DAY SIXTEEN

Hydrocarbons
Learning & Revision for the Day
u Alkanes u Alkenes u Aromatic Hydrocarbons
u Conformations u Alkynes u Benzene

Hydrocarbons means compounds containing carbon and hydrogen only. Single bond containing
hydrocarbons is saturated hydrocarbon and multiple bond hydrocarbons are called
unsaturated hydrocarbon.
Hydrocarbons are of different types and classified into three main categories :
(i) Saturated hydrocarbons (alkanes)
(ii) Unsaturated hydrocarbons (alkenes and alkynes)
(iii) Aromatic hydrocarbons.

Alkanes
l These are the simplest organic compounds formed by carbon and hydrogen only.
Chemically, these are almost inert that’s why also called Paraffins (Latin, Parum affinis =
Little affinity). The general formula for this series is C nH2n + 2. Hence, the first member is
CH4 (methane).
l Nomenclature Alkanes are named on the basis of their chain structure and adding suffix
‘ane’ in the end. IUPAC names of some simple alkanes are given below :
Molecular Formula IUPAC Name
Methane CH 4
Ethane C2 H 6
Propane C3 H 8
Decane C10H22

l Isomerism Alkanes exhibit only chain isomerism. e.g. possible chain isomers of C 5H12 ar
as follows :
CH3

CH3  CH2  CH2  CH2  CH3 , CH3  CH2  CH2  CH3 , H3C C  CH3
Pentane
 
CH3 CH3
2 − methylbutane 2,2-dimethyl propane

l Structure All the carbon-carbon bonds in alkanes are sp3 -sp3 hybridised where σ-bond
is quite strong. They have three dimensional structures where all the four bonds are
tetrahedrally arranged making a normal angle of 109 °28′, e.g. in CH4 , the carbon at
 the centre is bonded by four hydrogen atoms, where all l Action of water on aluminium carbide or beryllium
the bonds lie in different planes giving it a three carbide gives methane.
dimensional structure. Al4C3 + 12H2O → 4Al(OH)3 + 3CH4
H Be2C + 4H2O → CH4 + 2Be(OH)2
H These reactions produce methane, hence called
sp3-hybridised methanoids.
109°28′
C
H
C
H H
H Physical Properties
Physical properties depend upon the intermolecular forces of
attraction.
H H (i) Boiling point of alkanes increases steadily with increase
Structures of methane (CH4) molecule in molecular mass. If molecular mass is same, as the
contact surface area increases, boiling point increases.
Methods of Preparation More branched chain has less contact surface area so, less
These can be prepared by the following ways : has boiling point.
l Unsaturated hydrocarbons (alkenes or alkynes), (ii) Melting point increases with increase in molecular mass.
reduction in the presence of finely divided catalyst But symmetric molecules have higher melting point than
(e.g. Pt/Pd/Ni) give alkanes. This reaction is known as asymmetric ones. Therefore, alkanes with even number of
Sabatier-Sanderens reduction. carbon atoms have higher melting point than the
successive alkanes with odd number of carbon atoms.
Pt /Pd /Ni
CH2 ==CH2 + H2 → CH3  CH3 (iii) Solubility of a compound is governed by the principle
Ethene that like dissolves like. As alkanes are non-polar,
Pt /Pd /Ni therefore soluble in non-polar solvents such as
CH3  C ≡≡C  H+ 2H2 → CH3  CH2  CH3
petroleum, benzene etc.
Propyne
(iv) The densities of alkanes increase with increase in the
l Alkyl halides (except fluorides) on reduction give alkanes molecular masses till the limiting value of about 0.8 g/cm3
in the presence of Zn and HCl. is reached.
Zn, H+
CH3Cl + H2 → CH4 + HCl
Methane Chemical Properties
l Alkyl halides when treated with sodium metal in the Alkanes being saturated compounds undergo only
presence of dry ether gives higher alkanes. This reaction substitution reactions at C  H bond. Some of these are
is known as Wurtz reaction. discussed below :
Dry ether
2C2 H5Br + 2Na → C2 H5  C2 H5 + 2NaBr Halogenation
Ethyl bromide l Halogenation of alkanes is a free radical substitution
l Sodium salt of carboxylic acid (RCOONa) is heated with reaction which occurs in the presence of UV- light.
hot sodalime (CaO + NaOH) to give alkane and this Reactivity towards halogenation is
reaction is called as decarboxylation. 3°H >2°H>1°H
CH3COONa + NaOH →
CaO
∆
CH4 + Na2CO3 CH4 + Cl2 → CH3Cl →
hν 2 Cl / hν
CH2Cl2
Chloromethane Dichloromethane
l Sodium or potassium salt of carboxylic acid on
Cl 2 / hν Cl / hν
electrolysis gives alkane (R  R). This reaction is known → CHCl3 →
2
CCl4
as Kolbe’s electrolysis method. Trichloro Tetrachloro
methane methane
Electrolysis Bromination and chlorination proceed approx by same
2CH3COONa + 2H2O → l

way. Iodination is reversible but fluorination of alkanes is

C2 H6 + 2CO2 ↑ + H2 + 2NaOH
1442443 1442443 too vigorous.
Anode Cathode
l Grignard reagent (RMgX ) when reacts with H2O or ROH, Mechanism
gives alkane. The mechanism of halogenation can be discussed in the
− + following three steps:
CH3  C H2  MgBr + HO H →
(i) In initiation step, the homolysis of chlorine molecule
OH takes place in the presence of light or heat.
CH3  CH3 + Mg • •
Cl  Cl  hν→ Cl + Cl
Br Homolysis Chlorine free
radicals
 (ii) In propagation step, chlorine free radical reacts with Aromatisation
methane molecule and generates methyl free radical.
• •
Aromatisation take place when alkanes get converted into
CH4 + Cl  hν
→ C H3 + H  Cl benzene in the presence of Cr2O3 or V2O 5.
• • It is applicable to alkanes from hexane to decane.
C H3 + Cl  Cl  hν
→ CH3  Cl + Cl e.g.
• • Cr2O3 or V2O5
CH3Cl + Cl → C H2Cl + HCl n-hexane
773K, 10 – 20 atm
• •
Benzene
CH2 Cl+Cl  Cl → CH2Cl2 + Cl
Reaction with Steam
(iii) Termination step occurs as follows :
• • Alkanes reacts with steam as follows :
Cl + Cl → Cl  Cl Ni
• • CH4 + H2O(g) → CO + 3H2
1273 K
H3 C + CH3 → CH3  CH3
• • This method is used for industrial preparation of H2 gas.
H3 C + Cl → CH3  Cl
Pyrolysis or Cracking
Due to consumption of free radicals, chain is terminated.
Pyrolysis or cracking is a process in which higher alkanes on
Combustion heating to higher temperature decompose into lower alkanes.
l Complete combustion of alkanes give CO2 and H2O. C6H12 + H2
773K
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O(l ) C6H14 C4H8 + C2H6
l During incomplete combustion, alkanes give carbon C3H6 + C2H4 + CH4
black which is used in the manufacture of ink, printer
ink, black pigments and as fillers in tyre industry.

