CHAPTER

13
Hydrocarbons
As the name implies, hydrocarbons are the compo unds of carbon and
hydrogen only. The main sources of these compo unds are coal and
pee role urn.

Classification of Hydrocarbons • Saturated Hyd

single (-),
Any t\vo carbon acorns of a hydrocarbon may combi ne throug h (AIRanes)
r of
double (= ) or triple (==) bonds. Depen ding upon the manne • Unsa turate d H
be classified in three major
attachmenr of carbon acorns , hydrocarbons can (Alhenes and
classes chac are shown below : • Arom atic Hydr

Hydrocarbons
(Comp ounds of C and H only)

Aromatic hydrocarbons
Saturated bydrocarbon.s Un.s:aru.rated hydroc arbons
(Alrern ace single and
(Carbon atoms 2re (One or more multiple
bond(s) are presenr berween do uble bond , (4n + 2) p
jornt"d cogn:ht"r 1.hrough
srngle bon<h only). che carbon acorn). clecrro ns are prese nt). e.g.
~ ~
( , Jj (Benzen e)
AJlo.nn - Alk.cnt~
[Optn ch.arn, e.g. (have adc:-3.lt one double bc,nd
C H 3-C.H 3 (ethane )] berwcen carbon .1to11u) . c.~.
CH2= CH1 (cchcncJ.
CycloalbnCj CH3- CH=C H2( propcnc) (N.iphrh.ilcne)
t[C.
(Clo~ chain) e.g.

D, or H2C "-.. -- ~ 1
I CH2 (have ad<:a.)r one rriple bond
H 2C/ berween carbon aconu) .
(Cydopr opane) e.g. CH •CH (aceryle ne),
CH3- C • CH (propyn c) etc.

T
TOPIC
01 Sat~rated Hydrocarbons {Al Ranes)
These are the open chain saturated hydrocarbons in Nomenclature
which carbon atoms are joined together only thr~ugh The nomenclature of hydrocarbons has been discussed below:
single bonds. These are the simplest hydrocarbons and
were earlier. called 'paraffins' (Latin : parum-little
1. Writing IUPAC Name
affinis-affimty) because of their inert (non-reactive) nature
cowards many acids, bases and other reagents.
From a Given Structure
In the previous chapter, you have read that alkanes are
General molecular formula for these compounds is
named by adding the suffix 'ane' to the 'root word',
CnH2n+2 (where, n = 1, 2, 3, .... ). If n = 1, we get CH 4
(methane), the first member of alkane series. By replacing i.e. root word + ane = alkane
the hydrogen(s) of CH 4 by -CH 3 or other alkyl groups, Further recall that, in complex structures, the numbering
we get the complete series of members of this group. is done from the end which gives the lowest sum and in
H H H accordance with alphabetical order of the name of
\ Replace any H by- CH3 \ \ substituent. e.g.
H-C-H------~H-C-C-H
I I CIH3 c H2-CH3 (Sum= 4 + 2 = 6)
I 1 2 3 41 5 6 correct
H H H CH 3-CH-CH2-CH -CH2-CH3 (Sum = 3 + 5 = 8)
6 5 4 3 2 1 incorrect
• Groups having one H-atom less than the alkanes are called alkyl
(4-ethyl-2-methylhexane)
groups. General molecular formula for these groups is CnH 2n+ 1.
e.g. ---CH 3 is the alkyl grou p (methyl group) derived from ~
methane by replacing its one hydrogen atom. ('e' comes first in the alphabetical order)
The prefix sec, di, tri etc. are not considered in
Structure of Alnanes alphabetical order while writing the IUP AC name. Only
3 the first letter of root word is considered, if arranged in
In alkanes, the central C-atom is sp -hybridised and have
3 alphabetical order.
four half-filled sp -hybridised orbitals. These four orbitals
form four cr-bonds either with four H-atoms using their CH(CH 3)i .
ls-orbitals (sp 3 -s bonding) or with other carbon atoms 1 2 3 41 5 6 7 8 9 10
(sp 3 -sp 3 linkage) or both. CH3CH2CH2-C H--CH-CH 2CH 2CH 2CH 2CH 3
e.g. Consider the structure of methane. I
H 3C-CH-CH 2CH 3
5-sec-butyl-4-iso propyldecane

('b' comes first in alphabetical order, here 's' of sec is not

considered).
If the substituent group is also complex then separate
Structure of methane numbering is done in it. e.g.
1 2 3 4 5 6 7 8 9
The four cr-bonds are directed toward the corners of a CH3-CH2-CH2~ CH 2-CH-CH 2-CH 2-CH 2-cH 3
regular tetrahedron, i.e. they are multiplanar (not in one 1 I
plane). The H-C-H bond angle are 109.5° and C-C CH2 \ Substituem (number
and C-H bond lengths are approximately 154 pm and 2 I starts from the
112 pm respectively. CH3-C-CH 3 carbon that is linked
3 3
I with the principal chain).
Thus, methane have four sp -s cr bonds formed between CH 3
sp 3 -orbitals of C and ls-orbital of H. 5-(2, 2-dimethylpropyl)nonane
s4a I Allh,,one ISC Chemistry - Class 1l

! Example 1 1 .
Wnte the IUPAC names of the following: [ Example 2 , Write structures for each of the following
(i) (Cills)4C (ii) (CH 3h CHCH(CH 3) 2 compounds. Why are the given names incorrect? Write
Sol. CH 3 correct IUPAC names. NCERT Textbook
I (i) 2-ethylpentane (ii) 5-ethyl-3-methylheptane
CH 2
\
1 2
3
I 4 s Sol. (i)
(i) CH 3 - CH 2 - C-CH 2 -CH 3
I
CH 2
I Longest chain is of six carbon atoms and not of
CH 3 five. Hence, the correct name of the compound is
3-methylhexane.
3, 3-diethylpentane 7 6 5 4 3 2 I
(ii) CH 3-CH 2 -CH- CH 2 - CH- CH 2 -CH 3
CH3 CH3
I I
1 21 31 4 CH 3 C 2 H5
(ii) CH 3 - CH-CH -CH 3
2, 3 -dimethylbutane Numbering is always started from the end that
gives lower number to the ethyl group as compared
to methyl group (because in alphabets 'e' comes
2. Writing Correct Structure From the first than 'm'). Hence, the correct name is
Given IUPAC Name 3-ethyl-5-methylheptane.
To write the structure of a compound from its name,
first draw the longest chain of carbon atoms (according Occurrence: Sources of Alf?anes
to root word) and then number it. Now attach the The main sources of alkanes are natural gas and
different substituent at the mentioned places and satisfy petroleum. The natural gas is found near petroleum wells
the valencies of all the C-atoms by putting required and is a mixture of higher solid hydrocarbons. Bee's wax,
number of hydrogen atoms, e.g. the structure of which is mainly mynicyl palmitate (an ester) also contains
3-echyi-2, 2- dimethylpentane car1 be written as : small quantities of C 27 H 56 and C 31H 64 ·
St.ep I. Here 'pent' is the root word, so the principal
chain have five C-atoms. Thus, draw five Isomerism
C-atoms in a straight chain. First three members of alkane family methane, ethane
C-C-C-C-C and propane have only one structure but higher alkanes
can have more than one structure. Hence, exhibit isomerism
St.ep II. Give number to the carbon atoms (you can give
number from either sides) e.g. four carbon acorns can be joined in the following two
different ways with molecular formula C 4H 10 .
Cl-C2-C3-C4-CS
H H H H
St.ep III. Attach echyl group at third carbon and cwo
methyl group ac second carbon.
H-
1
t-2t-3t-4t-
I I I I
H
H H H H
CH 3
Butane (11-burane) (bp 273 K)
I 21 3 4 S
C-C--C-C-C H H H
I I ii 21 3/
H - C- C- - C - H
CH 3 C 2H 5 I I I
H H- C- H H
Step IV. Satisfy che valency of each carbon acorn by I
adding the required number of hydrogen atoms. H
2-merhylpropane (isoburane) (bp 261 K)
CH ,
I Similarly, C 5 H 12 ca n have three different structures
CH 3 - C - CH -CH 2 -CH 3 which are given below.
I I H H H H H
CH 3 C 2H~
ii 21 31 41 5/
T he obtained structure is the correct structure of the H-C- C- C- C- C- H
I I I I I
given compo~nd. H H H H H
Pentane (n-pentane) (bp 309 K)
 ~
Hydrocarbons 549

