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Exams K12 Halides of Phosphorus: Preparation, Structure, Proper ties, Uses

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Halides of Phosphorus:
Preparation, Structure, Properties,
Uses
Halides of Phosphorus: Chlorine is commonly used in swimming
pools, as you are probably aware. Phosphorus halide, on the other
hand, can be utilized as a cleaning and bleaching agent. Have you ever
tried to understand the meaning of phosphorus halides? In this post,
we will learn more about phosphorus halides in depth.

STUDY EVERYTHING ABOUT PHOSPHORUS HERE

Table of Contents 
1. Define Phosphorus Halide
2. Phosphorus Trichloride (PCl3)
3. Preparation of Phosphorus Trichloride
4. Structure of Phosphorus Trichloride
5. Properties of Phosphorus Trichloride
6. Uses of Phosphorus Trichloride
7. Phosphorus Pentachloride
 8. Preparation of Phosphorus Pentachloride
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9. Structure of Phosphorus Pentachloride EXAMS  Log In 

10. Properties of Phosphorus Pentachloride

11. Uses of Phosphorus pentachloride
12. FAQs On Halides of Phosphorus

Define Phosphorus Halide

A phosphorus halide is a compound formed when phosphorus reacts
with halogen. Phosphorus forms two types of halides, PX3 and PX5 .
Here, X is nothing but halides such as fluorine, chlorine, bromine, and
iodine. However, the main types of phosphorus halide are phosphorus
trichloride and phosphorus pentachloride.

Phosphorus Trichloride (PCl 3 )

Phosphorus trichloride is an inorganic compound with the chemical
formula PCl3 .
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Preparation of Phosphorus Trichloride

In the laboratory, phosphorus trichloride can be prepared by passing
dry chlorine gas overheated red phosphorus.

P4  + 6Cl2 → 4PCl3

I. It is also prepared by treating phosphorus with thionyl chloride.

P4  + 8SOCl2 → 4PCl3  + 4SO2  + 2S2 Cl2

Structure of Phosphorus Trichloride

P in PCl3 is 3
sp -hybridized. Three of its 3
sp - orbitals overlap with the
p-orbitals of three chlorine atoms to form three P − Cl , sigma-bonds,
while the fourth orbital contains a lone pair of electrons. Therefore,
PCl3 is pyramidal. The Cl − P − Cl bond angle in PCl3 is, however,
greater due to the steric crowding of the two atoms.
∘
(100.4 ) Cl
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Properties of Phosphorus Trichloride

Let’s discuss the physical and chemical properties of Phosphorus
Trichloride in this section

Physical Properties of Phosphorus Trichloride

1. Phosphorus trichloride is a colourless liquid with a pungent smell.
The boiling point of phosphorus trichloride is 349 K .

Chemical Properties of Phosphorus Trichloride

1. It reacts readily with water and forms phosphorus acid and
hydrochloric acid.
PCl3 + 3H2 O → H3 PO3 + 3HCl

2. When it reacts with concentrated sulphuric acid, chlorosulphonic

acid is formed.
2HO– SO2 – OH + PCl3 → HO– SO2 – Cl + HPO3 + SO2 + 2HCl
Sulphuric acid Chlorosulphonic acid

3. It acts as a reducing agent. For example, it reduces Sulphur trioxide

to Sulphur dioxide and sulphuryl chloride to Sulphur dioxide.
PCl3  + SO3 → POCl3  + SO2

PCl3  +  SO2 Cl2 → PCl5  + SO2

Sulphuryl chloride

4. Phosphorus trichloride reacts with Grignard reagents to form

substituted phosphine. For example,
PCl3  +  3C6 H5 MgCl → P(C6 H5 )  +  3MgCl2
3
Phenylmag chloride Triphenyl phosphine
5. Phosphorus trichloride on heating with finely divides metals forms
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metal chlorides. For example,
Δ Δ