CH4 (g) + O2 (g) →

Incomplete
C(s) + 2H2O(l )
Octane Number
combustion
The quality of petrol or gasoline is measured in terms of octane
l On controlled oxidation, alkanes give different number while that of diesel is measured in terms of cetane
products as : number. Octane number gives the percentage of iso-octane (by
volume) in a mixture of n-heptane and iso-octane while cetane
Cu /523K /100 atm
2CH4 + O2 → 2CH3OH number gives the percentage of octane (by volume) in a mixture
Methanol of octane ( 16 34 ) and α-methyl naphthalene.
Mo O, ∆
CH4 + O2 → HCHO+ H2O
Methanal Conformations (or Rotamers or Conformers)
(CH3COO)2 Mn Spatial arrangements of atoms which can be converted into one
2CH3  CH3 + 3O2 → 2CH3COOH+2H2O
∆
Ethanoic acid
another by rotation around a C  C single bond.
l Ordinarily, alkanes resist oxidation but iso-alkanes (3°H) Ethane has three main conformations:
on oxidation with KMnO 4 gives tertiary alcohol. (i) Eclipsed conformations are those in which the hydrogen
atoms attached to two carbons are as closed together as
KMnO
(CH3 )3 CH →
4
(CH3 )3 C  OH possible. This conformation is highly unstable and has
Oxidation 3 °alcohol maximum energy.
(ii) Staggered conformations are those in which hydrogens
Isomerisation are as far apart as possible. It is highly stable and has
n-alkane on heating in the presence of AlCl3 (anhydrous) and minimum energy.
HCl (g) isomerises to give branched chain alkanes. This (iii) Skew conformation is an intermediate conformation of
reaction is called isomerisation. the above two conformations.
AlCl 3 (anhy) + HCl H
CH3 (CH2 )4  CH3 →
n-hexane H H
CH3 CH  CH2  CH2  CH3 C C
 H H
H
CH3 H
2-methyl pentane C H
C
+ CH3  CH 2  CH  CH2  CH3 H H H H
 Eclipsed Staggered
CH3
3-methyl pentane Sawhorse projection of ethane
 Angle of rotation or angle of torsion, π-bond. The orbital diagram of ethene molecule is shown as :
HH H i.e. dihedral angle sp2-s
σ σ
H H H H
sp2
H
H H H
H H
H sp2-sp2(σ)
Eclipsed Staggered H σ σ H
Newman projection of ethane π-bond

The energy difference between two extreme forms is of the Methods of Preparation
order of 12.5 kJ/mol which is very small, therefore eclipsed
and staggered form cannot be isolated. Methods of preparation of alkenes are given below :
l Alkynes when treated with Lindlar’s catalyst[Pd / C / H2 (g)]
give cis-alkenes while on reduction with Na/liquid NH3
Alkenes give trans-alkenes.
l These are unsaturated hydrocarbons containing at least
R R′
one double bond. Their general formula is C nH2 n. Pd /C
e.g. R  C ≡≡C  R′ + H2 → C==C
l Nomenclature Following rules are followed for H H
nomenclature of alkenes in IUPAC system. cis -alkene
(i) The longest chain of carbon atom containing
R H
double bond is selected. R  C ≡≡ C  R′ + H2 →
3 Na /Liquid NH
C==C
(ii) Numbering of the chain is done from the end nearer H R′
to the double bond. trans -alkene
(iii) Compound is named by adding suffix ‘ene’ to the l Alkyl halides on dehydrohalogenation (β-elimination
root word. reaction) give alkenes.
β α KOH(alc. )
IUPAC names of a few members of alkenes are given
CH3  C H2  C H2 Br → CH3CH==CH2
below : 1-bromopropone or Propene
KOH + C2 H 5 OH
Structure IUPAC Name or
OH − /C2 H 5 O −
CH3  CH == CH2 Propene
3 2 1 Ease of reaction
4 3 2 1 ∴ 3° alkyl halide > 2° > 1°.
But–1–ene
CH3  CH 2  CH == CH2 RI > RBr > RCl
4 3 2 1
Buta–1,3–diene l Alcohols on dehydration give alkenes. In this reaction
CH2 == CH  CH == CH2
intermediate carbocation is formed and rearrange, therefore
CH2 == CH  CH  CH3 3–methylbut –1–ene double bond is formed at maximum degree of carbon.
 CH3  CH  CH2  CH2  OH
CH3 
CH3
l Isomerism Alkenes show structural as well as
Conc. H2SO 4
geometrical isomerism. For exhibiting of geometrical → CH3  C ==CH  CH3 + H2O
isomerism, restricted rotation of double bond should be 443 K |
present. CH3
H3C CH3 H3C H l Dehydration and dehydrohalogenation both are governed
e.g. C == C C == C by Saytzeff’s rule, i.e. the greater is the number of alkyl
H H H CH3 groups attached to double bonded ‘C’ atoms, the more
cis but-2 ene trans but-2 ene stable is the alkene.
l In structure of alkenes, double bond between two l If dehydrohalogenation of alkyl halide takes place in the
carbon atoms. Consists of one strong σ- bond and one presence of potassium t-butoxide, less substituted alkene is
weak. obtained due to steric hindrance.
 l Vicinal dihalides when treated with zinc metal give Dil. H2SO 4
CH3  CH  CH==CH2 →
alkenes. This reaction is known as dehalogenation. 
Heat CH3
C H2  C H2 + Zn → CH2 ==CH2 + ZnBr2 2 -methyl -but -l -ene
  OH
Br Br 
H3C C  CH2  CH3
Physical Reaction 
CH3
The physical properties of alkenes are listed below: 2 -methyl butan -2-ol

(i) The melting point of alkenes do not show regular In this reaction intermediate carbocation is formed, which
gradation. Alkenes have higher melting point than rearrange to form an alcohol.
corresponding alkanes.
(ii) The boiling point of alkenes vary in the same manner as Free Radical Addition Reactions
in alkanes. Their boiling points are higher than that of l Alkenes with HBr only in the presence of benzoyl peroxide
the corresponding alkanes. show free radical addition reaction according to
(iii) Solubility of a compound is governed by the principle anti-Markownikoff’s rule. This is also known as peroxide
that like dissolves like. Being non-polar, alkenes are quite effect or Kharasch effect.
soluble in non-polar solvents such as benzene, CCl4 etc. Benzoyl peroxide
CH3  CH ==CH2 + HBr →
Propene
Chemical Reaction CH3  CH2  CH2  Br
1-bromopropane
Alkenes show different types of reactions such as: l Alkenes readily undergo addition reactions with halogens
to give vicinal dihalides, such as
Electrophilic Addition Reactions
l Symmetrical alkenes undergo addition reaction with CCl
CH3  CH ==CH2 + Cl2 → 4
CH3 CH  CH2
hydrogen halides (HCl, HBr or HI) to form alkyl halides. Dark
 
CH2 == CH2 + HBr → H3C CH2 Br Cl Cl
Ethene Bromoethane 1, 2 -dibromopropane
In case of unsymmetrical alkenes, addition takes place
according to Markownikoff’s rule which states that l Alkenes undergo addition reaction with water to yield
negative part of the adding molecule gets attached to that alcohols. This reaction also follow Markownikoff’s addition.
carbon atom which possesses lesser number of hydrogen +
CH3  CH == CH2 + H2O  H
→ CH3  CH CH3
atoms. e.g.

