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s-Block Elements
Phase - III (2017 - 19)
PINNACLE-CBSE
s-BLOCK ELEMENTS
CONTENTS SYLLABUS
> Introduction 1
CBSE: General introduction to s- block elements -
> Anomalous behaviour offirst
abundance, occurrences, anomalous properties of the
elements 1
first element in each group, diagonal relation ship. -
> Physical properties • 3 Alkali metals - occurrence, electronic configuration,
> Chemical properties 5 trends in atomic and physical properties (including I.E.
-> General characteristic of the atomic and ionic radii), reactivity and electrode
potential, reaction With • oxygen, hydrogen, halogens
compound of the alkali metals 8
and liquid ammonia. Basic nature of oxides and
> Salts of oxoacids 12 hydroxides, halides. Li and Na occurrence, extraction,
> Extraction of lithium 14 properties and uses, Na2CO3. The .alkaline earth
> Properties of lithium metals - occurrence, electronic configuration, trends
16
in atomic and physical properties (including I.E. atomic
> Extraction of sodium 17 and ionic radii), reactivity and electrode potential,
> Properties ofsodium 18 reaction with non metals, oxides hydroxides- and
> Compounds ofalkali metals 19 halides. Solubility and thermal stability of their oxo
salts. Magnesium - occurrence, extraction, properties
> Solvay process 22 and uses. Compounds of alkaline earth metals - CaO,
> Alkaline earth metals. 26 C_a(OH)2, Plaster of paris and MgSO4 - industrial uses
> Chemical properties of group-II of lime, limestone and cement.
elements 33
> Magnesium Metal 41 JEE: Isolation/preparation and properties of the
> Compounds of alkaline earth following non-metals: Boron, silicon. Properties of
metals 44 allotropes of carbon (only diamond and graphite).
> Answers to Exercises Preparation and properties of the following
53
compounds: Oxides, peroxides, hydroxides,
> Miscellaneous Exercise 55 carbonates, bicarbonates, chlorides and sulphates
> Solved Problems 58 of sodium, potassium, magnesium, and calcium;
> Chapter Practice Problems 62 Boron: diborane, boric acid and borax;
Aluminium: alumina, aluminium chloride and
> Assignment Problem 64 alums; Carbon: oxides and oxyacid (carbonic add);
> Answers to CPP 72 Silicon: silicones, silicates and silicon carbide. •
> Answers to Assignments
Problems 73
INTRODUCTION
The elements in the long form of the periodic table has been divided into four blocks, namely
s, p, d & f blocks. The elements of group I & II receive their last valency electron in s-orbital. So
they are called as s — block elements.
The metals Lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium
(Fr) which have one electron in their outermost shell belongs to group I and are called alkali
metals as they react with water to form hydroxides which are strong bases or alkalies.
The elements of group II are BerryIlium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr),
barium (Ba) and radium (Ra) which have two electrons in their outermost shell. All these
elements are also metallic in nature and are commonly known as alkaline earth metals with the
exception of beryllium. Because of their low density, alkali metals and alkaline earth metals are
called lighter metals. Both alkali and alkaline earth metals are highly reactive and hence do not
occur in free state but found in combined state. Alkali metals mostly occur as halides, oxides,
silicates, borates and nitrates, whereas alkaline earth metals mainly occur as silicates,
carbonates, sulphates and phosphates. Some alkali & alkaline earth metals OCCUT abundantly in
nature. Calcium is the fifth, magnesium is the sixth, sodium is seventh and potassium is eight
barium is the fourteenth and strontium is the fifteenth most abundant element by weight in the
earth's crust. Sodium and magnesium are also present in sea water brine wells and few salt
lakes.
Anamolous behavour of first element
The first element of a group differs considerably from the rest of the elements of the same group.
This anomalous behaviour is due to •
Smaller size of their atoms
Their higher ionization energies
Their higher electronegativites
Absence of vacant d — orbitals in their valence shell
High polarizing power of its cation.
Thus Li differes from the rest of alkali metals (Na, K, Rb & Cs) and Be differs from rest of the
alkaline earth metals (Mg, Ca, Sr & Ba)
Diagonal relationships
On moving diagonally some members show similar properties with the members of next higher
group which is particularly seen in the elements of second and third periods of the periodic table. .
However the similarities shown are far less pronounced than the similarities with in a group.
Group1 Group2 Group13 Group14
Period-2 Li Be ---...‹...., B
Period-3 _____
Mg AI
Al Si
The main reasons for the diagonal relationship are

(i) Similarity in electropositive character
The electropositive character decreases along a period, but increases down a group. Hence on
moving diagonally the two opposing trend partially cancels out. As a result diagonally related
elements have similar electropositive character and hence exhibit similar properties.
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Similarity in polarizing power
On moving along a period from left to right, the charge on the ions increases while ionic size
decreases, hence polarizing power increases. On moving down the group, the ionic size
increases and hence polarizing power decreases. On moving diagonally, these two trends
partially cancel out. As a result thus diagonally related elements have same polarizing power and
thus exhibit similar properties.
Similarity in atomic or ionic radii

The atomic and ionic radii decrease across a period and increase in a group. Evidently on moving
diagonally, the two trends partially cancel out. As a result, diagonally related elements have
similar atomic & ionic radii and hence have similar properties.
Alkali Metals
The group, I comprising Li, Na, K, Rb, Cs & Fr are commonly called alkali metals. Francium is
radioactive and has a very short life (half life of 21 minutes), therefore very little is known about it.
Electronic Configuration
The general electronic configuration of 'alkali metals may be represented by [noble gas] nsl
where n = 2 to 7
Table — I: [Some Physical properties of group 1 elements (alkali metals)]
Atomic number 3 11 19 37 55 87
Electronic configuration 2s' 3s' 4s' 5s1 6s' 7s'
Atomic mass 6.94 22.99 39.10 85.47 132.91 223
Metallic radius (pm) 152 186 227 248 265 375
Ionic radius (M+ /pm) 76 102 138 152 167 180
520 496 419 403 376
Ionization enthalpy I
7298 3562 3051 2633 2230 •••
(kJmo1-1)
Electronegativity 0.98 0.93 0.82 0.82 0.79
(Pauling Scale)
Density /gern-3 (at 298K) 0.53 0.97 0.86 1.53 1.90
Melting point/K 454 371 336 312 302
Boiling point/K 1615 1156 1032 961 . 944
E°(V) at 298K for• -3.04 -2.714 -2.925 -2.930 -2.927
M+ (aq) + e-
Oqcurrence in
Atmosphere 18* 227** 1.84** 78.12* 2.6*
* ppm (parts per million) ** percentage by weight.

Illustration 1. Why are Group 1 elements called alkali metals?
Solution: The Group 1 elements are called alkali metals because they form water soluble
hydroxides.
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Exercise 1.
Write three general characteristics of the elements of s-block of the periodic table
which distinguish them from the elements of the other blocks.
Exercise 2.
Which alkali metal is most abundant in earth's crust?
. . . .
PHYSICAL PROPERTIES
All the alkali elements are silvery white solid. These are soft in nature and can be cut with the
help of knife except the lithium. When freshly cut, they have a bright lusture which quickly
fades due to surface oxidation. These are highly malleable and ductile. The silvery luster of
alkali metals is due to the presence of highly mobile electrons of the metallic lattice. These
atoms having only a single electron per atom, the metallic bonding is not so strong. As the
result, the metals are soft in nature. However, the softness increases with increase in atomic
number due to continuous decrease in metallic bond strength on account of an increase in
atomic size.
Atomic and Ionic radii .
The atoms of alkali metals have the largest size in their respective periods. The atomic radii
increase on moving.down the group among the alkali metals. -
Reason
On moving down the group a new shell is progressively added. Although, the nuclear charge also
increases down the group but the effect of addition of new shells ismore predominant due to
increasing screening effect of inner filled shell on the valence s-electrons. Hence the atomic size
increases in a group.
Alkali metals change into positively charged ions by losing their valence electron. The size of
cation is smaller than parent atom of alkali metals. However, within the group the ionic radii
increase with increase in atomic number.
The alkali metal ions get extensively hydrated in aqueous solutions. Smaller the ion more is the
extent or degree of hydration. Thus, the ionic radii in aqueous solution (hydrated radius) follow
the order
Li+ > Na+ >K+ > Rb+ >Cs+
The charge density on Li+ is higher in comparison to other alkali metals due to which it is
extensively hydrated.
Ionization Energy (Ionization enthalpy)
The first ionization energy of the alkali metals are the lowest as compared to the elements in the
other group. The ionization energy of alkali metals decreases down the group.
Reason
The size of alkali metals is largest in their respective period. So the outermost electron
experiences less force of attraction from the nucleus and hence can be easily removed.
The value of ionization energy decreases down the group because the size of metal increases
due to the addition of new shell along with increase in the magnitude of screening effect.
Oxidation State
The alkali metals shows +1 oxidation state. The alkali metals can easily loose their valence
electron and change into uni-positive ions
+e-
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Reason
Due to low ionization energy, the alkali metals can easily lose their valence electron and gain
stable noble gas configuration. But the alkali metals cannot form M2+ ions as the magnitude of
second ionization .energy is very high.
(v) Reducing Properties
The alkali metals have low values of reduction potential (as shown in table-l) and therefore have
a strong .tendency to lose electrons and act as good reducing agents. The reducing character
increases from sodium to caesium. However lithium is the strongest reducing agent.
Reason
The alkali metals have !ow value of ionization energy which decreases down the group and so•
can easily lose their valence electron and thus act as good reducing agents.
Melting and Boiling Points
The melting and boiling points of alkali metals are very low because the intermetallic bonds in
them are quite Weak. And this decreases with increase in atomic number with increases in atomic
size:
(vii) Density
The densities of alkali metals are quite low as compared to other metals. Li, Na and K are even
lighter than water. The density increases from Li to Cs.
Reason
,
Due to their large size, the atoms of alkali metals are less closely packed. Consequently have low
density. On going down the .group, both .the atomic size and atomic mass increase but the
increase in atomic mass compensates the bigger atomic size. As a result, the density of alkali
metals increases from Li to Cs. Potassium is however lighter than sodium. It is probably due to an
unusal increase in atomic size of potassium:.
Nature of bond formed
All the alkali metals form ionic (electrovalent) compounds. The ionic character increases from Li .
to Cs because the alkali metals have low value of ionization energies which decreases down the
group and hence tendency to give electron increases to form electropositive ion.
Conductivity
The alkali metals are good conductors of heat and electricity. This is due to the presence of
loosely held valence electrons which are free to move throughout the metal structure.
Photoelectric Effect
Alkali metals (except Li) exhibit photoelectric effect (A phenomenon of emission of electrons from
the surface of-metal when light falls on them). The ability to exhibit photoelectric effect is due to
low value of ionization energy of alkali metals. Li does not emit photoelectrons due to high value
of ionization energy.
Flame colouration
The alkali metals and their salts impart a characteristic colour to flame
„„ ,:‘: ,„: ::::K Rb,..::: :::Cs

Colour_ Crimson Red Golden Pale Violet Violet Sky Blue
Yellow
670.8 589.2 766.5 780.0 455.5 s
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On heating an alkali metal or its salt (especially chlorides due to its more volatile nature in a
flame), the electrons are excited easily to higher energy levels because of absorption of energy.
When these electrons return to their ground states, they emit extra energy in form of radiations
which fall in the visible region thereby imparting a characteristic colour to the flame.
Illustration 2. What is the most reactive alkali metal and why?

Solution: The most reactive alkali metal is cesium due to its lowest first ionization enthalpy
and lowest electronegativity.
Illustration 3. The alkali metals have low densities. Explain.
Solution: The alkali metals have low densities due to their large atomic sizes. In fact, Li, Na
and K are even lighter than water.
Illustration 4. The metallic lustre exhibited by sodium is explained by
Diffusion of sodium ions
Oscillation of loose electrons
Excitation of free protons
Existence of body—centered cubic lattice
Solution: (B)
Exercise 3.
Why is the density of potassium less than sodium?
Exercise 4.
Why is lithium the strongest reducing agent in the periodic table?
Exercise 5.
Name the metal which floats on water without any apparent reaction with it.
Exercise 6.
Which is softer— Na or K and why?
Exercise 7.
What makes sodium highly reactive?
; Exercise 8.
Alkali metals impart colour to Bunsen flame due to
The presence of one electron in their outermost orbital
Low ionization energies
Their softness
. (D) Their reducing nature
. . . . . • . • ... . „
. ..
CHEMICAL PROPERTIES
The alkali metals are highly reactive metals and the reactivity increases down the group. The
reactivity is due to-
low value of first ionization energy
large size
low heat of atomization
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Reaction with Oxygen

The alkali metals tarnish in air due to the formation of an oxide or hydroxide on the surface. Alkali
metals when burnt in air form different kinds of oxides. For example the alkali metals on reaction
with limited quantity of oxygen form normal oxides of formula, M20
4M + 02 ---*2M20 (Where M = Li, Na, K, Rb, Cs).
When heated with excess of air, lithium forms normal oxide, Li2O; sodium forms
peroxide, Na202 , whereas potassium rubidium and caesium form superoxides having general
formula MO2
4Li + 02 --> 2Li20 (Lithium oxide)
2Na +02 575K >Na202 (Sodium peroxide)
K + 02 ---->K02 (Potassium Superoxide)
Thus the reactivity of alkali metals with oxygen increases down the group. Further, the increasing
stability of peroxide or superoxide, as the size of the metal ion increases is due to the stabilization
of larger anions by larger cation through higher lattice energies.
Due to small size, Li+ has a strong positive field around it which attracts the negative charge so
strongly that it does not permit the oxide anion 0-2 to combine with another oxygen to form
peroxide ion, 0-22 . On the other hand, Na+ ion because of its large size than Li+ ion has
comparatively weaker positive field around it which cannot prevent 0-2 ion to combine with
another oxygen to form peroxide ion O;2. The larger K+ , Rb, and Cs+ ions have still weaker
positive field around them which cannot prevent even peroxide ion, 022- to combine with another
oxygen atom to form superoxide 0-2 .
Reaction with Hydrogen

Alkali metals react with dry hydrogen at about 673K to form colourless crystalline hydrides. All the
alkali metal hydrides are ionic solids with high melting points.
2M+ H2 ----->2MH (M = Li, Na, K, Rb or Cs)
Some important features of hydrides are
The stability of hydrides decrease from Li to Cs. It is because of the fact that M-H bond
becomes weaker due to increase in the size of alkali metals down the group.
These hydrides react with water to form corresponding hydroxides and hydrogen gas:
LiH +H20 —LiOH + H2
NaH +H20 —>NaOH + H2
These hydrides are strong reducing agents and their reducing nature increases down the
group.
Alkali metals also form complex hydrides such as LiAIH, and NaBH, which are good
reducing agents.
All these hydrides react with proton donors such as water, alcohols, gaseous ammonia and
alkynes liberating H2 gas.
NaH(s) + ROH (s) + H2 (g)
NaH (s) + NH3 (g) °NaNH2 (s) + H2 (g)
2KH(s)+HC CH(g)—°› - KC .a CK (s) + 2H2 (g)
The order of reactivity of the alkali metals towards hydrogen decreases as we move down the
group from Li to Cs. This is due to the reason that the lattice energies of these hydrides
decreases progressively as the size of the metal cation increases and thus the stability of
these hydrides decreases from LiH to CsH.
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(iii) Reaction with water

The alkali metals are known to have large negative reduction potential values. As a result they
can act as better reducing agents as compared to hydrogen. Hence, alkali metals react with water
and ether compounds containing acidic hydrogen atoms such as hydrogen halides (HX) and
acetylene (C2H2) and liberate H2 gas
2Na + H20 --›2NaOH + H2
2Na + 2HCI—›2NaCI + H2 -
2Na +2HC s CH —2NaC s CH+ H2
Sodium acetylide
The reaction becomes more and more violent as we move down the group. Thus, Lithium reacts
gently, sodium melts on the surface of water and the molten metal moves around vigorously and
may sometimes catch fire. Potassium melts and always catches fire and so are Rb and Cs.
(iv) Reaction with halogens
Alkali metals react vigorously with halogens to form metal halides of general formula MX, which
are ionic crystalline solids.
2M + X-2 —>21V1X
M = Li, Na, K, Rb or Cs and
X = F, Cl, Br or I
Reactivity of alkali metals with particular halogens increases from Li to Cs. On the other hand,
reactivity of halogens decreases from F2 to 12 .
Solubility in liquid ammonia

All alkali metal dissolve in liquid ammonia giving deep blue solutions which are conducting in
nature. These solutions contain ammoniated cations and ammoniated electrons as shown below:
M + (x + y)NH3 (NH3 )+ (NHA
The blue colour of the solution is considered to be due to ammoniated electrons which absorb
energy corresponding to red region of the visible fight for the their excitation to higher energy
levels. The transmitted light is blue which imparts blue colour to the solutions. The electrical
conductivity of the solution is due to both ammoniated cations and ammoniated electrons. The
blue solution on standing slowly liberates hydrogen resulting in formation of amide :
2M + 2NH3 ---> 2M N H2 ±H2
(Metal amide)
At concentrations above 3M, the solutions of alkali metals in liquid ammonia are copper-bronze
coloured. These solutions contains clusters of metal ions and hence possess metallic lusture. The
blue coloured solutions are paramagnetic due to presence of large number of unpaired electrons,
but bronze solutions are diamagnetic due to formation of electron clusters in which ammoniated
electrons with opposite spin group together
These solutions are stronger reducing agents than hydrogen and hence will react with water to
liberate hydrogen.
Reaction with sulphur and phosphorus
Alkali metals react with sulphur and phosphorus on heating to form sulphides and phosphides
respectively. •
-16Na + S8 > 8Na2S

Sodium sulphide
a
12Na + — > 4Na2P
Sodium Phosphide
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(vii) Reaction with Mercury

Alkali metals combine with mercury to form amalgams. The reactions is highly exothermic in
nature
Na +Hg---> Na(Hg)
Sodium amalgam
Illustration 5. What happens whed(give chemical equation only):

sodium is exposed to moist air
sodium reacts with water
Solution: (i) 2Na +1 02 +H20 +CO2 -->Na2CO3.H20
2
(ii) 2Na + 2H20 --->2NaOH +H2 +Heat
Illustration 6. On prolonged exposure to air, sodium finally changes to

Na2CO3 (B) Na2O
(C) NaOH (D) NaHCO3
Solution: (A)
Exercise 9.
Write balanced equations for reaction between
Na2O2 and water (ii) K02 and water (iii) Na2O and CO2
Exercise. 10.
Which reaction below is explosive?
(A) Lithium with water (B) Magnesium with water
(C) Beryllium with water (D) Caesium with water
General characteristic of the compounds of the alkali metals

