(a) NH 4NO 2 N2 + 2H 2 O
(b) (NH4)2Cr2O7 N2 + 4H2O + Cr 2O3
(c)
Ba(N3) 2 Ba + 3N2 Purest N2 obtained
2NaN 3 2Na + 3N2 by this method
(d) 2 NH 3 + 3NaOCl N 2 + 3NaCl + 3H 2O
(e) 2NO 2Cu 2CuO N 2
red over heated Black
(f) Cl2 passed into liquor NH3
3Cl 2 + 2NH 3 N 2 + 6HCl
6NH 3 + 6HCl 6NH 4 Cl
-----------------------------------------------------
3Cl 2 + 8NH 3 N 2 + 6NH 4Cl
In this method NH3 conc. should not be lowered down beyond an particular limit.
3Cl 2 + NH3 NCl 3 + 3HCl
(Trimendously explosive)
(a) It is inert due to high bond energy.
(b) It is absorbed by hot metal like Ca, Mg, Al etc.
3Ca + N2 Ca 3N2
2Al + N2 2AIN
Al2O3 + 3C + N2 2AIN + 3CO
White slippery solid having 2D-sheet structure.
3000 º C
(BN)x (BN)x
3–D network structure similar to diamond (Borazon) which is harder than diamond and used for dimond cutting.
Na 2B 4O 7 + 2NH 4Cl 2NaCl + 2NH 3 + 2B 2 O 3 + H 2O
B 2O 3 + 2NH 3 2BN + 3H 2 O
(c) N2 can be absorbed by calcium carbide at the temp around 1000ºC
1000 º C
CaC 2 N 2 CaNCN
(It is very good fertiliser)
nitrolim
2
N– C N
N= C= N
(Ca(NCN)+ C) + 3H 2O CaCO 3 + 2NH 3 + C
Slowly decomposes
NH2–CO–NH2
(Intermidiate formed)
– –
(a) Nitrate or nitrite reduction : NO 3 NO 2 + Zn Al + NaOH NH3 + [Zn(OH)4]2– [Al(OH)4]–
(b) Metal nitride hydrolysis : N3– + 3H2O NH3 +3OH–
450 º C
(c) Haber's process : N2 + 3H2
200-1000atm
2NH 3
catalyst Fe/Mo
NH3 can't be dried by H2SO4, P2O5 and anhydrous CaCl2 because –
2NH3 + H2SO4 (NH4)2SO4
H2O + NH3 + P2O5 (NH4)3PO4
CaCl2 + 8NH3 CaCl2 8 NH3 (forms adduct)
Quick lime is used for this purpose
CaO + H2O Ca(OH)2 (base)
Hence no interaction
NH3 (base)
(a) It dissolves several electropositive metals like Li, Na, K, Rb, Cs, Sr, Ba etc.
K in liq NH3 (i) Blue in colour
(ii) Conducts electricity
(iii) Having reducing property
K K+ + e–
K+(NH3)n e (NH3)x It is the cause
solvated e for above property
–
K 2 [Ni(CN ) 4 ]
K in liq
NH 3
K 4 [Ni(CN ) 4 ]
Square planar Tetrahedral
(b) Ag(NO3) (aq) + BaCl2 (aq) AgCl + Ba(NO3)2
Filtrate Residue
Ba(NO3)2 AgCl
liq NH3 Ba(NO3)2
crystal –
Cl– + [Ag(NH3)2]+ BaCl2 +[Ag(NH3)2]++NO3
(c) CH3COOH is strong acid in liquid NH3 while in water is weak acid.
–
AcOH AcO + H+
NH3 + H+ NH 4 and H2O + H+ H3O+
Basisity order NH3 > H 2O
(d) Hydrolysis and Ammonolysis occurs is a same way.
SiCl4 + 4H2O 4HCl + Si(OH)4 Si3O2 + 2H2O
SiCl4 + 8NH3 4NH4Cl + Si(NH2)4 Si 3N2 + NH3
Rate of hydrolysis and Ammonolysis will be affected by the presence of HCl vapour & NH4Cl vapour
respectively.