CH3  CH==CH2 + HX → CH3  CH  CH3 OH
( X = Cl,  2-propanol
Br, I)
X l Cold dilute KMnO 4 (Baeyer’s reagent) when treated with
alkene gives glycol (vicinal dihydric alcohol). This is a
Mechanism of Electrophilic Addition type of oxidation reaction of alkene.
l HBr provides an electrophile, H+ which attacks the Dil. KMnO 4
double bond to form carbocation. CH2 ==CH2 → CH2  CH2
Ethene 273 K
 
CH3  CH == CH2 + H  Br OH
Propene +
OH
CH3  CH2  C H2 + Br − (less stable) Ethan -1, 2-diol
(Ethylene glycol)
(1 ° carbocation)
+ (i) It is a test for unsaturation as purple colour of KMnO 4
CH3  C H  CH3 + Br − (more stable) disappears during the reaction and a brown
(2 ° carbocation )
precipitate of MnO2 is obtained.
l 2° carbocation is formed at a faster rate and it is attacked (ii) Acidic KMnO 4 or acidic K2Cr2O7 oxidises alkenes to
by Br − ion to form product. ketones and /or acids depending upon the nature of the
+
CH3  C H  CH3 → CH3  CH  CH3 alkene.
| KMnO 4 /H+
Br (CH3 )2 C ==CH2 →
2-bromopropane 2-methyl propene
major product)
(CH3 )2 C==O + CO2 + H2O
l Alkene when treated with dil. H2SO 4 gives alcohol and l Alkenes undergo addition reaction with hydrogen to form
OH gets attached to that carbon atom which has alkanes.
maximum degree.
 Alkenes react with ozone to give ozonides, which on
l

further reaction with water in the presence of water gives

Methods of Preparation
aldehyde or ketones. This reaction is called ozonolysis. Different methods of preparation of alkynes are as follows :
O l Alkyne (ethyne) is obtained by treating calcium carbide
H3C CH CH2 with water.
CH3 CH CH2 + O3 ∆
CaCO3 → CaO + CO2
Propene
O O
CaO + 3C → CaC2 + CO
Ozonide Calcium
Zn + H2O C carbide
CH3CHO + HCHO CaC2 or  Ca + 2HO H → CH ≡≡ CH+Ca(OH)2
C Ethyne
Ozonolysis is used to locate the position of double bond
in an alkene. l These are obtained by treating vicinal dihalides with
l Alkenes have the ability to form gaint molecules called alcoholic KOH followed by reaction with sodium amide.
polymer and the process is called polymerisation. KOH (alc.)
High temperature and pressure C H2  C H2 → CH2 ==CH  Br
  or
n(CH2 == CH2 ) → KOH + C2 H 5OH
Bromoethene
Catalyst Br Br
Ethene or
( CH2  CH2
)n 1,2-dibromoethane
C2 H 5 O − / OH −
Polythene
NaNH2
→ CH≡≡CH+ NaBr + NH3
Alkynes Ethyne
l These are also unsaturated hydrocarbons. They contain at l Lower alkynes on treatment with Na metal in liquid NH3
least one triple bond between two carbon atoms. Their give the sodium salt. Which further react with primary
general formula is C nH2 n − 2 . alkyl halide to give higher alkynes.
l Nomenclature The IUPAC name of alkynes is written by NaNH2 , liq. NH3
replacing-‘ane’ of alkane by a suffix -‘yne’. The position of R  C ≡≡ CH → R  C ≡≡ C  Na
triple bond is indicated by arabic numbers, the R′X
numbering being started from that end which lies closer → R  C ≡≡ C  R ′
to the triple bond. Physical Properties
Some examples of few member of alkynes with their l All alkynes are odourless, however acetylene has garlic
IUPAC names are given below : smell due to the impurity of phosphine.
Structure IUPAC Name l The melting and boiling points of alkynes are slightly higher
HC ≡≡ CH Ethyne than those of the corresponding alkenes and alkanes.
H3C  C ≡≡ CH Prop–1–yne Chemical Reactions
3 2 1

H3C 4 C ≡≡ C  CH3 But–2–yne The alkynes exhibit the chemical properties as given below:
3 2 1

H3 C  C ≡≡ C  CH2  CH3
1 2 3
Pent-2-yne Addition Reactions
4 5
l Alkynes undergo addition reaction with hydrogen to give
l Structure In structure of alkyne, triple bond is present alkenes or alkanes.
between two adjacent carbon atom. In triple bond, one Pt Pt
C  C bond is σ- bond whereas the remaining two bonds CH ≡≡ CH+ H2 → CH2 == CH2 + H2 → CH3  CH3
are π-bonds. The structure of ethyne can be shows as : (alkane)
In the plane Sideways l Alkynes gives addition reaction with halogens in which
of paper overlap Below the plane they react with two molecules of halogens to give tetrahalides.
of paper Cl Cl
2px π 2px  
2Cl2 BaCl 2
π CH ≡≡ CH → C H  C H → CCl2 ==CHCl
2py 2py Ethyne   Solvent Westrosol
σ σ σ Cl Cl
sp sp sp sp 1,1, 2, 2 − tetrachloroethane
H 1s 1s H
l Addition of hydrgen halides (HCl, HBr or HI) to alkynes
σ-bond π
follows Markownikoff’s addition in case of unsymmetrical
alkynes, to give haloalkene or haloalkane.
π
HX
CH ≡≡ CH+ HX → CH2 == CH  X → CH3CHX 2
π-bond ( X = Cl, Br, I)
 l The addition of water to alkynes (unsymmetrical) follows (iii) Complete delocalisation of the π-electrons in the
Markownikoff ’s rule to give an adduct called enol which ring.
undergo tautomerism to give stable product having (iv) Presence of (4n + 2) π-electrons in the ring, where, n
carbonyl group. is an integer (n = 0, 1, 2).
40%, H2SO 4
CH ≡≡ CH+ H2O → CH2 == CH OH
1%, HgSO 4 Vinyl alcohol (enol)
Tautomerises
[CH2 ==CH  OH] CH3CHO Cyclopentadienyl anion Naphthalene
Enol Acetaldehyde n=1 n=2
The reaction, called hydration of alkynes and is used (4n + 2) = 6π- electrons (4n + 2) = 10π- electrons
commercially for the preparation of aldehydes and ketones. Certain compounds such as pyrrole, furan, etc., although do
l Terminal alkynes have acidic character because C—H not contain benzene ring, but behaves like benzene. These
bond has ionic nature due to hybridisation. compounds are called non-benzenoid aromatic compounds.
Therefore, alkyne react with strong bases to form salts.
CH ≡≡ CH + NaNH2 196
 K
→ CH ≡≡ C Na + NH3
− + Resonance
Sodium When single Lewis dot structure is unable to explain all the
acetylide
properties of a compounds, two or more structure called the
l Acidic Nature of Alkynes Alkynes with terminal H-atom canonical forms or resonating structures. The drawn to
are acidic due to sp-hybridisation of C-atom attached to explain all the properties of that compound then the actual
hydrogen. structure of the compound is in the between these canonical
l Due to acidic nature of H–atoms, attached to a triple form and is called the resonance.
bond, acetylenes and terminal alkynes, form metal Structure of benzene can be explained on the basis of concept
acetylides with heavy metals salts such as Tollen’s of resonance.
reagent, Cu2Cl2 solution.
CH ≡≡ CH + 2[Ag(NH3 )2 ]+ OH− → AgC ≡≡CAg ↓ or
Tollen's reagent Silver acetylide
( white ppt.)
1442443 Delocalised π-bond
+ 2H2O + 4NH3 Kekule structure
Terminal alkynes give carboxylic acids on oxidation with
There is complete delocalisation of π-electrons.
l

cold alk. KMnO 4 (Baeyer’s reagent).

