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CHEMISTRY
INTRODUCTION :
The s- block elements of the periodic table are those in which the last electron enters the outermost s-orbital.
As the s-orbital can accommodate only two electrons, two group (1 &2) belong to the s-block of the periodic
table. Group 1 of the periodic table consists of the elements : lithium (Li), sodium (Na), potassium (K),
rubidium(Rb), caesium(Cs) and francium(Fr). They are collectively known as the alkali metals. These are
so called because they formhydroxides on reaction with water which are strongly alkaline in nature.
The elements of Group 2 include beryllium(Be), magnesium(Mg), calcium(Ca), strontium(Sr), barium(Ba)
and radium(Ra). These elements with the exception of berylliumare commonly known as the alkaline earth
metals. These are so called because their oxide and hydroxide are alkaline in nature and these metal oxides
are found in the earths crust .
The general electronic configuration of s- block elements is [ noble gas]ns
1
for alkali metal and [noble gas]ns
2
for alkaline earth metals.
Lithiumand beryllium, the first elements of Group 1 and Group 2 respectively exhibit some properties which
are different fromthose of the other members of the respective group. In these anomalous properties they
resemble the second element of the next group. Thus, lithiumshowsimilarities to magnesiumand beryllium
to aluminiumin many of their properties. This type of diagonal similarity is commonly referred to as diagonal
relationship in the periodic table. The diagonal relationship is due to the similarity in ionic size or (charged /
radius) ratio of the elements.
Electronic Configuration :
All the alkali metal have one valence electron, ns
1
outside the noble gas core. The single valence electron
is at a long distance from the nucleus and is only weakly held. Hence the loosely held s-electrons in the
outermost valence shell of these elements make them the most electropositive metals. They readily lose
electron to give monovalent M
+
ions. Hence they are never found in free state in nature.
Alkaline earth metals have two electrons in the s-orbital of valence shell. The compounds of these elements
are also predominantly ionic.
Atomic and Ionic Radii :
The alkali metal atoms have the largest size in a particular period of the periodic table. The atomic and
ionic radii of alkali metal increase on moving down the group i.e., they increase in size while going from
Li to Cs.
The atomic and ionic radii of the alkaline earth metals are smaller than those of the corresponding
alkali metals in the same periods. This is due to the increased nuclear charge in these elements. Within the
group, the atomic and ionic radii increase with increase in atomic number due to the increase in number of
atomic shells.
Ionization Enthalpy :
The ionization enthalpies of the alkali metals are considerably lowand decrease down the group fromLi
to Cs. This is because the effect of increasingsize outweighs the increasingnuclear charge and the outermost
electron is very well screened from the nuclear charge. The second ionisation energy is extremely high
because of the removal of 2nd electron froma stable noble gas electron configuration of monovalent metal
cation.
The alkaline earth metals have low ionization enthalpies due to fairly large size of the atoms. Since the
atomic size increases down the group, their ionization enthalpy decreases. The first ionisation enthalpy of
the alkaline earth metals is higher than those of the corresponding Group 1 metals for the same period. This
is due to their small size as compared to the corresponding alkali metals. The second ionisation enthalpies
of the alkaline earth metals are smaller than those of the corresponding alkali metals as in alkali metals the
second electron is to be removed froman inert gas configuration.
Hydration Enthalpy:
The hydration enthalpies of alkali metal ions decrease with increase in ionic sizes. Li
+
has maximum
degree of hydration and for this reasons lithiumsalts are mostly hydrated e.g., LiCl . 2H
2
O.
Like alkali metal ions hydration enthalpies of alkaline earth metal ions decrease with increase in ionic size
down the group.
Be
2+
> Mg
2+
> Ca
2+
> Sr
2+
> Ba
2+
s-Block Elementss
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The hydration enthalpies of alkaline earth metal ions are larger than those of alkali metal ions. Thus,
compounds of alkaline earth metals are more extensively hydrated than those of alkali metals, e.g., MgCl
2
and CaCl
2
exist as MgCl
2
.6H
2
Oand CaCl
2
. 6H
2
Owhile NaCl and KCl do not formsuch hydrates.
Physical properties:
All the alkali metal are silvery white, soft (because of having only one valency electron which participate in
bonding) and light metals. Because of the larger size, these element have lowdensity which increases down
the group fromLi to Cs. However, potassiumis lighter than sodiumbecause of larger atomic volume. The
melting and boiling point of the alkali metals are lowindicating weak metallic bonding due to the presence of
only a single valence electron in them. The strength of metallic bond decreases down the group, and the
melting point decreases accordingly. The melting point of lithiumis nearly twice as high as that for sodium
because of strong metallic bonding on account of its small size. However, the melting points of the other all
close together. The alkali metals and their salts impart characteristic colour to an oxidizing flame. This is
because the heat fromthe flame excites the outermost orbital electron to a higher energy level. When the
excited electrons come back to the ground state, there is an emission of radiation in the visible region as
given below:
Metal Li Na K Rb Cs
Colour Crimson
red
Yellow
Violet/
Lilac Red
violet
Blue
These elements when irradiated with light, the light energy absorbed may be sufficient to make an atomlose
electron. This property make caesiumand potassiumuseful as electrodes in photoelectric cells.
The alkaline earth metals, in general, are silvery white, lustrous and relatively soft but harder than the
alkali metals. Beryllium and magnesium appear to be somewhat greyish. The melting and boiling point of
these metals are higher than alkali metals due to smaller size and two valence electrons. Because of the low
ionisation enthalpies they are strongly electropositive in nature. The electropositive character increases
down the group fromBe to Ba. Calcium, strontiumand bariumimpart characteristic colour to the flame.
Metal Be Mg Ca Sr Ba
Colour No
colour
No
colour
Brick
red
Crimson Apple
green
The electrons in beryllium and magnesium are too strongly bound to get excited by flame. Hence these
elements do not impart any colour to the flame.
Like alkali metal, electrical and thermal conductivity of alkaline earth metal are high.
Chemical Properties:
The alkali metal are highly reactive due to their larger size and low ionization enthalpy. The reactivity of
these metal increases down the group.
The alkaline earthmetals are less reactive than the alkali metals. The reactivityof these elements increases
on going down the group.
Reactivity towards air and water : The alkali metals tarnish in dry air due to the formation of their
oxides which in turn react with moisture to formhydroxides. They burn vigorously in oxygen forming oxides.
Lithiumforms monoxide, sodiumforms peroxide, the other metals formsuperoxide. The superoxide O
2

ion
is stable only in the presence of larger cations such as K, Rb,Cs.
4 Li + O
2
2Li
2
O(oxide) ; 2 Na + O
2
Na
2
O
2
(peroxide)
M + O
2
MO
2
(superoxide) (where M = K, Rb, Cs).
All five metals can be induced to formthe normal oxide, peroxide or superoxide by dissolving the metal in
liquid ammonia and bubbling in the appropriate amount of oxygen. Lithium show exceptional behavior in
reaction directly with nitrogen of air to formthe nitride, Li
3
N. Li
3
N is ionic (3Li
+
and N
3
), and is ruby red.
2Li
3
N
. temp High

A
6Li + N
2
; Li
3
N + 3H
2
O 3LiOH + NH
3
.
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The alkali metals react with water to form hydroxide and dihydrogen. The reaction becomes increasingly
violent on descendingthe group. Although lithiumhas most negative electrode potential (E
O
) value, its reaction
with water is less vigorous than that of sodiumwhich has the least negative electrode potential (E
O
) value
among the alkali metals. This behavior of lithiumis attributed to its small size and very high hydration energy.
Other metals of the group react explosively with water.
2M + 2H
2
O 2MOH + H
2
(M = alkali metal cation).
They also react with proton donors such as alcohol, gaseous ammonia and alkynes.
Because of their high reactivity towards air and water, the alkali metals are normally kept in kerosene oil.
Berylliumand magnesiumare inert to oxygen and water because of the formation of an oxide filmon their
surface. However, powdered berylliumburns brilliantly on ignition in air to give BeOand Be
3
N
2
. Magnesium
is more electropositive and burns with dazzling brilliance in air to give MgOand Mg
3
N
2
. Calcium, strontium
and bariumare readily attacked by air to formthe oxide and nitride. They also react with water with increasing
vigour even in cold to formhydroxides.
Reactivity towards dihydrogen : The alkali metals react with dihydrogen at about 673 K (lithium at
1073 K) to formhydrides. All the metal hydrides are ionic solid with high melting points .
All alkaline earth metals except beryllium combine with hydrogen upon heating to form their hydrides,
MH
2
, which are also high melting solids.
BeH
2
. however, can be prepared by the reaction of BeCl
2
with LiAlH
4
.
2BeCl
2
+ LiAlH
4
2 BeH
2
+ LiCl + AlCl
3
Reactivity towards halogens : The alkali metals readily react vigorously with halogens to formionic
halide , MX. However lithiumhalides are some what covalent. It is because of the high polarisation capability
of lithium ion. The Li
+
ion is very small in size and has high tendency to distort electron cloud around the
negative halide ion. Since anion with larger size can be easily distorted , among halides lithiumiodide is the
most covalent in nature.
All the alkaline earth metals combine with halogens at elevated temperature forming their halides.
M + X
2
MX
2
(X = F, Cl, Br, l)
Reducing nature: The alkali metals, are strong reducing agents, lithiumbeing the most and sodium
the least powerful with the small size of its ion, lithiumhas the highest hydration enthalpy which account for
its high negative E
O
value and its high reducing power.
Like alkali metals, the alkaline earth metals are strong reducing agents. This is indicated by large
negative value of their reduction potentials. Berylliumhas less negative value compared to other alkaline
earth metals due to relatively large value of the atomization enthalpy of the metal. However, its reducing
nature is due to large hydration energy associated with the small size of Be
2+
ion.
Solution in liquid ammonia : The alkali metals dissolve in liquid ammonia giving deep blue solutions.
M+ (x + y) NH
3
[M(NH
3
)
x
]
+
+ [e(NH
3
)
y
]

