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9 - P-Block Elements PDF
9 - P-Block Elements PDF
P-BLOCK ELEMENTS
p-block elements: Elements belonging to group 13 to 18 of the periodic table are called p-block elements.
In p-block elements last incoming electron enters p-orbitals.,
Group
13
14
15
16
17
18
He
5
10
Ne
13
14
15
16
17
18
Al
Si
Cl
Ar
31
32
33
34
35
36
Ga
Ge
As
Se
Br
Kr
49
50
51
52
53
54
In
Sn
Sb
Te
Xe
81
82
83
84
85
86
Tl
Pb
Bi
Po
At
Rn
:
:
:
:
:
Ar > K
Decreases from group 17 to 18
F < Cl, inert gases is zero (+ve)
N > O, In < Tl, Sn < Pb.
Inert gases have zero oxidising power.
GROUP 15
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2
P-BLOCK ELEMENTS
Disproportionation Reaction .
3HNO2 HNO3 + 3NO + H2O
D
4H3PO3
3H3PO4 + PH3
Maximum Covalency:
N is 4. (due to absence of d-orbitals)
other elements More than 4.
N forms pp -pp bonds whereas other elements forms dp-pp and dp-dp eq. R3P = O
Chemical properties
Reaction with Hydrogen Form hydrides
NH3
PH3
AsH3
SbH3
BiH3
T
Stability decreases
Basicity decreases
Reducing character increases
B
Reaction with Oxygen : Forms oxides E2O3 and E2O5 Oxides with higher oxidation states are more acidic than
lower oxidation state.
E2O3
N2O3, P2O3 Acidic oxides
O
O
NON
Structure of N2O5
Preparation
1. Commercial Method : Liquifaction and fractional distillation of air.
2. Lab Method :
NH4Cl(aq) + NaNO2(aq) N2(g) + 2H2O(l) + NaCl(aq)
NO and HNO3 are formed as impurity which are removed by passing the gas through aqueous H 2SO4
containing K2Cr2O7 .
3. Thermal decomposition of Ammonium dichromate.
D
(NH4)2 Cr2O7
N2 + 4H2O + Cr2O3
4. Thermal decomposition of azides of Ba & Na.
Ba(N3)2 Ba + 3N2
2NaN3 2Na + 3N2
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P-BLOCK ELEMENTS
Properties of N2
1. Colourless, odourless, tasteless. non-toxic gas.
2. Low solubility in H2O
3. It is inert due to high bond energy
4. At high T form nitrides
D
6Li + N2
2Li3N
D
3Mg + N2
Mg3N2
2NH3(Habers process)
5. N2 + 3H3
2000 K
2NO
6. N2 + O2
Uses of dinitrogen
1. Making NH3 and calcium cyanamide
2. Liquid nitrogen is used as refrigerant
OXIDES OF NITROGEN
Preparation
Oxides
Nature
Oxidation state
N2O
Neutral
+1
NO
Neutral
+2
NO2
Acidic
+4
2Pb(NO3)2
673 K
N2O3
Acidic
+3
2NO + N2O4
250 K
NH4NO3
Structure
N2O + H2O
N
Fe2(SO4)3 +2NaHSO4 +2H2O +2NO
4NO2 + 2PbO
NO
N=O
N
O
O
O
2N2O3
O
NN
O
O
N2O4
N2O5
Acidic
Acidic
2NO2
+4
4HNO3 + P4O10
+5
cool
Heat
N2O4
NN
O
4HPO3 + 2N2O5
N
O
AMMONIA NH3
Shape : Pyramidal
hybridisation : sp3 H
N
H
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N
O
4
Preparation of NH3
1. Commercial method Habers process.
2NH3 ; DfH = 96.1 kJ/mol
N2 + 3H2 200700MPa
K
P-BLOCK ELEMENTS
Nitric Acid
O
H
ON
Preparation
1. Industrial Method Ostwald Process
4NH3 + 5O2
(Air)
500 K, 9 bar
Pt
4NO + 6H2O
2NO2(g)
2NO + O2
3NO2(g) + H2O(l)
2HNO3(aq) + NO(g)
2. Lab Method
NaNO3 + H2SO4
* NO formed is recycled
HNO3 + NaHSO4
mass.
