isomers of hydrated chromium(iii) chloride:

(Hex-aqua-chromium(iii) chloride)

(Chloropentaqua chromium(iii) chloride monohydrate)

(Dichlorotetra-aqua chromium(iii) chloride dihydrate)

Identification/test of the isomers

1. Using silver nitrate solution:

78
• The first isomer precipitates 3moles of silver chloride because all the 3Cl - ions are not directly bonded to
the central metal cation,
• The 2nd isomer precipitates 2moles of silver chloride.
• The 3rd isomer precipitates 1mole of silver chloride.

2. Using conductivity measurement:

This test provides the number of moles of conducting ions in solution for every mole of isomer.

 The 1st isomer contains 4moles of conducting ions i.e. [Cr(H2O)6]3+ and 3Cl-
 The 2nd isomer contains 3moles of conducting ions i.e.

[Cr(H2O)5Cl]2+ and 2Cl-

 The 3rd isomer contains 2moles of conducting ions

i.e.[Cr(H2O)4Cl2]+ and Cl-

Compounds of chromium in +6 oxidation states

Because of the high charge density of Cr6+ ion, it can only exists as Oxo- ions.eg , CrO3

, CrO42- , Cr2O72-

CHROMATES ,CrO42-

Chromates are salts of chromic acid, they have a characteristic yellow color. eg

K2CrO4 and Na2CrO4. It has a tetrahedral structure

Chromates are obtained when an alkaline solution is added to a solution of dichromate ions.

U
Orange yellow

Chromates are stable in alkaline medium, however Chromates react with acids to form dichromate.

79
 MS

e double sulphate salts with general formula M2SO4.M2(SO4)3.24H2O M is a group (I) metal e.g Li+, Na+, K+, NH4+, Rb+ ,
Cs+ etc

) M is a group (III) metal or a metal bearing a +3 charge e.g Al3+ , Cr3+, Fe s of common alums are:

alum K2SO4.Cr2(SO4)3.24H2O ion in water is acidic because the chromium (iii) ions undergo hydrolysis le
)
plex ion is acting as an acid by donating a hydrogen ion to water molecule
O) ter is, of course, acting as a base by accepting the hydrogen ion.

6]3+(aq)+H2O(l) → [Cr(H2O)5OH]2+(aq) + H3O+(aq) 5OH]2+(aq)+H2O(l) →

[Cr(H2O)4 2OH]+(aq) + H3O+(aq)

4 2OH]+(aq)+ H2O(l) → [Cr(H2O)3 3OH](s) + H3O+(aq) equation:

nium ions renders the resultant solution acidic.

f a colorless gas which turns lime water milky is formed and a greeen solid

80
 potassium dichromate, chrome alum is formed.

aq) + 2e

t proportion for the formation of chrome alum on crystallizing. en solution.

ed ammonia solution to form a purple solution.

m & Lead. olution.

81
g)

nd Pb4+ form
covalent
compounds e.g
PbCl4 and
CrCl6 um
ution.

82
rities.

rothing agent) so as to remove the unwanted earthly materials. The oil we

The oiled sulphide particles float on the surface while the impurities sink to zinc oxide.

heated in a blast furnace. xide. to form calcium silicate (slag). nt coke to carbon monoxide. The carbonmonoxide reduces
zinc oxide to zin the zinc produced leaves as vapor at the top of the blast furnace where its c

REACTIONS OF ZINC

. This layer prevents further reaction with the oxygen present in air.

drogen gas. orming salt and

2
ydrogen gas. rogen gas.
roducts.

onc.) are not easily defined. and hydrogen gas.

COMPOUNDS OF ZINC

odium hydroxide or aqueous ammonia to a solution containing zinc ions.

m hydroxide to form sodium zincates’ complex. colorless solution of tetra amine zinc ion.

ide through a solution of zinc

ons. alt, a metallic sulphide is
ormed but if the H2S is passed
hrough an acidic ied, the excess
83
H+ ions present suppresses the
ormation of sulphide ions in sis
of [Zn(H2O)6]2+

+ H3O+(aq),

olution of Zn2+ ions produces a white ppt which dissolves in excess to form

f zinc ions, produces a white ppt soluble in excess to form a colorless solut n of Zn2+ ions produces a white ppt. soluble in
sodium hydroxide.7

hite ppt soluble in dilute HCl acid. ed with zinc ions.

es . d the iron is exposed, iron does not rust. d iron undergoes oxidation in preference to iron forming a thin layer of Zn

1s t roasted in air to convert them to stable iron(iii) oxide. e.g

blast furnace

pipes called Tuyeres located at the lower part of the furnace. The other ma

CE

xide gas

to form carbonmonoxide

)
a( SiO2)

ent as impurities to form slag.

e and they can be tapped off separately. The molten iron is at the bottom co Bunsen burner bases, boiler plates etc ed the
onverter and air is blown into it to oxidize the impurities such as car

id of tri-iron tetra oxide. n(iii) oxide or rust.

hen different parts of iron act as anode and cathode. hydroxide is formed.

oxide.

gen gas and iron(ii) salts.