H H H H
11 2 I JI 41 Method s of Preparation
H -C --C--C-C-H
Fol/,owing methods can be used to prepare alkanes:
~ H-t-H ~ h 1. From Alnyl Halides
I
H Following methods are used to convert alkyl halides into alkanes are
2-methy\butan e (isopentane) (bp 301 K)
H as follows:
I (i) Reduction : All the alkyl halides, except fluorides , when
H H-C-H H treated with zinc and dilute HCl, get reduced to alkanes. e.g.
11 21 3\ ZnH +
H-C-C--C-H
\
H H--C-H
I \
H
✓ CH 3--Cl
Chloromethan e
+H2 ~ CH 4 + HCI
Methane
\ Alkyl iodide can also be reduced by using red P and HI.
H Here, red P is used to remove iodine as volatile PI 3 ,
2, 2-dimethylpro pane (neopentane) (bp 282.5 K)
otherwise the reaction being reversible goes in backward
We see, that the two structures derived from the direction.
molecular formula C 4 H 10 and three structure
d~rived from the molecular formula C 5H 12 have C 2H 51 + HI ~ C 2H 6 + 12
different properties (boiling point). Such Ethyl iodide Ethane
structures which differ in their properties due to (ii) Wurtz Reaction When alkyl halides are treated with sodium
difference in thier structures are called structural
metal in the presence of dry ether (free from moisture) it
isomers. And the structural isomers which differ
in chain of carbon atoms are known as chain results in the formation of an alkane having double the
isomers. number of carbons as that are present in parent halide. This
• The number of possible structural isome rs for C6 H14 and C7H16 are reaction is called \Vintt reaction.
respectively 9 and 75. . D ry ether
C 2 H 5Br+2Na+B rC 2 H 5 ---➔ C 2 H 5 - C 2 H 5
Bromoethane - 2 NaBr n-butane
[ Exam ple 3 1 Write structures of different
chain isomers of alkanes correspondi ng to the If different alkyl halides are used, the product 1s
molecular formula C6H 14 . Also write thei:r.: IUPAC non-separable mixture of alkanes, so this method is more
names. NCERT Textbook
suitable for the synthesis of symmetrical alkanes, 1.e.
Sol. s 6
alkanes having even number of carbon atoms. e.g.
1 2 3 4
(i) CH3-CH2 -CH 2-CH 2-CH 2-CH 3
n-hexane Ether
1 2 3 4 5 CH 3 X +2Na+C 2 H 5 X - - - " ' CH 3 -CH 3
(ii) CH3- CH-CH2- CH 2-CH 3 -NaX Ethane
I + CH3-C zH s + C 2H s--C 2Hs
CH 3
Propane Butane
2-methylpenta ne
1 2 3 4 5 (A small percentage of alkene is also obtained during this
(iii) CH3-CH 2- CH-CH2-C H3 reaction) .
I Note Methane cannot be prepared by this method .
CH 3
3-methylpenta ne (iii) Corer-Hous e _S~thesis It is a reaction that involves the
2 3 4
rea~tion of a lithmm dialkyl cuprate (R2 CuLi) with an alkyl
1
(iv) CH3- C H - CH-CH3 1de to form a new alkane. This is a good method to

1
(v) CH3-2C-C H2-CH3
I
CH 3 CH 3
2,3- dimethylbutan e

CH 3
I 3
I

4
fi epare hydrocarbon s (alkanes) having odd number of
carbon atoms. Methane cannot be synthes·1sed usmg
e th d
R- X
o .

(Any alkyl
halide)
Li
Diethyl
ether
RLi ~
·

R2 CuLi
(Gilman reagent)
R' X
t h is

I ~ R-R' +R Cu + LiX
CH 3
2,2-dimethylbu tane
 Allh,One ISC Chemistry - Class 11
550 I
Step II At anode
(This R' should be methyl, 1° alkyl or 2° cycloalkyl). 0
0
(i) Li 11 - 11 ••
(CH3 ) 2 CHBr -------4 [(CH3 )2 CHhLiCu 2CH3 -C-O- -z e > 2CH3 -C-~ • ->
(ii) Cu
Lithium di-iso-propy l Acetate
cuprate Acetate ion
free radical
(CH3 )2 CHCH 2 CH 2 CH3 2CH 3 + 2C0 2 i
Methyl free
For the second step to give a good yield of the alkane, the alkyl
radical
halide (say R' X) muse be either a methyl halide (a primary
alkyl halide) or a secondary cycloalkyl halide.
The alkyl groups of the lithium dialkyl cuprace (also
H 20+ e- ~ -oH +H
called Gilman reagent) may be methyl, 1°, 2° or 3°. Step N At cathode
•
Moreover, the two alkyl groups being coupled need not 2H~H 2 i
be different.
Because of the generation of OH- ions, the solution
~ From Carboxylic Acids
becomes alkaline.
, carboxylic acids can be converted into alkanes by following Note CH cannot be prepared by this method This method is not
\/1methods suit~ble for alkanes having odd number of carbon atoms, as
· in such case a mixture of hydrocarbons is formed which is
(i) Decarboxylation (Removal of-CO 2 ) When
difficult to separate.
sodium salts of carboxylic acids are heated with
sodalime (a mixture of NaOH and CaO), CO 2 is 3. By Reduction of Cfirbonyl Comp ounds
eliminated and alkanes having one carbon atom less (i) Carbonyl compou nds are easily reduced with
than the parent compoun d is obtained. Thus, hydrogen iodide in presence of red phospho rus to
sodalime acts as the decarboxylating agent. alkanes.
CH3COO-N a + +NaOH CaO CH 4 +Na 2C0 3 0
Sodium erhanoate ~ Methane II Red P + HI
Note • Purpose of using Cao in soda lime
RCH ----R CH 3
0
• Cao permits the rr: •ction to be carried out at a relatively higher
temperature so lh c comp lete decarboxylation is ensured. II Red P + HI
• Sodium hydroxide is hygroscopic in nature ( i.e abso rbs RCCH3
moisture from air) but Cao present in soda lime keeps it dry.
(ii) Carbonyl compounds react with hydrazine (NH 2 NH 2 )
(ii) Kolbe's Electrolytic Method When aqueous - +
solution of sodium or potassium salt of a carboxylic in presence of C 2 H 5 0 N a to give alkane. This
acid is subj ected co electrolysis, it gives an alkane reaction is called as Wolff-Kishner reduction.
having even number of carbon acorns at the anode.
0 N--NH2
J,n chis method, a new C-C linkage is developed.
II C2 H 5 ONa
NH 2- NH 2 II
CH3COO-Na+ +H20 Electrolysis CH3 R CCH3 - - - - - 4 RCCH3 ------- \ RCH 2 CH3
- H 20 K 450
+ I + C02t
CH 3Coo-Na + CH 3 (iii) Carbonyl compoun ds react with zinc amalgam in
Ac anode prese_nce. of cone. HCI to give the alkane. This
+Hi+ 2Na+oH- reaction ts called as Clemme nsen reduction.
0
Ac cathode
11 Zn - Hg + cone. HCI
Mechanism RCCH3 _ _ _ ____,.RCH 2CH3
It involves the following steps : From Alcohols, Aldehydes and l(etones
Stepl 2CH 3COO-Na+ ~
Ionisation The alcohols, aldehydes and ketones on reductio n with a
mixture of _red phosphorus and hydroiodic acid yield

2CH 3 -
~
c- o- + 2Na +
correspondmg alkanes.
R- OH+ 2 H I - ~ RH+ I +HO
2
Alcohol 423 K Alkane 2
 AllinOne ISC Chemistry - Class ~
552 I
If air or dioxygen is insufficient, incomplete combustion
Strp II Propagation The free radic.ds generated attack
of alkanes rake place and carbon black _is f~rmed ~s
on the alkane molecule to give alkyl free radical produce. Carbon black is used for making mk, pnnter
which in turn reacts with other chlorine
ink, black pigments and as filters.
molecule to give alk-yl chloride and chlorine free
Incomplete O(L)
radical. These reactions are repeated and CH (g) + 0 2 (g) b . C(s ) + 2H 2
4 com usnon
thereby setup a chain of reactions.
3. Catalytic Oxidation (Reaction with
• hv • Oxygen in Presence of Catalyst)
CH 4 +Cl~ C H 3 + H-Cl
· If alkanes are heated in controlled supply ot dioxygen or
• h •
CH 3 +CI-Cl~CH 3 -CI+ Cl . air and in the presence of suitable catalysts, a variety of
Chlorine
1
oxidation products (alcohol, aldehyde and carboxylic
free radical
. acid) are obtained as follows:
The chlorine and methyl free radicals generated Cu/523 K/100 atm
above repeat the above steps and thereby setup (i) 2CH 4 +0 2 - - - - - 2CH 30H
a chain of reactions. Methanol

The above reaction gives the required products HCHO+ H 20

bur many other side reactions also occur during Mechanal
the process. Two such reactions are as follows:
(CH3 C00) 2 Mn
• •
CH 3Cl+Cl ~ CH 2CI + HCl .1
• • 2CH 3 COOH + 2Hz0
CH 2 CI +Cl-Cl~ CH 2Cl 2 + Cl Ethanoic acid
Generally, alkanes do not undergo oxidation bur alkanes
Step III Termination The chain reaction is terminated
having tertiary H-atom undergo oxidation to corresponding
either by complete consumption of reactants or
alcohols by treating them with potassium permanganate.
also in the following termination process (due
to reaction of two free radicals). KMn0 4
(CH 3 ) 3 CH (CH 3) 3 COH
• • Oxidation
Cl+Cl ~ Cl-CI; 2- met hyIpropane 2-methylpropan- 2-o l
• • 4. lsomerisation
H 3C + CH 3 ~ H 3C-CH 3
• • When n-alkanes are heated with anhydrous AlCl and
H 3 C +Cl~ H 3C-Cl HCl g~s, they isomerise to give branched chain Jkanes as
Th~s, ethane is also produced as by product the maJor product which are given below:
. dunng rhe free radical chlorination of methane. Anhyd.AJ C l /HCI
3
CH3(CHz) 4CH3 _ _ _ _ ___,.
,~ - Combustion \, n- hexane
'Z · When alka~e~ are hea_red in excess of air or dioxygen, CH3CH(CH3)-(CH z)2 -CH3
2- merhylpenrane
they are ox1d1sed to give carbon dioxide and water. A
0 + CH3C}'f2-CH(C H 3)-CH2-CH3
large amount of hear is evolved during chis reaction .
_ Thut, alkanes are used as fuels. · ' 3- merhylpentane

1 ::1't
x'-1
,r CH4(g) + 20 2(g) ~ C0 2(g) + 2Hp([);
6 1
+ ~inor_ products (n"o; reported in organic synthesis)
5. Cychsat1on
l'lc H = - 890 k] mof -
+-(,.., 13 Al~ne~ having six or more carbon atoms u
C4H10(g) +
2 0 2(g) ~ 4C0 2(g) + 5Hp([); cycl1sanon to give cycloalkan
d h d
d b ndergoes
e an on su sequent
1',,c H 6 = - 2875.84 kj mo l- 1 e Y rogenarion at a higher tern .
catalyst such as Pt, Pd or Ni . perature m presence of
The general combustion equation for any alkane is