It is aromatic, (4n + 2) = 6 , Here, n = number of π-electrons
KMnO 4 / H+ delocalised (Huckel’s rule is followed).
R  C ≡≡ C  R′ → RCOOH + R′ COOH
Heat
NOTE Wilkinson’s catalyst reduces alkenes and alkynes without Benzene
affecting common functional groups such as C == O,  CN Benzene is the first member of aromatic-hydrocarbon having
and NO 2 etc.
formula C 6H6, i.e.
Aromatic Hydrocarbons
l These are specialised cyclic compounds which are known
for their characteristic unique smell (Aroma = fragrance). Methods of Preparation
The group is also called arenes. Benzene can be prepared by following ways :
l Nomenclature According to IUPAC system of l From acetylene
nomenclature, the prefixes 1,2; 1,3 and 1,4 are used.
Red hot iron tube (873 K)
e.g. Cl CH3 Br 3CH CH Polymerisation

Benzene
l Decarboxylation
Br CaO
COONa + NaO H + Na2CO3
Chloro benzene 1, 2-dibromo benzene ∆
Cl
1-chloro-4-methyl benzene l Reduction of diazonium salts
l Aromaticity of aromatic compounds whether having +
benzene ring or not is characterised by following points:
N NCl–

(i) Planarity
H3PO2/H2O
(ii) Contain one or more rings that have cyclic + N2
arrangement of π-orbitals.
 l Reduction of phenol l Halogenation is carried out with Cl2 or Br2 in the presence
OH of anhyd. AlCl3 .
Cl
Heat
+ Zn + ZnO
Anhy. AlCl3
+ Cl2 + HCl

Chemical Properties Attacking electrophile is Cl+ .

Chlorobenzene

Benzene exhibit the following chemical properties may be

l Sulphonation is carried out with conc. H2SO 4 .
given as :
SO3H
Electrophilic Substitution Reactions
Benzene shows electrophilic substitution reactions due to ∆
+ H2SO4 + H2O
6π-electrons and resonance.
Fuming
sulphuric acid Benzene
Mechanism of Electrophilic Substitution sulphonic acid
l Generation of Electrophile First of all electrophile is Attacking electrophile is SO3 .
generated with the help of catalyst provided. l In Friedel-Crafts alkylation reaction, benzene ring reacts
E  Nu → E + +Nu − with alkyl halide to given alkylbenzene.
l Formation of Carbocation Intermediate The electrophile CH3
E + approaches the π- electron cloud of the aromatic ring
and forms a bond with carbon creating a positive charge AlCl3 (anhy.)
on ring. This results in the formation of σ- complex. + CH3Cl + HCl
H
Methyl benzene
⊕ E (Toluene)
+E +
Electrophile is CH3 .
Electrophile σ-complex
(resonance stabailised)
l Friedel-Crafts Acylation Reaction
COCH3
l Elimination of Proton In this step, one H+ from the same
carbon atom of ring is removed to which the electrophile AlCl3 (anhy.)
was attached. +CH3COCl + HCl
H
Acetophenone
E E
+Z + ZH
Base Conjugate
Addition Reactions
σ−Complex acid Addition reactions of benzene are given below :
−
Z = FeX 4− (X = Cl, Br) in halogenation; in HSO −4 l Gives addition reaction with hydrogen to produce
nitration; H2O in sulphonation, AlX 4− (X = Cl, Br) in cyclohexane.
Friedel-Crafts alkylation/ acylation. Ni
+ 3H2 ∆
Some of the important electrophilic substitution reaction are as
follows: Benzene Cyclohexane
l Nitration is carried out with a mixture of l It gives addition reaction with chlorine to produce
conc.HNO3 and conc. H2SO 4 (nitrating mixture).
benzene hexachloride.
OH NO2 Cl
Cl Cl
323-333K
+ HNO3(conc.) + H2O +
UV
3Cl2 500 K
+ H2SO4 (conc.)

Nitrobenzene Cl Cl
Attacking reagent (electrophile) is NO+
2. Cl
Benzenehexachloride (BHC),
Directive Influence of Functional O
N
O O
N
O O
N
OO
N
O O
N
O

Group in Monosubstituted Benzene

l The ability of a group allready present on the benzene
ring to direct the incoming group to a particular position
is called directive influence of functional group. Resonating structures of nitrobenzene
According to the nature of functional groups, they can be
of two types: NO2 , CN, CHO, COR, COOH, COOR,
(i) o, p-directing groups activate the benzene ring. SO3 H are meta directing groups.
(ii) m-directing groups deactivate the benzene ring. In case of haloarenes, halogens are highly deactivating because
NOTE
e.g. OH group is ortho-para directing. of − I -effect but due to resonance, electron density on o-and
p -position increases, hence halogens are o -, p -directing.
l o, p-directing groups have tendency to release electrons
⊕ ⊕ Cl ⊕ Cl Cl
e.g. Cl Cl

⊕O ⊕O ⊕O H OH
OH H H

Resonating structures of chlorobenzene

Resonating structures of phenol Carcinogenicity and Toxicity

NH2 , NHR, NHCOCH3 ,  OCH3 ,  CH3 ,  C2 H5
are o and p-directing groups.
l m-directing groups decrease the over all electron density
over the benzene ring due to their strong I- effect.
e.g  NO2 group is meta directing.
Benzene and polynuclear hydrocarbons containing more than
two benzene rings fused together, are toxic and said to possess
cancer producing (carcinogenic) property. Such polynuclear
hydrocarbons are formed on incomplete combustion of
organic material like tobacco, coal and petroleum.

