CHM 122: GENERAL INORGANIC CHEMISTRY

MAIN GROUP CHEMISTRY

INRODUCTION:

The Periodic table is divided into 7 horizontal rows and 18 vertical columns. The horizontal rows are
called periods and are numbered from the top downwards-

(Period 1, Period 2 …Period 7). The vertical columns are called groups and are numbered from left to
right. Elements in a particular group have the same number and arrangement of the outermost shell
electron(s). Some of the groups of the Periodic Table have their specific names e.g.

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 namely: 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
groups are in the s-orbital hence are called the s-block elements.

-The p-block contains elements of Groups IIIA to VIIIA which are therefore called the p-block elements
because their outermost shell electrons are located in the p-sub shell.

Elements in the s-and p- blocks are known collectively as the representative elements. The d-block
constitutes elements that have their highest energy electrons in the d-sub shell; hence, d-block
elements. They are the transition metals.

NB: the representative elements form the ‘A’ part of the Periodic Table while the‘d’ block elements
constitute the ‘B’ part of the Table.

This segment of the course will focus on the representative elements in Groups IA- IVA.

GROUP IA:

The elements in this group include: Lithium (Li), Sodium (Na), Potassium (K), Rubidium (Rb), Caesium (Cs)
and Francium (Fr).

**Not much is known about francium. It is radioactive, very rare and all of its isotopes are exceedingly
short-lived-hence very little of its chemistry is known.
The Group IA elements are mostly metals and are known 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 down the group (metallic character refers to the
tendency of a metal to lose electron(s) thus yielding positive ions).

1
Electronic Configuration The Group IA elements have the electronic configuration ns in their
outermost shell-where n represents the principal quantum number which increases with the atomic
number.

3
Li : 1s 2 2s1

11
Na : 1s 2 2s 2 2 p 6 3s1
19
K : 1s 2 2s 2 2 p 6 3s 2 3 p 6 4s1
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 easily 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.

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
crystallography. Substances having different types of structures will have marked differences in their
physical properties like melting points, boiling points, electrical conductivity, hardness and solubility.

When substances having the same type of structure are compared, the strength of binding force (bond
strength) accounts for the difference in property.

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: PROPERTIES OF GROUP IA ELEMENTS

Symbol ATOMIC IONIC MP BP DENSITY 1ST I.E. E.N.

RADIUS(Ả) RADIUS(Ả)   3 (kJ mol-1 )
( C) ( C) (g/ cm )
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 that influence the chemical behaviours of elements.
From quantum mechanics, the exact position of an electron in an atom cannot be measured with
certainty. It follows therefore that the size of an isolated atom cannot be accurately measured. It can
only be estimated because the actual location of electrons orbiting the nucleus cannot be determined.

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.

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. Looking at sodium for example:

11
Na : 1s 2 2s 2 2 p 6 3s1 There are 10 inner electrons ( 1s 2 2s 2 2 p 6 -full shells of electrons) and 1 outermost
1
electron ( 3s ). These 10 inner electrons reduce the attraction of the nucleus for the 3s electron thereby
lowering its effective nuclear charge (charge felt by an electron).
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.

Going down the group, atomic sizes increase, so the strength of the metallic bond decreases. Melting
point decreases from lithium to ceasium.

NB: metallic bonding is as a result of the electrostatic attraction between the delocalized valence
electrons and metal cations. It holds the metal ions tightly in the lattice and confers a high melting point
on them.

The smaller the size of a metal atom, the stronger the metallic bond strength and the higher the melting
point.

NB: delocalized electrons are free-moving electrons. They are not restricted to a particular position
because they are mobile.

Boiling point for the group also decreases down due to the weakening of metallic bonds between atoms
as size increases. Melting and boiling points depict how strongly the atoms in an element are stuck
together.

Ionic Radius:

When an atom gains or loses electron, a charged particle called an ion is formed. Metal atoms lose their
valence electrons to form positive ions (cations) while non-metal atoms gain electrons to form negative
ions (anions). Ionic radius is therefore, the radius of a cation or anion in an ionic compound.

Just like atomic radius, ionic radius increases down the group as the principal quantum number
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.

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.

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+ 10electrons, 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:

Na( g )  Na  ( g )  e ; 1st I .E.  492kJmol 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.

Na  ( g )  Na  ( g )  e ; 2nd I .E.  4562kJmol1

From the above equation, the second ionization energy is the energy needed to convert a univalent ion
to a divalent ion.

