CHM 122: GENERAL INORGANIC CHEMISTRY

MAIN GROUP CHEMISTRY

By

DR. ADEKOYA, JOSEPH ADEYEMI

CHEMISTRY DEPT.
SNAS, CST,
COVENANT UNIVERSITY, OTA

OFFICE NO: P54

Module 2
Chemistry of Main Group Elements
Groups I - IV
Physical and Chemical Properties
Vertical/horizontal trends of physical/ch
emical properties
Chemical reactions of named compound
representative of each group
Uses
 INRODUCTION
 The Periodic table is divided into 7 horizontal row
s and 18 vertical columns. The horizontal rows ar
e called periods and are numbered from the top
downwards- (Period 1, Period 2 …Period 7).
 The vertical columns are called groups and are n
umbered from left to right.
 Elements in a particular group have the same nu
mber and arrangement of the outermost shell el
ectron(s). Some of the groups of the periodic tabl
e have their specific names e.g
 Periodic Table contd.
 Group IA - Alkali Metals
 Group IIA- Alkaline-earth Metals
 Group VIIA- Halogens
 Group VIIIA - Noble Gases.
 The Periodic Table is also divided into four blocks na
mely: s, p, d and f blocks.
 The s-block is made of elements in Groups IA and IIA
. The outermost electrons of elements in these grou
ps are in the s-orbital hence are called the s-block el
ements.
 The p-block contains elements of Groups IIIA to VIII
A which are therefore called the p-block elements b
ecause their outermost shell electrons are located i
n the p-sub shell.
Elements in the s-and p- blocks are known collective
ly as the representative elements
 Periodic Table contd.
 The d-block constitutes elements that have their highes
t energy electrons in the d-sub shell; hence, d-block ele
ments. They are the transition metals.
NB: the representative elements form the ‘A’ part of th
e Periodic Table while the ‘d’ block elements constitute
the ‘B’ part of the Table.
This segment of the course will focus on the representa
tive elements in Groups IA- VA.
GROUP IA
The elements in this group include: Lithium (Li), Sodium
(Na), Potassium (K), Rubidium (Rb), Cesium (Cs) and Fran
cium (Fr). **Not much is known about francium. It is radi
oactive, very rare and all of its isotopes are exceedingly s
hort-lived, hence very little of its chemistry is known.
 GROUP IA Elements
 The Group IA elements are mostly metals and are know
n as alkali-metals because they react with water to give
strong alkalis (basic solution).
2 Na(s)  2H 2O(l )  2 NaOH (aq)  H 2 ( g )
 They have strong metallic character which increases do
wn the group (metallic character refers to the tendency
of a metal to lose electron(s) thus yielding positive ions)
Electronic Configuration
 The Group IA elements have the electronic confi
guration in their outermost shell-where represe
nts the principal quantum number which increa
ses with the atomic number.
 GROUP IA Elements contd.
2 1
3
Li 1s 2s
2 2 6 1
11
Na 1s 2s 2 p 3s
2 2 6 2 6 1
19
K 1s 2s 2 p 3s 3 p 4s
37 2 2 6 2 6 10 2 6 1
Rb 1s 2s 2 p 3s 3 p 3d 4s 4 p 5s
 They are s-block elements and very reactive. They easil
y lose their outermost electrons to form positive ions.

Physical Properties and Structure:

The physical properties of a substance are
determined by its structure and the bond
strength between its constituent particles.
 GROUP IA Elements contd.
Metals have giant metallic structures which consist of a
regular lattice of metal ions and delocalized electrons.
Under this arrangement, metals could have a
hexagonal close-packed structure, face-centered cubic
structure or body centered cubic structure, etc.
All the metals in Group 1A have the body-centered
cubic structure as obtained from x-ray
When substances having the same type of structure
are compared, the strength of binding force (bond
strength) accounts for the difference in property.
 GROUP IA Elements contd.

Body-centered cubic structure as obtained from x-ray

 For this reason, the differences in the physical
properties of Group IA metals are mainly due to metallic
bond strength which is dependent on how tightly the
valence electrons are held by the nucleus.
• Group IA elements are silvery in appearance and show
typical metallic character by their ability to conduct heat
and electricity (due to the presence of mobile
electrons).
• The metals are soft and easy to cut due to weak metallic
bond.
• They have low densities and low melting points when
compared with other elements in the same period.
• Within a period, they have the largest size, lowest first
ionization energies and lowest electronegativity values.
Table 1
Symbol ATOMIC IONIC MP BP DENSITY 1ST I.E. E.N.
RADIUS(Ả) RADIUS(Ả) ( 0C) ( 0C) (g//cm3 ) (kJ mol-1 )

Li 1.55 0.6 180.5 1330 0.53 520 1.0

Na 1.90 0.95 97.8 892 0.97 498 0.9

K 2.35 1.33 63.7 760 0.86 419 0.8

Rb 2.48 1.48 38.9 701 1.53 402 0.8

Cs 2.67 1.69 28.7 690 1.90 377 0.7

MP = Melting Point BP = Boiling Point

I.P = Ionization Energy EN = Electronegativity
Atomic Size
The size of an atom is one of the physical properties tha
t influence the chemical behaviours of elements. From q
uantum mechanics, the exact position of an electron in
an atom cannot be measured with certainty. It follows
 Atomic Size contd.
 Therefore, the size of an isolated atom cannot be
accurately measured. It can only be estimated
 Atomic size can be defined in a more specific way
in terms of atomic radius which is half the
distance between the nuclei of adjacent (nearest
neighbour) atoms. For metals, it is called metallic
radius while for non-metals, it is called covalent
radius.
 From the above table, atomic radius increases
with increasing atomic number for the Group IA
elements. This is as a result of increasing principal
quantum number, hence, increase in atomic size
down the group.
 Atomic Size contd.
 This trend could be explained in terms of shielding effects
of the inner electrons on the outermost electrons, which
increases down the group.
 Shielding (screening) is the ability of inner electrons to
reduce the attraction of the nucleus for the outer
electrons. It is most effective whenever there is full shell
or shells of electrons between the outermost electrons
and the nucleus. Sodium for example:
11
Na : 1s 2 2s 2 2 p 6 3s1
 There are 10 inner electrons 1s 2 2s 2 2 p6 (-full shells of
electrons) and 1 outermost electron (3s ). These 10 inner
1

