The Mechanism of Free radical substitution

Alkanes with Cl2 or Br2

“A photochemical Reaction”
Reagent & Condition: Cl2(g) in the presence of ultraviolet light – or sunlight.

CH4(g) + Cl2(g) ⎯⎯ ⎯⎯ ⎯→ CH3Cl + HCl (g)

Sunlight / UV
4 organic products
would be obtained in
( CH2Cl2 ;CHCl3 ;CCl4) principle

Chain initiation
The gaseous mixture of CH4 & Cl2(g) is irradiated with U.V light (400 KJ/mol) which
breaks the chlorine molecule [Homolytic fission] into two chlorine radicals.

Cl Cl Cl + Cl H = +244 KJmol–1

radicals

Chain propagation reactions

CH4 + Cl CH3 + H–Cl

CH3 + Cl2 Cl + CH3–Cl

Chain termination reactions

The reactions which remove free radicals as it occurs between any two free radicals thus the
reaction stops.

They are all exothermic [bond formation]

Cl + Cl Cl2

CH3 + Cl CH3–Cl

CH3 + CH3 CH3–CH3 which is C2H6

1. Write an equation for the reaction between ethane and a chlorine free radical, and name
the type of step in the mechanism where this occurs. Curly arrows are not required.

2. C5H12 reacts with chlorine to form a mixture of products.

(i) Classify the type and mechanism of this reaction.
(ii) Write the equations for the two propagation steps for this mechanism. Use the
molecular formula, C5H12, in your first equation. Curly arrows are not required.
 MULTIPLE SUBSTITUTION
IN THE CH4 & Cl2 REACTION
All the hydrogens in the CH4 can in turn be replaced by chlorine atoms. So you can get
dichloromethane CH2Cl2, CHCl3 or tetrachloromethane CCl4

Dichloromethane, CH2Cl2

Chain propagation reactions For Making CH2Cl2

The chlorine radical takes (abstracts) a hydrogen from the chloromethane

CH3Cl + Cl CH2Cl + H–Cl

The chloromethyl radical formed can then interact with a Cl2 molecule.

CH2Cl + Cl2 CH2Cl2 + Cl

Tetrachloromethane CCl4

Chain propagation reactions For Making CCl4

The chlorine radical takes (abstracts) a hydrogen from the tri–chloromethane, CHCl3

CHCl3 + Cl CCl3 + H–Cl

The trichloromethyl radical formed can then interact with a Cl2 molecule.

CCl3 + Cl2 CCl4 + Cl

3. The equations below show some of the processes that occur when methane and chlorine
react.
A Cl2(g) → 2Cl•(g)
B Cl•(g) + CH4(g) → CH3•(g) + HCl(g)
C CH3•(g) + CH3•(g) → C2H6(g)
D Cl2(g) + CH4(g) → CH3Cl(g) + HCl(g)

(a) Which equation shows a propagation step? Answer B

(b) Which equation shows an initiation step? Answer A
(c) Which equation shows a termination step? Answer C

AS –Chemistry 2022-2023 [Topic 5_ ORGANIC _Mechanisms] AOUDI A. 2

 Larger Alkanes with Cl2 or Br2
A mixture of substitution products is obtained.
e.g propane, C3H8, you could get one of two monobrominated isomers:

Br Br 2 Br H = +193 KJmol–1

Chain propagation reactions

C3H8 + Br CH2CH2CH3 + H–Br

AND CH3CHCH3 which is (CH3)2CH

2o radical

CH3CH2CH2 + Br2 CH3CH2CH2–Br + Br

1 – bromopropane

CH3CHCH3 + Br2 CH3CHBrCH3 + Br

2–bromopropane

AS –Chemistry 2022-2023 [Topic 5_ ORGANIC _Mechanisms] AOUDI A. 3

Chain termination reactions

Br + Br Br2
CH3CH2CH2 + Br CH3CH2CH2–Br

CH3CH2CH2 + CH2CH2CH3 C6H14

C–C–C C–C–C C–C–C–C–C–C

n–hexane

C C

C–C–C C C–C–C–C

C C

CH3CH2CH2 CH(CH3)2 CH3CH2CH2–CH(CH3)2

2–methylpentane

(CH3)2CH CH(CH3)2 (CH3)2CH–CH(CH3)2

2,3–dimethylbutane

AS –Chemistry 2022-2023 [Topic 5_ ORGANIC _Mechanisms] AOUDI A. 4

 Electrophilic addition reactions of Alkenes
Alkenes are more reactive than alkanes. Most of their reactions are type electrophilic addition in
which a molecule adds across the double bond.
Explanation
➢ The  electrons are less tightly held than the  (sigma) electrons, since in a  bond,
the electron density lies above and below the sigma bond.