(i) Oxides and Hydroxides
All the alkali metals, their oxides, peroxides and superoxides readily dissolve in water to produce
corresponding hydroxides which are strong alkalies eg
2Na + 2H20 --->2Na0H+ H2
Na20 + 2H20---->2NaOH
Na202 +2H20 -->2Na0H+ H202
2K02 +2H20 -->2K0H+ H202 +02
Thus peroxides and superoxides also act as oxidizing agents since they react with H2O forming
H202 and 02 respectively. The hydroxides of all the alkali metals are white crystalline solids.
They are strongest of all base and readily dissolve in water with the evolution of much heat.
(a) Basic Strength
The basic strength of these hydroxides increases as we move down the group Li to Cs: The
hydroxides of alkali metals behave as strong bases due to their low ionization energies which
decrease down the group. The decrease in ionization energies leads to weakening of the bond
between metal and hydroxide ion and M — 0 bond in M — 0 H can easily break giving M± and
OH- . This results in the increased concentration of hydroxyl ions in the solution i.e increased
basic characters.
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Solubility and stability

All these hydroxides are highly soluble in water and thermally stable except lithium hydroxide.
2Li0H—Li20 +H20
Formation of salts with acids:
Alkali metals hydroxides being strongly basic react with all acids forming salts.
NaOH + HCI—>NaCI+H20
2NaOH +H2SO4 —Na2S0, + 2H20
Illustration 7: Name the alkali metal which forms superoxides when heated in excess of air and
why?
Solution: Potassium forms superoxides when heated in excess of air. This is due to the
stabilization of large size cation by large Size anion.
K +02 ----*K02
potassium superoxide
Illustration 8. Why lithium forms only lithium oxide and not peroxide or superoxides?
Solution: Due to the small size of lithium, it has a strong positive field around it. On
combination with the oxide anion (02-), the positive field of lithium ion restricts
the spread of negative charge towards another oxygen atom and thus prevents
the formation of higher oxides.
Exercise 11.
What happens when potassium superoxide is dissolved in water?
Exercise 12.
Account for the fact that the basicity of the alkali metal hydroxides increases down
the group.
(ii) Halides
The alkali metals combine directly with halogens under appropriate conditions forming halides of
general formula MX. These halides can also be prepared by the action of aqueous halogen acids
(HX) on metals oxides, hydroxides or carbonate.
M20 + 21-IX—) 2M X + H20
MOH + HX ---4/1X+ H20
M2CO2 +2HX--->2MX+ CO2 +H20 = Li, Na, K, Rb or Cs) (X = F, Cl, Br or I)
All these halides are colourless, high melting crystalline solids having high negative enthalpies of
formation.
Table — II [Standard enthalpies of formation in (Union]
Li -612 -398 -350 -271

Na -569 -400 -360 -288
-563 -428 -392. -328
Rb -549 423 -389 -329
Cs -531 -424 -395 -337
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The reactivity toward alkali metals decreases in the order: Fluoride > Chloride > bromides >
Iodide
The trends in melting points, boiling points and solubility of alkali metals halides can be
understood in terms of polarization effects, lattice energy and hydration of ions.
(a) Polarization effects
Comparison of ionic and covalent character of
alkali metal halides.
1
When a cation approaches an anion, the electron
cloud of the anion is attracted towards the cation Polarizina
cation Polarized anion Unpolarized anion
and hence gets distorted. This effect is called
polarization. The power of the cation to polarize the
anion is called its polarizing power and the tendency of the anion to get polarized is called its
polarizability. The greater the polarization produced more is the concentration of the electrons
between the two atoms thereby decreasing the ionic character or increasing the covalent
character. The covalent character of any compound in general depends upon the following
factors.
Size of the cations
Smaller the cation greater is its polarizing power and hence larger is the covalent character. The
covalent character decreases as size of cation increases.
LiCI > NaCI > KCI > RbCI > CsCI
Thus LiCI is more covalent than KCI.
Size of the anion
Larger the anion, greater is its polarizability. This explains the covalent character of lithium
halides is in order
Lil > LiBr > LiCI > LiF
Charge of the ion
Greater the charge on the cation greater its polarizing power and hence larger is the covalent
character. The covalent character of some halides increase in the order
NaCl- < Mg+2Cl2 < Al+3C1,
Similarly greater the charge on the anion, more easily it gets polarized thereby imparting more
covalent character to the compound formed eg covalent character increase in the order
NaCI < Na2S0, <Na3PO4
Thus the covalent character decreases as the charge of the anion decrease.
Electronic configuration of the cation
If two cations have the same charge and size, tne one with pseudo noble gas configuration i.e
having 18 electrons in the outermost shell has greater polarizing power than a cation with noble
gas configuration i.e having 8 electrons. For example CuCI is more covalent than NaCI.
(b) Lattice Energies
lattice energy is defined as the amount of energy required to separate one mole of solid ionic
compound into its gaseous ions. Evidently greater the lattice energy, higher is the melting point of
the alkali metals halide and lower is its solubility in water
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Table — Ill
LiCI -845 -. 876 . 63.7 887

NaCI -770 -776 35.7 1084
KCI -703 -700 34.7 1039
RbCI -674 -680 77.0 988
CsCI -644 -646 162 925
NaF -893 -919 4.22 1261
NaCI -770 -776 35.7 1028
NaBr -730 -745 116 1084
Nal -685 -685 184 944
LiF -1005 -1019 0.27 1115
Cs1 -582 -670 44.0 1115
(c) Hydration Energy
It is the amount of energy released when one mole of gaseous ions combine with water to form
hydrated ions.
(g) + (aq) + hydration energy
X- (g)+ aq—> X (aq)+ hydration energy
Higher the hydration energy of the ions greater is the solubility of the compound in water.
Further the extent of hydration depends upon the size of the ions. Smaller the size of the ion,
more highly it is hydrated and hence greater is its hydrated ionic radius and less is its ionic
mobility (Conductance).
From above arguments, the melting point and solubility in water or organic solvent of alkali metal
halides can be explained
A delicate balance between lattice enthalpy and hydration enthalpy determines the ultimate
solubility of a compound in water. For eg. Low solubility of LiF (0.27 g/100 g H20 ) is due to its
high lattice energy (-1005KJmoll whereas the low solubility of Csl (44g/100g I-120 ) is due
to smaller hydration energy of the two ions (-670 KJ/mol)
The solubility of the most of alkali metal halides except those of fluorides decreases on
descending the group since the decrease in hydration energy is more than the corresponding
decrease in the lattice energy.
Due to small size and high electronegativity, lithium halides except LiF are predominatantly
covalent and hence are soluble in covalent solvents such as alcohol, acetone, ethyl acetate,
LiCI is also soluble in pyridine. In contrast NaCI being ionic is insoluble in organic solvents.
Due to high hydration energy of Li+ ion, Lithium halides are soluble in water except LiF which
is sparingly soluble due to its high lattice energy.
For the same alkali metal the melting point decreases in the order
fluoride > chloride > bromide > iodide
because for the same alkali metal ion, the lattice energies decreases as the size of the halide
ion increases.
for the same halide ion, the melting- point of lithium halides are lower than those of the
corresponding sodium halides and thereafter they decrease as we move down the group
from Na to Cs.
The low melting point of LiCI (887 K) as compared to NaCI is probably because LiCI is covalent in
nature and NaCI is ionic.
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Illustration 9. Why are alkali metal halides soluble in water? .

Solution: Alkali metal halides are soluble in water due to their high ionic character and low
lattice energy.
Exercise 13.
Why is LiF less soluble in water?
Exercise 14.
Why is Cs1 less soluble in water?
(iii) Salts of oxoacids
Since the alkali metals are highly electropositive, therefore their hydroxides are very strong bases
and hence they form salts with all oxoacids (H2CO3,H3PO4,H2SO4 ,HNO3,HNO2 etc). They are
generally soluble in water and stable towards heat. The carbonates (M2CO3 ) of alkali metals are
remarkably stable upto 1273 K, above which they first melt and then eventually decompose to
form oxides. Li2CO3 , however is considerably less stable and decomposes readily.
Li2CO3 > Li2O +CO2
This is presumably due to large size difference between Li+ and CO23- which makes the crystal
lattice unstable.
Being strongly basic, alkali metals also form solid bicarbonates. No other metals forms solid
bicarbonates though NH4FIC03 also exists as a solid. Lithium, however does not form solid
bicarbonate though it does exist in solution. All the bicarbonate on gentle heating undergo
decomposition to form carbonates with the evolution of CO2 .
2MHCO3 +M2CO3 +CO2 +H20
All the carbonates and bicarbonates are soluble in water and their solubilities increase rapidly on
descending the group. This is due to the reason that lattice energies decrease more rapidly than
their hydration energies on moving down the group.
Illustration 10. Complete and balance the following:

LiNO3 Heat
Heat
NaNO3
Solution: (i) 4LiNO3 Ls > 2L120 + 4NO2 02

(ii) 2NaNO3 —°>2NaNO2 +02
. . . .
Exercise 15.
Which hydroxide is most basic?
(A) KOH (B) RbOH
(C) NaOH (D) CsOH
Exercise 16.
Which of the following alkali metal halides has the lowest lattice energy?
(A) LiF (B) NaCI
(C) KBr (D)Cs1
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Anomalous Behaviour of Lithium and its Diagonal fRelationship with Magnesium
The properties of lithium are quite different from the properties of other alkali metals. On the other
hand, it shows greater resemblance with magnesium, which is diagonally opposite element of it.
The main reasons for the anomalous behaviour of lithium as compared to other alkali metals are
The extremely small size of lithium atom and its ion.
Greater polarizing power of lithium ion (Li), due to its small size which result in the covalent
. character in its compounds.
Least electropositive character and highest ionization energy as compared to other alkali
metals.
Non availability of vacant d-orbitals in the valence shell.
The reason for resemblance of properties of lithium with magnesium is that these two element
have almost same polarizing power.
The following points illustrate the anomalous properties of lithium and its diagonal relationship
with magnesium:
The melting point and boiling point of lithium are comparatively high.
Lithium is much harder than the other alkali metals. Magnesium is also hard metal.
Lithium reacts with oxygen least readily to form normal oxide whereas other alkali metals
form peroxides and superoxides.
LiOH like Mg(OH)2 is weak base. Hydroxides of other alkali metals are strong bases.
Due to their appreciable covalent nature, the halides and alkyls of lithum and magnesium are
soluble in organic solvents.
Unlike elements of group 1 but like magnesium. Lithium forms nitride with nitrogen.
6Li + N2 >2Li3N
LiCI is deliquescent and crystallizes as a hydrate, LiCI.2H20 . Other alkali metals do not form
hydrates. MgCl2 also forms hydrate, MgC12.8H20
Unlike other alkali metals lithium reacts directly with carbon to form an ionic carbide.
Magnesium also forms a similar carbide.
The carbonates, hydroxides and nitrates of. lithium as well as magnesium decompose on
heating.
Li2CO3 > LO +CO2
MgCO3 ---›Mg0 +CO2
2Li0H—›Li20 +H20
Mg (OH)2 —Mg0 + H20
4LiNO3 -->2Li20 + 4NO2 +02
2Mg (NO3 )2 —°->2Mg0 + 4NO2 +02
The corresponding salts of other alkali metals are stable towards heat. -
Lithium nitrate, on heating, decomposes to give lithium oxide, Li2O whereas other alkali
metals nitrates decomposes to give the corresponding nitrite.
4LiNO3 > 2Li2O +4NO2 +02
2NaNO3 >2NaNO2 +02
2KNO3 --2KNO2 + 02
Li2CO3, Li0H, LiF and Li3PO4 are the only alkali metal salts which are insoluble in water. The
corresponding magnesium compounds are also insoluble in water.
(I) Hydrogen carbonates of both lithium and magnesium can, not be isolated in solid state.
Hydrogen carbonates of other alkali metals can be isolated in solid state.
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Illustration 11. Name the chief factor responsible for the anomalous behaviour of lithium.
Solution: The chief factors responsible for the anomalous behaviour of lithium are:
its very small size,
least electropositive
high ionization enthalpy
absence of vacant d-atomic orbital in the valence shell
Difficulties encountered during extraction of alkali metals

Alkali metals, can not be extracted from their ores by the usual methods of extraction of metals
because of the following difficulties:
Alkali metals are strong reducing agents and hence can not be extracted by reduction of their
oxides or chlorides.
Alkali metals being highly electropositive can not be displaced from the aqueous solutions of
their salts by other metals.
Alkali metals can not be isolated by electrolysis of the aqueous solution of their salts since
hydrogen is liberated at the cathode instead of the alkali metal because the discharge
potentials of alkali metals are much higher than that of the hydrogen. However, by using
mercury as cathode, the alkali metals can be deposited at the cathode but the alkali metals
so deposited readily combines with mercury to form an amalgam from which its recovery is
very difficult.
Therefore in view of above difficulties, only successful method is the electrolysis of their
molten (fused) salts usually chlorides.
Extraction of Lithium
Minerals of Lithium
Spodumene, LiAl(SiO3)2 - 6% Lithium
Triphylite (Li, Na)2PO4 (Fe, Mn)3(PO4)2 - 4% Lithium
Petalite LiAl(Si205)4 2.7 — 3.7% Lithium
Lepidolite (Li, Na, K)2(SiO3)3(FOH)2 1.5% Lithium
Amblygonite LiAl(PO4)F
It involves the following steps:
1. Preparation of Lithium chloride
The minerals are first of all converted into lithium chloride by any one of the following methods:
Acid treatment method

The finely powdered silicate ore is first heated to about 1373 K to make it more friable and then
treated with H2SO4 at 523 K. The Li2SO4.H2 0 thus formed is cooled, leached with water and
then filtered to remove silica (SiO2 ). The filtrate thus obtained is treated with a calculated amount
of Na2CO3 to precipitate aluminium and iron as carbonates which are filtered off. Excess of
Na2CO3 is then added to the filtrate to precipitate Li2CO3 . This is filtered and dissolved in HCI to
obtain LiCI which is purified by extraction with alcohol.
Fusion method
The powdered silicate mineral is fused with CaCO3 and the fused mass is extracted with HCI and
filtered. The filterate contains chlorides of Li, Al, Ca, Na and K whereas silicon is removed as
insoluble residue. The filterate is evaporated to dryness and the residue is extracted with pyridine
in which only LiCI dissolves. Pyridine is distilled off while LiCI is left behind. The method
discussed above may be summed up in the following flow-sheet.
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Lithium ore (spodumene or lepidolite)

Fuse with (CaCO3 ) and exfract
with HCI and filter
1
Insoluble Filtrate
(SiO2 )
(Chlorides of Li, Al, Ca, Na; K)
i
Evaporate to dryness and
extract with prydine
Soluble Insoluble
(LiCI) (NaCI, KCI, CaCl2, AlCl3 )
2. Electrolysis of Lithium chloride
A mixture of dry lithium chloride (55%) and potassium chloride (45%) is fused and electrolysed in
an electrolytic cell shown in the figure.
Potassium chloride is added to increase the conductivity of lithium chloride and fo lower the
fusion temperature. The cell is operated at a temperature of about 723 K and voltage of 8-9 volts
is applied.
As a result of electrolysis, the following reactions take place: LiC1,=—Lr + CI-
At cathode: Li+ + e-
At anode : 2CI- —2e- —>Cl2
Chlorine gas, a valuable by product liberated at the anode leaves the 'cell through the exit while
molten lithium rises to the surface of the fused electrolytes and collects in the cast iron enclosure
surrounding the cathode. The metal thus obtained is 99% pure and is preserved by keeping it
wrapped in paraffin wax. It may be noted here that lithium being the lightest metal known
(density = 0.534 g cm-3 ) can not be stored in kerosene oil since it floats on the surface.
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Properties of Lithium
(a) Physical Properties
(i) Lithium is a silvery white metal.
It is the hardest alkali metal but still is soft enough to be cut with a knife.
Atomic and ionic radii of lithium are the lowest amongst alkali metals.
(b) Chemical Properties
Lithium is highly reactive element. However, among alkali metals lithium is the least reactive.
Dry air
No effect
Moist air
*Tarnishes slowly
02 or air
Li2O (Burns with
375 K
brilliant white light
H20
LiOH + H2
(Slow reaction)
Lithium H2SO4
U2SO4 + H2
H2
.LiH (Lithium hydride)
A
N2
Li3N (Lithium nitride)
A
Reaction with
non — metals- Cl2
+LiCI (Lithium chloride)
A
s3
Li2S (Lithium Sulhide)
A
P4
Li3P (Lithium phosphide)
A
Lithium is the only alkali metal which combines directly with nitrogen to form lithium nitride.
Lithium nitride is ionic and is ruby red. On heating it decomposes to its constituent element. It also
reacts with water evolving ammonia.
2Li3N + N2
Li3N + 3H20 >3LiOH + NH3
Reaction with ammonia

Like other alkali metals, lithium dissolves is liquid ammonia to form a deep blue solution due to
formation of ammoniated electrons.
Li +(x + y)NH3 196-200K >Li(NH3+e(NH3)
However, when NH3 gas is passed over molten lithium.
Lithium amide is formed
2Li + 2N H3 L >2LiNH2 +H2
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Uses of Lithium
Lithium lead alloy (0.05% Li) which is used for making toughened bearings and sheets for
cables.
Lithium — Aluminium alloy has great tensile strength and elasticity like that of mild steel. It is
used for air craft construction.
Lithium — magnesium alloy (with 14% Li) is extremely tough and corrosion resistant which is -
used for armour plate and aerospace components.
(d). Lithium is used for refining of metal like copper and nickel as it combines readily with oxygen
and nitrogen and thus removes the last traces of oxygen and nitrogen.
Lithium chloride is used in air conditioning plants to regulate the humidity.
Lithium aluminium hydride (LiAIH4) is used as a reducing agent in- synthetic organic chemistry
(9) Lithium carbonate is used in making special variety of glass which is very strong and is
weather proof.
Sodium
Sodium is the 7th most abundant element by weight found in earth's crust.
Minerals of sodium
Rock salt — NaCI
Chile salt petre — NaNO3
Glauber's salt — Na2SO4.10H20
Borax or sodium borate — Na2B407.10H20
Albite or soda feldspar — Na20.A1203.6Si02 or NaAlSi308
Extraction of sodium
Sodium is extracted by Down's process through electrolysis of fused sodium chloride.
In this method, sodium is obtained by the electrolysis of mixture of sodium chloride (40%) and
calcium chloride (60%) in fused state. The function (5f calcium chloride is to lower the operating
temperature from 1080 K (m.pt. of NaCI) to about 850 K. The main reasons for lowering the
temperature are:
The melting point of sodium chloride is very high and it is very difficult to maintain it in the
molten state during electrolysis.
Sodium is considerably volatile at the temperature needed for the electrolysis and therefore,
a part of the metal produced is vapourised.
Molten sodium gets dispersed in molten chloride to form a metallic fog (colloidal solution) at
high temperature.
Both sodium and chlorine, the two produtts of the electrolysis, have a corrosive action on the
material of the vessel employed for the electrolysis at such a high temperature.
The cell consists of a steel tank lined with fire bricks. A circular graphite anode is placed in the
centre of the cell which is surrounded by a cylindrical iron cathode. The anode and cathode are
separated by a steel gauge cylinder through which molten sodium chloride can pass but molten
sodium cannot. The purpose of using steel gauge is to keep sodium separate from chlorine which
would otherwise react with chlorine. The anode is covered by a dome — shaped steel hood which
provides the out — let for the escape of chlorine gas. The molten metal liberated at the cathode
moves-up and flow into the receiver containing kerosene oil. The following reactions take place:
NaCI —› Na+ + CI- (Ionization)
At cathode: Na+ + Na
At node: cr CI +e
CI + CI >Cl2 1'
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Cl2
Fused NaCl, CaCl2
-Dome
Kerp ene oil
Molten
Sodiu
Iron Ca ode
Properties of Sodium
Physical Properties
Sodium is soft, silvery white metal.
It is lighter than water, its density is 0.97 g/cm3.
It imparts golden yellow flame when introduced into Bunsen flame.
Chemical Properties
Sodium is more reactive than lithium.
(i) Action of air and moisture
It is tarnished rapidly on exposure to moist air.
First a film of sodium monoxide, Na20 is formed which changes readily into sodium hydroxide by
action of moisture and finally into sodium carbonate by the action of CO2 present in air.
4Na +02 ---->2Na20 or Na2O +H20 —2NaOH
2NaOH +CO2 —.›Na2CO3 +H20 or Na2O + CO
__2 -- >Na2CO3
It is therefore kept under kerosene.

