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CHAPTER 5 P-BLOCK ELEMENTS

Group 13 elements (Boron group)


Write Electronic Configuration of Elements of Group 13
Name Symbol Electronic Configuration
Boron B [He] 2s
2
2p
1
Aluminum Al [Ne] 3s
2
3p
1
Gallium Ga [Ar] 3d
10
4s
2
4p
1
Indium In [Kr] 4d
10
5s
2
5p
1
Thallium Tl [Xe] 4f
14
5d
10
6s
2
6p
1
Occurrence :
The abundance of boron in earth's crust is less than 0.0001% by weight. It occurs in ore form. The main important
ores of boron are
Borax : (Na
2
B
4
O
7
10H
2
O),
Kernite : (Na
2
B
4
O
7
4H
2
O),
Colemanite : (Ca
2
B
6
O
11
- 2H
2
O)
Orthoboric acid : (H
3
BO
3
).
The boron is found in California (USA) and in Turkey State. While in India it is found as borax in Puga valley of Ladakh
region in Kashmir and also in Sambhar lake of Rajasthan. Aluminium is the third most abundant element found in
earth's crust, while the first is oxygen (45.5% by weight), the second is silicon (27.7% / by weight) and the third is
aluminiam (8.3% by weight).
Gallium (Ga), Indium (In) and Thallium (Tl) The valence shell electronic configuration is ns
2
, np
1
where n = 2 to 6.
Hence, there are two electrons in s orbital and one electron in p orbital, therefore, in total three electrons are there.
Bauxite : Al
2
O
3
XH
2
O
Orthoclase : KAlSi
3
O
8
Cryolite : Na
3
AlF
6
Corundum : Al
2
O
3
Beryl : Be
3
Al
2
Si
6
O
18
Mica : KAl
2
(Si
3
AlO
10
)(OH)
2
The important ores of aluminium are bauxite and cryolite. In India mica is found in Madhya Pradesh, Karnataka,
Orissa and Jammu. India is the world's largest supplier of mica.
Gallium, Indium and Thallium are less abundant. Gallium . (0.1 - 1%) is found in the mineral Germanite which is a
complex sulphide of Zn, Cu, Ga and As, while the traces of Indium are found in sulphide ore of lead.
Describe the trend in atomic radii and ionic radii for group 13 elements. [2 mark]
In elements of boron group as the atomic number increases, new electron shell gets added and so the distance
between the nucleus and outermost orbital having electron increases; hence the atomic radius increases. Similar
trends can be observed in ionic radius.
But there is exception in atomic radius of Al and Ga. The atomic radius of Al (143 pm) is more than atomic radius Ga
(135 pm) because there is no d-orbital in electronic configuration of Al while there is d-orbital in electronic
configuration of Ga.
As the d-orbitals are large in size, hence the magnitude of screening effect decreases with nucleus by electrons
present in them.[ decreasing order for screening effect of various orbital is s > p > d > f]
As the nuclear charge of Gallium is high; hence the attraction of outermost orbital electron towards the nucleus
increases. Hence, atomic radius of Ga is less than that of Al. However a regular trend is observed in ionic radii.
Describe the trend of Ionization enthalpy for group 13 elements. [3 mark]
The order of first ionisation enthalpy (A
i
H
1
) for boron group elements is B > Al < Ga > In < Tl.
The first ionization enthalpy of Al is less than that of B. Because atomic size of Al is more than B due to
introduction of new valence shell in Al more over it also increases the screening effect in Al compared to B.
consequently it decreases the attractive force of nucleus towards the outermost electrons, hence first ionization
enthalpy of Al is less than that of B.
While the first ionization enthalpy of Ga is little more (1 kJ mol
1
) compared to Al because in Ga the
addition of new valence shell which include presence of 3d-orbital, which decreases the magnitude of screening
effect. {Screening effect by d orbital electron is less than s &p orbital electrons} Thus in case of Ga attractive force
of nucleus towards valence electron is more as compared to Al therefore ionization enthalpy of Ga is more than Al.
The first ionization enthalpy of Indium is less compared to that of Ga. Because in case of In there is
increased in screening effect due to presence of 4d orbitals which outweighs the effect of increased nuclear charge
(49 31 = 18 units). Consequently valence electron of In (indium) possess less attractive force towards nucleus as
compared to Ga which result into its low first ionization enthalpy.
Now, the first ionization enthalpy of Tl is higher than that of Indium because in Tl as the nuclear charge
increases (81 49 = 32 units) and also presence of 4f and 5d-orbitals still the decreases in reactivity of screening
effect is overweighed by nuclear charge. As a result force of attraction towards nucleus by the outermost orbital
electrons increases. Hence the first ionization enthalpy increases.
Moreover, the value of second ionization enthalpy (A
i
H
2
) and third ionization enthalpy (A
1
H
3
) are very
high because when first electron is removed, then the size of ion decreases and the effective nuclear charge
increases and so the force of attraction towards the nucleus increases. Moreover, the second and third electrons are
removed from s-type orbital which has more attractive forces towards the nucleus, so more energy is required to
remove electron from them. Hence the value of A
i
H
2
and A
i
H
3
are very high.
Describe the trend of Metallic character for group 13 elements. [2 mark]
The elements of group 13 show variation in metallic character.
The metallic character is higher in Al than that of B. So Al is good conductor of heat and electricity.
The reduction potential values go on increasing from Al to Tl, so the values of electro positivity decreases as a result,
metallic character decreases. Thus, B is non-metal, while Al is metal and in Indium, Ga and Tl the metallic character
decreases successively. So Tl possesses non-metallic character.
Mention the trend of Electronegativity for group 13 elements. [1 mark]
On moving down the elements of group 13, electronegativity decreases suddenly from B to Al and after that it
increases gradually as moving from Al to Tl, because the atomic volume increases as the atomic number increases.
As the atomic volume increases, the attractive force for electron towards nucleus decreases.
Describe the trend of Melting points and Boiling points for group 13 elements.[2 mark]
The elements of group 13 show irregular trends in melting points, viz the melting point of B is the
highest, while melting point of Al is low and melting point of Ga is the lowest; the melting point of In is more than
that of Ga and Tl has little more.
The order of melting points of group 13 elements are in order B > Al > Ga < In < Tl. The crystal structure
of element is responsible for this.
The boiling points of the elements of group 13 on moving down the group show regular trend. As the
atomic number goes on increasing the boiling point decreases regularly.
Mention the trend of Density for group 13 elements. [1 mark]
The density goes on increasing as the atomic number increases for the elements of group 13 because as
the atomic number increases the volume increases but the increase in atomic mass is more compared to volume
and hence, density increases.
State the Characteristic as reducing agent for group 13 elements.[1 Mark]
The characteristic as reducing agent goes on decreasing on moving down the group, which means
moving from Al to Tl, because the values of reduction potential increase from Al to Tl and so the reduction power
decreases and the characteristic as reducing agent also decreases.
{Reduction potential means relative tendency of an electrode to donate electrons.}
Discuss the general trend in nature of compounds of boron family elements.[2mark]
The elements of group 13 have a decreasing tendency to form covalent bond compounds.
The elements of group 13 have increasing tendency to form ionic compounds.
Boron form covalent compound because the size of B is small and to form B
3+
ion the sum of three
ionization enthalpy values (A
i
H
1
+ A
i
H
2
+ A
i
H
3
) is high, so boron does not form B
3+
ion easily and hence, it forms
covalent bond.
Now, as the atomic number goes on increasing the atomic size also increases and total ionization enthalpy value
decreases. So, the tendency to form covalent bond decreases and tendency to form ionic bond increases.
Boron forms compounds having covalent bond, while Al forms covalent bond and also to some extent
has tendency to form ionic bond. While in Ga, In and Tl as the atomic number increases, the tendency to form
compounds having ionic bond becomes prominent.
Write a note on the trend of Oxidation state for group 13 elements. .[3 Mark]
General electronic configuration of group 13 element is ns
2
np
1
thus these elements have 3 valence
electrons in their valence shell.
Hence they possess +3 oxidation states. The oxidation state of boron and aluminium is +3 while Ga, In
and Tl have both +1 and +3 oxidation states.
Due to inert electron pair effect, as the atomic number is increasing the stability of +3 oxidation state
decreases and stability of +1 oxidation state increases. Because on going down the group as the atomic number is
increasing the tendency of s-electron to participate in bond formation decreases which means ns
2
electron of Ga, In
and Tl remain paired because of intervening of d and f orbitals.
[In p block elements in every group on moving from top to bottom tendency of heavier elements to
involved electrons present in ns orbital decreases hence in all group of p block on moving from top to bottom
stability of lower oxidation state increases. This effect is called inert electron pair effect. ]
The screening effect of ns
2
orbitals becomes poor and inert pair effect becomes more predominant as
atomic number increases and so the ns
2
orbital electrons are more strongly attracted towards the nucleus and
therefore, it is difficult to remove that electron, so the stability of oxidation state +1 increases and that of +3
oxidation state decreases. The stability of oxidation state is supported by following reaction.