➢ The energy released when 2 new () bonds are formed exceeds that needed to
break one , so the addition reactions are energetically favourable.

1. Addition of hydrogen (Hydrogenation)

• Reactant : Hydrogen gas
• Conditions : heated Nickel or platinum catalyst / at 150°C.

⎯Ni
⎯/ 150
⎯⎯ → CH3CH2CH2CH3
o
C
CH3CH = CHCH3 + H2
but–2–ene n – butane

2. Addition of halogens (Halogenation)

The addition of halogens produces di-substituted halogenoalkanes.
[vicinal dihalides i.e halides on adjacent carbons]

CnH2n + X2 ⎯room
⎯⎯ ⎯→ CnH2nX2
temp. Where X2 = {H2 , Cl2 ,Br2}
I2 is unreactive
• Reactant : liquid bromine
• Conditions : Bubble the gaseous alkene into bromine dissolved in CCl4
• Type of reaction : Electrophilic addition

H2C = CH2 (g) + Cl2 (g) ⎯room

⎯⎯ ⎯→
temp.
ClCH2CH2Cl

CH2 = CH2 + Br2(l) ⎯room

⎯⎯ ⎯→
temp.
BrCH2CH2Br
reddish Brown colourless solution

H H H H H H
     
H⎯C⎯C C⎯H + Br2(l) ⎯room
⎯⎯ ⎯→
temp.
H⎯C⎯C⎯C⎯H
   
H H Br Br
1,2 –dibromopropane

AS –Chemistry 2022-2023 [Topic 5_ ORGANIC _Mechanisms] AOUDI A. 5

3. Alkenes with cold , dilute manganate(VII)  Oxidation of Alkenes
cold
CH2 = CH2 + H2O + [O] CH2 ⎯ CH2
 
OH OH
Oxygen from the
Oxidising agent ethan -1,2 -diol

CH3CH=CHCH3 + H2O + [O] CH3CHOH-CHOHCH3

butan–2,3–diol
• Reactant : KMnO4(aq)
• Conditions : cold & dilute solutions
• Type of reaction : oxidation ( & addition)

If acidified i.e MnO4¯ / H+(aq) solution is used then the purple solution goes almost
colourless (decolourised) by an alkene .

4. Addition of hydrogen halides (Halogenation)

+ HX ⎯⎯⎯⎯→ CnH2n+1X Where HX = {HCl , HBr}

room temp.
CnH2n

The reactivity of these compounds, due to bond strengths, which is as follows

H – F  H – Cl  H – Br  H – I Weakest Bond

o Reagents : Hydrogen halide gas HX e.g HBr(g) , HCl(g)

o Conditions: reactions occur at room temperatures.
o Type of reaction : Electrophilic Addition

Symmetrical alkenes : When groups are the same on either side of the C=C double bond.
 You always get the same product:
because
Whichever way round, the electrophile H+ adds onto the
double bond , so ONLY ONE carbocation is formed as an
intermediate.

CH3CH = CHCH3 + HBr (g) ⎯

⎯→ CH3 CHCH2CH3

Br
but–2–ene 2-bromobutane Br

AS –Chemistry 2022-2023 [Topic 5_ ORGANIC _Mechanisms] AOUDI A. 6

 Electrophile
Unsymmetrical alkenes  TWO different isomeric products?
H+

H H H H H H H H H

H C C C H + HBr(g) ⎯room
⎯⎯ ⎯→ H
temp.
C C C H + H C C C H

H H Br H H H Br
2–bromopropane 1– bromopropane
Major Minor

As the electrophile H+ adds onto the double bond ,TWO different carbocation are
formed as an intermediate.

