CHAPTER13

HYDROCARBON

Hydrocarbons are composed of Carbon and hydrogen.

The important fuels like Petrol, kerosene, coal gas, CNG, LPG etc. are all
hydrocarbons or their mixture.
Sources:
Petroleum and natural gas are the major sources of aliphatic hydrocarbon while coal is an
important source of aromatic hydrocarbons. The oil trapped inside the rocks is known as
petroleum. PETRA–ROCK, OLEUM–OIL. The oil in the petroleum field is covered with
a gaseous mixture known as natural gas. The main constituents of the natural gas are
methane, ethane, propane and butane.
CLASSIFICATION OF HYDROCARBONS:
HYDROCARBON

Acyclic or Aliphatic Carbocyclic or Cyclic

(Open chain)

Alicyclic Aromatic
Alkanes Alkenes Alkyne

Cycloalkanes Cycloalkenes Cycloalkynes

Alkanes:-

Paraffins
  3
General formula CnH2n+2 sp
hybridisation

C–C bond length1.54A0

Chemically unreactive

Show chain, position and optical isomerism.

Heptane has 9 isomers, Octane18 and Decane 75.
Nomenclature:

171
Preparation:-

Wurtz reaction:-
Dry
2CH3CH2Br 2Na CH3CH2CH2CH3 2NaBr
ether

Follow mainly free radical mechanism
 an alkane containing
Useful in preparing even number of
carbon atoms
Stepping upreaction
Frankland reaction

RX+Zn+Rx R–R +ZnX2


FromGrignardreagent (RMgX)
RMgX+HOH RH+Mg(OH)X
RMgX+R'OH RH+ Mg(OR')X
RMgX+R'NH2 RH+ Mg(NHR')X

Fromunsaturatedhydrocarbons:-
Sabatier-Sendersen’s reduction
Ni/
R CH CH2 H2 R CH2 CH3
Ni/
R C CH H2 R CH2 CH3

4.Fromcarboxylicacids-
Decarboxylation.-

Kolbe’selectrolyticmethod-


PhysicalProperties:-
Nature:-Non-Polar due to covalent nature of C—C bond and C—H bond. C—
C bond energy=83 kJ/mole and C—H bond energy=99 kJ/mole. C1—
C4=gases, C5—C17=colourless odourless liquid and >C17=Solid.
Solubility:-Like dissolves like
Viz, Polar compounds dissolve in polar solvent and Non-Polar compound dissolve in
non polar solvent.
Boiling point:-Low boiling point due to non polar in nature.
172
 The molecules are held together only by weak Vander Waals’ forces.
Since we know that the magnitude of Van der Waals’ forces is directly proportional
to the molecular size. Therefore, the boiling point increases with increase in the
molecular size i.e. with increase in number of carbon atoms.
Note:- T he boiling points of the branched chain a lkanes are less than the straight
chain isomers.
This is due to the fact that branching of the chain makes the molecule more
compact and thereby decreases the surface area and consequently, the magnitudes of
Vander Waals’forces also decrease.
CH CH CH CH CH H C—CH—CH CH CH3
3 2 2 2 3 3 2 3

n-pentane CH H3C—C—CH3
4)( boilingpo t=309K
3
Meltingpoint:-t hemeltingpoint anesdonot show
iso-pentane CH3

ofAlkincreaseinmoleculboilingpoint=301Ksize.TheAlkaneswithe
neo-pentane
s comparedtothoseA
boilingpoint=282.5 K

Chemical Properties
1. Combustion:-

Alkanes on heating with air undergoes complete oxidation to give carbon

dioxide and water along with a large amount of heat energy.

Substitution reaction:-
Halogenation reaction
CH +Cl UV CHCl + HCl
4 2 3
UV UV
UV
CH3Cl CH2Cl2 CHCl3 CCl4
Note:-Iodination is a reversible reaction. So it is carried out by heating alkane in
The presence of some oxidizing agent like iodic acid (HIO3) or nitric acid (HNO3)
or mercuric oxide (HgO) which oxidizes HI formed during the reaction.

