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Phosphorus

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9 views

Phosphorus

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artistaaartista
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PHOSPHORUS :

I. Introduction :
The discovery of phosphorus is attributed to the German Hennig Brandt in 1969, who
obtained it from urine during his research on the philosopher's stone.
Its name comes from the Greek "phos" and "phoros" meaning respectively light and wear.
This is because white phosphor emits visible light in the dark when exposed to air.
Phosphorus is found in the environment in general in the form of phosphates. Phosphates are
important substances for the human body because they are a component of DNA and they
participate in the distribution of energy.
Phosphorus is one of the three fundamental elements for plant development along with
nitrogen and potassium. Phosphorus (P) has 23 known isotopes, with mass numbers ranging
from 24 to 46. Only one is stable : 31P.

II. Characteristics :
Phosphorus is the chemical element with atomic number 15, symbol P. It is a member of the
group of pnictogens, constituting subgroup VA of the periodic table. Its external electronic
configuration is 3s2 3p3.
Phosphorus comes in several different color forms : red, black, and white.
 White phosphorus : White phosphorus consists of tetrahedral P4 molecules associated
by Van der Waals type bonds. It is a toxic body that oxidizes slowly in air at room
temperature. It is always kept under water. White phosphorus turns into red phosphorus
under the influence of light.

 Red phosphorus : Red phosphorus consists of molecules of indeterminate length, but


very large. We can give the formula P2000 as an example. It is neither toxic nor readily
flammable. Red phosphorus is transformed into white phosphorus (gaseous) under the
influence of heat, i.e. 280 °C. Its structure is quadratic.

 Black phosphorus : Black phosphorus has a structure similar to that of graphite with
atoms arranged in hexagonal sheets. This shape is stable at high temperatures and high
pressures. It is an electrical current conductor.

III. Chemical compounds :


Phosphorus has several degrees of oxidation (from - III to V). With the degree of oxidation - III
phosphorus can combine with hydrogen and with some metals to give phosphides and with
positive oxidation degrees it combines with oxygen and halogens to give oxides and halides.
1
 Combination with hydrogen : PH3 is obtained by hydrolysis of a metal phosphide
according to the following reaction, unlike NH3 which is obtained by direct action of
hydrogen on nitrogen :
Mg3P2 + 6 H2O ──> 2 PH3 + 3 Mg(OH)2

 Combination with alkali and alkaline-earth metals : Phosphides are prepared by


direct action of the metal on the phosphorus, by heating. They form M3P and M3P2.

 Combination with halogens : Phosphorus leads to two types of halides PX3 and PX5.
In aqueous medium PCl3 leads to H3PO3 :

PCl3 + 3 H2O ──> H3PO3 + 3 HCl

 Combination with oxygen : Phosphorus forms oxoacids with oxygen and hydrogen
(H3PO2, H3PO3 and H3PO4) and oxides with oxygen (P2O3, P2O5 and P4O10). P2O3
exists in the form of P4O6 molecules, in the presence of water, there is formation of
H3PO4 according to the following reaction :

P4O6 + 6 H2O ──> 4 H3PO4

IV. Acid-base and redox properties :


IV.1/ Acid-base properties :
* Phosphonic acid or hypophosphorous acid of formula H3PO2 is a monoacid and not a
triacid.

There are two non-ionizable hydrogens that are directly bound to the phosphorus atom.
The dissociation equilibrium of H3PO2 in aqueous solution is as follows :

H3PO2 + H2O <──> H2PO2- + H3O+ pka = 1.2

* Phosphorous or orthophosphoric acid of formula H3PO3 is a diacid and not a triacid.

2
There is a non-ionizable hydrogen that is directly bound to the phosphorus atom. The
dissociation equilibria of H3PO3 in aqueous solution are as follows :

H3PO3 + H2O <──> H2PO3- + H3O+ pka1 = 2

H2PO3- + H2O <──> HPO32- + H3O+ pka2 = 6.7

* Phosphoric acid H3PO4 is a triacid. The dissociation equilibria of H3PO4 in aqueous solution are
as follows
H3PO4 + H2O <──> H2PO4- + H3O+ pka1 = 2.12

H2PO4- + H2O < ──> HPO42- + H3O+ pka2 = 7.21

HPO42- + H2O <──> PO43- + H3O+ pka3 = 12.67

IV. Redox properties :


PH3 has a more powerful reducing power than ammonia :
4 PH3 + 3 O2 ──> P4 + 6 H2O

PH3 + 2 O2 ──> H3PO4

PH3 + 4 Cl2 ──> PCl5 + 3 HCl

H3PO4 is an acidic oxidant and leads to H3PO2 and H3PO3.


H3PO4 + 2 H3O+ + 2 e─ ─> H3PO3 + 3 H2O

H3PO4 + 4 H3O+ + 4 e─ ─> H3PO2 + 6 H2O

V. Applications :
Phosphorus has multiple applications :
 Phosphorus is an essential nutrient for plants (the most often limiting nutrient after
nitrogen). Used in agricultural fertilizers, slowly up to 70 % to 75 % of P2O5.
 Phosphoric acid H3PO4 is used as a descaler for sanitary and household appliances and
as an acidifying agent in carbonated beverages, also used against steel corrosion.

VI. Production :
 The phosphorus is prepared by reduction in an electric oven at around 1500 °C of the
natural phosphate Ca3(PO4)2. A mixture of coke (C) and silicon dioxide SiO2 is used
as the reducing agent.

2 Ca3(PO4)2 + 6 SiO2 + 10 C ──> P4 + 6 CaSiO3 + 10 C

3
 H3PO4 is obtained by hydrolysis of its anhydride P4O10

P4O6 + 6 H2O──> 4 H3PO4

 Phosphorous acid H3PO3 is obtained by the action of water on PCl3

PCl3 + 3 H2O ──> H3PO3 + 3 HCl

• Phosphonic acid H3PO2 is obtained by the action of iodine I2 on PH3 in an aqueous medium.

PH3 + 2 I2 + 2 H2O──> H3PO2 + 4 HI

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