In dilute solutions the main species are metal ions (M

+
) and electrons, which are solvated (i.e. ammoniated).
The blue colour, corresponding to a broad absorption band near 1500 nmthat falls into the visible range, is
attributed to the solvated electron.
These dilute solutions conduct electricity better than any salt in any liquid and the conductivity is similar to
that of the pure metals. Conduction is due mainly to the presence of solvated electrons. While the life time
of the solvated electron in water is very short, in very pure liquid ammonia it may be quite long ( < 1%
decompositionper day). As thesolutions aremademoreconcentrated, themolar conductivityat first decreases,
reaching a minimum at about 0.05 molar ; thereafter, it increases again until in saturated solutions it is
comparable to that of the metal.
According to more satisfactory model of the solvated electron, the electron is not localised but is smeared
out over a largevolumeso that thesurroundingmolecules experienceelectronic and orientational polarisation.
The electron is trapped in the resultant polarisation field, and repulsion between the electron and the electrons
of solvent molecules leads to the formation of a cavity (of diameter approximately 3.03.4 ) within which the
electron has the highest probability of being found. This cavity concept is based on the fact that these dilute
solutions are of much lower density than pure solvent, that is, they occupy far greater volume than that
expected fromthe sumof the volumes of metal and solvent.
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Very dilute solutions of the metals are paramagnetic, with approximately one unpaired electron per metal
atom (corresponding to one solvated electron per metal atom) ; this paramagnetism decreases at higher
concentration. As the concentration of metal increases, metal ion clusters areformed. Above 3Mconcentration
the solutions are diamagnetic and, no longer blue but are bronze/copper-bronze coloured with a metallic
luster.
The blue solutions of alkali metals in liquid ammonia, decompose very slowly with liberation of hydrogen (i.e.
reduction of the solvent).
M
+
(am) + e

(am) + NH
3
() MNH
2
(am) + 1/2 H
2
(g)
(where am denotes solution in ammonia).
or, NH
3
+ e

NH
2
-
+
2
1
H
2
.
Decomposition is accelerated by the presence of many transition metal compounds, e.g., by stirring the
solution with a rusty iron wire. The solution of metals in liquid ammonia act as powerful reducing agents (it
even reduces the aromatic ring)
O
2
+ e

O
2

; O
2
+ 2e

O
2
2
(change of oxidation states from0 to 1).
[Ni(CN)
4
]
2
+ 2e

[Ni(CN)
4
]
4
(change of oxidation states from+ 2 to 0).
GeH
4
+ e

GeH
2

+
2
1
H
2
.
S + 2e

S
2
(change of oxidation states from0 to 2).
[Fe(CO)
5
] + 2e

[Fe(CO)
4
]
2
+ CO(change of oxidation states from0 to 2).
Like alkali metals, the alkaline earth metals, except beryllium, dissolve in liquid ammonia to give deep
blue black solutions forming ammoniated ions. The colour is due to the spectrumfromsolvated electrons.
M + (x + y) NH
3
[ M(NH
3
)
x
]
2+
+ 2 [e(NH
3
)
Y
]

These solutions decompose very slowly forming amides but the reaction is accelerated by many transition
metals and their compounds.
2NH
3
+ 2e

2NH
2

+ H
2
Evaporation of the ammonia fromsolutions of alkali metals yields the metal, but with alkaline earth metals
evaporation of ammonia gives hexammoniates of the metals, [M(NH
3
)
6
]
2+
. These slowly decompose to give
amides.
M(NH
3
)
6
M(NH
2
)
2
+ 4NH
3
+ H
2
.
Example-1 The correct order of size of the ions is :
(A) Li
+
> Na
+
> K
+
> Cs
+
(B) Cs
+
> K
+
> Na
+
> Li
+
(C) Cs
+
> Na
+
> K
+
> Li
+
(D) Cs
+
> Li
+
> Na
+
> K
+
Solution Down the group the size of ions increases because of the increase in number of atomic shells.
The increase in the number of atomic shells over weighs the increase in effective nuclear charge.
Therefore (B) option is correct.
Example-2 Which of the following has the highest hydration enthalpy in aqueous solution ?
(A) Na
+
(B) Be
2+
(C) Ba
2+
(D) Cs
+
Solution The hydration enthalpies of alkaline earth metal ions are larger than those of alkali metal ions on
account of higher charge density than that of alkali metal ions. The enthalpy of hydration of alkaline
earth metal ions decrease with increase in ionic size down the group.
Be
2+
> Mg
2+
> Ca
2+
> Sr
2+
> Ba
2+
Therefore (B) option is correct.
Example-3 Which one of the following metals is most commonly used in photoelectric cells ?
(A) Li (B) Ca (C) Cs (D) Fr
Solution The ionization enthalpies of the alkali metals are considerably low and decrease down the group
fromLi to Cs. This is because the effect of increasing size outweighs the increasing nuclear charge,
and the outermost electrons is very well screened fromthe nuclear charge.
The alkali metals when irradiated with light, the light energy absorbed may be sufficient to make an
atomlose electron. This propertymake caesiumand potassiumuseful as electrodes in photoelectric
cells.
Therefore (C) option is correct.
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Example-4 A blue coloured solution of sodiumin liquid ammonia at 33Cbehaves as strong reducing agent,
because of :
(A) the formation of ammoniated sodium (B) the formation of ammoniated electron
(C) the formation of sodiumamide (D) the formation of sodiumnitride
Solution The solution of metals in liquid ammonia act as powerful reducing agents (it even reduces the
aromatic ring) because of ammoniated electron, Na + (x + y) NH
3
[Na (NH
3
)
x
]
+
+ [e (NH
3
)
y
]

e.g., O
2
+ e

O
2

; O
2
+ 2e

O
2
2
(change of oxidation states from0 to I),
[Ni(CN)
4
]
2
+ 2e

[Ni(CN)
4
]
4
(change of oxidation states from+ II to 0).
GENERALCHARACTERISTICSOFTHECOMPOUNDSOFTHEALKALI METALSANDALKALINEEARTH
METALS:
All the compounds of the alkali metals are generally ionic in nature. On combustion in excess of air alkali
metals formdifferent type of oxides as given in the following table.
The increasing stability of the peroxide or superoxide, as the size of the metal ion increases, is due to the
stabilisation of large anions bylarger cation through lattice energy effects. These oxides are easilyhydrolysed
by water to formthe hydroxides according to the following reactions:
M
2
O + H
2
O 2M
+
+ 2OH

M
2
O
2
+ 2H
2
O 2M
+
+ 2OH

+ H
2
O
2
2MO
2
+ 2H
2
O 2M
+
+ 2OH

+ H
2
O
2
+ O
2
The oxides and the peroxides are colourless when pure, but the superoxides are yellowor orange in colour.
LiO
2
and NaO
2
are yellow, KO
2
and CsO
2
are orange whereas RbO
2
is brown in colour. The superoxides are
also paramagnetic. The hydroxide are all white crystalline solids. The alkali metal hydroxides are the strongest
of all bases and dissolve freely in water with evolution of much heat on account of intense hydration.
The melting and boiling points of alkali metal halides always followthe trend : fluoride > chloride > bromide
> iodide. All alkali metal halides are generally soluble in water. The lowsolubility of LiF in water is due to its
high lattice enthalpy whereas the low solubility of CsI is due to smaller hydration enthalpy of its two ions.
Other halides of lithiumare soluble in ethanol, acetone and ethylacetate; LiCl is soluble in pyridine also.
The alkali metals formsalts with all the oxo-acids. The thermal stability of oxy-acid salts generally increases
down the group with increasing metallic character, i.e. electropositive character. They are generally soluble
in water andthermallystable. Their carbonates (M
2
CO
3
) andin most cases the hydrogencarbonates (MHCO
3
)
also are highly stable to heat. As the electropositive character increases down the group, the stability of the
carbonate and hydrogencarbonates increases.
Because group 1 metals are so strongly basic, they (except lithium) also formsolid bicarbonates. No other
metals formsolid bicarbonates. Lithiumcarbonate is not so stable to heat. Its hydrogencarbonate does not
exist as a solid. Although NH
4
HCO
3
also exists as a solid. The crystal structures of NaHCO
3
and KHCO
3
both showhydrogen bonding, but are different.
(a) In NaHCO
3
, the HCO
3

ions are linked into an infinite chain and (b) in KHCO

3
, HCO
3

forms a dimeric
anion.
(a) (b)
The solubility of the alkali metal salts except fluorides, carbonates and hydroxides decreases down the
group fromLi to Cs. This is because of the fact that down the group with increasing size of cation the lattice
energy as well as hydration energy also decrease but the change in hydration energy is more as compare to
that of lattice energy.
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The alkaline earth metals forms compounds which are predominantly ionic but less ionic than the
corresponding compounds of alkali metals. This is due to increased nuclear charge and smaller size. The
oxide and other compounds of berylliumand magnesiumare more covalent than those formed by the heavier
and large sized member (Ca, Sr, Ba).
The alkaline earth metals burn in oxygen to formthe monoxide, MO which, except for BeO have rock-salt
structure. The BeO is essentially covalent in nature. The enthalpies of formation of these oxides are quite
high and consequently they are very stable to heat. BeO is amphoteric while oxide of other elements are
ionic in nature. All these oxides except BeOare basic in nature and react with water to formsparingly soluble
hydroxides.
MO + H
2
O M(OH)
2
The solubility, thermal stability and the basic character of these hydroxides increase with increasing atomic
number from Mg(OH)
2
to Ba (OH)
2
. The alkaline earth metal hydroxides are however, less basic and less
stable than alkali metal hydroxides. Beryllium hydroxide is amphoteric in nature as it reacts with acid and
alkali both.
Be(OH)
2
+ 2OH

