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Iit Jee - 2013 Chemistry "Boron Family"
Iit Jee - 2013 Chemistry "Boron Family"
Iit Jee - 2013 Chemistry "Boron Family"
CHEMISTRY P. JOY
EXERCISE # 1
Note
ELEMENTAL BORON :
Q.1 What are the elements of 3rd group ?
Q.19 Which element has the higher I.E. among all elements ?
Q.25 Give the trend of inert pair effect from top to bottom ?
Q.26 How inert pair effect affects the oxidation state of 13th group
element ?
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COMPOUNDS OF BORON
BORIC ACID :
Q.30 What are the important compounds of boron ?
Q.32 What are the various formula by which Boric acid can be shown?
Q.35 Show what happens when boric acid is dissolved in heavy water?
Q.36 Does there a lewis acid - base reaction take place when boric acid
is dissolved in water.
OH
Q.43 Two OH group on a carbon atom C is unstable but two
OH
Q.44 Although Carbon and Boron both belong to second row and both
donot have d-orbitals. Yet two hydroxy group on a Carbon is
unstable whereas on Boron there are stable.
Q.46 Although Boric acid is a weak acid but it can’t be titrated with
sodium hydroxide ............ explain why ?
Q.47 Why diols like ethylene glycol, catechol are added when boric
acid is titrated with sodium hydroxide ?
Q.48 Why catechol is added when boric acid is titrated with NaOH ?
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Note
DIBORANES :
Q.50 What are boranes ?
BORAX :
Q.63 What is the formula of Borax ?
Q.68 How many number of sp3 hybridised Boron are present in Borax.
Q.69 How many number of sp2 hybridised Boron are present in Borax.
Q.71 How many Boron units are connected by an oxygen atom diago-
nally ?
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Q.76 Write an equation to show reaction of Borax with HCl or H2SO4. Note
Q.77 How many moles of NaOH are consumed when Borax is treated
with NaOH
BORON HALIDE :
Q.81 What are the physical state of BF3 , BCl3 , BI3 ?
Q.86 What is the correct order of Lewis acid character of various boron
halide ?
Q.90 Pure BBr3 and BI3 are colourless but on exposure to light they
become coloured. Explain why ?
Q.91 BF3 has higher ∆Hf than other halides of Boron. Explain why ?
Q.96 What happens when any two of halides BF3, BCl3, BBr3 are mixed
together ?
Q.97 What happens if BCl3, BF3, BBr3 all are mixed together ?
Q.99 What happens when BF3 is reacted with RMgX [Grignard reagent]?
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ELEMENTAL ALUMINIUM : Note
Q.101 Aluminium belongs to which block elements ?
Q.110 Al is more reactive than Fe but Al is less easily corroded than Fe.
Why?
Q.111 Why Aluminium metal is corroded in coastal places near to the sea ?
Q.116 Why Aluminothermy used for on the spot welding of large iron
structures
HYDROXIDE :
Q.119 What are the various hydroxides of group III element and how do
their acidic and basic properties vary ?
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EXTRACTION OF ALUMINIUM :
Q.136 Which ore of Aluminium is used for its extraction ?
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Q.145 Which process is used for purification of bauxite containing Note
high silica content as impurity ?
Q.148 What are the reactions taking place at cathode and anode in
electrolytic reduction ?
HALIDES :
Q.153 Which halide of IIIA group element exist as a monomer ?
Q.159 Are the bonding states of Al2Cl6 in vapour phase and in aqueous
phase are different.
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Q.171 What happens when AlCl3 vapours are passed over fused Al2O3 at
1000ºC.
ALUM :
Q.177 What are alums ?
Q.185 How many water molecules act as ligands about mono and trivalent
metal cations in alum.