Tl + 2e

E
0
= + 1.25V
3+
(aq)
{Positive value of electrode potential indicates that the above reaction is spontaneous.}
The reaction indicates that the +1 oxidation state is more stable than + 3 because the reduction potential of this
reaction has positive value.
Trends in Chemical Reactivity:
The variation is observed in chemical reactivity of group 13 elements, because in the electronic
configuration of B and Al they have ns
2
np
1
type electronic configuration after the noble gas electronic configuration.
While electronic configuration of in Ga and In, the intervening of d-orbital after the noble gas electronic
configuration is followed by ns
2
np
1
-type electronic configuration.
Where as in electronic configuration of Tl there is intervening of both d and f-type orbitals and after that
ns
2
np
1
type electronic configuration takes place so that chemical reactivity of group 13 elements is as given below :
Write a note on hydride of group 13 elements. .[2 Mark]
Elements of group 13 do not combine directly with dihydrogen but they combine indirectly with
dihydrogen to form hydride compounds e.g. Boron hydride is obtained by reaction of BF
3
with LiH.
2BF
3
+ 6LiH B
2
H
6
+ 6LiF
450K
Boron forms number of hydrides, most of hydrides having molecular formula, B
n
H
n + 4
and B
n
H
n + 6
which are known
as Borane.
Other elements hydride are polymeric e.g. (AlH
3
)
n
, (GaH
3
)
n
and (InH
3
)n their structure contains M.....H......M bridge
(M = Al, Ga, In). The stability of hydrides decreases with increasing atomic number and so thallium hydride is quite
unstable. These hydrides are Lewis acids which readily combine with strong Lewis base (B :).
B: + MH
3
[B -> MH
3
] (M = Al or Ga)
In addition to these polymeric hydrides, Al or Ga also form complex tetra hydrides e.g. tetra hydro aluminate (III).
This is known as lithiumaluminium hydride, which can be obtained by the reaction of LiH and AlCl
3
in presence of
dry ether.
4LiH + AlCl
3
Li
+
[AlH
4
]

+ 3LiCl
Dry ether
Particularly in organic reaction LiAlH
4
is used as a reducing agent.
Write a note on Halide Compounds of boron family.[2 Mark]
Elements of group 13 form MX
3
type trihalides where X = F, CI, Br and I. TlI
3
is unknown.
Due to small size and high ionization enthalpy boron atom has tendency to form covalent bond by sp
2
hybridization
and form trihalide.
The trihalides BX
3
act as Lewis acid and the order of its strength is BI
3
> BBr
3
> BCl
3
> BF
3
In vapour form AlCl
3
exists in dimer form due to bridging of chlorine atoms and its structure is as shown in Figure
Cl 2
0
6
p
m
2
0
6
p
m
2
2
1
p
m
101
0
79
0
118
0
Cl
Al Al
Cl
Cl Cl Cl
Structure of AI
2
CI
6
(dimer) (gaseous state)
AICI
3
is Lewis acid. BF
3
and AlCl
3
are strong Lewis acids and therefore used as a catalyst in Friedel and Crafts
alkylation reaction and electrophilic aromatic substitution reaction.
Ga and Tl also form MX type halides where M = CI, Br, I. The stability of MX type halide increases as the atomic
number increases, so that TlX is more stable than GaX.
Write a note on Oxide and Hydroxide Compounds of boron family. .[2 Mark]
The group 13 elements form oxides having formula M
2
O
3
and hydroxide having formula M(OH)
3
. As the atomic
number of element goes on increasing the acidic character of oxide and the hydroxide decreases, and at the same
time the basic character goes on increasing .e.g. oxide and hydroxide of boron are acidic, those of Al and Ga are
amphoteric and In are basic while those of Tl are strong base.
Discuss Complex and Double Salt Compounds of boron family. .[2 Mark]
In elements of group 13, in the electronic configuration of boron the d-orbital is absent, so it forms only
tetrahedral complex like [BH
4
]

, [BI
4
]

, etc.
The electronic configuration of Al, Ga, In and Tl have d-orbital (in Al it is in form of 3d
0
), so they form octahedral
complexes like [AlF
6
]
3
, [GaCl
6
]
3
, [InCl
6
]
3
and [TlCl
6
]
3
, with octahedral aqua ions can be described as [M(H
2
O)
6
]
3+
,
(where M = Al, Ga, In, and Tl).
Aluminium sulphate reacts with sulphate of and alkali metal ions and form double salts known as
alums with formula M
2
SO
4
Al
2
(SO
4
)
3
24H
2
O or MAl(SO
4
)
2
12H
2
O (where M = Na
+
, K
+
, Rb
+
and ).
The uses of these double salts are to convert hard water to soft water and as a mordant in chemicals of
colour dye.
State the anomalous behaviour of the boron in group 13 [3 mark]
The first element of group 13, boron shows anomalous behaviour. Boron shows anomalous behaviour due to
exceptionally small atomic & iionic size, high ionization enthalpy and absence of d orbitals in its electronic
configuration.
(i) Boron is non-metal while other elements except boron show metallic- characters.
(ii) Boron trihalide is monomeric while in other elements trihalide exist as a dimer or polymer.
(iii) Boron hydride is monomeric while in other elements hydrides exist as a dimer or polymer.
(iv) Boron does not react with water while other elements react with water and form oxides.
(v) Oxides and hydroxides of boron are acidic while the oxides and hydroxides of other elements are amphoteric or
basic.
(vi) Except boron, trihalide of other elements on hydrolysis result in complex ions.
Write the Physical properties of boron. [2 mark]
(i) Boron is extremely hard substance. In order of hardness, it comes next to diamond.
(ii) The melting point and boiling point of boron are very high.
(iii) Boron is poor conductor of heat and electricity.
(iv) Boron has two isotopes
10
B and
11
B and its relative abundances is 20% and 80% respectively.
(v) Boron has two allotropes. The colour of amorphous form is dark brown whereas the crystalline form is found in
black metallic luster.
Describe Chemical properties of boron. [4mark]
Boron is chemically less reactive. It is almost inert towards normal chemical reagents at normal temperature, but
however, it reacts with strong oxidising agent and with some typical reagents as given below:
Reaction with non-metal: Non-metal dinitrogen, dioxygen and dihalogen react with boron at high temparature.
4B + 3O
2
A
2B
2
O
3
2B + N
2
A
2BN
2B + 3X
2
A
2BX
3
(where X = CI, Br, I)
Reaction with acid : Boron does not react with HCl but it reacts with con. HNO
3
and H
2
SO
4
and oxidises into boric
acid.
2B + 3H
2
SO
4
A
2H
3
BO
3
+ 3SO
2
B + 3HNO
3
A
H
3
BO
3
+ 3NO
2
Reaction with alkali: Boron reacts with fused alkalis like NaOH and KOH and converts into corresponding borates
and liberates dihydrogen.
2B + 6NaOH
(/)
A
2Na
3
BO
3
+ 3H
2
Sodium borate
2B + 6KOH
(/)
A
2K
3
BO
3
+ 3H
2
Potassium borate
Reaction with metal: Boron reacts with some metals on heating and converts in to borides which are very hard and
solid substance having high melting point, e.g.
B + Cr
A
CrB (Chromium boride)
Give chemical formula of borax powder and from where it is obtained? [1 mark]
Borax Powder (Na
2
B
4
O
7
) : The important compound of boron is borax or sodium tetraborate (Na
2
B
4
O
7
). The impure
form of borax is Tincal which contains 55% borax. It is found in certain dried up lakes of India, Tibet, Sri Lanka and
California.
Explain various method of Preparation of borax. [3mark]
(i) Borax from Tincal: Tincal is dissolved in water and boiled. On filteration insoluble impurities like sand, clay etc are
removed. While borax remains soluble in solution, the solution is concentrated, and on cooling crystals of borax
separates out.
(ii) Borax from colemanite : On boiling mineral colemanite with sodium carbonate, the borax, CaCO
3
and sodium
metaborate are formed. The CaCO
3
is obtained as insoluble so it is in form of precipitates and removed by filtration
and solution is obtained. Concentrate the solution and on cooling crystals of borax are obtained. Mother liquor still
having sodium metaborate is converted to borax by passing CO
2
in the solution.
Ca
2
B
5
O
11
+ 2Na
2
CO
3
A
2CaCO
3(s)
+Na
2
B
4
O
7
+ 2NaBO
2
Colemanite Borax Sodiummetaborate
4NaBO
2
+ CO
2
A
Na
2
B
4
O
7
+ Na
2
CO
3
Sodium metaborate Borax
(iii) Borax from boric acid : On neutralization of boric acid by Na
2
CO
3
borax is obtained.
4H
3
BO
3
+ Na
2
CO
3
A
Na
2
B
4
O
7
+ 6H
2
O + CO
2
Boric acid borax
The mixture is heated and on cooling borax separates as crystals.