electrons reduce the attraction of the nucleus for the 3s

electron thereby lowering its effective nuclear charge
(charge felt by an electron).
 Atomic Size contd.
 NB: nuclear charge increases down the group as atomic
number increases (because more protons are added to
the nucleus) but its effect on the outer electrons is
neutralized by the electrons of inner shells.
 The order of increasing atomic size for the Group IA
elements is:
 Li < Na < K < Rb < Cs
Melting Point
As the atomic sizes of Group IA metals are large, their
outermost shell electrons are weakly held by their nuclei.
Therefore, the strength of the metallic bond in these
metals is weak. Hence, only a relatively small amount of
energy is required to break it. As a result, they have low
melting melts.
 Melting Point contd.
• Going down the group, atomic sizes increase, so the streng
th of the metallic bond decreases. Melting point decrease
s from lithium to ceasium.
• NB: metallic bonding is as a result of the electrostatic attra
ction between the delocalized valence electrons and metal
cations. It holds the metal ions tightly in the lattice and co
nfers a high melting point on them.
• The smaller the size of a metal atom, the stronger the met
allic bond strength and the higher the melting point.
Boiling Point
Boiling point for the group also decreases down due to th
e weakening of metallic bonds between atoms as size incr
eases. Melting and boiling points depict how strongly the a
toms in an element are stuck together.
 Ionic Radius
 Metal atoms lose their valence electrons to for
m positive ions (cations) while non-metal atom
s gain electrons to form negative ions (anions). I
onic radius is therefore, the radius of a cation o
r anion in an ionic compound.
 Just like atomic radius, ionic radius increases
down the group as the principal quantum numb
er increases.
 Cations are smaller than the parent atom e.g.
Na+ is smaller than Na.
From Table 1, the atomic radius of sodium is 1.
90 Ả while its ionic radius is 0.95Ả. This trend is
similar for other elements in the group.
 Ionic Radius contd.
 The reduction in ionic radius when compared with the
atomic radius is readily explained by the fact that the
atom of the alkali-metals loses electrons from the
outermost shell and this invariably leads to the loss of
the outermost principal shell thus bringing about a
decrease in size.
 Conversely, anions are larger in size than the parent
atoms. The anions have more electrons than parent
atoms. Owing to the excess negative charge, there is
increased repulsion between the already existing
electrons and the newly added electrons. As a result,
the nuclear pull on each individual electron reduces,
leading to expansion of size. Hence, the anion is larger
than the corresponding atom.
 Ionic Radius contd.
 Note also that for iso-electronic ions (ions with equal
number of electrons), cations are smaller than anions.
e.g. Na+ and F- are isoelectronic.

Na+ 10 electrons, 11 protons

F- 10 electrons, 9 protons

 Both have the same number of electrons but sodium

ion, Na+, has more protons than the fluoride ion, F-. The
larger nuclear charge in Na+ exerts more attractive pull
on the electrons resulting in a smaller radius.
(K+ and Ca2+; Na+, Mg2+ and Al3+ are also iso-electronic).
 Ionization Energy
 This is another physical property of atoms which
influences their chemical behaviour. It is the energy
required to remove an electron from an atom, ion or
molecule.
• A multi-electron atom would have many ionization
energies thus atoms of an element can have several
ionization energies. Therefore there could be first,
second or third ionization energies e.tc.
• The first ionization energy of an atom is the energy
[expressed in electron volts (ev) or kilojoules per mole
(kJ/mole)] required to remove the first valence
(outermost or highest energy) electron from a neutral
atom in the gas phase.
For example: Ionization Energy contd.
 
Na( g )  Na ( g )  e 1 I .E.  492kJmol
st 1

 This reaction is endothermic because energy is required

to remove the electron.
 The first ionization energy in other words, is the energy
required for the conversion of one mole of gaseous
atoms into one mole of gaseous ions (or energy
required to remove the most loosely held electron from
an atom of an element).
 The second ionization energy of an atom refers to the
loss of the second electron.
   1
Na ( g )  Na ( g )  e ; 2 I .E.  4562kJmol
nd
TABLE 2:1st and 2nd Ionization Energies of Group IA

ELEMENT Li Na K Rb Cs
1st I.E. 521 492 415 405 376
2nd I.E. 7300 4560 3070 2370 2420

I.E. = Ionization Energy

 It can be seen from the above table that there is a decr
ease in the values of the first ionization energies as we
go down Group IA (same goes for the 2nd I.E.) because
the ease of removal of valence electrons increases as a
result of shielding effects of inner electrons on the oute
rmost electrons.
 In other words, it will take a lesser energy to remove an
electron that is not tightly held by the nucleus than to r
emove one that
 Ionization Energy contd.
 When an electron is removed from an atom, electron repul
sion reduces among the remaining electrons and because t
he nuclear charge remains constant, the attractive pull by t
he nucleus on the electrons becomes stronger, making it di
fficult to remove further electrons.
 The second ionization energy is much greater than the first
ionization energy for the Group IA metals because an elect
ron has to be removed from an inner shell that is much clo
ser to the nucleus.
 Ionization energies always increase in this order:
I1  I 2  I 3
 Going by the above trend in ionization energies, the
tendency to make positive ions and to behave as metals w
hich show these properties to a marked extent are the mo
st electropositive.
Ionization Energy contd.
From Table 2, Caesium (Cs) has the least first ionization
energy value and is therefore more electropositive and a
better reducing agent than the others.
Electronegativity
This is not a fundamental property of an isolated atom but
a property of an atom in a molecule. In other words, it is a
property of an atom in bonded form and so varies with the
nature of bonding of an atom in different molecules.
Definition
electronegativity is the tendency of an atom in a molecule
to draw electrons in the bond towards itself.
Ionization Energy contd.
 Apart from the noble gases (Group VIIIA) that have zero e
lectro- negativities, the alkali-metals (Group IA) have the
least electronegativity values.
 As can be seen from the table 1, electronegativity decrea
ses down the group. This is due to the fact that there is a
greater tendency for the elements to lose electrons (than
to attract). NB: Fluorine is the most electronegative elem
ent.