o,
Na202 4Na + 02 --+ 2Na20
Sodium'
H20
Sodium peroxide
NaOH + H2 { 2Na20 +.02 --0 2Na202
Cl2
• NaCI
A
Non - metals
S. *Na2S
A
P4
Na2P
A
HI
NaH
A
HCI
• NaCI + H2
C2H6OH
C2H60Na + H2
Sodium Ethoxide
Si02
Na20 + SI
BeCl2
•NaCI + Be Reducing action of Na
AICI,
NaCI + Al
A
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(ii) Action of ammonia

Sodium dissolves in liquid ammonia to form blue solution which is a good conductor of electricity.
196K
Na + (x + y)NH3--- —> Na(NH3) + e- (NH3 )y
ammoniated sodium ammoniated electrons
(blue)
However, when ammonia is passed through molten sodium, it yield sodamide evolving H2 gas.
475K
2Na + 21*13 --*2NaNH2 +H2
Uses Of sodium
Sodium is used as a reducing agent in the extraction of boron and silicon.
Liquid sodium or its alloy with potassium is used as cootent in nuclear reactors.
Sodium as well as sodium amalgam are used as reducing agents in organic synthesis.
It is used in Lassaigne's test for the detection of N, S and halogen in organic compounds.
Sodium is used in sodium vapour lamps.
It is largely used for production of artificial rubber, dyes, drugs etc.
Sodium-lead alloy is used for preparation of tetraethyl lead. Pb(C2H5)4 which is used as an.
anti-knocking agent in petrol.
Illustration 12. What happens when
sodium metal is dropped in water?
sodium metal is heated in free supply of air?
sodium peroxide dissolves in water?
Solution: (i) 2Na + 2H20 --> 2Na0H +H,

2Na +0, -->Na202
(free supply)
2Na202 +2H 0-34Na0H +H,0

Exercise 17.
Explain what happens when
sodium hydrogen carbonate is heated.
sodium amalgam reacts with water.
fused sodium metal reacts with ammonia. • . .
Compounds of Alkali Metals
Oxides of Metal
Oxides of Sodium: The possible oxides of Na are Na2O and Na202.
Sodium Monoxide
Preparation
It is obtained by burning sodium at 180° C in a limited supply of air or oxygen and distilling off the
excess of sodium in vacuum, or by heating sodium peroxide(Na202), nitrate(NaNO3) with sodium
2Na + 1/202 —> Na20
Na202 + 2Na --> 2Na20
2NaNO3 + 10 Na ---> 6Na 20 + N2
Properties
It dissolves in water violently gives caustic soda.

Na20 + H20 2Na0H
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Sodium Peroxide (Na202)
Preparation
It is formed by heating the sodium metal in excess air or oxygen. The air should be moisture free
and temperature required is 300° C.
2Na + 02 —> Na202
Properties
- It is pale yellow solid becoming white in air due to the formation of a film of sodium hydroxide
and carbonate.
It dissolves in ice - cold water with hydrolysis, gives hydrogen peroxide, which decomposes
into water and oxygen on warming; whereas it gives oxygen and caustic soda with water at
room temperature,
Ice-cold water
Na202 > 2Na0H + H202
Na202 + 2H20 25°C > 2Na0H + 02
It dissolves in ice-cold dilute mineral acid gives H202.
Na202 H2SO4 Na2SO4 + H202
Oxides of Potassium
Potassium forms number of oxides viz., K20, K202 and K02. Other two oxides can also exist
which are K203 and K03
Potassium monoxide (K20)
It is solid, yellow when hot and white when cold, obtained by heating potassium nitrate with
potassium.
2KNO3 + 10K --> 61<20 + N2
It dissolves in water to give KOH like Na2O
Potassium peroxide (K202) -
Controlled oxidation of potassium in excess air or oxygen at 300° C gives mainly K202. It gives
i-I202 when dissolves in water.
K202 + 21-120 2KOH + H202
Potassium superoxide (K02)
It is made by burning potassium in a good supply of air or oxygen. It is powerful oxidising agent. It
reacts with water giving both oxygen and hydrogen peroxide.
21<02 + 2H20 --> 2KOH + H202 +02
Illustration 13. Give some important uses of sodium peroxide.
Solution: Important uses of sodium peroxide are:
It is used as a bleaching agent.
It is used in the manufacture of sodium perborate, benzoyl peroxide.
It is used for the purification of air in confined spaces such as submarines.
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Exercise 18.
Potassium metal is commercially prepared by the reduction of molten KCI with
metallic sodium at 850°C (1,123 K). This method is based upon the following principle:
Sodium is more reactive than potassium at this temperature
Potassium, being more volatile, distils off thus shifting the reaction forward
(C) Sodium prefers to bind to chloride ions in preference to potassium ions
Potassium and sodium form an. alloy at this temperature ,
................
. . .
Hydroxides of Metals (Na, K)
Sodium Hydroxide (NaOH)
When calcium hydroxide is added to sodium carbonate solution, calcium carbonate is
precipitated, leaving sodium hydroxide in solution
Na2CO3 + Ca(OH)2 CaCO3 4, + 2NaOH
Properties
NaOH is stable towards heat but is reduced to metal when heated with carbon
2NaOH + 2C —+ 2Na +2C0 + H2
FeCl3 + 3NaOH Fe(OH)3 + 3NaCI
NH4CI + NaOH NaCl + NH3 (pungent smell) + H20
HgC12 + 2NaOH Hg0 (yellow powder) + 2NaCI + H20
Zn(OH)2 + 2NaOH Na2ZnO2 + 2H20
A1203 4, + 2NaOH 2NaA102 + H20
SiO2 + 2NaOH Na2SiO3 + H20
3P + 3 NaOH +3H20 -Y PH3 + 3NaH2P02
2AI + 2 NaOH + 2H20 3H2 + 2NaA102
Uses
It is used in the manufacture of paper, soap and artificial silk.
It is used in petroleum refining.
It is used for mercerizing cotton.
It is used for the preparation of sodium inetal and many salts of sodium.
Potassium Hydroxide or Caustic Potash (KOH)
Pure KOH is obtained by adding potassium sulphate to a hot saturated solution of Ba(OH)2.
BaSO4 is filtered off and filtrate is evaporated in a silver dish.
K2SO4 + Ba(OH)2 BaSO4 + 2K0H
Properties
In the absorption of carbon dioxide, caustic potash is preferred to caustic soda: since the
KHCO3 formed after sufficient absorption is soluble, while NaHCO3 is insoluble and
may,therefore choke the tubes.
As an alkaline reagent KOH is not used while NaOH is used because NaOH is cheaper than
KOH.
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Carbonates of Metals (Na, K)
Sodium Carbonate (Washing soda) (Na2CO3)
Solvay Process
Sodium carbonate is generally prepared by a process called the ammonia — soda process or
solvay process as described below:
Principle
When carbon dioxide gas is bubbled through a brine solution saturated with ammonia, it results in
the formation of sodium hydrogen carbonate.
NH3 + H20 + CO2 ---*NH4HCO3
Naa+ NH4HCO3 --NaHCO3 + NH4CI
Sodium hydrogen carbonate so formed precipitates out because of the common ion effect caused
due to the presence of excess of NaCI. The precipitated NaHCO3 is filtered off and then ignited to
get Na2CO3.
2NaHCO3 >Na2CO3 +CO2 +H20
Plant Process
The various parts for the manufacture of Na2CO3 by solvay process have been illustrated in figure
below.
NH3 + A little CO3
Brine
2
co
efst:N
Tower
Water Ca(OH)
Steam
Filter
H •
Filter
---NaHCO3 C(;:r Ignition)
NH4CI + A little NH4HCO3
CICI3
Plant used for the manufacture of washing soda

(i) Ammonia absorber
A 30% solution of brine is saturated with ammonia (from recovery tower) is introduced into
absorber tower. Various impurities like calcium and magnesium salts present in the commercial
NaCI precipitate out as corresponding insoluble carbonates. (which comes along with ammonia
from the ammonia recovery plant)
2NH3 + H20 + CO2 --->(N H4 )2 CO3
CaCl2 + (NH4 )2 CO3 --->CaCO3 +2NH4CI
MgCl2 + (NH4 )2 CO3 --->MgCO3 +2NH4CI
The ammoniated brine is filtered to remove the precipitated calcium and magnesium carbonate.
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carbonation Tower
It is high tower fitted with perforated plates. Ammoniated brine solution is made to trickle down
from the top of the tower while CO2 gas from the lime kiln is admitted from the base of the tower.
CO2 rises through the small perforations and its interaction with ammoniated brine results in the
formation of insoluble sodium hydrogen carbonate.
NH3 + H20 + CO2 --->NH4HCO3
NaC1+ NH4HCO3 --NaHCO3 st,+NH4C1
Filtration
The solution containing crystals of NaHCO3 is drawn off from the base of the carbonation tower
and filtered to get NaHCO3.
The NatIC03 obtained from the above step is heated strongly in kiln to covert it into sodium
carbonate (Na2CO3)
2NaHCO3 -->Na2CO3 +CO2 +H20
The carbon dioxide produced here is sent to carbonation tower.
Ammonia recovery tower

The filtrate, after removal of NaHCO3 contains ammonium salts such as NH4HCO3 and NH4C1.
The filtrate is mixed with Ca(OH)2 and is heated with steam in ammonia recovery tower.
NH4HCO3 NH3 + H20 + CO2
2N H4C1 + Ca (OH)2 --->2NH3 2H20 CaCl2

The mixture of ammonia and CO2 gases is obtained which is used for saturation of brine while
calcium chloride is obtained as a by — product.
Lime kiln
Here limestone is heated at about 1300 K to obtained CO2 and calcium oxide
CaCO3 -->Ca0 + CO2
The CO2 gas goes to the carbonation tower while lime is slaked with water in tank known as
slakes to form ca(OH)2.
The overall reaction taking place in solvay process is
2NaCI+CaCO3 ---->NaCO3 +CaC12
Flow sheet diagram of Solvay process
Brine (NaCI)(aq.)
Ammonia
Lime stone absorber
CaCO3(s)
NH2(g)
CO2(9) i
I Heat Ca(OH)2
Tower
NaCI (aq)
NaHCO3(s) Ammonia recovery
CaO(s) Filter (heat)
Heat
Slake with
water 1.
Na2CO3(s)
Soda ash
Ca(OH)2
Sent to Ammonia
recovery Tower
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Properties
The aqueous solution absorbs CO2 yielding sparingly soluble sodium bicarbonate.
Na2CO3 + H20 + CO2 —> 2NaHCO3
It dissolves in acids with an effervescence of carbondioxide and is causticised by lime to give
caustic soda.
Na2CO3 + 2HCI ---> 2NaCI + H20 + CO2
Na2CO3 + Ca(OH)2 —> 2NaOH + CaCO3
Fusion with silica, sodium carbonate yields sodium silicate.
Na2CO3 + SiO2 --> Na2SiO3 + CO2
Hydrolysis — being a salt of a strong base (NaOH) and weak acid (H2CO3), when dissolved in
water sodium carbonate. Undergoes hydrolysis to form an alkaline solution
Na2CO3 + 2H20—. H2CO3 + 2NaOH
Uses
It is used for softening hard water.
A mixture of sodium carbonate and potassium carbonate is used as fusion mixture.
As an important laboratory reagent both in qualitative and quantitative analysis.
It is used in paper, paints and textile industries.
It is used for washing purposes in laundry.
It is used in the manufacture of glass, borax, soap and caustic soda.
Potassium carbonate (K2CO3)
It is also known as pearl ash. It is made by passing CO2 into a conc. solution of the chloride,
containing hydrated mangesium carbonate in suspension at 20°C when an insoluble potassium
hydrogen magnesium carbonate is precipitated.
2KCI + 3(MgCO3. 3H20) + 2(MgCO3. KHCO3.4H20) + MgC12
The precipitate is separated by filtration, and then decomposed either by heating with water under
pressure at 140°C or by the action of magnesium oxide below 20°C.
2(MgCO3. KHCO3. 4H20)--> 2MgCO3 + K2CO3 + 9H20 + CO2
2(MgCO3. KHCO3. 4H20) + MgO —> 3(MgCO3. 3H20) + K2CO3
Properties
It is white, deliquescent solid
K2CO3 resembles Na2CO3 in properties, but is more alkaline and more soluble than Na2CO3.
Illustration 14. Sodium carbonate, which is one of the most important products of the chemical
industry, is prepared by the Solvay process based on the interaction of sodium
chloride with ammonia and carbon dioxide. The reaction yields
(A) NH4HCO3 (8) NH4C1
(C) NaHCO3 (D) (NH4)2CO3
Solution: (A)
Bicarbonates of Metals (Na, K)
Sodium Bicarbonate,
A concentrated solution of sodium carbonate absorbs CO2 to give sparingly soluble sodium
bicarbonate.
Na2CO3 + CO2 + H20 2NaHCO3
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Properties
It is sparingly soluble in water
When heated between 250°C and 300°C, it is converted into pure anhydrous sodium
carbonate which can be used for standardising acids.
2NaHCO3 --› Na2CO3 + H20 + CO2
Potassium bicarbonate
It is made by absorbing CO2 in moist potassium carbonate and then drying the product in a
porous plate.
K2CO3 + H20'+ CO2 —> 2KHCO3
Properties
KHCO3 resembles NaHCO3, but is much more soluble in water. The solution is strongly alkaline
owing to hydrolysis.
KHCO3 + H20 KOH + H2CO3
Chlorides of Metal (Na, K)
Sodium Chloride (NaCI)
It is also called common salt occurs abundantly in nature as rock salt or halite. The most
abundant source is sea-water where sodium chloride occurs to the extent of 2.6 — 2.9 percent.
The sea water is exposed to the sun and air in large shallow pits. The gradual evaporation of
water leading to the crystallization of the salt. The purification is done by dissolving the salt in
minimum volume of water and filtering, if necessary, to remove insoluble impurities. The solution
is then saturated with a current of dry hydrogen chloride whereby crystals of pure sodium chloride
separate out.
Properties
NaCI is a colourless crystalline salt, almost insoluble ;n alcohol and highly soluble in water.
It gives rise to HCI when heated with conc. H2SO4 and C12, with Mn02 plus H2SO4.
NaCI + H2SO4 NaHSO4 + HCIT
NaHSO4 + NaCI Na2SO4 + FICIT
2NaCI + Mn02 + 2H2SO4 —› MnSO4 + Na2SO4+ 2H20 + Cl2 T
Potassium Chloride
KCI is prepared from fused camallite — nearly pure KCI separates from the melt, leaving fused
MgCl2 behind.
KCI, MgC12•6H20 KCl + MgC12•6H20
Properties
It is colourless cubic crystal like solid soluble in water. Its solubility increases almost linearly with
temperature.
Sulphates of Metals: (Na, K)
Sodium Sulphate, Na2SO4
The anhydrous salt known as salt cake, is prepared on an industrial scale by heating strongly
sodium chloride with conc. sulphuric acid.
NaCI + H2SO4 %-= NaHSO4+ HCIT
NaCI + NaHSO4 Na2SO4 + HCIT
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Glauber's salt or hydrated sodium sulphate, Na2 SO4.10H20 is prepared from salt cake by
crystallisation from water below 32°C This temperature represents the transition temperature for
Na2SO4 and Na2SO4.10H20.
It is colourless salt, crystallising in large monoclinic prisms. It is exceedingly soluble in water.
Potassium Sulphate, K2SO4
It is obtained by strongly heating potassium chloride with conc. H2SO4
KCI + KHSO4 + HCI
KCI + KHSO4 —> K2SO4+ HCI
It is colourless crystalline salt, m.p. 1070°C. It is less soluble in water than sodium sulphate and
has no hydrate like the later.
Exercise19.
Plaster of paris by (i) giving out water and (h) uniting with water gives A and B
respectively. What are A and B?
Alkaline Earth Metals