[Be(OH)
4
]
2
(beryllate ion)
Be(OH)
2
+ 2HCl + 2H
2
O [Be(H
2
O)
4
]Cl
2
.
The anhydrous halides of alkaline earth metals are polymeric .Except for berylliumhalides, all other halides
of alkaline earth metal are ionic in nature. Berylliumhalides are essentially covalent and soluble in organic
solvents. Berylliumchloride vapour contains BeCl
2
and (BeCl
2
)
2
but the solid is polymerised.
Berylliumchloride in the solid state has a chain structure as shown below:
Cl Be Cl
Be
Cl
Cl
Be Be
Cl
Cl
In the vapour phase BeCl
2
tends to forma chloro-bridged dimer which dissociates into the linear monomer at
high temperature of the order of 1200 K. The tendency to form halide hydrates gradually decreases (for
example, MgCl
2
.6H
2
O, CaCl
2
.6H
2
O, SrCl
2
.6H
2
O and BaCl
2
.2H
2
O) down the group. The dehydration of
hydrated chlorides, bromides and iodides of Ca, Sr and Ba can be achieved on heating; however, the
corresponding hydrated halides of Be and Mg on heating suffer hydrolysis. The fluorides are relatively less
soluble than the chlorides owing to their high lattice energies.
Carbonate of alkaline earth metals are insoluble in water and can be precipitated by addition of a sodiumor
ammoniumcarbonate solution to a solution of a soluble salt of these metals. The solubility of carbonates in
water decreases as the atomic number of the metal ion increases. All carbonates decompose on heating to
give carbon dioxide and the oxide. Berylliumcarbonate is unstable and can be kept only in the atmosphere
of CO
2
. The thermal stability increases with increasing cationic size.
The sulphates of the alkaline earth metals are all white solid and stable to heat. BeSO
4
and MgSO
4
are
readily soluble in water; the solubility decreases fromCaSO
4
to BaSO
4
. The greater hydration enthalpies of
Be
2+
and Mg
2+
ions overcome the lattice enthalpy factor and therefore their sulphates are soluble in water.
The nitrates are made by dissolution of the carbonate in dilute nitric acid, magnesium nitrate crystallises
with six molecules of water, whereas barium nitrate crystallises as the anhydrous salt. This again show a
decreasing tendency to formhydrates with increasing size and decreasing hydration enthalpy. All of them
decompose on heating to give the oxide like lithiumnitrate.
2M (NO
3
)
2
2MO + 4 NO
2
+ O
\2
(M = Be, Mg, Ca,Sr,Ba)
The solubility of the alkaline earth metal salts except hydroxides and fluorides decreases down the group
from Be to Ba. This is because of the fact that down the group with increasing size of cation the lattice
energy as well as hydration energy also decrease but the change in hydration energy is more as compare to
that of lattice energy. Except BeF
2
all other fluorides are water insoluble. Solubility of beryllium fluoride in
water is due to higher solvation energy on account of higher polarising power of Be
2+
.
The thermal stability of oxy-acid salts of alkaline earth metals generally increases down the group with
increasing metallic character, i.e. electropositive character.
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Example-5 Select the correct set of statements.
(i) Solubility of alkali metal hydroxides is in order,
CsOH > RbOH > KOH >NaOH> LiOH
(ii) Solubility of alkali carbonates is in order,
Li
2
CO
3
> Na
2
CO
3
> K
2
CO
3
> Rb
2
CO
3
> Cs
2
O
3
(iii) Hydrated radii is in order,
Li
+
< Na
+
<K
+
< Rb
+
< Cs
+
(iv) Stability of peroxides is in order,
Na
2
O
2
< K
2
O
2
< Rb
2
O
2
< Cs
2
O
2
The options are :
(A) (i) , (iv) (B) (i), (iii) (C) (ii), (iii), (iv) (D) All
Solution (i) From going lithium to cesium hydroxide the decrease in lattice energy is more as compared to
that of hydration energy. So, the solubility of hydroxides increases down the group.
(iv) This is because of fact that bigger cation stabilises the bigger anion through crystal lattice
energy.
Therefore (A) option is correct.
ANOMALOUS PROPERTIES OF LITHIUM
The anomalous behavior of lithiumis due to the : (i) exceptionally small size of its atomand ion, and (ii) high
polarising power (i.e., charge/ radius ratio ). As a result, there is increased covalent character of lithium
compoundwhichis responsiblefor their solubilityinorganic solvent. Further, lithiumshows diagonal relationship
to magnesium.
Points of Difference between Lithium and other Alkali Metals
Lithiumis much harder. Its melting point and boiling point are higher than the other alkali metals.
Lithiumis least reactive but the strongest reducing agent among all the alkali metals. On combustion
in air it forms mainly monoxide, Li
2
O and the nitride, Li
3
N unlike other alkali metals.
The lithiumion itself, and also its compounds are more heavily hydrated than those of the rest of the
group. LiCl is deliquescent and crystallises as a hydrate, LiCl. 2H
2
O whereas other alkali metal
chlorides do not formhydrates.
Lithium hydrogencarbonate is not obtained in the solid form while all other elements form solid
hydrogencarbonates.
Lithiumunlike other alkali metal forms no ethynide on reaction with ethyne.
Lithiumnitrate when heated gives lithiumoxide, Li
2
O, whereas other alkali metal nitrates decompose
to give the corresponding nitrite.
4LiNO
3
2 Li
2
O + 4 NO
2
+ O
2
2NaNO
3
2NaNO
2
+ O
2
; 4NaNO
3
2Na
2
O+ 5O
2
+ 2N
2
2NaNO
2
+ 2HCl 2NaCl + H
2
O+ NO
2
+ NO; 2NO + O
2

2NO
2
2NaNO
3
+ C

2NaNO
2
+ CO
2
.
KNO
3
+ Zn

KNO
2
+ ZnO .
LiF and Li
2
Oare comparatively much less soluble in water than the corresponding compounds of
other alkali metals.
Lithium hydroxide is less basic than the other hydroxides in the group and therefore, many of its
salts are less stable, Li
2
CO
3
, LiNO
3
and LiOH all form the oxides on gentle heating; the analogus
compounds of the rest of the group are stable. Another example of its less basic nature is that
though lithiumforms a bicarbonates in solution, it does not forma solid bicarbonate, where as the
other all formstable solid carbonates.
Lithiumreacts directly with carbon to formanionic carbide. None of the other group 1 elements do
this, but group 2 elements all react similarly with carbon.
Lithiumhas a great tendency to formcomplexes than have the heavier elements, and ammoniated
salts such as [Li(NH
3
)
4
]
+
exist as solids.
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CHEMISTRY
Example-6 Which of the following alkali metal ions has the lowest mobility in aqueous solution ?
(A) Li
+
(B) Na
+
(C) K
+
(D) Cs
+
Solution Because Li
+
has the smallest size, so it is highly hydrated and its effective size becomes larger
therefore mobility decreases in aqueous medium.
Therefore (A) option is correct.
Example-7 Give the reaction of the thermal decomposition of the nitrate of sodium. Explain the occurrence of
the reaction in term of energy factor. What is the pH expected of an aqueous solution of NaNO
3
.
Why?
Solution NaNO
3
(s) NaNO
2
(s) +
2
1
O
2
(g)
Since the size of NO
2

is less than that of NO

3

, this results into formation of a more stable ionic

lattice when bonded to sodiumion. The pHof solution would be about 7 since neither the cation nor
the anion undergoes hydrolysis to any appreciable extent.
Points of Similarities between Lithiumand Magnesium
The similarity between lithium and magnesium is particularly striking and arises because of their
similar size: atomic radii, Li = 152 pm, Mg = 160 pm; ionic radii : Li
+
= 76 pm, Mg
2+
= 72 pm. The
main points of similarity are :
Both lithiumand magnesiumare harder and lighter than other elements in the respective groups.
Lithiumand magnesiumreact slowly with water. Their oxides and hydroxides are much less soluble
and their hydroxides decompose on heating. Both forma nitride, Li
3
N and Mg
3
N
2
, by direct
combination with nitrogen .
The oxides, Li
2
Oand MgOdo not combine with excess oxygen to give any superoxide.
The carbonates of lithiumand magnesiumdecompose easily on heating to formthe oxides and
CO
2
. Solid hydrogencarbonates are not formed by lithiumand magnesium.
Both LiCl and MgCl
2
are soluble in ethanol.
Both LiCl and MgCl
2
are deliquescent and crystallise fromaqueous solution as hydrates, LiCl.2H
2
O
and MgCl
2
.6H
2
O.
Example-8 About alkali metal-liquid NH
3
solution which of following statement is not true ?
(A) Blue colour is due to ammoniated electrons.
(B) Blue colour changes to bronze on dilution due to formation of metal ion clusters.
(C) With increase in concentration of alkali metals paramagnetic nature decreases due to electron
electron combination.
(D) On heating blue colour becomes colourless due to formation of metal amide and H
2
gas.
Solution Blue colour changes to bronze with increase in concentration of alkali metal due to formation of
metal ion clusters.
Therefore (B) option is correct.
Example-9 (A) Give the three different crystal structures of NaO
2
?
(B) Sodium sulphide is readily oxidised by air to form sodium thiosulphate. Write the chemical
reaction only.
(C) Group 1 sulphides hydrolyse appreciably in water, giving strongly alkaline solutions. Explain ?
Solution (A) NaO
2
exists in following three different crystal structures at different temperatures.
(i) Marcasite structure at 50C,
(ii) Pyrite structure between 77Cand 50C,
(iii) Calciumcarbide structure at roomtemperature.
(B) 2Na
2
S + 2O
2
+ H
2
O Na
2
S
2
O
3
+ 2NaOH
(C) Na
2
S hydrolyses in water according to the following reaction,
2Na
2
S + H
2
O NaSH + NaOH
Example-10 The properties of Li are similar to those of Mg. This is because,
(A) both have nearly the same size.
(B) the ratio of their charge to size is nearly the same.
(C) both have similar electronic configurations.
(D) both are found together in nature.
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CHEMISTRY
Solution They are diagonally related because of same polarising power.
polarising power = charge on cation / size of cation
Therefore, (B) option is correct.
Example-111 Melting point of calciumhalides decreases in the order,
(A) CaF
2
> CaCl
2
> CaBr
2
> CaI
2
(B) CaI
2
> CaBr
2
> CaCl
2
> CaF
2
(C) CaBr
2
> CaI
2
> CaF
2
> CaCl
2
(D) CaCl
2
> CaBr
2
> CaI
2
> CaF
2
Solution As the size of anion increases the covalent character increases according to Fajans rule and thus
melting point decreases.
Therefore, (A) option is correct.
Example-12 Magnesiumburns in air to give :
(A) MgO (B) Mg
3
N
2
(C) MgCO
3
(D) MgOand Mg
3
N
2
both
Solution Mg burns in air to formboth MgOand Mg
3
N
2
2Mg + O
2

A
2MgO ; 3Mg + N
2

A
Mg
3
N
2
Therefore, (D) option is correct.
Example-13 Among the following which of the peroxides is thermally most stable ?
SrO
2
, MgO
2
, CaO
2
, BaO
2
Solution Stability of the peroxide increases as the size of metal increases because the bigger cation stabilizes
bigger anion and vice-versa through crystal lattice energy. Thus BaO
2
is most stable.
ANOMALOUSBEHAVIOUROFBERYLLIUM
Beryllium the first member of the Group 2 metals, shows anomalous behaviour as compared to
magnesiumand rest of the members. Further, it shows diagonal relationship to aluminium.
Berylliumhas exceptionally small atomic and ionic sizes and thus does not compare well with other
members of the group. Because of high ionisation enthalpy and small size it forms compound which
are largely covalent and get easily hydrolysed.
Berylliumdoes not exhibit coordination number more than four as in its valence shell there are only
four orbitals. The remaining member of the group can have a coordination number of six by making
use of d-orbitals.
The oxide and hydroxide of beryllium, unlike the hydroxides of other elements in the group, are
amphoteric in nature.
The berylliumhydride is electron deficient and polymeric, with multi-center bonding like aluminium
hydride.
The most unusual oxygen containingcomplexes of Be have formula Be
4
O(O
2
CR)
6
and are formed by
refluxing Be(OH)
2
with carboxylic acids. These white crystalline compounds are soluble in non-polar
organic solvents, such as alkanes, but are insoluble in water and lower alcohol. In solution, the
compounds are unionised and monomeric.
The central oxygen atom is tetrahedrally surrounded by the four Be atoms and each Be atom is
tetrahedrally surrounded by four oxygen atoms. The six acetate groups are arranged along the six
edges of the tetrahedral ion.
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CHEMISTRY
Diagonal Relationship between Beryllium and Aluminium
The ionic radius of Be
2+
is estimated to be 31 pm; the charge/radius ratio is nearly the same as that
of the Al
3+
ion. Hence berylliumresembles aluminiumin some ways. Some of the similarities are:
Like aluminium, berylliumis not readily attacked by acids because of the presence of an oxide film
on the surface of the metal, i.e. they are rendered passive by nitric acid.
Berylliumhydroxide dissolves in excess of alkali to give a beryllate ion, [ Be(OH)
4
]
2
just as aluminium
hydroxide gives aluminate ion, [Al(OH)
4
]

The chlorides of both berylliumand aluminiumhave Cl

bridged chloride structure in vapour phase.