The table below shows the first and second ionization energies of the Group IA elements.

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 decrease 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 outermost electrons. In other words, it
will take a lesser energy to remove an electron that is not tightly held by the nucleus than to remove
one that is closer to the nucleus.

The magnitude of ionization energy is therefore a measure of how tightly an electron is held in the
atom. Group IA elements have the lowest first ionization energies.

When an electron is removed from an atom, electron repulsion reduces among the remaining electrons
and because the nuclear charge remains constant, the attractive pull by the nucleus on the electrons
becomes stronger, making it difficult to remove further electrons.

The second ionization energy is much greater than the first ionization energy for the Group IA metals
because an electron has to be removed from an inner shell that is much closer to the nucleus.

The second ionization energy of sodium as shown above is about 9 times greater than its first ionization
energy. As a result, Group IA elements do not form ions with a double positive charge.

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 reducing agents increases down the
group. Metals which show these properties to a marked extent are the most electropositive.

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.

Apart from the noble gases (Group VIIIA) that have zero electro- negativities, the alkali-metals (Group
IA) have the least electronegativity values.

As can be seen from the table 1, electronegativity decreases 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 element.
Chemical Properties

The alkali metals are so reactive that in nature, they occur as their compounds i.e. they are always found
combined with other elements. They exist as chlorides, nitrates, sulphates, carbonates, silicates, etc.

Their oxides and hydroxides are basic and they release hydrogen 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 oxidation.

Reactions:

With Hydrogen:

Alkali-metals react with hydrogen gas to form hydrides. The ease of formation of the hydrides decreases
down the group.

2M (s)  H 2 ( g )  2MH (s) (M = Group IA metal)

All the hydrides of the Group IA are white solids and ionic in nature. M+ H-. This is one of the reactions
where hydrogen furnishes the negative ion.

The above reaction is the direct synthesis of metal hydrides and the usual method of preparation.
However, the reaction is slow at room temperature –as heating is required to melt the metals before
reaction takes place. Temperatures of between 300◦C and 500◦Care required for such reactions. All the
hydrides of the alkali-metals are white solids.

The most important alkali-metal hydride is lithium hydride. On treatment with aluminum chloride in a
dry solution of ether, lithium aluminum hydride, (LiAlH4), is formed.

4LiH  AlCl 3 dry

ether
  Li  ( AlH 4 )   3LiCl LiAlH4 is one of the most useful reducing
solution

agents in organic chemistry. The alkali-metal hydrides react immediately with water, giving off
hydrogen:

LiH (s)  H 2O(l )  LiOH (aq)  H ( 2) ( g )

The stability of the hydrides decreases down the group which also implies that the reactivity of the
metal hydrides increases down the group.

With Oxygen:

Group IA elements react rapidly with oxygen to form three types of oxides namely: monoxides (normal
oxides), peroxides and superoxides. Lithium forms lithium oxide, Li2 O (i.e. lithium monoxide); sodium
forms mainly sodium peroxide, Na2O2 though it can also form sodium oxide, Na2O, while the other
metals- K, Rb, Cs, form mainly the superoxides as shown in the table below:
4Li(s)  O( 2) ( g )  2Li2O(s) (Lithium oxide)

2 Na(s)  O2 ( g )  Na2O2 (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 )  2K2 CO3 (s)  3O2 ( g )

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 ) 

 2 NaOH (aq)  H 2O2 (l )
cold

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.

The three oxides react with acids as follows:

Normal: Na2O(s)  2HCl(aq)  2 NaCl (aq)  H 2O(l )

Peroxide: Na 2 O2 (s)  2HCl(aq)  2 NaCl (aq)  H 2O2 (l )

Superoxide: 2KO 2 (s)  2HCl(aq)  2KCl (aq)  H 2O2 (l )  O2 ( g )

Except LiOH all Group IA hydroxides 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.

2LiOH (s) 


Li2O(s)  H 2O( g )
With Water:

All alkali metals react with water and reactivity increases down the group. Lithium reacts readily. Sodium
darts about 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 even more violent and best
not attempted because of explosions.

2M (s)  2H 2O(l )  2MOH (aq)  H 2 ( g ) (M = Group IA metal)

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.

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.