(3\+ 1
~ nCO +(n + CH3CH3
CnH211+ 2 + )02 2 l)H 20
CJ
Hexane
670 K, Pr

0
Cydohexan e
670 K, Pr

0Benzen e

(
~ydrocarbons I 55 3

... Aromatisat1on
..,.
'tr»tt H ch.un .llhn cs h~vin 6
Conformations
~ • J to --5 K .r 10-2 0 atrng or more C-acoms when
prcssu · h T he rotation of carbon-carbon singl e bond (a
-bon d), due ro
1-';irN
0
- () ,. , -'._ or ;,A,,o . . 0 re •n r c presence als) alon g
•u• sup _.J cylindrical symmetry of a-MOs (molecular orbit
• ' portc u over aluminJ spati al
•
ct· (t{ dd c ~ _cNcc:-d (1.c. loss h:·d rogen ) .tnd internuclear axis, in alkanes results into different
: ~ • ertib le.
,"'\'\': ~ to gi, c nun<" .tn<l th hon1oloKnU\. arrangement of atoms in space , that are inter conv
conformers
ition. fo . T hese arrangements are called conformations,
~ ' rcx,1on ,, kno " n ,b a_rom:ui$. or re mung. num ber of
· or rotamers. In general, alkanes possess infinite
c..f CH, conformations.
between
l f,l.\ ;0~ However, weak repul sive interaction are present
CH, rhe adjacent bonds in alkanes so the rotat ion of
OT\
C-C
CH~
0- 0
t \(o:O \ by a
single bond is nor completely free and1 is hind ered
mol - The repul sive
CH.. -:;1-. . small energy barriers of 1-20 kJ •
CH; !O .:o 11m interaction between the adjacent bond is called
torsional
Benzene
strai n.

l· ~ u ud 10 ph« of u-ha .rne, toluene, Conformations of Ethane

· C H\O i. u ohcu ncd ~ rhe prod uct. cule we see
As we write the structure of ethan e (C 2H 6 ) mole
each
... Pyrotysis or Cra cnin g rhat it contains a carbon-carbon si ngle bond with
re carbon atom actached to three hydrogen atoms.
h ~~ ~ -'hm h(".tted l< a higher rcmperacu H
like lower H
~ ~.:nmp,;,),C to gt\C (m.illcr fr·agmencs
H-"'c -c ~ H
~ £.;mn c1c Thu. ram on h c:aJled pyrolysis.
~g H/ "'
(Ethane, C2 HJ
H
C~ H !(; e, keep
1-tq,u .ttc Now, considering che baJI and stick model of erhan
the orhe r carbo n
one carbon acom scacionary and rocace
.... (_ . H ., + O rher produces acorn aro und rhe C-C axis.
flct1t..J\c

Tb 1cuu011 t .atn pl.u..c lt. Jrccr.u.111..iJ mt:ch.rni, .n and

1~ w JWcpuc o I ~ -H , , pctw! g... , frum kcru ~nt oil.

8 Rom on with Ste am

W\t,.. liidt' u, O u",t cJ A uh )l(', 111 .!l I l .... i K JnJ Ill

dle ptc.lC'nc.c o l nh.~.cl ..n ur.tl ) ,i, It ~,vn

~Jrbc,11
ogen atom
~a dt •r14J dthH ftogc n g,H A11 infinit e num ber of arrangeme nts of rhe hydr
l".1 ,Ht::K hcd ro une carbon arum wirh respect
to the hydr ogen
CH • It u - -.t {h- H l. .1 ro111 uf chc ~tcon d ca rbon .uom .ue poss ible.
' \ -
called
111 1rn.lu, u 1~1 ptu,l ,n\ for 1hc I he,e inli111cc num ber of dillerenr <1rrangemenrs are
l\t ..hc,..c rt ..i:llun " me case~
coof orm,uion .s. If owcver, dwre are rwo extre
Wllth t\u <>f d,hvJrc~t 11 Jhl,u ,,ed btlow .
U1e5 I Staggered Con form atio n
, rcachcd
The l1mlonn,11ion 111 whiLh the hydrogen ato m11 1
lO
1
Ai• lud '11d 1llumuun1.
th<" two urbo n Jrom1> are a~ fa r apar t a~
po111>iblc j_., called
11
In the prtp. uar,o n bl l J.rho n bla,k whlch I\ u}td
tor nl.illong pr111t1n~ inlc , blad, patnl \ J_ttd
"-' J_ the Haggc rcd conf orma tion.
filler tn rubt)("r mJu>trv 2. Eclipsed Con form atio n
(iu In the torm arton ol methyl .,lwhol,
lurmaldc.-hvJc.-,
att .it lied 1 )
c.hlorofo r m. c.ul-xin teer J(...holor u.ic ct(.. .
'\'he conformation in which the hydrogen acolll_.,
,
a. po," li't· 1,
r l t rwo c_arhon arom!I are as clo1>ed together
iv In the prep. iratio n o f hyJr ogtn . l allcd eclipsed confo rmat ion .
554 I AJJh,,()ne ISC Chemistry - Clas5!

Any intermedi ate conforma tion between the above two is Relative Stability of Conformations
called skew or gauche conformation. i: . since the electron clouds of
I n staggered comorma b d
tton,
as far apart as poSSI'bl e, so it
In all the conformat ions, the bond angles as well as bond
lengths remain the same. The staggered and eclipsed
carbon-hy drogen °~ s are · ·mum energy and
has minimum repulsive forces, mm1 d l' d
conforma tions of ethane in three dimension s can be . t b1'l1'ty On the other han ' ec ipse
maximum s a . . i: •
represented by following two projections. i: . h imum repulsive rorces, maximum
comormat 10n as max · · h I
I. Sawhorse Projections In this projection, there is a . . ·t bility because m It t e e ectron
energy an d mm1mum s a I h
long straight line, upper end of which is slightly en bonds are coo c ose to eac
clou d s o f car b on h Yd rog
tilted towards right or left hand side. This line shows other. The angle o f rotation • a bO ut C- C b on d 1s· call ed
. •
the central C-C bond. The lower end of this line the dihedral angle or torsional angle and i_s ~ax1mu~ , .
shows the front carbon and upper end represents the i.e. 1800 in staggered conforma tion and ~m~mu~ _(O) m
rear (the atom away from the eye) carbon atom. . • Th us, rors10 · nal stram
eclipsed conforma tion. . 1s mm1mum
.
Each carbon also has three lines attached to it, that .m staggered i: · d maximum m eclipsed _ 1
comorma uon an .
show three carbon atoms inclined at an angle of 120°
to each other. Sawhorse projections for eclipsed and
form. The rwo forms differ in energy by 12.5 kJ mo! •.
This energy barrier is so small th~t sm~l thermal or kinetic
staggered conforma tion of ethane are as follows: energy is sufficient to overcome 1t by mt_ermolecular
H collisions, hence the different conforma tions of ethane

H
H UHXH cannot be separated and isolated.

XH
H H H H
(i) Eclipsed (ii) Staggered
Sawhorse projections of ethane
II. Newman Projections In this projection, the front
carbon is represented by a point and the three
hydrogen attached to it by three lines attached to the
point at an angle of 120° from each other. The ~ear
carbon is shown by a circle and three shorter lmes
arising from the circle at an angle of 120° to each
other show the three hydrogen atoms attached to the ·
rear carbon atom. (carbon lying in the back)
The Newman's projections for staggered, eclipsed
skew conformations of ethane are shown below :
Torsional or
B Topic Practice 1
Very Short Answe r Typ~ Questi ons
( 1Mar~ )
1 Fill in the Blanks
(i) When unsaturat ed compoun d i.e alkenes are
treated with dihydrog en in the presence of
finely divided catalyst ...... are obtained.
(ii) When alkyl halides are treated with ...... in the
presence of dry ether (free from moisture ) it
results in the formation of an alkane having
double number of carbons as that present in
parent-ha lide.
(iii) Alkanes are ligher than ...... .
(iv} Complete the following reaction.

HI
Dihedral angle
C 12H 26 Pt / pd / Ni
l ......... + CsH 10 + oth er

~~H
973 K
products.
H H
2 Objective Type Questions.
(i) C5HnCl by Wurtz reaction forms
H H 2,2,5,5-tet ramethylh exane as the main
HH Skew H product. Hence, C5HnCl is
H
(a) 2,2-dimethyl-1-chloropropane

AH
Staggered
(b) 2-methyl-1-chlorobutane
(c) Both (a) and (b)
(d) None of the above
(ii} R 2 CuLi is the intermedi ate formed in the
Corey-Ho use synthesis. It is called
Eclipsed
(a) Corey-House reagent (b) Gilman reagent
Newman 's projections of ethane
(c) Frankland reagent (d) Schmidt reagent
_H_y_ _ r_b_o_ns_ __ __ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __j_l_::
dr_o_ca 55~

Structures of
C5~group
CorrMP')tl!Jtnq •'',01v1.1s
CH3
fJI'
(vii) I I
CH3-C - CH2 - ( ,ti I (, ( ►I ( II
I I
CH3
(,► I '

CH 3
CH, o~• ...,., ,·bot "ll
(viii) I I I
CH 3 -CH -C H- CH
3 U t1 (;H u, Cf ' 1