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P-BLOCK ELEMENTS
5
5. Attacks most metals except noble metals Au,
Pt,
3Cu + 8HNO3
3Cu(NO3)2 + 2NO + 4H2O
(dilute)
Cu + 4HNO3
Cu(NO3)2 + 2NO2 + 2H2O
(conc)
4 Zn + 10HNO3
4 Zn(NO3)2
+ N2O + 5H2O
(dilute)
Zn + 4HNO3
Zn(NO3)2 + 2NO2 + 2H2O
(conc.)
Some Metals (eg. Cr, Al) do not dissolve in conc. HNO3 because of formation of passive film of oxide on the
surface.
6. It oxidises non metals and their compounds.
I2 + 10 HNO3
2HIO3 + 10 NO2 + 4 H2O
Iodic acid
C + 4HNO3
CO2 + 4NO2 + 2H2O
S8 + 48HNO3
8H2SO4 + 48NO2 + 16H2O
P4 + 20HNO3
4H3PO4 + 20NO2 + 4H2O
(conc.)
Brown ring test: For nitrates
The test is carried out by adding dil FeSO4 solution to an aqueous solution containing nitrate ion and then
carefully adding conc. H2SO4 along the sides of the test tube. A brown ring at the interface b/w the solution and
H2SO4 layers indicate the presence of nitrate ion.
NO3 + 3Fe+2 + 4H+ NO + 3Fe+3 + 2H2O
[Fe(H2O)6]2+ + NO [Fe(H2O)5NO]2+ + H2O
brown ring
Uses of nitric acid
1. Making fertlizers (NH4NO3), explosives 2. As oxidiser in Rocket fuel.
nitroglycerin, TNT.
PHOSPHOROUS
P
P
P
P
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6
Red Phosphorous
1. Iron grey lustre
2. Non poisonous
3. insoluble in H2O
4. insoluble in CS2
5. Does not glow
6. Less reactive
7. It is polymeric , consisting of chains of
P4 tetrahedral.
P-BLOCK ELEMENTS
8.
P
P
P
99
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
2.
3.
PHOSPHINE (PH3)
Preparation
1.
2.
3.
4.
5.
3Ca(OH2) + 2PH3
Ca3P2 + 6H2O
3CaCl2 + 2PH3
Ca3P2 + 6HCl
Lab Method
P4 + 3NaOH + 3H2O
PH3 + 3NaH2PO2
(white)
PH4I + KOH
KI + H2O + PH3
473 K
3 H3PO4 + PH3
4H3PO3
Properties of PH3
1. Colourless gas with rotten fish smell.
2. Highly poisonous
3. Explodes in contact with traces of oxidising agents like HNO3 , Cl2 , Br2 vapours.
4. Slightly soluble in water.
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P-BLOCK ELEMENTS
5. Weakly basic PH3 + HBr PH4Br
6. Solution of PH3 in water decomposes in presence of light giving red P and H2 gas.
7. 3 CuSO4 + 2PH3 Cu3P2 + 3H2SO4
3 HgCl2 + 2PH3 Hg3P2 + 6HCl
Uses of PH3
1. In Holme's signals
2. In smoke screens
PHOSPHOROUS TRICHLORIDE (PCl3)
Shape : Pyramidal
hybridisation : sp3
P
Cl
Preparation of PCl3
1. P4 +
6Cl2
(white P)
2.
4
(white P)
(dry)
Cl
Cl
4PCl3
8SOCl2
(Thionyl chloride)
(sulphur monochloride)
Properties of PCl3
1. Colourless oily liquid.
2. PCl3 + 3H2O H3PO3 + 3HCl
(moisture)
3. 3C2H5OH + PCl3 3C2H5Cl + H3PO3
4. 3CH3COOH + PCl3 3CH3COCl + H3PO3
PHOSPHOURS PENTACHLORIDE (PC l5)
Cl
Cl
a
e
P 202 p m
Cl
Cl
240 pm
Cl
Axial bonds(a) are longer than equatorial bonds(e), because they suffer more repulsion than equitorial bonds.
Preparation of PCl5
1. P4 + 10Cl2 4PCl5
(white P)
2.
