Group 1

st
A
o Lithium (Z=87), Sodium (Z= 11), Potassium (Z=19), Rubidium (Z=37),
Caesium (Z=55) and Francium (Z= 87) are the elements of IA group of the
periodic table . These elements are known as alkali metals, because they form
water-soluble hydroxides, which are strongly alkaline. Francium is the
radioactive elements among IA group elements.
o Atoms of alkali metals have single valence electron and form cations with
only a single positive charge when they take part in compound formation. All
the alkali metals are paramagnetic because of the presence of one valence
electron in the valence shell. General outer electronic configuration of alkali
metals is ns1 (where n = 2 3, 4, 5, 6 and 7 ). Their penultimate quantum layers
have the stable electronic configuration of noble gas s
2
p
6
, (for lithium s
2
). The
alkali metal cations, Li
+
, Na
+
, K
+
, Rb
+
and Cs
+
all are diamagnetic because of
absence of unpaired electrons . All these cations have stable s
2
p
4
noble gas
configuration.
o The alkali metals are extremely reactive metals. They all readily lose one
electron, the outermost s-electron, to form a single positively charged ion
that has the same electronic configuration as one of the noble gases. The
relatively simple chemistry of alkali metals is probably due to the ease
with which their single outermost electron can be lost in order to achieve
stable rare gas electronic configuration. As a group, the alkali metals have
the lowest first ionization energies among all the elements in the periodic
table. Because of their strong chemical activity, the alkali metals occur in
nature only in the form of compounds. Alkali metals never occur in free state
in nature. Compounds of sodium and potassium are the most abundant, while
those of remaining alkali metals occur in nature rarely. Francium is radioactive
element and short lived. These metals are readily oxidised in air. The less
electropositive such as lithium is found as silicate and the most
electropositive elements of IA occur as chlorides. To prevent oxidation they
are stored in closed vessels of low density (0.53 g/cc). Lithium is the lightest
or least dense of all metals, with a density roughly half that or water.
Lithium is kept wrapped in paraffin wax.
o They are all silvery white, soft and malleable metals. They are so soft that they
can easily be cut with a knife.
o All the alkali metals show metallic luster, which can be explained by the
oscillation of free electrons. Alkali metals are most electropositive in the
periodic table. The metallic character increases from lithium to Caesium. The
elements are all metals and are good conductors of heat and electricity.
o The atomic radius in a group increases from lithium to Caesium. In each
period, the alkali metal has maximum atomic size. As the size of atom
increases from Li to Cs, there is more repulsion from the non-bonding
electrons, resulting in decrease in cohesive energy and an increased softness.
o Alkali metals have only one valence electron. Thus their metallic bonding is
weak. They are, therefore, soft metals of low density and have low melting
and boiling points. They also have low enthalpies of fusion, vaporization and
atomization.
o Alkali metals have low density because of their large atomic size. Density of
these elements gradually increases from lithium to Caesium. However,
potassium is lighter than sodium. Due to weak intermolecular attraction, these
metals have low melting points. Thus energy required for binding the atoms in
the crystal lattice of the metal is low. The melting point of alkali metals also
decreases from lithium to calcium. The boiling point of alkali metals also
decreases from lithium to Caesium.
o The ionisation energy of these elements is low and gradually decreases from
lithium to Caesium. Thus Caesium is the most electropositive element in
the periodic table. Because of low ionisation energies , these elements have
great tendency to lose 1st electron to form positive ions. Thus these elements
are said to have strong electropositive or metallic character. Because
ionisation energy decreases on moving down a group, from lithium to
Caesium, the electropositive character or metallic character increases
from lithium to Caesium.
o Alkali metals have very low electronegativities and this property decreases
from lithium to Caesium.
o All the alkali metals exhibit
+
1 oxidation state. Since after losing 1 electron,
the resulting cation possesses the stable noble gas configuration, other
oxidation states are not possible.
o The vapours of alkali metals impart characteristic colours to the flame. For
example, caramine red for lithium, yellow for Na, violet (lilac) for K, violet
rose for Rb and blue for Cs. The flame test is due to the excitation and de-
excitation of electrons of outer energy levels. In flame test, conc. HCl is added
to convert the given salt into volatile chloride.
o The metals form compounds mainly with ionic bonds, because they readily
give up the s-electron from the outermost shell. Small highly polarizing ion
such as Li
+
tend to form covalent compounds . Most other cations of IA group
elements are large and have low charge densities. Hence they form stable
compounds even with polarizing ions such as carbonate, peroxides, tri lodide
etc. LiCl is soluble in pyridine because of its covalent nature. Bond present in
the molecules like Li
2
, Na
2
, K
2
etc is covalent . It should be noted that alkali
metals form diatomic molecules such as Li
2
, Na
2
, K
2
, etc to the extent of 1% in
vapour state.
o Because of low ionisation energies and strong electropositive character,
alkali metals such as K, Rb and Cs show photoelectric effect .
o In the electrochemical series all alkali metals are arranged above hydrogen.
They are easily and readily oxidised by water. The reaction with water is so
exothermic that the heat generated often ignites the H
2
(g) produced, if air is
present. These metals replace hydrogen from water. The alkali metals readily
react with non-metals such as halogens and sulphur to form ionic salts. These
reactions are exothermic, frequently violent and can even be explosive.
o When these metals are heated at 350-400C in an atmosphere of hydrogen,
they form hydrides, in which hydrogen is electronegative. The ease of
formation ionic hydrides increases from Li to Cs.
o The alkali metals must be protected from exposure to air because they react
with O
2
, H
2
O and CO
2
. When burnt in air, lithium forms monoxide (Li
2
O),
sodium forms monoxide in limited O
2
and peroxide in excess O
2
. Other alkali
metals form largely the super oxides. In the presence of atmospheric oxygen
we will get the mixture of oxides.
v
The reactions of alkali metals with water and oxygen are so exothermic that
they can cause a fire or even an explosion. It is therefore, dangerous to expose
alkali metals to the air, which contains both oxygen and water vapour. The
hydroxides of alkali metals are hygroscopic, readily absorb CO2, form air and
destroy glass. They dissociate in solution almost completely.
o The alkali metals replace hydrogen from those acids which are not oxidizing
agents (eg. HCI, dilute H
2
SO
4
). While reacting with oxidizing acids such as
conc. H
2
SO
4
, conc. HNO
3
and dilute HNO
3
, these metals do not replace
hydrogen but H
2
S , N
2
O and NH
3
are respectively formed.