(e) NH 4 –
NaNO3
Gypsum suspension saturated CaCO3 + (NH4)2SO4 NH4NO3
with NH3 and CO2 passed
NaCl
NaNO2 CaCO3
NH4(NO2) NH4Cl (NH4)2CO3
N2O Dinitrogen monoxide NH4NO3 N2O + 2H 2O Colourless gas, rather
(Nitrous oxide) N N O (sp, Linear polar molecule) unreactive, diamegnatic
Laughing gas neutral to litmus
NO Nitrogen monoxide (a) 3Cu + 8HNO3 3Cu(NO 3) 2 + 2NO Colourless gas,
Pt
(Nitric oxide) (b) 4NH3 + 5O2
0
4NO + 6H O
2
paramagnetic, Neutral to
900 C
litmus
NO2 Nitrogen dioxide Pb(NO 3)2 2PbO + 4NO2 + O2 Brown gas, reactive,
Mixed anhydride N paramagnetic, angular
132º
O O and polar
2NO2 HNO2 + HNO3
N 2O 3 Dinitrogen trioxide NO + NO 2 N2O 3 Dark blue in liquid (–30ºC)
or solid state, unstable
O = N – O – N = O or in the gas phase
O H2O
O=N–N N 2O3 2HNO 2
O
N 2O 4 Dinitrogen tetroxide 2NO2 N 2O 4 Colourless, exists in
O O O equilibrium with NO 2
2N N– N both in the gaseous and
O O O liquid state, in solid state,
N2O 4 is unstable.
N2O 5 Dinitrogen pentoxide 2HNO 3 + P 2O 5 H2O + N2O 5 No existance in gas phase,
H2O + P2O5 2HPO 3 in the solid state exists as
nitronium nitrate
O O
[NO 2] +
[NO 3] –
N N
O
O O
[Link]
(a) M-nitrite
HCl or H 2 SO 4
HNO
2
(b) N2O3 + H2O 2HNO2
(a) : Because of its easy oxidation to liberate nascent oxygen, it acts as a strong oxidant
2HNO2 H2O + 2NO + (O)
2KI + 2HNO2 + 2HCl 2KCl + 2H2O + 2NO + I2
SnCl2 + 2HNO2 + 2HCl SnCl4 + 2NO + 2H2O
SO2 + 2HNO2 H2SO4 + 2NO
H2S + 2HNO2 2H2O + S + 2NO
2FeSO4 + 2HNO2 + H2SO4 Fe 2(SO4)3 + 2NO + 2H2O
Na3AsO3 + 2HNO2 Na3AsO4 + 2NO + H2O
(b) : Nitrous acid also acts as a reducing agent as it can be oxidised into nitric acid.
HNO2 + (O) HNO3
2KMnO4 + 5HNO2 + 3H2SO4 K2SO4 + 2MnSO 4 + 5HNO3 + 3H2O
K2Cr2O7 + 3HNO2 + 4H2SO4 K2SO4 + Cr 2 (SO4)3 + 3HNO3 + 4H2O
H2O2 + HNO2 H2O + HNO3
2HNO2 + NH2CONH2 2N2 + CO2 + 3H2O
Urea
HNO2 + NH3 NH 4NO2 N 2 + 2H 2O
HNO 2 + C 2H 5NH2 C 2H 5OH + N 2 + H 2O
5 º C
HNO2 + C6H5 - NH2 HCl C6H5N = NCl + 2H2O
Benzene diazonium chloride
It was named aqua fortis (means strong water) by alchemists.
(a)
KNO3 + conc. H2SO4 KHSO4 + HNO3 (vap)
vapours of nitric acid evolved are condensed in a glass receiver.