The group 2 of the periodic table consists of six metallic elements. They are Beryllium (Be),
Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba) and Radium (Ra). The name alkaline
earth metals was given to magnesium, calcium, barium & strontium since their oxides were
alkaline in nature and these oxide remained unaffected by heat or fire and existed in earth.
Occurrence
Like alkali metals, alkaline earth metals are also highly reactive and hence do not occur in the
free state but are likely distributed in nature in the combined state as silicates, carbonates,
sulphates and phosphates.
Minerals
Be — Beryl (Be3Al2Si6018) & Phenacite (Be2S104)
Mg — Magnesite MgCO3, Dolomite CaMg(CO3)2, Epsomite MgS0.4.&H20
Ca — Limestone (CaCO3), fluoropatite [3(Ca3(PO4)3.CaF2], Gypsum (CaSO4.2H20),
Anhydrite (CaSO4)
Sr — Celestite (SrS0.4), Strontianite (SrCO3)
Br — Barytes (BaSO4)
Electronic Configuration
The general electronic configuration of alkaline earth metals is ns2.
Be — 1s 2s Mg — 1s22s22p63s2
Ca — 1s22s22p63s23p64s2 Sr — [KrI5s2
Ba — [Xe]6s2 Ra — [Rn]7s2
Physical Properties of Group II elements
Atomic and ionic radii
The atomic radii as well as ionic radii of the members of the family are smaller than the
corresponding members of alkali metals.
Ionization energy
The alkaline earth metal owing to their large size of atoms have fairly low values of ionization
energies as compared to the p — block elements. However with in the group, the ionization energy
decreases as the atomic number increases. It is because of increase in atomic size due to
addition of new shells and increase in the magnitude of screening effect of the electrons in inner
shells. Because their (1E)1 is larger than that of their alkali metal neighbours, the group IIA metals
trend to the some what less reactive than alkali metals. The general reactivity trend is
Ba > Sr > Ca > Mg > Be.
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Illustration 15. The 2nd ionization energy of the elements of group I are higher than those of the
elements of group II. Explain.
Solution: The 2nd electron in case of alkali metal is to be removed form a cation (unipostive
ion) which has already acquired a noble gas configuration whereas in case of
alkaline earth metals, the second electron is to be removes fro a cation which is
yet to acquire the stable noble gas configuration therefore, removal of 2nd
electron in case of alkaline earth metals requires much less energy than that in
case of alkali metals.
There is sharp increase in third ionization energy due to stable inert gas configuration of m+2 ions.
This explains the upper limit of +2 oxidation state for the elements.
(iii) Oxidation state
The alkaline earth metal have two electrons in their valence shell and by losing these electrons,
these atoms acquire the stable noble gas configuration. Thus, unlike alkali metals, the alkaline
earth metals exhibit +2 oxidation state in their compounds.
M > M+2 + 2e
[noble gas]
Illustration 16. The alkaline earth metals shows +2 oxidation state i.e. they always form divalent
cations (M2+). Explain.
Solution: If ionization energy were the only factor involved, than group II elements should
have formed monovalent ions i.e. Mg, Ca+ etc rather than Mg2+, Ca+2 etc.
This can be explained as follows:
The divalent cations of alkaline earth metals acquires stable inert gas
configuration.
The divalent cations results in stronger lattices then monovalent cations and
hence a lot of energy called lattice energy released during formation of
divalent cations than monovalent cation which compensates the high second
ionization energy.
The existence of divalent ions in the aqueous solution is due, to greater
hydration of the divalent ions which counter balance the high value of second
ionization energy.
Hydration energy
The heat of hydration (hydration energy) of alkaline earth metals are approximately four times
higher than alkali metals of comparable size.
e.g.
Al-lhyd for Na+ (size 102 pm) = —397 KJrno1-1
AHhyd for Ca+2 (size 100 pm) = —1650 KJmorl
Larger hydration energy is due to the fact that the alkaline earth metals ions, because of their
much larger charge to size ratio, exert a much stronger electrostatic attraction on the oxygen of
water molecule.
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Lattice energies decreases as atomic number increases
-3923 -3178 -2906

-3517 -2986 -2610
-3312 -2718 -2459
-3120 -2614 -2367
Nature of metallic bonding in alkaline earth metals
The alkali metal two electrons are involved in the metallic bonding. Moreover, sizes of alkaline
earth metal ions are smaller than those of alkali metal ions. Consequently, stronger metallic
bonds are formed which result in the close packing of the atoms. Due to the presence of stronger
metallic bonds, alkaline earth metals have
(a) Higher melting points (b) Higher boiling points
(c) higher densities (d) Harder than the corresponding alkali metals.
Density
The alkaline earth metals are denser and harder than the corresponding alkali metals.
The atoms of alkaline earth metals have smaller size and are hence held by stronger metallic
bonds, as compared to alkali metals. Therefore, they are more closely packed in their crystal
lattice which accounts for high density and increased hardness of these elements.
Characteristic flame colouration
Expect Be & Mg (due to high ionization energy), the alkaline earth metals impart characteristic
colour when introduced into flame of a burner. This property is due to the ease of excitation of
their valence electrons. When elements or their compounds are introduced to flame, the electron
absorbs energy from the flame and gets excited to higher energy levels. When these electrons
return to their ground state, they emit absorbed energy in form of visible light having characteristic
wavelengths. Depending upon the wavelength of light emitted, different colours are impart to the
flame. Salts (generally chlorides) impart characteristic colours to the Bunsen flame.
ca' Brick-red
s Crimson
Ba2+ Apple green
Ra2+ Carmine — red
Illustration 17. Mg forms Mg2+, but Na2+ does not exist. Explain.
Solution: Na metal after the loss of one electron attains a noble gas configuration of neon.
Therefore, the removal of second electron is energetically unfavourable. Hence,
Na2+ does not exist.
Exercise 20.
Which group 2 metal burns with dazzling brilliance in air?
Exercise 21.
The second ionization enthalpy of calcium ,is more than that of the first and yet
calcium form CaCl2 not CaCL Why?
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Pinnacle- Study Package
Exercise 22.
Which of the -alkaline—earth metal ion does not impart any colour to the flame?
(A) Mg (B) Ca
(C) Sr (D) Ba
Electropositive or Metallic Character
The alkaline earth metals are highly electropositive and hence metallic and their electropositive or
metallic character increases down the group. However they are less electropositive or metallic
than the alkali metals. It is due to smaller size and higher ionization energies as compared to
alkali metals, hence have less tendency to loose electron than those of alkali metals (group I)
Like the alkali metals they also form predominantly ionic compounds but tendency of covalency is
greater, particularly with Be and Mg because of their smaller atomic and ionic radii. Be forms
compounds which are essentially covalent.
Melting and boiling points
The alkaline earth metals have higher melting and boiling points as compared to those of alkali
metals which is attributed to their small size and more close packed crystal lattice as compared_to
alkali metals and presence of two valence electrons.
Heat of Hydration
The heats of hydration of M2+ decreases with an increase in their ionic size and their
values are greater than that of alkali metal ions.
Alkaline earth metal ions, because of their larger charge to size ratio, exert a much
stronger electrostatic attraction on the oxygen of water molecule surrounding them.
Since the alkaline earth metals (except Be) tend to lose their valence electrons readily,
they act as strong reducing agents as indicated by E°red values. The particularly less
negative value for Be arises from the large hydration energy associated with the small
size of Be2+ and the relatively large value of heat of sublimation.
(xi) Solubility
Basic , nature of oxides increases down the group but solubilities of sulphates and
carbonates decrease as ionic size increases.
The solubility of most salts decreases with increased atomic weight, though usual trend is
reversed with fluorides and hydroxides in this group.
Physical Properties of groupe 2 elements (alkaline earth metals)
Atomic number 4 12 20 38 56 '88
Atomic mass 9.01 24.31 40.08 87.62 137.33 226.03
Metallic radius/pm 112 160 197 215 222

Ionic radius/pm 51 72 100 118 135 148
Ionization enthalpy I 899 737 590 549 503 509

(kJ mó1 1) II 1757 1450 1146 1064 965 979
Enthalpy of hydration of —2494 —1921 —1577 —1443 -1305
M2+ ions (kJ mol-1)
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Electronegativity 1.57 1.31 1.00 0.95 0.89 0.9

(Pauling Scale)
Density/g mol- at 298 K 1.85 1.74 1.55 2.63 3.62 5.5
Melting Point/K 1562 924 1124 1062 1002 973
Boiling point /K 2745 1363 1767 1655 2078 (1973)

(uncertain)
E°(V) at 298 K for
M2+(aq) + 2e- —> M(s) -1.97 -2.37 -2.87 -2.89 -2.90 -2.92
- .
Occurrence in 4.6 384 390* 10-13**
.
Lithosphere 2 2.76
* ppm (parts per million) ** Percentage by weight
Reactivity and Electrode potential
All the alkaline earth metals are highly reactive elements since they have a strong tendency to
lose the two valences s-electrons to form the corresponding dipositive ions having inert gas
configuration. The high reactivity arises due to their low ionization energies and high negative
values of their standard electrode potentials. Further, the chemical reactivity of alkaline earth'
metals increase. on moving down the group because the I.E. decreases and electrode potentials
become more and more negative with increasing atomic number from Be to Ra. Thus, beryllium
is•the least reactive while Ba (or Ra) is the most reactive element. Further since the ionization
energies of alkaline earth metals are higher and their electrode potential is less negative than the
corresponding alkali metals. They are less reactive than corresponding alkali metals.
Reducing Character
The alkaline earth metals are weaker reducing agents than the alkali metals. Like alkali metals,
their reducing character also increases down the group. This is due to the reason that the alkaline
earth metals have greater tendency to lose electrons so, they act as reducing agent but since
their I.E. are higher and their electrode potentials are less negative than the corresponding alkali
metals, therefore alkaline earth metals are weaker reducing agents than alkali metals. The
sulphates are stable to heat whereas the carbonates decompose to give MO and CO2, the
temperature of decomposition increasing from Mg to Ba. BeCO3 is kept in the atmosphere of CO2
to prevent its decomposition.
BeCO3 MgCO3 CaCO3 SrCO3 BaCO3
<100°C 540°C 900°C 1290°C 1360°C
Occurrence and uses of alkaline earth metals
amsMiner
Beryllium 2.8 x First detected in 1798 in the Used in corrosion resistant
gemstone beryl and emerald alloys.
(Be2Al2Si6018)
Magnesium 2.33%, Pure Mg first prepared in 1800, When alloyed with Al, Mg is
7th most named after the magnesia widely used as structural
abundant district in Thessaly Greece materials because of its high
element in where large deposits of the strength, low density and
earth's crust mineral are found
ease in machining.
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Calcium 4.15%, 5th CaCO3.2H20 obtained_ in pure As an alloying agent for

most - form in 1808, calcium is derived hardness in aluminium
-abundant from latin word calx, meaning compounds. Calcium is the
element in "lime" primary constituent of teeth
earth's
and bones.
crust.
Strontium 0.038% Discovered in 1787 and named SrCO3 is• used for the
,
after the small town of strontion manufacture of glass for
(Scotland) colour TV picture tubes.
Barium 0.042% Found in minerals witherite BaSO4 is used in medicine as
(BaCO3) and barite (BaSO4) a contrast medium for
after which it is named. stomach and intestine
X—rays
Radium Traces Isolated as chloride in 1898 from Used in cancer radiotheraphy
the mineral pitchblende
Group IIA (Alkaline earth metals) and groups IIB (Zn, Cd, Hg) Mg acts as a bridge element
between IIA and IIB.
Ca —Sr —Ba—Ra IIA(2)
20 38 56 88
Be
4
Zn —Cd —Hg 11/3 (14)

30 48 80
Bridge Element
. .
Sr No Propeities UABe Mg, Cat . 1 -
1 Electronic Tined gas] ns2 [Inert gas] (n— 1)d10ns2 -
configuration '
• Block S — block d — block
Oxidation +2 +2, mercury also forms dimeric
state Hg
Nature of Be0 is amphoteric, other oxides ZnO is amphoteric, CdO and
oxide are basic. MgO are basic
Nature of Electron — deficient BeX2, others ZnCl2, CdC12 are ionic but less
Halides (MX) are ionic: than IIA, HgC12 is covalent.
, _ MgCl2 < CaC12 < SrC12 < BaCl2
Nature of Less soluble in water and solubility More soluble than IIA
sulphates decreases down the group BeSO4
> MgSO4 > CaSO4 > SrSO4 >
BaSO4
Nature of Solubility of hydroxides increases Solubility of hydroxides
hydroxides as we move down the group. decrease as we move down
the group.
Nature of Soluble ZnS, CdS, HgS insoluble and
sulphides precipitate in salt analysis.
Reactivity . Increases as we move down the Decreases as we move down
group Be < Mg < Ca < Sr < Ba the group Zn > Cd > Hg
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Difference between alkaline earth metals and alkali metals

Both alkaline earth metals and alkali metals are s — block elements as the last electron enters the
ns — orbital. They resemble with each other in some respects but still there are certain
dissimilarities in their properties on account of different number of electrons in the valency shell,
smaller atomic radii, high ionization potential, higher electro negativity etc.
r e I ka me a 1 the
Electronic Two electrons are present in the One electron is present in the
configuration valency shall. The configuration is valency shell. The
2
ns (bivalent) configuration is nsi
(monovalent) more
electropositive
Valency Bivalent Monovalent
Electropositive Less electropositive More electropositive
nature
4-. Hydroxides Weak bases, less soluble and Strong bases, highly soluble
decompose on heating. and stable towards heat.
Bicarbonates These are not known in free state. These are known in solid
Exist only in solution. state.
Carbonates Insoluble in water. Decompose on Soluble in water. Do not
heating. decompose on heating (LiCO3
is an exception)
Action of nitrogen Directly combine with nitrogen and Do not directly combine with
form nitrides . nitrogen except lithium
Action of carbon Directly combine with carbon and Do not directly combine with
form carbides carbon
Nitrates Decompose on heating evolving a Decompose on heating
mixture of NO2 and oxygen evolving only oxygen
Solubility of salts Sulphates, phosphates fluorides, Sulphates, phosphates,
chromates, oxalates etc are fluorides, chromates, oxides
insoluble in water etc are soluble in water.
Physical properties Comparatively harder. High Soft, low melting points
melting points. Diamagnetic. paramagnetic.
Hydration of The compounds are extensively The compounds are less
compounds hydrated. MgC12.6H20, hydrated. NaCI, KCI, Rbel
CaC12.6H20, BaCl2.2H20 are form non — hydrated chlorides
hydrated chlorides.
Reducing power Weaker as ionization potential Stronger as ionization
values are high and oxidation potential values are low and
potential values are low, oxidation potential values are
high.
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Chemical Properties of Group — II elements

Reaction with water — (Formation of hydroxides)
The electrode potential of Be (Be2+/Be = —1.97 V) is least negative amongst all the alkaline earth
metals. This means that Be is much less electropositive than other alkaline earth metals and
hence does not react with water or steam even at red heat.
The electrode potential of Mg (Mg+2/Mg = —2.37 V), although more negative than that of Be yet is
still less negative than those of alkali metals and hence it does not react with cold water but
reacts with boiling water or steam.
Mg + H20 --->Mg0 + H2
or, Mg + 2H20 --> Mg (OH)2 +H2
Mg, infact, forms a protective layer of oxide on its • surface, therefore, despite its *favourable
electrode potential it does not react readily with water unless the oxide layer is removed by
amalgamating it with mercury. In the formation of oxide film, Mg resembles Al.
Ca, Sr and Ba have more negative electrode potentials similar to those of the corresponding
group I alkali metals and hence react with even with cold water, liberating 'H2 and forming the
corresponding metal hydroxides.
Ca + 2H20 Ca(OH)2 + H2
Reactivity of alkaline earth metals increases as we move down the group. However, the reaction
of alkaline earth metals is less vigorous as compared to alkali metals.
Reaction with air (Nitrogen and Oxygen)
Formation of oxides and nitrides
Be metal is relatively unreactive in the massive form and hence does not react below 873K.
However, powdered Be is more reactive and burns brilliantly on ignition to give' a mixture of Be()
& Be3N2.
2Be + 02 (air)_' >2BeO
3Be + N2 (air)°> Be3N2

,
magnesium is more electropositive than Be and hence burns with dazzling brilliance in air to form
a mixture of MgO and magnesium nitride.
Mg + air +Mg3N2
Ca, Sr and Ba being even more electropositive react with air readily to form a mixture of their
respective oxides and nitrides.
The reactivity towards oxygen increases as we go down the group. Thus Ca, Ba and Sr are
stored in paraffin but Be and Mg are not because they form protective oxide layer on their
surface.
Formation of Nitrides
All the alkaline metals burn in dinitrogen to form ionic nitrides of the formula, M3N2. This is in
contrast to alkali metals where only Li forms L13N.
3M + N2 — 6.--M3N2
•
Be3N2 being covalent is volatile while the nitrides of all other elements are crystalline solids.
All these nitrides decompose on heating and react with water liberating NH3.
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Be3N2 A >3Be+ N2
Ba3N2 + 6H20_A >3Ba(OH)2 + 2NH3

Ca3N2 + 6H20 3Ca (OH)2 + 2NH3
(c) Formation of Peroxides
Since larger cations stabilize larger anions. Therefore, tendency to form peroxide increases as
the size of the metal ion becomes larger. Thus Ba02 is formed by passing air over heated Ba0 at
773K.
2Ba0 + 02 773K > 2Ba02
773K
2Sr0 +02 High pressrue > 2Sr02
Sr02 is prepared in similar way but under high pressure and temperature. Ca02 is not formed this
way but can be prepared as the hydrate by treating Ca(OH)2 with H202 and then dehydrating the
product.
Ca (OH)2 +H202 --> Ca02 .2H20
Crude Mg0-2 has been made using H202 but peroxide of beryllium is not known.
All peroxide are white crystalline ionic solids containing the peroxide ion 022- . Treatment of
peroxide with acids liberates H202.
Ba02 + 2HCI --> BaCl2 + H202
Reaction with hydrogen — (Formation of hydrides)

All the alkaline earth metals except Be combine with hydrogen directly on heating to form metal
hydrides of formula MI-12.
M + H2 —2'—>MH2
The hydride of beryllium can also be obtained by the reduction of BeCl2 with LiAIH4.
2BeCl2 + LiAlH4 2BeH2 + LiCI + A1C13
Both BeH2 and MgH2 are covalent compounds having polymeric structures in which H — atoms
between beryllium atoms are held together by three centre — two electron (3C — 2e) bonds as
shown below:
Be \
Be / Be
Be
H
The hydrides of other elements of this groups i.e. CaH2, Sri-f2 and BaH2 are ionic and contain the
1-1- ions.
All the hydrides of alkaline earth metals reacts with water liberating H2 gas and thus act as
reducing agents.
MH2 +2H20 >M (OH)2 +2H2
CaH2 is called Hydrolith and is used for production of H2 by action of water on it.
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Reaction with carbon — (Formation of carbides)

When Be0 is heated with carbon at 2175 — 2275 K a brick red coloured carbide of the formula
Be2C is formed
2175-22751<
2Be0 + 2C >Be2C + 2C0.
It is a covalent compound and react water forming methane.
Be2C + 4H20-->2Be(OH)2 + CH4
The rest of the alkaline earth metals (Mg, Ca, Sr: 8, Ba) form carbides of the general formula, MC2
either when the metal is heated with carbon in an electric furnace or when their oxides are heated
with carbon.
Ca + 2C 137" >CaC2
CaO +3C 2275K >CaC2 +CO
All these carbides react with water producing acetylene gas.
CaC2 +2H2 0-->HC E.. CH +Ca(OH)2
Reaction with Halogens
The alkaline earth metals react with halogens at elevated temperature to form the halides of the
types MX2.
Action of Acids
The alkaline earth metals readily react with acids liberating hydrogen.
M +2HCI-->MC12 +H2 = Be, Mg, Ca, Sr, Ba)
Reaction with Ammonia