(excess)
+ 10SO2Cl2
4
(Sulphuryl chloride)
4PCl5 + 10 SO2
Properties of PCl5
1. Yellowish white powder.
2. Hydrolyse in moist air to POCl3 and finally to
PCl5 + H2O POCl3 + 2HCl
POCl3 + 3H2O H3PO4 + 3HCl
3. When heated it sublimes but decomposes on
Heat
PCl5
PCl3 + Cl2
4. C2H5OH + PCl5 C2H5Cl + POCl3 + HCl
5. CH3COOH + PCl5 CH3COCl + POCl3 + HCl
D
6. Sn + 2PCl5
SnCl4 + 2PCl3
D
2Ag + PCl5 2AgCl + PCl3
7. PCl5 in solid state exists as ionic solid.
[PCl4]+ [PCl6]
H3PO4
strong heating.
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Oxacids of P
HO
P-BLOCK ELEMENTS
OH
OH
HO
OH
OH
OH HO
OH
O OH
OH
OH
HO
OH
OH
OH
OH
P
O
O
P
P
O
OH
OH
(HPO3)3
P
O
OH
The acids which confain PH bonds have strong reducing properties. Thus hypophosphorous acid (H3PO2) is a
good reducering agent as it contais two P H bonds. It reduces AgNO3 to Ag,
4 AgNO3 + 2H2O + H3PO2 4Ag + 4HNO3 H3PO4
PH bonds are non-ionisable to give H+. Only those H atoms which are attached with oxygen in POH are
ionisable and cause basicity.
GROUP 16
(CHALCOGENS)
(O, S, Se, Te, Po)
Occurence:
Oxygen Most abundant of all the elements on earth
Sulphur Gypsum CaSO4. 2H2O
Epsom salt MgSO4. 7H2O
Baryte BaSO4
Zinc blende ZnS.
Copper pyrite CuFeS2
as H2S in volcanoes
in eggs, onion, mustard, proteins, wool etc.
Se and Te As metal selenides or tellurides in sulphide ores.
Polonium Decay product of throium and uranium minerals.
Oxidation state:
oxygen exhibit ; 2 (In OF2 , + 2 and in O2F2 + 1)
other elements ; +2, +4, +6
Stability of +6 decreases down the group and +4 increases. (due to inert pair effect)
Reaction with Hydrogen : form hydrides H2E (E = S, Se, Te, Po)
H2O , H2S, H2Se, H2Te
Acidic character increases
H E bond energy decreases
Reducing property increases
Thermal stability decreases
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P-BLOCK ELEMENTS
Reaction with oxygen : form oxides EO2 and EO3 :
(E = S, Se, Te, Po) both oxides are acidic in nature.
from SO2 to TeO2
Reducing property decreases
SO2 is reducing while TeO2 is an oxdising agent
Preparation
heat
1.
2KClO3
2.
D
4Ag + O2 ; 2Pb3O4 6PbO + O2
2Ag2O
D
2Hg + O2 ; 2PbO2 2PbO + O2
2HgO
2H2O2 2H2O + O2
Electrolysis of water (large scale)
Liquifection and fractional distllartion
3.
4.
5.
MnO2
2KCl + 3O2
(industrial Method)
Properties of Dioxygen
Reacts with nearly all metals and non metals. except noble gases and Au, Pt,
Ca + O2 2CaO
4 Al + 3O2 2Al2O3
P4 + 5O2 P4O10
C + O2 CO2
2 ZnS + 3O2 2ZnO + 2 SO2
CH4 + 2O2 CO2 + 2H2O
V2 O5
SO2 + O2
SO3
CuCl2
4 HCl + O2
2Cl2 + 2H2O
Uses of Dioxygen:
1. Respiration and combustion process.
2. Used in oxyacetylene welding
3. Oxygen cylinders are widely used in hospitals,
high altitude flying and in mountaineering
4. Hydrazines in liquid oxygen, provides
tremendous thrust in rockets.
Simple oxides eg. MgO, Al2O3
Classified as
Acidic oxides SO2, Cl2O7, CO2 , N2O5, Mn2O7, CrO3, V2O5 etc.
Basic oxides Na2O, CaO, BaO etc
Amfhoteric oxides Al2O3 . etc.
Neutral oxides CO, NO, N2O etc
Mixed oxides Pb3O4. Fe3O4 etc.
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10
P-BLOCK ELEMENTS
OZONE : O3
Allotropic form of oxygen formed from atmospheric oxygen in the presence of sunlight.