Both the chloride are soluble in organic solvents and are strong Lewis acids They are used as
Friedel Craft catalysts.
Berylliumand aluminiumions havestrongtendencytoformcomplexes, BeF
4
2
andAlF
6
3
respectively.
COMPOUNDS OF ALKALI METALS :
SODIUMOXIDE (Na
2
O) :
PREPARATION:
By reduction of nitrites and nitrates of sodiumwith metallic sodium:
2NaNO
3
+ 10Na 6Na
2
O + N
2
; 2NaNO
2
+ 6Na 4Na
2
O+ N
2
By heating sodiumin limited supply of air at 180C :
Na + O
2
Na
2
O
Pure sodiumoxide is formed when the mixture of sodiumazide and sodiumnitrite is heated
3NaN
3
+ NaNO
2
2Na
2
O+ 5N
2
PROPERTIES:
It is a white amorphous substance. It reacts with water violently forming sodium hydroxide and
evolving a large amount of heat energy
Na
2
O + H
2
O 2NaOH
On heating at 400C, it decomposes forming sodiumperoxide and metallic sodiumvapour.
2Na
2
O
C 400
Na
2
O
2
+ 2Na
Reaction with liquid ammonia
Na
2
O + NH
3
NaNH
2
+ NaOH
USE: It is used as dehydrating and polymerising agent in organic chemistry.
SODIUMPEROXIDE(Na
2
O
2
) :
PREPARATION:
It is formed by heating sodiumin excess of air free frommoisture and carbon dioxide or in excess of
pure oxygen.
2Na + O
2
(excess)
C 350
Na
2
O
2
Industrial method : It is a two stage reaction in the presence of excess air.
2Na +
2
1
O
2
Na
2
O ; Na
2
O+
2
1
O
2
Na
2
O
2
PROPERTIES:
It is a pale yellow(when impure) hygroscopic powder stable towards heat in dry air. On exposure to
moist air, it becomes white as it reacts with moisture and carbon dioxide.
2Na
2
O
2
+ 2H
2
O 4NaOH + O
2
2NaOH+ CO
2
Na
2
CO
3
+ H
2
O; 2Na
2
O
2
+ 2CO
2
2Na
2
CO
3
+ O
2
Action of water :
Na
2
O
2
+ 2H
2
O
cold
2NaOH + H
2
O
2
; 2Na
2
O
2
+ 2H
2
O
warm
4NaOH + O
2
Action of acid :
Na
2
O
2
+ H
2
SO
4

cold
Na
2
SO
4
+ H
2
O
2
; 2Na
2
O
2
+ H
2
SO
4

warm
2Na
2
SO
4
+ 2H
2
O + O
2
Reaction with COand CO
2
:
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11
CHEMISTRY
Na
2
O
2
+ CO Na
2
CO
3
; 2Na
2
O
2
+ 2CO
2
2Na
2
CO
3
+ O
2
So, it is used to purify the air in submarine and confined spaces as it removes both COand CO
2
and
gives oxygen.
As an oxidising agent : It is a powerful oxidant and many of its reactions are dangerously violent,
particularlywith the reducing agents, such asAl powder, charcoal, sulphur and many organic liquids.
(a) Chromic compounds are oxidised to chromates
2Cr(OH)
3
+ 3Na
2
O
2
2Na
2
CrO
4
+ 2NaOH+ 2H
2
O
or
2Cr(OH)
3
+ 3O
2
2
2CrO
4
2
+ 2OH

+ 2H
2
O
(b) Manganous salt is oxidised to sodiummanganate.
MnSO
4
+ 2Na
2
O
2
Na
2
MnO
4
+ Na
2
SO
4
or
Mn(OH)
2
+ 2O
2
2
MnO
4
2
+ 2OH

(c) Sulphides are oxidised to corresponding sulphates

Na
2
O
2
Na
2
O+ [O] ; Na
2
S + 4[O] Na
2
SO
4
(d) Na
2
O
2
Na
2
O+ [O] ; 2Al + 3 [O] Al
2
O
3
Benzoyl peroxide (bleaching agent) is formed when C
6
H
5
COCl reacts with Na
2
O
2
.
2C
6
H
5
COCl + Na
2
O
2
(C
6
H
5
CO)
2
O
2
(benzoyl peroxide) + 2NaCl
Reduces stronger oxidising agent such as acidified KMnO
4
2MnO
4

+ 16H
+
+ 5O
2
2
2Mn
2+
+ 8H
2
O+ 5O
2
Na
2
O
2
+ O
2
atm 300
450


2NaO
2
USE:
Used for the production of oxygen under the name oxone.
It is used as bleaching agent for bleaching wood pulp, paper and fabrics such as cotton and linen.
POTASSIUMSUPEROXIDE(KO
2
) :
PREPARATION:
It is prepared by burning potassiumin excess of oxygen free frommoisture.
K + O
2
KO
2
;
PROPERTIES:
It is a orange coloured (chrome yellow) powder and reacts with water accordingto followingreaction.
2KO
2
+ 2H
2
O 2KOH + H
2
O
2
+ O
2
It reacts directly with CO and CO
2
.
2KO
2
+ CO K
2
CO
3
+ O
2
; 2KO
2
+ CO
2
K
2
CO
3
+
2
3
O
2
If more CO
2
, in presence of moisture is present; then
4KO
2
+ 4CO
2
+ 2H
2
O 4KHCO
3
+ 3O
2
On heating with sulphur, it forms potassiumsulphate
2KO
2
+ S K
2
SO
4
USE:
It is used as an oxidising agent and air purifier in space capsules, submarine and breathing mask as it
produces O
2
and removes CO
2
.
POTASSIUMSESQUIOXIDE (K
2
O
3
) :
It is obtained when oxygen is passed through liquid ammonia containing potassium.
4K (dissolved in liquid NH
3
)
2
O 3
2K
2
O
3
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CHEMISTRY
SODIUMHYDROXIDEORCAUSTICSODA(NaOH) :
PREPARATION: It is most conveniently manufactured by one of the following processes.
(a) Methods involving sodium carbonate as a starting material :
Gossageprocess (causticisingprocess) :
Na
2
CO
3
+ Ca(OH)
2
CaCO
3
+ 2NaOH
The most suitable concentration of sodiumcarbonate taken in this process is 15 20%. The caustic soda
produced by this method is not pure and contains some calciumcarbonate, sodiumcarbonate and calcium
hydroxide as impurities.
Lowigs process :
Na
2
CO
3
+ Fe
2
O
3

heat red
2NaFeO
2
+ CO
2
The sodiumferrite is cooled and thrown into hot water, the hydrolysis of sodiumferrite occurs forming NaOH.
2NaFeO
2
+ H
2
O 2NaOH + Fe
2
O
3
Methods involving sodiumchloride as starting material :
Electrolysis of sodiumchloride solution occurs according to following principle.
NaCl Na
+
+ Cl ; H
2
O H
+
+ OH
On passing electricity, Na
+
and H
+
ions move towards cathode and Cl and OH ions move towards anode.
The discharge potential of H
+
ions is less than Na
+
ions, thus hydrogen ions get discharged easily and
hydrogen is liberated. Similarly, at anode Cl ions are easily discharged as their discharge potential is less
than that of OH ions. Cl
2
gas is, therefore, liberated at anode.
It is necessary that chlorine should not come in contact with sodiumhydroxide during electrolysis, otherwise
following reaction take place.
2NaOH + Cl
2
NaCl + NaClO + H
2
O
To overcome this problem, the anode is separated fromthe cathode in the electrolytic cell either by using a
porous diaphragmor by using a mercury cathode.
(a) The mercury cathode cell (Castner-Kellner cell) :
In this cell mercury flows along the bottomof the cell and is made cathode (as shown in figure (a)). The brine
solution flows in the same direction and anode consists of a number of graphite blocks. The brine electrolyzes
and since, hydrogen has a high overvoltage at mercury cathode, sodiumis preferentially discharged forming
amalgamwith mercury.
The sodiumamalgamflows out and is reacted with water to give NaOH
2NaHg + 2H
2
O2NaOH+ 2Hg + H
2
The mercury is re-circulated to the cell. Hydrogen and chlorine are the two important by-products.
(b) Diaphragm cell :
In this type of cell (as shown in figure (b)) alkali and chlorine are kept separate by use of a diaphragm
and on contact with a negative wire gauze, electrolysis begins. Chlorine is liberated at graphite anode and
sodiumhydroxide is formed at the outside edges of cathode.
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13
CHEMISTRY
(c) Using Nafion Membrane Cell :
The natural brine (NaCl) is nowelectrolysed in a membrane cell in which the anolyte and the catholyte
areseparatedbyaNAFIONmembrane. Nafionis acopolymer of tetrafluoromethyleneandpentafluorosulphonyl
ethoxyether. The copolymer is supported by a Teflon mesh.
2NaCl (aq) + H
2
O()