25. (i) The

.
stability f t .
. o . s ructural isomers generally Th"'" illt thrrt' d1fft'n·nt p<,1thOU.'1 ,..., tht, u,ubk
mcreases with mcrease in branching. Thus, hond , hf'nr.- th.,. thrrl' 1it1Ternir ~lkirM, ,,~
Pentane [CH3(CH 2)3CH 3) < iso-pentane rt l,-t. C' H~ 'H, .C H, C CHI H,
[(CH3)2CHCH 2CH 3] < neo-pentane, [(CH 3)4 Cl Ill
r H,
(ii) (a) CH3CH = CH 2 + H 2 Pt, Pd or Ni CH CH CH
( 11, nt nt cu~
J:'ropene Catalyst 3 2 3
Propane [ 1J
< ll,
(b) CH3-CH2-CH2Cl Zn /HCI CH - CH - CH
or LiAIH 3 2 3
(iv) The Cl < 1 bo.rul n,u,;t ht' brok,·n io for111 < ·1 r ~
... ) Th alk
(lll 4 Il l
e enes must have the same carbon skeleton as befort- the ceJCoon w,th 111r.th<1J1t- l1w1 ti;,n••ly-t;"< ~ "
2-methylbutane. energy. wtm.· h t, ,upphrd t'tlht'r hy ht"<ll ot h11,hl Il
C-C-C-C
I
C

TOPIC I nsaturated Hydrocarbons (A IRenes)

The unsaturated hydrocarbons having atleast one double
bond are called alkenes. Their general formula is C n H ln
(where, n =2, 3, 4 ... ) as they have two carbon atoms less
than the alkanes. These are also named as olefins
(oil forming) as the first member of this class, i.e. ethene
forms oily liquid when treated with chlorine.
Structure of Double Bond
In alkenes, double bond between two carbon atoms
consists of one stron; O' - bond formed by the head on
overlapping of the sp -hybrid orbitals an? one weak
1t-bond formed by the sideways overl~pru~g of two .
2p-orbitals of two C-atoms. The orb1ta diagram ot
ethene molecule is shown as:
2p 2p
1t-bond
H
H Sl,lblc ll\1:.' tnbc:r ot .ilkcnc '>enc:)_ lt:. l..'ommon n:imc ~
1t-bond
Ethylene molecule
Both the C-atorns \hown above: arc: -hybridised with s/
triangular shape. The C=L double bond (1 .34 pm ) il
shorter than C-C si ngle bond ( l 54 pm).
As 7t-bo nd is a weak bond therefore, can be easily
attacked by the electron defi cient ~peci~ called
electrophiles. Hence, the presence of exposed 1t-bon<l
makes alkene an easier target for the dearophiles.
, Nomenclature
While naming :ilkenes. foUow the foUowing rule~
(according ro lUPAC systcm).
(i) Choose che longest chain bearing double bond.
(ii) Number che (h:iin from che end that i.::. closer co the
, ,;;. - s double bond.
(iii) Write (hc- n.:ioc word and adJ suffL'C 'cne' .
(iv) If ,1ny :iub~cituc.'nt is presenc , ,-.rice i~ name before
che root worJ. The gener.il formul.i of .ilkrne j.,
c ,, H1,,· l'.1..)l 11 = l, \\ c gee : CH 2 (mc:thcne). le h.i.s
very sholl h.df-lik It n=.2, ,,c gt:c C~H-¼' the tirsc
cC h}1k·11c .tnd ll lPAC n.1.mc b cthcnc.
 Che mist ry - Class 11
AJJh,,One lsc
560 I
CH3
IUPAC names of other alkenes are as follows : I CH CH3
IUPAC name (e) CH3 -CH - CH= -
Structure
4 - methylpent - 2- ene
Propene
CH3
But-1-ene
I
But-2-ene (f) CH3 - CH2 -C= CH- CH3
3-methylpent- 2- ene
CH2 =CH- CH= CH2 Buta-1 , 3-diene
2-methylprop-1-ene CH 3
I
(g) CH 2 = C- CH 2CH2CH3
2 _methylpent-1- ene
CH2 =CH- CH-C H3 3-methylbut-1-ene
CH 3
I
CH 3 I
(h) CHz = CH-C H - CH2CH3
3- methylpent-1- ene
Isomerism CH 3
Alkenes can exhibit structural as well as stereoisomerism. I
(i) CH 2 =CH - CH 2CHCH3
I. Structural Isomerism 4 - methylpent-1 - ene
Becatise of the possibility of several structures for a single CH 3
mdlecul;i.r formula, alkenes having adeast 4C-atoms are
able to exhibit structural isomerism. e.g. Alkene with
I
(j) H 3C-C -CH = CH 2
molecular formula C 4 H 8 can have following three structures. I
I 2 3 4 CH 3
I. CH2 =CH -CH 2 -CH3 3, 3 - dimethylbut-1 - ene
But-1-ene (C 4 H 8 )
CH 3 CH 3
2 3 4
I
II. CH3 -CH =CH -CH3 I I
(k) H 3C-C H- C= CH 2
But-2-el!_e (C 4H 8 )
2,3- dimethylbut- 1- ene
J 2 3
III. CH 2 =C- CH3 CH 3 CH 3
I I I
CH3 (l) H 3C - C = C - CH 3
2, 3-dime thylbu t- 2- ene
2-merhylprop-1-ene (C4Hs)

Structure I andll differ in the position of double bond, so 2. Stere oiso meri sm
these are call d p.,,,o sition isome ~ But structure I and III (Geometrical Isom erism )
di · am of carbon atoms, so these are called
~hain isomers. T
us, it is obvious that alkenes generally Alkenes also exhibit geometrical isomerism (a type of
exhibit chain position isomerism. stereoisomerism) due co the possibility of differ ent
geometrical arrangements in space, as rotatio n aroun d the
[Exam ple 11 , Write structures and IUPAC names of double bond is restricted, not free.
different structural isomers of alkenes coresponding to Thus, alkenes having the general formula ITC =CX Y or
C5H12· XrC= CXZ or XYC= CZW generally exist in following
Sol. (a) CH 2 = CH- CH 2CH 2CH 2CH 3 geometrical arrang ements.
Hex-1 - ene (i) Cir-for~ If the identical atoms or group s lie on the
(b) CH 3 -CH= CH-C H 2CH 2CH 3 same side of the doubl e bond, the isome r is called
Hex - 2- ene cis-form. e.g.
Same
(c) CH 3- CH 2 - CH=C H-CH 2 CH 3
Hex-3 - ene
CH 3
I
(d) CH 3- C= CH- CH 2 - CH 3
2- methylpent- 2- ene
 I 561~
- - - - - - - - - -- - - - ---_!----
Hydrocarbons

(ii) Trans-fo rm If the identical at

the oppos ite side of the doub i°:s or group s
.
lte 0~1 1 low,·ver, if Na i11 l1qu1d an,1110111 .1 i-. used in place of
called trans- form . e.g. e ond, the isomer 1s Pd/C, tmns-aH,cnc, a1c the m,1Jor produ ct .
R R'
'-c·,= c ~
~ - C"/y ...
1•.J i<.
fxl z NC • CN'+ Jl l - - I
"'
/ C- or - ""C =c / H H
y [Kl y/ ""IX] Ci1-alkene

R" c--C / H
Due ro differ ent geom etrica l arran . Na/l1qu1dNII ,
RC - CR'+ H 1 - - -~ "-
cis and trans- isome rs differ in theirgpemroent l 'kace, the
,_n sp
• perues I e H/ R'
·1· d I ·
tmg point 1
s solubility , d.1po e mome nt
Alkync
bo1 mg anh me · . ' lram -alkenc
ere; e.g. t e czs, trans- isome rs of but-2 -ene h ave th e
following struct ures. /2.. From Dehydrohalogenation of Al~ Halides
lic po .ash
H When alkyl halides are hea ted wi ch alcoho
CH3 ~
(KOH in alcohol or ethanol), a HX (halogen acid)
or
/ C= C~ molec ule is elimin ated ro give alkene.
H CH3
Due to the elimin ation of H as well as halogen , rhe
Cis-bur-2-ene (bp 277 K) Tram-but-2-ene (bp 274 K) reaction is called dehyd rohalo genat ion .
(DiPole mome ntµ = 0.33 D, polar) µ = 0 (Non-polar)
H H
The bond dipole s of C-C H 3 in trans-form cancel each
I~ la H.
'-C= cl
H
H-C - C-H Ale. KOH
other and thus~ mak~ the molec ule non-p olar. I I ~ ✓ \ H
However, meltm g pomt of trans- form is highe r than that H X
of cis-form. (For more details about the nome nclatu re ~
(X=C l,Br, 0
and isomerism of alkenes, also see the previous chapter.)
This reaction is also know n (s ~-elim inatio n reaction
,
atom
[ Example 12 , Which of the following compounds will since hydrogen atom is elimin aced from the ~-car bon
show cis-trans isomerism? · (carbon atom next ro the carbo n co which halog en i)
rhi'>
(i) (CH 3hC = CH-C2H 5 (ii) CH 2 = CBr2 attached). T he order of reacri viry of halog em cowards
NCERTTextbook reactio n is 12 > Br2 > Cl] .
(ill) CJI 5CH = CH-{ :H 3 X
_(iv) CH 3CH . CClCH-3 · This is because as rhe sjze of halogen increases, C-
bond srrengrh decreases, i.e. ic hcrom«!ii wea.lu:r. l unht:
r,
Sol. For exhib iting cis-tr~ns (or geome trical isomerism, a the order uf re,1erivicy of llkyl group is ,3° > 2° > 1°
molecule must fulfill the following conditions.
(i) It must have atleas t one doubl e bond. Saytz etf Rule l he ,lbove dinun anon i) gover nc\.l h)
(ii) The group s attach ed to each double bonded carbon Sayrzeff rule, :iccor<ling ro which, more ~ub5m utcd (or
atom must be differe nt. more srable, i.e. symm ecricil) alkcne) are chc:- m.11or
(iii) Atleast one same group is present on the two double produ cr of an elimin .uion re.11..1ion
bonded carbon. Structure (iii) and (iv) fulfill all the above A u

conditions, so both will exhibit cis-tran s isomerism. 1. , ·. l'11 1 - ( 111 -l'll -- \ll 1