(b)
(i)
3000 º C
Step 1 N2 + O2
Electric Arc 2NO - heat
Step 2 NO + O2 NO2
Step 3 NO2 + H2O HNO2 + HNO3
Step 4 HNO2 HNO3 + NO + H2O
(ii)
[Link]
Step 1 NH3 + O2
700 –800 º C
2NO - heat
Step 2 NO + O2 NO2
Step 3 NO2 + H2O HNO2 + HNO3
Step 4 HNO2 HNO3 + NO + H2O
Nitric acid usually acquires yellow colour due to its decomposition by sunlight into NO2.
sunlight
4HNO3 4NO2 + 2H 2O + O2
The yellow colour of the acid can be removed by warming it to 60-80ºC and bubbling dry air through it. it has
extremely corrosive action on the skin and causes painful sores.
It is very strong acid and it exhibits usual properties of acids. It reacts with basic oxides, carbonates, bicarbonates
and hydroxides forming corresponding salts.
CaO + 2HNO3 Ca(NO 3)2 + H 2O
Na2CO 3 + 2HNO 3 2NaNO 3 + H 2O + CO 2
NaOH + HNO 3 NaNO3 + H 2O
Nitric acid acts as a strong oxidising agent as it decomposes to give nascent oxygen easily.
2HNO3 H2O + 2NO 2 + O
or 2HNO3 H2O + 2NO + 3O
(a) The nascent oxygen oxidises various non-metals to their corresponding
highest oxyacids.
(i) Sulphur is oxides to sulphuric acid
[Link] hot
S 6HNO 3 H2SO4 + 6NO2 + 2H 2O
(ii) Carbon is oxidised to carbonic acid
C + 4HNO3 H2CO3 + 4NO2 + 2H2O
(iii) Phosphorus is oxidised to orthophosphoric acid.
[Link] hot
2P 10HNO 3 2H3PO4 + 10NO2 + 2H2O
(iv) Iodine is oxidised to iodic acid
[Link] hot
I 2 10HNO 3 2HIO3 + 10NO2 + 4H2O
(b) Metalloids like non-metals also form highest oxyacids
(i) Arsenic is oxidised to arsenic acid
As + 5HNO3
[Link] hot
2H3AsO4 + 5NO2 + H2O
(ii) Antimony is oxidised to antimonic acid
[Link] hot
Sb + 5HNO3 2H3SbO4 + 5NO2 + H2O
(iii) Tin is oxidised to meta-stannic acid.
Sn + 2HNO3 H2SnO3 + 4NO2 + H2O
(c)
(i) Sulphur dioxide is oxidised to sulphuric acid
SO2 + 2HNO3 H2SO4 + 2NO2
(ii) Hydrogen sulphide is oxidised to sulphur
H2S + 2HNO3 2NO2 + 2H2O + S
(iii) Ferrous sulphate is oxidised to ferric sulphate in presence of H2SO4
6FeSO4 + 3H2SO 4 + 2HNO3 3Fe2(SO4)3 + 2NO + 4H 2O
(iv) Iodine is liberated from KI.
6KI + 8 HNO3 6KNO3 + 2NO + 3I2 + 4H2O
(v) HBr, HI are oxidised to Br2 and I2, respectively.
2HBr + 2HNO3 Br2 + 2NO2 + 2H2O Similarly
2HI + 2HNO3 I2 + 2NO2 + 2H2O
(vi) Ferrous sulphide is oxidised to ferric sulphate
FeS + 8HNO3 Fe2(SO4)3 + 8NO2 + 4H2O
(vii) Stannous chloride is oxidised to stannic chloride in presence of HCl
2HNO3 + 14H NH2OH + NH 3 + 5H2O
Hydroxylamine
NH3 + HNO3 NH4NO3
----------------------------------------------------------------------------------------------------------------------
7SnCl 2 + 14 HCl + 3HNO 3 7SnCl 4 + NH2 OH + NH 4NO 3 + 5H 2O
(viii) Cane sugar is oxidised to oxalic acid
C 12H 22 O 11 + 36 HNO 3 6(COOH) 2 + 36NO 2 +23H 2 O
Nitric acid reacts with most of the metals except noble metals like gold and platinum.