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Note
–3
Elements Atomic No. Relative atomic M.P. Density/kgm
mass
B 5 10.81 2573 2390
Al 13 26.98 933.52 2698
Ga 31 69.72 302.9 5967
In 49 114.82 429.32 7310
Tl 81 204.36 576.7 11850
Ans. B
Al
Ga
In
Tl
B
Tl
Al In
Ans. M.P.
Ga
B Al Ga In Tl
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Q.8 Boron is the only Non-metal of group - 3 which element of group Note
3 has highest M.P.
Ans. Boron
Q.19 Which element has the higher I.E. among all elements ?
Ans. Helium has the highest I.E. among all elements
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Q.21 Arrange third group elements in decreasing order of I.E. Note
Ans. B > Tl > Ga > Al > In
Q.25 Give the trend of inert pair effect from top to bottom ?
Ans. Inert pair effect increases down a group and thus the elements present
in the lower part of the group show lower oxideation states. In group 13
elements, inert pair effect is more pronounced in Tl.
Q.26 How inert pair effect affects the oxidation state of 13th group
element ?
Ans. B and Al show an oxidation state of +3 only while Ga, In and Tl show
oxidation states of both +1 and +3. Since in case of Ga and In, +3
oxidation state is more stable than +1 oxidation state, therefore, both
Ga+ and In+ salts undergo disproportionation.
+1 0 3+
3GaX(x) → 2Ga(s) + Ga(aq) + 3X– (aq)
+1 0 3+
3InX(s) → 2In(s) + In(aq) + 3X– (aq)
as we move down the group, the stability of +3 oxidation state decreases
while that of +1 oxidation state increases.
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Note
COMPOUNDS OF BORON
BORIC ACID :
Q.30 What are the important compounds of boron ?
Ans. (a) Boric acid : H3BO3
(b) Boron Sesquioxide : B2O3
(c) Boranes : B2H6
(d) Boronhalide : BF3, BCl3, BBr3, BI3
(e) Borax : Na2B4O7
(f) Boron nitride : BN
(g) Borazole : B3N3H6
Q.32 What are the various formula by which Boric acid can be shown?
H
O
B
Ans. (a) (b) H3BO3 (c) B(OH)3
O O
H H
Q
OH OH
B
OH OH
Q.35 Show what happens when boric acid is dissolved in heavy water?
H
H H
O O O Q
Q OH OH
Ans. B + D2O → B → B + D⊕
Å OH OD
O O O O
H H H D D
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Note
Q.36 Does there a lewis acid - base reaction take place when boric acid
is dissolved in water.
Sol. Yes, there is a lewis acid - base reaction in which water acts as lewis base
and boric acid acts as lewis acid.
H3PO4
1. Mg 3 B2 ¾¾¾¾¾ ® H3 BO 3
HCl
2. B ¾¾¾¾
® H3 BO 3
H2SO4
H2O
3. BCl3 ¾¾¾¾ ® H3 BO 3
H2O
4. BH3 ¾¾¾¾ ® H3 BO 3
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OH
C C = O + H2O
OH
OH
Q.43 Two OH group on a carbon atom C is unstable but two
OH
Ans. Carbon has no d-orbital but silicon has vacant d-orbital. Thus a double
bond character is generated by a slight back bonding from lone pair into
vacant d-orbital of silicon.
Q.44 Although Carbon and Boron both belong to second row and both
donot have d-orbitals. Yet two hydroxy group on a Carbon is
unstable whereas on Boron there are stable.
Ans. Because Boron has vacant p-orbital which stabilizes three OH group by
back donation.
Q.46 Although Boric acid is a weak acid but it can’t be titrated with
sodium hydroxide ............ explain why ?
Ans. There are two reasons :
(i) The borate ion produce in the titration produce back boric acid by the
hydrolysis.
(ii) The pH change on titration curve is not sharp thus end point of titration
is not clear.
Q.47 Why diols like ethylene glycol, catechol are added when boric
acid is titrated with sodium hydroxide ?
Ans. The tetrahydroxo borate ion produced in the titration dissociates in reversed
direction producing back orthoboric acid.