is Electrolys
2NaOH(aq) + H
2
(g) + Cl
2
(g)
Presently the method makes use of Nafion membrane in place of diaphragm.
Preparation of pure sodium hydroxide :
Commercial sodium hydroxide is purified with the help of alcohol. Sodium hydroxide dissolves in alcohol
while impurities like NaCl, Na
2
CO
3
, Na
2
SO
4
etc., remain insoluble. The alcoholic filtrate is distilled. The
alcohol distills off while pure solid sodiumhydroxide is left behind.
PROPERTIES:
(i) It is a white crystalline solid and has soapy touch.
(ii) Its density is 2.13 g/mL and melting point is 318.4C.
(iii) It is highly soluble in water and is bitter in taste, and is corrosive in nature.
(iv) Neutralisation and hydrolysis reactions :
3NaOH + H
3
PO
4
Na
3
PO
4
+ 3H
2
O ; NaOH + HNO
3
NaNO
3
+ H
2
O
These are non-redox type of reactions.
(v) Reaction with acidic oxides :
2NaOH + CO
2
Na
2
CO
3
+ H
2
O
2NaOH + 2NO
2
NaNO
2
+ NaNO
3
+ H
2
O; 2NaOH + SO
3
Na
2
SO
4
+ H
2
O
(vi) Reaction with amphoteric oxides :
PbO + 2NaOH Na
2
PbO
2
+ H
2
O; ZnO+ 2NaOH Na
2
ZnO
2
+ H
2
O
SnO + 2NaOH Na
2
SnO
2
+ H
2
O; SnO
2
+ 2NaOH Na
2
SnO
3
+ H
2
O
(vii) Reaction with non-metals :
(a) Halogens
With cold & dilute NaOH :
2NaOH + Br
2
NaBr + NaOBr + H
2
O
With hot & concentrated NaOH:
6NaOH + 3Br
2
5NaBr + NaBrO
3
+ 3H
2
O
F
2
with cold & dilute NaOH gives OF
2
and with hot & concentrated NaOH gives O
2
(b) With white phosphours :
3NaOH + P
4
3NaH
2
PO
2
+ PH
3
(c) With sulphur :
6NaOH + 4S 2Na
2
S + Na
2
S
2
O
3
+ 3H
2
O
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CHEMISTRY
(d) With boron :
2B + 6NaOH 2Na
3
BO
3
+ 3H
2
(e) With silicon :
2NaOH + Si + H
2
O Na
2
SiO
3
+ 2H
2
(viii) Reaction with metals and salts :
(a) Reaction with amphoteric metals (e.g. Al, Pb, Sn, Zn etc.) :
They liberate hydrogen gas.
4NaOH + 2H
2
O+ 2Al 2NaAlO
2
+ 3H
2
6NaOH + 2Al 2Na
3
AlO
3
+ 3H
2
; Zn + NaOH Na
2
ZnO
2
+ H
2
(b) Reaction with salts of amphoteric metals :
Salts dissolves in sodiumhydroxide (excess)
SnCl
2
+ 2NaOH Sn(OH)
2
+
(white) + 2NaCl
Sn(OH)
2
+ 2NaOH Na
2
SnO
2
+ 2H
2
O
(c) Reaction with salts of Cr, Ni, Fe, Mn, Cu etc., :
Forminsoluble hydroxides
CrCl
3
+ 3NaOH Cr(OH)
3
+
(green) + 3NaCl
CuCl
2
+ 2NaOH Cu(OH)
2
+
(blue) + 2NaCl
(d) Reaction with salts of Hg and Ag :
HgCl
2
+ 2NaOH Hg(OH)
2
+
+ 2NaCl ; Hg(OH)
2
HgO
+
(yellowor brown) + H
2
O
2AgNO
3
+ 2NaOH 2AgOH+ 2NaNO
3
; 2AgOH Ag
2
O
+
(black) + H
2
O
(e) Reaction with ammoniumsalts : It liberates ammonia fromboth ammoniumsalts and coordination
complexes where ammonia acts as ligand.
(NH
4
)
2
SO
4
+ NaOH
A
Na
2
SO
4
+ 2NH
3
+ 2H
2
O
6NaOH+ 2 [Co(NH
3
)
6
]Cl
3
12NH
3
+ Co
2
O
3
+ 6NaCl + 3H
2
O
(ix) Reaction with carbon monoxide :
NaOH+ CO
atm 10 5
C 200 150

HCOONa
(x) Reaction with H
2
S :
NaOH + H
2
S NaSH + H
2
O ; NaSH + NaOH Na
2
S + H
2
O.
It is used to remove mercaptans frompetroleumproducts.
(xi) Reaction with alcohols :
NaOH + EtOH NaOEt + H
2
O.
Caustic property
Sodiumhydroxide is a powerful cautery and breaks down the proteins of skin to a pasty mass. On account
of this property, it is commonly called caustic soda.
POTASSIUM HYDROXIDE (KOH) :
It is prepared by electrolysis of KCl solution.
KOHresembles NaOHin all its reactions. However KOHis much more soluble in alcohol. This accounts for
the use of alcoholic KOH in organic chemistry.
KOHis called caustic potash, because of their corrosive properties (for example on glass or on skin) and its
aqueous solution is known as potash lye.
2KOH + 4NO 2KNO
2
+ N
2
O+ H
2
O
4KOH + 6NO 4KNO
2
+ N
2
+ 2H
2
O
It is used for the absorption of gases like CO
2
, SO
2
, etc. It is used for making soft soaps.
SODIUMCARBONATEORWASHINGSODA(Na
2
CO
3
.10H
2
O) :
PREPARATION:
By Solvay ammonia soda process :
It involves followings steps.
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CHEMISTRY
(a) Saturation of brine with ammonia and CO
2
(In ammonia absorber) :
2NH
3
+ CO
2
+ H
2
O (NH
4
)
2
CO
3
CaCl
2
+ (NH
4
)
2
CO
2
CaCO
3
+
+ 2NH
4
Cl ; MgCl
2
+ (NH
4
)
2
CO
3
MgCO
3
+
+ 2NH
4
Cl
Ammoniated brine is filtered to remove calcium and magnesium impurities as their insoluble
carbonates.
(b) Formation of insoluble NaHCO
3
(In carbonation tower) :
NH
3
+ CO
2
+ H
2
O NH
4
HCO
3
; NH
4
HCO
3
+ NaCl

C 30
NaHCO
3
+ NH
4
Cl
Reaction is exothermic and hence there is a cooling arrangement.
NaHCO
3
is insoluble in cold brine solution because of the common ion effect. It is separated by
filtration and the filtered is used for recovering NH
3
&CO
2
(c) Calcination to get sodiumcarbonate :
2 NaHCO
3

C 150
Na
2
CO
3
+ CO
2
+ H
2
O
(d) Recovery of ammonia and carbondioxide (In recovery tower) :
NH
4
HCO
3
) steam (

A
NH
3
+ CO
2
+ H
2
O ; 2NH
4
Cl + Ca(OH)
2
) steam (

A
2NH
3
+ 2H
2
O+ CaCl
2
CaCl
2
is obtained as by product.
(e) Preparation of CO
2
(In lime kiln) :
CaCO
3
K 1375
CaO+ CO
2
; CaO+ H
2
O Ca(OH)
2
(slaked lime)
Le-Blanc process : It involves following steps
(a) NaCl + H
2
SO
4
(conc.)
furnace

A
NaHSO
4
(salt cake) + HCl
(b) NaHSO
4
+ NaCl
furnace

A
Na
2
SO
4
+ HCl
(c) Na
2
SO
4
+ CaCO
3
+ 4C
furnace

A

ash Black
3 2
CaS CO Na + + 4CO
Black ash contains 45% Na
2
CO
3
is extracted with water when Na
2
CO
3
dissolves leaving behind
insoluble as impurities called as alkali sludge or waste.
PROPERTIES:
It is white crystalline solid. It is known in several hydrated forms. The common formis decahydrate,
Na
2
CO
3
.10H
2
O. This formis calledwashingsoda. Thedecahydrateformonstandinginair effloresces
and crumbles to powder. It is the monohydrate, Na
2
CO
3
.H
2
O.
It is soluble in water with evolution of considerable amount of heat. The solution is alkaline in nature
due to hydrolysis.
Na
2
CO
3
+ 2H
2
O 2NaOH + H
2
CO
3
Na
2
CO
3
+ NO+ NO
2
2NaNO
2
+ CO
2
Bicarbonates precipitate normal carbonates while carbonates precipitate basic carbonates from
some metal salt solutions.
MgCl
2
+ NaHCO
3
MgCO
3
+
+ 2NaCl + CO
2
+ H
2
O
MgCl
2
+ 2Na
2
CO
3
+ H
2
O MgCO
3
. Mg(OH)
2
+
+ 4NaCl + CO
2
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CHEMISTRY
NaNO
3
+ HCl KNO
3
+ NaCl
POTASSIUM CARBONATE, POTASH OR PEARL ASH (K
2
CO
3
) :
PREPARATION:
By Le-Blanc process :
KCl + H
2
SO
4
KHSO
4
+ HCl
KHSO
4
+ KCl K
2
SO
4
+ HCl
K
2
SO
4
+ CaCO
3
+ 2C K
2
CO
3
+ CaS + 2CO
2
By Prechts process :
(a) 2KCl + 3(MgCO
3
. 3H
2
O) + CO
2
2(Mg CO
3
. KHCO
3
. 4H
2
O) + MgCl
2
(b) 2(MgCO
3
. KHCO
3
. 4H
2
O)
C 140
2Mg CO
3 +
+ K
2
CO
3
+ 9H
2
O+ CO
2
or
2(MgCO
3
. KHCO
3
. 4H
2
O) + MgO
C 20
3(Mg CO
3
. 3H
2
O)
+
+ K
2
CO
3
It is a white powder and deliquescent in nature. The mixture of K
2
CO
3
and Na
2
CO
3
is used as a fusion
mixture in laboratory.
2HNO
3
+ K
2
CO
3
2KNO
3
+ CO
2
+ H
2
O
The potassium carbonate like sodium carbonate, can not be prepared by Solvay process because the
intermediate, KHCO
3
formed is soluble in appreciable amount in water.
SODIUMBICARBONATEORBAKINGSODA(NaHCO
3
) :
It is obtained as the intermediate product in the Solvay ammonia soda process. Normal carbonate can be
changed to bicarbonate by passing carbon dioxide through its saturated solution.
Na
2
CO
3
+ CO
2
+ H
2
O 2NaHCO
3
(sparingly soluble)
PROPERTIES:
It is a white crystalline solid, sparingly soluble in water. The solution is alkaline in nature due to hydrolysis.
The solution is weakly basic and gives yellowcolour with methyl orange but no colour with phenolphthalein.
NaHCO
3
+ H
2
O NaOH + H
2
CO
3
On heating, it loses carbon dioxide and water forming sodiumcarbonate.
2NaHCO
3
Na
2
CO
3
+ H
2
O + CO
2
USE:
It is largely used for making baking powder. Baking powder contains NaHCO
3
, Ca(H
2
PO
4
)
2
and starch. The
Ca(H
2
PO
4
) is acidic and when water is added, it reacts with NaHCO
3
, giving CO
2
. The starch is a filler.
Improved baking powder contains about 40%starch, 30%NaHCO
3
, 20%NaAl(SO
4
)
2
and 10%Ca(H
2
PO
4
)
2
.
The NaAl(SO
4
)
2
slows the reaction down so the CO
2
is given off more slowly.
Example-14 What happens when ?
(A) Anhydrous potassiumnitrate is heated with excess of metallic potassium.
(B) Solution containing sodiumcarbonate and sodiumsulphide is treated with sulphur dioxide.
Solution (A) 2KNO
3
+ 10 K 6K
2
O + N
2
(B) Na
2
CO
3
+ 2Na
2
S + 4SO
2
3Na
2
S
2
O
3
+ CO
2
SODIUMSULPHATE(Na
2
SO
4
.10H
2
O) :
It is also known as Glaubers salt.
PREPARATION:
By heating NaCl with concentrated. H
2
SO
4
:
2NaCl + H
2
SO
4
Na
2
SO
4
+ 2HCl
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CHEMISTRY
By Hargreaves process :
4NaCl (dry lumps) + 2SO
2
(g) + 2H
2
O(g) + O
2
(g) 2Na
2
SO
4
+ 4HCl
PROPERTIES:
It is a white crystalline solid and effloresces readily in dry air to formanhydrous sodiumsulphate.
It is reduced to sodiumsulphide when heated with carbon.
Na
2
SO
4
+ 4C Na
2
S + 4 CO |
It forms sodiumbisulphate when reacted with concentrated H
2
SO
4
.
Na
2
SO
4
+ H
2
SO
4
2NaHSO
4
Reaction with metal salts.
BaCl
2
+ Na
2
SO
4
BaSO
4
+ + 2NaCl ; Pb(NO
3
) + Na
2
SO
4
PbSO
4
+ + 2NaNO
3
POTASSIUM SULPHATE (K
2
SO
4
) :
PREPARATION:
It is prepared by the reaction of potassiumchloride or hydroxide with concentrated. H
2
SO
4
.
2KCl + H
2
SO
4
K
2
SO
4
+ 2HCl ; 2KOH + H
2
SO
4
K
2
SO
4
+ 2H
2
O ;
K
2
SO
4
. MgSO
4
. 6H
2
O+ 2KCl 2K
2
SO
4
+ MgCl
2
+ 6H
2
O
PROPERTIES:
It is a white crystalline solid and soluble in water . It is used as a fertilizer for tobacco and wheat.
Example-15 KO
2
+ CO
2
+ H
2
O
2
CO more
[X] + [Y]
Products [X] and [Y] are respectively :
(A) K
2
CO
3
, O
2
(B) KHCO
3
, O
2
(C) KOH , K
2
CO
3
(D) KHCO
3
, H
2
O
Solution 4 KO
2
+ 4CO
2
+ 2H
2
O
2
CO more
4KHCO
3
+ 3O
2
Therefore, (B) option is correct.
Example-16 A compound of sodiumwhich when heated gives CO
2
is :
(A) Na
2
CO
3
. 10H
2
O (B) NaHCO
3
(C) Na
2
CO
3
. 7H
2
O (D) Na
2
CO
3
. H
2
O
Solution NaHCO
3
is less stable, on heating decomposes to give CO
2
2NaHCO
3
Na
2
CO
3
+ CO
2
+ H
2
O
Therefore, (B) option is correct.
Example-17 Why white deposit in glass vessel containing NaOHsolution is noticed after some time?
Solution SiO
2
present in glass reacts with NaOH to give insoluble silicate.
2NaOH + SiO
2
Na
2
SiO
3
+ H
2
O
Example-18 Sodium super oxide can not be prepared directly from sodium, but from Na
2
O
2
. Write balanced
chemical equation.
Solution Sodiumsuper oxide can not be prepared directly fromsodiumbecause Na
+
is smaller cation and O
2

