General Chemistry

ASSIGNMENT 03
YOUNAS HANIF MUGHAL
FA20-BPH-077
Alkyl halides
When one or more halogen atoms (X = F, Cl, Br, I) bonds with carbon atoms alkyl halides forms.
There may be single bonds, double bonds, triple bonds between carbon atoms in alkyl halides.
Aliphatic or aromatic hydrocarbons which are halogen substituted are defined as alkyl halides.
In this tutorial, we will lean about physical and chemical properties of alkyl halides.

Alkyl halides examples and nomenclature (IUPAC naming)

Some examples are CH3CH2Cl, CH3Br, CH3CH2I. CFC (Freon), HFC compounds which are used now
in refrigerators instead of CFC are alkyl halides.
A/C gas - 1,1,1,2-tetrafluoroethane
More examples

   

Classification Of Alkyl Halide

Alkyl Halide can be classified based on various aspects. They are as follows.

Number of Halogen Atoms

Here, the classification mainly depends on whether they contain one, two, or more halogen
atoms in their structure. Under this category we have.
1. Mono Haloalkane
Example: CH3-CH2-X [Where X can be Cl, F, Br or I]
2. Dihaloalkane
Example: X-CH2-CH2-X [Where X can be Cl, F, Br or I]
3. Trihaloalkane
Example: X-CH2-CHX-CH2-X [Where X can be Cl, F, Br, or I]

The Position of Halogen atom Along the Chain of Carbon Atom

The classification depends on how the halogen atom is positioned on the chain of carbon
atoms.
 1. Primary alkyl halide
2. Secondary alkyl halide
3. Tertiary alkyl halide

Primary Alkyl Halide

In this type of haloalkanes, the carbon which is bonded to the halogen family will be only
attached to one other alkyl group. It doesn’t matter how much bulky group is attached to it.
Some examples of primary haloalkanes are,

Secondary Alkyl Halide

In this type of haloalkanes, the carbon atom which is bonded with the halogen atom is joined
directly to the other two alkyl groups which can be the same or different. Some examples are:

Tertiary Alkyl Halide

In this type of haloalkanes, the carbon atom which carries the halogen atom is directly bonded
to three alkyl group. This alkyl group maybe with a combination of the same or different. Some
examples are,

Physical properties of alkyl halides

1. All alkyl halides are covalent apart tertiary halides and benzylic halides.
2. All alkyl halides are insoluble in water. But they dissolve in nonpolar organic solvents
such as CCl4, Benzene, hexane.
3. First members in alkyl halide series are in gaseous state due to less molecular weight,
but alkyl halides with high molecular mass are in liquid state.
4. C-X bond is polarized because electronegativity of Cl is higher than C. Therefore, there
are bipolar attractions between molecules. This results, having higher melting and
boiling points for alkyl halides than corresponding molecular masses of alkanes.
5. melting and boiling points increase with molecular mass.
6. When halogen changes F to I, boiling and melting points increase.
Aryl halides characteristics
When a halogen atom is connected directly to benzene ring, they are called aryl halides.
py orbital of halogen interacts with benzene ring. Thus, that C-X bond shows partial double
bonds characteristics. Due to partial double bonds characteristics, that C-X bond is the
strongest C-X bond in organic compounds. Therefore, aryl halides show a special inert behavior
and differ from the typical aliphatic alkyl halide compounds reactions.
Preparing alkyl halides

Preparing alkyl halides by alcohols

Alkyl halide can be prepared by the reaction of halogen acids with alcohols. Hydrochloric (HCl),
hydrobromic acid (HBr), Hydrogen iodide acid (HI) are halogen acids. Alcohols react with these
acids and give alkyl halides. In this reaction, a halogen is substituted instead of OH.
ROH + HX → RX + H2O

Alkyl halides chemical properties and reactions

Nucleophilic substitution reactions of alkyl halides

Carbon halogen bond (C-X) is polarized in alkyl halides. Therefore, carbon atom gets a small
positive charge(δ+). Hence, nucleophilic reagents react with that carbon atom.
When nucleophile attacks to the carbon atom, halogen atom is removed as a halide ion(X-).
Therefore, these reactions are defined as nucleophilic substitution reaction. When eliminated
aqueous halide anion becomes more stable, the reaction gets easier to occur.

Nucleophilic substitution reactions - Alkyl halides

 Aqueous dilute alkaline (NaOH, KOH) and alkyl halides

 Aqueous cyanide (CN-) ions and alkyl halides

Prepare Grignard reagent by alkyl halides

Magnesium and dry ether is mixed with alkyl halide to prepare Grignard reagent. For keep
Grignard stable, dry ether is essential. These Grignard reagents are used to extend carbon
chains. In aqueous medium, Grignard slowly hydrolyzes and give hydrocarbons.

Bromoethane, Mg and dry ether

Bromobenzene, Mg and dry ether

Sources and uses of alkyl halides

Chloroform, methyl chloride is used as solvents. Tetrachloroethylene,
trichlorofluoromethane are used for dry cleaning processes. Ethyl chloride is used to
manufacture tetraethyl lead which uses as antiknock agent in petrol.
Freons are used in refrigerators. Freons are fluoro halo hydrocarbon such as CCl 3F, CCl2F2.
CHBrClCF3 is used as an anesthetic.