CH4 +I2 Heat CH3I+ HI

173
 5HI + HIO3 3H2O+3I2

2HI + 2HNO3 2H2O+I2 +2NO2

Noted:-Fluorination of alkane takes place explosively resulting even in the rupture of

C—C bond in higher alkanes.
Features of Halogenations:-
(i) The reactivity of Halogens:- F2>Cl2>Br2>I2.
The rate of replacement of Hydrogen atoms of alkanes is:
3°>2°>1°
Cl
CHCHCHCH 2 CHCHCHCHCl + CH CHCH CH
3 2 2 3 3 2 2 2 3 2 3
hv
n-Butane Cl

CH3

° CH3 C CH3
1

CH3 3° 1° Cl2 Cl
° CH-CH3
1
CH3 h 36% (3°)
CH3
Isobutane CH-CH2 Cl
CH3
64% (1°)

Mechanism:-halogenation reactions take place by free radical mechanism. The

reaction proceeds in the following steps:
Initiation
(i) Chain initiation step:-
Cl—Cl 2Cl

Chain Propagation step:-

CH4 Cl CH3 HCl

C
CH Cl2 3 l
3 Cl2 CH3Cl Cl
Chain Termination step:-
Cl Cl Cl CCl
2 2
CH3 CH3 CH3 CH3

CH3 Cl CH3Cl

174





Nitration:-

The reaction takes place by free radical mechanism at high temp (4500C).

At high temp C—C bond is also broken so that mixture of nitro alkanes is obtained.
450°C
CH3CH2CH3 CH3CH2CH2NO2 +CH3CHCH3 +CH3CH2NO2+CH3NO2
Conc.HNO3
NO2
25% 40% 10% 25%

166175
 Thereactionoccurs as: 4500C
HO-NO2 Homolytic fission HOo +oNO2

RH+ 0OH Ro +HOH

Ro +oNO2 RNO2

Sulphonation:- replacement of hydrogen atom of alkane by–SO3H group.
CH3
CH3
CHCH oleum CH3C CH3
3
CH3
SO3H
isobutane tertbutylsulphonicacid

The reaction occurs as:

 4500C
Isomerization:- Homolytic fission
HO-SO3 HOo +oSO3H

RH+ 0OH Ro +HOH

Ro +oSO 3H RSO3H

CH3
AlCl3 /HCl
H3C(CH2)3CH3 H3CCHCH2CH3
n-Pentane 2-Methylbutane

Aromatization:-
Cr2O3
H3C(CH2)4CH3
773K
10-20atm
Hexane Benzene
This method is also called dehydrogenation or reforming
Similarly, heptanes gives toluene, n-Octane give o-Xylene and 2-Methylheptane
give m-Xylene.

Thermal decomposition or Pyrolysis or cracking or Fragmentation:- When higher
alkanes are heated at high temp (about700-800K) in the presence of alumina or silica
catalysts, the alkanes break down to lower alkanes and alkenes.

CH3-CH2-CH3 CH3-CH-CH2 +CH3-CH3 + C2H4 + CH4 Actionofsteam:-
catalyst: nickel, aluminaAl2O3
0
1000 C
CH4 +H2O(Steam) CO+3H2
This reaction is used for the industrial preparation of hydrogen from natural gas.
8.Isomerisation:-
176

CONFORMATIONAL ISOMERISM:
The different molecular arrangements arising as a result of rotation around carbon
carbon single bonds are called conformational isomers or rotational isomers and the
phenomenon is called conformational isomerism.
Numerous possible arrangements of ethane are possible.Two extreme conformations
are known. These are eclipsed conformation and staggered conformation.
SAWHORSE REPRESENTATION

H H
H
H H
H
H H
H H
H
H

STAGGERED ECLIPSED

NEWMAN PROJECTION
H
H H

H
H

H H
H
H H
HH

STAGGERED SKEW ECLIPSED

177
 Alkenes

Unsaturated hydrocarbons which have double bond.

General molecular formula CnH2n

C–C bond hybridization1.34A0

sp2hybridization

When we treated Alkene with chlorine, oily products are obtained. So Alkenes are also
known as Olefins. (Greek olefiant meaning oil forming).

Show chain, positional and geometrical isomerism

Structure of double bond:-


Preparation:-
From Alkynes:-Alkynes on partial reduction with Partially deactivated
Palladised charcoal known as Lindlar’s catalyst give alkynes.