/p"' ~I ~
Methods of Preparation 11 .. ,u ll ..11"11"
With ln-...r II .11 u 111.- \\ 111.
Following methods can be used to prepare alkenes from 'I hu., lurm, u1<,1 r- pn·l.-11 ..1 I lul• t.., II ~, l, ,.., p,d, 1 rt ti
w m,1101 p1t'<l u-t , 1 .- , ,, 11111~" p1, .. h1, r, 1 t '
different substances:
{ 11 1 l ll 1 11 ! II i ll 1 ! II l ll 1 11 ,
I. From Alt?ynes
When alkynes are treate d with calcul ated quant ity of
dihydrogen in the prese nce of palladised charcoal
partially deacti vated with poiso ns such as sulph ur
c?mpounds, quino line etc., they get reduc ed to .
of
czs-alkenes, i.e. hydro gens are added to the same side
the double bond. Partia lly deacti vated pallad ised 11< 11
C:11 i<'! I ,< II < I l .z , < II 1< !I <
charcoal is know n as Lindlar' s catalyst. M11ur
 _ _ ~ :..=:
AJ .
/~i n~O _ h_ e_m
~n_e_ lS_C_C - -C_la_ss_ ll
.:--
_ is_try
562 / _ _ _ _ _ _ _ _ _ _ _
0 1, =L l I ,
or .RCH =C HR > R(H =( H ,,,.
.' 11 , h t11 1d111 !:' \\ ere given by I /ofm a1111
while working on e(.
pound,. He :rnd ia me ;~ rhc ~rahdirv order nf .l lkcn
J; ,·l1 m111.tr11111 in q11Jtc1n ary ammonium com e ba~i~ of rhc f·...i,c 0 ( form.i11on for ~eom erric JI ,~om
er~ follow cl, e
on th
, , rl.n11,'\f da· dtlkrcn c.c in remi t
f'ln ,·m ,· ,,t bull-.r N(U I~), grou p in
rhc wmpo11n wh ichd orde r: R
·1he findmg~ of H R / R
,k ,r.d, d,,r ~ 11 .1mi1in11 qa 1c i11 tlm tJ~c. R
(, -= (
ann rul e (1 lo(mann " ( '- ( /
f,/
l i,,t111.11111 .11 c know n ,H I Jo(m
he med in place r( ,- , R ~ H JI' f-I
dim .H ll' •t 1. It 1N (tric thyl J minc) can .tlm r,,,l'JJ
( II
y base and poo r
,,( .1k'\, h111" · ~( )II. l:, 1 N i~ a bulk c-nc. chc more
By general rule The mor e- ~ub lc th e ;i_Jk
m1, h 11,h1k dn1~ 111i11imiscs, "l ;,.: 2 reac tion .
easily ir is Form ed.

Q 3. From Vic ina l Dihalid es

D ihali des hav111g rwo h,ilo ge n ,Hom
s Jr .idja ccnr ~ rbon
bu lk_,. h,t!-e as above giv~ I l ofm ann p rodu ce n rnch halide~ arc
A.lro acorns are c.illed vicin a.l diha.lides. Whe
gen aron n .ue caken
(le.~-sub., r-iru ie<l) as maj or product. creaced wirh zinc mec,d. borh chc halo
rhc removal ~f
up by Zn co give .rn ,dke nc. Du e ro
d dehaJogenatJO~ , e.g.
halo gen ,uo ms, che reac tio n is caJJe

CH2 Br- CH 2 Br+ Zn ~ CH 2 = CH 2 + ZnB r2

CH ,CHBr - CH2 8r ~Z n ~ CH JCH

Mil101 Majo r = CH 2 + ZnB r2

T eni ~- buco ride is also a bul ky base. H

subst:iruced (f-iufma nn p rodu ct) a~
ence, gives less
m ajor p rod uce. /4.From Dehydration of Alcohols n cen tra ted
Alco hols (R- O H ) whe n crea ted w ith co
o b tain ed . i.e.
CH _; sulp huric acid at I 70 °C, alke n e is
Conc. H 2S04
CH 3 CH 2 OH 17 0 0
c) CH 2 =CH 2 + H 2 O
Ethanol Erhene

ec ule of wa cer, tbe

Beca use of the elim inac ion of a mol
+ CH 3 CH 2 /= CH 2 reaction is called deh ydration . Sinc
e, presen ce of an acid
is esse ntia l for the deh yd ratio n p roce
ss, so th e reac tion is
hols . It is also
CH 3 also kno wn as acidic dehydration of alco
, beca use o f the
Major (Hofmann ) an exar.1p le of ~ -elim in atio n reac tion

~eh ydro halo gena cion occu r faster whe

reaccion with KO H gives a conj ugat
below
n alkyl hali de on
ed prod uce as show n

KOH (ale .) CH2 = CHCH= CH2

i ::;';;;;•;;~::::: lic
l<olbe's Electrolysis
Acid :

CH-, CH CH= CH 2 ium sal ts o f

~ I ll ~ The elec trolysis of sodi um o r po tass
alke ne and
Br 7C-bonds in conjugation dicarboxylic acid solu tion s releases
ss is kno wn as
carb on diox ide at ano de. Thi s p roce
s whe re
Ho-11e-1er, it occu rs wirh difficu lty in case Kolbe's electrolysis .
. e.g.
u.1njugacion is al read y present in subs trate -+
cl H2COOK Electrolysis CH2
CH3 -C = CH- CH3 --- --- 41/ + 2C0 2 i + 2K0 H + H 2 i
~t; \
-+
CH2C00 K CH2
H \\ (Di-potass iu m ~

I.,,,,, . pai r\ and 7C· bond in conj uga tion succ inact::) At anod e Ar c:11ho'-lt•

orde r
• L;,_•,1; rA rhc f()rm atio n of alkenes is in H and h en ce :i.Jkaline.
T h e resu lting solu tion co nrai ns KO
k/ , ( J<'I,... R2C =C HR > R 2C= CH 2
 I 563
~ ~~ -- -- -- -- -- -- -- -
...,
Hydrocarbons

. dd. · roduct.
Step III Attack of nucleophile to give a mon P
Physical Properties
"-- + / •.Nu- ~ "--C -C(
I'
l. Physical State . Colour and Odour /C-C ~ + / I
alkenes are gases , next 14 are 1·iqui·ds and
First three .d I
E
~ E Nu
l
rest are so i s. Al~enes are colourless and odourless Addition product
except ethene which has faint sweet odour.
A briefdescription of the reactions gi,ven by alkenes is as foll.ows :
2. Boilin·g and Meltin g Points
1. Addition of Hydrogen
Al~enes show simi~ar ~rend of boiling and melting Alkenes when treated with H 2 in the presence of finely
points as alkanes (i.e. mcreases with increase in divided Ni, Pd or Pt, give alkane as the product.
molecul~r m_ass but decreases with branching) but
geomet n~ isom~rs behave differently. Cis-alkenes have I I Ni,Pd I I
higher boilmg pomt as compared to their -C= C-+ H - H - ~ - C - C -
104 kcal or Pt I I
trans-iso~ers. However, melting point is higher in case 40 kcal
of trans-isomers. _ H H
2 x87 kcal

3. Dipole Mome nt and Densi ty !!,,Jf = - 30 kcal mol - 1

In general, trans-form has almost zero dipole moment The evolved heat is called heat of hydrogenation.
and thus, exhibits weaker intermolecular attractions.
These are lighter than water and the density gradually 2. Addition of Halog ens
increases with rise in molecular mass. Alkenes give addition product, i.e. vicinal dihalides, when
treated with halogens like Cl 2 or Br2 . 12 does not give this
Chemical Properties reaction under normal conditions of temperature and
Alkenes generally undergo electrophilic addition pressure.
reactions because of the presence of a double bond CC1 4
+Br-Br--➔ CH 2 -CH 2 These
(a strong a and a weaker 1t-bond), 7t electrons of which CH 2 =CH 2
being loosely held are easily polarisable. Ethene I I
Br Br
These reactions involve cleavage of a 7t-bond and 1, 2-dibrom oethane
formation of two new a-bond s.

