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Important Compounds of P - Plock
Important Compounds of P - Plock
2 Dinitrogen
Preparation:
NH,Cl+NaNO, N,T +2H,0 +NaCl (NH,),Cr,0, N,î+ 4H,0 + Cr0,
Ba(N)2 Ba + 3N,t
Chemical properties:
6Li+N22Li3N; 3Mg + N2A Mg,N
A, 2000 K 773 K, 200 atm
2NO ; N2+ 3H2 2NH.: AcH° = -46.1 kJ mol' (Haber's process)
N2)+O2)
7.3 Ammonia
Preparation:
Laboratory preparationof NH3:
2NH,CI+Ca(OH)2 -> 2NH,+ CaClh + 2H,0
(NH)SO4 + 2NaOH> 2NH3 + Na^SO4 + 2H,0
All the ammonium salts react with alkali to give ammonia.
NH,CONH, + 2H,0 > (NH,),COg 2NHs+COa+H,O
Urea Ammonium
carbonate
2NO+0, 2NO,
3NO, +H,0 2HNO, + NO
NO thus formed is recycled and the aqueous HNO, can be concentrated by distillation upto - 68% by
mass. Further concentration to 98% can be achieved by dehydration with concentrated n2o4
Properties
Pure HNO, is colourless, however impure HNO, is yellow in colour due to soluble H 102
1 2p
1 m
6 Phosphorus-Allotropic Forms P
P4 + 50 P,O10
well as
It is odourless, non-poisonous, insoluble in water as
Red phosphorus
does
CS2, less reactive than white phosphorus and
not
in
chains of
glow in the dark. It is polymeric consisting of
P tetrahedra.
Blacka-black
phosphorus: It has two forms :
phosphorus is formed when red phosphorus is heated in a sealed tube at 803 K. It has qn
oxidise in air.
aque
monoclinic or rhombohedral crystals and can be sublimed in air. It does not
B-black phosphorus is prepared by heating white phosphorus at 473 K under high pressure. It does not h
burn
in air upto 673 K. It has layered structure.
7.7 Phosphine
Preparation:
CaP2 +6H,0 3Ca(OH)2 +2PH; Ca,P2 +6HCl: 3CaCl, +2PH3
PHI+KOH KI + H,O +PH P4+ 3NaOH +3H,0 3NaH,PO2 + PH3
Properties: It is a colourless gas with rotten fish smell and is highly poisonous.
H,
4PH3 P + 6H 3CuSO4 +2PH, Cu,P2 + 3HSO4;PH3 + HBr PH,Br
Red phosphorus Copper phosphide Phosphonium bromide
+ PH3 reacts with anhydrous HX (HCI, HBr and HI) not with aqueous HX because phosphonium
halide formed are decomposed by water to give back PH3.
8 Phosphorus Halides
Compound Preparation Properties Uses
PCls P4+10Cl, > 4PCls PCl+4H,0 (excess) >H,PO4 + Used as chlorinating
L a (white 5HCI and dehydrating
CIp orred) PCls +SO2SOClh + POCl agent.
CP4+ 10 SO,Clh-> 4PCls + 10SO 6PCls +P4010 10POCl,
Cl
PCls +ZnZnCl2 +PCl
PCl P4 +6Cl2 4PCl PCl + 3H0-> H,P0, + 3HCI Used as reagent
i"
s
and as a precursor
+ HPO, and
3CH,OH + PCly >3C,H,Cl + of PCl, POCl,
a PSCl3
H,PO
of Phosphorus
79 Oxoacids
Name Formula Oxidation state Structure
Preparation
of phosphorus
O
Hypophosphoric acid Red P4+ alkali
HPO6 +4
HO
P-P
iOH
HO OH
Phosphoric
Pyrophosphoric acid HP2O +5
HOOH oTOH acid + heat
OH
OH
Metaphosphoric acid (HPO3), +5 Phosphorus acid +Br2
oi o heat in a sealed tube
OH OH
7.11 Dioxygen
Preparation:
In laboratory, dioxygen is prepared by heating oxo salts, such as chlorates, nitrates and permanganates
2KCIOMn2KCI+302(
A
MnO, is added with in the ratio 1: 4. MnO2 reduces the melting point
KCIo, of KCI0, it
and
startsgiving oxygen at 523 K instead of 650 K i.e., increases the rate of reaction. But this Mn0,
must be free from carbon as KCIO3 and carbon mixture is explosive in nature.
7.13 Ozone
electric discharge 20,
Preparation: 30,
blue liquid and violet black solid.
Properties: It is a pale blue gas, dark
0, O, +0 Oxidising action
Rhombic sulphur crystals are formed on evaporating the solution ofroll sulphur in CS
It is insoluble in water but dissolves to some extent in benzene, alcohol and ether.
It is readily soluble in CS.
Monoclinic sulphur (B-sulphur) has Sg molecules, colourless needle shaped crystals, melting point 393 K
specific gravity 1.98, soluble in CS,
S s ring (both in rhombic and monoclinic sulphur) is puckered and crown shaped.
I n cyclo Sg, the ring has chair form.