Preparation of Ozone
When slow stream of oxygen is passed through a silent electrical discharge conversion of oxygen to Ozone
occur : 3O2 2O3
;
DH(298K) = +142 kJmol1
Properties of Ozone
1. Pure ozone is pale blue gas, dark blue liquid
and violet black solid .
2. Small concentration is harmless. Its
concentration above 100 parts per million
causes headache and nausea.
3. Act as powerful oxidising agent (due to
liberation of atoms of nascent oxygen
O3 O2 + O)
PbS(s) + 4O3(g) PbSO4(s) + 4O2(g)
2I(ag) + H2O(l) + O3(g) 2 OH(aq) + I2(s) + O2(g)
4. When ozone reacts with excess of KI solution
buffered with a borate buffer (pH 9.2), iodine
is liberated which can be titrated against a
standard solution of sodium thiosulphate . This
is a quantitative method for estimation of O3
5. Depletion of ozone layer Due to
(1) Freons
(2) Nitric oxide emitted from exhaust of superjet planes.
NO + O3 NO2 + O2
Resonance structure of ozone
O
O
12
8p
m
O
O
O
O
O 117 O
Uses of Ozone:
1. As germicide disinfectant and for sterilising
2. For bleaching oils, ivory, flour, starch etc.
3. as oxidising agent in making of KMnO4.
4. Ozone layer protects from ultraviolet
water
radiations.
SULPHUR
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P-BLOCK ELEMENTS
11
S
S
S
S
S
Other modifications of S
S
S
S
1.
S6 chair form
2.
S
S
SULPHUR DIOXIDE
Preparation
1. S + O2 SO2
2. Treating sulphite with dil H2SO4 (Lab. Method)
SO32(aq) + 2H+(g) H2O (l) + SO2(g)
3. As by -product of roasting of sulphide ores (industrial method)
4FeS2(s) + 11 O2(g) Fe2O3(s) + 8SO2(g)
The gas is stored in steel cylinders
Properties:
1. Colourless gas with pungent smell.
2. highly soluble in water.
3. liquifies at room T under a pressure of 2 atmospheres
4. b.p. 263K .
5. SO2 + H2O H2SO3
6. 2NaOH + SO2 2Na2SO3 + H2O
Na2SO3 + H2O + SO2 2NaHSO3
charcoal
SO2Cl2
7. SO2 + Cl2
sulphuryl chloride
V2O5
SO2 + O2
2SO3
Moist SO2 behaves as reducing agent
2Fe+3 + SO2 + 2H2O 2Fe+2 + SO42 + 4H+
5SO2 + 2MnO4 + 2H2O 5SO42 + 4H+ + 2Mn2+
test for SO2 gas)
SO2 molecule Shape Angular
Resonance structures
8.
9.
S
O
S
O
Uses of SO2
1. Refining petroleum and sugar.
2. In bleaching wool and silk
3. As anti -chlor, disinfectant and preservative
4. In making H2SO4, NaHSO3 , Ca(HSO3)2
5. Liquid SO2 to dissolve organic and inorganic chemical
Oxoacids of Sulphur.
S
HO
OH
HO
OH
OH
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OH
12
P-BLOCK ELEMENTS
Sulphurous aicd Sulphuric acid Peroxodisulphuric acid
H2SO3
H2SO4
H2S2O8
O
S
O
OH
S
O
OH
S + O2 SO2
V2O5
SO2 + O2
SO3
SO3+ H2SO4 H2S2O7
H2S2O7 + H2O 2H2SO4
Conc. H2SO4
SO3
Quartz
Oleum
(H2S2O7)
12 C + 11 H2O
11. It Oxidises metals and non metals and reduces itself to SO2
Cu + 2H2SO4
CuSO4 + SO2 + 2H2O
3S + 2H2SO4
3 SO4 + 2H2O
C + 2H2SO4
CO2 + 2SO2 + 2H2O
Uses of sulphuric acid :
1. Manufacture fertilizers (eq. ammonium sulphate, superphosphate)
2. Petroleum refining
3. Making paints pigments
4. Detergent industry
5. Cleansing metals
6. In storage, batteries
7. Making nitrocellulose products
8. As laboratory reagent.
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P-BLOCK ELEMENTS
13
GROUP 17
+
4I (aq) + 4H (aq) + O2 2I2(s) + 2H2O
Reactivty towards hydrogen : Form hydrogen halide. Affinity for hydrogen decreases from F to I
Acidic strength HF < HCl < HBr < HI
Stability HF > HCl > HBr > HI (due to dicrease in bond ( H X) dissociation enthalpy down the group)
Reducing character HF < HCl < HBr < HI
Reactivity towards oxygen : form oxides but most of them are unstable. F forms OF 2 and O 2F 2
(OF2 is thermally stable at 298 K)
* These oxides are essentially oxygen flourides because of the higher electronegativity of flourine than oxygen.