+ –
H Br

CH3CH CH2 CH3CH CH3 + CH3CH2 CH2

2o carbocation 1o carbocation

Br
CH3CH CH3 CH3CHBr CH3
2– bromopropane

Br
Lear
n
Major product
The major product is formed via a mechanism which involves the
formation of the MOST stable carbocation as an intermediate.

4. Pent –1–ene reacts with hydrogen bromide to produce 2– bromopentane as

the major product.
(a) Outline the mechanism for this reaction
(b) Explain why 2– bromopentane is the major product.
(c) Identify the minor product formed in this reaction.

AS –Chemistry 2022-2023 [Topic 5_ ORGANIC _Mechanisms] AOUDI A. 7

 The electrophilic addition of bromine water Electrophile
Br+

H H H H H H H H H

H C C C H + BrOH ⎯room
⎯⎯ ⎯→ H
temp.
C C C H + H C C C H

H H OH Br H Br OH

1-bromopropan-2-ol 2-bromopropan-1-ol
Major product

As the electrophile Br+ adds onto the double bond ,TWO different carbocation
are formed as an intermediate.

+ –
Br OH

CH3CH CH2 CH3CH CH2Br + CH3CHBr CH2

2o carbocation 1o carbocation

O H
CH3CH CH2Br CH3CHOH CH2Br
Br
1– bromopropan-2-ol
OH
Major product

5. But-2-ene polymerizes to form poly(but-2-ene).

Draw a section of this polymer, showing two repeat units.

6. But-1-ene is an alkene with properties similar to ethene.

Write an equation, using skeletal formulae for the organic compounds, showing
the conversion of but-1-ene to butane. State the essential condition needed.

7. Alkenes react with hydrogen gas in the presence of a nickel catalyst.

0.2 mol of an alkene reacted completely with 19.2 dm3 of hydrogen gas at room
temperature and pressure.
How many C = C bonds are there in a molecule of this alkene?
[The molar volume of a gas is 24.0 dm3 mol–1 at room temperature and pressure]
AS –Chemistry 2022-2023 [Topic 5_ ORGANIC _Mechanisms] AOUDI A. 8
8. Alkenes are able to exhibit stereo (E-Z) isomerism, whilst alkanes do not exhibit
stereo isomerism.

Explain why this is the case as fully as possible. You should incorporate ideas about
bonding using pent-2-ene as an example, illustrating your answer with diagrams where
appropriate.

H H H H H H3C C2H5

H C C C C C H

H H H H H

No rotation about this cis– pent–2–ene

double bond (stereocenter)

Each sp2 carbon ( of the C = C )

is bonded to 2 different groups

H H H H H C2H5

H C C C C C H

H H H H H3C H

trans– pent–2–ene

• Stereoisomers: compounds have the same structural formulae (i.e. the same
atoms connected by the same bonds) but different spatial
arrangements of the atoms.

Stereoisomerism arises when two different groups are attached to

either end of a C = C double bond ( or ring) about which there is
restricted rotation.

AS –Chemistry 2022-2023 [Topic 5_ ORGANIC _Mechanisms] AOUDI A. 9

• Geometric isomers: the two common atoms or groups can either be on the same
side or opposite sides of a double bond or ( stereo-centre)

cis-1,2-dichlorocyclohexane Trans-1,2-dichlorocyclohexane

Conditions for geometrical isomerism

1. Restricted free rotation due to the presence of double bond or presence

of cyclic structure.
2. Each sp2 carbon atom (the double bonded or stereo-centre) is bonded to
two different groups or atoms.

Z – isomer A stereoisomer in which the two higher priority groups

are on same sides of the double bond.

   
Cl Br H3C Cl
   
C C C C
   
H F H CH3

E – isomer A stereoisomer in which the two higher priority groups

are on opposite sides of the double bond.
It has two CH3 groups on the
same side of the double bond.
  This is a cis- isomer
Cl F H Cl
    BUT
C C C C two higher priority groups are
    on opposite sides of the double
H Br H3C CH3 bond, and so this is an
  E –isomer.

AS –Chemistry 2022-2023 [Topic 5_ ORGANIC _Mechanisms] AOUDI A. 10

Homolytic fission: The bonding pair of electrons split equally so that each atom retains
(takes) ONE electron of the bonded electron pair.
This bond breaking results in the formation of radicals.