Towards its reaction with metals, HNO3 acts as an acid as well as an oxidising agent. Like Other acids, HNO3
liberate nascent H from metals which further reduces the nitric acid into number of products like NO, NO2,
N2O, N2, NH2OH or NH3 according to the following reactions :
Metal + HNO3 Nitrate + H
2HNO3 + 2H 2NO + 2H2O
2HNO3 + 6H 2NO + 4H2O
2HNO3 + 10H N 2 + 6H 2O
2HNO 3 + 16H 2NH 3 + 6H 2O
The progress of the reaction is controlled by a number of factors :
(a) The nature of the metal
(b) The concentration of the acid,
(c) The temperature of the reaction
(d) The presence of other impurities
Mg, Mn (2% ) H 2 + Me tal nitrate
Ve ry dilute HNO 3(6% )
Fe , Zn, Sn NH 4N O 3 + m etal nitrate + H 2O
Pb, Cu, Ag, Hg NO + m etal nitrate + H 2O
Dilute HN O 3 (20% ) Fe , Zn N 2O + me tal nitrate + H 2O
Sn NH 4N O 3 + Sn(N O 3) 2
Zn, Fe, Pb, Cu, Ag, Hg NO 2 + m etal nitrate + H 2O
Conc. HN O 3(70% )
Sn NO 2 + H 2SnO 3
(a) Nitric acid attacks proteins forming a yellow nitro compound called xanthoprotein. It, therefore, stains
skin and renders wool yellow. This property is utilized for the test of proteins.
(b) Number of organic compound are oxidised.
Sawdust catches fire when nitric acid is poured on it. Turpentine oil bursts into flames when treated with
fuming nitric acid. Toluene is oxidised to benzoic acid with dil. HNO3.
Nitric acid is a monobasic acid, i.e. the molecule consist of one hydroxyl group as it is formed by the hydrolysis
of nitryl chloride, NO2Cl. It may be structurally represented as below :
O
HO–N
O
Gaseous nitric acid is a planar molecule. The bond lengths and bond angles as present in the molecule are
represented in the figure :
H O
Å
22
6º 1.
0.
102º
11
96
Å
O N 130º
1.2
1.44Å 2Å
O
Phosphorus exists in a number of allotropic forms. These forms are :
(a) Yellow or white phosphorus (b) Red phosphorus (c) Black phosphorus
(a)
1200ºC
Bone ash or Apatite rock Ca3(PO4)2 + 3SiO2 3CaSiO3 + P2O5
(i) both have same formula 1500ºC
2P2O5 + 10C P4 + 10CO
(Coke) white 'P'
conc.
(ii) Ca 3(PO4)2 + 3H2 SO 4 3CaSO4 + 2H 3PO 4
320ºC
H3PO4 HPO3
–H2O
meta phosphoric acid
1000ºC
12C + 4HPO3 2H2 + 12CO + P4
Coke white 'P'
(i) It has characteristic garlic smell and is poisonous in nature. Persons working with phosphorus develop a
disease in which the jaw bones decay. This disease is knwon as
(ii) In contact with air, it undergoe s slow combustion and glows in dark. This proper t y is called
(iii) Its ignition temperature is low (about 30 C). It readily catches fire giving dense fumes of phosphorus
pentoxide. It is, therfore, kept in water.
P4 + 5O2 P4O10 or 2P2O5
< P – P – P 60
(b)
Red phosphorus is formed by heating yellow phosphorus, between 240–250 C, in presence of an inert gas.
240-250º C
White 'P' Red 'P'
in an inert atm. like
N2 or CO2
I2 : catalyst
heated to 550ºC
Red 'P' White 'P'
in an inert atm and then
rapid cooling to room temp.
It is regarded as a polymer consisting of chains of P 4 tetrahedral linked
together by covalent bond.
P P P P
P P P P P P P
P P P P
proposed molecular structue of red phosphorus
(c)
This is most stable form of Phosphorus
470 K
White(P) Black P
at high P
Black P contain zig-zag & double layered structure.
Order of density & mp
Physical state Soft waxy solid. Brittle powder.
Colour White when pure. Red.
Attains yellow colour
on standing.
Odour Garlic Odourless.
Solubility in water Insoluble. insoluble
Solubility in CS2 Soluble. Insoluble.