Chemical Properties
The alkali metals are so reactive that in nature, they occur a
s their compounds i.e. they are always found combined wit
h other elements. They exist as chlorides, nitrates, sulphate
s, carbonates, silicates, etc.
 Chemical Properties contd.
• Their oxides and hydroxides are basic and they release h
ydrogen with acids.
• They rapidly tarnish in air and react violently with water-
for both reasons they are kept under a layer of oil or in a
vacuum -sealed ampoule to prevent atmospheric oxidati
on.
Reactions:
With Hydrogen:
• Alkali-metals react with hydrogen gas to form hydrides. T
he ease of formation of the hydrides decreases down th
e group.
2M (s)  H 2 ( g )  2MH (s)
(M = Group IA metal)
 Reactions With Hydrogen contd.
• All the hydrides of the Group IA are white solids and ioni
c in nature. M+ H-. This is one of the reactions where hydr
ogen furnishes the negative ion.
• However, the reaction is slow at room temperature -as h
eating is required to melt the metals before reaction take
s place. Temperatures of between 300◦C and 500◦Care re
quired for such reactions.
.
• The most important alkali-metal hydride is lithium hydrid
e. On treatment with aluminum chloride in a dry solution
of ether, lithium aluminum hydride, (LiAlH), is formed.
 
4LiH  AlCl3  Li ( AlH 4 )  3LiCl
dry ether solution
 Reactions With Hydrogen contd.
• LiAlH 4 is one of the most useful reducing agents in orga
nic chemistry.
• The alkali-metal hydrides react immediately with water, gi
ving off hydrogen:
LiH (s)  H 2O(l )  LiOH (aq)  H (2) ( g )
The stability of the hydrides decreases down the group wh
ich also implies that the reactivity of the metal hydrides in
creases down the group.
Reaction With Oxygen
Group IA elements react rapidly with oxygen to form three
types of oxides namely: monoxides (normal oxides), peroxi
des and superoxides. Lithium forms lithium oxide, Li O (i.e.
lithium monoxide); sodium forms mainly sodium peroxide.
 Reaction With Oxygen contd.
 Na though it can also form sodium oxide, NaO, while the
other metals- K, Rb, Cs, form mainly the superoxides as s
hown in the table below:
Lithium oxide
4Li(s)  O( 2) ( g )  2Li2O(s)
2 Na(s)  O2 ( g )  Na2 O2 (s) Sodium peroxide

K ( s)  O2 ( g )  KO2 ( s) Potassium superoxide

KO2 is used for generating oxygen. It has the ability to
absorb CO2 while giving out oxygen at the same time.

4KO2 (s)  2CO2 ( g )  2K2CO3 (s)  3O2 ( g )

:

Reaction With Oxygen contd.

This property is made use of in breathing equipment
e.g. for mountaineers, in submarines and space craft.
All the three types of oxides are basic, crystalline solids
and react vigorously with water to form hydroxides:
• Normal: Na2O( s)  H 2O(l )  2 NaOH (aq)
• Peroxide:
Na 2 O 2 ( s)  2H 2O(l ) cold

 2 NaOH (aq)  H 2O2 (l )
2 Na 2 O 2 (s)  2H 2O(l ) warm
 4 NaOH (aq)  O2 ( g )
• Superoxide:
2KO 2 (s)  2H 2O(l )  2KOH (aq)  H 2O2 (l )  O2 ( g )
All the hydroxides are strongly basic (except LiOH) and
soluble in water. The solubility generally increases
down the group.
 Reaction With Oxygen contd.
The three oxides react with acids as follows:
Normal:
• Peroxide: Na2O(s)  2HCl(aq)  2 NaCl (aq)  H 2O(l )
• Superoxide Na 2 O 2 ( s )  2 HCl ( aq )  2 NaCl ( aq )  H 2 O2 (l )
2KO2 (s)  2HCl(aq)  2KCl (aq)  H 2O2 (l )  O2 ( g )
• All Group IA hydroxides except LiOH are stable to heat.
This implies that only LiOH decomposes on heating
while others do not:
• It is the least stable in the group because the extremely
small lithium ion Li+ has a very high polarizing power
and distorts the electron cloud of the hydroxide ion to
such an extent that decomposition occurs on heating.
Reaction With Oxygen contd.
2 LiOH ( s) 

 Li2O( s)  H 2O( g )
Reaction With Water
All alkali metals react with water and reactivity increases
down the group. Lithium reacts readily. Sodium darts ab
out on the water surface with a hissing sound. Potassium
reacts almost explosively that the hydrogen evolved may
catch fire. The reactions of rubidium and caesium are eve
n more violent and best not attempted because of explos
ions.
2M (s)  2H 2O(l )  2MOH (aq)  H 2 ( g )

(M = Group IA metal)
Reaction With Halogens
The Group 1A elements react with halogens to form halides

2M (s)  X 2 ( g )  2MX (s)

(M = Group IA metal; X = Cl, Br, F or I)

 The halides are useful starting materials for laboratory

preparations of hydrogen halides and their acidic
solution.
 Hydrogen fluoride and hydrogen chloride can
be prepared by warming concentrated sulphuric acid
with sodium fluoride or chloride while phosphoric acid
is reacted with sodium bromide or iodide to produce
hydrogen bromide or iodide.
 Reaction With Halogens
NaCl (s)  H 2 SO4 (l )  NaHSO4 (s)  HCl( g )
NaI ( s )  H 3 PO4 (l )  NaH 2 PO4 (s)  HI ( g )
The halides are ionic and soluble in water. Their
aqueous solutions conduct electricity.