1- 1(
reactions proceed through the formation of cyclic haloniu m
) c=c ( + E - N u - ) ion (more about which you will read in higher classes). The
E Nu solution of bromine in CC1 4 is reddish orange in colour.
In polar solvents, addition proceed by ionic mechanism When any unsaturated compou nd is added to this solution ,
( at low temperature), whereas in the presence of light its colour gets discharged due to the additio n of bromin e at
or non-polar solvents , the addition occurs by free the unsaturation site ( = bond). This reaction is used as a
radical mechanism (at high temperature). Apart from te~t for unsaturation.
addition reactions, alkenes also participate in the
oxidation, ozonolysis and polymerisation reaction. 3. Addition of Hydro gen Halid es
The mechanism involved in ionic electrophilic addition When alkenes react with hydrogen halides (HCl, HBr, HI),
reaction are as follows : alkyl halides are obtained. The order of reactivity _of
Step I Ionisation of reagent to generate electrophile hydrogen halides toward this reaction is
and nucleophile. HI> HBr > HCl
E-Nu ---? E+ + :Nu - (i) If the alkene is symmetrical, only one produc t is
formed. e.g.
Step II Attack of electrophile on alkene. CH 2 =CH 2 + H-Br ~ CH 3 -CH 2 -Br
~ / Slow CH 3 -CH= CH-C H 3 + HBr
e + ) C = C"-._ ~
~ CH 3 -CH 2 - C H CH 3
Alkene
E I
Carbocation
Br
 AJJin()ne ISC Chemistry - Cla ss~
564 I
(C6H 5CO) i O~ CH -CH
are CH3-CH =C H2 +HB r . 3 I 2
(ii) If the alkene is unsymmetrical, several prod ucts
obtained and the nature of major prod uct depe nds CH 2Br
upon the reaction conditions. e.g. If HBr is adde
d 1-bromopropane
to an unsymmetrical alkene, say prope ne, the
e as majo r prod uct can also
following products are possible. the reaction.
Form ation of 1-brchom~pllrop:g mech anism of
CH 3-CH =CH 2 + H-B r be understood by e ro owt
H-C H3 Mechani sm
---+
CH 3-
1
Br
. . k la byftee radical mechanism and
This reaction ta es P ce
2-brom ?ropan e involves the follo wing steps: •
[
CH 3-CH 2- CH 2- Br Step I Initiation Gene ratio n of free radical (Br)
1-bromopropane 0 0
II 11 11 Homo lysis

Howeyec I is rbe majoc p ~ce with_ c 6H 5- C - 0 - 0 -C -C 6H 5

MarkownikofF s rule It states that negative part of Benroyl peroxide
0
the addendum (adding molecule) gets attached to • •
of 11
'-!!1at carbon atom which possesses lesser numb er H
2C 6 5 - C-R : ~ 2 C 6H 5 + 2C0 2
hy?in,grn arqm . This can also be understood by
consi dering the mechanism of the reaction. Homolysis C H ·
C 6 H 5 +H -B r - - - -
8 6 6+ r
Mechanism
Sup I Generation of eleccrophile H Br ~ H + + Br - Step II Propagation Attack of Br · at doub le bond
(0 •
Sup II Attack of elecuophile on double bond C H 3-CH =C H 2 + Br
(gene ration of carbocation)
2 I l Homolysis
H 3C-C H=C H 2 + H-B r
lw
H3C -CH 2-C H 2 + Br-
+ +
H 3C-C H- CH 3 + Br- I -CH J~
CH~ -CH
.,
(b) More SLable
Br
Ca) 1--= sc.able primary
r.econdary carbocarion (a) (Less scable (b) (More sra ble
c.arl>ocacion
(so readily arcacked by Nu -) primary free radical) secon dary free radi cal)

Step III Attack of nucleophil e (here Br - ) on rhe more (ii) CH 3 - C:H- CH zBr+ H- Br Homolysis
stable carbocari on.
,-- C H3 -C H 2- C H 2 Br + Br
Br- \
( Major produ ce)
Hl:- --CH-CH 3- H3C -CH - CH3
I (iii) CH 3 - CH - Cl-l.z + f-1 - Br Homolysis
Br I
2-bromopropane Br
(major produ ce) CH + n•
C H3 - CH-
Note Less stable carboca11on 1s also auacked by
Br but with a I 3 r
rate so, gives a lesser amoun t of prOdu ct
slower
Kharash effect
Br
Ant1 -Markownikoff add1t1on or peroxide effect or (M ino r produ ct)
/ al alkene say propen e 1n the •
If HBr 1s added to an unsymmetric Br
presence of peroxi de, 1-brom opropa ne 1s the maior produ ct in Step III Termination Br + Br ~ 2
(It states that the
accordance with anti Markown1koff or Kharash rule HF, HCI and HI th .
negat ive part of the addendum goes to that carbon
atom which has In case of , e OlaJor prod u rcmarn .
rhe same whether rh e alkene •, . ct
more number of hydrogen atoms). is symm etri cal
This is also called peroxide effect or Kharash
effect (first observed unsymmetrical in case 0 ( anr I·- markown.ikoffo, r add· .
Khara sh and FR Mao 1n 1933). It Jon .
by MS
 ~ -r-,~J
Hydrocarbons V\ \..l.. •"" ·• .,.at fr- l w""
-
This is because
Note th
.
(a) The bonds between halogen and h Yd rogen 1s If an alkene is treated with Hg(OCOCH 3 )2 , Na8H4 I Na_OH, ~
. very reaction a~
strong m HF and HCl that's why frRo·
, eera
dical.1s reaction is called oxymercuration-d emercurat1on
the product is obtained by adding a water molecule in
unable to break them homolyticall Th . accordance with Markownikoff's rule .
procedure is not modified. y. us, reactton

(b) In the case of HI, although RO. free radical

produces homolytic cleavage but 1·, free radical
formed has more tendency to form I 2 as compared to
c fr
rorm ee ra
dical f carbon.
O
If an alkene is treated with B2H6 /H 20 2 , OW the reaction is called
hydroboration-oxidation and the product is obtained by adding
[ Ex~mple ~4 1. ~rite IUPAC names of the products a water molecule in accordance with Kharash effect. I
obtained by addition reactions of HBr to hex-1-ene.
NCERT Textbook
(i} In the absence of peroxide (ii) In the presence of peroxide.
CHlH = CH2 H O
Propene
B2H6
2 2'
ow CH3CHlH20H
.

Propanol
)
Sol. (i) CH 2 = CH-C H 2-CH 2-CH 2-CH
3 6. Oxidation -- -
Hex-1-ene
+ H-B r---- + (i) Complete Combustion In the presence of oxygen,
alkenes burn to give carbon dioxide and water
No peroxide

CH 3 -CH- CH 2-CH 2 -CH 2 -CH 3 (steam) along with large amoun t of heat
I
Br
2-bromohexane e.g. CxH Y + (x+ f)0 2 ~ xC0 2
(according to Markownikoff's rule)
CH 3 + y H 2 O+he at
(ii) CH 2 = CH- CH 2 - CH 2 - CH 2 -
2
+H- Br~
■
Peroxide
C 2 H 4 + 30 2 ~ 2C0 2 + 2H 2 0 + heat
Br-CH 2 -CH 2 -CH 2-CH 2 -CH 2-CH 3 ■
Heat ·or con~bustion of alkanes contai"rung mo re
1-bromohexane (according to anti- Markownikoff 's rule) ~ ing
hydrogen atoms is greater than the correspon
4. Addition of Sulphuric Acid ~kenes._ The c~-isomer, which is de~tabi lise~ by the
mteractton of two large groups (stenc. repuk on
Alkenes react with cold concen trated sulphuric acid to heat
give an addition produc t in accordance with the same side of the double bond, has a higher
Markownikoff' s rule. of combustion than does the trans-isomer. Since the
0 reaction is exothermic, smaller the !1H is
II (numerically) , the more stable is the alkene relative
H 3C-CH =CH 2 + H-O -S-0 -H ~
II to its parent alkane. For isomeric alkenes, !1H
0 increases with increase in stabi~
OSOzOH (ii) Cold Alkaline KMnO 4 or'Baeyer's Reagent ~d
I Al~)lig.e 1'Mn ~ Gxidises_ alkene ·to- glycol and its
CH 3 -CH- CH 3 or C 3H 7HS0 4 pink colour fades (decolourt°es)~ t is also considered
Ethyl hydrogensulphate
as a test for unsaturated hyd-.iocarbons called Baeyer
of Water (Hydr ation) test and alk.KMnO 4 is called Baeyer reagent.
5. Addition 298-303K
When alkenes are treated with a few drops of 3CH 2 = CH 2 + 2KMn0 4 + 4H 20--- -4
concentrated sulphuric acid, additio n of water takes place CH 2-0H
.in accordance with Marko wniko ff s rule and alcohols are 3I + 2Mn0 2 + 2KOH
obtained as the produc t. CH2- 0H
~ - H+ H3C"-. The reagent is used at room temper ature, otherwise at
-C=C H 2 + HOH - . /C-C H3
CH 3 higher temperature carboxylic acid and ketone are formed.
\~ H3C I
CH 3 OH The addition of 2 - OH groups by alk. KMnO 4 1s
2-methylpropene 2-methylpropan- 2-ol .ryn-addition.
I 56 6 I Allin-One ISC Ch em istr y - Class 11

CH3 7. Polymerisation
I Whe n a large num ber of mono°?'ers (~ma
H-C -O H ll molecules)
I combine to give a molecule bearing high
molecular mass,
H-C -O H called the polymer, the process is called
polymerisation.
I The polymerisation reactions can be seen
CH3 as :
meso
High temperature/pressure) tCH -CH
n(C Hz- CHz ) c al };,-
CH3 0 0 Ethen e ~ 2 2n
at yst
CH 3 CH = CCH 3 ~4
I KMn0 I I Polythene
CH 3 COH + CH3 CCH High temp eratu re/pr essur e
3
Li n( CH3 -CH = CHz) Catalyst -{C H-C Hz\ -
Propene 1
0 CH 3
KMn0 4
C3 H 7 CH = CH 2 ~ II ·
C3 C7 C OH+ CO 2
Polyp ropen e
Li
Above reaction also concludes that heat or Polymers are used for mak ing plastic bags
acidic KMnO 4 is , squeeze
bottles, refrigerator, dishes, toys, pipes,
the stronger oxidising agent than alkaline radi o and TV
or cold KMnO 4 cabinets etc. Poly prop ene is used for mak
or Bayer'. s reagent. ing milk crates,
plastic buckets and othe r mou lded artic
(iii) Ozo noly sis Alkenes react with 0 les. Poly then e is a
polymer of ethene. Excessive use of poly
3 to give ozonide then e and
whic h on redu ctio n with Zn -H 0 cleav polypropylene is a mat ter of great conc
2 ed to give ern.
smaller molecule. e.g.
0
Us es
CH 3CH =CH 2 + 03 -C H -C JIC The impo rtan t uses of ethylene are as follo
3 H 2 ws:
Propene I I (i) It is used for the artificial ripe ning of
fruits.
0 0 (ii) Ethylene is used to prep are the poly
Propene ownid e then e whi ch is ar
Zn+ H 20 imp orta nt plastic and finds a vari ety of
CH3CHO appl icati ons.
+ HCH O (iii) It is used as a general anaesthetic.
Ethanal Methanal
Note (i) To determine product by ozonolysis (iv) It is used as a start ing mate rial for
of alkenes, break
the synt hesi s of :
/ C= C bond and place oxygen at breaking large num ber of orga nic com pou nds such
point. as ethylene
glycol, ethyl halides, ethyl alco hol etc.
H3C""- ?H 3 H3C" "- ~H 3
H/C =C" "-H -- H/c c ""- H LJ
/
/ Hypothetical interm ediates
double bond is cleaved B Topic Practice 2
H3C-C H~C H-C H (il
03
3
/ ' t Ve ry Short An sw er Type Qu est ion s
(ii) (CH3)2S

