Nitrogen and Phosphorus

Dr. A.A. Adebisi

 Nitrogen and Phosphorus
• They are members of group VA elements.
• Nitrogen is highly abundant making up 78%
by volume in air as dinitrogen (N2).
• Phosphorus is highly abundant in crustal
rocks, mostly as orthophosphate of the apatite
group, Ca5(PO4)3X.
• They are essential constituents of the living
system.
• Because of the availability of N2 in the
atmosphere and its requirement by living
organisms (in which N is present as proteins), the
fixing of nitrogen in forms in which it may be
assimilated by plants is of great importance.
• Phosphorus on the other hand is an essential
constituent of plant and animal tissues; calcium
phosphate occurs in bones and teeth, and
phosphate esters of nucleotides (e.g DNA) which
are of immense biological significance.
• They show the typical properties of non-
metals.
• For example, they are poor conductors of heat
and electricity and give acidic oxides.
• Their compounds are predominantly covalent.
• They have lower melting and boiling point
than the metals.
 Extraction
Laboratory preparation of Nitrogen
• Decomposition of sodium azide, NaN3
2NaN3 → 2Na + 3N2
• Decomposition of ammonium nitrite
NH4NO2→ N2 + 2H2O
Industrially, large amount of nitrogen are
obtained as by-product during isolation of
oxygen by fractional distillation of liquid air.
 Extraction
• Phosphorus is obtained by reducing phosphate
rock with coke in the presence of sand at 1400
- 1500℃ in an electric furnace; phosphorus
vapour distils out and is condensed under water
to yield white phosphorus.

2Ca3(PO4)2 + 6SiO2 + 10C → 6CaSiO3 + 10CO + P4

 Uses
•Nitrogen is widely used to provide inert atmosphere both
industrially and in laboratories.
•Liquid nitrogen is a useful refrigerant.
•Besides the use of elemental nitrogen, compounds of nitrogen
have extensive applications in various fields. Ammonia is used in
various forms as a fertiliser, e.g., as NH4NO3, (NH4)2SO4,
(NH4)2HPO4, etc. Its applications also include refrigeration, as a
pH controller in food and beverage industry, pharmaceuticals and
in water purification. Nitric acid is another important compound
of nitrogen. Its major uses include manufacture of NH4NO3,
explosives like nitroglycerine, nitrocellulose and trinitrotoluene
(TNT).
 Uses
• The most important application of phosphorus is in
the production of phosphate fertilizers.
• Phosphorus is also used to make very pure
phosphoric acid.
• Some P is converted to P4S10 (used in making
organo-phosphorus) and P4S3 (used to make safety
matches and in the generation of fireworks).
• Phosphorus is also important in steel manufacture
and production of phosphor bronze.
 Physical Properties
• Nitrogen is gaseous in nature and exists as a
diatomic molecule N2. The dinitrogen molecule
has a triple bond N≡N of unusual stability.
• The stability of this bond is responsible for the
low reactivity of this molecule thus making it
suitable as an inert environment for many
chemical studies of reactions that are either
oxygen or moisture sensitive.
• It has no allotropes.
 Physical Properties
• Phosphorus is solid at room temperature.
• Solid phosphorus has several allotropic forms with
the most common of these been white phosphorus.
Other allotropes include red phosphorus and black
phosphorus which is the least reactive allotrope but
most thermodynamically stable.
• Phosphorus exists as tetrahedral P4 molecules in the
liquid and gas phases. At very high temperature, P4
molecules dissociate into P2 molecules.
Figure 14.16 allotropes of phosphorous.

White phosphorous (P4) Strained bonds in P4

Red phosphorous
 Anomalous Properties of Nitrogen
• Due to its high electronegativity compare with
phosphorus, it has ability to form strong hydrogen bond.
• Absence of d-orbitals in the valency shell.
• Nitrogen is a gas while phosphorus is a solid.
• Nitrogen molecule is diatomic while phosphorus form
tetratomic molecules such as P4.
• Nitrogen exhibits a large number of oxidation states
from -3 to +5 while phosphorus do not exhibit such a
variety of oxidation states.
 Chemical Properties
• Nitrogen is quite inert at room temperature
because of the great strength of the N≡N bond.
• White phosphorus is very reactive while red
and black allotropes are not.
• With oxygen, nitrogen combines only at very
high temperatures to yield nitric oxide; white
phosphorus combines so readily giving trioxide
and pentoxide that is stored under water.
Chemistry of Nitrogen and Phosphorus
Hydrides
Both of them form hydrides with unpleasant sources.
Nitrogen forms ammonia with a strong pungent smell
while phosphorus forms phosphine with a faint garlic
smell.
Like ammonia, phosphine PH3, can accept a proton out of
its lone pair and give the phosphorium ion PH 4+ and it
will combine to make phosphornium iodide, PH4I.
However, phosphine will not accept protons as readily as
ammonia.
 Halides and oxohalides
• Nitrogen and phosphorus form trihalide with F, Cl,
Br and I and pentahalides such as PF5, PCl5, PBr5,
while those of nitrogen do not exist.
• Phosphorus penta chloride fumes in air. It reacts in
water to gives the oxochloride
PCl5(s) + H2O(1) → PoCl3(1) + 2HCl(g)
and in excess of water it gives
PCl5(s) + 5H2O(1) → H3PO4(aq) + 5HCl(g)
 Oxides of nitrogen
Formula Name Colour Remarks
N2O Nitrous oxide Colourless Unreactive
NO Nitric oxide Colourless Moderately reactive
N2O3 Dinitrogen Dark blue Extensively
trioxide dissociated as gas
NO2 Nitrogen dioxide Brown Moderately reactive
N2O4 Dinitrogen tetroxide Colourless Extensively
dissociated to NO2 as
gas and partly as
liquid
N2O5 Dinitrogen pentoxide Colourless Unstable as gas; ionic
solid
NO3,N2O6 Nitrogen trioxide, Not well characterised
dinitrogen hexoxide and quite unstable
 Oxide of nitrogen
• Nitrogen oxides are oxidizing agent.
• N2O and NO are neutral oxides, while the other
oxides are acidic.
• Some are acid anhydrides (a compound that
forms an oxoacid when it reacts with water) e.g
N2O5
• The oxides of phosphorus are P4O6 and P4O10
which are of +3 and +5 oxidation state.
 Oxoacids of nitrogen
• The two better known oxoacids of nitrogen are nitrous acid
and nitric acid.
• Nitrous acid HNO2 is an unstable, weak acid which is
known only in aqueous solution.
• Nitric acid HNO3 is a strong acid as well as a strong
oxidizing agent
• It is made in the three-step Ostwald process
• STEP 1: Oxidation of ammonia
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
• STEP 2: Oxidation of nitrogen oxide
2NO(g) + O2(g) → 2NO2(g)
• STEP 3: Disproportionation of NO2 in water;
3NO2(g) + H2O(l) → 2HNO3(aq) + NO(g)
 Oxoacid of Phosphorus
• Phosphorous forms various oxoacids like H3PO4,
H3PO3(phosphorus acid), H3PO2(Hypophosphorus acid)
etc
• The simplest phosphoric acid is H3PO4 called
orthophosphoric acid.
• H3PO4 can also be made from phosphate rock by
treating it with H2SO4.
Ca3(PO4)2 + 3H2SO4 → 2H3PO4 + 3CaSO4
• Used primarily for the production of fertilizer, food
additives, and detergent.