With Nitrogen:

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

6M (s)  N 2( g )  2M 3 N (s) (M = Group IA metal)

The alkali-metal nitrides decompose at low temperatures and react with water vapour to form ammonia
and the metal hydroxide:

Na3 N  3H 2O  NH 3  3NaOH

With Ammonia:

Alkali-metals dissolve in ammonia to form ionic amides

2 Na  2 NH 3  2 NaNH 2  H 2 (or any other alkali-metal)

With Alkyl halides:

Group IA metals react with alkyl halides to form the metal alkyl. e.g.

2Li  CH 3Cl  CH 3 Li  LiCl

THE CARBONATES/HYDROGEN CARBONATES

The carbonates and hydrogen carbonates of the alkali-metals are white solids and have the general
formula,

M2 CO3 and MHCO3respectively (M = Group IA metal).

They are all soluble in water except lithium carbonate. Note that lithium does not give a hydrogen
carbonate i.e. LiHCO3 does not exist.

The two sets of carbonates evolve CO2 when reacted with acids. This is a general property of carbonates.
Example:

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

NaHCO3( s )  HCl( aq)  NaCl( aq)  CO2 ( g )  H 2O(l )

All Group IA carbonates except lithium carbonate are stable to heat. That is, only lithium carbonate
decomposes on heating:

Li2CO3 (s) 


Li2O(s)  CO2 ( g )

Na2CO3 (s) 


No reaction (also K, Rb, Cs)

On the other hand, all the hydrogen carbonates decompose on heating. Remember, LiHCO3 does not
exist. Example:

2 NaHCO3 (s) 


Na2CO3 (s)  CO2 ( g )  H 2O( g )

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 naturally in substantial amount. Except
lithium nitrate, the Group IA nitrates decompose on heating to the corresponding nitrite and oxygen.
Example:

2KNO3 (s) 


2KNO2 (s)  O2 ( g )
2 NaNO3 (s) 


2 NaNO2 (s)  O2 ( g )

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). Na2SO4 is the major compound in the group.
Generally, sulphates are usually more thermally stable than nitrates and carbonates.

Anomalous Properties of Lithium

Lithium stands at the head of Group IA metals. Many of its properties quite differ from those of the
other members of the group. The main reason for this anomalous behaviour is the small size of lithium
ion. This causes the behaviour of lithium 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 fluoride and by the fact that
some lithium compounds are soluble in organic solvents e.g. lithium chloride is soluble in ethoxy ethane.

From Fajan’s rule, an ionic compound will have a high degree of covalency if the positive ion is small and
highly charged- i.e. covalency is promoted by small cations and large anions.

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 manufactured through the Solvay process. It is a
fine white powder used for the manufacture of glass. It is widely used in the paper industry and in the
manufacture of soap and detergents. It is used as a water softener and in the laboratory; it is used to
standardize acids and also used as an analytical reagent. It is by far the most commercially important
Group IA carbonate.

Sodium hydrogen carbonate: this is a white crystalline solid and used in baking powder and fire
extinguishers. It is responsible for the rising of flour by the release of carbon (iv) oxide on decomposition
by heat.
Sodium hydroxide: this is used in soap and detergent manufacture. Also used for rayon and in paper
industries. In the laboratory, it is used as a strong alkali and analytical reagent.

Sodium nitrate: this is used in fertilizer production and also in the production of nitric acid.

Potassium superoxide: this is used in air purifiers, submarines, spacecraft, and portable breathing
apparatus. It has the ability to absorb CO2 while giving off oxygen at the same time.

GROUP IIA

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 alkaline-earth metals.
They are so called because they form alkaline solution when they react with water and 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 ns 2 electronic
configuration. 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 metals and always occur in nature as compounds because they are too electropositive to occur
free in nature. Just as the alkali metals the metallic character increases down the group. The table below
shows some of their properties:

TABLE 4: PROPERTIES OF GROUP IIA ELEMENTS

SYMBO ELECT. ATOMIC IONIC MP BP DENSITY 1ST I.E. E.N.

L CONFIG. RADIUS( RADIUS   3 kJ mol-1
Ả) (Ả)
( C) ( C) (g/ cm )
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, radium, 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.

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.

Ionization Energy:

As a general trend, values of ionization energies decrease down the group. This is as a result of the
increasing distance 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 electrons have to be removed from an inner
shell much closer to the nucleus. That is why Group IIA elements do not form trivalent ions

TABLE 2: 1st, 2nd and 3rd Ionization Energies of Group IIA

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.

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.

This is due to the fact that the alkaline-earth metals are relatively smaller in size than the alkali metals
and as a result, their valence electrons are held stronger by the nucleus. This stronger nuclear attraction
makes it difficult for electrons to be removed from the outermost shells of the alkaline-earth metals
thereby making them to have higher first ionization energies than the alkali metals in the same period.