12Ag + 4PCl3 −
→ 12AgCl + P4 ; 6Na + PCl3 −
→ 3NaCl + Na3 P

6. Phosphorus trichloride reacts with organic compounds containing

hydroxyl groups and replaces the hydroxyl groups with chlorine atoms.
For example,

3C2 H5 OH + PCl3 → 3C2 H5 Cl + H3 PO3

Ethyl alcohole Ethyl chloride Phosphorus acid

3CH3 COOH + PCl3 → 3CH3 COCl + H3 PO3

Acetic acid Acetyl chloride Phosphorus acid

7. It reacts with chlorine and forms phosphorus pentachloride.

PCl3  + Cl2 → PCl5

8. It reacts with oxygen to give phosphorus oxytrichloride.

2PCl3  + O2 → 2POCl3

Uses of Phosphorus Trichloride

Phosphorus trichloride is widely used as an important reagent in
organic chemistry for replacing hydroxyl groups with chlorine atoms in
organic reactions.

3C2 H5 OH + PCl3 → 3C2 H5 Cl + H3 PO3

Ethyl alcohole Ethyl chloride Phosphorus acid

3CH3 COOH + PCl3 → 3CH3 COCl + H3 PO3

Acetic acid Acetyl chloride Phosphorus acid

Phosphorus Pentachloride
Phosphorus pentachloride is a chemical compound with the formula
PCl5 . It is a very important phosphorus chloride.
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Preparation of Phosphorus Pentachloride

I. Phosphorus pentachloride may be prepared by the action of
sulphuryl chlorides on phosphorus or phosphorus trichloride.
P4 + 10SO2 Cl2 → 4PCl5 + 10SO2
Suphuryl chloride

PCl3 + SO2 Cl2 → PCl5 + SO2

Suphuryl chloride

ii. Laboratory Preparation: In the laboratory, it is prepared by the

action of an excess of dry chlorine on phosphorus trichloride.
PCl3  +  Cl2 → PCl5
Phosphorus trichloride Phosphorus pentachloride

The apparatus used is depicted in Fig. It is made up of a wide-

mouthed flask with a dropping funnel and two tubes. With the help of
a dropping funnel, phosphorus trichloride is slowly dropped into the
flask.
Through one of the two tubes fitted into the flask’s mouth, a current of
pure and dry chlorine is passed into the flask. The other tube is an
outlet for the used gas. A freezing mixture is used to cool the flask.
Phosphorus trichloride reacts with chlorine to form solid phosphorus
pentachloride. The chlorine that is not used escapes through the
outlet.
Structure of Phosphorus Pentachloride
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In PCl5 , phosphorus undergoes 3

sp d -hybridization and has a trigonal
bipyramidal geometry in gaseous and liquid states. It has three P − Cl

bonds that are equatorial and two P − Cl bonds that are axial. Since
two axial P − Cl bonds are repelled by three bond pairs, while three
equatorial bonds are repelled by two bond pairs. Therefore, axial
bonds are longer (240 pm) than equatorial bonds (202 pm) .

Properties of Phosphorus Pentachloride

The physical and chemical properties of Phosphorus Pentachloride are
explained below:

Physical Properties of Phosphorus Pentachloride

Although pure phosphorus pentachloride is nearly colourless, impure
samples are typical greenish-yellow in colour. It has a pungent smell.

Chemical Properties of Phosphorus Pentachloride

I. Dissociation: When phosphorus pentachloride is heated, it sublimes
but decomposes on stronger heating into PCl3 and Cl2 .
PCl5 ⇌ PCl3  + Cl2

II. The action of water: Phosphorus pentachloride reacts violently with

water. Phosphorus oxychloride is formed when there is insufficient
water, whereas phosphoric acid is formed when there is an excess of
water.