(O2F2 oxidises Pu to PuF6 and the reaction is used in removing Pu as PuF6 from spent nuclear fuel).
Decreasing order of stability of oxides formed by helogene
I > Cl > Br
Higher oxides of halogens are more stable than lower ones.
Chlorine oxides Cl2O, ClO2, Cl2O6, Cl2O7 are highly reactive oxidesing agents & tend to explode. ClO2 is
used as bleaching agent and in water treatment.
Bromine oxides : Br2O, BrO2, BrO3 (are least state and exist at low T).
Are powerful oxidising agents.
Iodine oxides : I2O4, I2O5, I2O7 (decompose on heating)
I2O5 Very good oxidesing agent and is used in estimation of CO.
O
Cl
111
Cl
Cl
O 118 O
O
O
O
Cl
Cl
O
O
O
Cl
Cl
O
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O
O
Cl
O
O
Cl
O
O
14
P-BLOCK ELEMENTS
Reactivity towards metals : Form Metal halides
Mg(s) + Br2(l) MgBr2(s)
Ionic character MF > MCl > MBr > MI ( M = Monovalent metal)
If metal exhibts more than one oxidetion state, the halides in higher oxidation state are more covalent.
eq. SnCl4 > SnCl2
PbCl4 > PbCl2
SbCl5 > SbCl3
UF6 > UF4
CHLORINE : Cl2
CuCl2
HCl + O2
2Cl2 + 2H2O
723 K
Electrolysis of brine : (NaCl solution )
2NaCl + 2H2O
2NaOH + Cl2 + H2
(Anode)
Properties of Cl2
1. Greenish yellow gas with pungent and
2. 25 times heavier than air.
3. liquified easily
4. soluble in water.
5. With number of metals and non metals forms
2Al + 3Cl2 2AlCl3 ; P4 + 6Cl2 4PCl3
2Na + Cl2 2NaCl ; S8 + 4Cl2 4S2Cl2
2Fe + 3Cl2 2FeCl3
6. Reacts with H containing compound to form
H2 + Cl2 2HCl
H2S + Cl2 2HCl + S
C10H16 + 8Cl2 16 HCl + 10 C
9. 8 NH3 + 3Cl2 6NH4Cl
+
3HCl
(excess)
suffocating
chlorides
HCl
(Nitrogen trichloride)
NaCl + NaOCl
(sodium hypochlorite)
+ H2O
(bleaching powder)
C2H4Cl2
1,2 Dichloro ethane
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P-BLOCK ELEMENTS
15
13. Chlorine water on standing loses its yellow colour due to the formation of HCl and HOCl. (Hyprochlorous
acid). HOCl formed gives nascent oxygen which is responsible for oxidising and bleaching properties of chlorine.
2FeSO4 + H2SO4 + Cl2 Fe2(SO4)3 + 2HCl
Na2SO3 + Cl2 + H2O Na2SO4 + 2HCl
SO2 + 2H2O + Cl2 H2SO4 + 2HCl
I2+ 6H2O + 5Cl2 2HIO3 + 10 HCl
14. It is a powerful bleaching agent; bleaching action is due to oxidation
Cl2 + H2O 2HCl + O
Coloured substance + O Colourless substance.
Bleaching action is permanent. Bleaches vegetables and organic matter in the presence of moisture.
Uses of chlorine:
(a) As bleaching agent.
(b) estrection of gold & Pt
(c) Making dyes, drugs, organic compound.
(CCl4, CHCl3 DDT)
(d) Sterilising drinking water.
(e) Making poisonous gases like Phosgene COCl2, tear gas (CCl3NO2) mustard gas
(ClCH2CH2SCH2CH2Cl).