o Compounds of alkali metals are ionic crystalline solids and with very few
exceptions these compounds are soluble in water. Alkali metals crystallise in
body centred cubic lattices. The co-ordination number is 8. Seawater
contains sodium in the form of ionic salt, NaCl. NaCl is essential for digestion
in animals and humans, but too much salt can cause high blood pressure and
retention of water in tissues. Potassium is an important element for plant
growth. Potassium salts such as KNO
3
or KCl are used as fertilizers.
o Because of strong tendency to lose the s-electron , the alkali metals are
powerful reducing agents. Lithium in aqueous solution is as strong a
reducing agent as Caesium. This is probably due to high hydration energy of
small lithium ion, which compensates for high ionisation energy. The
hydration energy of alkali metal ions follows the order: Li
+
> Na
+
> K
+
> Rb
+

> Cs
+
. Due to extensive hydration, Li
+
ion has the highest hydration energy,
as a result of which reduction potential of Li is higher than other alkali metals.
Thus most powerful reducing agent in solution is lithium.
o The reactivity of alkali metals towards all reagents (except nitrogen) increases
as the ionisation energy decreases from lithium to Caesium. Fox example, the
vigorous nature of the reaction of water with alkali metals increases from Li to
Cs. Lithium is only slowly attacked by water at 298 K, though it liberates
more energy in its reaction with water. Sodium reacts more vigorously,
whereas potassium catches fire and rubidium and cesium react violently or
explosively.
o The fact that lithium reacts with water less vigorously may probably be due to
its higher melting point. Other alkali metals have low melting points (below
373 K) and melt due to the heat liberated in their initial reaction with water,
thus exposing more metal surface to attack. The reaction, therefore, proceeds
much more rapidly than with lithium which remains in solid state.
o Despite its high ionisation energy, lithium is the only alkali metal, which
reacts directly with nitrogen and carbon to form the nitride and carbide
respectively. Other alkali metals do not react directly with either nitrogen
or carbon. This is probably due to the fact that small size of the nitride
and carbide ions coupled with the small size of Li
+
ions results in high
lattice energies for these compounds. Thus heats of formation of these
compounds are also high resulting in more stability.
o All alkali metals form amalgams with mercury and the reaction is exothermic.
Sodium amalgam is less reactive than the sodium metal. All alkali metals
combine directly With P, As, P and S.
o When heated with NH
3
gas at 300-400C in presence of Fe, alkali metals form
amides of the type MNH
2
. The expected order of reactivity of the metal and
the corresponding stability of the salt formed is Cs > Rb > K > Na > Li.
o Except lithium nitrate, the nitrates of alkali metals are thermally stable.
Alkali metal sulphates form double salts called alums. Lithium does not form
these alums because of its small size.
o The only monoxide obtained by direct combination of the metal with oxygen
is that of lithium, Li
2
O. Monoxides are ionic and colourless compounds and
contain the oxide ion O
2
-. They are strongly basic. With the exception of
lithium monoxide, all others can be produced by reducing the nitrite or nitrate
with free metal.