Chemical Properties/Reactions:

The reactivity of the metals increases down the group, a reverse trend when compared with the
ionization energies.

It is good to note that the alkali-metals are more reactive than the alkaline-earth metals due to the
lower ionization energies of the Group IA metals as explained earlier.

With Hydrogen:

With the exception of beryllium, all the Group IIA metals react with hydrogen to form hydrides.
M (s)  H 2 ( g )  MH 2 (s)
(M = Group IIA metal)

They are ionic hydrides and react with water as follows:

MH 2 (s)  2H 2O(l )  M (OH ) 2 (aq)  2H 2 ( g )

(M = Group IIA metals except beryllium)

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)

Beryllium oxide, BeO, is more like the oxide of aluminum 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 )

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 beryl late.

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

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)

With Nitrogen:

All members of Group IIA elements form nitrides when heated in Nitrogen. The ease of formation of the
nitrides 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)

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)

Apart from beryllium halides, the Group IIA halides are predominantly ionic. Reactivity increases in the
order: I2  Br2  Cl2  F2 ; Be  Mg  Ca  Sr  Ba

THE CARBONATES:

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 ) (M = Group IIA metal).

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)  4 NO2 ( g )  O2 ( g )

*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 nitrates*

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 stable to heat. Beryllium, magnesium and calcium sulphates are often found as hydrated
crystals e.g. BeSO4 .4H 2O, MgSO4 .7 H 2O, CaSO4 .2H 2O .

BaSO4 is extremely insoluble in water.

THE HALIDES:

The elements all give fluorides, chlorides, bromides and iodides but the chlorides are the most common.
They are soluble in water but the fluorides are much less soluble than the others due to higher lattice
energies of the fluorides compared to other halides.

Anomalous properties of Beryllium:

Beryllium exhibits a diagonal relationship. It resembles aluminum and differs from other members of
Group IIA elements:

 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.

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 substantial covalent character.

USES OF SOME COMPOUNDS OF GROUP IIA ELEMENTS

Magnesium hydroxide: it is a very good antacid. It neutralizes excess hydrochloric acid which causes
gastric pain in people.

It has advantage over other antacids as it does not produce carbon dioxide which causes belching.

Calcium hydroxide is used in the industry to neutralize acids in effluents.

Gypsum, CaSO4.2H2O is used for plaster casts to immobilize broken bones.

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 [He]2s22p1 [Ne]3s23p1 [Ar}4s24p1 [Kr]5s25p1 [Xe]6s26p1
Configuration
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)
1st
2nd 801 578 579 558 589
3rd 2427 1817 1971 1813 1961
3660 2745 2952 2692 2867
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
M 3  3e  M (s)
- - 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
elements 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 predominantly covalent.

Boron is a metalloid while the other elements are metallic and fairly reactive.
 Table 6: Reactions of Al, Ga, In and Tl

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
+ 3+
2M+6H 2M +3H2 Tl also gives Tl+
2M + 2OH- + 6H2O With Al and Ga only
2M(OH)-4 + 3H2
M = Group IIIA Element
Note:
1. The sulfates, nitrates and the halides are water soluble, but M3+ ions hydrolyse readily.
2. Oxides and hydroxides exhibit the usual trend in decreasing 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.
Al2O3 (s)  6H  (aq)  2 Al 3 (aq)  3H 2O(l )
Al2O3 (s)  6OH  (aq)  3H 2O(l )  2 Al (OH )36 (aq)

In2O3, Tl2O3 – are basic, no acid character at all.

Table 7: Occurrence and Extraction of B an Al

Occurrence As borax, Na2B4O7. 10H2O 3rd most abundant metal in the

As Kernite, Na2B4O7. 4H2O earth’s crust. Occurs As bauxite,
Al2O3.2H2O.

Extraction Borax + HCl Boric acid Electrolysis of the fused salt.

(H3BO3) 4Al3+ + 6O2- + 3C(s)
H3BO3 -H2O B2O3 Electrolysis 4Al(s) + 3CO2(g)
 (Boric Oxide)

B2O3 +3Mg(s)  2B(s) + 3MgO(s).

2BX3(g) + 3H2(g)
W
1500 C
 2B(s) +
6HX(s)

(X = Cl, Br) (W = tungsten)

Two types of boron: Crystalline B – Hard. It is chemically inert Amorphous B – highly reactive.