Like alkali metal, the alkaline earth metals dissolve in liquid ammonia to give deep blue black
, -12+
solution from which ammoniates [M (NH3 )6 ] can be recovered.
Illustration 18. How does the basicity of oxides of group 2 increases down the group?
Solution: The basicity increases down the group

Be() < Mg0 < CaO < Sr0 < BaO
amphoteric strongly-basic
Exercise 23.
Why is BeCl2 covalent in nature?
General characteristics of compounds of the Alkaline earth metals

(a) Oxides
The oxides MO are obtained either by heating the metals in oxygen or by thermal decomposition
of their carbonates.
2M + 02 -=
6 —>2M0 (M = Be, Mg, Ca)
MC03 —°>M0 +CO2 (M = Be, Mg, Ca, Sr,Ba)
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Expect Be° all other oxides are extrem

-ely stable ionic solids due to their high lattice energies.
These have high melting point, have very low vapour pressure,--are very good conducts of heat,
are chemically inert and act as electrical insulators. Therefore, these oxides are used for lining
furnaces and hence used as refractory materials.
Due to small size of beryllium ion, Be° is covalent but still has high melting point because of its
polymeric nature.
(b) Hydroxides
The hydroxides of Ca, Sr & Ba are obtained either by treating the metal with cold water or by
reacting the corresponding oxides with water. The reaction of these oxides with H20 is also
sometimes called as slaking.
M +2H20 >M (OH)2 -F H2 (M = Ca, Sr, Ba)
MO +H20---->M(OH)2 (M = Ca, Sr, Ba)
Be(OH)2 and Mg(OH)2 being insoluble are obtained from suitable metal ion -Solutions by
precipitation with OH- ions.
BeCl2 + 2NaOH >Be(OH)2 +2NaCI
MgSO4 + 2NaOH —)Mg(OH)2 +Na2SO4
Properties
Basic Character
All the alkaline earth metal hydroxides are bases except Be(OH)2 which is amphoteric. This basic
strength increases as we move down the group. This is because of increase in size which results
in decrease of ionization energy which weakens the strength of M — 0 bonds in MOH and thus
increase the basic strength. However, these hydroxides are less basic than the corresponding
alkali metal hydroxides because of higher ionization energies, smaller ionic sizes and greater
lattice energies.
Solubility in Water
Alkaline earth metals hydroxides are less soluble in water as compared to alkali metals.
The solubility of the alkaline earth metal hydroxides in water increases with increase in atomic
number down the group. This is due to the fact that the lattice energy decreases down the group
due to increase in size of the alkaline earth metals cation whereas the hydration energy of the
cation remains almost unchanged. The resultant of two effects i.e.
AHsolution = AHlattice AHHydration
becomes more negative as we move from Be(OH)2 to Ba(OH)2 which accounts for increase in
solubility.
(c) Halides
The alkaline earth metals combine directly with halogen at appropriate temperature forming
halides MX2.
These halides can also be prepared by the action of halogen acids .(HX) on metals, metals
oxides, hydroxides and carbonates.
M + 2HX *MX2 + H2
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MO + 2HX--->MX2 +H20
M(OH)2 +2HX -->MX2 +2H20
MC03 +2HX--->MX2 +H20 +CO2
Properties
All beryllium halides 'are essentially covalent and are soluble in organic solvents. They are.
hydroscopic and fume in air due to hydrolysis. On hydrolysis, they produce acidic solution.
BeCl2 + 2H20 Be (OH)2 + 21-1C1
The halides of all other alkaline earth metals are ionic. Their ionic character, however
increases as the size of the metal ion increase.
Except BeCl2 all other chlorides of group 2 form hydrates but their tendency to form hydrates
decreases for eg — MgC12.6H20,
The hydrated chloride,. bromides and iodides of Ca, Sr and Ba can be dehydrated on heating
.but those of Be and Mg undergo hydrolysis.
BeF2 is very soluble in water due to the high hydration energy of the small Be+2 ion. The other
fluorides (MgF2, CaF2, SrF2 and BaF2) are almost insoluble in water. Since on descending the
group lattice energy decreases more rapidly than the hydration energy. Therefore whatever
little solubility these fluorides have that increase down the group. .
The chlorides, bromides and iodides of all other elements i.e. Mg, Ca, Sr, Ba are ionic have
much lower melting points than the fluorides and are readily soluble in water. The solubility
decreases some what with increasing atomic number. -
Except of BeCl2 and MgCl2 , the other chlorides of alkaline earth metals impart characteristics
colour to flame.
CaCl2 = Brick red colour
SrC12 = Crimson colour
BaCl2 = Grassy green colour
Uses
Calcium fluoride or fluorospar (CaF2) is by far the most important of all the fluorides of the -
alkaline earth metals since it is the only large scale source of fluorine.
CaCl2 is widely used for melting ice on roads, particularly in very cold countries because 30%
eutectic mixture of CaCl2 /ice freezes at 218 K as compared to NaCI /ice at 255K.
CaCl2 is also used as a desiccant (drying agent) in the laboratory.
Anhydrous MgCl2 is used in the electrolytic extraction of magnesium.
Solubility and Thermal stability of oxo salts
The salts containing one or more atoms of oxygen such as oxides, hydroxides, carbonates,
bicarbonates, nitrites, nitrates, sulphates, oxalates and phosphates are called oxo salts.
(d) Sulphates
The sulphates of alkaline earth metals (MS04) are prepared by the action of sulphuric acid on
metals, metals oxides, hydroxides and carbonates.
M +H2SO4 -->MS04 + H2
MO + H2SO4 ---> MS04 + H20
M (OH)2 + H2SO4 --+ MS04 +21120
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MC03 +H2SO4 >MSO4 + CO2 +H20
Properties of sulphates
The sulphates of alkaline earth metals are all white solids.
Solubility
The solubility of the sulphates in water decreases down the groups i.e. Be > Mg > Ca > Sr > Ba.
Thus BeSO4 and MgSO4 are highly soluble, CaSO4 is sparingly soluble but the sulphates of Sr,
Ba and Ra are virtually insoluble.
Reason
The magnitude of the lattice energy remains almost constant as the sulphate is so big that small
increase in the size of the cation from Be to Ba does not make any difference. However the
hydration energy decreases from Be+2 to Ba+2 appreciably as the size of the cation increase down
the group. Hence, the solubilities of sulphates of alkaline earth metals decrease down the group
mainly due to the decreasing hydration energies from Be+2 to Ba+2. The high solubility of BeSo4
and MgSO4 is due to high hydration energies due to smaller Be+2 and Mg+2 ions.
Stability
The sulphates of alkaline earth metal decomposes on heating giving the oxides and S03.
MsQ, °A\AO + SO3
The temperature of decomposition of these sulpahtes increases as the basicity of the hydroxide
of the corresponding metal increase down the group
(e) Carbonates and Bicarbonates
Alkaline earth metal carbonates are obtained as white precipitates when.

Calculated amount of carbon dioxide is passed through the solution of the alkaline metal
hydroxides.
M (OH)2 (aq) + CO2 (g) ->MC03 (s) + H20(e)
Sodium or ammonium carbonate is added to the solution of the alkaline earth metal salt such
as CaCl2.
CaCl2 (aq) + Na2C0 (aq) CaCO3 (s) + 2NaCI (aq)
Properties
All carbonates are stable but beryllium carbonate is prone to hydrolysis. It contains the hydrated
12+
ion [Be (H20)4 ] rather than Be+2 and hence is precipitated only in an atmosphere of CO2.
Absence of CO, -12+ _ n
BeCO3 + 4H20,
presence of Co,
[Be (H20)4 + CO3`
Solubility
The carbonates of magnesium and other alkali earth metals are sparingly soluble is water and
their solubility decreases down the group from Be to Ba. For e.g MgCO3 is slightly soluble in
water but BaCO3 is almost insoluble. The solubility can be explained by the reason same as for
sulphates.
All the carbonates of alkaline earth metals are however, more soluble in the presence of CO2 due
to the formation of corresponding bicarbonates.
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CaCO3 (s) + CO2 (g) + H20 (g) > Ca (HCO3 )2 (aq)
StabiliZy
The carbonate of all alkaline earth metals decompose on heating to form the corresponding metal
oxide and CO2.
MC03 --°4110 + CO2
The temperature of decomposition, i.e thermal stability of these carbonates, however increase
down the group from Be to Ba as the basicity of metal hydroxide increases from Be(OH)2 to
Ba(011)2.
The sulphates are stable to heat whereas the carbonates decompose to give MO and CO2. Thus
BeCO3 is unstable and kept in the atmosphere of CO2 to prevent its decomposition.
BeCO3 MgCO3 CaCO3 SrCO3 BaCO3
<100°C 540°C 900°C 1290°C 1360°C
(f) Bicarbonates
The bicarbonates of alkaline earth metals are prepared by passing CO2 through a suspension of
metal carbonates in water.
M2CO3 + H20 + CO2 > M(HCO3 )2
(In soluble) (soluble)
All the bicarbonates of alkaline earth metals are stable only in solution and have not been isolated
in the pure state.
(i) Nitrates
Alkaline earth metals nitrates are prepared in solution and can be crystallized as hydrated salts
by the action of FIN03 on oxides hydroxides and carbonates.
MO + 2HNO3 (NO3 + H20
M (OH)2 + 2H NO3 —>M (NO3 )2 +2H20
MC03 + 2H NO3 —>M (NO3 )2 +CO2 +H20
(M = Be, Mg, Ca, Sr or Ba)
Magnesium nitrate crystallizes as Mg(NO3)2.6H20
White Ba(NO3)2 crystallises as unhydrous salt.
All nitrates on heating give the corresponding oxides.
2M (NO3 )2 --->2M0 + 2N H3 + 02
(M = Be, Mg, Ca, Sr or Ba)
Illustrthon19. Arrange the following in order of the property indicated:

(I) carbonates of group 2 > order of increasing thermal stability
(ii) sulphates of group 2 —> order of decreasing solubility
Solution. (i) BeCO3 < MgCO3 < CaCO3 < SrCO3 <BrCO3
BeSO, < MgS0, < CaSO, < SrSO, < BaS0,,
most soluble • insoluble
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Exercise 24.
Why is BeCO3 stored in carbon dioxide atmosphere?
Anamolous Behaviour of Beryllium
The properties of berrylium the first member of the alkaline earth metal, differ from the rest of the
member. Its is mainly because of
,Its small size and high polarizing power. •
Relatively high electronegativity and ionization energy as compared to other members.
Absence of vacant d — orbitals in its valence shell.
Some _important points of difference between beryllium and other members (especially
magnesium) are given below:
Be is harder than other members of its group.
Be is lighter than Mg.
Its melting and boiling points are higher than those of Mg & other members.
Be does not react with water while Mg reacts with boiling water.
Be() is amphoteric while Mg0 is weakly basic.
Be forms covalent compounds whereas other members form ionic compounds.
Beryllium carbide reacts with water to give methane whereas carbides of other alkaline earth
metals gives acetylene gas.
Be2C + 4H20 ---> 2Be (OH)2 + CH4
Mg2C2 +2H20 ---> Mg (OH)2 +C2112
CaC2 +2H20 ---+ Ca (OH)2 + C2H2
Beryllium does not exhibit coordination number more than four as it has four orbitals in the
valence shell. The other members of this group has coordination number 6.
Resemblance of Beryllium with Aluminium (Diagonal relationship)
The following points illustrate the anomalous behaviour of Be and its resemblance with Al.
(i) Unlike groups — 2 elements but like aluminium, beryllium forms covalent compounds.
(ii) the hydroxides of Be, [Be(OH)21 and aluminium [Al(01-I)3] are amphoteric in nature, whereas
those of other elements of group — 2 are basic in nature.
(iii) the oxides of both Be and Al i.e. Be° and A1203 are high melting insoluble solids.
BeCl2 and AlC13 have bridged chloride polymeric structure.
CI CI CI
CI
AI
AI
CI—Be
Be—C1
Nci CI
Z
I/ NCI
The salts of beryllium as well as aluminium are extensively hydrolysed.
Carbides of both the metal reacts with water liberating methane gas.
Be2C + 4H20 > 2Be (Oft + Cl-I4
Al4C3 + 12H20 >4Al (011)3 +3C114
The oxides and hydroxides of both Be and Al are amphoteric and dissolve in sodium
hydroxide as well as in hydrochloric acid.
Be0 + 2HCI --> BeCl2 +H20
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Be() + 2Na0H-->Na2Be02,+ H20

A1203 +6HCI-->2A1C13 +H20
A1203 +2Na0H-->2NaA102 +H20
(viii) Like Al, Be is not readily attacked by acids because of the presence of an oxide film.
Illustration 20. Give the structure of BeCl2 in the
vapour state .(ii) solid state
Solution: (i) Linear molecule

Polymeric structure with bridged chlorine atom
CI CI
Be /1i3 / f3e,
CI .CI
CI — Be — CI
Exercise 25.
An aqueous solution of beryllium chloride is acidic in nature. Explain.
Magnesium Metal
Magnesium occurs as magnesite MgCO3, dolomite CaMg(CO3)2, Epsomite (MgSO4.7H20) and

carnalite k2MgC14.6H20 and langbeinite K2M92(SO4)3 deposits. The chloride and sulphate of
magnesium occurs in sea water from which it being extracted on an increasing scale.
Extraction
(a) From magnesite or Dolomite
The ore is first calcined to form the oxide

MgCO3 --› MgO + CO2
CaO.Mg0 + 2CO2'
The metal is obtained from the oxide or the mixed oxides as follows:
From MgO:'
The oxide is mixed with carbon and heated in a current of chlorine gas.
MgO + C + Cl2 —+ MgCl2 + CO
The chloride thus obtained is subjected to electrolysis.
The mixed oxides [CaO.Mg0] obtained from calcination of DoComite [CaCO3.MgCO3] are
redcued by ferrosilicon under reduced pressure above 1273 K.
2Ca0 + 2Mg0 + 2Mg + Fe + Ca2SiO4
(b) From Carnallite
The ore is dehydrated in a current of hydrogen chloride and the mixture of fused chloride is
electrolysed.
(c) From Sea water
Sea water containing magnesium chloride is concentrated under the sun and is treated with
calcium hydroxide Ca(OH)2. Mg(OH)2 is thus precipitated, filtered and. heated to give the oxide.
The oxide so obtained is treated as in (a) (i) above and then electrolysed.
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Electrolysis of Magnesium Chloride

MgCl2 obtained by any of the above methods is fused and mixed with additional mixture of NaCl
and CaCl2 in the temperature range of 973 — 1023 K. The molten mixture is electrolysed.
Magnesium is liberated at the cathode and-chlorine is evolved at the anode.
At cathode: Mg+2 + 2e- Mg
At anode: 2CI- Cl2 + 2e-
•
Graphite Anod •
Porclean
Hood I Exit for chlorine
Coal gas.— 4—Inert gas
MI MINIM "
WI I 1.IM Molten Mg
Porcelain hood
Steel cell cathode (-ye)

Extraction of Magnesium
Electrolysis of Magnesium Chlorine

A stream of coal gas is blown through the cell to prevent oxidation of Mg metal. Mg metal is
obtained in liquid state which is further distilled to give pure magnesium.
Properties of Magnesium
Physical Properties
Magnesium is a silvery white metal which soon becomes dull in air.
It is a light metal with a density of 1.74 g cm-3.
It is fairly malleable and ductile.
Chemical Properties
Action of oxygen or air
Magnesium does not react with dry air but slowly gets tarnished in most air due to the formation
of a thin film of the oxide, MgO. It burns in oxygen or air with a dazzling light.
2Mg + 02 2Mg0
Action of CO2 and SO2

Because of its great affinity for oxygen magnesium keeps on burning even in CO2 or SO2;
2Mg + CO2 °->2Mg0 + C
2Mg + SO2 ----°>2Mg0 + S
Action of nitrogen
1
1
On heating magnesium combines with nitrogen to form magnesium nitride.

3Mg + N2 -->Mg3N2
Thus when magnesium burns in air both the oxide and the nitride are formed.
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Action of halogens
Magnesium on heating with halogens readily forms the halides e.g.
Mg + Cl2
Action of water
Magnesium does not decompose water in cold but decomposes boiling water or steam.
Mg + H20(steam) -->Mg0 + H2
NO Action of Acids
Dilute acids reacts with magnesium to produce dihydrogen.
Mg +2HCI—÷MgC12 + H2
Mg + H2SO4 --4.4gSO4 + H2 .
However with conc. H2SO4, SO2 is produced

Mg + 2HNO3 ---> Mg (NO3 )2 +H2
(2% dilute)
However with concentration HNO3, the NO2 will produce.

Mg + 2H2SO4 —>MgSO4 +S02 +2H20
(conc.)
Reaction with alkyl halide

Magnesium reacts with alkyl halides in dry ether to form covalent compound called Grignard
reagent.
Dry ether
Mg + C2H5I >C2H5Mg1
Uses of Magnesium
The chief use of magnesium is in the preparation of alloys with aluminium, zinc, manganese
and tin.
Duralium (Al = 95%, Cu = 4%. Mn = 0.5%, Mg = 0.5%)
Mangnalium (Al = 90% & Mg = 10%)
Duralium being light, tough and durable is used for the manufacture of airplanes and
automobiles parts. Magnalium being light, tough and hard is used for making balance beams,
Magnesium bums with an intense lights, therefore, Mg (as power or ribbon) is_used in flash
bulbs for photography, fireworks and signals fibres.
Mg is used for ignition of thermite charge in aluminothermy. •
A suspension of magnesium hydroxide known as milk of magnesium is used as an antacid
for patients suffering from acidity.
In preparation of Grignard reagent.
Being a reducing agent, magnesium is used in the extraction of boron and silicon from their.
respective oxides.
B203 + 3Mg-->3Mg0 + 2B.
SiO2 + 2Mg—>2Mg0 + Si
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Illustration 21. The chemistry of Lithium is very much similar to that of magnesium even though
they are placed in different groups - Explain.
Solution: The ratio of their charge to size is nearly same by which they show the diagonal
relationship.
Illustration 22. Name some minerals of magnesium.