Write a note on properties of Borax. [3 mark]
(1) Borax is found in three forms, (a) Prismatic Na
2
O
7
10H
2
O (b) Octahedral Na
2
B
4
O
7
5H
2
O (c) Borax glass Na
2
B
4
O
7
(2) Borax is white, crystalline solid substance sparingly soluble in cold water and highly soluble in hot water.
(3) Aqueous solution of borax is basic due to its hydrolysis.
Na
2
B
4
O
7
+2H
2
O H
2
B
4
O
7
+2NaOH
(4) On heating borax, due to its decomposition swells and loses water of crystallization g and becomes anhydrous;
on further heating it melts and forms glassy, transparent bead known as borax bead.
Na
2
B
4
O
7
10H
2
O
A
Na
2
B
4
O
7
+ 10H
2
O
Na
2
B
4
O
7
2NaBO
2
+ B
2
O
2
A
Sodium
Metaborate
Boron oxide or
boric anhydride
glassy transparent borax bead.
(5) When the glassy, transparent bead is dipped in coloured ions like Ni
2+
, Co
2+
, Cr
3+
, Cu
2+
, Mn
2+
and heated, they are
converted into their metaborates respectively and they are coloured and their colours are brown, blue, green
and pink respectively e.g.
NiO B
2
O
3
Ni(BO
2
)
A
Nickel metaborat
(Brown colour)
State uses of borax [2 mark]
(i) It is used in laboratory to perform borax bead test in qualitative analysis.
(ii) It is used in manufacturing of enamels and glazing of earthen pots.
(iii) Used in preparation of candles.
(iv) Due to its antiseptic properties it is used in preparation of medicinal soap.
(v) It is used in making optical glass,
(vi) Used in softening of hard water.
What is the formula of boric acid? Give its trivial name. [1 mark]
Chemical formula of Boric acid is H
3
BO
3 .
Its trivial name is orthoboric acid.
Write a note on preparation of boric acid by various method. [3mark]
(i) Boric acid fromborax: Acidifying we aqueous solution of borax by adding HCl or Na
2
SO
4
, Boric acid is obtained
which on condemnation and cooling gives crystals of boric acid.
Na
2
B
4
O
7
+2HCl + 5H
2
O
A
4H
3
BO
3
+2NaCl
Na
2
B
4
O
7
+ H
2
SO
4
+5H
2
O
A
4H
3
BO
3
+Na
2
SO
4
(ii) Boric acid from mineral colemamtes : Powder the mineral colemanite, d water and boil it. On passing SO
2
gas
boric id and calcium bisulphite are obtained, ilcium bisulphite is highly soluble in water while boric acid is sparingly
soluble; so on cooling boric acid gets separated.
Ca
2
B
6
O
11
+ 11H
2
O
A
2Ca(OH)
2
+ 6H
3
BO
3
2Ca(OH)
2
+4SO
2
A
2Ca(HSO
3
)
2
Net reaction: Ca
2
B
6
O
11
+ 11H
2
O + 4SO
2
A
6H
3
BO
3
+ 2Ca(HSO
3
)
2
(iii) Boric acid from hydrolysis of boron compounds: On hydrolysis of BCl
3
and BN, they give boric acid.
BCl
3
+3H
2
O
A
H
3
BO
3
+3HCl
BN + 3H
2
O
A
H
3
BO
3
+NH
3
Write detail note on chemical properties boric acid. [3 mark]
(i) Boric acid is a white crystaline solid substance with a soft soapy touch.
(ii) It is sparingly soluble in cold water but fairly soluble in hot water.
(iii) At different temperatures the effects of heat on it are as given below :
H
3
BO
3
HBO
2
H
2
B
4
O
7
B
2
O
2
373 k
H
2
O
433 K
H
2
O
red hot
H
2
O
Orthoboric
aidc
Metaboric
aidc
Tetraboiric
aidc
Boron
oxide
(iv) It is a weak monobasic acid and acts as a Lewis acid.
(v) In presence of H
2
SO
4
it reacts with ethanol and form ethyl borate.
H
3
BO
3
+3C
2
H
5
OH
[H
+
]
B(OC
2
H
5
)
3
+ 3H
2
O
Ethyl borate
(vi) the structure of boric acid having H-bond is given in following figure.
Fig. Structure of boric acid having H-bond
(The dotted lines represent hydrogen bonds)
State the Uses of boric acid. [2mark]
(i) In food industry it is used as a preservative for the preservation of food.
(ii) Used in the preparation of pigments and borax.
(iii) It is used (in medicine) as an eye wash.
(iv) Used in the manufacturing of enamels and pottery glazes.
What is meant by Boron hydrides? Explain its preparation by various methods.[3mark]
Boron forms a number of hydride compounds having general formula B
n
H
n + 4
and B
n
H
n + 6
. Bqron hydrides are also
called Boranes. B
2
H
6
(diborane) is a boron hydride. [ remember in diborane between two BH
3
molecule there is
banana bond (3C 2 ) is present it is electron deficient compound.]
Preparation of Diborane (B
2
H
6
) : In the laboratory, diborane is prepared by the reaction of iodine with sodium-
boroliydride in the presence of polyether as a solvent.
2NaBH
4
+ I
2
polyether
B
2
H
6
+ 2NaI + H
2
Diborane
On an industrial scale, diborane is obtained by the reaction of boron trifluoride or boron trichloride with Murium
iodide at 450 K temperature.
2BF
3
+ 6LiH
450K
B
2
H
6
+ 6LiF
O
O
H
O
H
B
H
O O
H
O
H B
H
O O
H
O
H B
H
O O
H
O
H B
H
2BCl
3
+ 6LiH
450K
B
2
H
6
+ 6LiCl
Describe Properties of di borane.[ 4 mark]
(i) Diborane is colourless and highly toxic gas.
(ii) Diborane has strong affinity for O
2
and therefore it catches fire spontaneously on exposure to air and releases
energy. The heat of combustion is very high.
B
2
H
6
+ 3O
2
B
2
O
3
+ 3H
2
O AH = 2008 kJ mor
1
(iii) At 450 K temperature, if diborane is heated with NH
3
, forms Borazine (B
3
N
3
H
6
) having structure like benzene and
hence it is also called inorganic benzene.
3B
2
H
6
+ 6NH
3
450K
2B
3
N
3
H
6
+ 12H
2
(iv) Diborane on hydrolysis gives boric acid and liberates H
2
gas.
B
2
H
6
+6H
2
O 2H
3
BO
3
+ 6H
2
(v) The structure of diborane is given in Figure
H H
B
B
H
H
H
H
97
0
120
0
119pm
1
3
4
p
m
The structure of diborane, B
2
H
6
State Uses of Boron and its Compounds. {any 6} [3 mark]
(i) Isotope of boron
10
B has ability to absorb neutrons and therefore used as metal borides, in nuclear reactor as a
protective shield and the controlling rods and also used in chemotherapy to cure cancer.
(ii) Boron fibres are used in making light composite materials for air craft industries.
(iii) Boron and boric acid are used in manufacturing of heat resritant borosilicate pyrex glass. They are also used in
metallurgy as a flux for soldering metals.
(iv) Borax is used for making porcelain enamels.
(v) In laboratory, borax powder is used in borax bead test for detection of coloured metallic ions.
(vi) Aqueous solution of boric acid is used as a mild antiseptic.
(vii) In leather industry borax is used for cleaning skirl (leather) while in food industry it is used as a preservative.
(viii) The heat of combustion for diborane is very high, so it is used as a high energy fuel.
State the properties and of uses Aluminium. [3 mark] { 3 each} { note this question is important for objective and
mcq)
(i) Aluminium is a soft, silvery white metal.
(ii) It has high tensile strength, high electrical and thermal conductivity, (twice than that of Cu).
(iii) It is highly electropositive.
(iv) It readily reacts with O
2
and forms a protective layer of Al
2
O
3
on its surface, which makes it passtive.
Uses :
(i) Aluminium is used extensively in industries and in daily life.
(ii) It forms useful alloys with Cu, Mn, Mg, Si and Zn.
(iii) Al and its alloys are used in making utensils, aeroplane parts and also in some preparations.
(iv) It is used in Aluminothermite process for obtaining the chromium and manganese metals from their oxides.
(v) Aluminium is used as a strong reducing agent.
Explain amphoteric nature of Al [ 2 mark]
Aluminium reacts both with acid and base. Thus, it is amphoteric.
With acid : Aluminium dissolves in dil HCl, dil H
2
SO
4
and liberates H
2
gas slowly.
2Al + 6HCl + 12H
2
O 2[Al(H
2
O)6]Cl
3
+ 3H
2
On heating with concentrated H
2
SO
4
aluminium produces SO
2
gas.
2Al + 6H
2
SO
4
A
Al
2
(SO
4
)3 + 3SO
2
+ 6H
2
O
Aluminium reacts with concentrated HNO
3
and forms inactive, passive protective layer of Al
2
O
3
on surface which
stops the further reaction on its surface.
Reaction with base:
Aluminium dissolves in strong alkali (NaOH or KOH) to form sodium aluminate or potassium aluminate and H-gas is
evolved.
