1

convert

1.methane to ethane 2.sodium acetate to ethane 3.sodium acetate to methane

4.ethyl chloride to butane 5.sodium propanoate to butane 6.hexane to benzene

13. Hydrocarbon – Alkenes (CnH2n.)

• Alkenes are unsaturated hydrocarbons containing at least one double bond.
• Alkenes are also known as olefins (oil forming) since ethene form an oily liquid on reaction with Cl 2 .

Q. Alkenes are reactive. Why? or, Alkenes are easily attacked by electrophilic reagents, why?
Due to the presence of weaker π-bond.

Geometrical or Cis – trans isomerism:

It is the different geometrical arrangement of atoms arises due to the restricted rotation of atoms
around the doubly bonded carbon atoms.
Cis isomer
Isomer in which two identical atoms or groups lie on the same side of the double bond.
Trans isomer
Isomer in which two identical atoms or groups lie on the opposite sides of the double bond.
Q. Draw the geometrical or cis-trans isomers of but-2-ene: CH3CH═CHCH3

Conditions to exhibit geometrical isomerism

i. Presence of double bond.
ii. Two groups attached to the doubly bonded carbon atom must be different.

Q. Among cis and trans isomer, which has high boiling point and why?
Cis isomer is more polar than the trans form, hence cis has high b.pt.
Trans is non-polar with zero dipolemoment, hence less b.pt.

Q. Among cis and trans isomer, which has high melting point and why?
Trans isomer has higher melting point than the cis form due to its symmetry and can fit well in the crystal
lattice (closely packed).

Q. Draw cis and trans isomers of the following compounds. Also write their IUPAC names :
(i) CHCl = CHCl (ii) C2H5CCH3 = CCH3C2H5
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Q. Which of the following compounds will show cis-trans isomerism?

(i) (CH3)2C = CH – C2H5 (ii) CH2 = CBr2 (iii) C6H5CH = CH – CH3 (iv) CH3CH = CClCH3 (iv) propene
Solution (iii) and (iv) show geometrical isomerism.
In structures (i), (ii) and (iv), two identical groups are attached to one of the doubly bonded carbon atom.

Preparation of alkenes
1. From alkynes: Alkynes on partial reduction with H2 in the presence of palladised charcoal [Lindlar’s
catalyst] give alkenes. Partially deactivated palladised charcoal is known as Lindlar’s catalyst.
Alkenes thus obtained are having cis geometry. Alkynes on reduction with sodium in liquid ammonia form
trans alkenes.

2. β-elimination reaction.
Alkyl halides (R-X) on heating with alcoholic KOH (potash) form alkenes (undergo
dehydrohalogenation).
In β-elimination reaction, hydrogen atom is eliminated from the β carbon atom

CH3 −CH2Br + alcoholic KOH → CH2 = CH2 + KBr + H2O

CH3CH2-CH2Br + alcoholic KOH → CH3CH=CH2+ KBr + H2O

3. From vicinal dihalides:. Vicinal dihalides on treatment with zinc metal form an alkene. This reaction is
known as dehalogenation.
CH2Br −CH2Br + Zn → CH2 = CH2 + ZnBr2
CH3CHBr-CH2Br + Zn → CH3CH=CH2 + ZnBr2

Vicinal dihalides - Dihalides in which two halogen atoms are attached to two adjacent carbon atoms.
Geminal dihalides - Dihalides in which two halogen atoms are attached to the same carbon atom.
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4. Acidic dehydration of alcohols - β-elimination reaction

Alcohols on heating with concentrated sulphuric acid form alkenes with the elimination of one water molecule.

Conc. H2SO4, ∆
CH3 −CH2OH → CH2 = CH2 + H2O
Conc. H2SO4, ∆
CH3CH2-CH2OH → CH3CH=CH2+ H2O
Chemical properties
1.Addition of dihydrogen:
H2 is added to alkenes in the presence of finely divided Ni, pd or Pt to form alkanes.
Ni
CH2 = CH2 + H2 → CH3 –CH3

2. Addition of halogens :
Halogens like Br2 or Cl2 add up to alkene to form vicinal dihalides.

Test for unsaturation

When Br2 in CCl4 is added to alkenes/alkynes, the reddish orange colour of bromine solution is decolourised.
This reaction is used as a test for unsaturation.
CH2 = CH2 + Br2 → CH2Br- CH2Br
reddish orange colourless

