Phosphorus and its Compounds

Introduction
• Phosphorus is a chemical element with
the symbol P and atomic number 15. Elemental
phosphorus exists in two major forms, white
phosphorus and red phosphorus, but because it is
highly reactive, phosphorus is never found as a free
element on Earth. It has a concentration in the Earth's
crust of about one gram per kilogram (compare copper
at about 0.06 grams). In minerals, phosphorus
generally occurs as phosphate.
• Elemental phosphorus was first isolated as white
phosphorus in 1669.
• Phosphorus is essential for
life. Phosphates (compounds containing the phosphate
ion, PO43−) are a component of DNA, RNA, ATP,
and phospholipids.
 Allotropes
• The two most common allotropes are white
phosphorus and red phosphorus
• White P is a soft, waxy solid which consists of
tetrahedral P4 molecules
• White phosphorus exists in two crystalline forms: α
(alpha) and β (beta). At room temperature, the α-
form is stable, which is more common and it has
cubic crystal structure and at 195.2 K (−78.0 °C), it
transforms into β-form, which has hexagonal
crystal structure. These forms differ in terms of the
relative orientations of the constituent
P4 tetrahedra.
• White phosphorus is the least stable, the most
reactive, the most volatile, the least dense, and
the most toxic of the allotropes. White phosphorus
gradually changes to red phosphorus. This
transformation is accelerated by light and heat.
• When exposed to oxygen, white phosphorus
glows in the dark with a very faint tinge of green
and blue. It is
highly flammable and pyrophoric (self-igniting)
upon contact with air.
Red phosphorus
• It is polymeric in structure. It
can be viewed as a
derivative of P4 wherein one
P-P bond is broken, and one
additional bond is formed
with the neighbouring
tetrahedron resulting in a
chain-like structure.
• Red phosphorus may be
formed by heating white
phosphorus to 250 °C
(482 °F) or by exposing
white phosphorus to sunlight
 Sodium Phosphates
• Quantitywise, pentasodium triphosphate
[sodium tripolyphosphate (STPP)] is the most
important sodium phosphate, which is
primarily used in detergents and cleaning
agents.
 Applications for mono-, di-, and tri-
sodium phosphates
• Sodium phosphates have many applications in food and for water
treatment. For example, sodium phosphates are often used
as emulsifiers (as in processed cheese),[thickening agents,
and leavening agents for baked goods.
• They are also used to control pH of processed foods.
• They are also used in medicine for constipation and to prepare the
bowel for medical procedures
• Also in metal cleaning, phosphatizing, boiler water treatment, buffer
systems, in animal nutrition
• for disodium dihydrogen phosphate:
• as baking powder
• for tetrasodium diphosphate: in industrial cleaning agents
• for high molecular weight sodium polyphosphates:
• in food manufacture, for stabilization ofpigment suspensions and in
tanning
 Applications: Ammonium Phosphates
• Their main application is as ammonium phosphates in
fertilizers.
• In fire protection e.g. as an additive in fire-
extinguishing agents
• for fighting forest fires, as flame retardants in paper,
textiles and poly(urethanes),
• in the prevention of afterglow in matches and as a
component of intumescent paints
• (flame retarding coatings).
• Small quantities in animal nutrition, particularly for
cattle.
 Calcium Phosphates
• The main use of calcium phosphates outside the
fertilizer sector is in animal feedstuffs.
• The different calcium phosphates used are:
• monocalcium phosphate - Ca(H2PO4)2
• dicalcium phosphate – CaHPO4
• defluoridated apatite – Ca5(OH)(PO4)3
• Other applications:
• as baking powder
• as a cleaning agent in toothpastes
 Sodium monophosphates:
Manufacture

Sodium di- and polyphosphates:

 Polyphosphates:
• Pentasodium triphosphate is obtained by the
condensation of sodium dihydrogen
phosphate and disodium hydrogen phosphate
in a 1 : 2 ratio:
 Ammonium Phosphates
• Industrially, three compounds are produced and
utilized: Ammonium dihydrogen phosphate and
• ammonium dihydrogen phosphate, diammonium
hydrogen phosphate and ammonium polyphosphate
 Potassium Phosphates
• Only tetrapotassium diphosphate is of major
industrial importance, due to its high water
solubility. It is produced in an analogous way
to the sodium compound fromdipotassium
hydrogen phosphate
Calcium Phosphates
 Applications
• White phosphorus is utilized in the production of:
• "furnace" phosphoric acid or phosphates
• phosphorus sulfides
• phosphorus oxides
• phosphorus halides
• red phosphorus
• Red phosphorus utilized:
• for matchboxes
• for- pyrotechnical applications
• as flame retardant
Manufacture of White Phosphorus
• White phosphorus from apatite by
electrothermal reduction with coke in the
presence of SiO2
 Byproducts:
• carbon monoxide - valuable energy source
• calcium silicate slag - limited use in road
building
• ferrophosphorus - usable in metallurgy
 Production of one ton of phosphorus
entails the consumption of:
• 8.0 t Florida phosphate (3 1 % P2OS)
• 2.8 t of gravel (97% silicon dioxide)
• 1.25 t of coke (90% carbon)
• 0.05 t Soederberg electrodes
• ca. 13 . 10^3 kWh of electricity
The production of the following quantities of byproducts:
• 7.7 t silicate slag (90% calcium silicate)
• 0. 15 t of ferrophosphorus
• 0.1 t filter dust (20% P,O,)
• 2500 m3 flue gas (85% carbon monoxide)
Manufacture of Red Phosphorus
The conversion of white phosphorus to red
phosphorus is an exothermic reaction producing red
phosphorus as a solid product, making heat removal
from the reaction difficult.
In a modern process developed by Hoescht A.G. (FRG),
the conversion is carried out semi-continuously in a
ball mill at 350°C.
 Products Manufactures from
Phosphorus
• Diphosphorus(V) oxide
• About 85% of the white phosphorus produced
is burnt to diphosphorus(V) oxide.

P(V) oxide P4O10

P (III) oxide P4O6

 Applications of P4O10
• mainly in the manufacture of pure phosphoric
acid
• as a drying agent
• in dehydration reactions in organic chemistry
• for improving the properties of asphalt
• in the production of additives for plastics and
lubricating oils
 Phosphorus(V) sulfide
• It is produced by the exothermic reaction of
liquid phosphorus with liquid sulfur at over
300°C:

The reaction product can either be directly poured onto cooling

rollers or first purified by distillation (b.p. 513 to 5 15 oC). If a
non-discolored phosphorus(V) sulfide is required, organic
impurity-free phosphorus and very pure sulfur have to be used.
The former can be obtained by sulfuric acid extraction and the
latter from natural gas purification.
Applications: Phosphorus(V) sulfide is used in the manufacture of
insecticides (ca. 40%), lubricating oil additives (ca. 50%) and
flotation agents.
 Phosphorus Halides
Phosphorus(lll) chloride
• Phosphorus(III) chloride is manufactured from
white phosphorus and chlorine in an
exothermic reaction:

This reaction can be carried out in a number of ways. Chlorine can be passed
into a suspension of phosphorus in phosphorus(III) chloride. The heat liberated
during the reaction is sufficient to evaporate off the phosphorus(III) chloride,
which is condensed in reflux condensers and in part returns to the reaction
mixture. Part of the distillate is run off and purified by fractional distillation.
Direct reaction of stoichiometric quantities of phosphorus and chlorine in a
burner is also possible with subsequent working up. Technical phosphorus(II1)
chloride has a purity of greater than 99.7% and does not contain elemental
phosphorus.
 Applications of PCl3
• In the manufacture of the intermediate phosphorous acid
• 19.4% to phosphorus(\/) oxychloride. Di and trialkylphosphonates,
triarylphosphonate, phosphorus(\/) sulfochloride and
phosphorus(V) chloride are also manufactured directly from
phosphorus(III) chloride.
• 53.6% was utilized for pesticide production (mainly for
glyphosphate),
• 18% for the manufacture of water treatment chemicals (phosphonic
• acids) and tensides (acid chlorides of fatty acids and secondary
products),
• 17.1 % in the manufacture of polymer additives (flame retardants,
stabilizers etc.)
• Small quantities for the production of hydraulic fluids, lubricants
• and additives for lubricating oils.
 Phosphorus( V ) chloride
• Phosphorus(V) chloride is manufactured continuously in lead-
lined towers in which phosphorus(III) chloride is fed in from
above and chlorine from below:

The phosphorus(V) chloride formed sinks to the

bottom and is removed by a screw conveyor.