2Al + 2NaOH + 6H
2
O 2Na[Al(OH)
4
] + 3H
2
.
sodium aluminate
General Introduction of Group 14 Elements
Give the name of the elements which are present in group fourteen.[1 mark]
Group 14 includes the elements. Carbon (C), Silicon (Si), Germanium (Ge), Tin (Sn) and Lead (Pb). The first element of
this group is carbon, so they are also called carbon group elements.
Why carbon shows catenation? .[1 mark]
Carbon shows catenation characteristic due to its small size, high eletronegativity and very high carbon-
carbon bond enthalpy. Due to typical character of catenation, it forms chain and cyclic compounds having carbon-
carbon o - bond as well as t - bond.
Moreover, one carbon can form one or more than one bond with another carbon or with other atoms,
also e.g. C = C, C = C, C O, C = O, C N, C = N, C = N and compounds having such type of bonding are studied in
Organic Chemistry. Organic compounds have their contribution in the fields like living organism, non-living organism,
medicine, plastic etc.
What is meant by binary inorganic compound? Give its example. .[1 mark]
Compounds of carbon with metals, metalloids and with non-metals are called binary inorganic compounds. The
compounds like calcium carbide, silicon carbide, carbon monoxide, carbon dioxide, hydrogen cyanide are inorganic
compounds.
What is general electronic configuration of group 14 elements? .[1 mark]
Carbon group elements have electronic configuration ns
2
np
2
in outermost valence orbital where n = 2 to 6. The
electronic configurations of carbon group elements are given in
Write electronic Configurations of Elements of Group 14.[2mark]
Name Symbol Electronic Configuration
Carbon C [He] 2s
2
2p
2
Silicon Si [Ne] 3s
2
3p
2
Germanium Ge [Ar] 3d
10
4s
2
4p
2
Tin Sn [Kr] 4d
10
5s
2
5p
2
Lead Pb [Xe] 4f
14
5d
10
6s
2
6p
2
Mention the occurrence of elements of carbon family. [2 mark] { note this question is important for objective and
mcq}
- Carbon is the seventeenth most abundant element by weight out of elements obtained from the earth's crust. In
earth's crust it occurs in form of coal, petroleum and metal carbonate of electropositive metals. In atmosphere it
is in the form of CO
2
. All living organisms contain carbon in form of organic compounds.
- Silicon is present in nature in the form of silica (SiO
2
) and silicates. Moreover it is an important component used
in ceramics, glass and cement. Silicon is the second most abundant (27.7 %) by weight in the earth's crust.
- Germanium occurs as a trace element and is mainly recovered from the flue dust arising from roasting of zinc
ores.
- Tin and Lead are found in nature in the amount 2 ppm and 13 ppm respectively. Galena (PbS) is the principal ore
of lead. Found along with zinc blend (ZnS). Other ores of lead are anglesite (PbSO
4
) and cerussite (PbCO
3
)
Questions based on periodic properties of Group 14 Elements
(i) What is the trend in atomic radii of carbon family elements? [1 mark]
On moving down the group the atomic radii of group 14 elements go on increasing.
But from silicon and onwards, Ge, Sn and Pb due to introduction of d and f - orbitals in electronic
configuration and ineffective shielding effect the atomic radii increases gradually.
(ii) What is the trend of ionisation enthalpy in group 14 elements?[2 mark]
In group 14 elements as the atomic number increases there is decrease in ionization enthalpy but ionization
enthalpy of Sn is less than Pb. Thus ionization enthalpy order is C > Si > Ge > Sn < Pb.
From C to Sn as the atomic number increases the atomic size also increases and hence the ionisation
enthalpy decreases.
But compare to Sn the ionisation enthalpy of Pb slightly more because of the presence of d and f- both types
of orbitals in electronic configuration of Pb, the force of attraction between valence electron and the nucleus
increases due to poor shielding effect of 4f orbital and hence, ionisation enthalpy decreases.
(iii) Describe trend of electro positivity / Metallic character group 14 elements.[2 mark]
On moving down the group 14 the electro positivity increases.
Carbon is non-metal. Silicon is essentially a non-metal and Germanium is metalloid (having pronounced
metallic character) while tin and lead are typical metals.
Elements of group 14 are less electropositive; hence, the metallic character observed is less.
(iv) State the trend in eletronegativity group 14 element.[1 mark]
The elements of group 14 are more electronegative than elements of group 13. The electrongativity
decreases in group 14 as the atomic number increases due to increase in the atomic size. But it remains
almost same from Si to Pb.
(v) What is the trend in melting points and boiling points in carbon family? [2mark]
The melting points and boiling points of group 14 elements are much higher than those of group 13
elements. Because elements of group 14 form four covalent bonds; there exists a strong binding between the
atoms. Therefore their melting points and boiling points are higher.
As the atomic number increases, melting point and boiling point decreases in group 14 because the
intermolecular forces decrease in group 14.
(vi) What is the order of density in group 14? [1 mark]
On moving down in the elements of group 14 there is regular increase in density is observed because there is
a greater increase in atomic mass than increase in atomic size, so the density increases.
(vii) Mention the trend of catenation in group 14 elements? Why carbon has maximum catenation power? [1
mark]
Group 14 elements show catenation property in the order C > > Si > Ge ~ Sn > > Pb. Because the atomic size
of carbon is less and eletronegativity is higher, further the C C bond enthalpy is also very high, so it
indicates maximum catenation properties at the same time remarkable decrease in silicon.
(viii) Give information about the allotropes of group 14 elements. [2 mark]
Elements of group 14 show allotropy. Carbon has number of allotropic forms out of which diamond, graphite,
and fullerene are the crystalline forms of carbon; fin has two allotropes, white tin of | tin. It gets stable at
room temperature whereas grey tin or o tin remains Unstable, and it can be obtained from | tin at 286 K
temperature.
white tin | white tin (o - tin)
286 K
Write a note on oxidation states arid trends in chemical reactivity. [4 mark]
Group 14 elements have outermost valence shell electronic configuration ns
2
np
2
and hence, these elements have
common oxidation state +4.
But due to intervening of d and f-orbitals in Ge, Sn and Pb the inert pair effect becomes more and more prominent
so they all show oxidation state +2 with +4 and the stability of +2 oxidation state increases as atomic number
increase. (Ge < Sn < Pb). Thus, the divalent state of lead is more prominent.
The trends in chemical reactivity are given below :
(i) Simple M
4+
ions in this group are not known.
(ii) Except carbon the other elements of the group form compounds with co-ordination number higher than 4, like
e.g. [SiF
5
]

[SiF
6
]
2
[PbCl
6
]
2
.
(iii) In divalent state, stable compounds of MX
2
type for carbon and silicon are rare. The stability of divalent state
increases in the order Ge < Sn < Pb.
(iv) Tendency of catenation decreases in the order as C >> Si > Ge ~ Sn > Pb.
(v) Ability to form p - p bonds with element itself and ability to form such bond with other elements like
dinitrogen and dioxygen decreases from carbon to lead. So, CO
2
is a gas but silica (SiO
2
) is a solid.
(vi) Group 14 elements can form two type of halides MX
4
and MX
2.
MX
4
type tetrahalides are tetrahedral and
covalently bonded compounds. The ionic character and thermal stability of halides decreases with increasing
atomic number of halogen and they are hydrolysed by water.
(vii) Ge, Sn and Pb also form MX
2
type halides. The stability of dihalides increases in order CX
2
< < SiX
2
< < GeS
2
< <
SnX
2
< PbX
2
The divalent state becomes more stable on moving down the group.
(viii) Si, Ge, Sn and Pb form MO
2
type oxides. Sn and Pb both form MO type stable oxides.
Write a note on halides of group 14 elements.[3mark]
Tetra halides of group 14 elements.
Si, Ge, Sn, and Pb form MX
4
type tetrahedral and covalently bonded compounds. The ionic character and
thermal stability of halides decreases with increasing atomic number of halogen and they are hydrolysed by
water, e.g.
SiCl
4
+ 4H
2
O Si(OH)
4
+ 4HCl
SnCl
4
+ 2H
2
O SnO
2
+4HCl
Di halides of group 14 elements
- Ge, Sn and Pb also form MX
2
type halides. The stability of dihalides increases in order CX
2
< < SiX
2
< < GeS
2
< <
SnX
2
< PbX
2
- The divalent state becomes more stable on moving down the group. Sn(II)Cl
2
is obtained by dissolving Sn in
concentrated HCl. On cooling this solution, Sn(II)Cl
2
crystallises in form of SnCl
2
.2H
2
O.
- Anhydrous SnCl
2
acts as a reducing agent in acidic solution.
2Fe
3+
+ Sn
2+
Sn
4+
+ 2Fe
2+
- Pb(II) halides are obtained by adding halide ions into a soluble lead salts.
Pb
2+
+ 2X

PbX
2
(where X = F, CI, Br, I)
- Pbl
2
is yellow; other halides are colourless and sparingly soluble in water.