DAY PRACTICE SESSION 1

FOUNDATION QUESTIONS EXERCISE

1 When ethyl bromide is heated with sodium in dry other, it 6 Cracking of hexane gives mixture of
gives (a) C4H10 and CH4 (b) C4H8 and C2H6
(a) C4H10 (b) C2H6 (c) C3H8 (d) C2H5OH (c) H2 and C5H2 (d) C3H6 and C2H4
2 Aqueous solution of potassium acetate is electrolysed. 7 In the following the most stable conformation of n-butane
Possible organic products is/are is ª CBSE-AIPMT 2010
(a) CH3 CH3 (b) CH3 COCH3 CH3 CH3
(c) CH3 CH2 CH2 CH3 (d) Both (a) and (b) H CH3 H H
3 Iodoethane reacts with sodium in the presence of dry (a) (b)
ether. The main product is H H H H
(a) ethane (b) propyne (c) butane (d) butyne H CH3
4 In alkanes, the boiling point decreases as branching CH3 CH3
CH3 H
increases. This is due to
(a) dipole–dipole interactions (c) (d)
(b) decreased surface area for intermolecular attraction H H
H H H H
(c) Both (a) and (b) H H3 C
(d) None of the above
8 The correct statement regarding the comparison of
5 Liquid hydrocarbons can be converted to a mixture of
staggered and eclipsed conformations of ethane, is
gaseous hydrocarbons by ª CBSE-AIPMT 2010 ª NEET 2016, Phase I
(a) oxidation (b) cracking (a) The eclipsed conformation of ethane is more stable
(c) distillation under reduced pressure than staggered conformation, because eclipsed
(d) hydrolysis conformation has no torsional strain
 (b) The eclipsed conformation of ethane is more stable than 15 Which of the following compounds shall not produce
staggered conformation even though the eclipsed propene by reaction with HBr followed by elimination or
conformation has torsional strain direct only elimination reaction? ª NEET 2016, Phase II
(c) The staggered conformation of ethane is more stable H2
than eclipsed conformation, because staggered (a) H2C CH2 (b) H3 C  C  CH2OH
conformation has no torsional strain C
(d) The staggered conformation of ethane is less stable H2
H2
than eclipsed conformation, because staggered (c) H2 C == C == O (d) H3 C  C  CH2Br
conformation has torsional strain
16 Ozonolysis of an organic compounds gives
9 The reaction of 2- methyl-propanol in the presence of
formaldehyde as one of the products. This confirms the
conc. H2SO4 at 443 K temperature gives
presence of
(a) but-1-ene (b) 2-methyl-propene
(c) 2-methyl-propane (d) 2-methyl-propyne (a) two ethylenic double bonds
(b) a vinyl group
10 Which does not follow Markownikoff’s rule? (c) an iso-propyl group
(a) CH3 — CH == CH2 (b) CF3 CH == CH2 (d) an acetylenic triple bond
H2 SO 4 /HgSO 4
(c) CH3 — CH— CH == CH2 (d) CH3 — CH2 — CH == CH2 17 CaC2 + H2O → A → B

CH3 Identify A and B in the given reaction
11 Addition of HI on double bond of propene yields (a) C2H2 and CH3 CHO
isopropyl iodide as major product. It is because the (b) CH4 and HCOOH
addition proceeds through (c) C2H4 and CH3 COOH
(a) more stable carbocation (b) more stable carboanion (d) C2H2 and CH3 COOH
(c) homolysis (d) more stable free radical 18 Which of the following reagents will be able to distinguish
12 Acid catalysed hydration of alkenes except ethene leads between 1-butyne and 2-butyne? ª CBSE-AIPMT 2012
to the formation of (a) NaNH2 (b) HCl
(a) primary alcohol (c) O2 (d) Br2
(b) secondary or tertiary alcohol 19 Predict the product C obtained in the following reaction
(c) mixture of primary and secondary alcohols
of butyne-1.
(d) mixture of secondary and tertiary alcohols
HI
13 In the following reaction, ª CBSE-AIPMT 2012 CH3CH2  C ≡≡ CH + HCl → B → C
CH3 (a) CH3  C H  CH2  CH2I
 H2 O / H⊕ 
H3C C CH == CH2 → A + B CI
 Major
product
Minor
product (b) CH3  CH2  CH2  C HI
CH3 
The major product is I Cl
CH3 CH3 
  (c) CH3  CH2  C H  CH2 Cl
(a) H3 C  C  CH  CH3 (b) CH2  C  CH2  CH3
   I

OH CH3 OH CH3 
(d) CH3 CH2  C  CH3
CH3 CH3 
Cl
 
(c) H3 C  C  CH  CH3 (d) H3 C  C  CH2  CH2
    20 When acetylene is passed through dil. H2SO4 in
CH3 OH CH3 OH presence of HgSO4, the compound formed is
(a) ether (b) ketone
14 2,3-dimethyl-2-butene can be prepared by heating which
(c) acetic acid (d) acetaldehyde
of the following compounds with a strong acid?
ª NEET 2016, Phase I 21 Hydrocarbon (A) reacts with bromine by substitution to
(a) (CH3 )2 CH—CH — CH == CH2 form an alkyl bromide which by Wurtz reaction is
 converted to gaseous hydrocarbon containing less than
CH3 four carbon atoms. A is ª NEET 2018
(b) (CH3 )3 C —CH == CH2 (a) CH3  CH3 (b) CH2 == CH2
(c) (CH3 )2 C == CH — CH 2 —CH3 (c) CH ≡≡ CH (d) CH4
(d) (CH3 )2 CH — CH2 — CH == CH2
22 Which of the following molecules represents the order of 29 The compound X in the reaction,
hybridisation sp 2, sp 2, sp, sp from lift to right atoms? Anhy. AlCl3
+ ICl X is
ª NEET 2018
(a) CH2 == CH  CH == CH2 Cl I I I

—
—
(b) CH2 == CH  C == CH
(c) CH ≡≡ C  C ≡≡ CH (a) (b) (c) (d)
(d) CH3  CH == CH  CH3 —
Cl

—
23 Which one is the correct order of acidity? ª NEET 2017 Cl
(a) CH2 == CH2 > CH3  CH == CH2 30 Which of the following compounds will not undergo
> CH3  C ≡≡ CH > CH ≡≡ CH Friedel-Crafts reaction easily? ª NEET 2013
(b) CH ≡≡ CH > CH3  C ≡≡ CH > CH2 == CH2 > CH3  CH3 (a) Xylene (b) Nitrobenzene
(c) CH ≡≡ CH > CH2 == CH2 > CH3  C ≡≡ CH > (c) Toluene (d) Cumene
CH3  CH3 31 Identify the major products P , Q and R in the following
(d) CH3  CH3 > CH2 == CH2 > CH3  C ≡≡ CH >
sequence of reactions : ª NEET 2018
CH ≡≡ CH
24 Which of the following compounds is aromatic? Anhy.
+ CH3CH2CH2Cl AlCl3
OH
—

(i) O2
P (ii) H3O+lD
Q+R
(a) (b)
P Q R
O CH(CH3)2 OH
C2H5
—
—

(a)
—

⊕C , , CH3CH(OH)CH3
(c) (d)
—
—

HC == CC 6H 5 CH2CH2CH3 CHO COOH

25 Which one of the following is aromatic?

(b)
(a) Cyclopentadienyl cation , ,
(b) Cyclooctatetraene
(c) Cycloheptatriene CH2CH2CH3 CHO
(d) Cycloheptatrienyl cation
26 Select the true statement about benzene amongst the (c)
, , CH3CH2 OH
following.
(a) Because of unsaturation benzene easily undergoes OH
addition CH(CH3)2
(b) There are two types of C—C bonds in benzene molecule (d) , ,CH3 CO CH3
(c) There is cyclic delocalisation of pi-bonds in benzene
(d) Monosubstitution of benzene gives three isomeric products
27 The reaction of C6H5CH == CHCH3 with HBr produces Direction (Q. Nos. 32) Following question contains two
ª CBSE-AIPMT 2015 statements : Assertion and Reason. Each of these questions
Br also has four alternative choices, only one of which is the
correct answer. You have to select one of the codes (a), (b), (c)
(a) C6H5CHCH2CH3 (b) C6H5CH2CHCH3 and (d) given below.
CH== CHCH3 (a) Assertion is true, Reason is true; Reason is a correct
explanation for Assertion
(b) Assertion is true, Reason is true; Reason is not a correct
(c) C6H5CH2CH2CH2 (d) explanation for Assertion
(c) Assertion is true, Reason is false
Br (d) Assertion is false, Reason is true