is bigger. Na
2
O
2
+ O
2
atm 300
C 450
2 NaO
2
COMPOUNDS OF ALKALINE EARTH METALS :
MAGNESIUMOXIDE ORMAGNESIA(MgO) :
PREPARATION:
it can be prepared by following reaction.
2Mg + O
2

burning
2MgO ; Mg(OH)
2

heated
MgO + H
2
O
2Mg(NO
3
)
2

heated
2MgO + 4NO
2
+ O
2
; MgCO
3

heated
MgO + CO
2
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18
CHEMISTRY
PROPERTIES:
It is slightly soluble in water and forms magnesiumhydroxide.
MgO + H
2
O Mg(OH)
2
It is basic in nature. It reacts with acids to form corresponding salts.
MgO + 2HCl MgCl
2
+ H
2
O
It is reduced by carbon at very high temperature.
MgO + C Mg + CO
Magnesiumoxide when mixed with a saturated solution of magnesiumchloride sets to a hard mass
like cement known as magnesia cement or Sorels cement. The composition is MgCl
2
.5MgO.xH
2
O.
MAGNESIUMHYDROXIDE [Mg(OH)
2
]
PREPARATION:
MgO + H
2
O Mg(OH)
2
MgCl
2
+ Ca(OH)
2
Mg(OH)
2
+ CaCl
2
,
MgCl
2
+ 2NaOH Mg(OH)
2
+ 2NaCl
PROPERTIES:
It is a white powder. It is sparingly soluble in water. It is basic in nature and forms salt with acids. It
decomposes on heating. It readilydissolves in ammoniumchloride solution and is, therefore, not precipitated
in group III
rd
of qualitative analysis.
Mg(OH)
2
+ 2NH
4
Cl MgCl
2
+ 2NH
4
OH
USE:
A suspension of Mg(OH)
2
in water is used in medicine as an antacid under the name, milk of magnesia.
MAGNESIUM CHLORIDE (MgCl
2
.6H
2
O)
It occurs in nature as mineral carnallite, KCl, MgCl
2
.6H
2
O.
PROPERTIES:
It is a colourless crystalline solid, highly deliquescent and highly soluble in water.
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CHEMISTRY
QUICK LIME, SLAKED LIME AND LIME WATER.
3Ca(OH)
2
+ 2Cl
2
Ca(OCl)
2
. Ca(OH)
2
. CaCl
2
. 2H
2
O(bleaching powder).
MAGNESIUM CARBONATE (MgCO
3
)
PREPARATION:
It can be prepared by adding sodiumbicarbonate to a hot solution of magnesiumsalt.
MgSO
4
+ 2NaHCO
3
MgCO
3
+ Na
2
SO
4
+ H
2
O + CO
2
2MgSO
4
+ 2Na
2
CO
3
+ H
2
O MgCO
3
. Mg(OH)
2
+ 2Na
2
SO
4
+ CO
2
When CO
2
gas is passed through the suspension of basic carbonate of magnesium, magnesium
bicarbonate is formed which on heating forms Mg CO
3
.
MgCO
3
. Mg(OH)
2
+ 3CO
2
+ H
2
O 2Mg(HCO
3
)
2
; Mg(HCO
3
)
2
A
MgCO
3
+ H
2
O+ CO
2
PROPERTIES:
It dissolves readily in water containing excess of carbon dioxide.
MgCO
3
+ CO
2
+ H
2
O Mg(HCO
3
)
2
It dissolves in acids forming salts with evolution of CO
2
.
MgCO
3
+ 2HCl MgCl
2
+ H
2
O + CO
2
On heating, it decomposes with evolution of CO
2
.
MgCO
3
MgO + CO
2
It forms double carbonates with alkali metal carbonates.
MgCO
3
+ Na
2
CO
3

le lub So
2 3 2
) CO ( Mg Na (soluble)
CALCIUM CARBONATE (CaCO
3
)
PREPARATION:
It can be obtained by passing carbon dioxide through lime water or by adding sodiumcarbonate solution to
CaCl
2
.
Ca(OH)
2
+ CO
2
CaCO
3
+ H
2
O ; CaCl
2
+ Na
2
CO
3
CaCO
3
+ 2NaCl
The precipitate of CaCO
3
thus obtained is known as precipitated chalk.
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20
CHEMISTRY
PROPERTIES:
it is a white powder, insoluble in water. It dissolves in presence of CO
2
due to formation of calciumbicarbonate.
CaCO
3
+ H
2
O+ CO
2
Ca(HCO
3
)
2
USES:
Precipitated chalk is used in tooth pastes and face powders, in medicine for indigestion, in
adhesives and in cosmetics.
Chalk is used in paints and distempers.
MAGNESIUM SULPHATE (MgSO
4
)
It occurs in nature as minerals kiesserite (MgSO
4
.H
2
O), epsom salt (MgSO
4
.7H
2
O)and kainite
(KCl.MgSO
4
.3H
2
O).
PREPARATION:
It is prepared by reacting magnesite (MgCO
3
) or dolomite with dilute sulphuric acid.
MgCO
3
+ H
2
SO
4
MgSO
4
+ H
2
O + CO
2
MgCO
3
.CaCO
3
(dolomite) + 2H
2
SO
4
MgSO
4
+ CaSO
4
+ 2CO
2
+ 2H
2
O
PROPERTIES:
Heating effect :
When heated to 150C, it changes to monohydrate. On further heating, it becomes anhydrous at
200C. On strong heating, it decomposes into MgO.
MgSO
4
.7H
2
O
C 150
MgSO
4
.H
2
O
C 200
MgSO
4
heating
strong
MgO + SO
2
+
2
1
O
2
.
Magnesiumsulphate when heated with lamp black at 800Cproduces SO
2
and CO
2
gases.
2MgSO
4
+ C 2MgO + 2SO
2
+ CO
2
It forms double salts with alkali metal sulphates, e.g., K
2
SO
4
. MgSO
4
. 6H
2
O.
CALCIUM SULPHATE (CaSO
4
)
It is found in nature as anhydride (CaSO
4
) and gypsum(CaSO
4
.2H
2
O)
It can be prepared by reacting any calciumsalt with either sulphuric acid or a soluble sulphate.
CaCl
2
+ H
2
SO
4
CaSO
4
+ 2HCl ; CaCl
2
+ Na
2
SO
4
CaSO
4
+ 2NaCl
PROPERTIES:
It is a white crystalline solid. It is sparingly soluble in water and solubility decreases as
temperature increases.
It dissolves in dilute acids. It also dissolves in ammoniumsulphate due to the formation of double
sulphate, (NH
4
)
2
SO
4
.CaSO
4
.H
2
O.
Gypsumwhen heated first changed frommonoclinic formto orthorhombic formwithout loss of water.
At 120C, it loses three-fourth of its water of crystallisation and forms hemihydrate, (2CaSO
4
.H
2
O)
which is commonly known as Plaster of Paris. At 200C, it becomes anhydrous. The anhydrous
form is known as burnt plaster or dead plaster.
Dead plaster has no setting property as it takes up water only very slowly.
A suspension of gypsum when saturated with ammonia and carbon dioxide forms ammonium
sulphate, a nitrogenous fertilizer.
2NH
3
+ CaSO
4
+ CO
2
+ H
2
O (NH
4
)
2
SO
4
+ CaCO
3
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CHEMISTRY
When strongly heated with carbon, it forms calciumsulphide.
CaSO
4
+ 4C CaS + 4CO
USE:
For preparing blackboard chalk.
In anhydrous formas drying agent.
PLASTER OF PARIS (2CaSO
4
.H
2
O)
(Calcium sulphate hemihydrate)
PREPARATION:
It is obtained when gypsum, calciumsulphate dihydrate (CaSO
4
.2H
2
O), is heated at 120C(393 K).
2[CaSO
4
.2H
2
O] 2CaSO
4
.H
2
O(calciumsulphate hemihydrate) + 3H
2
O
Gypsum Plaster of Paris
PROPERTIES:
Plaster of Paris is a white powder.
It has the property of setting to a hard mass when a paste with water is allowed to stand aside for
sometime. Slight expansion occurs during the setting as water is absorbed to reformCaSO
4
.2H
2
O(gypsum).
The setting process is exothermic. The process of setting takes place in stages. In the first stage, there is
conversion of Plaster of Pairs into orthorhombic form of gypsum (setting step) and in the second stage
orthorhombic formchanges into monoclinic form(hardening step).
Paris of Plaster
O H . CaSO 2
2 4
O H
Setting
2