Write a note on oxide of group 14 [3 mark]
MO
2
type oxide (preparation; properties and uses)
- Si, Ge, Sn and Pb form MO
2
type oxides. In silica, silicon and oxygen atoms combine by covalent bond and form
infinite three dimensional network of four oxygen atoms. In SiO
2
each Si atom is covalently bonded to four
oxygen atoms. In SiO
2
is Si atom combines with oxygen atoms tetrahedral manner.
- Crystalline silicon dioxide occurs in quartz, cristobalite and tridymite minerals. Quartz is used as a piezoelectric
crystal, crystal oscillator and in transducers.
- Silica gel is obtained by acidification of sodium silicate. When this gel is dehydrated, the obtained silica gel is
extensively used in chromatography and for the drying of other substances, and therefore, it acts as a drying
agent.
- GeO
2
, SnO
2
and PbO
2
are solid and exist in several modifications. SiO
2
is acidic but GeO
2
and SnO
2
are
amphoteric while PbO
2
is basic.
- Sn(IV) oxide is prepared by heating Sn and O
2
or reaction or Sn with con HNO
3
. SnO
2
is used in polishing powder
and in manufacturing of glass and pottery.
- PbO
2
is prepared by reaction of Pb
3
O
4
with dil HNO
3
.
Pb
3
O
4
+4HNO
3
2Pb(NO
3
)
2
+PbO
2
+ 2H
2
O
- PbO
2
is a strong oxidising agent and liberates O
2
when treated with acids.
MO type oxides. (Preparation; properties and uses)
- Sn and Pb both form MO type stable oxides. SnO is obtained by heating tin oxalate.
- SnC
2
O
4

SnO + CO + CO
2
- PbO exists in red, orange and yellow colour depending upon the method of preparation. It can be prepared by
heating lead carbonate. On heating PbO with air in a reverbatory furnace at 773 K temperature gives red Pb
3
O
4
.
It is a combination mixture of 2(PbO) (PbO
2
).
List the anomalous behaviour of carbon. [3 mark]
Carbon differs from the other members of its group, because the atomic size of carbon is small and has higher
electronegativity. The ionisation enthalpy of carbon is high and also lacks d-orbital in its electronic configuration.
Due to following characteristics, it differs from the other members of its group.
(i) Carbon forms only four covalent bonds while other elements have d or d and f-orbitals. So they can form more
covalent bonds. (5 or 6)
(ii) Carbon atom forms single bond as well as double or triple bond with the other carbon atoms and some other
atoms like O,N and S which are small in size and have high eletronegativity. It forms C = O, C = S, C = N, C = N
with p p (over lapping of 2p orbitals) bonding. If the atomic size of atoms are very big then overlapping of
pt pt over lapping does not remain effective.
(iii) Catenation property of carbon is maximum due to its high value of carbon-carbon single bond enthalpy (348 kJ
mol
1
). So it forms number of organic compounds having chain and cyclic structure while in other elements, this
trend goes on decreasing in the group.
(iv) Carbon forms only pt pt type bonding while other elements form pt pt and also dt pt type of
bonding.
Explain catenation in carbon. [2 mark]
The carbon atom has tendency to link with another carbon atom by covalent bond and forms chain or cyclic
structure of carbon which is called catenation.
This trend is observed due to small size and high eletronegativity of carbon atom.
Tendency of catenation also depends upon the bond enthalpy of covalent bond between two carbon atoms; higher
the bond enthalpy more is the tendency of catenation. The bond enthalpy of C C is 348 kJ mol
1
which is highest
than the other elements in its group
Therefore carbon forms a number of chain and cyclic structure compounds due to catenation and pt pt bond
formation the carbon exhibits different allotropes.
Why carbon exhibit allotrope? Mention the various allotropes of carbon. [2 mark]
Due to catenation in carbon and pt pt bond formation, it exhibits many allotropes. The diamond and graphite
are the crystalline allotropes. In 1985, H. W. Kroto, R. E. Smalley and R. I. Curi discovered the third crystalline
allotrope fullerene. Coal wood charcoal, animal charcoal lamp black, coke, gas carbon etc are amorphous allotropes
of carbon. The structure and properties of crystalline allotropes are given below:
Write a note on structure of diamond [2 mark]
Due to sp
3
hydridisation in carbon, it combines with other four carbon atoms by single covalent bond. The bonded
four carbons are arranged towards the corner of me tetrahedron as shown in Fig. Each carbon atom, due to sp3
hybridisation joins with other four carbon atoms by single covalent bond and forms three dimensional network
structure. The distance between two carbon atoms is 154 pm. All the carbon atoms are bound to each other by
covalent bonding and these bonds are very strong. So diamond is extremely hard solid substance.
Fig structure of Diamond
Write a note on structure of Graphite. [2 mark]
As the result of sp
2
hybridisation in carbon atom, it combines with other three carbon atoms and as a result
hexagonal layer structure is formed as shown in Figure .
The distance between two carbon atoms is 141.5 pm and distance between two layers is 340 pm and have weak
Vander Waals attractive forces between the two layers.
According to the circumstances there might be a little change possible between the two layers. Due to weak van der
Waals forces the graphite is soft.
Graphite
Write a note on structure of Fullerene.[3 mark]
The crystalline form of carbon is made up of porous cage like molecules. It possesses C
2n
structure.
The two important members are having number of carbon atoms C
60
and C
70
.
Crystalline fullerene was first prepared by evaporation of graphite using lasers but presently preparation involves
the heating of graphite in an electric arc in the presence of an inert gas such as He or Ne, that gives sooty material
on condensation, mainly C
60
with small quantity of C
70
and traces of other fullerene, consisting of even number of
carbon atom upto 350 or above are obtained.
As shown in Figure the C
60
molecule has shape like soccer ball and also called Buckminister Fullerene.
Fig Fullerene
The shape of fullerenes resembles to shape of football.
The special shape of fullerene is also called bucky ball. It contains twelve rings having five carbon atoms and twenty
rings having six carbon atoms. The ring structure having six carbon atoms is fused to both types of ring, while the
ring structure having five carbon atoms is fused only to six member ring.
All the carbon atoms in Fullerene are equivalent and they undergo sp
2
hybridisation. So each carbon atom combines
with other three carbon atoms with o - bond. The remaining electron forms t - bond and hence, the t - bond
electron gets delocalised in molecular orbital which gives aromatic character in fullerene.
In fullerene the carbon-carbon single and double bonds with distance 143.5 pm and 138.3 pm are there respectively.
C
60
and C
70
fullerene are soluble in toluene solvent and give purple and orange-red coloured solution. Fullerenes are
the only pure forms of carbon because they have no dangling bond so possess smooth structure.
Write a note on physical properties of Carbon. [2 mark] {4 point required}
(i) Carbon has a number of allotropes from which diamond, graphite and fullerene are crystalline, and different
types of coal, coke, gas carbon are the amorphous allotropes.
(ii) Diamond is hard whereas graphite is soft.
(iii) Diamond is insulator while graphite is good condutor of electricity.
(iv) Fullerene is the crystalline synthesized form of carbon. It has cage like structure.
(iv) Diamond and graphite have network structure while fullerene has molecular structure.
(v) Diamond and graphite are insoluble in liquid solvent, while fullerence is soluble in suitable solvent (benzene).
(vi) Charcoal is porous, hence, it possesses the adsorption property.
Write a note on Chemical Properties (Chemical reactions)of carbon. [4 mark] (any three with all necessary
equations)
(i) All the allotropic forms of carbon burn in air and form CO or CO
2
. If the proportion of O
2
is limited, then CO is
formed and if the proportion of O2 is more, then CO
2
is formed. This combustion reaction is exothermic
reaction.
2C + O2 2CO +Energy
C + O
2
CO
2
+ Energy
(ii) Reduction properties : Carbon is a strong reducing agent. It reduces many metallic oxides and form
corresponding metals. During reduction, sulphide is obtained from metal sulphate.
ZnO + C Zn + CO
PbO + C Pb + CO
Fe
2
O
3
+3C 2Fe + 3CO
BaSO
4
+ 4C BaS + 4CO
PbSO
4
+ 4C PbS + 4CO
On passing water vapour over red hot coke H
2
gas can be evolved.
C + H
2
O CO + H
2
(iii) Reaction with other elements: Passing vapour of sulphur over the red hot carbon gives CS2.
C + 2S CS
2
(carbon disulphide)
When an electric spark is struck between carbon electrodes in the presence of H
2
, acetylene is formed.
2C + H
2
C
2
H
2
Electric spark
When carbon is heated with berylhum, it forms beryllium carbide.
2Be + C Be
2
C (Beryllium carbide)
A
(iv) Reaction with acid : When charcoal is heated with hot and dil HNO
3
, it slowly dissolves and gives brown
substance which is known as artificial tannin. When carbon reacts with con. HNO
3
it gets oxidised and forms CO
2
C + con. 4HNO
3
CO
2
+ 4NO
2
+ 2H
2
O
Carbon reacts with hot con. H
2
SO
4
, it gets oxidised to CO
2
and H
2
SO
4
is reduced to SO
2
and a small quantity of
mellitic acid (Beneze hexacarboxylic acid) is also formed.