Solution: Minerals of magnesium are:
(i) Magnesite (ii) Dolomite (iii) Epsom salt
Illustration 23. Write the chemical formulae of the following ores:

Dolomite (ii) Epsom salt
(iii) Camallite (iv) Magnesite
Solution: (i) Dolomite — MgCO3.CaCO3
Epsom salt — MgSO4.7H20
Camallite — KCI.MgC12.6H20
Magnesite — MgCO3
. . .
i Exercise 26.
What is milk of magnesia? Give its one use.
Exercise 27.
What happens when magnesium reacts with (i) CO2 (ii) SO2 gas?
. .
Compounds of alkaline earth metals
Magnesium sulphate, Epsom salt MgSO4.7H20
Magensium sulphate occurs as kieserite MgSO4.H20 in Stassfurt (Germany) deposit or as Epsom

salt in the mineral water of the Epsom springs in England.
Preparation
From dolomite
The dolomite ore is boiled with dil. H2SO4'

CaCO3.MgCO3 + 2H2SO4 --> CaSO4 + MgSO4 2H20 + 2p02
The ppt of calcium sulphate are filtered off and the solution on concentration and cooling gives
crystals of MgSO4.7H20.
From Magnesite
The magensite ore is powdered and dissolved in dilute H2804. The resulting solution is
concentrated and cooled when crystals of MgS0.4.7H20 separate out.
MgCO3 + H2SO4 — MgSO4 + H20 + CO2
From Kieserite
The mineral Kieserite (Mg§04.H20) is powdered and .dissolved in water. The resulting solution
upon concentration and cooling gives crystals of MgSO4.7H20.
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(iv) Laboratory Preparation
In the laboratory MgSO4 is prepared by dissolving Mg metal or MgO or MgCO3 with dilute H2SO4.
Mg +H2SO4 -->MgSO4 +H2
Mg0 + H2SO4 --IN/IgSO4 +H20
MgCO3 +H2SO4 --->MgSO4 +CO2 +H20
The resulting solution upon concentration and cooling gives crystals of MgSO4.7H20.
Properties
It is deliquescent and readily dissolves in water. Hydrates with 12, 6 and 1 molecule of water of
crystallisation are also known. All these hydrates are converted into the. anhydrous salt, when
heated to 200°C and on further heating they decompose to form the oxide. Magnesium sulphate
gives rise to double salt with the alkali sulphate.
(I) Magnesium sulphate is a colourless efflorescent crystalline solid highly soluble in water.
(ii) Isomorphism
MgSO4.7H20 is isomorphous with ZnSO4.7H20 & FeSO4.7H20 compounds having same crystal
structure are called isomorphous and the phenomenon is called Isomorphism.
(iii) Action of Heat
When heated it losses 6 Molecules of water to give Magnesium sulphate monohydrate which
becomes amhydrous when heated to 503 K and finally decomposes to MgO & SO3 gas on strong
heating. -
MgSO4.7H20 423K
-6H20
>MgS0., H,0 5°3K
-H20
>MgSO4
4
heating >Mg0+ SO
strong 3
Uses
MgSO4 is used as purgative medicine.

It is used as mordant for cotton in dyeing industry.
It is used in preparation of fire proof textile and wood.
Anhydrous MgSO4 is used as a drying agent in organic chemistry.
It is used in preparation of platinised asbestors which is used as a catalyst in the contact
process for the manufacture of H2S0..ii
Illustration 24. What are isomorphous salts?
Solution: The salts having the similar crystal structure are called isomorphous salts.
Examples: MgSO4.7H20, ZnSO4.7H20, FeSO4.7H20
Oxides of Mg, Ca
MgO(Magnesia)
It is made by heating magnesite (MgCO3).

MgCO3 --› MgO +'CO2
It is very slightly soluble in water imparting an alkaline reaction to the solution.
Mg0 + H20 Mg(OH)2
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Calcium oxide, Quick lime CaO

Preparation
It is prepared by heating limestone in a rotatory kiln at 1070— 1270 K.

1070-1270K
CaCO3 , '-CaO +CO2; AH = +179.9 KJ
The temperature should not be raised above 1270 K. Otherwise silica present as impurity in lime
,
will combine with calcium oxide to form infusible calcium silicate.
Above 1270K
CaO + SiO2 >CaSiO3
Properties
It is a white amorphous solid with m.p. of 2870 K.

When exposed to atmosphere, it absorbs moisture and CO2 forming slaked lime and calcium
carbonate respectively.
Ca0 + H2O (Moisture) Ca(OH)2
CaO + CO2 CaCO3
On adding water, it produces, a hissing sound a large amount of heat is evolved which
converts water into steam. This process is called slaking of lime and the fine powder obtained
is called slaked lime.
CaO + H2O Ca(OH)2 ; AH = —63KJ
Action of acids and acidic oxides
It is a basic oxide and hence combines with acids and acidic oxides forming salts.
CaO + 2HCI CaCl2 + H2O
CaO + SO2 CaS03
Reaction with coke
When heated with coke in electric furnace at 2273 — 3273 K, it forms calcium carbide.
2273-3273K
CaO + 3C >CaC2 + CO
Reaction with ammonium salt
On heating with ammonia salts, it liberates ammonia gas.
Ca0 + 2NH4CI CaCl2 + 2NH3 + H20
Uses
It is used as a building materials.

It is used for drying alcohols and non acidic gases.
It is used in the preparation of ammonia and soda lime (CaO + NaOH).
It is used as a basic lining in furnaces.
f
Illustration 25. Why does a piece of burning magnesium continue to burn in SO2?
Solution: This is because the reaction of Mg with SO2 is exothermic.

1
21VIg + SO2 --›2Mg0 + -6S8 +Heat
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Exercise 28.
Name the substance used for drying alcohol and non-acidic gases.
Hydroxides of Mg & Ca
Magnesium Hydroxide [Mg(OH)2]

It is obtained by adding caustic soda solution to a solution of magnesium sulphate or chloride.
MgSO4 + 2NaOH Na2SO4 + Mg(OH)2
Properties
It is converted into its oxide on heating.
M,Y0F02 --* Mg0 + H20
It dissolves in NH4CI solution easily.
Mg(OH)2 + 2NH4CI MgCl2 + 2N1H4OH
Calcium hydroxide, Slaked lime [Ca(OH)2]
Preparation
From Quick lime

Calcium hydroxide is prepared on commercial scale by adding water to quick lime (Slaking of
lime)
Ca0 + H20 —> Ca (OH)2
During the process of slaking, lumps of quick lime crumble to aline power.
From calcium chloride
It is obtained by treating calcium chloride with caustic soda.
CaCl2 + 2NaOH --> Ca (OH)2 + 2N aCI
Properties
Physical
It is a white amorphous powder sparingly soluble in water, the solubility decreasing further with
rise in temperature. An aqueous solution is known, as lime water and a suspension of slaked lime
in water is called milk of lime.
Chemical properties
Action of heat
it loses water only at temperature above 700 K.
Ca (OH)2' 70°K >Ca0 + H20
•
Reaction with chlorine
It forms calcium hypochlorite a constituent of bleaching power.

2Ca (OH)2 + 2Cl2 -->CaC12 + Ca (0C1)2 +2H20
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(iii) Reaction with carbon dioxide

When CO2 is passed through lime water, it turns milky due to formation of insoluble calcium
carbonate
Ca (OH)2 + CO2 ---> CaCO3 +2H20
milkines
If excess of Co2 is passed CaCO3 (ppt) dissolves to form soluble calcium bicarbonate due to
which milkiness disappears.
CaCO3 +002 +H20 Ca (HCO3 )2
soluble
If this clear solution of calcium bicarbonate is heated, the solution again turns milky due to the
decomposition of ca(HCO3)2 back to CaCO3.
Ca (HCO3 )2 (aq) —°› CaCO3 (s) + CO2 (g) + H20(t)
(iv) Reaction with acids
„ Slaked lime being a strong base reacts with acids and acidic gases forming salts.
Ca(OH)2 + 2HCI*CaCl2 +H20
Ca (OH)2 + SO3 CaSO4 + H20
However, Ca(OH)2 does not dissolve in dil. H2SO4 because the CaSO4 formed is sparingly
soluble in water.
Uses
Calcium hydroxide is used for absorbing acidic gases such as CO2, NO2, SO2, SO3 etc.
For preparing ammonia from ammonium salts.
(ii) For softening of hard water.
(iv) In the laboratory, as lime water for detection of CO2.
(v) In white washing due to its disinfectant properties.
(vi) In the production of mortar which is used as a building material.
Illustration 26. Which is the weakest base among NaOH, Ca(OH)2, KOH and Be(OH)2
Solution: Be(OH)2 is weakest base , because alkali metal hydroxides are more stronger
base than alkaline earth metal hydroxides. Also basic character of hydroxides of
alkaline earth metals increases down the group. So Be(OH)2 is the weakest one.
Calcium Carbonate (CaCO3 )
It occurs in nature as marble, limestone, chalk, coral, calcite, etc. It is prepared as a white
powder, known as precipitated chalk, by dissolving marble or limestone in hydrochloric acid and
removing iron and aluminium present by precipitating with NH3, and then adding ammonium
carbonate to the solution; the precipitate is filtered, washed and dried.
CaCl2 + (NH4)2CO3 CaCO3 + 2NH4CI
Properties
It dissolves in Water containing CO2, forming Ca(HCO3).2 but is precipitated from solution by
boiling.
CaCO3 + H2O + CO2 Ca(HCO3)2
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Illustration 27. Thermal decomposition of a compound 'X' yields, a basic oxide ( Y) and acidic
oxide( 2) simultaneously. The acidic oxide(Z) can be absorbed by alkaline KOH.
What is X,Y,Z.
Solution: CaCO3 > Ca0+ CO2
.x.
Basic Acidic
(Y) (Z)
CO2 + 2KOH > K2CO3 +H20
Magnesium Carbonate (MgCO3)
It is obtained as magnesite in nature. It can be prepared as a white precipitate by adding sodium
bicarbonate to a solution of a magnesium salt.
MgCl2 + NaHCO3 —+ MgCO3 + NaCl + HCI
Properties "
(i) It is very much moresoluble in water.
(ii) It dissolves in water containing CO2 due to formation of soluble bicarbonate.
MgCO3 + H2O + CO2 Mg(HCO3)2
Bicarbonates of Mg & Ca
Calcium bicarbonate [Ca(HCO3)2]
It is obtained when CaCO3 is dissolved in water containing CO2 but it remains in the solution
form CaCO3 + H20 + CO2 Ca(HCO3)2.
Magnesium bicarbonate [Mg(HCO3)21
Same as in Ca(HCO3)2
Illustration 28. NaHCO3 and NaOH cannot exist together in solution- Why?
Solution: NaHCO3 is an acid salt which must react with ,NaOH which is strong base. The
reaction is as follows:
NaHCO3 + NaOH —÷Na2CO3 + H20
Halides of Mg & Ca
"Calcium Chloride (CaCl2-6H20)
It separates out as deliquescent crystals when a solution of lime or calcium carbonate in HCI is
evaporated.
CaCO3 + 2HCI CaCl2 + H2CO3
But it separates out from the reaction mixture as CaCl2.6H20. The anhydrous salt is obtained on
heating above 200°C.
Properties •
It is a colourless, deliquescent salt, highly soluble in water. The anhydrous salt is .an excellent
drying agent. •
Exercise 29.
What is being used as a laboratory dessicant?
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Magnesium chloride (MgC12•6H20)

It is prepared in the laboratory by crystallizing a solution of the oxide, hydroxide or carbonate in
dilute hydrochloric acid.
Mg0 + 2HCI MgC12 + H20
Properties
It is colourless, crystalline salt, deliquescent in nature and exceedingly soluble in water.
Illustration 29. Complete the following reactions:
MgC12.61-120 heat
• (ir) M gC12.6H20 HT) >
Solution: (i) MgCl2 .6H20 heat > MgO + 2HCI + 51-120

(ii) MgC12.6H20 HT) >MgC12 +6H20
Exercise30.
Which magnesium compounds are the constituents of toothpaste?
.. . . . .
Plaster of paris, CaSO4.1/2 H20 or (CaSO4)2.H20
It occurs in nature as gypsum and the anhydrous salt as anhydride. It is prepared by precipitating
a solution of calcium chloride or nitrate with dilute sulphuric acid.
The effect of heat on gypsum or the dihydrate presents a review of interesting changes. On
heating the monoclinic gypsum is first converted into orthorhombic form without loss of water.
When the temperature reaches 120°C, the hemihydrate or plaster of paris is the product. The
latter losses water, becomes anhydrous above 200°C and finally above 400°C, it decomposes
into calcium oxide.
2CaSO4 --> 2Ca0 + 2S021' + 021'
,„ Heating , 120°C 1 200o

°
CaSO4.2H2,a . H20 CaSO4.H20 Setting
CaSO4. H20 >CaSO4
H2O 2
Gypsum Hardening
(Monoclinic) Plaster of Paris
The following conditions are necessary
The temperature should not be allowed to rise above 393 K because above this temperature
the whole of water of crystallization is lost. The resulting anhydrous CaSO4 is called dead
burnt plaster because it does not have the properties of setting with water.
The gypsum should not be allowed to come in contact with carbon containing fuel otherwise
some of it will be reduced to calcium sulphite.
Properties
It is a white powder. On mixing with 1/3rd its weight of water, it forms a plastic mass which sets
into a hard mass of interlocking crystals of gypsum within 5 to 15 minutes. It is due to this reason
that it is called plaster. The addition of common salt accererates'the rate of setting, while a little
borax or alum reduces it. The setting of plaster of paris is believed to be due to rehydration and
its reconversion into gypsum.
1
2CaSO4 .- 2 H2 0+ 3H20—> 2CaSO4.2H20
Gypsum
Plaster of Paris
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Uses
Plaster of pairs is used for producing moulds for pottery and ceramics & casts of statues &
busts.
It is used in surgical bandages used for plastering broken or fractured bones.
It is also used in dentistry.
Industrial uses of lime and Limestone
Uses of lime
Calcium oxide is called lime or quick lime. It main industrial uses are
It is used in steel industry to remove phosphates and silicates as slag.
It is used to make cement by mixing it with silica, alumina or clay.
It is used in making glass. -
It is used in lime soda process for the conversion of Na2CO3 to NaOH & vice versa.
It is used for softening water, for making slaked .lime Ca(OH)2 by treatment with water and
calcium carbide CaC2.
Uses of Slaked lime [Ca(OH)21
Slaked lime is used as a building material in form of mortar. It is prepared by mixing 3 — 4
times its weight of sand and by gradual addition of water. Its sets into a hard mass by loss of
H20 and gradual absorption of CO2 from air.
In manufacture of bleaching powder by passing Cl2 gas.
In making glass and in the purification of sugar and coal gas.
It is used in softening of hard water.
Uses of lime stone (CaCO3)
It is used as building material in form of marble.
In manufacture of quick lime.
It is used as a raw material for the manufacture of Na2Co3 in solvay — ammonia process.
Commercial limestone contains iron oxide, alumina, magnesia, silica & sulphur with. a CaO
content of 22 — 56% MgO content upto 21%. It is used as such as a fertilizer.
Cement
Cement is essentially a finely powdered mixture of calcium silicates and aluminates along with
small quantities of gypsum which sets into a hard stone like mass when treated with water.
The chief compounds of cement are tricalcium silicate 3CaO.Si02, dicalcium silicate, 2CaO.Si02
and tricalcium aluminate 3Ca. A1203. Out of these tricalcium silicate is the most important since it
has property of setting quickly and acquiring considerable strength within a few, days. It usually
constitute 50% of the cement.
Composition of Portland cement
Lime (CaO) - 50 — 60%
MgO 2 — 3%
Silica (SiO2) - 20 — 25%
Ferric oxide (Fe2O3 ) - 1 — 2%
Alumina (A1203) - 5 — 10%
Sulphur trioxide (SO3) 1 — 2%
For a good quality cement, the ratio of alumina A1203 to silica (SiO2) should lie between 2.5 & 4
while that of lime CaO to silica + alumina + ferric oxide should be as close to 2 as possible.
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Manufacture of cement
Calcium Silicate
Limestone and clay are powdered &
Burnt at (1770— 1870K) Calcium Aluminate
mixed. Palverised and
•Ca3S105.Ca2S104
homogenized Rotary Kiln
Ca3A1206, Ca2A1205
Cement clinker
Addition of 2-5%
of gypsum finely
ground
!
Portland cement
Illustration 30. Differentiate between (i) quick-lime (ii) slaked lime and, (iii) lime water
Solution: (i) Quick lime is CaO and is obtained by heating CaCO3 in a kiln at 1273 K.
CaCO3 °->Ca0 +CO,
Slaked lime is calcium hydroxide, Ca(OH)2
Ca0 +H2 0--->Ca(OH)2
Lime water is a solution of Ca(OH)2 in water.
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ANSWER TO EXERCISES
Exercise 1:
The three general characteristics are:
The compounds of the s-block elements are mainly ionic.
The valency is equal to the group number.
Due to low ionization energy, s-block elements are good reducing agents.
Exercise 2:
Sodium is the most abundant alkali metal in the earth's crust.
Exercise 3:
This is due to abnormal increase in the atomic size of potassium.
Exercise 4:
The E° value (reduction potential) depends on the three factors i.e. sublimation, ionization
and hydration enthalpies. With the small size of its ion lithium has the lightest hydration
enthalpy which accounts for its high negative E° value and its reducing power.
Exercise 5:
Lithium
Exercise 6:
Potassium is softer than sodium due to weak metallic bonding because of the large size
of K atoms.
Exercise 7:
Low ionization enthalpy, strongly electropositiVe nature, tendency to attain noble gas
configuration by the loss of one valence electron makes sodium highly reactive.
Exercise 8:
(B)
Exercise 9:
Na202 + 2H20---2Na0H +H202
2K02 + 2H20--->2KOH +H202 +02
Na20 +CO2 --Ma2CO3
Exercise 10:
(D)
Exercise 11:
Potassium superoxide hydrolyse to form KOH and 1-1202 and 02 gas.
2K02.+ 2H20--.>2KOH +H202 +02
(superoxide disproportionates in water)
Exercise 12:
This is due to increase in IE and increase in the size of the cation that the distance
between the M — 0 bond increases. This results in the greater separation of the cation
from the hydroxide ion resulting in the greater concentration of the hydroxide in the
solution consequently, the basicity increases from LiOH to Cs0H.
Exercise 13:
This is to due to small size of Li+ and F- ions, which leads to high lattice energy of LiH,
hence less soluble in water
Exercise 14:
The less solubility of Cs1 in water is due smaller hydration energy of its ions.
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Exercise 15:
(D). Basicity of hydroxides of group-I elements increases from top to bottom. Hence (D) is
correct
Exercise 16:
(D)
Exercise 17:
2NaHCO3 —±-{e-Na2CO, +H20 +CO,
2Na/Hg +2H20—>2Na0H+1-12 +2Hg
Na +NH, --->NaNH, +H2
Exercise 18:
(B)
Exercise 19:
A CaSO4
CaSO4 • 2H20
Exercise 20:
Magnesium burns in air with dazzling brilliance due to the formation of MgO and Mg3N2.
Exercise 21:
The higher IE is more than compensated by the higher enthalpy of lattice formation.
Exercise 22:
(A)
Exercise 23:
This is due to small size and high electronegativity of beryllium. •
Exercise 24:
BeCO3 is the least stable alkaline earth metal carbonate. To slow down its
decomposition, we store it in an atmosphere of carbon dioxide.
BeCO, --->Be0 +CO,
Exercise 25:
This is due to the hydrolysis of the beryllium ion.
Be2+ +2H20—>B(OH)2 +2H+
Exercise 26:
The milk of magnesia is magnesium hydroxide. It is used as an antacid to neutralise
excess of acid in the stomach.
Exercise 27:
(i) 2Mg +CO2 --°›2Mg0 +C 1
(ii) 2Mg +SO2 °---2Mg0
Exercise 28:
Calcium (or CaO) is used for drying alcohol and non-acidic gases.
Exercise 29:
Anhydrous CaCl2
Exercise 30:
Mg(OH)2 and MgCO3 are the constituents of toothpaste.
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Miscellaneous Exercises
Exercise 1: Complete and balance the following reactions:

K + 02
K + H20
K + H2
Exercise 2: What happens when NaOH is added to Zn (+II) solution?
Exercise 3: When an alkali metal dissolves in liquid ammonia the solution acquires different
colours. Explain the reasons for this type of colour change.
Exercise 4: Name one reagent or one operation to distinguish between

(i) BeSO4 and 13,90 4 (ii) Be(OH)2 and Ba(OH)2
Exercise 5: Write the chemical formulae of the following minerals.