o Lithium monoxide is slowly hydrolysed (due to its lattice energy ) and all
other monoxides are hydrolysed with water to form hydroxides.
o The peroxides contain [ - O - O - ]
2
- ion and are salts of H
2
O
2
. The peroxide
ion has two electrons more than O
2
molecule. The peroxides are diamagnetic
and slightly yellow in colour due to the defects in crystal structure. Peroxides
are powerful oxidising agents.
o Superoxides are the direct oxidation products of K, Rb and Cs, in excess of
oxygen. Sodium super oxide can also be prepared by heating sodium peroxide
with oxygen under pressure in a sealed vessel.

o Super oxides contain O
2
2-
ion which has one electron more than the oxygen
molecule.
o The stability of peroxides and Superoxides increases with increase with
increase in size of cation and shows stabilisation of large anions by large
cation through lattice energy effects. The inability of lithium to form a
peroxide or superoxide may probably be due to strong polarisation power of
its ion. The Li
+
ion is strong enough to restrict the oxidation of an oxide
ion,O
2
- to the peroxide ion ,O
2
2-
. Similarly Na+ prevents the oxidation of O
2
2-

to O
2
-.
o Nickel and cast iron are resistant to fused caustic alkalis. Elements having
electronegativity values less than 1.5 are not attacked by alkali
hydroxides. Those elements having electronegativity values between 1.5
and 2 .0 dissolve in hydroxides and H
2
is evolved with the formation of
alkali metal salt of the oxide . Elements having electronegativities greater
than 2 dissolve without evolution of hydrogen forming their hydride or
the alkali metal derivative of that hydride as one of the products.
o Hydrides of the type MH have been prepared for all alkali metals, except
francium. They are colourless, crystalline, ionic solids. The hydrides are
largely ionic with the negative hydride ion H- , present in the lattice . The
alkali metal hydride posses Na Cl -type structure. The ionic character of
the bonds in these hydrides increases as the atomic number of metal
increases. Their stability decreases in the same order.
o Hydroxides of all alkali metals are thermally very stable except LiOH , which
decomposes to the oxide when calcined.

o Lithium hydride is by fact the most stable hydride which dissociates above
1273 K. Sodium and potassium hydrides dissociate below 773K. The stability
decreases from LiH to CsH.
o The Li-H bond has been fond to be only 25% ionic. As the ionic character of
M-H bond increases with increase in size of the metal, it would appear that
M+ H- is less stable than the covalent M-H bond . The alkali metal hydrides
are strong reducing agents and reducing property increases with decrease
in stability. Lithium also forms some complex of the Li AlH4 and LiBH4 ,
which like simple hydrides , are also good reducing agents.
o Alkali metals readily react with halogens to form MX type of halides . These
are mainly ionic compounds having NaCl typoe of structure with a co-
ordination number of 6, except for Cs Cl , Cs Br and CsI , whiich have a Cs Cl
type structure with a co- ordination number of 6, although of 8. Due to more
favourable lattice energy , lithium also exhibits a co-ordination number of 6,
although the theoretically expected value is 4. Because of small size of Li+
ion, all form hydrated salts more readily than other alkali metals . In fact ,
LiCl, LiBr and LiI , all form trihydrates , LiX.3H
2
O . Other alkali metal
halides are anhydrous . The melting and boiling point of halides almost metal
halides comprise only singly charged ions and hence have low lattice energies
. The all alkali metal halides (except LiF) are soluble in water .
o For a substance to dissolve , the hydration energy must be greater than
lattice energy . Due to small size of Li+ ion , the hydration energy of LiF is
considerably high , but it has low solubility in water because its lattice
energy is even higher . The hydration and lattice energies of LiF are -1034
and - 1039 kJ/ mole respectively.
o The alkali metals are highly electropositive and hence their oxysalts are quite
stable. Carbonates are remarkable stable . Li
2
CO
3
is less stable and
decomposes readily. The strong polarising action of the small cation on the
large carbonate ion presumably assists the decomposition.