Cl Cl Cl + Cl
radicals

Heterolytic fission: The bonding pair of electrons split unequally so that ONE atom
retains(takes) TWO electron of the bonded electron pair.
This bond breaking results in the formation of cations & anions.

H Br H + Br
Anion

9. Why are alkenes not used as fuels?[ Both alkanes & alkenes have very close
enthalpy of combustion value !

Alkenes are too valuable as synthetic intermediates / used to make polymers

10. What do you understand by the term :

(a) homologous series

is series of organic compounds with the same functional group OR /similar
chemical properties and exhibit trends in their physical properties.

Members of homologous series have the same general formula (each

member differs from the previous or successive one by one –CH2 unit)

(b) Functional group: is an atom or group of atoms in an organic

compound which shows similar reactions
regardless of the structure to which it is
bonded. e.g. –OH (alcohol)

Structural isomers: Compounds that have the same molecular formula but
different structural formulae.
i.e. structural isomers contain the same number of each type of
atom, connected together with different bonding patterns

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• Sigma (σ) bond A region of electron density for which the maximum
density lies along the line joining the centres of two atoms.
Due to end-on (axial) overlap between atomic orbitals.

• Pi (π) bond A region of electron density for which the maximum

density lies above and below the line joining the centres
of two atoms
Due to sideways (lateral) overlap between two p orbitals

Dative bond A covalent bond in which both electrons come from the
same (a single) atom. “ Co-ordinate bond”

• Free radical A chemical species with an unpaired electron. e.g Cl

• Electrophile A chemical species that accepts a pair of electrons.

• Nucleophile A chemical species that donates a pair of electrons.

It forms a dative covalent bond with a positive (electron deficient)
centres.

• Addition Reaction A type of chemical reaction in which two or more chemical

species react to form a single product.

H2C = CH2 + HBr ⎯

⎯→ C2H5Br

• Substitution A type of chemical reaction in which one atom or group of

atoms in a molecule is replaced by another atom or group

e.g. CH4(g) + Cl2(g) ⎯U⎯

.V
→ CH3Cl(liq) + HCl(g)

• Addition
Polymerisation A chemical reaction in which many small molecules (monomers)
join together to form a long chain molecule (a polymer).

Carbocation: A positively charged ion that contains carbon resulted when

an organic molecule loses an atom or group of atoms.
e.g +CH3

Hydrocarbon An organic compound of hydrogen and carbon ONLY

Saturated Hydrocarbon: A compound that contains only (C—C) single bonds.

Cannot undergo addition (reactions) and has maximum
number of hydrogen atoms .

Empirical formula: is a formula that gives ONLY simplest whole-number ratio

of the atoms of each element in a compound.

e.g. The empirical formula of butane C4H10 is C2H5

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Molecular formula: is a formula that gives the exact (actual) number of atoms
of each element in ONE molecule of a compound.

Cracking: is the breaking of a long chain hydrocarbon into smaller

hydrocarbon one of which is an alkene.
It involves the breaking of C – C bonds in alkanes.

Economic reasons for Cracking:

1. Cracking satisfies the high demand for smaller products like petrol and
unsaturated hydrocarbons (e.g ethene H2C = CH2) used in making
plastics.

2. Cracking preserves the oil stock

Reforming: converting straight chain to a branched chain or ring/ or

to aromatic(arenes) compound

Reforming (Isomerisation)

n – hexane 2,3 – dimethyl butane

Reforming (cyclisation)

+ H2

cyclohexane

Economic reasons for Reforming:

1. Reforming produces branched– chain alkanes which are better fuels because
they burn smoothly & efficiently.
[So that maximum amount of energy is transferred to the pistons]

2. Reforming produces cycloalkanes / arenes for the chemical industry.

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Polarising power A measure of the ability of a cation to distort the electron cloud
in neighbouring anion.

Polarisability (of an anion) A measure of the ease with which the electron cloud
of an anion may be distorted by a neighbouring cation.

Periodicity “Repeating trend (properties) in each period”

OR
The repeating variation of physical & chemical properties of
the elements in a similar pattern with atomic number.

AS –Chemistry 2022-2023 [Topic 5_ ORGANIC _Mechanisms] AOUDI A. 14