H,S is also called sulphurated hydrogen. H2S is poisonous and proves fatal in large amount. Antidote
+ for this is dilute chlorine which destroy the effect of HS by oxidising it to sulphur.
HS+Cl 2HCI+S
7.15 Sulphur Dioxide
Preparation
S+O SO2
so+2H H,O+ SO, (Lab preparation)
4FeS2 +110,-2Fe,O, + 8S0, (By productof roasting of sulphide ores)
Physical properties: Colourless gas with pungent smell, highly soluble in water, liquefies at room temperature
at 2 atm, boils at 263 K.
Chemical Properties:
sO +H,OeH,S0, 2NaOH +SO2 Na,SO, + H,O
Na,SO+ H,0 +SO 2NaHSO3 SO +Clh- SO,Cl22S0, +O -
VOs2SO3
Bleachingaction:
SO +2H,0 H,SO, + 2[H] : Coloured matter + [H] Colourless matter
Reducing nature:
2Fe +SO, +2H,0 2Fe* +4H 5SO, +2MnO +2H,O. 5S0+4H' +2Mn
Structure: The molecule ofSO, is angular. It is a resonance hybrid of the two canonical forms
HOo
HO
HOTo
HO o-oo
HO
oTo
HO HO H0
H,5O, H,SO H,S,O H,S,O,
Sulphurous acid Sulphuric asid Perovadisulobur (Olm
F17 Sulphuric Acid
It is also known as oil of vitriol and king of chemicals.
Preparation: It is manufactured by contact process which involves the following steps
V
S+O SOgi 250+O 2s0,
sO3+ HS04 H,S,0,; H,S,0, + H,02H,S04
Oleum
Physical properties:
H,SO, is a colourless, dense, oily liquid with specific gravity of 1.8 at 298 K.
Dissolution of sulphuric acid in water is highly exothermic hence conc. acid must be added into water W
constant stirring.
Chemical properties:
HSO +H,0 H,O"
+HSO4 | Strong dibasic acid
+H,0>H,O' +SO Drong dibasic acid
HSO,
NaOH+H,SO, NaHSO, +H,O (Acid sulphate)
2NaOH+H,SO, Na,sO, +2H,O (Normal sulphate)
2MX + H,SO 2HX
(More volatile acid)
+M,SO (X=F, CI, NO,)
(Less volatile acid) (M=Metal)
7
Fe,(SO^), + 2HCI ; SO, + 2H,0 + Cl, H,SO4 +
21 Oxoacids of Halogens
Variation of the general properties of oxoacids of halogens
Acidity increases
central atoms remains the
Electronegativity of the
same -
22 Interhalogen Compounds
Halogens combine amongst themselves to
torm interhalogens of the type XX', XX', XX'; and XX'7,
a number of
where X is a larger size halogen (more electropositive) and X is smaller size halogen.
Preparation:
3Cl 21Cl, ; Cl + 3, 2CIF,
Cl,+F 7 2ClF 1 t
(excess)
(excess)
(cqual volume)
sp Linear
XX
sp'a2
Square
XX'5 Pyramidal
Pentagonal
XX7 sp'ds
bipyramidal
lons which consist of two or more electronegative atoms of which atleast one is nitrogen and have
properties similar to those of halide ions are called pseudohalide ions and the corresponding dimeric
molecules are called pseudohalogens.
-Pseudohalides: CN, SCN", OCN, etc.
Pseudohalogens: (CN)2» (SCN)2, (OCN)2, etc.
Melting points and boiling points are very low due to weak interatomic dispersion iorces.
Chemical properties: Noble gases are least reactive due to high ionisation enthalpy and more positive eiectro
gain enthalpy.
Xenon-fluorinecompounds:
573 K, 60-70 barXeF
Xe+F- 673 K.1 bar Xefzi
XeF,; Xe+2FE 873 K. 7 bar XeF,: , X e +3PE-
(excess) (1:5ratio)) (1:20ratio)
XeFg can also be prepared by the interaction of XeFj and O,F2 at 143 K.
XeF4 + O,F2 XeF, + O2
Aef2 AeF and XeF, are colourless crystalline solids and sublime readily at 298 K. They are powerful
fluorinating agents. They are readily hydrolysed even by traces of water. For example, XeF, is hydrolysea
to give Xe, HF and 0,.
2XeF + 2H,0 2Xe + 4HF + O2
Xenon fluorides react with fluoride ion acceptors to form cationic species and fluoride ion donors to form
fluoroanions.
XeF2 +PFs XeF]" [PF%l; XeF4 +SbFs- [XeF3]* [SbE%]
XeF + ME M XeF7] (M = Na, K, Rb or Cs)
Xenon-oxygen compounds:
6XeF +12H,O > 4Xe+2XeO, +24HF+30, XeF, +3H,0 Xe0, +6HF;
XeF, +H,O XeOF, +2HF Partial hydrolysis of XeF,
XeF, +2H,0 XeO, +4HF
Xe Xe
Xe
F F O
F
XeF4
XeF2 Square planar F XeO3
Linear Pyramidal
spd
spd2 XeF6
Distorted octahedral sp3
sp3d3
Melting point, boiling point ease of liquefaction, solubility, adsorption and polarizability increases
as He < Ne < Ar < Kr < Xe.