84
 sulphur dioxide and water.

2O(aq)
O hloride. n solution. It undergoes hydrolysis making the resultant solution acidic. n is added drop wise to a solution
2+
f Fe solution. The ppt is insoluble in e

aqueous Fe2+ solution

H
]

cid and crystallizing the salt from solution. te forms as green crystals.

2(g) acidic fumes olution turns to yellow/ brown due to formation of iron(iii) ions.
3+
and undergo hydrolysis in water making resultant solution acidic. drolysis in aqueous solution to
release hydrogen ions or hydroxonium ions t H3O+(aq)

iron(iii), the color of the solution changes to green.

lution of standard potassium permanganate.

+5Fe3+ (aq)

g Fe3+ ion, the color of the solution changes from yellow to green with form

orm oxide and hydrogen gas.

ydrogen gas. de.

d
hloride. iron does not.

85
riable valencies of +2 &+3.

e forms compounds which are colored.

-subshell) while Zn is diamagnetic( due to paired electrons in its 3d-subshe moist air to form hydrated iron(iii) oxide (rust).

sium.

e is then mixed with water and oil(frothing agent). The earthly materials sin ,
ashed and dried. per(i) sulphide, iron(ii) oxide and sulphur dioxide.

nd silica added. On strong heating, the iron(ii)oxide reacts with silica to form (i)oxide.

er(i)sulphide react in the heat of the blast furnace with limited air supply t

er copper and contains impurities . The last process in the extraction is puri les is mixed with water and oil
and shaken for a while.

ereas the ore particles (low density) float on the surface, where they are rem

g to copper.

sis.

86
 or

olution.

Uses of copper

city and is easily drawn out into wires. easily bent into
hape. heat and doesn't react with water.

roduces a metal harder than either copper or zinc individually. Bronze is an copper alloys - this time with nickel. These are
nown as cupronickel alloy copper(ii)carbonate(protective layer). oC) to form black copper(ii) oxide. gen to form
opper(i)oxide.

e.

e.

trate, nitrogen monoxide and water.

per(ii)nitrate, nitrogen dioxide gas and water.

2H2O(l)

87
m copper(ii) sulphate, sulphurdioxide and water. ompounds in +1 oxidation state are unstable. ueous
solution exists as [Cu(H2O)4]2+ which is a blue solution. added to copper(ii) ions. hydroxide. However
dissolves in excess ammonia solution to form a deep b

ated copper metal.

o form a yellow solution of tetra-chlorocupprate(ii) ions [CuCl4]2-

its ligands are replaced by a different ligand which is more willing to dona

nge.

Cu(NH3)4]2+ Deep blue

ER(II) SALTS

ric acid)

otassium iodide, a white precipitate of copper(i) iodide is formed which is s ing the resultant solution with a standard solution
of sodium thiosulphate u two equations above :

s . that
of
copper
ions
present
in the
solution
can be
determi
ned. l)

potassium iodide solution followed by dilute sulphuric acid .

berated iodine is then titrated with a standard solution of sodium thiosulph

88
 ies (atomic number= 25):

eason for your answer.

olution containing Mn2+ ,state what was observed and write equation for th in an oxidation state of

on state? owing similarities. er

using the 4s-electrons, a half
filled 3d -orbital that is
stable is left.

asing oxidation state.

e fact that both the 4s and the 3d- electrons take part in bond formation. cally similar 4s and 3d- orbitals. or bond formation,
orming stable Mn2+. For higher oxidation states, both th

wn due to aerial oxidation .

onia solution.

n state of +7 by using both the 4s and 3d- electrons in the bond formation b
+
7 to +4 since potassium manganate (vii) is a mild oxidizing agent in alkali

s an oxidizing agent which include the following: ints of titrations.

n conc hydrochloric acid is reacted with it.

ation because KMnO4 is a very strong oxidizing agent, oxidizes Cl- ions fr

) +8H2O(l)

heated. nitrides
89
o liberate hydrogen gas.

Magnesium react with steam in the same way.

solution. entrated nitric acid and little solid lead (IV) oxide or sodium bismutha

O4-(aq) + 5Bi3+(aq) + 7H2O(I)

(aq) + 5Pb2+(aq) + 2H20(1)

for simple cobalt salts; they are colored pink . The simplest ion t

de ions

o a solution containing hexaaquacobalt(II) ions, the solution turns fro ide ions.

rns to the pink colour. ss and turns pink on

standing

gen peroxide you can add an oxidising agent such as hydrogen

peroxide hen you add the sodium hydroxide solution.

ts of bubbles of oxygen and a dark chocolate brown precipitate.

90
+3 oxidation state.

(s)

n excess to form a brown solution and turns to a deep red -brown so

3
2+ (aq) + 2 OH-(aq) aq) + e

xide you can add an oxidising agent such as hydrogen peroxide

d by hydrogen peroxide produces the same dark reddish-brown sol

med. s in excess to form a blue solution

+ 2OH-(aq)

91
a solution drop-wise until excess followed by a drop of dimethylglyo

nd red precipitate is formed .

92