Table 8: Chemistry of amorphous B and Al

Reactions B Al
4M+3O2 At high temp; high heat of reaction At high temp.
2M2O3
2M+N2 2MN At white heat Forms
0
2M+3S M2S3 Passage of S vapour over B at 1200 C At high temperature

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 vigorously hotconc 2H3BO3(aq) + 3SO2(g) 6H2O + 3SO2(s)
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 to
BnHn+4 e.g B2H6, B5H9, B6H10, B10H14 and BnHn+6 e.g. 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, NaBH4. 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, H3BO3 Amphoteric
hydroxides pyroboric acid, H2B4O7; Al(OH)3 + 3HCl
 metaboric acid, HBO2 AlCl3 + 3H2O

Al(OH)3 + NaOH
NaAlO2 + 2H2O
(Sodium aluminate)
With H2O Reacts only with steam at red heat to form boric acid No Reaction
and hydrogen.
2B(s) + 6H2O(g) 2H3BO3
( steam) +
3H2O(g)

With alkali Dissolves in fused strong base to form metaborate and Dissolves in strong base to form
H2(g) aluminate and H2
2B(s) + 2NaOH(l) +2H2O 2Al(s)+2NaOH(aq) + 6H2O
2NaBO2 + 3H2(g)
2NaAl(OH)4(aq)+3H2(g)
Double Salts None
Aluminium sulphates form important series of double salts called alums.
MAl(SO4)2 . 12H2O
OR
M2SO4 . Al2(SO4)3 . 24H2O
where M is almost any univalent cation.
Na+,K+, Rb+, CS+, NH4+,Ag+, Te+) except Li+ (too small to be acommodated without loss in
stability of the structure)
In addition to Al3+ other M3+ are Fe3+, Cr3+, Mn3+, Tl3+, CO3+, Ga3+, In3+,Rh3+ and Ir3+.

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.
6. Aluminium is used to remove oxygen and nitrogen from molten iron and steel, thus preventing
blow-holes in castings.
7. Aluminium is used in the preparation of chromium from chromium (III) oxide; manganese from
manganese (IV) oxide and titanium (IV) oxide.
8. Aluminium is used as foil for wrapping foods and confectionery and for milk bottle tops.
9. Aluminium is used for surfacing mirrors of large telescope.
 10. Gallium and indium have been used to make semiconductors for solid-state electronics.
NB: A diagonal relationship exists between boron and silicon.

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 Table 9

Occurrence

C-occurs as diamond, graphite, in coals, mineral oils (Petroleum – hydrocarbon), limestone, marble
CaCO3; magnesite MgCO3 and dolomite (CaCO3.MgCO3) and of course as CO2 in the atmosphere.

Si – occurs in silicate minerals, Ge – rare element., Sn – occurs in cassiterite (SnO2). Pb – occurs chiefly as
galena (PbS).

Table 9: Electronic Configuration and Physical

Properties of Group IVA Elements.

Carbon Silicon Germanium Tin Lead

Properties
C Si Ge Sn Pb
Ground State Electronic
[He]2s2p2 [Ne]3s23p2 [Ar]4s24p2 [Kr]5s25p2 [Xe]6s26p2
Configuration
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)

- - 0.0 -0.136 -0.126

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.

Example Pb from galena (PbS)

(i) PbS is roasted to the oxide

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

Some Pb 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. 2PbO(s) + C(s) 2Pb(s) + CO2

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.

Expansion of Coordination Number.

Except for carbon, all the other elements in the Group can extend their coordination number beyond
the Group valency of 4 i.e. tetravalency (4) because of the presence of empty d orbitals.

General Properties

1. The size increases down the group. The difference in size between Si and Ge is less than
might be expected, because, the filling of the 3d shell increases the nuclear charge and provides
only poor shielding d electrons. In a similar way, the small difference in size between Sn and Pb
is because of the 4f shell.

2. The ionization energies decreases from Carbon to Si but then change in an irregular manner
because of the filling of the d orbitals in Ge and Sn and filling of f orbital in Pb.

3. Carbon and Silicon are non metals (Graphite is a non metal and diamond a metal).
Germanium has some metallic properties, Sn and Pb are metals.

4. The first member of the group like every first member in every group differs from the rest of
the group because of its smaller size, higher electronegativity and non availability of d orbitals.