3. Addition of hydrogen halides:

Hydrogen halides (HCl, HBr, HI) add up to alkenes to form alkyl halides.
CH2 = CH2 + HBr → CH3 −CH2Br
CH3CH=CH-CH3 + HBr → CH3CH2CHBr-CH3

Markovnikov Rule
The rule states that when HX is added to unsymmetrical alkene, negative part of the addendum (adding
molecule) gets attached to that carbon atom with lesser number of hydrogen atoms.
Eg: Addition of HBr to propane gives 2-bromopropane.
CH3CH=CH2 + HBr → CH3CHBr-CH3 (2-bromopropane)

Anti Markovnikov addition or peroxide effect or Kharash effect

In the presence of peroxide, addition of HBr to unsymmetrical alkenes like propene takes place contrary
to the Markovnikov rule i.e, negative part of the addendum (adding molecule) gets attached to that
carbon atom with greater number of hydrogen atoms.
(C6H5COO)2
CH3CH=CH2 + HBr → CH3CH2-CH2Br (1-bromopropane)

Q. Write IUPAC names of the products obtained by addition reactions of HBr to hex-1-ene
(i) in the absence of peroxide an(ii) in the presence of peroxide
CH3CH2CH2CH2CH=CH2 + HBr → CH3CH2CH2CH2CHBr-CH3 (2-bromohexane)
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Peroxide
CH3CH2CH2CH2CH=CH2 + HBr → CH3CH2CH2CH2CH2CH2Br (1-bromohexane)

4. Addition of sulphuric acid : Markovnikov addition

CH2 = CH2 + H2SO4 → CH3 −CH2OSO3H (Ethyl hydrogensulphate)
CH3CH=CH2 + H2SO4 → CH3CH(OSO3H)-CH3 (Propyl hydrogensulphate)

5. Addition of water : Markovnikov addition

Alkenes react with water in the presence of conc. H2SO4 to form alcohol
CH2 = CH2 + H2O → CH3 −CH2OH (Ethanol)
CH3CH=CH2 + H2O → CH3CH(OH)-CH3 (Propan-2-ol)

6. Oxidation:
Alkenes on reaction with cold, dilute, aqueous solution of potassium permanganate (Baeyer’s reagent) produce
vicinal glycols. Decolorisation of KMnO4solution is used as a test for unsaturation.

b) Acidic KMnO4 or acidic potassium dichromate oxidises alkenes to ketones and/or acids.

7. Ozonolysis :
Ozonolysis of alkenes involves the addition of ozone molecule to alkene to form ozonide, and then cleavage of
the ozonide by Zn-H2O to form aldehydes / ketones. Ozonolysis is used to detect the position of the double
bond in alkenes.
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8. Polymerisation:
Ethene polymerise to polyethene at high temp, pressure and in presence of catalyst.

Polythene are used for the manufacture of plastic bags, squeeze bottles, toys, pipes, radio and T.V. cabinets etc
Polypropene is used for the manufacture of milk crates, plastic buckets and other moulded articles.

Important Questions
1.Write a short note on
i. Markownikov’s rule ii. Anti - Markownikov’s rule/ peroxide effect /Kharash effect
iii. β-elimination reaction iv. Ozonolysis
2. Write IUPAC names of the products obtained by the ozonolysis of the following compounds :
(i) Pent-2-ene (ii) 3,4-Dimethylhept-3-ene (iii) 2-Ethylbut-1-ene (iv) 1-Phenylbut-1-ene
Ans. (i) Ethanal and propanal (ii) Butan-2-one and pentan-2-one
(iii) Methanal and pentan-3-one (iv) Propanal and benzaldehyde
3. An alkene ‘A’on ozonolysis gives a mixture of ethanal and pentan-3-one. Write structure and IUPAC name

of ‘A’. [Ans. 3-Ethylpent-2-ene]

4. An alkene ‘A’ contains three C – C, eight C – H σ bonds and one C – C π bond. ‘A’ on ozonolysis gives two
moles of an aldehyde of molar mass 44 u. Write IUPAC name of ‘A’. [Ans. But-2-ene]
5. Propanal and pentan-3-one are the ozonolysis products of an alkene? What is the structural formula of the
alkene? [Ans. 4-Ethylhex-3-ene]
6. An unknown alkene A on ozonolysis gives two isomeric carbonyl compounds B and C of the molecular
formula C3H6O. Write the structure of A, B and C.
7. Write chemical equations for combustion reaction of the following hydrocarbons:
(i) Butane (ii) Pentene (iii) Hexyne (iv) Toluene
8. What effect does branching of an alkane chain has on its boiling point?
9. Draw the cis and trans structures of hex-2-ene. Which isomer will have higher b.p. and high meling point
and why? Ans.