28 The function of AlCl 3 in Friedel-Crafts reaction is 32 Assertion (A) CH bond in ethyene is shorter than CH
bond in ethene.
(a) to absorb HCl
(b) to absorb water Reason (R) Carbon atom in ethene is sp-hybridised,
(c) to produce nucleophile while it is sp 2 hybridised in ethyne.
(d) to produce electrophile
DAY SIXTEEN HYDROCARBONS 173

DAY PRACTICE SESSION 2

PROGRESSIVE QUESTIONS EXERCISE

1 Identify B and D in the following sequence of reactions. Which factor causes easy removal of proton?
Conc. H2SO4 (a) Bond strength of C  H bond: I<II<III
CH2 —
—CH2 A (b) Electronegativity of C in I>II>III
(c) Bond strength of C  H bond: I>II> III
∆ H2O (d) Electronegativity of C in I<II<III
D

PBr3 7 Intermediate (X) changes to chlorohydrin due to attack of H2O

C B (nucleophile). Select correct statement about this reaction.
(a) Methanol and bromoethane +
a
Cl b
(b) Ethyl hydrogen sulphate and alcoholic KOH
(c) Ethyl hydrogen sulphate and aqueous KOH R CH––––CH2 + H2O
α β
(d) Ethanol and alcoholic KOH (A )
2 In the presence of platinum catalyst, hydrocarbon A (a) H2O attacks β − carbon and bond (a) is cleaved
adds hydrogen to form n-hexane. When hydrogen (b) H2O attacks α − carbon and bond (a) is cleaved
bromide is added to A instead of hydrogen only a single (c) H2O attacks β − carbon and bond (b) is cleaved
(d) H2O attacks α − carbon and bond (a) is cleaved
bromo compound is formed. Which of the following is A?
(a) CH3 — CH2 — CH == CH — CH2 — CH3 AlCl 3
(b) CH3 — CH2 — CH2 — CH == CH — CH3 8 + Cl  CH2  CH2  CH3 →
(c) CH3 — CH == CH — CH2 — CH2 — CH3 (i) O 2 / ∆
Q → R + Phenol
(d) CH2 == CH — CH2 — CH2 — CH2 — CH3 +
(ii) H3 O

3 Which would be the best sequence of reactions used to In the above reaction, benzene reacts with chloropropane
prepare is non–3–ene from 1–butyne? in the presence of anhy. AlCl3 to give Q, which further
(a) (1) NaNH2 in NH3 ; (2) 1− bromopentane (3) H2 , Lindlar reacts with O2 to give R. Q and R are respectively.
catalyst
(a) and CH3 CH2 CHO
(b) (1) NaNH2 in NH3 ; (2) 1– bromopentane (3) Na, NH3
(c) (1) H2 , Lindlar catalyst; (2) NaNH2 in NH3 ;
(3) 1–bromopentane (b) and CH3 COCH3
(d) (1) Na, NH3 ; (2) NaNH2 in NH3 ; (3) 1– bromopentane
4 6 L of an alkene require 27 of oxygen at constant tempera- (c) and CH2 COCH3
ture and pressure for complete combustion. The alkene is
(a) ethene (b) propene (c) 1- butene (d) 2-butene
(d) and CH3 CH2 CHO
5 Which of the following reaction statements best explains
the greater acidity of terminal alkynes compared with
monosubstituted alkenes? 9 Reaction of one molecule of HBr with one molecule of
(a) The sp- hybridised carbons of the alkyne are less 1,3- butadiene at 40°C gives predominantly.
electronegative than the sp 2 - carbons of the alkene (a) 3-bromobutene under kinetically controlled conditions
(b) The two π- bonds of the alkyne are able to stabilise (b) 1-bromo-2-butene under thermodynamically controlled
better the negative charge of the anion by resonance conditions
(c) The sp-hybridised carbons of the alkynes are more (c) 2-bromobutene under kinetically controlled conditions
electronegative than sp 2 - carbons of the alkene (d) 1-bromobutene under thermodynamically controlled
(d) The question is incorrect alkenes are more acidic than conditions
alkynes
10 Identify the correct order of reactivity in electrophile
6 Different hydrocarbons release proton in the following order.
substitution reactions of the following compounds.
 Benzene (1), toluene (2), chlorobenzene (3)
≡≡ C H > == CH >  C H
 nitrobenzene (4).
I II III (a) 1 > 2 > 3 > 4 (b) 4 > 3 > 2 > 1
(c) 2 > 1 > 3 > 4 (d) 2 > 3 > 1 > 4
11 Ozonolysis of an organic compound A produces acetone COOH OCH3
and propionaldehyde in equimolar mixture. Identify ‘A’ (c)
from the following compounds HO H3C NO2
(a) 1–pentene NO2
(b) 2– methyl–1–pentene
(c) 2–methyl–2–pentene O
(d) 2– pentene C
O
12 The compounds P, Q and S
COOH OCH3
COOH OCH3
(d)
H 3C H3C
HO H 3C NO2
P Q NO2
O
O
C
C O O NO2

S
13 In the following sequence of reactions, the alkene affords
separately subjected to nitration using HNO 3/H2SO4 the compound ‘B’.
mixture. O H2 O
The major product formed in each case respectively is CH3CH == CHCH3  
3
→ A  → B
Zn
COOH OCH3 The compound B is
(a) (a) CH3 CH2 CHO (b) CH3 COCH3
HO H3C (c) CH3 CH2 COCH3 (d) CH3 CHO
NO2 NO2 14 What would be the product formed when
1-bromo-3-chlorocyclo-butane reacts with two
O equivalents of metallic sodium in ether?
C Br
(a) (b)
O
Br
COOH OCH3 (c) (d)
(b)
15 An organic compound having molecular formula C7H12 in
HO NO2 H3C catalytic hydrogenation over platinum gives C7H16. The
NO2 parent hydrocarbon adds bromine and also reacts with
O [Ag(NH3 )2 ] OH to give a precipitate. The parent
hydrocarbon is
C (a) CH3  CH2  C ≡≡ C  CH (CH3 )2
O (b) CH3  CH == CH  CH2  CH == CH  CH3
(c) (CH3 )3 C  CH2  C ≡≡ CH
(d) CH3  CH == CH  CH == CH  CH2  CH3