o The gain in lattice energy resulting from the substitution of a smaller
oxide ion from larger CO
3
2-
ion enables the decomposition. Bicarbonates
of all alkali metals , except that of Li, can be obtained in the solid form.
All carbonates and bicarbonates are soluble in water . Lithium carbonate
is sparingly soluble.
o Due to the presence of a single loosely held electron in the valence shell,
the alkali metals are excellent conductors of heat and electricity and show
photoelectric effect .
o The alkali metals can not be prepared by the reduction of their oxides, as
the metals themselves are strong reducing agents. Electrolysis of the
aqueous solutions of their salts produces the metal hydroxide, as the
metals are very reactive towards water. For these reasons, the isolation of
alkali metals is usually carried out by the electrolysis of their molten salts
.
o Lithium is extracted by the electrolysis of a fused mixture of LiCl and KCl (
1:1) . KCl reduces the m.p of of LiCl from 883K to 673 K . Sodium is
extracted by the electrolysis of a mixture of NaCl and CaCl
2
(Down's process) .
CaCl
2
decreases the m.p of NaCl from 1076K to 778K. Potassium cannot be
prepared by the electrolysis due to its low melting point and ready
vapourisation. It can be prepared by passing sodium vapour over molten KCl
in a counter current fractionating tower. Rubedium and caesium are made by
similar methods.
o The alkali metals are best purified by distillation .
o The alkali metals are soluble in liquid ammonia giving a solution which is
paramagnetic , highly conducting, highly reducing and deep blue in
colour . The solution is blue when dilute and acquires and intense blue
colour as more metal is added . Colour of these solutions is independent of
the metal involved. Dilute solutions are paramagnetic and blue solutions have
a broad absorption band at 1450nm. The blue solution has remarkably high
electrical conductivity, which varies with concentration in an anomalous
manner. Properties of these solutions strongly suggest that alkali metal atoms
ionise in liquid ammonia forming solvated cations and solvated electrons. The
solutions are strong reducing agents due to the presence of free electrons. It
reduces (a) Metal halides to metals (b) N
2
O to N
2
(c) O
2
to O
2
- and then to O
2
2-