2.From Haloalkanes:- dehydrohalogenation

(E2or1,2-elimination or β-elimination)
H
2 1 Alc.KOH
CH2 CH2 CH2 CH + KBr+HO
Mechanism:- 2 2
Br

–
H
OH H H OHH H H
Slow
C C
C C
C C +Br- +H2O
H H
H Br H H
H H
H
Br
–
Transitionstate

predominant formation of a substituted alkene occurs
According to Saytzeff’s rule.

178
CH3-CH2-CH2-CH3 Alc.KOH CH -CH=CH-CH +CH -CH -CH=CH
3 3 3 2 2
| Major Minor
Br

179
3.From Dihaloalkanes:-dehalogenation
H
Zn/HOAC H
H H C C + ZnBr2
H H
H C C H
H H
Br Br Na
C C +I2 +2 NaBr
acetone
H H

4.From Alcohols:-Dehydration
(E1-elimination)

CH3CH2CH2OH Conc.H2SO4
CH3CH=CH2+H2O
160°

CH3CH2CH2CH2OH Al2O3 CH3CH2CH CH2

Mechanism 300°C
H+ +
CH -CH -CH -OH CH -CH -CH -O H -H2O
3 2 2 3 2 2 2 CH3 CH2 CH2
CH3 CH CH2 H CH3 CH CH2
1 propen e

H
lossofH2O
OH CH3 C CH CH3
12
from1,2
position
H3C C CH2 CH3 CH3

(major)
CH3 lossofH2O
3 CH3 C CH2 CH3
from1,3
position CH2
(Minor)


Chemical Properties:-

Addition Reaction:- Alkenes show electrophilic addition reactions.
1.Additionof Hydrogen:-
H /Ni
RCH=CH 2 RC H 2 2CH3

2.AdditionofHalogens:-
CH2-CH2
| |
CCl4
CH2=CH2 +Br2 Br Br
Solvent
H 2O
CH2 CH2 Br2 Solvent
Br —CH2—CH2—OHHBr

(Browncolour) (Colourless)
3.Addition of hydrogen halides-
Addition reaction of HBr to symmetrical alkenes

180
Addition reaction of HBr to unsymmetrical alkenes takes place according to
Markovnikov’s Rule
Markownikov’s rule:-negative part of the addendum (adding molecule) gets attached
to that carbon atom which possesses less number of hydrogen atoms.eg
H+
CH3 Br CH
3

2 AtPosition C CH3 C CH
CH3 1 (1) CH3 CH 3
3
C 3°
CH2 morestablecation Br
CH3 MajorProduct

H+ CH3
Br CH3
CH CH2 CH2 Br
CH 3 CH
AtPosition CH3
(2) 1°
lessstablecation MinorProduct

Peroxide effect or Kharasch (AntiMarkownikoff’s addition):-In1933 Kharasch and

Mayo observed that when HBr is added to an unsymmetrical double bond in the
presence of organic peroxide, the reaction takes place opposite to the Markovnikov’s
rule.
HBr
CH3 CH CH2 CH3 CH2 CH2Br
Peroxide

181
 Propylbromide

Noted:-peroxide effect is applicable onlyto HBr and not to HF, HCl and HI.
Addition of HF,HCl and HI takes place according to Markovnikov’s rule even in the
presence of peroxide.
4.Addition of water (Hydration):-Acid catalyzed addition of water
65-70%H2SO4
CH3 CH CH +H O CH 3 CH CH3
2 2
OH
CH3
H2O/H CH3
CH C CH2 CCH3
3 CH3
 OH
Oxidation:-

Combustion:- CO2 +H2O

Hydroboration–oxidation:-Alkanesreactwithdiboranetoformtrialkylboranes which on
oxidation with alkaline H2O2 give alcohols.
CH CH -
3CH2=CH2 BH3 3 23 B H2O2 /OH 3CH3CH2OH
Triethylborane Ethylalcohol

Oxymercuration–demercuration:-
Hg(OAC) NaBH4
2 HgOAC
H2C CH2 THF,HO CH2 CH2 OH CH3CH2OH+Hg
OH
2