ANSWERS
SESSION 1 1 (a) 2 (a) 3 (c) 4 (b) 5 (b) 6 (b) 7 (b) 8 (c) 9 (b) 10 (b)
11 (a) 12 (b) 13 (a) 14 (b) 15 (c) 16 (b) 17 (a) 18 (a) 19 (d) 20 (d)
21 (d) 22 (b) 23 (b) 24 (d) 25 (d) 26 (c) 27 (a) 28 (d) 29 (b) 30 (b)
31 (d) 32 (c)

SESSION 2 1 (d) 2 (a) 3 (a) 4 (b) 5 (c) 6 (b) 7 (b) 8 (c) 9 (b) 10 (c)
11 (c) 12 (c) 13 (d) 14 (d) 15 (c) 16 (b) 17 (a) 18 (a) 19 (d) 20 (d)
DAY SIXTEEN HYDROCARBONS 175

Hints and Explanations

SESSION 1 H O /H +
12 (a) CH2 == CH2 →
2
CH3CH2OH
1 2 C 2H5Br  → CH3CH2CH2CH3 (C 4H10 )
2Na 1° - alcohol
Dry
ether H O /H +
(b) CH3  CH == CH2 →
2
CH3CHCH3
Electrolysis
2 2CH3COOK + 2H2O → C 2H6 + 2CO 2 + H2 + 2NaOH 
OH
⊕
3 CH3CH2I Na/Dryether
  → CH3CH2CH2CH3
2°- alcohol through 2°- carbocation (CH3 CHCH3 ).
Iodoethane Butane

4 More branched chain has less contact surface area and so CH3 CH3 CH3

— —

— —
lesser the boiling point. 1, 2 Me shift
13 H3C —C—CH==CH2 H3C —C— C — CH3

+
5 On cracking or pyrolysis, the hydrocarbon with higher molecular
mass gives a mixture of hydrocarbons having lower molecular CH3 H
3° carbocation (more stable)
mass. Hence, we can say that by cracking a liquid hydrocarbon
can be converted into a mixture of gaseous hydrocarbons. H 2O
6 C6H12+H2 CH3 CH3 CH3 H

— —

— —

— —
773 K – H+
C6H14 C4H8+C2H6 H3C —C— CH— CH3 H3C —C— CH—CH3

C2H6+C2H4+CH4 OH +
O CH3
2, 3-dimethyl butan-2-ol
(major product) ‘A’ H H
7 Among the given conformations of n-butane, the conformation CH3 CH3
shown in option (b), i.e. anti conformation is most stable as in it + +
the bulkier group, i.e. CH3 group are present at maximum 14 CH3 C CH CH2
H
CH3 C CH CH3
possible distance and get lower energy.
8 Due to the absence of torsional strain staggered conformation of CH3 CH3
ethane is more stable than eclipsed conformation of it. CH3 CH3
1-2-methyl
H HH shift
CH3 C CH CH3
+
H H CH3 CH3
∆
–H+
CH3 C C CH3
H 2,3-dimethyl-2-butene
H H H H
H H 15 The said reactions can be visualised as :
Staggered conformation Eclipsed conformation (a) Br
H 2C CH2
HBr
Conc. H 2SO 4 CH3 CH2 CH2
9 CH3  CH  CH2  OH → CH3  C == CH2 + H2O C Electro-
philic
 443K
 H2
addition
Cyclopropane
CH3 CH3 Elimination
2 -methyl propene H3 C CH CH2
HBr
H (b) CH3  CH2  CH2  OH →
Electrophilic addition
Propanol
 + X−
+
10 CF3 ← CH == CH2 + H → CF3  CH  CH2 → CH3  CH2  CH2  Br
Bromopropane
Elimination
H X → H 3C  CH == CH 2
  Br
CF3  CH  CH 2 
HBr
(c) CH2 == C== O → H2C==C  OH
δ+ δ− + Nucleophilic
11 CH3CH == CH2 + H  I → CH3 CH CH3 + I− addition
2 ° - carbocation O
 Tautomerism
I H3C  C Br
+  Direct elimination
−
CH3  CH  CH3 + I → CH3  CH  CH3 CH3  CH2  CH2  Br → CH3 CH ==CH2
2 -iodopropane Thus, option (c) is correct answer.
 O / Zn / H O sp 2 sp 2 sp sp sp sp sp sp
16 Alkene →
3 2
HCHO + other carbonyl compound (ii) CH 2 == CH  C ≡≡ CH (iii) CH ≡≡ C  C ≡≡ CH
A
 R1  sp 3 sp 2 sp 2 sp 3
  (iv) CH 3  CH == CH CH 3
 C == O
R 
 2 B
 Therefore, the correct option is (b).
To determine alkene, place carbonyl compounds with their 23 Greater the s-character of C-atom in hydrocarbons, greater the
O-atom face to face, i.e. Replace O-atom by a double bond. electronegativity of that carbon and thus greater the acidic
R1 R1 nature of the H attached to electronegative carbon.
Replace
C == O O == CH2 → C == CH2
B R O -atom by ( == ) bond CH ≡≡ CH CH2 == CH2 CH3  CH3
R2 R2 Vinyl group

O -atoms face to face

Hybridisation : sp sp2 sp3
17 CaC2 + 2H2O → C2H2 + Ca(OH)2 s-character : 50% 33% 25%
(A) Electronegativity : Max.
CH CH2 ←
Dil. H2SO4/HgSO4
 →  → Tautomerism Acidic character of ←
Max.
CH3CHO terminal H
CH CH––OH Acetaldehyde
(A ) Vinyl alcohol (B) Thus, CH ≡≡ CH > CH3C ≡≡ CH > CH2 == CH2 > CH3  CH3
Acetylene
24 It is aromatic because the compound is cyclic and number of
18 NaNH2 is used to distinguish between 1-butyne and 2-butyne. π-electrons is 2, which is in accordance with the Huckel’s rule,
(4n + 2 ) π. When n = 0, according to this rule, number of
NaNH 2 1
CH3CH2C ≡≡ CH → CH3CH2C ≡≡ CNa + H2 ↑ π- electrons is 4 × 0 + 2 = 2.
1-butyne 2 HC—
—C — C6H5
NaNH 2
CH3  C ≡≡ C  CH3 → No reaction ⊕C

—
2-butyne

19 CH3  CH2  C ≡≡ CH + HCl → C6H5

CH3 25 According to Huckel, an aromatic compound must be cyclic
 HI
planar having (4n + 2)π -electrons.
or CH3  CH2 C == CH2 → CH3  CH2 C I H ⊕
 
—
—
Cl

—
Cl (a)
—
—

(b)

—
2 - chloro -2-iodobutane —
Cyclopentadienyl cation Cyclooctatetraene
20 Hydration of alkyne,
(4πe–) (non-aromatic) (8πe–) (anti-aromatic)
Hg 2+ /H+
CH ≡≡ CH + H2O → CH2 == CH H — ⊕