Reaction With Nitrogen

The elements react directly with nitrogen to form nitride
s. The ease of formation of these nitrides
decreases down the group.

6M (s)  N 2( g )  2M 3 N (s)
(M = Group IA metal)
 Reaction With Nitrogen contd.
The alkali-metal nitrides decompose at low
temperatures and react with water vapour to form
ammonia and the metal hydroxide:
Na3 N  3H 2O  NH3  3NaOH
Reaction with Ammonia
Alkali-metals dissolve in ammonia to form ionic amides
2Na  2NH3  2NaNH 2  H 2
Reaction with Alkyl halides
Group IA metals react with alkyl halides to form the metal a
2Li  CH 3Cl  CH 3 Li  LiCl
lkyl. e.g.
THE CARBONATES/HYDROGEN CARBONATES
• The carbonates and hydrogen carbonates of the alkali-m
etals are white solids and have the general formula,
M2 CO3 and Mrespectively (M = Group IA metal).
• They are all soluble in water except lithium carbonate.
• Note that lithium does not give a hydrogen carbonate, ie
LiHCO3 does not exist.

Na2CO3(s)  2HCl(aq)  2NaCl(aq)  CO2 ( g )  H 2O(l )

NaHCO3( s)  HCl(aq)  NaCl(aq)  CO2 ( g )  H 2O(l )
THE CARBONATES/HYDROGEN CARBONATES contd.
The two sets of carbonates evolve CO2 when reacted
with acids. This is a general property of carbonates.
Example:
Li2CO3 (s) 


Li2O(s)  CO2 ( g )
All Group IA carbonates except lithium carbonate are
stable to heat. That is, only lithium carbonate
decomposes on heating:
Na2CO3 (s)  

No reaction
(also K, Rb, Cs)
On the other hand, all the hydrogen carbonates decomp
ose on heating. Remember, LiHCO3 does not exist.
Example:
2 NaHCO3 (s) 


Na2CO3 (s)  CO2 ( g )  H 2O( g )
 THE CARBONATES/HYDROGEN CARBONATES contd.
The hydrated crystalline forms of the Group IA
carbonates lose water on exposure to air
Na2CO3 .10H 2O  Na2CO3.H 2O  9H 2O
THE NITRATES
• The nitrates of the alkali metals are of the form, MNO3
(M = alkali metal). Sodium nitrate is the most important
of the Group IA nitrates and the only nitrate to occur nat
urally in substantial amount.
• Except lithium nitrate, the Group IA nitrates decompose
on heating to the corresponding nitrite and oxygen. Exa
mple:
2KNO3 ( s)  

2KNO2 (s)  O2 ( g )
2 NaNO3 ( s) 

2 NaNO2 (s)  O2 ( g )
 THE NITRATES contd.
• Only lithium nitrate decomposes on heating to the oxide
4LiNO3 (s)  2Li2O(s)  4 NO2 ( g )  O2 ( g )
• All the nitrates of the alkali metals are soluble in water.
As a matter of fact, all nitrates are soluble. This is one
rule in chemistry that has no exception.

THE SULPHATES:
• All the sulphates and hydrogen sulphates of the group
are soluble in water but thermally stable (except at very
high temperatures). Na is the major compound in
the group.
• Generally, sulphates are usually more
thermally stable than nitrates and carbonates
 THE SULPHATES contd.

Sulphate ion 2D dimension

resonance structure of
sulphate
Anomalous Properties of Lithium
• Lithium stands at the head of Group IA metals. Many of i
ts properties quite differ from those of the other membe
rs of the group.
• The main reason for this anomalous behaviour is the sm
all size of lithium ion. This causes the behaviour of lithiu
m compounds to show differences from the compounds
of the other elements in the group.
• Due to the small size of lithium ion, its compounds have
a greater tendency towards covalency.
• This is demonstrated by the lower solubility of lithium flu
oride in aqueous solution and by the fact that some lithi
um compounds are soluble in organic solvents e.g. lithiu
m chloride is soluble in ethoxy ethane.
 Anomalous Properties of Lithium contd.
• From Fajan’s rule, an ionic compound will have a high degr
ee of covalency if the positive ion is small and highly charg
ed- i.e. covalency is promoted by small cations and large a
nions.
• Lithium rather shows similarities to magnesium with
which it exhibits a diagonal relationship. This
relationship refers to the resemblance of each of the
first three elements of the second period of the
Periodic Table to the elements located diagonally to it.

Period 2: Li Be B
Period 3: Mg Al Si
USES OF SOME COMPOUNDS OF GROUP IA ELEMENTS
Compounds of the Group IA elements have wide
industrial applications:
• Sodium carbonate: this is also known as soda ash and m
anufactured through the Solvay process. It is a fine whit
e powder used for the manufacture of glass. It is widely
used in the paper industry and in the manufacture of so
ap and detergents. It is used as a water softener and in
the laboratory; it is used to standardize acids and also us
ed as an analytical reagent. It is by far the most commer
cially important Group IA carbonate.
• Sodium hydroxide: this is used in soap and detergent m
anufacture. Also used for rayon and in paper industries.
In the laboratory, it is used as a strong alkali and analytic
al reagent.
 USES OF SOME COMPOUNDS OF GROUP IA ELEMENTS
contd.