HYDROGEN CHLORIDE : HCl
O
Cl
O
Cl
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P-BLOCK ELEMENTS
H
Cl
Cl
O
Perchloric acid(HClO4)
Hybridisation
Shape
-sp3d
TShape
sp d
3 2
3 3
sp d
XX'7(IF7)
Square Pyramidal
Pentagonal bipyramidal
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P-BLOCK ELEMENTS
17
GROUP 18
4
(By Dorn)
Ra 222
86 Rn + 2 He
Physical Properties
1. Monoatomic
2. Colourless , Odourless, tasteless gas.
3. Sparingly soluble in water.
4. Very low m. p. and b.p. (weak dispersion forcess) eg. He has lowest m.p. (4.2K) than any known substance.
It has unusual property of diffusing through rubber, glass or plastics.
Chemical properties : least reactive or inertness is due to (i) completely filled valence shell (ii) high I. E.
(iii) More + ve electron gain enthalpy.
Neil Bartlett prepared first compound of Xe
PtF6 + Xe Xe+[PtF6] (I. E. of Xe = 1170 kJ/mol, I. E. of oxygen = 1175 kJ/mol)
(red)
Compounds of Krypton are fewer .
Only KrF2 studied in detail.
Compound of Rn are identified
(eg. RnF2) by radiotracer technique.
No compounds of Ar, Ne or He are known
Xe and F Compounds
Xe(g) + F2(g)
(excess)
Xe(g) + 2F2(g)
(1 : 5 ratio)
Xe(g) + 3F2(g)
(1 : 2 ratio)
673 K
1 bar
873 K
7 bar
XeF2(s)
XeF4(s)
573 K
60-70 bar
XeF6(s)
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Compound of Xe and O
6XeF4 + 12H2O 4Xe + 2XeO3 + 24 HF + 3O2
XeF6 + 3H2O XeO3 + 6HF
2XeF2 + 2H2O 2Xe + 4HF(aq) + O2(g)
P-BLOCK ELEMENTS
XeF4, XeF6 hydrohyse to give XeO3 (Colourless solid , 22 times more explosive than TNT)
Partial hydrolysis of XeF6 gives Oxyfluorides, XeOF4 and XeO2F2\.
XeF6 + H2O XeOF4 +
2HF
(Colourless volatile liquid)
4HF
(Xenon dioxydifluoride)
Shapes.
F
F
Xe
Xe
Xe
F
Xe
O
F
F
XeF2
XeF4
XeF4
(Linear)
(Square planar)
O
F
F
Xe
Xe
Xe
XeOF4
XeO3F2
(Square pyramidal)
(Trigonal bipyramidal)
F
O
F
Xe
XeF6
F
O
XeO3
XeO2F2
(Sea-saw )
(Octahedral)
2.
3.
4.
5.
6.
divers
7.
in green houses.
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P-BLOCK ELEMENTS
19
SOLVED PROBLEMS
1.
Sol.
Its structure is
O
||
P
HO
OH
Since it contains only two ionizable H-atoms which are present as OH groups, it behaves as a dibasic acid.
2.
Sol.
H 3N : + H +
PH4+
However, due to smaller size of N over P, N H bond thus formed is much stronger than the P H bond.
Therefore, NH3 has higher proton affinity than PH3. In order words, NH3 is more basic than PH3.
3.
Sol.
4.
Sol.
NO (Nitric oxide) is paramagnetic in the gasesous state but diamagnetic in the liquid and solid states.
Why ?
NO has an odd number of electrons (7 + 8 = 15 electrons) and hence is paramagnetic in the gaseous state.
But in liquid and solid states, it exists as a dimer and hence is diamagnetic in these states.
Give the chemical reaction to support that +5 oxidation state of Bi is less stable than +3 state.
Due to inert pair effect, Bi can show +3 and +5 oxidation states. Since the inert pair effect is maximum in
case of Bi, therefore, its +5 oxidation state is less stable than +3 oxidation state. This is evident from the
observation that BiCl3 even on prolonged heating with Cl2 does not form BiCl5
BiCl5
BiCl3 + Cl2
5.
Sol.
In the structure of NHO3 molecule, N O bond (121 pm) is shorter than N OH bond (140 pm).
HNO3 is a resonance hybride of the following two canonical structures :
+
HO N
O
O
+
HO N
O
O
Due to resonance N O bond has some double bond character. In contrast, N OH has only pure single
bond character. Since single bonds are longer than double bonds, therefore, N OH bond is longer
(140 pm) than N O bond ( 121 pm) in NHO3.