. The solution of a metal in liquid ammonia causes a large increase in
volume (decrease in density). This solution of a metal in liquid ammonia
causes a radius 300-400 pm. As a result , the solutions occupy far greater
volume than expected from the sum of volumes of metal and solvent. This
causes a decrease in density .
o Most abundant alkali metal in earth's crust is sodium . It was first isolated by
Davy in 1807 . It is one of the most reactive metals and so it does not occur in
free combines vigorously with water and many other elements and
compounds, where it acts as a strong reducing agent . It occurs in combined
form as rock salt (NaCl) , chile saltpetre or caliche (NaNO
3
), borax
(Na
2
B
4
O
7
, 10H
2
O), cryolite (Na
3
AlF
6
) and felspar (NaAiSi
3
O
8
). Sodium is
extracted by Castener's process and Down's process. Sodium is soft silvery
white metal, lighter than water .Its density is 0.972 g./cc. It is malleable as
well as ductile.
o There are number of important sodium compounds such as NaOH (caustic
soda), sodium carbonate (Na
2
CO
3
. 10 H
2
O ) , Na
2
CO
3
, (soda ash) and
sodium bicarbonate , NaHCO
3
(baking soda). Sodium hydroxide is
hygroscopic. When it is dissolved in water, a large amount of heat is evolved
(exothermic). NaOH is prepared by the electrolysis of NaCl solution
(brine). Industrially it is prepared by mixing lime with sodium carbonate.
Sodium carbonate is obtained from mines or by Solvay process. Sodium
chloride can be obtained from sea or underground deposits. Sodium carbonate
is widely used in the manufacture of soaps, detergents and glass etc. Sodium
bicarbonate or baking soda is used to make breads and cakes light and fluffy
because when it is heated, CO2 is evolved. 2NaHCO
3
NaCO
3
+ CO
2
+
H
2
O , Sodium bicarbonate is also used in fire extinguishers . Zinc uranyl
acetate is one of the few fairly insoluble compounds of sodium. Its
formula is NaZn (UO
2
)
3
(CH
3
COO)
9
. It is pale yellow in colour . Sodium
metal is used in Wurtz reaction. Sodium is also used as a coolant in atomic
reactors.
o Electrolysis of aqueous NaCl gives H
2
gas at cathode . Metallic sodium is
released at cathode, if aqueous NaCl is electolysed-using mercury as cathode.
o Soda lye is solution of NaOH in water. Common name for KOH is caustic
potash.
o NaOH can be prepared by (a) Causticizing process or lime soda process (b)
Nelson's method (c) Castner Kellner methid . NaOH is deliquescent and so a
standard solution ofNaOH cannot be prepared simply by weighing.
o Al , Zn, Sn , Pb, Cr and Sb are the metals which dissolve in NaOH
solution and liberate H
2
.
o The amphoteric substances such as Al
2
O
3
, ZnO, Al (OH)
2
dissolve in excess
of NaOH solution forming aluminates and zincates.
Al (OH)
3
+ 3NaOH NaAlO
3
+ 3H
2
O
Zn(OH)
2
+ 2 NaOH NaZnO
2
+ H
2
O
o Aqueous solution of NaOH and KOH can CO
2
from the atmosphere.
o Alcoholic KOH is used as dehydrohalogenating agent.
o Na
2
CO
3
is called soda ash and Na
2
CO
3
. 10H
2
O is called washing soda.
o Na
2
CO3 can be prepared by Le Blanc process and Solvay process or
ammonia soda process.
o Solvay process is based on low solubility of NaHCO
3
. The end product of
Solvay process in NaHCO
3
. In soda process, the raw materials usedare Ca
CO
3
, NH
3
and NaCl .
o K
2
CO
3
, known as pearl ash , can not be prepared by Solvay process due to
high solubility of KHCO
3
.
o NaHCO
3
, known as baking soda, is less soluble in water than Na
2
CO3
because of polymeric anions formed by hydrogen bonding .
o All baking powders contain NaHCO
3
and acid salt such as potassium
hydrogen tartrate or calcium dihydrogen phosphate .
o An equimolar mixture of Na
2
CO
3
and K
2
CO
3
is called fusion mixture .
o Sodium bicarbonate is used to make breads and cakes light and fluffy because
when it is heated CO
2
is evolved. Sodium bicarbonate is also used in cold
drinks, as antacid and in baking powders.
o Na
2
CO
3
is widely used in the manufacture of soaps, detergents and glass. Both
NaOH and Na
2
CO
3
are among the top 20 chemicals used in industries .
o A deliquescent compound such as NaOH is that which absorbs water
readily from the atmosphere and thereby form concentrated solutions
containing the alkali metal cation (Na+) and OH- ions.
o Na
2
O is used as a dehydrating agents as well as polymerising agent in organic
chemistry.
o Anhydrous sodium sulphate is called salt cake and hydrated sodium sulphate
is called Glauber's salt (Na
2
SO
4
. 10 H
2
O). Glauber's salt shows efflorescence
in dry air and it is used as purgative in medicine. Na2 SO4. 10H2O becomes
anhydrous (Na
2
SO
4
), above 32.5C (efflorescence).
o Na
2
O
2
is a yellow powder (Na
2
O
2
. 8H
2
O). It is capable of absorbing gases
like CO, CO
2
, SO
2
, NO
2
, etc. Hence it is used to purify air in submarines.
o Under trade name oxone, Na
2
O
2
is used as a bleaching agent.
o K
2
O
2
is a white hygroscopic solid . KO
2
is orange paramagnetic powder .
K
2
O
2
is a yellow hygroscopic solid and highly poisonous substance. It is more
poisonous than NaCN.
o Potassium was first isolated by Davy in 1808 . It is soft, low malting (mp =
63C) and more reactive than sodium . Carnallite , KCl . MgCl2. 6H
2
O is the
important mineral source of potassium . In India potassium is found largely as
saltpetre (KNO
3
). The chemical properties of potassium closely resemble
those of sodium, but its reactions are more vigorous. Potassium is one of the
few elements that form a super oxide (O
2
-) on reaction with air.
o An alloy of potassium with sodium (Na = 78% , K = 22%) is a liquid
resembling mercury, It is low melting (mp = 13C ) and high boiling (b.p
1450 C ) . It is used as a high temperature heat exchange fluid for use in
power plants. At 100C , it is less corrosive than steam and has a much higher
thermal conductivity . Since potassium attack the glass electrodes, the same
can not prepare potassium those of sodium.
o The potassium ion (K+ ) is chemically inert . The compounds of potassium
are, in general more soluble than those of sodium. The main uses of potassium
compounds are as fertilizers, where KCl and KNO
3
are commonly used.
o Potassium salts of fatty acids are used in making soft soaps, because they are
more soluble than those of sodium . Potassium is mainly obtained from
deposits of NaCl and form brines in various lakes.
o Potassium salts are occasionally called potash, independent of the associated
anion.
o Potassium ion gives a characteristic purple colour in a Bunsen flame.
o Yellow potassium sodium hexa nitro cobaltate (III) , K
2
Na [ Co(NO
2
)6 ] and
yellow potassium hexachloroplatinate , K
2
Pt Cl
6
are the less soluble
potassium salts.
o Black ash is impure Na
2
CO
3
produced in Leblanc process when salt cake is
reduced with coke
o Hypo is Na
2
S
2
O
3
. 5H
2
O.
o Fire extingushers contain H
2
SO
4
, Na
2
CO
3
and NaHCO
3
.
o Soda lime is NaOH + CaO.
They belong to s-block and have general electronic configuration ns
2