When catechol or other diols are added then an esterification take place
and tetrahydroxo borate units get bind with diols irreversibly this doesn’t
produce back orthoboric acid.
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Q.48 Why catechol is added when boric acid is titrated with NaOH ? Note
Ans. H3BO3 is added with vicinal diols like glycol, catechol, sorbitol, mannitol
etc. for effective titration which removes BO33– ion from solution and
prevent its hydrolysis.
Ans.
The pH change of titration is not sharp, thus end point of titration is not
clear. BO33– ion produced in titration produces back boric acid by hydroly-
sis.
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DIBORANES :
Note
Q.50 What are boranes ?
Ans. Boron forms binary compounds with hydrogen known as boranes.
H 3Å H H
1.2
122º B 97º B 122º
H 9Å H H
1.1
1.77Å
dimer monomer
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Examples :
Note
H :O
B
H H
H ..
B + NH3 NH3
H H
BH3 + CO C O
H B H
NÅ Q ÅN
Q
B Å QB
H N H
H H Cl
B H B H
H H
N N N N
H H
3HCl
¾¾¾¾
® H H
B B B B
H N H Cl N Cl
H H H
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Note
BORAX :
Q.63 What is the formula of Borax ?
Ans. Na2B4O7.10H2O
OH 2—
+ B
Na
O O
H—O—B O
Ans. B — OH ≡
+ O O
Na
B
OH
Q.68 How many number of sp3 hybridised Boron are present in Borax.
Ans. 2
Q.69 How many number of sp2 hybridised Boron are present in Borax.
Ans. 2
Q.71 How many Boron units are connected by an oxygen atom diago-
nally ?
Ans. Two
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OH 2—
+
B
Na
O O
H—O—B O B — OH
H2O 2B(OH)3 + 2 NaB(OH)4
+ O O
Na
B
OH
OH 2—
+ B
Na
O O
Ans. H—O—B O B — OH + HCl → 2H3BO3 + 2[B(OH)4]–
+ O O
Na
B +
H
OH
2H3BO3
Q.77 How many moles of NaOH are consumed when Borax is treated
with NaOH
Ans. 2 moles of NaOH is consumed by 2 moles of [B(OH)4]–
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BORON HALIDE :
Note
Q.81 What are the physical state of BF3 , BCl3 , BI3 ?
Ans. BF3 - gas
BCl3 - liquid
BI3 - solid
Q.86 What is the correct order of Lewis acid character of various boron
halide ?
Ans. BI3 > BBr3 > BCl3 > BF3
Q.90 Pure BBr3 and BI3 are colourless but on exposure to light they
become coloured. Explain why ?
Ans. BBr3 and BI3 trihalides decompose on exposure to light and turns into the
respective halogen i.e. Br2 and I2. Br2 and I2 are already coloured.
BBr3 and BI3 undergoes partial photolysis in presence of sunlight which
gives Br2 and I2 which are responsible for imparting colour.
Down the group, the colour of halogens increases.
Q.91 BF3 has higher ∆Hf than other halides of Boron. Explain why ?
Ans. BF3 has highest heat of formation due to following reason.
(a) Small size and highest electronegativity of halogen atom results into a
strong sigma bond formation making ∆Hf a large value.
(b) Due to back bonding there is further strengthening of bond and result-
ing more loss of heat as ∆Hf.
Note : One should remember that ∆Hf depends on bond strength.
Stronger the bond formed, larger the ∆Hf.
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F H .. F
Ans. B—F + O: B — OH
F H F
OH OH
B — OH B — OH
F OH
Q.96 What happens when any two of halides BF3, BCl3, BBr3 are mixed
together ?
Ans. Redistribution of halogen takes place and an equilibrium is established.
Q.97 What happens if BCl3, BF3, BBr all are mixed together ?
