0% found this document useful (0 votes)
22 views37 pages

SplitPDFFile 5 to 41

Organic chemistry is defined as the chemistry of carbon compounds, which includes hydrocarbons and their derivatives. The study of organic compounds is justified due to their vast number and unique chemical properties, comprising about 90% of all known compounds. Organic compounds are essential in daily life, serving as food, clothing, fuels, medicines, and more, with sources being both natural and synthetic.
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
0% found this document useful (0 votes)
22 views37 pages

SplitPDFFile 5 to 41

Organic chemistry is defined as the chemistry of carbon compounds, which includes hydrocarbons and their derivatives. The study of organic compounds is justified due to their vast number and unique chemical properties, comprising about 90% of all known compounds. Organic compounds are essential in daily life, serving as food, clothing, fuels, medicines, and more, with sources being both natural and synthetic.
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 37

1

·INTRODUCTION. TO
ORGANIC CHEMISTRY

1.1 DEFINITION OF ORGANIC CHEMISTRY


2C + H2 Electric) HC=CH Dil. H 2S0 4 )
(HISTORICAL BACKGROUND) arc Acetylene HgS0 4
A large number of organic compounds*have been discovered
and isolated from natural sources by the first quarter of CH 3CHO Oxidation) CH COOH
3
nineteenth century but till then none of the organic Acetaldehyde Acetic acid
compounds could be prepared in laboratory. This led to Modern definitiou of organic chemistry : Since,
believe that organic compounds followed laws. of fonuation carbon is an .essential constituent of all organic compounds,
different from inorganIc compounds. Berzelius assumed that organic chemistry is defined as the chemistry of carbon
some vital force (life force) was necessary to prOduce organic compounds.
compounds and synthesis of these compounds iIi the Simplest ~rganic compounds are those which are
laboratory was impossible due to the absence of this vital . composed of carbon and hydrogen only and are called
force which only existed in living organisms. . hydrocarbons. Other organic compounds maybe regarded as
derivatives of hydrocarbons obtained by replacement· of
The vital force theory suffered the first deathblow, in hydrogen by any other element or group. Thus, organic
1828, when·. ,¥ohler synthesised first organic compound, chemistry may also be defined as the chemistry of hydro-
urea, in the laboratory by heating ammonium cyanate (an carbons and their derivatives.
inorganic compound).
Heat .
1.2 JUSTIFICATION OF SEPARATE STUDY OF
NH 4CNO -~~) NH 2CONH 2 . ORGANIC COMPOUNDS
Ammonium cyanate Urea
Organic compounds are studied separately because of the
Undergo isomeric change, i.e., (molecular rearrangement)
following two points;. . .
Heat . (i) Large number of organic compounds: Compared
[(NH4hS04 + 2KCNO ) 2NH4CNO+ K 2S04 ]
with the compounds of other elements, the number of organic
[Pb(~Oh + 2NH 40H Heat) 2NH 4CNO+Pb(OHh] compounds is very large. Organic compounds comprise about
90% of all the known compounds.
(ii) Unique chemical and physical properties: . Most
[NH 4CI + KCNO Heat) NH 4CNO + KCI]
of the reactions in inorganic chemistry are ionic and· occur
A further blow to vital force theory was·given by Kolbe, rapidly while most of the organic reactions involve covalent :
in 1845, when he synthesised acetic acid, the first organic bonds and are relatively slow. The phenomenon ofisomerlsm
compound, in ·laboratory from its elements and . later by . and tendency of catenation are unique properties of organic
Berthelot, in 1856, who synthesised methane. compounds.

·Scheele, in the years 1769-85, isolated taf!aric acid from grapes, citric acid from lemons, malic acid from apples, lactic acid from milk and uric acid
from urine, Roulle, in 1773, isolated urea from human urine. Liebig, in 1829, isolated hippuric acid from horse urine and Serturner, in 1805 isolated
morphine from opium.
2 G.R.B. Organic Chemistry for Competitions

Catenation property (long chains of identical atoms) Now-a-days, many of the natural products such as dyes, fibres,
depends upon the value of bond energy which is maximum in rubber, drugs, vitamins, etc., are prepared by synthetic re3btions.
the case of carbon. SOURCES OF ORGANIC COMPOUNDS· .
Bond C":""C Si-Si S...,-SP-P N-N 0-0 I .