Oxidation with potassiumpermanganate:-
2KMnO4+H2O 2KOH+ 2MnO2 +3[O]

+2MnO2 +2KOH
182
3 C H2 C + 2KMnOO+O4H
O Cold 3 C C
4 2

FromKMnO4 OH OH
Pink colour Colourless

183
 
This reaction is also calledHydroxylation
Cis product i.e.cis-diol is obtained.
Noted:-The alkaline potassiumpermanganate solution is known a sBaeyer’sreagent.
It has bright pink colour. It oxidizes alkenes to glycols which is colourless. This
reaction is used as a test for the presence of double bond in a molecule. This is also
known as Baeyer test.

(i)Alk.KMnO4
CH3 CH CH2 CH COOH+CO + HO
3 2 2
(ii)H+
  
Oxidation with Ozone:-
Ozonolysis–give carbonyl compounds

Noted:-Bromine water test and Baeyer’stest are used to detect the presence of
double bond while ozonolysis is used to detect the position of double bond.
Alkynes

Unsaturated hydrocarbon which have triple bond.

General molecular formula CnH2n–2

sp hybridization

Shows chain, positional and functional isomerism

Preparation:-
184
From vicinal dihalides:-dehalogenation
2KOH(alc)
CH3 CH CH2 CH3 C CH+2KBr+2H2O
Br Br

By the action of water on calcium carbide:-

CaC HO HC CHCa(OH)
2 2 2

Chemical Properties:-

Addition Reaction:-Alkynes show electrophilic addition reaction.

Addition of Hydrogen:- Hydrogenation.
Ni
CH3C CH+2H2 CH3CH2CH3
Propyne

185
Note:-It may be noted that the hydrogenation can be controlled at the alkene stage
only. This is possible by using a Lindlar’s catalysts or sodium in liquid NH3 at 200 K
temp.
Noted:-It may be again noted that the catalytic reduction of alkynes in the presence
of Lindlar’s catalyst gives cis-alkenes while in the presence of sodium in liquid NH3
(Birch reduction) gives trans-alkenes.

H3C CH3
H2 /Lindlar C
CH C CCH C
3 3
Catalyst H
H

H
CCH Na/NH3 (liq.) H3C C
Q.Write IUPACHCnameofalkenewhich C
3 3
H
CH3

Additiono fHalogens:- Br Br
| |
HC CH 2Br2 H C C H

| |
Br Br

Additionofhydrogenhalides:-
HC CH 2HBr CH3CHBr2

Polymerisation-
a. Linear polymerisation:of ethyne gives polyacetylene or poly ethyne
which is a high molecular weight polyene containing repeating units of
(CH=CH– CH=CH) and can be represented as—(CH=CH–
CH=CH)n—
b. Cyclic polymerization- results in the formation of aromatic compound.

186
Acidity of Alkynes-Terminal Hydrogen atoms in alkynes are acidic in nature.

Alkanes, alkenes and alkynesfollow the following trend in their acidic

behaviour:

AROMATIC HYDROCARBON

Aromatic compounds containing benzene ring are known as benzenoids and those
not containing a benzene ring are known as non-benzenoids.
Structure of Benzene- Kekulé structure

Resonanceand stabilityof benzene-Benzene is a hybrid of various resonating

structures.

The orbital overlapping picture of benzene-All the six carbon atoms in benzene are
sp2 hybridized and these hybrid orbitals form sigma bonds.

187
The unhybridised p orbital of carbon atoms are close enough to form a π bond by
lateral overlap.

188
The six π electrons are thus delocalized and can move freely about the six carbon
nuclei. The delocalized π electron cloud is attracted more strongly by the nuclei of
the carbon atoms than the electron cloud localized between two carbon atoms.
Therefore, presence of delocalized π electrons in benzene makes it more stable.

Aromaticity:- The compounds that follow the following features are to be

considered aromatic.
(i)Planarity
(ii)Complete delocalization 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,) This is often referred to as Hückel Rule.
Preparation of Benzene:
(i)Cyclic polymerization of ethyne:
(ii)Decarboxylation of aromatic acids:

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

heated zinc dust

Physical properties:
Aromatic hydrocarbons are non-polar molecules and are usually colourless
liquids or solids with a characteristic aroma.
Aromatic hydrocarbons are immiscible with water but are readily miscible
with organic solvents.
3.They burn with sooty flame.