6.
Sol.
7.
Why the compounds of fluorine with oxygen are called fluorides of oxygen and not the oxides of
fluorine ?
This is because fluorine is more electronegative than oxygen.
Sol.
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20
8.
Sol.
P-BLOCK ELEMENTS
Give reasons for the following observations :
(i) Why SF4 undergoes hydrolysis but not SF6 ?
(ii) Sulphur exhibits greater tendency for calenation than selenium.
(iii) Sulphur has a higher tendency for catenation than oxygen.
(i) In SF6, S sterically proctected by six F atoms and hence does not allow H2O molecules to attack the S
atom. Furthermore. F does not have d -orbitals to accept the electrons denotes by H2O molecules. As a
result of these two reason. SF6 does not undergo hydrolysis. In contrats, in SF4. S is not sterically protected
since it is surrounded by only four F atoms. As a result, attack of H2O molecules on S atoms can take place
easily and hence hydrolysis occurs.
(ii) As we move from S to Se, the atomic size increase and hence the strength of E E bond decreases. As
a result, S S bond is much stronger than Se Se bond and consequently, S show greater tendency for
catenation than selenium.
(iii) Due to small size, the lone pairs of electrons on the O atoms repel the bond pair of the O O bond to
a greater extend that the lone pairs of electrons on the S atom in S S bond. As a result, S S bond is
much stronger (213 kJ mol1) than O O bond (138 kJ mol1) and hence S has a such stronger tendency for
catenation than O.
9.
Sol.
10.
Sol.
F-atom is more electronegative than I-atom, yet HF has lower acid strength than HI. Explain.
F atom being smaller in size than I atom, the bond dissociation energy of H F is very high as compared to
that of H I bond. Consequenntly, H I bond breaks more easily than H F bond and thus HI is a stronger
acid than HF.
11.
Sol.
12.
Sol.
Arrange HClO4, HClO3, HClO2, HClO in order of (i) acidic strength (ii) oxidizing power. Give reasons.
(i) Acidic strength : HClO4 > HClO3 > HClO2 > HClO
Reason : As the stability of the oxoanion (conjugate base) left after the removal of a proton increases, the
acid strength increases in the same order. Since the stability of the anions decreases in the order :
ClO4 > ClO3 > ClO2 > HClO, therefore, acid strength decreases in the same order :
HClO4 > HClO3 > HClO2 > HClO
Oxidising power : HClO4 < HClO3 < HClO2 < HClO
Reason : As the stability of the oxoanion increases, its tendency to decompose to give O2 decrease and
hence its oxidising power decreases. Since the stability of the oxoanion decreases in the order :
ClO4 > ClO3 > ClO2 > ClO, therefore, the oxidising power of their oxoacids increases in the reverse
order, i.e., HClO4 < HClO3 < HClO2 < HClO.
13.
Sol.
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P-BLOCK ELEMENTS
14.
Assign appropriate reasons for each of the following statements.
Perchloric acid is a stronger acid than sulphuric acid.
Sol. (v) The oxdation state of Cl in perchloric acid is +7 while that of S in sulphuric acid is +6
O
+6 ||
Cl
O
O
||
||
O
||
O
+7 ||
Cl
O
21
Due to higher oxidation sate and higher electronegativity of Cl, ClO3 part of HClO4 pulls the electrons of
the O H bond more strongly and hence can break the O H bond more easily to liberate a proton than
SO2 part in H2SO4. Thus, perchloric acid is a stronger acid than sulphuric acid.
15.
Sol.
16.
Sol.
17.
Sol.
18.
Sol.
overlap
5p
5d
19.
Sol.
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22
P-BLOCK ELEMENTS
..
..
..
..
NO2 molecules
Each N has 7 electrons
in the valence shell
(less stable)
O
||
NN
||
..
N
..
..
..
..
.. ..
O
..
..
..
..
O
..
..
O
..
.
.
or
..
O
..
..
O
.. ..
.. ..
O
..
..
O
.. ..
N.
N2O4 molecules
Each N has 8 electrons
in the valence shell
(more stable)
21
Sol.
When HCl reacts with finely powdered iron, it forms ferrous chloride and not ferric chloride. Why ?