(where n 1). The atoms of IIA group elements have two electrons in
their outermost shell. The penultimate layer has, as in case of alkali
metals, 8 electrons (s
2
p
6
) , except beryllium , which contains 2
electrons in the penultimate shell , that is , in the s-subshell Thus they
possess an inert gas core and two electrons in the s-orbital of the
valence shell (ns
2
) Radium is the radioactive element in IIA group.
When compared with alkali metals
(a) They are less reactive than alkali metals
(b) They are less electropositive than alkali metals. Hence they are less metallic than
alkali metals
(c) Their reducing power is much less than those of alkali metals
(d) They are less basic than alkali metals.
Covalent character is predominant in the compounds of beryllium,
because of its small size and high nuclear charge. Beryllium and
magnesium form many covalent compounds whereas the
compounds of other metals of the group are essentially those of
dipositive (M
2+
) ions.
The gradation of the properties of the IIA group elements is not as
regular as in case of alkali metals, because of different structures of
their crystal lattices.
As compared to alkali metals , the alkaline earth metals have :
o Small size of atoms and ions
o Stronger metallic bonds
o Higher melting and boiling points
o Are denser and harder.
These atoms are large in size but smaller than the corresponding alkali
metals, since the increased nuclear charge draws the orbital electrons
in. The second group metallic ions are also large but smaller than those
of alkali metals are. The metal atom changes into a bipositive ion by
the loss of two electrons present in the outermost shell.
Because their atoms are smaller, the metals are denser and have high
melting and boiling points than the alkali metals. Density also
decreases on moving down the group upto calcium but increases
considerably thereafter. Density of Ca is less than that of Mg, because
of the presence of vacant 3d- orbital leading to much increase in
atomic volume.
The melting and boiling points are not regular in the group,
mainly due to different crystal structures of the metals. However,
these are higher than those of alkali metals.
Solid Be and Mg has hexagonal colsed packed lattice . Ba has body
centred cubic lattice. Ca and Sr have cubic close packed lattice at
ordinary temperature, which changes to hexagonal close packed
lattice at 500K and to body centred cube near their melting points.
Since they have two valence electrons, hence they have are
stronger metallic bonding and higher cohesive energy than those of
alkali metals. Thus they are harder than alkali metals but become
increasingly soft as the atomic number increases. They can be cut
by a sharp knife.
Due to larger nuclear charge and smaller atomic radius of IIA group
elements (as compared to alkali metals), the valence electrons are more
tightly held. Thus the first ionization energies of these elements are
higher than those of alkali metals. The elements form colorless, largely
ionic compounds in + 2 oxidation state, for example Mg Cl2.
The ionization energy decreases on moving down from Be to Ra.
Alkaline earth metals are not as electropositive as the corresponding
alkali metals. The electropositive character increases on moving down
the group.
The heat of hydration of these elements decrease from Be to Ba .
All these elements have hydrated salts. Ca, Sr, Ba and Ra impart
flame colors of brick red, crimson red, apple green and crimson
respectively. The Be and Mg do not impart color to the flame because
the electrons in smaller Be and Mg atoms (2s and 3s orbitals) are more
strongly bound and are not excited by the energy of the flame.
The high negative values of standard reduction potentials indicate that
metals of IIA group are good reducing agents comparable to alkali
metals. Although the energies required to vaporize and ionize the
atoms of IIA group elements to M
2+
ions are high, the high lattice
energies in the solid salts and high hydration energies of M
2+
(Aq) ions
compensate for this.
Calcium , which is a constituent part of a large number of
compounds , is the most abundant element in the IIA group.
Each of these elements has a lot of isotopes which are natural .
The IIA metal ions have considerably higher ionic charge to ionic
radius ratio than group IA elements. As a consequence:
(a) The first hydration energy of the alkaline earth metal ion is about 5 times that of
the alkali metal ions of the same period,
(b) Since the polarizing power of the cations is much greater, the compounds of Be
and Mg have appreciable covalent character,
(c) Their compounds with large polarizing anions such as carbonates, bicarbonates,
triiodides etc. are less stable.
The extremely small size of Be
2+
makes it so strongly polarizing that
Be (II) compounds are almost covalent in nature. The number of
covalent bonds can even be increased to four by donation and the use
of sp3 hybrid orbitals, provided electron rich ligands are available. For
the elements Ca to Ra, although M
2+
ions are smaller than the
corresponding M+ ions of alkali metals, they have low polarizing
power and compounds are largely ionic. Magnesium as M
2+
forms
compounds, which are ionic as well as covalent in nature.
The high hydration energy of IIA ions shows that their salts should be
more soluble than the corresponding alkali metal salts. But the lattice
energy is also greater and the solubility is a delicate balance between
hydration energy and lattice energy. Actually, the alkaline earth metal
salts are generally less soluble than the corresponding alkali metal
salts, because lattice energy, in general, decreases less rapidly than the
hydration energy. The hydration energy of the alkaline earth metal ions
follows the order Be
2+
> Mg
2+
> Ca
2+
> Ba
2+
. The solubility of the
alkaline earth metal sulphates decreases with increasing cation size.
BeSO
4
> MgSO
4
> CaSO
4
> SrSO
4
is fairly soluble, but BaSO
4
is
insoluble. The trend in the solubility of hydroxides is reverse of that of
sulphates. Be (OH)2 is least soluble and solubility increases down the
group as Be (OH)2 < Mg (OH)
2
< Ca (OH)
2
< Sr (OH)
2
< Ba (OH)
2
.
The solubility of some halides follows the order:
o BeF
2
> MgF
2
> CaF
2
> SrF
2
> BaF
2