C + 2H
2
SO
4
CO
2
+ 2SO
2
+ 2H
2
O
12C + 9H2SO
4
C
6
(COOH)
6
+ 6H
2
O + 9SO
2
Uses of some important compounds of carbon:
(1) state uses of Halides of carbon : [2mark]
The reaction of carbon with halogen forms carbon tetrahalides. CF
4
is a gaseous; CCl
4
is liquid while CBr
4
and CI
4
are solids. Its order of stability is CF
4
> CCl
4
> CBr
4
> CI
4
(i) CCl
4
is used as a solvent and fire extinguisher.
(ii) CF
2
Cl
2
, which is known as Freon, was earlier used in refrigerator as a coolant.
(iii) CCl
4
is used as medicine for antihookworm in intenstine.
(2) (2) state uses of Carbon disulphide : (CS
2
) : [2mark]
(i) It is used in the manufacture of Viscose Yarn.
(ii) It is used as an insecticide for curing infected seeds.
(iii) It is used in vulcanisation of rubber.
(iv) It is used as solvent in the manufacture of varnishes and boxes.
(v) It is used in the manufacture of carbon tetrachloride
(3) state uses of Carbide Compounds : [2mark]
The compounds of carbon with high electropositive elements are known as carbide compounds, e.g. SiC, Fe
3
C,
CaC
2
, WC, Al
4
C
3
, Be
4
C
(i) SiC, which is known as carborandum, is very hard, so used as refractory and abrassive for sharpening and
grinding metals and other substances.
(ii) WC is used for making tools and dyes, for making cans etc.
(iii) CaC
2
is used for preparing acetylene and it is used for welding and in manufacturing of number of organic
compounds such as ethyl alcohol, acetic acid etc.
(iv) Be
4
C is very hard and is used as a shield against radioactive radiation.
(4) Oxides of carbon :
Carbon can bum in air or O
2
and gives carbon monoxide (CO) and carbon dioxide (CO
2
).
(i) Carbon Monoxide (CO) :
Describe various method of preparation of CO. [3mark]
(i) Carbon monoxide is prepared by incomplete combustion of carbon or carbon containing compounds in a limited
supply of O
2
C + O
2
CO
A
1
2
Incomplete combustion of petrol and diesel produces CO.
(ii) CO is prepared by the reduction of oxides of heavy metals with carbon.
ZnO + C Zn + CO
Fe
2
O
3
+ 3C 2Fe + 3CO
(iii) Pure CO can be prepared in a laboratory on small scale by heating formic acid (HCOOH) with con H
2
SO
4
at about
373 K to 413 K temperature. Here, H
2
SO
4
acts as a dehydrating agent.
HCOOH CO + H
2
O
372 K 413 K
Con. H
2
SO
4
(iv) On commercial scale CO is prepared by passing water vapour at 473 K to 1273 K temperatures over hot coke and
produce mixture of CO and H
2
which is known as water gas or synthesis gas.
C
(s)
+ H
2
O
(g)
CO
(g)
0
2(g)
473K 1273K
Water gas
Instead of water vapour if air is used then it produces mixture of CO and N
2
which is known as producer gas. !
2C
(s)
+ O
2(g)
+ 4N
2(g)
2CO
(g)
4N
2(g)
1273K
Producer gas
Write a note on Properties of CO. [3 mark]
(i) Carbon monoxide is colourless and odourless gas, and it is sparingly soluble in water.
(ii) It is highly toxic in nature because it forms stable (nearly 300 times) complex with haemoglobin present in blood
and stops die oxygen carrying capacity of die blood, hence it causes death.
(iii) CO on combustion gives pale blue flame
C + O
2
CO
A
1
2
(iv) Reducing character : It reacts with many metal oxides and reduces to corresponding metals e.g.
ZnO + CO Zn + CO
2
CuO + CO Cu + CO
2
Fe
2
O
3
+ 3CO 2Fe + 3CO
2
(v) Formation of metal carbonyl character : CO combines as ligand with many transitional metals, such as Ni, Fe, Co
etc and form metal carbonyl complex compounds, e.g.
Ni + 4CO [Ni(CO)
4
]
333 K - 343K
Nickel tetracarbony
Fe + 5CO [Fe(CO)
5
]
Iron pentacarbonyl
State the Uses of CO.[3mark]
(i) CO is useful for extraction of some metals from their oxide. For example, used in blast furnace.
Fe2O
3
+ 3CO 2Fe + 3CO
2
(ii) CO is used to prepare tetracarbonyl nickel in Mond's carbonyl process to obtain pure nickel metal from impure
nickel metal.
Ni
(s)
+ 4CO
(g)
Ni(CO)
4(g)
A
(iii) In industrial field CO is used as a fuel in the form of water gas and producer gas.
(iv) It is used in manufacturing of methyl alcohol and formic acid. '
(v) It is used in manufacturing of magnetic tapes (Iron carbonyl) for tape recorder.
(ii) Write a note on preparation of Carbon Dioxide (CO
2
). [3 mark]
Preparation :
(i) Carbon dioxide is prepared by burning carbon, hydrocarbon like CH4 or carbon monoxide in excess of air.
C + O
2
CO
2
CH
4
+ 2O
2
CO
2
+ 2H
2
O
2CO + O
2
2CO
2
(ii) In laboratory, CO
2
is obtained by reaction of CaCO
3
with dil HCl
2CaCO
3
+ 2HC1 CaCI
2
+ CO
2
+ H
2
O
(iii) On industrial scale, CO
2
is obatined as a by-product during manufacturing of lime and manufacturing of ethyl
alcohol.
CaCO
3
CaO + CO
2
A
1600 K
Lime
C
6
H
12
O
6
2C
2
H
5
OH + 2CO
2
Zymase
enzyme
Ethyl alchol
Write a note on Properties CO
2
. [3 mark]
(i) It is colourless, odourless gas and about 1.5 times heavier than air.
(ii) It is not poisonous but it does not support life of animal and human being but they die in its presence due to lack
of O
2
, gas.
(iii) At room temperature and 50 to 60 atm. pressure CO
2
gas can be liquefied, when liquid CO
2
is allowed to
evaporate rapidly i.e. expands rapidly, it is converted into solid which is known as dry ice.
(iv) CO
2
gas is neither combustible nor supporter of combustion. However, in its presence certain active metals such
as Na, K, Mg etc. continue to burn.
2Mg + CO
2
2MgO + C
(v) CO
2
rums blue litmus paper red so it is acidic in nature.
(vi) It is sparingly soluble in water but when dissolved in water, carbonic acid (soda water (H
2
lCO
3
) can be obtained
which is dibasic acid and it dissociates in two stages.
H
2
CO
2
+ H
2
O HCO
3

+ H
+
3
O
H
2
CO
2
+ H
2
O HCO
3
2
+ H
+
3
O
(vii) On passing CO
2
through lime water it turns milky due to formation of insoluble CaCO
3
and on passing it in excess
milkiness disappears due to formation of soluble calcium hydrogen-carbonate (calcium bicarbonate)
Ca(OH) + CO
2
CaCO
3
+ H
2
O
Lime water Calcium carbonate
CaCO
3
+ CO
2
+ H
2
O Ca(HCO
3
)
2
Calcium hydrogencarbonate
(viii) In the presence of sunlight and chlorophyll of green plants, CO
2
reacts with water to form glucose. This reaction
is called photosynthesis.
6CaCO
2
+ 6H
2
O C
6
H
12
O
6
+ 6O
2
In presence of
chlorophyl
hv
State the Uses CO
2
. [3 mark] (any 6)
(i) Mixture of ether and solid CO
2
creates low temperature upto 165 K, hence it is used in liquefying other gases
and act as a coolant in cold storage.
(ii) CO
2
is neither combustible nor supporter of combustion. Therefore it is used as a fire extinguisher.
(iii) CO
2
is used in preparation of soft drinks and soda water.
(iv) CO
2
used in manufacturing of washing soda (Solvay's Process).
(v) Dry ice is used in curing of local burns and in hospital for surgical operation of sores.
(vi) During artificial respiration for the victims of CO poisoning it is used in form of carbogen (85% O
2
+ 5% CO
2
mixture known as carbogen).
(vii) CO
2
is used for the purification of cane sugar juice in manufacturing of sugar.
(viii) CO
2
is used in photosynthesis by green plants.
(ix) To control the pH(7.26 to 7.42) of blood CO
2
gas is used in carbonic acid buffer system (H
2
CO
3
+ HCO
3

).
(x) Large amount of CO
2
is used in production of fertiliser like urea.
Important Compounds of Silicon:
(1) Give brief note on Silicon hydrides [2mark]
Hydride compounds of silicon have general formula Si
n
H
2n+2
. The value of bond enthalpy for silicon-silicon is 297
kJmor1 hence, catenation character is observed in it so it forms limited hydride compounds Si
n
H
2n+2
where n = 1
to 8. This compound is also known as silane. The stability of silanes are less compared to hydrides of carbon,
hence, they have more reduction power.