bic hom Orthor
O H 2 . CaSO
2 4

Hardening
Monoclinic
O H 2 . CaSO
2 4
The setting of Plaster of Paris may be catalysed bysodiumchloride while it is retarded by borax or alum.
Addition of alumto Plaster of Paris makes the setting very hard. The mixture is known as Keenes cement.
Example-19 An element X exhibits only the +2 oxidation state in its compounds. The compounds are white and
frequently crystallize as hydrates. Its hydroxide used as an antacid is the least soluble one in its
family and can be precipitated fromsolutions containing X
2+
by NH
3
(g). Identify the element and give
the balanced equations.
(a) for the effect of heat on its (hexahydrate) chloride.
(b) for the precipitation of the hydroxide using aq. NH
3
.
Solution The element is magnesiumas its hydroxide known as milk of magnesia is used as an antacid.
MgCl
2
. 6H
2
O(s)
A
MgO(s) + 2HCl(g) + 5H
2
O(g)
Mg
2+
(aq.) + 2NH
3
(aq) + 2H
2
O() Mg(OH)
2
(s) + 2NH
4
+
(aq)
Example-20 The difference in the number of water molecules between gypsumand plaster of paris is :
(A) 3 (B) 1/2 (C) 3/2 (D) 1
Solution Formula of gypsum is CaSO
4
. 2H
2
O and that of plaster of paris is 2CaSO
4
. H
2
O. Hence the
difference in the number of water molecules is 3/2.
Therefore, (C) option is correct.
Example-21 What product is formed when hydrated magnesium chloride is heated in presence of ammonium
chloride ? Write only chemical reaction.
Solution MgCl
2
. 6H
2
O+ NH
4
Cl MgCl
2
. NH
4
Cl. 6H
2
O(double salt)
Example-22 Which none-metals give disproportionation reaction with concentrated sodiumhydroxide ? Name at
least three with complete balanced chemical equations.
Solution 6NaOH + 3Cl
2
5NaCl + NaClO
3
+ 3H
2
O
3NaOH + P
4
3NaH
2
PO
2
+ PH
3
6NaOH + 4S 2Na
2
S + Na
2
S
2
O
3
+ 3H
2
O
Example-23 When CO
2
is bubbled into an aqueous solution of Na
2
CO
3
, which of the following is formed ?
(A) NaOH (B) NaHCO
3
(C) H
2
O (D) HCOONa
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CHEMISTRY
Solution When CO
2
is bubbled into an aqueous solution of Na
2
CO
3
, an insoluble NaHCO
3
precipitates out.
Na
2
CO
3
+ H
2
O+ CO
2
2NaHCO
3
Therefore, (B) option is correct.
Example-24 Sodiummetal was heated in excess of air and then product was treated with cold dilute H
2
SO
4
. The
final products obtained are :
(A) Na
2
SO
4
, SO
2
and H
2
O (B) Na
2
SO
4
and H
2
O
2
(C) Na
2
SO
4
, O
2
and H
2
O (D) Na
2
SO
4
and NaOH
Solution 2Na + O
2
(fromair)
A
Na
2
O
2
; Na
2
O
2
+ H
2
SO
4
(cold dilute) Na
2
SO
4
+ H
2
O
2
.
SOME OF THE IMPORTANT ORDER OF THE PROPERTIES WITH HINTS/EXPLANATION :
1. MgO < SrO < K
2
O< Cs
2
O(Basic character) :
Hint : Increasing electropositive nature of the element makes its oxide more basic.
2. Cs
+
< Rb
+
< K
+
< Na
+
< Li
+
(Ionic radii in water) :
Hint : The smaller size of the ion, the greater extent of hydration, so the size of hydrated ions becomes larger for
smaller size ions.
3. Li
+
< Na
+
< K
+
< Rb
+
< Cs
+
(Molar conductivity in water) :
Hint : Li
+
ion heavily hydrated so lowest mobility while Cs
+
ion less hydrated has the highest mobility.
4. Li < Na < K < Rb < Cs (Reactivity with water) :
Hint : Reactivity increases down the group, due to decrease in ionisation energy.
5. Cs < Rb < K < Na < Li (Reactivity with hydrogen) :
Hint : The ease of formation of hydrides decreases down the group.
6. Cs < Rb < K < Na < Li (Melting point) :
Hint : Melting point decreases down the group due to decrease in strength of metallic bond as size of atom
increase.
7. LiOH < NaOH < KOH < RbOH < CsOH (Basic nature of hydroxides) :
Hint : Basic nature of hydroxides increases down the group. The strength of a base depends on ionisation of the
hydroxide which in turns depends on polarity of bond and internuclear distance between the oxygen of the
hydroxide and metal atom.
8. LiOH < NaOH < KOH < RbOH < CsOH (Thermal stability of hydroxides) :
Hint : Thermal stability of hydroxides increases down the group. Bigger cation is stabilised by bigger anion and
vice-versa.
9. LiCl < LiBr < LiI (Covalent character) :
Hint : According to Fajans rule Li
+
ion polarizes the larger anion more, giving larger covalent character.
10. BeCl
2
< MgCl
2
< CaCl
2
< SrCl
2
< BaCl
2
(Ionic character) :
Hint : According to Fajans rule as the size of cation increases, the polarising power of cation decreases and thus
covalent character decreases and ionic character increases.
11. BaCO
3
< CaCO
3
< MgCO
3
< BeCO
3
(Solubility) :
Hint : On moving down the group the lattice energy of carbonates do not decrease more while the degree of
hydration decreases more so solubility decreases down the group.
12. Be(OH)
2
< Mg(OH)
2
< Ca(OH)
2
< Ba(OH)
2
(Solubility) :
Hint : Lattice energy is dominating factor. (refer also Hint of 12)
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CHEMISTRY
13. Be(OH)
2
< Mg(OH)
2
< Ca(OH)
2
< Ba(OH)
2
(Basicity) :
Hint : Basicity of hydroxides increases down the group. (Refer Hint of 7)
14. Ba
2+
< Sr
2+
< Ca
2+
< Mg
2+
< Be
2+
(Hydration of ions) :
Hint : The extent of hydration of ion decreases with increase in ionic size.
15. Be < Mg < Ca < Sr < Ba (Reactivity with water) :
Hint : Reactivitywith water increases down the groupas the metallic character i.e. electropositive character increases
on account of decreasing ionisation energy.
16. Be < Mg < Ca < Sr < Ba (Reactivity towards air) :
Hint : Reactivity towards air increases down the group.
17. BaSO
4
< SrSO
4
< CaSO
4
< MgSO
4
< BeSO
4
(Solubility) :
Hint : Decrease in hydration energy is more as compared to lattice energy down the group.
18. CaI
2
< CaBr
2
< CaCl
2
< CaF
2
(Melting point) :
Hint : As the size of anion increases, its polarisation by the cation increase, so covalent character increases and
so, the melting point decreases.
19. CsH < KH < NaH < LiH (Stability of hydrides) :
Hint : Stability of hydrides decreases down the group due to decrease in the bond dissociation enthalpies because
of the increase in the bond lengths.
20. BeCO
3
< MgCO
3
< CaCO
3
< BaCO
3
(Thermal stability) :
Hint : BeO is more stable than BaO, so BeCO
3
have a greater tendency to decompose to give stable BeO. So
BeCO
3
is least stable and BaCO
3
is most stable in other words, the stability of carbonates increases with
increase in the metallic character down the group.
21. LiBr < NaBr < KBr < RbBr < CsBr (Ionic character) :
Hint : According to Fajans rule, as the size of cation increases its polarising power decreases and thus covalent
character decreases and ionic character increases.
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CHEMISTRY
MISCELLANEOUSSOLVEDPROBLEMS(MSPs)
1. Give the comparative studies of the followings properties with respect to the Li and Mg.
(A) Thermal stability of carbonates. (B) Size of hydrated ions. (C) Nature of oxides.
Sol. (A) Both decompose easily on heating to give CO
2
and metal oxides and the order of stability is LiCO
3
>
MgCO
3
as thermal stability increases with increasing metallic character.
(B) Hydrated Mg
2+
ion is bigger than that of Li
+
due to greater charge to size ratio.
(C) Both formbasic oxides but LiOis slightly more basic than MgOdue to more electropositive character of
Li because of lowionisation energy.
2. Arrange the following in the decreasing order of their thermal stability.
(A) Nitrates of alkali metals fromLi to Cs.
(B) Carbonates of alkaline earth metals fromBe to Ba.
Sol. Thermal stability of oxy-acid salts of alkaline earth metals and alkali metals increase with increasing metallic
character. So the correct orders are as follows :
CsNO
3
> RbNO
3
> KNO
3
> NaNO
3
> LiNO
3
; BaCO
3
> SrCO
3
> CaCO
3
> MgCO
3
> BeCO
3
.
3. Explain the following :
(a) Why should an alkali metal never be put into a burette ?
(b) LiF has the lowest solubility of the group 1
st
metal halides.
(c) BeCl
2
in aqueous solution exists as [Be(H
2
O)
4
]
2+
rather than Be
2+
.
Sol. (a) It gives a deposit of a carbonate with CO
2
of atmosphere, which can jamthe tap.
(b) LiF has very large lattice energy because of the small size of both the Li
+
and F

ions. Thus its lattice

energy exceeds the hydration energy and so is water insoluble.
(c) Be
2+
on account of vacant p-orbital and it high polarising power formcomplex with water as ligands.
BeCl
2
+ 4H
2
O [Be(H
2
O)
4
]
2+
+ 2Cl