10. Addition of HBr to propene yields 2-bromopropane, while in the presence of benzoyl peroxide, the same
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reaction yields 1-bromopropane. Explain.

11. How will you detect the presence of unsaturation in an organic compound?
12. Convert
i. 2- Bromopropane to 1- Bromopropane

ii. 1-Bromopropane to 2- Bromopropane

iii. Propan -1-ol to propene

13. Give the structure of alkene (C4H8) which adds on HBr in presence and in the absence of peroxide to give
the same product C4H9Br.
14. What happens when ethanol is heated with conc, H2SO4 at 443K?
15. Which of the following exhibits geometrical isomerism?
i. 2- methylpropene ii. 1- Butene iii. 2-Butene iv. 2,3-Dibromobutene
16. Complete the reaction:

Hydrocarbons – Alkynes (CnH2n)

Preparation
1. Industrial preparation: Ethyne is prepared by treating calcium carbide with water.
CaC2 + 2H2O → Ca(OH)2 + C2H2
Calcium carbide ethyne

2. Vicinal dihalides on treatment with alcoholic KOH undergo dehydrohalogenation which further treated with
sodamide gives alkyne.
alcoholic KOH NaNH2
CH2Br-CH2Br → CH2 ═ CHBr → CH ≡ CH

Chemical properties
Acidic character of alkyne:
Q. Why are ethyne or alkynes acidic?
Alkynes / Ethyne have sp hybridized carbon which has more s – character, more electronegative and hence
more acidic than sp2 and sp3.

Q. Arrange in decreasing order of acidic character.

i. Ethyne > Ethene > Ethane
CH≡CH > CH2═CH2 > CH3-CH3
ii. Ethyne > Propyne > But-2-yne
CH≡CH > CH3-C≡CH > CH3-C≡C-CH3
(2 acidic H) (1 acidic H) (no acidic H)
iii. Ethyne > Hexane > Benzene
sp sp2 sp3
Strong bases like sodium metal and sodamide (NaNH2) react with ethyne to form sodium acetylide with
the liberation of H2 gas.

Q. Give example for acidic nature of alkynes.

HC ≡ CH + 2Na → Na+C- ≡ C-Na+ + H2
Disodium ethynide
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CH3-C ≡ C-H+ Na+NH2- → CH3-C ≡ C-Na++ NH3

sodium propynide

B. Addition reactions:
(i) Addition of dihydrogen

(ii) Addition of halogens

HC ≡ CH + 2Br2 → CHBr2 - CHBr2
Ethyne 1,1,2,2- Tetrabromoethane
Reddish orange colour of the Br2 in CCl4 is decolourised. This is used as a test for unsaturation.

(iii) Addition of hydrogen halides

Two molecules of hydrogen halides (HCl, HBr, HI) add to alkynes to form gem dihalides.
HC ≡ CH + HBr → [CH2 ═ CHBr] → CH3 - CHBr2
Bromoethene 1,1-Dibromoethane
CH3-C ≡ CH + HBr → [CH3-CBr ═ CH2] → CH3 - CBr2- CH3
2- Bromopropene 2,2-Dibromopropane

(iv) Addition of water

Water adds to alkynes on warming with mercuric sulphate and dilute H2SO4 at 333 K to form carbonyl
compounds [aldehyde/ketone].

(v) Polymerisation
(a) Linear polymerisation: Linear polymerisation of ethyne produce polyacetylene or polyethyne
• Polyacetylene conducts electricity hence can be used as electrodes in batteries.
• Polyacetylene are good conductors, lighter and cheaper than the metal conductors.

(b) Cyclic polymerisation: Ethyne on passing through red hot iron tube at 873K undergoes cyclic
polymerization to form benzene
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Q. How will you convert ethanoic acid into benzene?

13- Hydrocarbon – Aromatic hydrocarbon/ Arenes

Aromaticity - Hückel Rule
Aromatic compounds possess the following characteristics.
(i) Planarity
(ii) Complete delocalisation of the π electrons in the ring
(iii) Presence of (4n + 2) π electrons in the ring where n is an integer (n = 0, 1, 2, . . .).
Some examples of aromatic compounds are given below:

Preparation of Benzene
(i) Cyclic polymerisation: Ethyne on passing through red hot iron tube at 873K undergoes cyclic
polymerization to form benzene
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(ii) Decarboxylation of aromatic acids: Sodium salt of benzoic acid on heating with sodalime gives benzene.