=0 here 0= here H3C CH= O + O=C ( 1 Mart? )

HCH 3 .
(ii) This reaction is also helpful for deci 1. Fill in the Bla nks
ding the structure
of alkene and location of double bond
. To decide the (i) The gen eral form ula of alke ne is ......
structure of alkene from ozonolysis prod .
ucts, bring the
products together in such a way that their (ii) Alc oho ls whe n trea ted with con cen
O-atoms are trat ed
face to face , replace O byC =Cb ond .
Thus, sulp hur ic acid at 170°C ...... is obta ined .
H3C "-._ ,- - - - - -, / CH3 Reversely (iii) Com plet e the foll owi ng reac tion
-. ./C= O+O =;=C , :
H<- L - - H replac e O by C =
- - - ' '-
C bond CH 3-C H = CH 2 + HB r~ CH -C H
3 2
I
CHzBr
(iv) Alk yne s on hyd rog ena tion with ........
. or with
Na or Li in liqu id amm onia give s alke
nes.
 1
()v,nol f"'
1 \ low
C ll 1
('11 ( II ., I IJ - _. CH -1- Cfl - ('IJ ,1 CH / ..J-JzCI IO + CH,,C..OU r.j '
flropcrrc ~" carbon,tion (Ff) /f I
CH1
( More s1nblc) I Jlut Y\in0 1
CIJ 1 CH/ ' H = C- Cl f3
-1•,;nt
11
'-➔ Cil 1- C1l-
I Clf1 ( A) <.. H~

Hr C.H-,CH 2COOH + CH 3 -C = <J

(~ if1
2- bromopropane 11 J
CH1 CH 1 29 Refer to the text on pages 563 and 564. (Chemical
I I Hea t properti es of alkenes ) ..
27. C I-1 3 - C - C- CH 1 + KOH ----+ 30. Peroxide effect is not observed in a~dl Jbtiondobf 1:fCl and Ht
I I · (Ale.)
This is due to the fact that the H---- on emg
Cl £1 1
(X)
s tronger (430.5 k] mol - ) than H -B r bo nd

CH 3 CH 3 (363.7 k] mol - 1) is not cleaved by the fr~e radical _whereas

CH 3 CH 3
I I I I the H- I bond is weaker (296.8 k] mol - ) and iodme free
CH 3 - C = C - CH 3 + CH 2 = C- C- CH 3 radicals combine to form iodine molecules instead of
2,3 -dimethyl but-2-ene I adding to the double bond.
H
2,3-dimethyl · but-1-ene 31. (i) 2, 8-dimethyldeca-3, 6-diene
(Z) [3) CJ-bonds = 33, rt- bonds = 2
28. (B) a nd (C) are CH 3CH 2CHO (propanal) and (ii) Octa- I, 3, 5, 7-tetraene
CH 3 COCH 3 (propanone). Hence, A is CJ-bonds = 17, 1t-bonds = 4
H CH 3 (iii) 2-propylpent - 1-ene
I I CJ-bonds = 23, rt-bonds = 1
CH 3 CH 2-C= O+ O=C-CH3 ~CH3CH 2CH=C-CH3 (iv) 4-ethyl- 2, 6-dimethyldec-4-ene
JH 2-melhylpent-2-ene (A) CJ-bonds= 41, 1t-bonds = I
3

TOPIC
03 Unsaturated Hydrocarbons (AIRynes)

The compounds contammg adeast one triple bond are 2. IUPAC System
called alkynes. It is another class of unsaturated The IUPAC name of alkyne is written by replacing -'ane'
compounds, having 4C-atoms less than the alkanes, so, of alkane by a suffix -'yne'.
general formula of these compounds is CnH zn - 2 (where The position of triple bond is indicated by arabic
n = 2, 3, 4). The first stable member of this series is ethyne numbers, the numbering being started from that end
(or acetylene) which is commonly used for arc welding in which lies closer to the triple bond.
the form of oxyacetylene flame obtained by mixing
Common and IUPAC name of alkynes (CnH 2 "_ 2 )
acetylene and oxygen gas.
Formula Structure Common name IUPAC name
Nomenclature C2H2 H- . C= C-H Acetylene Ethyne
Nomenclature ofalkynes can be done by the following systems :
C3H4 H3C-C= CH Methylacetylene Prop-1-yne
1. Common System C4H5 H3C-C = C- CH 3 Dimethylacetylene But-2-yne
According to this system, higher members of alkyne ale
CsHs H3C--C =C--CH 2CH 3 Ethylmethylacetylene Pent-2-yne
named as the sk_rivatiyes a£ aq;cyleoe, i.e. CH == CH , e.g.
CH 3 - C === CH, methylacerylene.
--
Hydrocarbons I 573