(0 Limestone (ii) Fluorspar
(iii) hydroxyapetite (iv) Anhydrite
Exercise 6: What is the mixture of CaCN2 and carbon known as?
Exercise 7: What is 'potash magnesis'?
Exercise 8: Sodium peroxide forms a white compound when it comes into contact with moist
air. Explain.
Exercise 9: How can sodium chloride be purified?
Exercise 10: What is magnesia cement? Give its composition.
Exercise 11: Why is it that hydrated chlorides of Ca, Sr and Be. can be dehydrated by heating
but those of Be and Mg suffer hydrolysis?
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ANSWERS TO MISCELLANEOUS EXERCISES

Exercise 1: K +02 —>K02
2K +2H20—*2KOH + H2
2K + H2 > 2KH
Exercise 2: First addition of NaOH to Zn(+1I) solution gives a white precipitate of Zn(OH)2
which dissolves in excess of sodium hydroxide.
Zn2+(aq) + 20H- (aq)—›Zn(OH)2
(white ppt)
Zn(OH)2(g) -r- 20H- --->[Zn(OH)412-
(excess) (soluble tetrahydroxizincate
(II) ion)
Exercise 3: The solution of alkali metal in liquid ammonia is coloured and metastable.
The dilute solutions are blue and the blue colour is due to the presence of
solvated electrons.
M +(x + y)NH, —4M(NH3 ),( ]* + [e(NH,)j-
solvated solvated
metal ion electron
The blue solution is also paramagnetic in nature:
In concentrated solutions, the ammoniated (solvated) metal ions are bound by
the free unpaired electron which have been described as expanded metals. The
colour is bronze and the solution is diamagnetic.
[M(NH,),, ] [e(NH,)]- + NH, (0—>MNH2 H2 (g)
Exercise 4: BeSO4 is soluble in water while BaSO4 is not.

Be(OH)4 dissolves in NaOH while Ba(OH)2 is insoluble.
Exercise 5: (i) Limestone — CaCO3 (ii) Fluorspar — CaF2

Hydroxyapetite — Ca5(PO4)3.01-1 Anhydrite — CaSO4
Exercise 6: A mixture of calcium cyanamide (CaCN ) and carbon is known as nitrolim. It is

used as a fertilizer.
Exercise 7: 'Potash magnesis' is a double salt used as a fertilizer. Its formula is

K2SO4.MgSO4.6H20
Exercise 8: Sodium peroxide when exposed to moist air turns white due to formation of
NaOH and Na2CO3.
2Na202 +2H20-->4Na0H +02
2Na202 +2CO2 --2Na2C0 +02
Exercise 9: The salt obtained by various manufacturing processes is contaminated. Hence,

to purify sodium chloride, it is first of all treated with ammonium carbonate to
precipitate down the carbonates of calcium and magnesium.
CaCl2 + (NH4 )2 CO, ---> CaCO3 +2N1-14C1
The solution is filtered to remove these precipitates and through the filtrate,
hydrochloric add is passed. As a result, sodium chloride settles down. This is
found to be quite pure. Only KCI is present as impurity which is removed by
repeated crystallisation.
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Exercise 10: When a saturated solution of magnesium chloride is mixed with magnesium
oxide, it sets to a hard mass. This hard mass is known as magnesia cement. Its
composition is MgC12.5MgO.H20.
Exercise 11: CaC12.6H20—A-121-4CaC12 +6H20

MgC12.6H20 +2HCI+5H20
MgC12.6H20 or BeC12.4H20 on heating suffer hydrolysis due to the small size of
Mg2+ (or Be2+).
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SOLVED PROBLEMS
Subjective:
Prob 1. Na2SO4 is soluble in water whereas BaSO, is insoluble. Why?
Sol. The lattice energy of Na2SO4 is less than the hydration energy whereas the lattice
energy of the BaSO, (because of bivalent charge) is very high so that hydration energy
released is not sufficient to break the lattice and BaSO, remains insoluble.
Prob 2. Sodium fire in the laboratory should not be extinguished by pouring water. Why?
Sol. Sodium reacts violently with water producing H2 gas which also catches fire. As a
result, the fire spreads rather than being extinguished. Therefore, water should not be*
used for extinguished sodium fire. Pyrene (CCI4 ) should be used.
Prob 3. Why potassium carbonate can not be prepared by solvay process?
SoL This is due to the reason that potassium bicarbonate (KHCO3 )formed as an
intermediate (when CO, is passed through ammoniated solution of potassium chloride)
is highly soluble in water and can not be separated by filteration.
Prob 4. Why alkali metals are not prepared by the reduction of their oxides?
Sol. Alkali metals having lowest values of ionization enthalpy are strongest reducing agents.
Thus they can not be reduced by any other element.
Prob 5. Why table salt get wet in raining season?
Pure NaCI is not hygroscopic but table salt is impure. NaCl contains impurities of
Na2SO4 , CaSO, . All of these being hygroscopic absorb moisture from air in rainy
season. As a result table salt gets wet.
Prob 6. When Mg metal is burnt in air; a white powder is left behind as ash. What is the white
powder?
SoL Mg on burning in air reacts with oxygen and nitrogen resulting in the formation of MgO
and magnesium nitride.
2Mg + 02 --->MgO
3Mg + N2 —>M g3N2
Prob 7. In aqueous solution Li ion has the lowest mobility. Why?
SoL Li+ ions are highly hydrated in aqueous solution which result in decrease in its mobility.
Prob 8. Explain, why lithium is kept rapped in paraffin wax and not stored in kerosene oil?
SoL It is because lithium is a light metal and therefore it floats at the surface of kerosene oil.
To prevent its exposure to air it is kept wrapped in paraffin wax.
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Prob 9. Why cesium can be used in photoelectric cell, while lithium can not be?
Sol. Caesium has the lowest while lithium has the highest ionization energy among all the
alkali metals. Hence, caesium can lose electron very easily while lithium cannot.
Prob 10. Which alkali metal ion has the maximum polarizing power and why?
Sol. Li+ ion has the maximum polarizing power among all the alkali metal ions. Thus is due
to small size of Li+ ion as result of which it has maximum charge/radius ratio:
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Objective:
Prob 1. The oxidation state of the most electronegative element in the products of the reaction,
Ba02 with diL H2SO4 are
(A) 0 and -1 (8) -1 and -2
(C) -2 and 0 (p) -2 and +1
SoL (B)
Prob 2. Among K02 , A10-2 , Ba02 and N0+ . Unpaired electron is present in
2.
(A) NO; and Ba02 (B) K02 and A102
(C) K02 only • (D) Ba02 only
(C)
Prob 3. A solution of sodium metal in liquid ammonia is strongly reducing due to the presence
of
(A) sodium atoms (B) sodium hydride
(C) sodium amide (D) solvated electrons
SoL (D)
Prob 4. The compound insoluble in acetic acid is

(A) calcium oxide (B) calcium carbonate
(C) calcium oxalate (D) calcium hydroxide
SoL (C)
Prob 5. Which of the following on heating do not decompose?

(A) Li2CO3 (B) BaCO,
(C) Na2CO3 (D) none
Sol. (C)
Prob 6. The solubility in water of sulphates down the group is Be>Mg>Ca > St- > Ba. This is due
to
(A) increase in melting point (B) high ionization energy -
(C) higher coordination number (D) all of these
SoL (C)
Prob 7. -Solubilltes of carbonates decreases down the magnesium group due to decrease in
(A) entropy of solution formation (B) lattice energies of solids
(C) hydration energy of cations (D) inter-ionic attraction
Sol. (C)
Prob 8. The paramagnetic species is

(A) K02 (B) Si O2
(C) TiO2 (D) Ba 02
SoL (A)
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Prob 9. Which of the following substances can be used for drying gas?
(A) calcium carbonate (B) sodium carbonate
(C) sodium bicarbonate (D) calcium oxide
Sol. (D)
Prob 10. KO, (potassium superoxide) is used in oxygen cylinders in space and submariners
because it
(A) absorbs CO, and increases 02 content (B) eliminates moisture
(C) absorbs 'CO, (D) produces ozone
Sol. (A)
Fill in the blanks
Prob 11. Sea water is a major source of where it is present as
Sol. Na, NaCl

Prob 12. An alloy of Na with Hg is called
Sol. Sodium amalgam
Prob 13. is used to neutralise acidity of stomach.
Sol. NaHCO3
Prob 14. In the Castner-Kellner cell, mercury acts as in the central and as
in the outer compartments.
So/. Anode, cathode
Prob 15. Ca2Mg2S/9022(OH)2 is known as
Sol. Asbestos
True/False
Prob 16. Lithium is the hardest .alkali metal.

Sol. True
Prob 17. Alkali metals are strong reducing agents and hence can't be isolated by reduction of
their oxides or compounds.
Sol. True
Prob 18. Sodium reacts vigorously with oxygen to form sodium superoxide.
Sol. False
Prob 19. Pure NaCl isn't hydroscopic but in the presence of impurities like CaCl2.2H20 and
MgCl2. 2H20 becomes slightly hygroscopic.
Sol. . True
Prob 20. K2SO4.MgSO4.61-120 is a double salt and is known as potash alum.
Sol. False
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'CHAPTER PRACTICE PROBLEMS (CPP)
Subjective:
Level — I
1. The Solvay process can be represented by the following scheme:

CaCO3
H20
Ca° + CO2
Identify A, B, C, D and E.
2. A certain compound (X) imparts a golden yellow flame and shows the following reactions:
Zinc powder when boiled with a concentrated solution of (X) dissolves and hydrogen is
evolved.
When an aqueous solution of (X) is added to an aqueous solution of stannous chloride, a
white precipitate is obtained first which dissolves in excess of solution of (X).
Identify (X) and write equations for reactions at steps (i) and (ii).
Level — II
3. A certain compound (X) is used in the laboratory for analysis, its aqueous solution gives the
following reactions:
On addition to copper sulphate, a brown precipitate is obtained which turns white on
addition of excess of Na2S203.
On addition of Ag+ ion solution, a yellow curdy precipitate is obtained which is insoluble in
ammonium hydroxide.
Identify (X) and give equations for reactions at step(I) & (II).
4. An unknown inorganic compound (X) loses its water of crystallization 9n heating and its
aqueous solution gives the following reactions:
It gives a white turbidity with dilute HCl solution.
It decolourizes a solution of iodine in potassium iodide.
It gives a white precipitate with silver nitrate solution which turns black on standing.
Identify the compound (X) and give chemical equations for the reactions at steps (a), (b) and
(c).
5. On treatment with cold water, an element (A) reacted quietly, liberating a colourless,
odourless gas (B) and a solution (C). Calcium reacted with (B) yielding a solid product (D)
which reacted with water to give a basic solution (F). When carbon dioxide was bubbled
through solution (C) initially a white precipitate (G) is formed, but this redissolved forming
solution (H) when more CO2 was added. Precipitate (G) effervesced when moistened with
concentrated hydrochloric acid and gave a deep red coloration to the burner flame. When (G)
was heated with carbon at 1000°C, a white compound (I) was formed which when heated
with a carbon at 1000°C gave a solid (J) of some commercial importance. Identify the
substances (A) to (J).
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Objective:
1. Which of the following is not correct as shown?

(A) Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3; (solubility in water)
(B) BeCO3 < MgCO3 < CaCO3 < SrCO3 <BaCO3; (solubility in water)
Li <K < Na < Rb < Cs; (densities)
Li > K > Rb > Cs > Na; (reducing power)
2. The metallic sodium dissolves in liquid ammonia to form a deep blue coloured solution. The
deep blue colour is due to the formation of
(A) solvated electrons, e(NH3)y- (B) solvated atomic solution, Na(NH3)x
(C) Naf + Na- (D) NaNH2 + H2
3. Which of the following is wrong when alkali metals react with oxygen?
(A) Li gives Li2O and Li202 (B) Na gives Na2O and Na202
(C) K gives K20, K202 and K02 (D) Cs gives Cs20, Cs202 and Cs02
4. K02 is used in space crafts and submarines because it

absorbs CO2 and moisture to increase 02 concentration
absorbs moisture
absorbs CO2
produces ozone
5. What is the best description of the change that occurs when Na20(s) is dissolved in water?
oxidation number of oxygen increases
oxidation number of sodium decreases
oxide ion accepts sharing in a pair of electrons
(D) oxide ion donates a pair of electrons
6. Which chemicals in Solvay process are recirculated?

(A) NH4CI and CaCl2 (B) NH4CI and CO2
(C) NH3 and CO2 (D) CaCl2 and CO2
7. A white water soluble polymeric solid "A", on heating releases CO2 gas. The residue is water
soluble and reacts with acids to produce CO2. What is "A"?
(A) NaHCO3 (B) KHCO3
(C) LiHCO3 (D) RbHCO3
8. The reaction of Br2 with Na2CO3 in aqueous solution gives sodium bromide and sodium
bromate with evolution of CO2 gas. The number of sodium bromide molecules involved in the
balanced chemical equation is:
(A) 3 (B) 4
(C) 5 (D) 2
9. Which of the following does not exist as solid?

(A) LiHCO3 (B) NaHCO3
(C) KHCO3 (D) CsHCO3
10. CO2 gas is bubbled through cold aqueous solution of Na2CO3. The main product is
(A) NaOH • (B) NaHCO3
(C) H20 (D) Na2O2
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ASSIGNMENT PROBLEM
Subjective:
Level- 0
1. Why alkali metals are normally kept in kerosene oil?
2. Why alkali metals impart colour to the flame?
3. Explain why Lithium chloride has more covalent character than potassium chloride. -
4. Why BeCO3 is kept only in an atmosphere of CO2?
5. Why Be and Mg do not give characteristics colour to the flame whereas other alkaline earth
metals do give?
6. Lithium has highest ionization energy in group 1 element, yet it is strongest reducing agent.
Why?
7. What happens when?

NaH reacts with water.
Sodium reacts with excess oxygen.
Water is dropped over sodium peroxide.
Write balanced chemical equation for each.
8. Why are alkali metals strong reducing agents?
9. Sodium can not be obtained by the electrolysis of an aqueous solution of sodium chloride.
Explain.
10. Account for the following:
Be and Mg do not impart any colour to the flame.
Be has less negative value of the reduction potential (E°).
11. The chemistry of beryllium is not essentially ionic'. Justify the statement by making a
reference to the nature of oxide, chloride and fluoride of beryllium.
12. Why is it that BeSO4 and NAgSO4 are soluble but BaSO4 is insoluble in water?
13. Why is calcium preferred over sodium to remove last traces of moisture from alcohol?
14. What is the difference between milk of lime and lime water?
15. Why alkaline earth metals forms divalent ions inspite of the fact that 1E2 > 1E1 of alkaline earth
metals?
16. Mg3N2 when reacted with water gives off NH3 but He, is not obtained from MgCl2 on reaction
with water at room temperature.
17. Explain why halides of Be dissolve in organic solvents while those of Ba do not.
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P-.1719-P3-CBSE-CH-sB-65
Level — I
A white solid is either Na2O or Na202 . A piece of litmus paper turns white when it is dipped
into a freshly made aqueous solution of the white solid.
Identify the substance and explain with balanced equation.
Chlorination of calcium hydroxide produces bleaching powder. Write its chemical equation.
Give reason for decreasing order of conductivity of following.

Conductivity of Li+ < Na+ <.K < Rb+ < Cs+
Explain the stability of oxides of alkali metals.
Li is extracted by electrolysis of a fused mixture of LiCI 8, KCI. Why KCI is added?
6.. State any reason for alkaline earth metals having a greater tendency to form complex than _
alkali metals.
7. What happens when K02 reacts with water? Write the balanced chemical equation for the
reaction.
Why superoxides of alkali metals are paramagnetic while normal oxides are diamagnetic?
The crystalline salts of alkaline earth metals contain more water of crystallization than the
corresponding alkali metals salts why?
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Level — II
1. What happens when

magnesium is burnt in air.
quicklime is heated with silica.
chlorine reacts with slaked lime.
calcium nitrate is heated?
2. Explain why
Lithium on being heated in air mainly forms the monoxide and not peroxide.
An aqueous solution of sodium carbonate gives alkaline tests.
3. How is anhydrous magnesium chloride prepared from magnesium chloride hexahydrate?
4. Alkaline earth metal impart a characteristic colour to the flame? Explain.
5. Explain
The hydroxides of alkaline earth metals are weaker bases than their corresponding alkali
metals.
Ca, Br, Sr are stored in paraffin but Be & Mg are not?
6. (a) What is nitrolim and how it is useful?

(b) Blue colour of the solution of alkali metals in liquid ammonia fades on standing why?
7. Calcium burns in nitrogen to produce a white powder which dissolves in sufficient water to
produce a gas (A) and on alkaline solution. The solution on exposure to air produce a solid
layer of (B) on the surface. Identify the compounds A & B.
8. Explain why halides of beryllium fume in moist air but other alkaline earth metals halides do
not.
9. A piece of burning magnesium ribbon continuous to bum in sulphur dioxide. Explain.
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Objective:
Level —
The solution of alkali metals as in liquid ammonia is used for reduction of ethylenic double
bondd, acetylenic triple bonds to double bonds and aromatic compounds under the name
Birch reduction
(A) Li (B) Na
(C) K (D) all of them
Which of the following carbide is known by the name hydrolith?