4. The order of mobilities of the alkali metal ions in aqueous solution is Li

+
< Na
+
< Rb
+
< Cs
+
. Comment on the
observation.
Sol. The smaller the size of the ions, the greater is the extent of hydration. So the size of hydrated ions becomes
larger. Thus bigger hydrated ions move slowly.
5. When gas (A) is passed through dry KOHat lowtemperature, a deep red / orange coloured compound (B)
and a gas (C) are obtained. Identify (A), (B) and (C).
Sol. (i) 5O
3
+ 2KOH 2KO
3
(deep red / orange) + H
2
O
(g)
+ 5O
2
(A) Potassiumozonide (C)
(B)
Ans. Thus, A,B and Care O
3
, KO
3
, and O
2
respectively.
6. (A) is binary compound of a univalent metal. 1.422 g of (A) reacts completely with 0.321 g of sulphur in an
evacuated and sealed tube to give 1.743 g of a white crystalline solid (B) that formed a hydrated double salt
(C) withAl
2
(SO
4
)
3
. Identify (A), (B) and (C).
Sol. (i) (B) forms double salt with Al
2
(SO
4
)
3
and thus, may be K
2
SO
4
(ii) (A) + S (B) K
2
SO
4

1.743 g K
2
SO
4
is obtained by 1.422 gA
174 g K
2
SO
4
is obtained by
743 . 1
174 422 . 1
= 142 g AA
174 g K
2
SO
4
requires 32 g S
1.743 g K
2
SO
4
requires
174
743 . 1 32
Thus, given data confirms that (B) is K
2
SO
4
Now, 2(A) + S K
2
SO
4
(A) potassiumsalt)
"manishkumarphysics.in"
25
CHEMISTRY
M wt. of (A) 2 = 142
M wt. of (A) = 71
Since (A) is potassium salt
Molecular weight of left component = 71 39 = 32
Thus, salt if KO
2
2KO
2
+ S K
2
SO
4
. aq
3 4 2
) SO ( Al

K
2
SO
4
.Al
2
(SO
4
)
3
.24H
2
O
(A) (B) (C)
Ans. (A) = KO
2
; B = K
2
SO
4
(C) = K
2
SO
4
. Al
2
(SO
4
)
3
.24H
2
O
7. Element (A) burns in nitrogen to give an ionic compound B. Compound B reacts with water to give (C) and
(D). Asolution of (C) becomes milky on bubbling CO
2
. The chloride of element (A) imparts brick red colour to
Bunsen flame. Identify (A) to (D).
Sol. 3M + N
2
M
3
N
2
(A) (B)
M
3
N
2
+ 6H
2
O 3M(OH)
2
+ 2NH
3
(B) (C) (D)
M(OH)
2
+ CO
2
MCO
3
+ (milky) + H
2
O
As the colour of the flame is brick red, metal (A) can be Ca.
Ans. A = Ca , B = Ca
3
N
2
, C = Ca(OH)
2
, D = NH
3
.
8. The crystalline salts of alkaline earth metals contain more water of crystallisation than the corresponding
alkali metal salts, why ?
Ans. Alkaline earth metals have smaller size and high nuclear charge. So they attract more number of water
molecules as compared to the alkaline metals. Hence they contain more water of crystallisation than the
corresponding alkali metal salts.
9. The incorrect statement among the following is :
(A) beryllium hydroxide is amphoteric in nature.
(B) solubility of sulphates of second group elements decreases down the group.
(C) reducing power of hydride of alkali metal decreases down the group.
(D) beryllium has diagonal relationship with aluminium.
Sol. (A) Berylliumhydroxide is amphoteric in nature as it reacts with acid and alkali both.
Be(OH)
2
+ 2OH [Be(OH)
4
]
2
(beryllate ion)
Be(OH)
2
+ 2HCl + 2H
2
O [Be(OH
2
)
4
]Cl
2
.
(B) The solubility of the alkaline earth metal sulphate decreases down the group from Be to Ba. This is
because of the fact that down the group with increasing size of cation the lattice energy as well as hydration
energy also decrease but the change in hydration energy is more as compare to that of lattice energy.
(C) Down the group, the bond dissociation enthalpies decrease fromLiH to CsH. So reducing power of
hydride of alkali metal increases down the group.
(D) The ionic radius of Be
2+
is estimated to be 31 pm; the charge/radius ratio is nearly the same as that of the
Al
3+
ion. Hence berylliumhas diagonal relationship with aluminum.
So option (C) is incorrect.
10. A + H
2
O

NaOH ; A
C 400
O
2

B
C 25 at
O H
2

NaOH + O
2
.
B is used for oxygenating in submarine. Aand B are :
(A) Na
2
O
2
and Na
2
O (B) Na
2
Oand Na
2
O
2
(C) Na
2
O
2
and O
2
(D) Na
2
Oand O
2
.
Sol. Na
2
O + H
2
O

NaOH ; Na
2
O
C 400
O
2

Na
2
O
2 C 25 at
O H
2

NaOH + O
2
.
Therefore, (B) option is correct.
"manishkumarphysics.in"
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CHEMISTRY
11. On heating sodiummetal in a current of dry ammonia, the compound formed is :
(A) sodiumamide (B) sodiumazide (C) sodiumnitride (D) sodiumhydride
Sol. 2Na + 2NH
3
2NaNH
2
+ H
2
Therefore, (A) option is correct.
12. Statement-1 : As the electropositive character increases down the group, the stability of carbonates and
hydrogen carbonates of alkali metals increases.
Statement-2 : Lithiumcarbonates is not so stable to heat : lithiumbeing very small in size polarises a large
CO
3
2
ion leading to the formation of more stable Li
2
Oand CO
2
.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
Sol. Bigger cation stabilises bigger anions and vice-versa. The carbonates (M
2
CO
3
) and in most cases the
hydrogencarbonates (MHCO
3
) also are highly stable to heat. As the electropositive character increases
down the group, the stability of the carbonate and hydrogencarbonates increases.
Therefore, (B) option is correct.
13. Which of the following statement is not correct ?
(A) KOHis a stronger alkali than NaOH.
(B) Milk of magnesia is aqueous suspension of Mg(OH)
2
.
(C) MgOis a refractory material used for lining electrical furnaces.
(D) Mg(OH)
2
precipitates on heating hydrated MgCl
2
.
Sol. MgCl
2
.6H
2
O
A
Mg
2
OCl
2

A
MgO
Therefore, (D) option is correct.
14. Which is not correctly matched ?
(1) Basic strength of oxides Cs
2
O<Rb
2
O< K
2
O< Na
2
O< Li
2
O
(2) Stability of peroxides Na
2
O
2
< K
2
O
2
< Rb
2
O
2
< Cs
2
O
2
(3) Stability of bicarbonates LiHCO
3
< NaHCO
3
< KHCO
3
< RbHCO
3
< CsHCO
3
(4) Melting point NaF < NaCl < NaBr < NaI
(A) 1 and 4 (B) 1 and 3 (C) 1 and 2 (D) 2 and 3
Sol. (1) Basic strength of the oxides increases in the order Li
2
O< Na
2
O< K
2
O < Rb
2
O< Cs
2
O. The increase in
basic strength is due to the increase in metallic character down the group.
(4) The melting and boiling points of alkali metals always follow the trend : fluoride > chloride > bromide >
iodide. As the size of anions increase, their tendency to get polarised increases and therefore, their covalent
character increases and thus melting points decrease. So the melting points of the halides increases in the
order NaF > NaCl > NaBr > NaI,
Therefore, (A) option is correct.
15. When Na
2
O
2
is added to water, the peroxide ion serves as :
(A) an oxidising agent (B) an reducing agent
(C) a bronsted acid (D) a bronsted base
Sol. When Na
2
O
2
is added to water, the peroxide ion serves as a Bronsted base. The reaction takes place as
Na
2
O
2
+ 2H
2
O 2NaOH + H
2
O
2
O
2
2
ion accepts protons in this reaction hence it behaves as a Bronsted base.
Therefore, (D) option is correct.
16. NaNO
3
is not used as gun powder because it is :
(A) hygroscopic (B) very costly (C) amorphous (D) soluble in water
Sol. NaNO
3
is not used as gun powder because it is hygroscopic in nature and becomes wet by absorbing water
molecules fromthe atmosphere.
Therefore, (A) option is correct.
"manishkumarphysics.in"
27
CHEMISTRY
17. Consider the following statements,
S
1
: Concentrated solution of an alkali metal in liquid ammonia is bronze coloured and diamagnetic.
S
2
: Increasing stability of the peroxide or super oxide of alkaline earth metal down the group, is due to the
stabilisation of large anions by large cations through lattice energy effects.
S
3
: In the vapour phase BeCl
2
tends to forma chloro - bridged dimer.
S
4
: Berylliumhydroxide reacts with acid and alkali both to form[Be(OH
2
)
4
]Cl
2
and [Be(OH)
4
]
2
respectively.
and arrange in the order of true/false.
(A) T T T T (B) F F F F (C) T F T F (D) F T F T
Sol. S
1
: Very dilute solutions of the metals are paramagnetic, with approximately one unpaired electron per metal
atom ; this paramagnetism decreases at higher concentration. As the concentration of metal increases,
metal ion clusters are formed. Above 3Mconcentration the solutions are diamagnetic and, no longer blue but
are bronze/copper-bronze coloured with a metallic luster.
S
2
is correct statement because smaller cation stabilises smaller anion and bigger cation stabilises bigger
anion.
S
3
Berylliumchloride vapour contains BeCl
2
and (BeCl
2
)
2
Cl Be Cl .
S
4
: Be (OH)
2
+ 2OH

[Be (OH)
4
]
2
beryllate ion
Be (OH)
2
+ 2HCl + 2H
2
O [Be (OH
2
)
4
] Cl
2
Therefore, (A) option is correct.
18. Match the reactions given in Column-I with the nature/characteristic(s) of the products given in Column-II.
Column-I Column-II
(A) Na
2
SO
4
+ C + CaCO
3

A
(p) One of the products has sp
2
hybridisation of central atom.
(B) NaCl + NH
4
HCO
3
(q) One of the products has sp
3
hybridisation of central atom.
(C) Na
2
CO
3
+ Ca (OH)
2

(r) One of the products is insoluble as precipitate.
(D) KOH + NO (2 : 4 by mole ratio) (s) One of the products is a neutral oxide.
Ans. (A p, r, s) ; ( B p, q, r) ; (C p) ; (D p, q, s)
Sol. (A) NaSO
4
+ 4C + CaCO
3

A
Na
2
CO
3
(sp
2
) + CaS + + 4CO(neutral oxide)
(B) NaCl + NH
4
HCO
3
NaHCO
3
+ (sp
2
) + NH
4
Cl(sp
3
)
(C) Na
2
CO
3
+ Ca (OH)
2
Ca CO
3
+ (sp
2
) + NaOH
(D) 2KOH+ 4NO 2KNO
2
(sp
2
) + N
2
O(neutral oxide) + H
2
O(sp
3
)
If 4 KOH + 6NO 4KNO
2
+ N
2
+ 2H
2
O.