Isomerism
Structure of Triple Bond
t)irncs, cycloalkcnes and bicyclo lk I
,c ncd formula of C H a ane a so have the ln cthyn e (the first member of alkyne series), both th e
~ . f . lk ~ n 211 - 2' hen ce they are the isomeri c carbon atoms has two sp hybridised orbitals. Out of
for111~ o ,1 ync . 1 hus, alkyne shows .. h .
· · I d · . · posmon , c a1n, whi ch one form sp-s a bond with ls orbital of H atom.
hJn(tiona an ring chain isomerism. The other .rp-hybridised orbital of one carbon atom
&_,1111ples of isomerism of alkyne are tabulated below : ove rl aps axially with the sp -hybridised orbital of other
Isomerism to form a C- C <J bond.
Examples
Pos1t1onal isomerism
The H- C -C bond angle is 180°. Each carbon atom
~~~ CCH2CH3 a~d CH~ C
_ ==
_ C_C_H also contain two unhybridised p-orbitals that are
3
Chain isomerism perpendicular to each other and also to the plane of
CH3CH2CH 2C 15 CH and
(CH 3)2CH-C == CH C-C cr bond, but the 2 p -orbitals of one carbon atom are
functional isomerism CH3- CH 2- c == CH , parallel to the 2 p-orbitals of other C-atom. These two
CH2 = CH-CH = CH2 t. \ 2 p-orbicals overlap laterally or sideways to give two pi (1t)
and CH2 = C = CH - CH3 C'-l r • ..) bond between two carbon atoms as shown below :
Ring-chain isomerism /\
ls ls
CH 3C = CH and ~
~d=>c~
~ p sp (a) cr
Note Alkynes are linear molecules that have an angle of 180°.
Therefore, alkynes does not show geometrical and In chc plane
stereoisomerism . of paper

[Exam ple 5 1 Write structure of different isomers

corresponding to the 5th member of alkyne series. Also write
IUPAC names of all the isomers. What type of isomerism is 2~ n GAC
exhibited by different pairs of isomers? NCERTTextbook n ~
Sol. Molecular formula of 5th member of alkyne is C 6H 10 . Above the plane ""'- In the plane
of the paper (b) of the paper
The possible isomers are :
Orbital picture of ethyne showing
(a) HC = C-CH 2 -CH 2 -CH 2 -CH 3 (al sigma overlap (bl pi overlap
Hex-1-yne
Thus, in ethyne molecule, there are one C-C cr bond,
(b) CH 3-C= C-CH 2 -CH 2 -CH3
Hex-2 -yne
two C-H cr bonds and two C-C 1t bonds. The C===C
bond is stronger (bond enthalpy 823 kJ mol - 1 ) and shorter
(c) CH 3-CH 2 -C = C-CH 2 -CH3
(120 pm) than the C=C and C-C. Electron cloud
Hex - 3 - yne
between two C-atoms of ethyne is cylindrically symmetrical
(d) HC=C-CH-CH 2 -CH3 about the internuclear axis, so ethyne is a linear molecule.
I
CH 3 Methods of Preparation
3-methylpent-1-yne
Following methods are used to prepare alkynes.
(e) HC = C-CH 2 - CH -CH3
I 1. From Calcium Carbide
CH 3 When calcium carbide is treated with water, ethyne is obtained.
4-methylpent-1-yne
CaC 2 + 2H 2 O ~ Ca(OH)i + C 2 H 2
(f) CH 3-C= C-CH-CH 3
I Calcium carbide is prepared by heating the lime stone
CH3 and then treating the obtained quicklime with coke at
4-methylpent-2-yne high temperature.
CH 3 CaCO 3 ~ CaO + CO 2 i
I (
(g) HC = C-C-CH 3 CaO+3C~ CaC 2 +CO
I C.tlcium carbide
CH 3 Note Other metallic carbide of group II (alkaline earth metals) also
3,3-dimethylbut ~1-ync give the similar reaction with water.
 2. From Natural Gas Chemical Properties
Natural gas (mostly CH 4 ) can be converted into acetylene Alkynes exhibit the following characteristic reactions.
when it is heated for a shorter period.
1770 K
1. Acidic Character of AIRyne
6CH 4 +20 2 -----+ 2CH==CH + 2CO 2 + 10H 2 In ethyne (or alkynes) the sp-hybridised carbon .atom
Cracking
possesses maximum s-character and hence, maximum
1
2CH 4 ;~~ : HC == CH+ 3H 2 electronegativity. Due to which, it attracts the shared
electron pair of C-H bond to a greater extent and
This method is also considered as industrial method for makes removal of proton easier. That's why the
the preparation of ethyne.
hydrogen(s) attached with the tr~ply bonded c~rbon
3. l<olbe's Electrolysis atoms are acidic in nature and gives the followmg
Electrolysis of concentrated solution of sodium or reactions.
potassium salt of fumaric acid gives acetylene. Other (i) Reaction of alkyne with Na in liq. NH 3 or
alkynes can also be obtained by this method. NaNH 2 : Alkynes form monosodium ethynide and
disodium ethynide.
CHCOO-Na+ CH
II Current) Ill + 2CO + 2NaOH + H CH 3 -C==C-H + Na+NH 2 ~
+ + 2H2 O 2 2
CHCOO-Na CH ~ CH 3 -C====C-Na+ + NH 3
Sodium fumarate ~
Sodium propynide
4. From Vicinal Dihalides (ii) Reaction with Tollen's reagent With Tollen's
(Dehydrohalogenation) --·-·<: ~. reagent (ammoniacal AgNO 3 ), a white precipitate
Vicinal dihalides when treated with alcoholic KOH 'and of silver salt is obtained.
N aNH~ undergo dehydrohalogenati~iv:@..fespec;ive H-C==C-H + 2AgNO 3 + 2NH4OH ~
alkyn,es; e.g. Ag-C==C-Ag+2NH 4NO 3 +2H 2 O
H Silver acetylide
(white ppt-)
I
H C-C-H ,.. KOH Alcohol
H"- /H
2 /C=C""- These reactions are not shown by alkenes and alkanes,
/ / f I -KBr H Br hence used for distinction between alkynes, alkenes and
' I -H2 0
Br Br \J Na+NH;j" J-NaBr
alkanes. The order of acidity of different compounds is
? -NH 3 (i) HC==CH> H 2 C=CH 2 > CH 3 -CH 3
\. /.,
(ii) HC . CH>CH 3 -C==CH
~ CH==CH
>> CH 3 -C==C-CH 3
Alkyne
2. Addition Reaction
Physical Properties Alkynes also undergo electrophilic addition reactions.
(i) First three members of alkynes are gases, next eight Because of the presence of a triple bond, two moles of
are liquids and higher alkynes are solids. the reagent are added to it.
(ii) All alkynes are colourless and odourless except Mechanism
acetylene which has garlic odour. It involves the formation of vinylic cation and then
(iii) Melting and boiling points and densities of alkynes addition product.
are slightly higher than that of corresponding · H H Z
alkenes and alkanes. These properties generally H+ I Gl - I I
increases with increase in molecular mass. -C=C-+ H-Z ~ -C=C-+ :z --? -C=C-
Vinylic cation
(iv) These are lighter than water and also insoluble in it.
However, they are soluble in non-polar solvents like The addition product obtained depends upon the
benzene, ether etc. Alkynes are weakly polar in stability of vinylic cation.
nature.
 0 t<J d v--, A
I
Jr
~ va \ I s1~
Hydrocarbons
- / ' /lo f; u /' \
~ . ·1 r co alkenes .
or less s1m1 a d isJ resent m
. I . . . al bon
accordance to (ii) Ozonolys1s t 1s more
The addition of reagent takes place in except the fact that an ad~ 1t1onh roducts s follows
Markownikoff' s rule. ozonide. Its presence modify t e P
(i) Addition of Dihydrogen Ste p I Ozonide form atio n
/ 0\
CH2Cl2 R C-- C- R ~
--
Hc == CH + 8 2 _ _Ni_,. [H 2 C= CH 2 ]
Prl_Pd/ I Reductive
R-C == C-R +0 3 ~ -
1 hydrolys is 2
Alkene :,
0- -0 (Strong reducing
Ste p II Ozonide hydroly sis Ozo nide
agen t like
LiAJ H4)
Alkane Oxidative hydrolys is H H
(ii) Addition of Halogens (H20 2)
- Br R- C- OH
I I
2
HB r] Redu ctive R- C- -C -R
CH 3-C == CH ~ [CH 3CB r=C I hydrolys is 1 .
I I
1, 2-dibromopropene 0 + (Moderate reducmg
I i agent like Zn) OH OH
R- C- OH
Br2
~ CH 3CBr2CHBr2 I R- C- C- R ,_________,
o 11 II
1, 1,2,2-tetrabromopropane 0 0
red brown colour of bromine as one of the pro duc ts
Note Alkynes also decolourise the for unsaturation. Terminal alkyne gives HC OO H
water (in CCl 4 ). This is used as
a test and H2 0, CH == CH
which is further oxidised to CO2
as
(iii) Addition of Hydrogen Halide gives glyoxal as well as formic acid
CHO
~l fy -_C===CH + H- Br ~
- I
3 +H CO OH
[CH 3 -C (B r) =C H 2 ] ~
(i) 0
CH == CHH-- CH O Formic acio
(iil 2 0
2- bromopropene
~
CH 3 -C (B r) 2 -C H 3
2, 2-dibromopropane (iii) Oxidation with KMtfC5'.;
r's reagent) term ina l
the presence of (a) With cold alk. KMnO 4 (Baeye
(iv) Addition of Water It occurs in non -ter min al
mercuric sulphate and dilute sulp
huric acid at alkynes give carboxylic acids while
the product of this alkynes give diketones .
333 K. Carbonyl compounds are
reaction. Oxidised to Ter min al -C H oxidised
Hg2 +/H +
K carboxylic1 / to CO2 and H2 0
CH == CH + H- OH 333
Ethyne

CH 2 =C -H
I
OH
-
Isomerisation
CH 3-C -H

Ethanal
II
0 CH3 -C ==
l KMnO,, KOHr
CH +3 [0] - - -
Ter min al alky ne
0
11

CH - C -C OO H
3
]

3. Oxidation Reactions ~ CH3COOH + CO 2 i + H 2 0

n reactions by
Alkynes give following types of oxidatio -- -4
KM n0 4 , KOH
combining with different oxidising age
nts. CH3 - C= =C -C H3+2 [0 ]-
presence of air Non-ter min al alky ne 0 0
(i) Complete Combustion In the
(or 0 2 ), alkynes undergo combus
tion to give carbon I I
e amount of heat CH3 - C - C- CH
dioxide and water along with larg
combustion But an-2, 3 -dio ?
and light energy. The generalised
reaction is
con diti ons give
C n H ln- l
-1)
+ ( -3n -
2
0 2 ~ nC0 2
However, acetylene und er these
oxalic acid .
-2 ) H 0 + Energy
+ ( -2n -
CH CO OH
. 2
2
Ill + 2[0 J
KM n0 4 / KOH CH =O j
I 2[0 1 I
373-383K
CH
r
CH =O
Gly oxal
CO OH
Oxa lic ac id
 576 I Allh,,One ISC Chemistry - Class 11

(b) With hot KMnO 4 Cleavage occurs at the C=== C give a high molecular weight polyene, called
polyacetylene -tCH=CH-CH=CH1n .'
resulting in the formation of carboxylic acids.
which is a conductor of electricity under special
With non-terminal alkynes a mixture of two conditions. Thin film of polyacetylene is good
carboxylic acids are obtained while with terminal conductor, lighter and cheaper than the metal
alkynes, one carboxylic acid and CO2 is produced. conductors, so it is used as electrode in batteries.
In general, ==CH is oxidised to CO2 and =CR is
(ii) Cyclic Polymerisation When ethyne is passed
oxidised to RCOOH.
through red hot iron tube at 873 K, it undergoe~
CH3-C==C-CH CH KMn0 4 ! KOH cyclic polymerisation to give benzene, an aromatic
2 3 373-383K compound. Thus, this reaction is the best route for
entering from aliphatic to aromatic compounds.
CH3COOH + CH3CH2 C00H
Red hot
CH3-C==CH + 4[0] KMn04 /KOH iron tube
373-383K 3CH==CH 873 K
CH3COOH+ CO 2
However, acetylene under these conditions gives
CO2 andH2 0. Uses
(i) It is used for the artificial ripening of fruits and
IIIH+4[0] KMn04! KOH [,OOH] vegetables.
CH 373-383 K COOH (ii) It is used as a starting meterial for the formation of
acetaldehyde, acetic acid, ethyl alcohol etc.
[OJ
~ 2C02 + H2 0 (iii) It is used as a starting material for the preparation
of plastics, synthetic rubbers and synthetic fibre
orion.
4. Polymerisation
(iv) It is used for cutting and welding of iron and steel.
(i) Linear Polymerisation Under suitable conditions,
ethyne molecules undergo linear polymerisation to

Distinguishing Test between Alhane. Alhene and Alhyne

Different distinguishing tests are as follows:
Ethane and Ethyne
Ethane Ethyne
s. Reagent
No. Observation Reaction Observation Reaction

1. Br2 solution No effect Br2 solution is Br Br

(in CCl 4 ) decolourised due to I I
electrophilic addition . CH == CH+ 2Br2 CCI 4 CH-CH
Red I I
Br Br
Colourless

2. Aqueous No effect Aqueou s KMnO 4 CHO

KMn0 4 (neutral) (pink) is decolourised 3CH == CH+ 4Mn0 4 + 2H 20 ~ 3 I + 4Mn0 2 + 40H-
and black/ brown CHO
precipitate of Mn0 2
are formed .
3. Warm alkaline No effect Warm alkaline KMn0 4 , 0
KMn0 4 gives oxidative Mn0 4/ 0W II
RC=CR 2Rco-
cleavage of (C =C) ~
bond to form salts of
carboxylic acids.