o BeCl
2
< MgCl
2
< Ca Cl
2
< Sr Cl
2
< BaCl
2

o CaF
2
< CaCl
2
< CaBr
2
< Cal
2
.
On descending the group, the metal ions increase in size and both
the lattice energy as well as hydration energy decrease. If, on
descending the group the lattice energy decreases more rapidly
than the hydration energy, the compounds become soluble. In case
of hydroxides, the lattice energy depends on size of the cation. Be
(OH)
2
has the largest lattice energy of any group IIA hydroxide.
The hydroxides become more soluble because of rapid decrease in
lattice energy down the group.
The lattice energies of the sulphates do not change greatly from BeSO
4

to BaSO
4
, because the anion is such larger than any group IIA cation.
The trend in the solubilities of the sulphates is perhaps similar to the
trend in hydration energy of the ions. The hydration of the small Be
2+

ion is by far the most exothermic of any ion of the group. Thus BeSO
4

is the most stable sulphate.
The thermal stabilities of the carbonates varies directly with the
size of the cation. The increasing order of thermal stabilities of the
carbonates is BeCO
3
< Mg CO
3
< Ca CO
3
< Sr CO
3
< BaCO
3
.
BeCO
3
is very unstable mainly due to the enhanced stability of
BeO over BeCO
3
. Cations with large ionic potential have large power
of polarization.
All the alkaline earth metals are highly electropositive (but less
electropositive than IA group elements ) as shown by their
respective electrode potentials , high chemical reactivities and ionic
nature of their compounds . The chemistry of the elements is
demonstrated by their tendency to lose their two valence electrons
to form cation with two positive charges. These cations Be
2+
, Mg
2+
,
Ca
2+
, Sr
2+
and Ba
2+
are all diamagnetic and have noble gas
configuration. The metals are strong reducing agents and combine
to form ionic compounds (except Be, which has remarkable
polarizing power due to its small size and high charge density).
The reactivity of the elements increases with increase with increase
in atomic number.
In general, metallic nature, reactivity and reducing power
increases from Be to Ba. Tendency to form peroxides increases
from Be to Ba. Oxides of these metals become more basic and
soluble as we pass from Be to Ba. Hydroxides become more basic
and soluble as we go from Be to Ba. Hydration energy increases
from Be
2+
to Ba
2+
.
All the alkaline earth metals react with water, but these reactions are
much less violent than the corresponding reaction of an alkali metal.
With beryllium and magnesium the reaction with water is slow. In fact,
beryllium does not react with water, magnesium decomposes hot
water, whereas other elements react with cold water liberating H2 gas
and forming the corresponding hydroxide.
Alkaline earth metals become more reactive as the outer electrons are
further remote from the nucleus. Thus barium is the most reactive
member of the family, excluding radium, which is radioactive. Be is
less electropositive and less and less likely to lose its two outer
electrons than the other elements because of its small size. Many of the
compounds of Be are not ionic, but polar covalent.
All the elements react with oxygen when heated in the gas forming the
monoxide of the type MO. Be and Mg react less readily because of the
formation of a protective oxide film on their surface. Barium also
forms some peroxide alongwith monoxide. If the reaction is carried out
under pressure, peroxides are formed both by Sr and Ba. On heating in
air the elements form a mixture of both oxides and nitrides.
On heating with nitrogen all the elements of the group form nitrides of
the type M3 N2. The nitrides contain N3- ion and are ionic nature.
With the exception of Be, all alkaline earth metals react directly with
hydrogen to form ionic hydrides of the type MH2.
Since the alkaline earth metal ions have rare gas configuration , they
are colorless and diamagnetic.
All alkaline earth metals form halides of the type MX
2
. All halides of
Be are covalent and electron deficient. Anhydrous beryllium halides
are polymeric and contain three central bonds. MgBr
2
and MgI
2
are
soluble in acetone because of their covalent nature.
The hydroxides may be obtained by slaking the oxides with water.
MgO slakes very slowly, but the oxides of Ca, Sr and Ba slake
readily.
BeO as well as Be (OH)
2
are amphoteric, Mg(OH)
2
is mild base and
its aqueous suspension, known as milk of magnesia is used as an
antacid. The Ca(OH)
2
and Sr(OH)
2
are moderately strong bases, while
Be(OH)
2
is almost as strong as the alkali hydroxides. All the oxides,
BeO, MgO, CaO, SrO and BaO have NaCl - type structure (4: 4
Coordination).
Beryllium halide are covalent, hygroscopic and fumes in air because of
hydrolysis. BeF2 is one of the few metal fluorides, which does not
ionize completely in solution. BeF2 is soluble in water, MgF
2
is
sparingly soluble, while CaF
2
, SrF
2
and BaF
2
are insoluble . All other
halides are soluble. The solubility decreases from BeF
2
to BaF
2
due to
difference in their structures. BeF2 has a linear polymeric chain
structure, while others have crystal lattice structures. In the vapor state
BeCl
2
molecule is linear and has no dipole moment. This corresponds
to Be in sp-valenece state. Other halides are hygroscopic and form
hydrates of the type MgC
2
. 6H
2
O, BaCl
2
. 2H
2
O, CaCl
2
. 6H
2
O etc.
The alkaline earth metals generally dissolve in dilute mineral acids, but
Be is rendered passive by nitric acid. With acid solutions all of them
react to yield the respective salts. Most salts of alkaline earth metals
(Ca, Sr, and Ba) such as fluorides, sulphates and phosphates are
sparingly soluble in water.
Beryllium dissolves in cold conc. aqueous alkali evolving hydrogen
and forming alkaline earth metal beryllate.
Be + OH- + H
2
O HBeO
3
- + H
2