(iii) Reduction of phenol: Phenol is reduced to benzene by passing its vapours over heated zinc dust

Physical properties
Naphthalene balls are used in toilets and for preservation of clothes because of unique smell of the compound
and the moth repellent property.
Chemical properties - Electrophilic substitution reactions
(i) Halogenation: Benzene react with halogens in the presence of a Lewis acid like anhydrous FeCl 3, FeBr3 or
AlCl3 to yield haloarenes.

Benzene on treatment with excess of Cl2 in the presence of anh AlCl3 in dark yields hexachlorobenzene(C6Cl6)

(ii) Nitration: Benzene is heated with a mixture of concentrated nitric acid and concentrated sulphuric acid
(nitrating mixture) to give nitrobenzene.

(iii) Sulphonation: Benzene is heated with fuming sulphuric acid (oleum) to form benzene sulphonic acid.
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(iv) Friedel-Crafts alkylation reaction: When benzene is treated with an alkyl halide (CH3Cl) in the presence
of anhydrous AlCl3, alkylbenzene (Toluene) is formed.

(v) Friedel-Crafts acylation reaction: The reaction of benzene with an acyl halide or acid anhydride in the
presence of Lewis acids (AlCl3) yields acyl benzene.

Addition reactions
i. Hydrogenation of benzene in the presence of nickel catalyst at high temp and pressure gives cyclohexane.

ii. Three chlorine molecules add to benzene in the presence of uv light to produce benzene hexachloride,
C6H6Cl6 which is also called gammaxane.

Combustion: When heated in air, benzene burns with sooty flame producing CO 2 and H2O
C6H6 + 15/2 O2 → 6CO2+3H2O
Directive influence of a functional group
Ortho and para directing groups: Meta directing group:
The groups –OH, -NH2, -OCH3,-CH3 etc. increases The groups -NO2, -CN, -CHO,-COOH, -SO3H, etc.
the electron density at ortho and para positions (+R deactivate the benzene ring (reduces the electron
effect). They are ortho and para directing groups. density in the benzene ring due to its strong-I
Therefore substitution take place at ortho and para effect), therefore meta position become electron rich
position. than ortho and para position. Hence electrophilic
substitution take place in the meta position.
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Questions
1. Why is benzene extra ordinarily stable though it contains three double bonds? Ans.Due to resonance.
2. What are the necessary conditions for any system to be aromatic? [Explain Huckel rule]
3. Explain why the following systems are not aromatic?

Ans. Lack of delocalisation of (4n +2) π electrons in the cyclic system.

4. How will you convert benzene into
(i) p-nitrobromobenzene (ii) m- nitrochlorobenzene (iii) p – nitrotoluene (iv) acetophenone?
5. In the alkane H3C -CH2- C(CH3)2 – CH2 -CH(CH3)2, identify 1°,2°,3° carbon atoms .
6. Arrange benzene, n-hexane and ethyne in decreasing order of acidic behaviour. Give reason.
7. Why does benzene undergo electrophilic substitution reactions easily and nucleophilic substitutions with
difficulty? Ans. Benzene ring is electron rich with 6 ∏ electrons
8. How would you convert the following compounds into benzene? (i) Ethyne (ii) Ethene (iii) Hexane
9. Arrange the following compounds in order of their decreasing relative reactivity with an electrophile, E +
(a) Chlorobenzene > p-nitrochlorobenzene > 2,4-dinitrochlorobenzene
(b) Toluene > p-H3C -C6H4 – NO2 > p-O2N-C6H4 – NO2.
10. Out of benzene, m-dinitrobenzene and toluene which will undergo nitration most easily and why?
Toluene because it is electron donating group.
12. Write struct formulas and IUPAC names for all isomers (a) C4H8 (1 double bond) (b) C5H8 (1 triple bond)
Ans. (a) (i) CH2 = CH – CH2 – CH3 But-1-ene (b) (i) HC ≡ C – CH2 – CH2 – CH3 Pent-1-yne
(ii) CH2 – CH2 = CH – CH3 But-2-ene (ii) CH3 – C ≡ C – CH2 – CH3 Pent-2-yne