• Sodium hydrogen carbonate: this is a white crystalline s

olid and used in baking powder and fire extinguishers. It
is responsible for the rising of flour by the release of car
bon (iv) oxide on decomposition by heat.
• Sodium nitrate: this is used in fertilizer production and a
lso in the production of nitric acid.
• Potassium superoxide: this is used in air purifiers, subm
arines, spacecraft, and portable breathing.apparatus. It
has the ability to absorb CO while giving off oxygen at th
e same time.
 GROUP IIA
General Properties
• Elements in this group include: Beryllium (Be), Magnesium
(Mg), Calcium (Ca), Strontium (Sr),
• Barium (Ba) and Radium (R).
• They show typical properties of metals and are known as a
lkaline-earth metals. They are so called because they form
alkaline solution when they react with water
• They are found widely in different kinds of rock on the
earth’s crust.
• They are chemically reactive but less than the alkali metals
.
• They have two electrons in their outermost shell and are
characterized by ns2 electronic configuration.
 General Properties contd.
• Just as the alkali metals, the alkaline-earth metals have
their outermost electrons in the s-orbital and are thus
called s-block elements.
• They form divalent ions by losing their ns2 valence
electrons.

Physical properties:
• They are all metals and always occur in nature as compou
nds because they are too electropositive to occur free in
nature.
• Just as the alkali metals the metallic character increases
down the group.
• The table 4 below shows some of their properties:
 TABLE 4: PROPERTIES OF GROUP IIA ELEMENTS
SYMBOL ELECT. ATOMIC IONIC MP BP DENSITY 1ST I.E. E.N.
CONFIG. RADIUS (Ả) RADIUS ( 0C) ( 0C) (g/ ) kJ mol-1
(Ả)

Be [He]2s2 1.12 0.31 1277 2770 1.85 900 1.5

Mg [Ne]3s2 1.60 0.65 650 1107 1.74 736 1.2

Ca [Ar]4s2 1.97 0.99 838 1440 1.55 590 1.0

Sr [Kr]5s2 2.15 1.13 768 1380 2.60 548 1.0

Ba [Xe]6s2 2.22 1.35 714 1640 3.50 502 0.9

 The last element in the group, rubidium, is omitted

because it is uncommon and radioactive.
• The atoms of the alkaline-earth metals have two delocalized
electrons and their sizes are smaller than those of alkali metals
hence the force of attraction between metal ions and the
delocalized electrons increases.
Physical properties contd.
• This explains why Group IIA metals are stronger and
have higher melting points than the Group IA metals.
• However, the pattern for the melting points of Group II
metals is irregular. The irregularity can be explained in
terms of the different metallic crystal structures of the
element. Boiling points of the metals also follow a similar
trend.
Unit Cell

Face-centered End face-centered

 Ionization Energy
• As a general trend, values of ionization energies decrease
down the group. This is as a result of the increasing distan
ce between the valence electrons and the nucleus as the
principal quantum number increases.
• The first and second ionization energies of this group of
metals are relatively low but the third ionization energies
are far larger (see table below) due to the fact that electr
ons have to be removed from an inner shell much closer t
o the nucleus. That is why Group IIA elements do not for
m trivalent ions
TABLE 2: 1st, 2nd and 3rd Ionization Energies of Group II

ELEMENT Be Mg Ca Sr Ba

1st I.E. 900 736 590 548 502

2nd I.E. 1760 1450 1150 1060 966

3rd I.E. 14800 7740 4940 4120 3390

 I.E. is ionization energy

 By comparing values of ionization energies for the alkali
and alkaline-earth metals, it could be seen that the
alkali metals have lower first ionization energies than
the alkaline-earth metals within the same period.
 Chemical Properties/Reactions:
• The reactivity of the metals increases down the group, a
reverse trend when compared with the ionization energi
es.
• It is good to note that the alkali-metals are more reactive
than the alkaline-earth metals due to the lower ionizatio
n energies of the Group IA metals as explained earlier
Reaction with Hydrogen
• All the Group IIA metals, exception beryllium, react with
hydrogen to form hydrides.
M ( s)  H 2 ( g )  MH 2 ( s)
• They are ionic hydrides and react with water as follow
MH 2 (s)  2H 2O(l )  M (OH ) 2 (aq)  2H 2 ( g )
(M = Group IIA metal)
 Reaction with Oxygen
• All the Group IIA elements react with oxygen to form the
oxide. Barium also forms the peroxide.
2M ( s)  O2 ( g )  2MO( s)
(M = Group IIA metals)
2Ba ( s)  O2 ( g )  Ba 2 O2 ( s)
(Barium peroxide)
• Only beryllium oxide is insoluble in water.
MO(s)  H 2O(l )  M (OH )2 (aq)
(M = Group IIA metals except beryllium)
 Properties of BeO and other group II oxides
• Beryllium oxide, BeO, is more like the oxide of
aluminium in Group IIIA rather than the oxides of
the other elements in Group IIA. It has a high
degree of covalency which is lacking in the other
oxides.
• It is amphoteric in nature and dissolves with great
difficulty in acids.
• The oxides and hydroxides of the Group IIA are
generally less basic than those of Group IA.
• The Group IIA oxides react with acids to form salts
and water. Example:
CaO(s)  2HCl(aq)  CaCl2 (aq)  H 2O(l )
 Properties of BeO and other group II oxides
• Note: there is no reaction between the oxides of the s-
block elements (Groups IA and IIA) and alkalis.
• However, beryllium oxide which is amphoteric reacts
with sodium hydroxide to give sodium beryllate.

BeO(s)  2NaOH (aq)  H 2O(l )  Na2 Be(OH )4 (aq)

Reaction with Water
All Group IIA elements react with water to form the
hydroxides except beryllium which does not react with
water, whether cold or hot.
M (S )  2H 2O(l )  M (OH )2 (aq)  H 2 ( g )
(M = Group IIA metals except beryllium)
 Reaction with Nitrogen:
• All members of Group IIA elements form nitrides when
heated in Nitrogen. The ease of formation of the nitride
s decreases down the group.