Applications: Phosphorus(V) chloride is mainly

used as a chlorination agent in organic chemistry
 Phosphorus(V) oxychloride
• It is manufactured by reacting pure phosphorus(III)
chloride with oxygen with cooling at ca. 5O to 60°C:

This is a free radical reaction, which is inhibited by small

quantities of sulfur, sulfur compounds, iron, copper etc. The
reaction product is further purified by fractional distillation.
The extent to which phosphorus(V) oxychloride is still
industrially produced from diphosphorus(V) oxide and
phosphorus(\/) chloride (from phosphorus(lII) chloride
andchlorine) according to the reaction:
 Applications:
• Phosphorus(V) oxychloride i s mainly used in the
manufacture of aliphatic and aromatic esters of
phosphoric acid, which are used as flame
retardants and plasticizers in plastics, as hydraulic
fluids and as extraction agents.
• 58% of the phosphorus(V) oxychloride was
utilized in the manufacture of polymer additives,
• 14% in the synthesis of hydraulic fluids and
lubrication additives.
 Phosphorus( V ) sulfochloride
• Phosphorus(V) sulfochloride can either be manufactured from
phosphorus(III) chloride and sulfur at 180°C in an autoclave or
by passing phosphorus(III) chloride vapor through molten
sulfur:

Catalysts such as e.g. aluminum chloride reduce the

reaction temperature to such a degree that the
reaction can be carried out in phosphorus(V)
sulfochloride. Purification is by distillation
Application; Phosphorus(V) sulfochloride is mainly
utilized in the manufacture of ester chlorides of
thiophosphoric acids (precursors for pesticides).
 Acids and Salts of Phosphorus with P<5+:
Phosphinic acid and Hypophosphites
• Hypophosphites, the salts of phosphonic acid,
are manufactured by the reaction of white
phosphorus with boiling calcium hydroxide,
according to the following equation:

Hydrogen and calcium phosphite are formed as byproducts. Excess

calcium hydroxide is precipitated by passing carbon dioxide through the
solution and is filtered off together with the poorly soluble calcium
phosphite.
Upon addition of sodium carbonate and subsequent filtration a solution
of sodium hypophosphite is obtained, which can be converted into
phosphinic acid by passing over an ion exchanger.
 Applications:
• Hypophosphites are mainly used in electroless
nickel plating (e.g. deposition of nickel
phosphorus layers with 8 to 10% P in the
KaniganB process).
 Phosphorous Acid
• In the elegant process developed by Hoechst A.G.,
phosphorous acid is manufactured by spraying
phosphorus(III) chloride and steam (maintained in
excess) together, whereupon the heat of reaction of
the hydrochloride formed distils off the excess water.
Phosphorous acid is formed as a byproduct in the
chlorination of fatty acids and in the manufacture of
phosphinic acid.
 Applications:
• Phosphorous acid is mainly directly used by the
producer for the manufacture of phosphonic
acids.
• The manufacture of N-phosphonomethyl-glycine
(glyphosphate), quantity wise the most produced
phosphonic acid.
• Other phosphonic acids produced from
phosphorous acid are utilized as water treatment
chemicals.
• Basic lead phosphite is used as a PVC-stabilizer.
Organophosphorous compounds
• Organophosphorus compounds are organic
compounds containing phosphorus. They are used
primarily in pest control as an alternative
to chlorinated hydrocarbons that persist in the
environment.
• Some organophosphorus compounds are highly
effective insecticides, although some are
extremely toxic to humans,
including sarin and VX nerve agents.
• Phosphorus can adopt a variety of oxidation
states, and it is general to classify
organophosphorus compounds based on their
being derivatives of phosphorus(V) vs
phosphorus(III), which are the predominant
classes of compounds.
Phosphate esters and amides
• Phosphate esters have the general structure P(=O)(OR)3 with P(V).
Such species are of technological importance as flame
retardant agents, and plasticizers.
• Lacking a P−C bond, these compounds are in the technical sense
not organophosphorus compounds but esters of phosphoric acid.
• Many derivatives are found in nature, such as phosphatidylcholine.
Phosphate ester are synthesized by alcoholysis of phosphorus
oxychloride.
• A variety of mixed amido-alkoxo derivatives are known, one
medically significant example being the anti-cancer
drug cyclophosphamide. Also derivatives containing the
thiophosphoryl group (P=S) include the pesticide malathion.
• The organophosphates prepared on the largest scale are the zinc
dithiophosphates, as additives for motor oil. Several million
kilograms of this coordination complex are produced annually by the
reaction of phosphorus pentasulfide with alcohols.
Illustrative organophosphates and related compounds:
phosphatidylcholine, triphenylphosphate, cyclophosphamide, parathion,
and zinc dithiophosphate.