(2) Describe the various form of Silicon dioxide (Silica SiO
2
)and mentioned it chemical properties. [3 mark]
- It is a solid substance having three dimensional structure.
- A silicon atom combines with four oxygen atoms by covalent bonding which is shared by four other si atoms.
Thus, SiO
2
does not exist as a single molecule but the arrangement of number of atoms forms a giant crystal.
- More than 22 allotropic structures are known in which some are crystalline e.g. quartz, tridimite, crystobelite
etc., while amorphous like silica gel and kieselgur, SiO
2
are acidic, hence, it dissolves in liquid alkali or alkali
carbonate to form silicate compounds.
- At high temperature SiO
2
reacts with NaOH to form Na
2
SiO
3
. SiO
2
+ 2NaOH Na
2
SiO
3
+ H
2
O
- SiO
2
react with HF and gives SiF
4
SiO
2
+ 4HF SiF
4
+ 2H
2
O
- SiO
2
reacts with halogen (only F
2
) and SiF
4
is obtained and O
2
is liberated. SiO
2
+ 2F
2
SiF
4
+ O
2
Write the Uses of Silica. [2 mark]
(i) It is used as a Piezoeletrical crystal, crystal oscillators and as transducer.
(ii) It is used in laboratory glassware and preparation of optical components such as lens and prisms.
(iii) Used in sample cell for U.V. spectrophotometers.
(iv) Used as a drying agent in form of silica gel and also in material for adsorption in chromatography.
(v) Used as catalyst
(vi) Used in water Alteration plants in form of Kieselghur
(3) Write a note on preparation of silicon tetrachloride (SiCI
4
) . {with mechanism} [4mark] {note in this question
draw necessary figure from the text book.
Reaction of silicon with chlorine on heating gives SiCl
4
Si + 2Cl
2
SiCl
4
A
In silicon tetrachloride silicon has sp
3
hybridisation and so it is tetrahedral in shape and forms covalent bond with
chlorine atom. Hydrolysis of SiCl
4
give silicic acid (H
4
SiO
4
)
SiCl4 + 4H2O Si(OH)
4
+ 4HCl
Silicic acid
The mechanism for hydrolysis of SiCl
4
are in two steps as given below :
(i) In the first step the oxygen atom of H
2
O molecules donates pair of electron to empty d-orbital of silicon
in SiCl4 and forms co-ordination covalent bond. [redraw following figure from text book]
(ii) In second step as the HCl molecule is removed, the chlorine atom of SiCl
4
is substituted and finally silicic
acid is obtained.
Cl Cl H Cl HO OH
Si O Si
Cl Cl H Cl Cl OH
l OH
Si
l OH
HCI
+3H O
2
Hcl
Explain the structure and preparation of Silicones [3 mark]
Silicones are synthetic materials containing Si O Si bond linkage. These compounds are polymeric substances
containing R
2
SiO repeating unit. They have general formula (R
2
SiO)n where R is methyl or phenyl group. Its empirical
formula R
2
SiO is similiar to that of ketone of organic compound, so they are called silicones.
2CH
3
C1 + Si (CH
3
)
2
SiCl
2
(CH
3
)2Si(OH)
2
Powder of Cu
570 K
Hydrolysis
2H
2
O
2HCI
Dimethyl
chloro silane
Dimethyl
Silanol
Preparation : Methyl chloride reacts with silicone in the presence of copper powder as a catalyst at 570 K
temperature, dimethyl chlorosilane is obtained and its hydrolysis is followed by condensation polymerisation that
gives silicones.
The length of this polymer chain can be controlled by (CH
3
)
3
SiCl
n(CH ) Si(OH) O Si O Si
3 2 2
Condensation
polymerisation
H O
2
CH
3
CH
3
CH
3
CH
3
Silicones
n
State the Properties and uses of silicones.[3mark]
Properties :
(i) Short chain silicones are oily liquid, medium chain behave as viscous oil jellies and greases and those with very
long chain behave as rubbery elastomers and resins
(ii) Silicones resist the organic reagent, oxidation and thermal decomposition. Hence, they are chemically inert.
(iii) Silicones are heat resistant and electric insulator substances; more over, possess the character of water
repellent.
Uses:
(i) For making water-proof paper, wool, textiles, wood, etc they are coated with a thin film of silicones.
(ii) Silicones are used as sealants and electrical insulators.
(iii) Used as lubricant at high and low temperatures.
(iv) Used as surgical implants.
(v) Used as antifoaming agents in cosmetics
General Information and Structure- of Silicates: Approximately 95% of the earth crust consists of silicates and silics.
Silicate compounds contain independent or such type of ions joined to form combined silicate ions and their
charges are being balanced by cations such as Na
+
, K
+
, Mg
2+
, Ca
2+
. The basic structural building block in silicates is the
having tetra-hedral structure.
Types of silicates : In the structure of silicates depending upon the number of corner (0, 1, 2, 3, 4) of the
tetrahedron shared with other tetrahedrons and based on that they ate classified which are indicated in Table
In a three dimensional structure of SiO
2
, Si
4+
is partially substituted by Al
3+
which gives alumi-nosilicate called
feldspar. In aluminosilicate the and tetrahedrons join with each other in a simple way to form three
dimensional networks known as zeolites.
Classification of silicates
Type of
Silicate
Figure Anionic unit example
Ortho
silicate
[SiO
4
]
4
Olivine
(Mg Fe
2
SiO
4
)
zircon(ZrSiO
4
)
Di or pyro
silicate
[Si
2
O
7
]
6
thortveitite
Ring silicate
-2n
3 n
[SiO ]
[Si
3
O
9
]
6
Wollastonite
Ca
3
Si
3
O
9
[Si
6
O
18
]
12
Beryl
Be
3
Al
2
Si
6
O
18
gemstone
emerald
Chain
silicate
-2n
3 n
[SiO ]
Two
dimensiona
l silicate
Amphiboles [Si
4
O
11
]
n
6n
Talc
-2n
2 10 n
[Si O ]
Amphiboles
-6n
4 11 n
[Si O ]
Talc
-2n
2 5 n
[Si O ]
Kaolin
Al
2
(OH)
4
Si
2
O
5
,
Talc
-4
4 10
[Si O ]
Mg
3
(OH)
2
Si
4
O
1
0
Biotite,
Muscovite
Asbestos
-4
4 10
[Si O ]
Three
dimensiona
l silicate
SiO
2
Quartz,
Feldspar,
Zeolite
Uses of zeolite : Zeolite has a network of cavities linked by channels. In these channels only small molecules can
enter, hence, zeolite is used as a molecular sieve for separating small molecules from big molecules; zeolite is used
as a catalyst (shape-selective catalyst). One important calayst of zeolite is ZSM-5. It is used in petrochemicals. It
converts alcohol directly into gasoline (petrol) by dehydration and the mixture of hydrocarbons is formed.
MCQ CH-5
1. When formic acid is treated with conc. H2SO
4
, the gas evolved is :
(a) H2S (b) SO
2
(c) CO (d) CO
2
2. Thermodynamically the most stable form of carbon is
(a) Diamond (b) Graphite (c) Peat (d) Coal
3. Diamond and graphite are
(a) Homologues (b) Allotropes (c) Isomers (d) None of the above.
4. Which of the following is the hardest substance?
(a) Graphite (b) Carborundum (c) Diamond (d) Coke.
5. Which of the following is the least stable carbon halide?
(a) CCl
4
(b) CF
4
(c) CBr
4
(d) CI
4
6. What is the correct order of ionisation enthalpy for group 14 elements?
(a) C> Si > Ge > Sn < Pb (b) C> Si > Ge > Sn > Pb (c) C< Si < Ge < Sn < Pb (d) none
7. Which of the following is correct order of catenation for group 14 elements?
(a) C > > Si > Ge >> Sn > > Pb (b) C > > Si > Ge Sn > > Pb (c) C > > Si > Ge < Sn > > Pb (d) can not predict
8. Boric acid is polymeric due to
(a) Its acidic nature (b) The presence of hydrogen bonds (c) Its monobasic nature (d) Its geometry
9. Which of the following statements about boric acid is false? ~
(a) It acts as a monobasic acid (b) It is formed by the hydrolysis of boron halide (c) It has planar structure (d) It acts
as a tribasic acid.
10. From B
2
H
6
all the following can be prepared except
(a) H
3
BO
3
(b) B
2
(CH
3
)
4
H
2
(c) B
2
(CH
3
)
6
(d) NaBH
4
.
11. Which of the following oxides is neutral?
(a) CO (b) SnO2 (c) ZnO (d) SiO2.