Fe reacts with HCl to form FeCl2 and H2, Fe + 2 HCl FeCl2 + H2
H2 thus liberated prevents the oxidation of FeCl2 to FeCl3
22
Sol.
H2SO4 is a dibasic acid, it ionizes in two stages and hence has two dissociation constants.
(i) H2SO4(aq) + H2O(l) H3O+ (aq) + HSO4 (aq) : K a1 > 10
(ii) HSO4 (aq) + H2O(l) H3O+ (aq) + SO42 (aq) ; K a2 = 1.2 10 -2
K a2
is less than K a1 because the negatively charged HSO4 ion has much less tendency to donate a proton to
24
Sol.
25
Sol.
+5
+1
+3
2 A g + P Cl3 2 Ag Cl + P Cl3
+5
+3
+5
+4
+3
; Sn + 2 PC l5 Sn Cl4 + 2 P Cl3
+1
P Cl5 + H2 PC l3 + 2 H Cl
26
Sol.
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P-BLOCK ELEMENTS
23
27
Why are halogens stong oxidising agents ?
Sol. Due to low bond dissociation enthalpy, high electronegativity and large negative electron gain enthalpy
halogens have a strong tendency to accept electrons and thus get reduced.
X 2 + 2e - 2X -
29
Sol.
30
Give the formula and describe the structure of a noble gas species which is isostructural with :
(iii) BrO3
(ii) IBr2
(i) ICl4
(i) Structure of ICl4.
Sol.
..
Cl
Cl
I
Cl
Cl
..
SQUARE PLANAR
12
2
=6
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24
P-BLOCK ELEMENTS
= 12). Like ICl , it also has 4 bond pairs and 2 long pairs. Therefore, like ICl , XeF4 is also square planar.
Similarly (ii) XeF2 (iii) XeO3
31.
Sol.
Why does H3PO3 act as a reducing agent but H3PO4 does not ?
H3PO3 contains one P H bond and hence acts as a reducing agent but H 3PO4 does not contains a P H
bond and hence does not act as a reducting sgent. For structures, refer to pages 7-38-7-39
32.
Ans.
33.
Sol.
+1
-1
233 K
F 2 (g) + H2O(s )
HOF(l ) + HF(l )
34.
Sol.
I2, because of the presence of vacant d - orbitals, accepts electrons from I ions to form I3 ions but F2
because of the absence of d - orbitals does not accept electrons from F ions to form F3 ions.
35.
Sol.
36.
Sol.
37.
Sol.
38.
Sol.
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P-BLOCK ELEMENTS
25
EXERCISE - I
UNSOLVED PROBLEMS
Q.1
The negative value of electron gain enthalpy is less for fluorine than for chlorine.
Q.2
Q.3
Arrange HClO, HBrO and HIO in order of decreasing acidic strength giving reason.
Q.4
Q.5
Why do noble gases form compounds with fluorine and oxygen only ?
Q.6
Q.7
Q.8
Q.9
Q.10
Q.11
What happens when white phosphorus is heated with concentrated NaOH solution in an inert atmosphere
of CO2 ?
Q.12
Q.13
Q.14
Q.15
Q.16
Q.17
Q.18
Q.19
Why does R3P = O exist but R3N = O does not (R = alkyl group ) ?
Q.20
Q.21
Q.22
Q.23
Q.24
Q.25
Q.26
Q.27
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26
P-BLOCK ELEMENTS
EXERCISE - II
BOARD PROBLEMS
Q.1
Q.2
Q.3
Q.4
Q.5
Q. 6
Q.7
(excess)
Q.8
Q.9
Q.10
Q.11
Q.12
(a)
(b)
Mention the optimum conditions for the industrial manufacture of ammonia by Haber's process
Explain the following giving appropriate reasons.
[CBSE 2011]
(i) Sulphur vapour exhibits paramgnetic behaviour
(ii) Red phosphorus is less reactive than white phosphorus
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P-BLOCK ELEMENTS
Q.13 Draw the structures of the following molecules
(i)
NF3
(ii)
H2S2O8
(iii)
H3PO3
Q.14
Q.15
(excess)
What is the basicity of H3PO3 and why ?
27
[CBSE 2011]
[CBSE 2011]
[CBSE 2013]
Q.16
How are interhalogen compounds formed ? What general compositions can be assigned to them?
[CBSE 2013]
Q.17
Q.18
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[CBSE 2013]