Physiological action Poisonous. Non-poisonous.
Chemical activity Very active. Less active.
Stability Unstable. Stable.
Phosphorescence Glows in dark Does not glow in dark.
Reaction with NaOH Evolves phosphine. No action.
Molecular formula P4 Complex polymer.
(a) 4H3PO3 PH3 + 3H3PO4
(b) PH4I + KOH KI + PH3 + H2O
(PH3 + HI)
purest PH 3
(c) 2AIP + 3H 2SO 4 Al2(SO 4)3 + PH3
(a) It is having 'rotten fish' smell.
(b) It is soluble in CS2 and insoluble in water.
PH3 + H2O PH + OH–
in s-orbital, so donating capacity is less
PH 4 is formed with acids.
(c) Like NH3, PH3 also can form addition product.
CaCl2 8NH3, Cu2Cl2 • 2PH3, AlCl3 • 2PH3, SnCl4 • 2PH3
PH3 can be absorbed by Ca(OCl)Cl.
PH3 + 3Ca(OCl)Cl + 3H2O PCl3 + 3HCl + 3Ca(OH)2
2NH3 + 3Ca(OCl)Cl N2 + 3CaCl2 + 3H2O
150 º
(a) PH3 + O3 P2O5 + H2O
(b) PH3 + 3Cl2 PCl3 + 3HCl
electrical
(c) PH3 + 4N2O
sparking
H3PO4 + 4N2
(d) 2PH3 + 3CuSO4 Cu3P2 + 3H2SO4
Detection of PH3 Black ppt.
(e) PH3 + 6AgNO3 Ag 3 P •3AgNO 3 + 3HNO3
Yellow ppt.
Ag3 P • 3AgNO3 + 3H2O 6 Ag + 3HNO3 + H3PO3
Balck ppt.
(f) PH3 + 4HCHO + HCl [P (CH 2 OH ) 4 ] Cl – (which is used for making fire-proof cotton fabrics)
white / colourless solid
It forms three important oxides which exist in dimeric forms.
Phosphorus trioxides is formed when phosphorus is burnt in a limited supply of air.
P4 + 3O2 (limited) P4O6
(a) On heating in air, it forms phosphorus pentoxide.
P4O6 + 2O2 P4O10
Phosphorus (V) oxide
(b) It dissolves in cold water to give phosphorus acid.
P4O6 + 6H2O (cold) 4H3PO3
Phosphorus acid
It is, therefore, considered as anhydride of phosphorus acid.
With hot water, it gives phosphoric acid and inflammable phosphine.
••
P
(a) Each atom of phosphorus in P4O6 is present at the corner of a tetrahedron O O
(b) Each phosphorus atom is covalently bonded to three oxygen atoms and O P
P
••
••
each oxygen atom is bonded to two phosphorus atoms.
O
O O
(c) It is clear from the structure that the six oxygen atoms lie along the edges
P
••
of the tetrahedron of P atoms. Structure of P4O6
It is prepared by heating white phosphorus in excess of air.
P4 + 5O2 (excess) P4O10
(a) It is snowy white solid.
(b) It readily dissolves in cold water forming metaphosphoric acid.
P4O10 + 2H2O (Cold) 4HPO3
Metaphosphoric acid.
With hot water it gives phosphoric acid.
P4O10 + 6H 2O (Hot) 4H 3PO 4
Phosphoric acid
(c) Phosphorus pentoxide has strong affinity for water and, therefore, acts as a
powerful dehydrating agent. It extracts water from many inorganic and organic compounds.
(d) P4O10 is a very strong dehydrating agent and extracts water from many compounds including sulphuric
acid and nitric acid.
P4O10
2HClO4 Cl2O7
– H2O
Chlorine (VII) oxide
P4O10
2CH 3 CONH 2 CH 3 CN
– H2O
Acetamide Methyl cyanide
O
(a) Its structure is similar to that of P4O6.
P
(b) In addition, each phosphorus atom forms a double bond with oxygen
atom as shown in figure. O O
O P O P O
O
O O
P