Phosphorous

Dr. Rajeev Singh

http://people.du.ac.in/~rajeev/index.htm

No copyright claim on pictures by the author.

Document written and compiled from various sources for the benefit of students
and academic purpose.
 Phosphorous
Important allotropes

• White/ yellow: most common variety

• Red
• Black
• Scarlet
• Violet

• Basic unit of phosphorous is P4

• P4 tetrahedron occurs as a structural unit,
in which each atom is bound to the other
three atoms by a single bond.
• Angle P-P-P: 60o
• Due to a small angle a lot of strain is present in the molecule.
Therefore, it is unstable and highly unreactive.

• It is soft, waxy in nature, reacts with moist air giving out light: Chemiluminisence.

•It ignites spontaneously in dry air at 25oC to give P4O6 and P4O10.
Therefore stored under water.
White Phosphorus
• White phosphorus (P4) has a tetrahedral structure.
• It is a hard waxy substance, pure white when fresh but yellow as it ages and slowly
converts to the red allotrope.
• White phosphorus is an exciting substance that glows in the dark if just a trace of
oxygen is present and which if allowed to dry spontaneously bursts into flame
producing prodigious amounts of white phosphorus pentoxide smoke.
• Its glow occurs as a result of its vapors slowly being oxidized by air.
• It is usually stored under water or mineral oil.
It is so thermodynamically unstable that it combusts in air.
• It was once used in fireworks and the U.S. military still uses it in incendiary bombs.
RED PHOSPHOROUS
POLYMER OF P4 tetrahedra
• Red phosphorus is the only form of pure phosphorus that is readily found.
• It is the safest allotrope being stable at ordinary temperatures and much less toxic
than white phosphorus.
P4 (white) =================Red P (polymeric chain)
(250oC, I2 as a catalyst in inert atmosphere of Argon)

• Red Phosphorus has more atoms linked together in a network, which makes it
much more stable than white phosphorus. The strain in each tetrahedra is reduced
so quite stable and therefore, less reactive.

Reason, we now use red phosphorus in

matches.
• It does not react with dry or moist air.
• It is not quite as flammable, but still reacts with air
given enough energy.
Black phosphorous
• Black phosphorus has an orthorhombic structure and is the least reactive allotrope,
• It consists of many six-membered rings which are interlinked.
• Each atom is bonded to three other atoms.
• Black phosphorus is the most stable form; the atoms are linked together in puckered
sheets, like graphite. Because of these structural similarities black phosphorus is also
flaky like graphite and possesses other similar properties.

•Black P is used as a semi-conducting material.

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
Strain is almost absent, therefore very stable.
Violet phosphorous

Violet phosphorus is obtained from heating

and crystallizing red phosphorus in a certain way.
The phosphorus forms pentagonal "tubes"
 OXIDES OF PHOSPHOROUS

PHOSPHOROUS P4O6
TRIOXIDE
PHOSPHOROUS P4O10
PENTOXIDE
PHOSPHORUS TRIOXIDE P4O6
PHOSPHORUS (III) OXIDE/
TETRAPHOSPHORUS HEXOXIDE

PREPARATION

P4 + 3O2 ==========P4O6
limited supply

600 oC
P4 + 6N2O ============ P4O6 + 6N2
nitrogen (I) oxide

PROPERTIES

P4O6 + 6H2O =======4H3PO3

Phosphorus acid
P4O6 is also called anhydride of phosphorous acid

P4O6 + 2O2 ====== P4O10

P4O6 + 6H2O (hot water) ==========3H3PO4 + PH3
P4O6 + 8NaOH ============4Na(HPO3) + 2H2O
sodium hypophosphite
PHOSPHORUS PENTOXIDE P4O10
PHOSPHORUS (V) OXIDE/ TETRAPHOSPHORUS DECOXIDE

PREPARATION

P4O6 + 2O2 ========P4O10

P4 + 5O2 ============P4O10
(ample supply)
P4 + 10CO2 ======== P4O10 + 10 CO

REACTIONS

P4O10 + 2H2O ===========4HPO3

metaphosphoric acid

P4O10 + 4H2O ========== 2H4P2O7

pyrophosphoric acid

P4O10 + 6H2O ========== 4H3PO4

orthophosphoric acid
P4O10 is hygroscopic. It absorbs water from various compounds like HNO3,
H2SO4 etc and thus, dehydrates them.

P4O10 + 2H2SO4 ========= 4HPO3 + 2SO3

P4O10 + 4HNO3 ========== 4HPO3 + 2N2O5

(meta phosphoric acid)

P4O10 + 6 C2H5OH ======== 2[O=P-(OC2H5)(OH)2] + 2[O=P-(OC2H5)2OH]

phosphate esters
P4O10 + 6 C2H5 – O – C2H5 ========= 4 [O=P-(OC2H5)3]
diethyl ether
 Structure O

P
O O
O

P O co-ordinate bond is formed by donation of lone pair on P-atom.

Here, P-O bond (=1.39 Ao) is much shorter than actual P-O bond (=1.65 Ao) in the
molecule this is due to the fact that p¶ (O) – d¶ (P) back bonding via lateral
overlap of a filled p-orbital of oxygen atom with the vacant d-orbital of Phosphorus atom.
OXO ACIDS OF PHOSPHORUS

NAME FORMULA OXIDATION

STATES