3M (s)  N 2 ( g )  M 3 N 2 (s)
(M = Group IIA metal)
• The nitrides dissolve in water to form ammonia and the
metal hydroxide.
M 3 N 2 (s)  6H 2O(l )  3M (OH )2 (aq)  2 NH 3 ( g )
(M = Group IIA metal)
 Reaction with Halogens
• The alkaline-earth metals react with halogens to form the
halides.
M (s)  X 2 ( g )  MX 2 ( g )
(M = Group IIA metal X = Cl, F, Br or I)
I 2  Br2  Cl2  F2 ; Be  Mg  Ca  Sr  Ba
Apart from beryllium halides, the Group IIA halides are
predominantly ionic. Reactivity increases in the order:
CARBONATES of Group IIA:
• The Group IIA carbonates have the general formula,
MCO3 and are slightly soluble in water.
• They all decompose on heating to give the metal oxide
and CO2
MCO3 (s) 

MO( s )  CO2 ( g )
THE NITRATES:
• The nitrates of the alkaline-earth metals are of the form,
M(NO3)2 they decompose on heating as follows:

2M ( NO3 ) 2 (s) 


2MO(s)  4NO2 ( g )  O2 ( g )
(M = Group IIA metal).
• Note the difference in the decomposition products of
Group IA and IIA nitrates. Also note that lithium has
similar decomposition products as those of Group IIA
• The difference arises because the Group IIA oxides are
more stable than oxides of Group IA. The lattice
energies of the Group IIA oxides are larger than those
of Group IA.
 THE SULPHATES
They show varying solubilities in water. The solubility of the
sulphates decreases down the group. They are relatively sta
ble to heat. Beryllium, magnesium and calcium sulphates
are often found as hydrated crystals e.g.

BeSO4 .4H 2O, MgSO4 .7H 2O, CaSO4 .2H 2O

BaSO4 is extremely insoluble in water.
 THE HALIDES
The elements all give fluorides, chlorides, bromides and i
odides but the chlorides are the most common. They are
soluble in water but the fluorides are much less soluble t
han the others due to higher lattice energies of the fluori
des compared to other halides.

Anomalous properties of Beryllium

Beryllium exhibits a diagonal relationship. It resembles alu
minum and differs from other members of Group IIA eleme
nts:
• Their ratios of ionic charge to ionic radius are very similar
• Their electronegativities are the same.
• The hydroxides of both metals are amphoteric.
• Their sulphates are readily soluble in water
 Anomalous properties of Beryllium contd.
• The compounds of beryllium tend to have significant
covalent character because it is very small. Its high
charge density makes it highly polarizing.
• The Be2+ ion distorts the electron density of an adjacent
negatively charged ion. Electron density becomes
concentrated between two ion centres giving the bond su
bstantive covalent character.
 USES OF SOME COMPOUNDS OF GROUP IIA ELEMENTS
• Magnesium hydroxide: it is a very good antacid. It neutral
izes excess hydrochloric acid which causes gastric pain in
people. It has advantage over other antacids as it does no
t produce carbon dioxide which causes belching.
• Calcium hydroxide is used in the industry to neutralize aci
ds in effluents.
• Gypsum, CaSO4 for plaster casts to immobilize broken bo
nes.
Strontium compounds are used for fire works because
they give a persistent and intense red flame when
burning.
 Table 5. Electronic Configuration and
Properties of the Elements of Group IIIA
Properties Boron Aluminium Gallium Indium Thallium
B Al Ga In Tl
1 Ground State
. Electronic Configuration [He]2s22p1 [Ne]3s23p1 [Ar}4s24p1 [Kr]5s25p1 [Xe]6s26p1
2 Atomic radius (Ao) 0.98 1.43 1.41 1.66 1.71
.
3 Ionic radius (Ao)
. (M3+) 0.20 0.52 0.62 0.81 0.95
(M+) 1.13 1.32 1.40
4 Ionization Potential
. (kJ/mol) 801 578 579 558 589
1st 2427 1817 1971 1813 1961
2nd 3660 2745 2952 2692 2867
3rd
5 Melting Point (oC) 2030 660 29.8 156 303
.
6 Boiling Point (oC) 2550 2450 2237 2000 1457
.
7 Density (g-cm-3) 2.34 2.70 5.90 7.30 11.85
.
8 Electronegativity 2.0 1.5 1.6 1.7 1.8
.
9 Electrode Potential Eo - 1.67 -0.52 - 0.34 +0.72
. M3+/M(volt) -
 CHEMICAL PROPERTIES
• This is governed by the electronic configuration of the
element.
• From the electronic configuration, the most important
oxidation state is +3. In addition, the heavier element
s of the group show lower oxidation state of +1.This
is due to inert pair effect.
The +1 state of Tl is considerably more stable than
the +3 state.
• Compounds of the elements in the +3 states are pred
ominantly covalent.
• Boron is a metalloid while the other elements are met
allic and fairly reactive
 CHEMICAL PROPERTIES CONTD.
Reaction Remark
2M +3X2 2MX3 X2 = all halogens; Tl also gives TlX; no iodide of Tl3+

4M + 3O2 2M2O3 High temp; Tl also gives Tl2O

2M + 3S M2S3 High temperatures, Tl also gives Tl2S; also with Se and Te

2M + N2 2MN Al only
2M+6H+ 2M3++3H2 Tl also gives Tl+
2M + 2OH- + 6H2O With Al and Ga only
2M(OH)-4 + 3H2
 CHEMICAL PROPERTIES CONTD.
• The sulfates, nitrates and the halides are water
soluble, but M3+ ions hydrolyse readily.
• Oxides and hydroxides exhibit the usual trend in decr
easing acidity with increasing atomic number .
• B2O3 and B(OH)3 are acidic.
B2O3 > Al2O3 >Ga2O3 > In2O3>Tl2O
• The oxides and hydroxides are insoluble in H2O
• while those of aluminium and gallium are amphoteric.
 3
Al2O3 (s)  6H (aq)  2 Al (aq)  3H 2O(l )
 3
Al2O3 (s)  6OH (aq)  3H 2O(l )  2 Al (OH )6 (aq)
- In2O3, Tl2O3 are basic, they have no acid character at
all
 CHEMICAL PROPERTIES contd.
B Al
Occurrence As borax, Na2 B4O7 .10 H 2O AsBauxite : Al2O3.2H2O
As Kernite, Na2 B4O7 .4 H 2O
Extraction Borax  HCl  Boricacid Electrolysis of the fused
H 3 BO3 salt
 H 2O
H3 BO3  B2O3 3 2
 .boricoxide 4 Al  O  3C( s )
B2O3  3Mg(s) 