Other elements of the group do not dissolve in alkali.
Sulphates, carbonates and hydroxides of these metals
decompose on heating to yield oxides.
Nitrates of these metals are water soluble and decompose to
oxide, NO
2
and O
2
gases.
When Ca, Sr and Ba are dissolved in liquid ammonia, a
paramagnetic, highly reducing and highly conducting deep
blue colored solution is obtained . These properties are due
to the presence of solvated electrons in solution.
Marie and Pierre Curie discovered radium in 1898. They
produced pure radium in 1911. It was the first radioactive
element to be discovered. Radium is extracted from
pitchblende, a uranium ore. About 7 tonnes of pitchblende
are required to produce 1g of pure radium. All isotopes of
radium decay spontaneously to other elements, emitting
dangerous radiations. The final product of the nuclear
disintegration is lead.
Barium and strontium are found frequently as sulphates,
BaSO4 and SrSO4 or the carbonates, BaCO
3
and SrCO
3
.
Magnesium occurs in the earth crust as magnesite (MgCO
3
),
dolomite (CaCO
3
), carnallite (KCl, MgCl
2
. 6H
2
O), Epsom salt
(MgSO4. 7H2O) and asbestos CaMg
3
(SiO
3
) 4. Magnesium
ions are present in seawater to the extent of 2%. Magnesium is
also present in chlorophyll.
Beryllium forms the carbide Be2C while other metals give
ionic carbides of the MC2 type. When reacted with water Be2C
liberates methane, while other carbides liberate
acetylene.Mg
2
C
3
liberates propyne.
The nitride of Be, (Be3N
2
) is volatile, while nitrides of other
metals are non-volatile.
The tendency of common salt (NaCl) to get sticky in humid
summer is partly due to the presence of small amounts of
MgCl
2
in it.
Heating gypsum at 120 C 5C gives Plaster of Paris
(CaSO4. 1/2H
2
O) which combines vigorously with water and
sets to a hard mass. Setting of plaster of Paris is accompanied
by evolution of heat (exothermic reaction), catalyzed by
common salt (NaCl) and retarded by borax and alum. Setting
of plaster of Paris is due to hydration as well as transition.
Hardening of plaster of Paris is because of transition of
orthorhombic gypsum to monoclinic gypsum. Strength of
plaster of Paris on hardening is because of interlacing of
needles of monoclinic gypsum On setting, plaster of Paris
undergoes expansion .
Gypsum or alabaster or selenite is calcium sulphate dihydrate,
CaSO
4
. 2H
2
O. Heating gypsum at 200C gives dead burnt
(CaSO
4
). Heating gypsum at 400C gives CaO, O
2
and SO
2
.
When Ca CO
3
is heated to high temperature, it decomposes to
form CO
2
and CaO, commonly known as lime or quick lime.
Quick lime reacts vigorously with water to form a strong base,
Ca (OH)
2
, which is much less soluble in water than Ba (OH)
2
.The formation of Ca (OH)
2
is an exothermic reaction . Ca
(OH)
2
is known as slaked lime because it is formed when CaO
has slaked its thirst for water. When mixed with sand, Ca (OH)
2
hardens as mortar (1 part lime +3parts sand) and cement, by
absorbing CO
2
from air.
Barium is not found free in nature. In combined state it occurs
as Barytes or heavy spar, BaSO4 and BaCO3. Barium burns in
air producing mostly BaSO
4
. It also burns in CO
2
to form BaO
and carbon or CO.Barium is strong reducing agent (SRP Ba
2+

Ba = -2.90 V ) . It is silvery white metal and m.p. is 850 C .
Barium is good conductor of heat and electricity. Barium forms
alloys with other metals and these alloys are used in vacuum
tubes and sparking plugs, where the low ionization energy of
Ba facilitates of good sparks. Barium forms two oxides, BaO
and BaO
2
. BaO
2
is peroxide, containing O
2
2-
ion.
Magnesium is used as a de-oxidizer in metallurgy and as a fuse
in aluminothermite process. It is also used in flash bulbs,
pyrotechnics and in fireworks. Magnalium is an alloy of Al
and Mg. Elecktron is an alloy of Mg and Zn.