(A) MgC2 (B) CaC2
(C) SrC2 (D) BeC2
Sodium reacts with water more vigorously than lithium because it has
(A) has higher atomic weight (B) is a metal
(C) is more electropositive (D) more electronegative
2+
The hydration energy of Mg is greater then
(A) Al+3 (B) .Na
(C) Be+2 (D) mg+3
5. Property of alkaline earth metals that increase with this atomic number is
(A) Ionization energy (B) solubility of their hydroxides
(C) solubility of their sulphates (D) electronegativity
6. The correct order of solubility of sulphates of alkaline earth metals are

BeSO4 >,MgSO4 > SrSO4 > CaSO4
BeSO4 > MgSO4 > CaSO4 > SrSO4
BeSO4 > MgSO4 < CaSO4 < SrSO4
MgSO4 <CaSO4 < SrSO4 > BeSO4
7. Which of the following metals do not impart colour to the flame?

(A) Na (B) Mg
(C) Ca (D) Sr
8. A fusion mixture is a mixture of

(A) Na2CO3 +MgCO3 (B) Na2CO3 +K2CO3
(C) Mg CO3 +CaCO3 (D) K2CO3 +CaCO3
9. Which of the following alkaline earth metals sulphates is least soluble in ‘Arter?
(A) BaSO4 (B) MgSO4
(C) SrSO4 , (D) CaSO4
10. The drying agent — which absorbs carbon dioxide and reacts violently with water is
(A) sodium carbonate (B) alcohol \
(C) conc. H2SO4 . (D) calcium oxide
11. The compounds of alkaline earth metals have the following magnetic nature
(A) diamagnetic (B) paramagnetic
(C) fen-omagnetic (D) anti ferromagnetic
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Which of the following alkali metals halides has the lowest lattice energy? -
(A) LiF (B) NaCI
(C) KBr (D) Csl
Which of the following alkali metals ions has the lowest mobility in aqueous solution?
(A) Li+ (B) Na+
(C) K+ (0) CS+
Which has minimum hydration energy?

(A) K+ (B) Li+
(C) Ca+2 (D) Al+3
Alcohol dissolves in
(A) KCI (B) NaCI
(C) RbCI (D) LiCI
LiNO3 on heating gives

(A) 02 (B) NO2
(C) 02 + NO2 (D) none of the above
A compound of sodium which when heated gives CO2 is

(A) Na2CO3.10H20 (B) NaHCO3
(C) Na2CO3.7H20 (0) Na2003.H20
Which of the following carbonate decompose on heating to evolve CO2?

(A) Na2CO3 (B) Li2CO3
(C) K2CO3 . (D) Rb2CO3
Which of the following has the highest solubility product?

(A) KOH (B) CsOH
(C) LiOH (D) RbOH
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Pinnacle. Study Package P- 1719-P3-CBSE-CH-sB-69
Level — II
MULTIPLE CORRECT QUESTIONS
Which of the following metals on treatment with NaOH will liberate H2 gas?
(A) Zn (B) Sn
(C) Al (D) Mg
When zeolite, which is hydrated sodium aluminium silicate is treated with hard water, the
sodium ions are exchanged with
(A) H+ ions (B) S042- ions
(C) Ca2+ ions (D),Mg2+ ions
The pairs of compounds which cannot exist together in aqueous solution are
(A) NaH2PO4 and Na2HPO4 (B) Na2C0"3 and NaHCO3
(C) NaOH and NaH2PO4 (D) NaHCO3 and NaOH
Highly pure dilute solution of sodium in liquid ammonia

(A) shows blue colour (B) exhibits electrical conductivity
(C) produces sodium amide (D) produces hydrogen gas
. In which of the following reactions, MgO is formed?

" (A) Mg +CO2 (B) Mg +dil HNO3
(C) Mg +NO--> (D) Mg +6203
6. Select the correct statements about barium

It shows photoelectric effect
It is silvery white metal
It forms Ba(NO3)2 which is used in preparation of green fire
Its ionization energy is less than radium
ASSERTION REASON TYPE QUESTIONS
The questions given below consist of statements 'Assertion' (A) and 'Reason' (R).
If both 'A' and 'R' are correct and 'R' is correct reason for 'A'.
If both 'A' and 'R' are correct but 'R' is not the correct explanation for 'A'.
If 'A' is true but 'R' is false.
If both 'A' and 'R' are false.
7. (A) Potassium and caesium are used in photoelectric cells.

(R) Potassium and caesium emit electrons on exposure to light.
8. (A) Barium is not required for:. normal biological function in human.

(R) Barium does not show variable oxidation state.
9. (A) Helium and beryllium have similar outer electronic configuration of the type ns2.
(R) Both are chemically inert.
10. (A) The process of adsorption of hydrogen on palladium is known as occlusion

(R) The adsorbed hydrogen is more active than ordinary hydrogen.
11. (A) NaCI is less soluble in heavy water than in ordinary water.
(R) Dielectric constant of ordinary water is more than that of heavy water.
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P- 1 7 19-P3 -CBSE-CH-sB- 70 Pinnacle Study Package
COMPREHENSION — I
The salt of alkli metals are ionic and soluble in water. The solubility of an ionic compound
depends on two factors: (i) lattice energy and (ii) hydration energy.
These two factors oppose each other. Higher is the hydration energy, higher is the solubility of an
ion. The smaller the ion, grater is its degree of hydration and greater is the heat of hydration
liberated.
12. Among the alkali metals which will have higher degree of hydration
(A) Cs+ (6) Na+
(C) K+ (D) Li+
13. Which has least solubility?

(A) LiF (B) NaF
(C) KF (D) CsF
14. The solubility in water of sulphates down the IIA group is

Be > Mg > Ca > Sr > Ba
This is due to
increasing molecular mass
increasing melting point
decreasing lattice energy
high heat of salvation for smaller ions
COMPREHENSION —II
Both alkali metals and alkaline earth metals are s — block elements. They resemble with each
other in many respects but still there are certain dissimilarities in their properties on account of
different number of electrons in the valence shell, smaller atomic radii, higher ionization potential,
higher electronegativity etc.
15. The correct sequence of increasing covalent character is represented by
(A) BeCl2 < LiCI < NaCI (B) BeCl2 < NaCI < LiCI
(C) NaCI < LiCI < BeCl2 (D) LiCI < NaCI < BeCl2
16. Which is least thermally stable?
(A) Li2CO3 (B) MgCO3
(C) CaCO3 (D) BeCO3
MATRIX TYPE QUESTIONS

17. Match the Column — I with Column — II:
(A) Chile salt petre (9) NaAlSi208

(B) Albite (q) NaNO3
(C) Glauber's salt (r) KN 03
(D) Microcasmic salt Na2SO4.1 0H20
NaNH4HPO4.4H20
18. Match the following:
.. •:• ... • . . • .. • . .. 9 . .. . ... . ...
(A) Boron (9) Sapphire
(8) Aluminium (q) Tincal
(C) Carbon (r) Carborundum
(D) Silicon (s) Magnesite
(t) Colemanite
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Naivetele Study Package
P-1719-P3-CBSE-CH-s13-71
NUMERICAL BASED QUESTIONS

19. When sodium reacts with excess of oxygen, change in oxidation number of oxygen is
OH heating a mixture containing 1 mole each of Li2CO3 and K2CO3 is/are formed.
Valency of carbon in acetylene is
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P-1719-P31CBSE-CH-sB-72
ANSWERS TO CHAPTER PRACTICE PROBLEMS (CPP)
Objective:
1. B 2. A 3. A 4. A
D 6. C 7. A 8.
/ 5.
9. A 10. B
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P-1719-P3-CBSE-CH-s.B-73
ANSWERS TO ASSIGNMENT PROBLEMS
Subjective:
_ Level-0
1. Alkali metals, when exposed to atmosphere react with oxygen, moisture and CO2 present in
the air forming oxides, hydroxides and carbonates. In order to prevent the reaction the alkali
metals are stored in kerosene oil.
2. Alkali metals have low I.E. Their valence electrons absorbs energy from the flame and gets
excited to higher energy level When they return to the ground state, the energy is emitted
back in the form of radiations frequencies of which fall in the visible range imparting a
characteristic colours to flame.
3. Lithium ion due to its small size, has high polarizing power. Thus it can polarize the electron
cloud of chloride ion to much greater extent as compared to potassium ion. Hence LICI has
more covalent character.
4. The temperature of decomposition of BeCO3 is less than 373K. Hence it is unstable and can
be kept only in an atmosphere of CO2.
5. Be and Mg have high ionization energies. Their valence electrons are not easily excited.
6. The strength of an element as reducing agent depends not only on ionization energy but also
on heat of hydration and heat of sublimation of the element. Li+ ion has very high hydration
energy due t its small size which more than compensates for the higher value of I.E. of
lithium. As a result is Li behaves as strongest reducing agent.
7. (i) NaH reacts with water to form sodium hydroxide arid hydrogen gas.
NaH +H2O—NaOH + H2
Sodium on reaction with excess oxygen forms sodium peroxide
2Na + 02 > Na2O2
Na202 on reaction with water is hydrolysed to sodium hydroxide and hydrogen peroxide.
Na202 +2H20--->2NaOH + H202
8. The ionization enthalpies of the alkali metals is very low. It is because of this reason that they
form unipositive ions very easily. This implies that they have a great tendency to donate an
electron to another atom e.g.
2Na + X2 2NaX
The alkali metals have low value of E°. The E° value depends on the three parameters i.e.
sublimation, ionization and hydration enthalpies.
1
or M +NH3 MNH + — H
2 2
9. Sodium metal cannot be isolated by the electrolysis of their aqueous solutions because the
metal deposited at the cathode, reacts at once with water to form metal hydroxide and
hydrogen gas. Thus, at the cathode, metals are not liberated but only hydrogen gas is
evolved.
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Pinnacle Study Package 1
(i) Be and Mg do not impart any colour to the flame because the electrons are very strongly
bound to the nucleus and very high amount of energy is required to excite the electrons
to higher energy level. When these electrons drop back to the original state, energy
emitted falls outside the visible region. Hence, no colour to the flame.
(ii) The less negative value for Be arises from the large hydration energy associated with the
small size of Be2+ and the relatively large value of the enthalpy of atomization of the
metal.
Due to exceptionally small size and high ionization enthalpy, the compounds of beryllium are
largely covalent. For example:
Be0 is amphoteric while oxide of other group 2 elements are basic in nature. Be() dissolves
in alkali to form beryllate
Be0 + 20H- +H20--qBe(OH)412-
BeC12 is largely covalent and is soluble in organic solvents.
BeF2 is also highly covalent and due to high lattice enthalpy, the solubility is very less. A
The greater hydration energies of Be2+ and Mg2+ ion overcome the lattice energy of the salts
and their sulphates are soluble. In BaSO4, lattice energy is higher than the hydration energy
and hence it is insoluble.
Both Na and Ca react with water forming their respective hydroxide. In contrast, Na reacts
with alcohol to form sodium alkoxide but Ca does not.
A suspension of slaked lime, i.e Ca(OH)2 in water is called milk of lime but a clear decanted
solution of slaked lime in water is called lime water.
This is due to their high lattice energies in the solid state and high hydration energies in
aqueous solution.
Mg3N2 is a salt of a strong base, Mg(OH)2 and a weak acid (NH3) and hence gets hydrolysed
to give NH3. In contrast, MgCl2 is salt of strong base Mg(OH)2 and strong acid HC1 and does
not undergo hydrolysis to give HCI.
Halides of Be are covalent because of high I.E. of Be while those of Ba are ionic due to low
I.E. of Ba.
Level — I
Bleaching powder is obtained by passing Cl2 into Ca(OH)2. Though bleaching powder is often
written as Ca(0C1)2. It is actually a mixture of
3Ca (OH) 2 +2C12 Ca (0C1)2 .Ca(OH)2 .CaCl2.2H20
Ions are hydrated. Since Li is very small it is heavily hydrated. This makes the radius of the
hydrated ions large and hence it move only slowly (although Li+ is very small) and the radius
of hydrated Cs+ ion is smaller than the radius of hydrated Li.
KCl is added to increase the conductivity of LiCI and to lower the fusion temperature.
Because of smaller size and higher charge on alkaline earth metals cations as compared to
the corresponding alkali metal cations, alkaline earth metals cations have greater tendency to
form complexes.
2K02 +2H20 2KOH + H202 +

9. Due to smaller size and higher nuclear charge alkaline earth metals have a higher tendency
than alkali metals to attract H20 molecules and thus contain more water of crystallization than
alkali metals.
e.g. LiC12.H20 & MgC12.6H20
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Pinnacle Study Packag e
Level — II
1. 1\49 4-72 +,72 -->2Mg0+Mg3N2
air
CaO +SiO2 CaSiO,
2Ca(OH)2 +2C12 —>CaC12 +Ca(C1C1)2 +2H20
2Ca(NO3)2 —s'-42Ca0 + 4NO2 +02
(i) Li+ ion is smaller in size. It is stabilized more by smaller anion, oxide ion (0-2) as
compared to peroxide (021 .
(ii) An aqueous solution of sodium carbonate gives alkaline tests because Na2CO3
undergoes hydrolysis forming sodium hydroxide.
Na2CO3 + H20 —>NaHCO3 + NaOH
Anhydrous MgCl2 can not be prepared by simply heating MgC12.6H20 because it get
hydrolysed by its own water of crystallization.
MgCl2 .6H20 --> MgO + 2HCI + 5H20
However if hydrated magnesium chloride is heated in an atmosphere of FIC1 gas at 650 K, it
checks the above hydrolysis reaction and the hydrated magnesium chloride now loses water
of crystallization to form anhydrous MgCl2.
I-ICI gas
MgCl2 .6H20 650 K > MgC12 + 6H2 0
When alkaline earth metals or their compounds are put into a flame, the electron absorbs
energy and are excited to higher energy levels. When they retums to their ground state
(normal state), they emit the - absorbed energy in the form of radiations having particular
wavelength.
(a) Due to high ionization energies and less solubilities of alkaline earth metals as compared
to alkali metals.
(b) Ca, Ba, Sr are much reactive towards oxygen and forms respective oxide but Be & Mg
are not so reactive and they form a protective layer of oxide on their surface so they are
not stored in paraffin.
(a) The mixture of calcium cyanamide and carbon is called nitrolim and is used as show
acting nitrogenous fertilizers as it hydrolysis slowly over a period of months evolving NH3
gas.
CaC2 12 CaNCN +C
cal cyanamide
CaNCN+3H20----+CaCO3 + 2NH3
(b) On standing the ammoniated ions and electrons combine to form metal amide, hence the
colour fades.
Ca bums in air to form CaO and Ca3N2.

Calcium nitride on hydrolysis with H20 gives ammonia (A).
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Ca3N2 +6H20 (OH)2 + 2NH3 (A)

The alkaline solution of Ca(OH)2 thus formed reacts with CO2 present in the air to form
CaCO3 (B)
Ca (OH)2 + CO2 --CaCO3 (B) + H20
Thus
A = NH3
B = CaCO3 white powder
BeCl2 reacts with the moisture to form HCI while other halides do not.
BaCl2 + 2H20 Be(OH)2 + 21-ICI
9. A piece of Mg ribbon continues to burn in SO2 since it reacts to form MgO and S
heat 2mgo s
2Mg SO2
This reaction is so much exothermic that heat evolved keeps the Mg ribbon burning.
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Objective:
Level - I
1. D 2. B 3. C
4. B 5. B 6. B
7. B 8. B 9: A
10. D 11. A 12. D
13. A 14. A • 15. 0
16.. C 17.. B 18. B
19. B
Level - II
1. A, B, C 2. C, D 3. • C, D
4. A, B 5. A, C, D 6. B, C, D
7. A 8. B 9. C
10. B 11. A 12. D
13. A 14. D 15. C
16. D
(A) --> (q); (B) -> (p); (C) -+ (s); (D) -> (t)
(A) -> (q, t); (B) -> (p); (C) --> (s); (0) -> (r)
1 1
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NOTES
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The main reasons for the diagonal relationship are

Similarity in polarizing power

Similarity in atomic or ionic radii

* ppm (parts per million) ** percentage by weight.

„„ ,:‘: ,„: ::::K Rb,..::: :::Cs

Illustration 2. What is the most reactive alkali metal and why?

Reaction with Oxygen

Reaction with Hydrogen

(iii) Reaction with water

Solubility in liquid ammonia

-16Na + S8 > 8Na2S

(vii) Reaction with Mercury

Illustration 5. What happens whed(give chemical equation only):

Illustration 6. On prolonged exposure to air, sodium finally changes to

General characteristic of the compounds of the alkali metals

Solubility and stability

M2CO2 +2HX--->2MX+ CO2 +H20 = Li, Na, K, Rb or Cs) (X = F, Cl, Br or I)

Li -612 -398 -350 -271

LiCI -845 -. 876 . 63.7 887

Illustration 9. Why are alkali metal halides soluble in water? .

(iii) Salts of oxoacids

Illustration 10. Complete and balance the following:

Solution: (i) 4LiNO3 Ls > 2L120 + 4NO2 02

Anomalous Behaviour of Lithium and its Diagonal fRelationship with Magnesium

Difficulties encountered during extraction of alkali metals

Acid treatment method

Lithium ore (spodumene or lepidolite)

2. Electrolysis of Lithium chloride

Reaction with ammonia

It is therefore kept under kerosene.

(ii) Action of ammonia

Solution: (i) 2Na + 2H20 --> 2Na0H +H,

2Na202 +2H 0-34Na0H +H,0

Compounds of Alkali Metals

Oxides of Sodium: The possible oxides of Na are Na2O and Na202.

It dissolves in water violently gives caustic soda.

New Delhi -110016, Ph 46106000, Fax 26513942

Sodium Peroxide (Na202)

Potassium monoxide (K20)

Carbonates of Metals (Na, K)

Sodium Carbonate (Washing soda) (Na2CO3)

Plant used for the manufacture of washing soda

Ammonia recovery tower

2N H4C1 + Ca (OH)2 --->2NH3 2H20 CaCl2

Alkaline Earth Metals

Lattice energies decreases as atomic number increases

-3923 -3178 -2906

Electropositive or Metallic Character

Atomic number 4 12 20 38 56 '88

Atomic mass 9.01 24.31 40.08 87.62 137.33 226.03

Metallic radius/pm 112 160 197 215 222

Ionization enthalpy I 899 737 590 549 503 509

Electronegativity 1.57 1.31 1.00 0.95 0.89 0.9

Melting Point/K 1562 924 1124 1062 1002 973

Boiling point /K 2745 1363 1767 1655 2078 (1973)

Calcium 4.15%, 5th CaCO3.2H20 obtained_ in pure As an alloying agent for

Zn —Cd —Hg 11/3 (14)