 2 B(s)  3MgO( s ) 
electrolysis
 4 Al( s )  3CO2( g )

2 BX 3( s )  3H 2( g ) 
W 
1500o C

2 B( s )  6 HX ( g ) (X = Cl, Br)
(W = tungsten)
 CHEMICAL PROPERTIES contd.

Alumina

Borax
Boric acid
Reactions B CHEMICAL PROPERTIES CONTD. Al
4M+3O2 At high temp; high heat of reaction At high temp.
2M2O3
2M+N2 At white heat Forms
2MN
2M+3S Passage of S vapour over B at 12000C At high temperature
M2S3

2M + 3X2 With all Halogens With all Halogens

2MX3
Reaction with 2B + 6KOH 2K3BO3 +3H2 2Al + 2KOH + 6H2O
alkali (Fusion with alkali) 2Al(OH)4- + 3H2

With HCl No Reaction Reacts, releasing H2.

2Al(s)+6HCl(aq)
2AlCl3 +3H2
With H2SO4 2B(s)+ 3H2SO4 2Al(s)+6H2SO4(aq) Al2(SO4)3 +
-Reacts hotconc 2H3BO3(aq) + 3SO2(g) 6H2O + 3SO2(s)
vigorously as an
oxidizing agent
With HNO3 2B(S) +6HNO3(aq) Unreactive or passive because of
(Reacts as an oxide coating which forms a
oxidizing agent) protective layer.
2H3BO3 + 6NO2(s)
With Hydrogen Forms series of hydrides: Does not form hydrides analogous
BnHn+4 e.g B2H6, B5H9, B6H10, B10H14 and BnHn+6 e.g. to those of boron.
B4H10, B5H11 e.t.c.
Volatile and readily hydrolysed e.g.
B2H6(s)+6H2O(l) 2H3BO3(s) + 6H2(s)

Borohydrides Forms AlH-4 e.g

-
Forms BH 4 e.g. sodium borohydride, NaBH 4. Lithium aluminium hydride,
LiAlH4.

Halides Readily hydrolysed e.g Are water soluble.

BX3(s) + 3H2O H3BO3 AlCl3(s)+ 3H2O(l)
+ Al(OH)3+ 3HCl
3HX
(X = Cl, Br) AlCl3(s)+6H2O(l) Al(H2O)63++
3Cl-
The ions hydrolyse readily.
AlCl3 dimerizes to give Al2Cl6.
Oxides or Acidic in character, forms boric acid, H 3BO3 Amphoteric
hydroxides pyroboric acid, H 2B4O7; Al(OH)3 + 3HCl
metaboric acid, HBO2 AlCl3 + 3H2O

Al(OH)3 + NaOH
NaAlO2 + 2H2O
(Sodium aluminate)
Uses of Group IIIA Elements
1. Boron is used both as a deoxidiser in the
manufacture of some metals.
2. Boron is used as neutron absorber in the
production of nuclear energy.
3. Boron is used as an additive to the semi-
conductors, silicon and germanium.
4. Aluminium is used in making pans, kettles and
teapots because of its high electrical and thermal
conductivity.
5. Aluminium is used to replace copper for
conductors where lightness is of paramount
importance.
Explaining the Concept of Shielding effect
Why do we use the term “effective nuclear charge”
when describing nuclear charge?
• The answer to this question is very important
when discussing the chemistry of the elements.
Since we know that, the chemistry of an element
depends upon its electronic configuration and
thus on the relative energies of the electrons
within the atom.
• The energy of one electron within the atom
depends upon the energies of the other electrons
present
 Shielding effect Contd.
• This is, in fact, why the orbital
energy diagram for hydrogen
is different from that of the
other elements.
• Hydrogen only has one electro
n and therefore there are no
MO diagram for dihydrogen.
electron-electron interactions. Here electrons are shown by dots
All of the other elements have electron-electron •
interactions and these interactions depend on the
shape of the orbital, l that each of the electrons is
You will also recall that the energy of the electrons in multi-electron •
atoms depends on both the quantum numbers n and l (l determines
the shape of the orbital).
 Shielding effect Contd.

Here the electron experiences the full nuclear charge.

However, if we now add some more electrons to the
atom:
 Shielding effect Contd.
• Then we can see that the valence (outer) electron
no longer experiences the full nuclear charge. It
experiences only the difference between the
attractive and repulsive forces. It is said to
experience only the effective nuclear charge.
• The core electrons are said to shield the valence
electrons from the nuclear charge. Why does this
ability of the core electrons to shield the valence
electrons depend on the shape of the orbital that
the core electron is in? It’s a simple case of
geometry
 Shielding effect Contd.
• The closer a core electron is to the nucleus the
better it will be at shielding the valence electrons.
Which electrons are closest to the nucleus for a
given value of n? The answer is the s-electrons.
• That is why the s-orbital is of a more negative
energy than the p-orbitals in the orbital diagram of
the multi-electron atoms. Thus the ability to shield
valence electrons is greatest for an s electron.
• The full order of shielding ability is –
s>p>d>f
• i.e. the same order of stabilities of the orbitals for
a given n value.
 Shielding effect Contd.
• The f - electrons for instance are in very diffuse o
rbitals away from the nucleus and are very poor at
shielding valence electrons from the nuclear charg
e.
• When more than one valence electron is present t
hen it must be remembered that they are very po
or at shielding each other from the nuclear charge
 Shielding effect Contd.
Thus as we go across a period adding valence electrons, •
the effective nuclear charge experienced by the valence
electrons increases because the nuclear charge has
increased and the added electrons are poor at shielding
each other
There are (of course!) exceptions to the trends stated •
above. If we look at the ionisation energies for the
second period.
 Shielding effect Contd.