5. The inert pair effect is evident in the heavier members of the group. There is a decrease in
stability of +IV oxidation state and an increase in the stability of the +II state on descending the
group.

Chemical Properties

1. The elements in this group are relatively unreactive but reactivity increases down the group.

2. They are generally attacked by acids, alkalis and the halogens. Graphite by F, Si by HF, Ge by
H2SO4, and Sn and Pb by a number of acids.

3. Reaction with Hydrogens

They all form covalent hydrides. Carbon forms a vast number of chain and ring compounds. The
ability to form chain is called catenation. Silicon also forms saturated hydrides with the general
formula SinH2n+2, called silanes. Unlike alkanes, silanes are strong reducing agents, burn in air,
explode in Cl2 and are readily hydrolysed by alkaline solution.
trace of alkali
Si12H26 +H2O 2SiO2.nH2O + 7H2

Ge also forms germanium hydrides or germanes, similar to silanes but less inflammable and less
readily hydrolysed.
Sn forms stannane SnH4 which is less stable and difficult to prepare. Distannane Sn2H6 is also
known to exist.

Pb forms plumbane PbH4 which is less stable and more difficult to prepare.

4. Reaction with Halogens

They react with halogens to form tetrahalides. PbI4 is not known. They are all tetrahedral and
very volatile and covalent except SnF4 and PbF4 which are ionic and high melting.

CF4 is very unreactive and stable. Mixed chlorofluoro hydrocarbons such as CFCl3, CF2Cl2 and
CF3Cl are known as Freon.

5. Reaction with Oxygen

Carbon reacts with oxygen to give five different oxides CO, CO2, C3O2, C5O2 and C12O9. Two
oxides of silicon are known SiO and SiO2 (Silica).

The oxides of germanium, tin and lead are GeO2, SnO2 and PbO2. They follow the usual trend of
decreasing in acidity (ie. Increasing in basic strength) on descending the group GeO2, SnO2 and
PbO2 are amphoteric and they dissolve to form germinates, stannates and plumbate
respectively.

The lower oxides GeO, SnO and PbO are also formed. They exist as layer lattices. They are
slightly more basic and ionic than the corresponding higher oxides. GeO is acidic whilst SnO and
PbO are amphoteric.

6. Formation of Silicates

Silicates are prepared by fusing an alkali metal carbonate with silica

1500oC
Na2CO3 CO2 + Na2O + SiO2 Na4SiO4 (Na2SiO3)n and others.

A large percentage of the earths crust consists of silicate minerals or aluminosilicate clays.
Silicones are a group of organosilicon polymers.

7. Reaction with Carbon (Carbides)

Compounds of carbon and less electronegative element are called carbides. Carbides are of 3
main types – ionic or salt like (Group I – III metals) react and make more explicit. They can be
prepared generally by heating the metal or its oxide with carbon or a hydrocarbon at
temperatures of 2000oC

8. Reaction with Organic Compounds

Tetra organic derivatives of Si, Ge, Sn and Pb may be prepared from the halides using Grignard
or organolithium reagents

SiCl4 + CH3MgCl CH3SiCl3 (CH3)2SiCl2 (CH3)2SiCl (CH3)4Si

PbCl2 + C2H5Li Pb(C2H5)2 Pb(C2H5)4.

Uses of Group IV element

1. Silicates from silicon are important in the ceramic and cement industries.

2. PbO is used in ceramics Pb3O4 in paint and PbO2 in lead accumulators.

3. Silica is useful in the manufacture of optical components such as lenses and prisms since it is
very transparent to visible and ultraviolet light. It is also used for laboratory glassware.

4. Silica gel is employed as a drying agent and as a catalyst.

5. CO2 in the solid from sublimes directly to vapour state at – 78oC under atmospheric pressure.
It is widely used as a refrigerant and otherwise known as “dry ice” or cardice.

6. CO is useful as a reducing agent in the extraction of iron. It reduces many metal oxides to the
metal.

7. Biologically CO2 is important in the processes of photosynthesis, respiration and

fermentation.
sunlight
6CO2 + 6H2O C6H12O6 + 6CO2 Photosynthesis
Glucose

C6H12O6 + O2 6CO2 + 6H2O + energy respiration

C6H12O6 2C2H5OH + 2CO2

Ethanol

blast furnace
Fe2O3 + 3CO 2Fe + 3CO2

CuO + CO Cu + CO2
8. CO is an important ligand which can donate or share a lone pair of electrons. It can form a
coordinate bond with many transition metals and form compounds.