Cl Cl Br
Ans. B + B
Cl Br Br
Cl Br I
B + B
Cl I Cl
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Q.98 Draw the structure of B4Cl4 ? Note
Cl
B
Ans. Cl — B B — Cl
B
Cl
Q.99 What happens when BF3 is reacted with RMgX [Grignard reagent]?
F R R
Ans. RMgX RMgX
B B B
R F R F R R
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Q.110 Al is more reactive than Fe but Al is less easily corroded than Fe.
Why?
Ans. Because Al forms a protective oxide layer around it.
Q.111 Why Aluminium metal is corroded in coastal places near to the sea ?
Ans. Because protective oxide film (Al2O3) is attacked by salt present in sea water.
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Q.115 What is Alumino-thermite process ? Note
Ans. It is an exothermic reduction of metal oxides by heating with Al.
Q.116 Why Aluminothermy used for on the spot welding of large iron
structures
Ans. As compared to iron, aluminium has greater affinity for oxygen & releases
more amount of energy.
(a) O2 (b) N2
↓H2O
Al(OH)3 + 3HCl
High Temp.
(l) 2Al + AlCl3
→ 3AlCl
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HYDROXIDE : Note
Q.119 What are the various hydroxides of group III element and how do
their acidic and basic properties vary ?
Ans. Acidic character decreases from top to bottom.
Basic character increases from top to bottom
B(OH)3
Al(OH)3
Ga(OH)3
In(OH)3
Tl(OH)3
Below 450ºC
(c) Al(OH)3 → Al2O3 (α-form)
Above 450ºC
(d) Al(OH)3 → Al2O3 (γ-form)
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Q.128 What is the nature of oxides of IIIA group elements ? Note
Ans. B2O3 - Acidic
Al2O3, Ca2O3, In2O3 - Amphoteric
Tl2O - Basic
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electric arc
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Q.147 Which substance is used to remove SiO2 in the serpeck’s process Note
of purification of bauxite
Ans. Coke
Q.148 What are the reactions taking place at cathode and anode in
electrolytic reduction ?
Ans. Electrolytic reduction
At cathode :
2AlF3 ¾¾¾
® 2Al3+ + 6F–
2Al3+ + 6e– ¾¾¾
® 2Al
6F– + Al2O3 ¾¾¾
® 2AlF3 + 3O2–
At anode :
3O2– + 3C ¾¾¾
® 3CO + 6e–
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HALIDES : Note
Q.153 Which halide of IIIA group element exist as a monomer ?
Ans. BCl3
Q.159 Are the bonding states of Al2Cl6 in vapour phase and in aqueous
phase are different.
Ans. Yes
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Q.165 How Al2O3 can be converted into Al2Cl6 Note
Ans. Al2O3 + 3C + 3Cl2 → 2AlCl3 + 3CO
Q.171 What happens when AlCl3 vapours are passed over fused Al2O3 at
1000ºC.
Ans. 2Al2O3 + 2AlCl3 → 6AlCl + 3O2
In the dimer of trimethyl aluminium the CH3 group will act as a bridge
between two aluminium atoms. The electron cloud which involved in the
bridge is distributed on two aluminium atoms and one carbon atom. Even
then it should not be considered that the carbon is pentavalent. The carbon
will have only eight electrons one shared by two aluminium atoms.
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ALUM : Note
Q.177 What are alums ?
Ans. Alums are double salts
Q.185 How many water molecules act as ligands about mono and trivalent
metal cations in alum.
Ans. 6 water molecule act as ligands about mono valent metal cations and 6 water
molecule act as ligands about trivalent metal cations.
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Q.188 What happens when alums are heated. Note
Ans. On heating strongly, all the water of crystallisation of an alum is eliminated
and a swollen mass of oxides is formed. This mixture of oxides is known as
slaked alum.
D
K2SO4.Al2(SO4)3.24H2O ¾¾¾
® K2O + Al2O3 + 4SO3↑ + 24H2O↑
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