You will notice that in general, the trend is as predict

ed; an increase from left to right. However two value
s seem to ignore our reasoning. I1 for boron is less
than that for Be and I1 for O is less than that for N.
Again, these discrepancies can be explained by lookin
g at the electronic configuration of the elements
involved.
 Shielding effect Contd.
(i) Boron and Beryllium
• Be 1s22s2
• B 1s22s22p1
For beryllium we are removing a 2s electron during
ionisation. For boron a 2p electron is removed. The
2p orbital is at a higher (less negative) energy than
the 2s orbital and we would therefore expect that it
would be easier to remove and that is borne out by
the numbers
 Shielding effect Contd.
(ii) Nitrogen and Oxygen
A more subtle explanation is required for these
elements as in both cases we are removing a 2p
electron. We will in fact have to go to the orbital
diagram for each of the elements.
 Shielding effect Contd.
• When ionising oxygen which electron will be rem
oved? The answer is the one marked . This electr
on is paired with another electron in a p-orbital a
nd will thus experience a repulsive interaction fro
m that other electron. This repulsive interaction
results in it being easier to remove than electron
that would be expected from the more simplistic
atomic-size approach.
• The result is that oxygen has a lower ionisation
energy than expected and in fact it is less than
the I value of nitrogen
 Shielding effect Contd.
Tutorials
(a) Which element in each of the following pairs of e
lectrons has the higher I1 value?
(i) Na or Mg (ii) Mg or Al (iii) As or Sn
(b) Predict which of the following ions has the larger
ionic radius: Mg2+ or Al3+.
(c) Predict which of the following elements has the
more exothermic (i.e. the most negative) electron
affinity: fluorine or sodium.
GROUP IV A ELEMENTS
Introduction
Group IVA elements have 4es in their valence shell
characterized by ns2np2 ground state electronic
configuration.

Classification
C is strictly nonmetallic, Si and Ge are metalloid. Sn and Pb
are metallic.
The electronic configuration and physical properties of the
elements are shown in the following Figure.
GROUP IV A ELEMENTS Carbon Silicon Germanium Tin Lead
Properties
C Si Ge Sn Pb
Ground State Electronic [Xe]6s26
[He]2s2p2 [Ne]3s23p2 [Ar]4s24p2 [Kr]5s25p2
Configuration p2
m. pt (oC) 3570 1420 959 232 327
b.pt (oC) 4200 2355 2700 2360 1755
D 3.51 W 7.31
Density g/cm-3 2.33 5.36 11.34
G 2.22
Covalent radius (Ao) 0.77 1.17 1.22 1.41 1.47
Ionization Potential (eV)
1st 11.3 8.1 8.09 7.30 7.38
2nd 24.4 16.3 15.86 14.5 14.96
3rd 47.9 33.5 34.10 30.5 31.9
4th 64.5 45.1 45.5 39.4 42.1

Ionic radius in crystals

(Ao)
M4+
- 0.41 0.53 0.71 0.84
M2+
- - - 1.10 1.27
Electronegativity 2.5 1.8 1.8 1.8 1.8

Electrode Potentials
*Eo(V)
M2+ + 2e M(s) -
Extraction

C – by burning natural gas (CH4) or petroleum in a limited

supply of air.

CH4(g) + O2 C(s) + 2H2O(g)

(Carbon black)

Si – by reduction of SiO2 with carbon or CaC2 in an electric furnace.

Ge – by reduction of GeO2 with C or H2.

Sn and Pb are obtained from their ores in various ways, commonly by reduction of their oxides with
carbon.
 Extraction of Pb
Example Pb from galena (PbS)
(i) PbS is roasted to the oxide

blast furnace. 2PbO(s) + C(s) 2Pb(s) + CO2

But some lead is formed in the process

PbS + 2PbO 3Pb + SO2(g)

(ii) The oxide formed in (i) is reduced with coke (pure C)
in a blast furnace

2PbS(s) + 3O2 (g) 2PbO(s) + 2SO2(g)

Some Pb is formed in the process.
Some Properties of the Elements

C & Sn exist in allotropic forms:

Diamond: Hardest substance known. Nonconductor of electricity.

Carbon

Graphite: 2-Dimensional sheet-like polymeric structure. Good conductors of electricity due to

the

mobile pi (π) electrons.

Sn exhibits 2 main crystalline allotropic forms namely white

and gray forms.

α – Sn

18 C
  β – Sn 
16 1 C
  Sn 
232 C
  Sn(l)

• Gray • White Rhombic

• Diamond Structure • More well known (Brittle)

Density: 5.75 7.28 6.56

CATENATION

Carbon has the unique ability to form compounds in which many carbon atoms are bonded to each
other in chains or rings. This property is called CATENATION. This property is also exhibited by other
elements near carbon in the periodic table (B, N, P, S, O, Si, Ge, & Sn) but to a much lesser extent
than carbon. This property of carbon accounts for the large number of organic compounds.

In Group IVA, the tendency to catenation is in the following order C  Si >Ge  Sn>>Pb
Oxidation States (-4, 4+, 2+)

The elements exhibit variable oxidation state. Carbon exhibits +4 in most of its compounds –
tetravalency

C & Si have some compounds in -4 oxidation state

e.g. Al4C3; Be2C, Mg2Si, Ni2Si

-1 oxidation state is exhibited by carbon e.g. CaC2. They are essentially covalent compounds; the
covalent bond is usually tetrahedral involving sp3 hybridization.

Ge, Sn, & Pb show inert pair effect. Form more +2 ions (or divalent); the stability of which increases
down the group e.g. Ge2+ ions are very unstable but Pb2+ ions are stable. PbO is more stable than
PbO2.

The elements behave more like metals in the lower oxidation states.