—

—
—

OH (c) (d)
Unsaturated alcohol — —
(unstable)
Cycloheptatriene Cycloheptatrienyl cation
 Tautomerisation (6πe– but non-planar, (6πe– and planar,
↓ so non-aromatic) so aromatic)
CH3  CHO
Actaldehyde 26 According to the orbital concept, each carbon atom in benzene
is sp2 -hybridised and one p-orbital of each carbon remains
21 The given reaction takes place as follows : unhybridised. The π-electron charge in benzene is not confined
Br / hν Na/dry ether to space between two carbon atoms as in ethylene, but is
CH4 →
2
CH3Br → CH3 CH3 spread over a greater area. This is known as the delocalisation
Step 2 Wurtz reaction
(A) (A)
(Step2) of the electron charge.
Step I Alkyl halide is formed by free radical halogenation of 27
alkane in the presence of UV-light. Slow
C6H5CH == CHCH 3 + H + → +
Step II The formed alkyl halide reacts with sodium in presence of dry C 6H 5  CH  CH 2  CH 3
ether to form alkane containing double number of carbon atoms
Stable carbocation
present in alkyl halide. This reaction is known as Wurtz reaction.
22 Key Idea While judging the hybridisation in the given type of +
Fast
organic molecules always look for the number of σ and π-bonds C6H5  CH  CH 2  CH 3+Br – →
formed by C-atom involved. C 6H 5  CH  CH 2  CH 3
The hybridisation of the given molecules are. 
sp 2 sp 2 sp 2 sp 2 Br
(i) CH 2 == CH  CH == CH 2 Addition product
28 The function of AlCl 3 , in Friedel-Crafts reaction, is to produce 3 CH —CH —C CH
NaNH2
CH3—CH2—C≡≡ CNa+NH3
3 2 Ammonia
electrophile, which later add to benzene nucleus. 1-butyne
+ 1-bromopentane
CH3  CH2  CH2Cl + AlCl 3 → CH3  CH2  CH2 + AlCl 4−
CH3—CH2—C C—CH2—CH2—CH2—CH2—CH3
+
CH3 —CH—CH3 ift CH3 —CH—CH3
Sh Lindlar catalyst H2
H-
+ CH3—CH2—CH CH—CH2—CH2—CH2—CH2—CH3
+ CH3 —CH—CH3 Non-3-ene
(More stable)
4 General reaction for the combustion of alkene is
CH3 —CH—CH3 3n
– H+ C nH2 n + O 2 → n CO 2 + nH2O
2
Given, 6 L alkene require O 2 = 27 L
27 9
∴1 L alkene will require O 2 = L = 4.5 or L
29 The ICI on reaction with anhydrous AlCl 3 produces I + 6 2
(electrophile) consequently the final product is iodobenzene. 3n 9
On comparing the amount of O 2 . =
I 2 2
—

∴ 3n = 9 or n = 3
+ [O] Anhy.AlCl3 On putting the value of n in general formula of alkene, we get
+ CHI
[C nH2 n ] × 3 = C 3H6 . Hence, the alkene is propene
(CH3CH == CH2 ).
30 Due to the presence of most deactivating NO 2 group,
Nitrobenzene does not undergo Friedel-Crafts reaction easily.
5 The sp-hybridised carbons of the alkynes are more
electronegative than sp2 -carbons of the alkenes. Electro
31 The given reaction takes place as follows : negativity of the carbon atom depends upon the ‘s’ character
H 3C CH3 present in it.
CH Hybridisation– sp3 sp2 sp
Anhydrous % s character– 25% 33% 50%
AlCl3
+ CH3CH2CH2Cl Hence, order of their electronegativity is as follows
sp-hybridised carbon > sp2 hybridised carbon > sp3
Cumene
(P)
hybridised carbon
(i) O2 (ii) H3O+/D 6 Acidic strength (tendency to release proton) of carbon atom
OH depends upon its electronegativity which directly depends on
O its hybridisation.
sp- hybridised carbon is more electronegative than sp2 and
+ CH3C CH3
Acetone sp- hybridised carbon atoms.
Phenol (R) There order of electonegativity is as sp > sp2 > sp3
(Q)
Hence, there tendency to release proton will be − sp > sp2 > sp3
2
32 The correct reason is the carbon atom is sp - hybridised in ethene Therefore, option (b) is correct.
and sp- hybridised in ethyne.
7 The mechanism for reaction is as follows
SESSION 2
α β
1 (A) R CH==CH2 + Cl—Cl R CH—CH2 + Cl
Conc.
CH2==CH2 CH3CH2OSO2OH a b
H2SO4 Cl
(D) KOH (alcoholic) ∆ H2 O O
H H
PBr3
CH3—CH2—Br CH3—CH2
α β
(C) (B) OH R CH—CH2—Cl

2 CH3—CH2—CH==CH—CH2—CH3 HOH

(A ) Cl
HBr
H2 Ni
CH3—CH2—CH—CH2—CH2—CH3 R CH—CH2+ HCl

Br OH
Hence, H2O attacks α-carbon and bond (a) is cleaved.
CH3—CH2—CH2—CH2—CH2—CH3
 8 CH3 12 COOH COOH
CH
AlCl3 CH3
+ CH2—CH2—CH3 HNO3
(Q)
H2SO4
Cl NO2
(i) O2/∆
(ii) H3O+ CH3 OH
(P) (Major product)
CH3—C—CH3 + Phenol
OCH3 OCH3
O
(R) HNO3
9 CH2 == CH  CH == CH2 + HBr H2SO4
NO2
→ CH3 CH CH == CH2 + CH3CH == CHCH2 Br
 CH3 CH3
Br (Q) (Major product)
1,2 addition product 1,4 addition product
Addition is through the formation of allylic carbocation. O O
⊕ ⊕
CH2 ==CH C CH3 ←→ CH3  CH == CH CH2 C—O C—O
 HNO3
H 1° allylic less stable H2SO4
2° allylic more stable
(S) (Major product)
Under mild conditions (temp ≈ − 80° C) kinetic product is the
1,2-addition product and under vigorous conditions (temp 13 O
≈ − 40° C) thermodynamic product is the 1,4, addition product. O3
CH3 CH==CHCH3 CH3—CH CH—CH3
Thus, under given conditions 1- bromo–2–butene is the major
product.
10 Toluene is highly reactive towards electrophite substitution O O
reaction among the given compounds because toluene has (A)
CH3 group which increases electron density at o/p position of Ozonide
the ring. While in case of (3) and (4), both have electron Zn+H2O
withdrawing groups i.e. —Cl and NO 2 respectively. NO 2 CH3—CHO
has more capacity to attract or to withdraw the electrons from (B)
ring. Hence, their reactivity order will be 2 > 1 > 3 > 4.
14 Br
11 A ozonolysis
 → CH3 C CH3 Na
 ether
O Cl
+
O 15 As the hydrocarbon can react with Tollen’s reagent

{[Ag(NH3 )2 ] OH } and gives ppt, therefore it is alkyne because
CH3CH2 C  H only alkyne’s having terminal triple bond gives white ppt with
To obtain or to identify ‘A’ we need to remove oxygen atom Tollen’s reagent.
replace it with double bond. Hence, ‘A’ is, As its molecular formula is C 7H12 and it has terminal triple
CH3 C ==CH CH2 CH3 bond, hence the hydrocarbon is (c) among the given options
 as only option (c) has terminal triple bond.
CH3