12. Conc, HNO
3
is stored in containers made up of
(a) Cu (b) Zn (c) AI (d) Sn. (Haryana C.E.E.T. 1999)
13. The geometry and the type of hybrid orbital present about the central atom in BF3 is
(a) linear, sp (b) trigonal planar, sp2 (c) tetrahedral, sp3 (d) pyramidal, sp3. (I.I.T. 1998)
14. Unlike PbCI
4
, PI
4
and PBr
4
are not found because (Haryana C.E.E.T. 2000)
(a) Chlorine is more electropositive (b) Iodine and bromine are of large size
(c) Iodine and bromine are unable to oxidise Pb to Pb
+4
(d) The statement is wrong
15. Which of the following allotropic forms of carbon is isomorphous with crystalline silicon?
(a) Graphite (b) Coal (c) Coke (d) Diamond (E.A.M.C.E.T.2001)
16. Specify the co-ordination geometry around and hydridisation of Nand B atoms in a 1 : 1complex ofBF
3
and NH
3
(a) N : tetrahedral, sp
3
; B : tetrahedral, sp
3
(b) N: pyramidal, sp
3
; B : pyramidal, sp
3
(c) N : pyramidal, sp
3
; B : planar, sp
2
(d) N : pyramidal, sp
3
; B : tetrahedral, sp
3
(I.I. T. 2002)
17. Graphite is a soft solid lubricant extremely difficult to melt. The reason for this anomalous behaviour is that
graphite
(a) has carbon atoms arranged in large plates of rings of strongly bound carbon atoms with weak interplate
bonds
(b) is a non-crystalline substance (c) is an allotropic form of carbon
(d) has molecules of variable molecular masses like polymers (A.I.E.E.E.2003)
18. Which of the following is not a protonic acid?
(a) B(OH)
3
(b) PO(OH)
3
(c) SO(OH)
2
(d) SO
2
(OH)
2
(A.I.P.M.T.2003)
19. H
3
BO
3
is
(a) Monobasic and weak Lewis acid (b) Monobasic and weak Bronsted acid
(c) Monobasic and strong Lewis acid (d) Tribasic and weak Bronsted acid (I.I.T. 2003)
20. Which of the following is only acidic in nature
(a) Be(OH)
2
(b) Mg(OH)
2
(c) B(OH)
3
(d) AI(OH)
3
(A.I.I.M.S.2004)
21. The soldiers of Napolean army while at Alps during freezing winter suffered a serious problem as regards the tin
buttons of their uniforms. White metallic tin buttons got converted into grey powder. This transformation is
related to
(a) an interaction with nitrogen of the air at very low temperatures.
(b) a change in the crystalline structure of tin.
(c) a change in the partial pressure of oxygen in the air.
(d) an interaction with water vapour contained in the humid air. (A.I.E.E.E.2004)
22. Which of the following does not exist in free state
(a) BF
3
(b) BCI
3
(c) BBr
3
(d) BH
3
(e) None of the above (Kerala P.M.T. 2004)
23. Which of the following imparts green colour to the burner flame ?
(a) B(OMe)
3
(b) NaOMe (c) AI(OPr)
3
(d)Sn(OH)
2
(A.I.I.M.S. 2004)
24. Heating an aqueous solution of aluminium chloride to dryness will give
(a) AlCI
3
(b) Al
2
Cl
6
(c) AI
2
O
3
(d) Al(OH)CI
2
(A.I.E.E.E. 2005)
25. The structure of diborane (B
2
H
6
) contains
(a) four 2c-2e bonds and two 3c-2e bonds (b) two 2c-2e bonds and four 3c-2e bonds
(c) two 2c-2e bonds and two 3c-3e bonds (d) four 2c-2e bonds and four 3c-2e bonds (A.I.E.E.E. 2005)
26. Which gas is evolved when PbO
2
is treated with conc. HNO
3
?
(a) NO
2
(b) O
2
(c) N
2
(d) N
2
O (I.I.T. 2005)
27. Borax is used as a cleansing agent because on dissolving in water, it gives
(a) alkaline solution (b) acidic solution (c) bleaching solution (d) amphoteric solution (A.I.I.M.S. 2006)
28. A metal, M forms chlorides in + 2 and +4 oxidation states. Which of the following statements about these
chlorides is correct?
(a) MCl
2
is more volatile than MCI
4
. (b) MCI
2
is more soluble in anhydrous ethanol than MCI
4

(c) MCI
2
is more ionic than MCI
4
. (d) MCI
2
is more easily hydrolysed than MCI
4
. (A.I.E.E.E. 2006)
29. In which of the following silicates, cyclic structure is present?
(a) mica (b) asbestos (c) emerald (d) talc (GuJrat C.E.T. 2006)
30. Germanium is transparent in
(a) visible light (b) infrared region (c) ultraviolet region (d) infraviolet region (GuJrat C.E.T. 2006)
31. AI
2
O
3
can be converted to anhydrous AlCl
3
by heating
(a) AI
2
O
3
with CI
2
gas (b) AI
2
O
3
with HCI gas (c) AI
2
O
3
with NaCI in solid state
(d) a mixture of AI
2
O
3
and carbon in dry CI
2
gas. (A.I.P.M.T. 2006)
32. Amorphous form of silica is
(a) tridymite (b) cristobalite (c) fumed silica (d) asbestos (H.P.P.M.T. 2006)
33. The number of isomers possible for disubstituted borazine, B
3
N
3
H
3
X
2
is
(a) 3 (b) 4 (c) 6 (d) 2 (e) 5 (Kerala P.M.T. 2006)
34. Which of the following statements about diborane is not true?
(a) the B atoms in it are sp
2
-hybridized (b) it contains two 3-centre-2-electron bonds
(c) all B-H bond lengths are equal due to resonance (d) the molecule is non-planar
(e) the molecule contains 12 valence electrons (Kerala P.M.T. 2006)
35. Which is strongest Lewis acid?
(a) BF
3
(b) BCI
3
(c) BBr
3
(d) BI
3
(D.C.E.2006)
36. Which of the following anions is present in the chain structure of silicates?
(a) SiO - (b) Si O (c) (Si O ) (d) ( ) (A.I.P.M.T. 2007)
37. Which of the following oxidation states are the most characteristic for lead and tin respectively?
(a) + 2, + 2 (b) + 4, + 2 (c) + 2, + 4 (d) + 4, + 4 (A.I.P.M.T.2007)
38. The correct order of C- O bond length among CO, CO , CO
2
is
(a) CO < CO2 < - (b) CO2 < CO - < CO (c) CO < CO < CO2 (d) CO < CO2 < CO
39. White lead is
(a) Pb
3
O
4
(b) PbO (c) 2 PbCO3 . Pb(OH)
2
(d) Pb(CH
3
COO)
2
. Pb(OH)
2
(C.P.M.T. 2007)"
40. Which of the following is a combustion reaction 'f
(a) C + O
2
CO
2
(b) CH
4
+ O
2
CO
2
+ H
2
O
(c) 2 Mg + O
2
2 MgO (d) All of these (C.P.M.T. 2007)
41. The stability of dihalides of Si, Ge, Sn and Pb increases steadily in the sequence
(a) PbX
2
< <Sn X
2
<< GeX
2
<<SiX
2
(b) Ge X
2
<<Si X
2
<< Sn X
2
<< Ge X
2
(c) Si X
2
< <Ge X
2
<<Pb X
2
<< Sn X
2
(d)Si X
2
<<Ge X
2
<< Sn X
2
< < Pb X
2
(A.I.E.E.E. 2007)
42. How many O-atoms are shared per SiO4 tetrahedral in silicate anion of beryl mineral '!
(a) 4 (b) 3 (c) 2 (d) 1. (Gujrat C.E.T. 2007)
43. Water transported through lead pipes becomes poisonous due to the formation of
(a) Pb(OH)
2
(b) PbO (c) PbO
2
(d) Pb
3
O
4
(West Bengal J.E.E. 2007)
44. The repeating structural unit in silicone is
(a) SiO
2
(b)
R
Si
R
O
(c)
R
Si
R
O O
(d)
R
Si
R
O
O
(A.I.I.M.S. 2007)
45. The type of hybridization of boron in diborune is
(a) sp-hybridization (b) sp
2
hybridization (c) sp
3
-hybridization (d) sp
3
d
2
-hybridization
(A.I.P.M.T. 1999 ; A.I.E.E.E. 2007)
46. Which one of the following is the correct statement?
(a) B
2
H
6
. 2 NH
3
is known as 'inorganic benzene'. (b) Boric acid is a protonic acid.
(c) Beryllium exhibits coordination number of six.
(d) Chlorides of both beryllium and aluminium have bridged chloride structures in solid phase.(A.I.E.E.E. 2007)
47. Among the following substituted silanes the one which will give rise to cross linked silicone polymer on hydrolysis
is
(a) R
3
SiCI(b) R
4
Si(c) RSiCl
3
(d) R
2
SiCl
2
(A.I.E.E.E. 2008)
48. The ion(s) that act/s as an oxidising agent in solution is/are
(a) Tl
+
and Al
3+
(b) B
3+
and AI
3+
(c)TI
3+
only(d) B
3+
only (e) Tl
+
only (Kerala P.M.T. 2008)