Chemical properties
Arenes are characterized by electrophilic substitution reactions that proceed
via the following three steps:
(a)Generation of the eletrophile
(b)Formation of carbocation intermediate
(c)Removal of proton from the carbocation intermediate

189
 Nitration

Halogenation
+Cl2

Anhyd.AlCl3

Chlorobenzene

Sulphonation

Fumingsulphuricacid
H2SO4(SO3)

Friedel-Craftsalkylation

+C2H5Cl
Ethylbenzene
Anhyd.AlCl3

Friedel-Craftsacylation

+CH3COCl
Anhyd.AlCl3
acetphenone

benzene on treatment with excess of chlorine in the presence of anhydrous AlCl 3

in dark yields hexa chlorobenzene (C6Cl6)

190
Addition reactions of benzene-

Directive influence of a functional group in mono substituted benzene:-

1.Ortho and para directing groups and activating-–OH,–NH2,–NHR,–
NHCOCH3, –OCH3,–CH3,–C2H5,etc.

Meta directing group and deactivating:–NO2,–CN,–CHO,–COR,–COOH,–

COOR,–SO3H,etc.

3.Ortho and para directing groups and deactivating-Halogens because of their

strong–I effect, overall electron density on benzene ring decreases. However,

191
 due to resonance the electron density on o–and p–positions is greater
than that at the m-position. Hence, they are also o–and p–directing
groups.

CARCINOGENICITY AND TOXICITY-Benzene and polynuclear

hydrocarbons containing more than two benzene rings fused together are toxic
and are said to possess cancer producing (carcinogenic) property.

ONE MARK
QUESTIONS
1.What are hydrocarbons?
Ans.Compounds of hydrogen and carbon.
2.What is the general formula of alkanes?
Ans. CnH2n+2
3.Write the general formula of alkenes.
Ans.CnH2n
4.What is the general formula of alkynes?
Ans. CnH2n-2
5.Give the IUPAC name of lowest molecularweight alkane that contains a
Quaternary carbon.
Ans. 2,2-Dimethylpropane.
6.Arrange the following in the increasing order of C-C bond
length -C2H6 C2H4 C2H2
Ans. C2H2 <C2H4<C2H6
7.Out of ethylene and acetylene which is more acidic and why?
Ans.Acetylene, due to greater electonegativity of the sp hybrid carbon.
8.Nametwo reagents which can be used to distinguish between ethane
and ethyne.
Ans.Tollen’s reagent and ammonical CuCl solution.
9.Arrange thefollowing in order of decreasing reactivity towards alkanes.
HCl,HBr,HI,HF
Ans.HI>HBr>HCl>HF
10.How will you detect the presence of unsaturation in an organic compound?
Ans.Generally Unsaturated organic compounds decolourise Baeyer’s
reagent
and Bromine water.
11.What is Grignard reagent?
Ans.Alkylmagnesiumhalides

TWO MARKS QUESTIONS

1.Write the IUPAC names of the following-

192
 a. b.
Ans.a .Pent-en-3-yne b.2-methylphenol

2.Write chemical equations for combustion reaction of(i)Butane(ii)Toluene

Ans.

(ii)
Toluene

3.What are the necessary conditions for any system to be aromatic?

Ans.A compound is said to be aromatic if it satisfies the following three
conditions: (i)It should have a planar structure.
(ii)The π–electrons of the compound are completely delocalized in the ring.
(iii)The total number of π–electrons present in the ring should be equal to
(4n+2), where n=0,1,2… etc.This is known asHuckel’srule.
4.What effect does branching of an alkane chain has on its boiling point?
Ans. As branching increases, the surface area of the molecule decreases which
results in a small area of contact. As a result, the Vander Waals force also
decreases which can be over come at a relatively lower temperature. Hence,
the boiling point of an alkane chain decreases with an increase in branching.
5.How would you convert the following compounds
into benzene?(i) Ethyne(ii)Ethene

Ans.(i)Benzene from Ethyne:

193
 (ii)Benzene from Ethene:

6.Suggest the name of Lewis acids other than anhydrous aluminium chloride which can
be used during ethylation of benzene.
Ans. Anhydrous FeCl3,SnCl4,BF3etc.
7.Write the name of all the possible isomers of C2H2Cl2 and indicate which
of them is non-polar.
Ans.(i)cis-1,2-dichloroethene (ii)trans-1,2-dichloroethene (iii)1,1-
dichloroethene.trans-1,2-dichloroethene is non-polar.
8.Although benzene is highly unsaturated, it does not undergo addition reactions,
why? Ans.Because of extra stability due to delocalization of π-electrons.
9.What are alkanes? Why are they called paraffins?
Ans. Those hydrocarbons which contain single bond between carbon-carbon are called
alkanes. They are called paraffins because they are very less reactive (Latin-
Parum=little,affins=affinity)
10.How can ethane be prepared from (i) ethanol (ii) ethylbromide?
Ans.(i)Ethene from ethanol- by acidic dehydration of alcohols

Ethene from ethyl bromide- by dehydrohalogenation of ethylbromide

CH3CH2Br+KOH(alc)→ H2C=CH2+KBr+H2O

THREE MARKS QUESTIONS

1.What is Wurtz reaction?How can it be used to prepare butane?
Ans-When alkyl halide is treated with metallic Na in presence of dry ether, alkanes are
194
 formed. This reaction is called Wurtz reaction.
Butane is prepared by the reaction of bromo ethane with metallic Na in presence
of dry ether

2.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. Deduce IUPAC
name of‘A’.
Ans..The formation of two moles of an aldehyde indicates the presence of identical
structural units on both sides of the double bond containing carbon atoms.Hence, the
structure of‘A’can be represented as:
XC=CX
There are eight C–H σ bonds.Hence, there are 8 hydrogen atoms in ‘A’. Also,
there are three C–C bonds. Hence, there are four carbon atoms present in the
structure of ‘A’.

Combining the inferences, the structure of‘A’can be represented as:

the IUPAC name of ‘A’ is But-2-ene.

Ozonolysis of ‘A’takes place as:

The final product is ethanal with molecular mass

3.In the alkane H3C–CH2–CH(CH3)–CH2–CH2-(CH3)2, identify 1°,2°,3° carbon atoms

and give the number of H atoms bonded to each one of these.
Ans.

195
 The given structure has three 1°carbon atoms and each such carbon atom is
attached with three H – atoms.
The given structure has two 2° carbon atoms and two hydrogen atoms remain
attached to such a carbon atom.
The given structure has one 3°carbon atom and only one hydrogen atom is attached
to it
FIVE MARKSQUESTIONS

4.Addition of HBr to propene yields 2-bromopropane, while in the presence of benzoyl

peroxide, the same reaction yields1-bromopropane. Explain and give mechanism

Ans.Addition of HBr to propene is an example of an electrophilic substitution reaction.

Hydrogen bromide provides an electrophile, H+. This electrophile attacks the double
bond to form1°and 2°carbocations as shown:

Secondary carbocations are more stable than primary carbocations. Hence, the former
predominates since it will form at a faster rate.Thus, in the next step, Br –attacks
the carbocation to form 2–bromopropane as the major product.

This reaction follows Markovnikov’srule

In the presence of benzoyl peroxide, an addition reaction takes place according to anti
196
Markovnikov’s rule. The reaction follows a free radical chain mechanism as:

Secondary free radicals are more stable than primary radicals. Hence, the
former predominates since it forms at a faster rate.Thus, 1–
bromopropane is obtained as the major product.

HOTS QUESTIONS

1.How will you demonstrate that double bonds of benzene are some
what different from that of olefins?
Ans.The double bonds of olefins decolourize bromine water and
discharge the Pink colour of Bayer’s reagent while those of
benzene do not.
2.How will you separate propene from propyne?
 Ans. By passing the mixture through ammonical silvernitrate solution
when propyne reacts while propene passes over.
3.Write the structure of the alkene which on reductive ozonolysis gives
butanone and ethanal,
Ans.-CH3CH2C(CH3)=CHCH3