III. Action on metals: When heated, it reacts with finely divided metals
to produce the corresponding chlorides.
For example,
PCl5  + Zn → PCl3  + ZnCl2

PCl5 + 2Cu → PCl3 + 2CuCl

PCl5 + 2Ag → PCl3 + 2AgCl

PCl5 + Cd → PCl3 + CdCl2

IV. Reaction with sulphuric acid: It reacts with concentrated sulphuric

acid to form chlorosulphonic acid.
PCl5 + H2 SO4 → Cl. SO3 H + POCl3 + HCl
TRYChloro
NEW sulphonic
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V. Reaction with Sulphur dioxide: It reacts with sulphur dioxide to

form thionyl chloride.
PCl5 + SO2 → SOCl2 + POCl3
Thionyl chloride

VI. Reaction with hydroxyl compounds: It reacts with compounds,

particularly organic compounds containing hydroxy (−OH) groups,
and replaces the −OH groups with chlorine atoms. For example,
CH3 CH2 OH + PCl5 → CH3 CH2 Cl + POCl3 + HCl
Ethyl alcohol Ethyl chloride

CH3 COOH + PCl5 → CH3 COCl + POCl3 + HCl

Acetic acid Acetyl chloride

HO– SO2 – OH + 2PCl5 → Cl ⋅ SO2 Cl + 2POCl3 + 2HCl

Sulphuric acid Sulphuryl chloride

NO2 ⋅ OH + PCl5 → NO2 Cl + POCl3 + HCl

Nitric acid Nitrosyl chloride

VII. Reaction with diphosphorus decaoxide, diphosphorus

decasulphide and sulphur dioxide: The reactions occurs as follows:
6PCl5 + P4 O10 → 10POCl3 ; 6PCl5 + P4 S10 → 10PSCl3
Phosphorus oxychloride Phosphorus pentasulphide Phosphorus triochloride

PCl5 + SO2 → POCl3 + SOCl2

Thionyl chloride

VIII. Reaction with chloride ion acceptors: With chloride ion acceptors
like boron trichloride and niobium tetrachloride, it forms addition
compounds containing tetrachloride +
[PCl4 ] species.
+ – + –
PCl5 + BCl3 → [PCl4 ] [BCl4 ] ; PCl5 + NbCl4 → [PCl4 ] [NbCl5 ]

IX. Reaction with potassium fluoride: With KF, PCl5 forms potassium
phosphorus hexafluoride, .
+ −
K [PF6 ]

+ –
PCl5 + 6KF → K [PF6 ] + 5KCl

Uses of Phosphorus pentachloride

In Organic chemistry, phosphorus pentachloride is widely used as a
chlorinating agent, replacing −OH groups with chlorine atoms.

Summary
Phosphorus halide is a compound formed when phosphorus reacts
with halogen. Phosphorus forms two types of halides, PX3 and PX5 .
Phosphorus trichloride is an inorganic compound with the chemical
formula PCl3 . Phosphorus pentachloride is a chemical compound with
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the formula PCl5 . It is a very important phosphorus chloride.
Phosphorus trichloride is widely used as an important reagent in
organic chemistry for replacing hydroxyl groups with chlorine atoms in
organic reactions. In organic chemistry, phosphorus pentachloride is
widely used as a chlorinating agent, replacing −OH groups with
chlorine atoms.

FAQs On Halides of Phosphorus

Q.1. What is the formula for phosphorus halide?
Ans: The formula for Phosphorus halide is PX3 and PX5 . Where
X = F, Br, Cl and I.

Q.2. When alcohol reacts with phosphorus halides, what product is

formed?
Ans: When phosphorus halides react with alcohol, an alkyl halide is
formed. For example,
3C2 H5 OH + PCl3 → 3C2 H5 Cl + H3 PO3
Ethyl alcohol Ethyl chloride Phosphorus acid

Q.3. Is phosphorus halide a compound of phosphorus?

Ans: Yes, phosphorus halide is a compound of phosphorus.

Q.4. What is the function of phosphorus in the human body?

Ans: The primary function of phosphorus is the formation of bones
and teeth.

Q.5. What type of halides does phosphorus form?

Ans: Phosphorus forms two types of halides, PX3 and PX5 .

Q.6. Which halide of phosphorus does not exist?

Ans: Phosphorus pentaiodide (PI5 ) does not exist.

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