t!1:i~ '~J~ ,5ff


,54
~~}~ I
Natural (t ()oAl)
I
Synthetic (90%)
~ ,',:i
'; ."_J ~J~: ;~r "~ .:~ i: . \::t:.:~":-
The stability or strength of the bond decreases as the bond
.el)ergy"d~~$ ~,~t:\'fe~e;lc~\of catellt'tto~ ~r'''''."".~",,~ Pungiand Coal Natural gas
'" )'t·th' ,,,,~ II":' .-.i" ~_~ ~~:~ :H~~ rT '~'~" J-.':~
Ill e ·,0 oWUlg: tnalllllI'.)>(,..,... " ..,\<,., •.'
:',i _ ,> ( t~:t-l:~: .;'..
'."p' ,'." ,Y, ',J" .c micro-organism 'and
C > Si .,. S > P > N > 0 .petroleum
Carbon has the ability to fonn strong covalent bonds with 1.4 IMPORTANCE OF ORGANIC COMPOUNDS
many other atoms such as II, 0, S, N, CI, Br, I, etc. The C-C
bond energy is ,approximately equal to the magnitude of bond Organic compounds play an impljrtant role in our daily
energies between carbon and various other atoms .. activities.. ,Jll~ fo,lc?)ying l!st (:1~!D'JY i!lus~t€:§ th,e i~p'ortance
of organrc'cdl'ilpOUnds;-'f"':" ;;,),".:~ ~'i"}"'J;:iq,:"., : .'
Bond'C-C C..,..,H C-:O G-CI C-N C-Br
1•. FOod: C~y~te~;; !Prt>teiJ1s;j;FatS;~~J\f'itamins;
Bondenergy 83.0 '97.0;' 86.0 81.0 73.0 68.0. Enzymes, etc. '.
(keal mol-I) '. z,•. ClOthes:: Cotton; .Silk; Wool; Nylon;' Rayon;
Dacron,etc. , .
i •. Fuels,:: Coal; Wood; Natural gas'; Petrol, etc.
4'., Mediemes: Penicillin; Streptomycin; Chloromycetin;
.There are two major sources of organic compounds: Sulphadiazine; Sulphathiazole; Morphine; Aspirin; Iodoform;
(i) Natural and (ii) Synthetic. . Cocaine; etc." ,
(@) Natumdl SiluMeSl 5'. Expfosives: Nitroglycerine; Nitrocellulose; T:N:B.;
T:N.T., etc.
. (.,) mimtli:: Carbohydrates (glucose, sucrose, starch, 6l.. Dyes: Indigo; Malachite green; AliZarin,etc.
celhdose), acids, esters, vegetable oils, vitamins, gums, 7.., lnseetielCles: D.D.T; Gammexane; Malathion, etc:
alkaloids, .essential oils, perfumes, ~cohol, acetone, etc., are 8~ Household and otlier commOR artktes.: . Soaps;
some of the iptportant organic compounds which are obtained Cosmetics; Perfumes; Detergents; Paper, Rubber; Plastics;
from plants. . . '., . "
Leather; Resins; Inks; Paints; Varnishes; Photographic films;
@J;») &:niinalS;:: Some of the important organic
etc.
compOunds~ 'which aredel'ived:from 'animals; are proteins,
hormones, fats and urea,;;', ' . " , : . , . ; , ',' '. ,; 1.5 BONDING IN: ORGANIC COMPOUNDS
(~) FUngji andl milu!oJ.oEgfttriSml:: This is the ·source
. responsible for the· production of hosts of useful substances Organic compounds are essentiaUy covalent compounds
like alcohols, acids, antibiotics (penicillin, streptomycin, or covalent bonding is present in organic compounds.
tetracycline) 'and" vitaininsby 'llsing""theprocess of In all organic molecules, carbon atom is tetravalent, i. e.,
fermentation. its valency is four. One carbon atom can share its four
«cl~) COdt ,Coal-tar obtained during destructive . electrons with four atoms of an univalent element (H), i.e.,
distillation of coal is the main source of aromatic hydrocarbons, forming four single covalent bonds, .
phenols, heterocyclic colliPOundS, dyeS~ drUgs; perfumes, etc.
H
H
(~») Naamdtps;amIl~:;. It is one of the major • ·x 1
sources of organic', cotnpOunds.. Gasoline, k~rosene, .C. + 4H x ~H~ C ~ H or H-C-H
lubricating oil, vaseline, paraffin wax, etc., ate few examples
• .x
H
'I
which are obtained directly from peti'oleumby fractional H .'t.

. distillation. Hundreds of useful organic compounds are or one carbon atom can share its four electrons with two atoms
prepared from the wide range of hydrocarbons which serve as of a bivalent element (0), i. e., forming two double covalent
starting materials for the synthetic reactions. . . bonds,
•. xx xx xx
(~») SlIDihetk; Sources; .C.+20~ ~ O~:C:~o~ or O=C=O
• xx xx
More than 90"10 of the known organic compounds are
or one carbon atom can share its four electrons with one atOm
synthetic, i.e., prepared by artificial methods. Simple organic
of a bivalent element along with two atoms of an univalent
·compounds derived from petroleum and coal have been
element, i. e., fonning one double bond and two single bonds,
converted into useful products by synthetic methods.
Introduction to Organic Chemistry .;3
-- ;:

H (ii) Sidewise or parallel or hlteral ~)V(lrlapping: Such


H
• xx •x -x x I overlapping is possible betweeri p-p atomic orbitals. The
2Hx+·C·+0~ ~ H~C:~O~ or H-C=O molecular bond formed is termed as pi (1t) ~ond. .
• xx
Sigma bond is stronger than 1t-bond. The electrons in the
or one carbon atom can· share its four electrons with one atom 1t-bond are loosely held. The bond is easily broken and is
of a trivalent element (N) along with one atom of an univalent more reactive than sigma bond. The amount· of energy
element, i. e.,· forming one triple bond and one single bond,
released during overlapping indicates the strength of the bond.
• xx xx
HX+·C·+N~ ~ H~t:~N or H-C=N Greater· will be the 'strength of bond if higher energy is
. • x ·X
released during overlapping. Energy· released during sigma
Carbon atom has also the wonderful property of uniting bond formation is always more than 1t-bond because of greater
with other carbon atoms through covalent bonds. They can extent of overlapping in the former.. The valency of the atom
link together by single, double or triple covalent bonds depends on the number of cr- bonds formed or cr- and 1t-bonds .
forming long chains or closed structures. formed.
H H H H Tetravaltmcy of Carbon (Hybridization)
ex ex I I
H~C:C~H or H-C-C-H (C-Cbond) The electronic configuration of carbon in ground state is
ex .X
H H 1·" I Ii 2i 2p! 2p~ 2p2. Two Jrorbitals are half filled and there-
H H: ,~ . '-" '. fore, carbon is expected to show a valency of two. But in all
H H H H organic molecules, the carbon atom has a valency of four. It is,
eX .X I I therefore, believed that under the conditions of bond
H~C::C~H or H~C=C-H (C=Cbond)
formation, the 2s paired orbital gets unpaired and one electron
is promoted to the vacant 2 p z -orbital. Thus, in excited state
H-C=C-H (C=Cbond) the . carbon .' •. has' .~ the electronic ,. .- .configuration
H ls2 2S1 2p; 2p~ 2p;, i. e., it has four half filled orbitals which
H
.x I
.c. H-C/ ~C-H
C can be available for overlapping. Under this condition, it can
HxC· ···cxH form four bonds with other atoms. This explains the
or II I tetravalency of carbon.
HxC.
·c····
.cxH H-C,~C~H
.x 2s 2p
H I ;~ I· t·l· I
H
Carbon in ground state'
It
(C-C and C=C bond)
The four valencies of carbon atom are similar and they are
Carbon in excited state ID .1 i Ii Ii I
symmetrically arranged around the carbon atom. According to Available for bond fonnatio~
Le Bel and van't Hoff the four valencies of carbon do not lie in
one plane,:'Theyru:ediJ;ected towards. the £omers of,a·regular On the basis of excited state configuration of carbon atom, it
. tetrahedron with carbon atom at the centre and the angle can combine with four hydrogen atoms to form a molecule,
between any two valencies is 109°28' (or 109.5°). . CH 4.. The three C-H bonds have been formed by the overlap
Modern concept of covalent bonding: According to of three 2p-orbitals with the Is-orbital of each hydrogen atom.
the modem concept, a covalent bond is formed between two The fourth C-H bond is formed by the overlap of2s-orbital
atoms if there is an overlapping of an atomic orbital of one of carbon with Is-orbital of a hydrogen atom. Thus, one bond
atom with an atomic orbital of another atom. For an effective is different from the other three. But this is not true: The
overlap, it is necessary that two atomic orbitals of the two methane molecule possesses the following characteristics':
different atoms must be half filled and approach each other in (i) All the four C-H bonds are identical. This has been
.proper direction. The resultant orbital after overlapping is shown experimentally as methane forms pnly one monochloro
known as molecular orbital and has two electrons with methane.
opposite spins. The effective overlapping is possible by two -H
ways: CH 4 +Cl) CH 3Cl
(i) End to end overlapphlg: This type of overlapping
is possible between s-s, s-p and Jr p atomic orbitals. The . (ii) All the four bonds are not present in the same plane.
molecular orbital formed by the inphase end to end overlap of Actually, there is tetrahedral arrangement, i.e., the bond.,gle .
atomic orbitals on adjacent atoms is c.alled sigma molecular is 109°28' (or 109.5°).
orbital. Such orbitals are lower in energy than the To have' four identical C-H bonds, carbon must
corresponding atomic orbitals. The bond formed is termed as contribute a set of four equivalent orbitals. This is possible if
. si.gn:Ia (cr) bond. one 2s and the three 2 p-orbitals in the excited state mix
together to form four equivalent orbitals. Tbe process of
4 G.R.B, Organic Chemistry (or Competitions

mixjng atomic or.bitals to form a set' of new equivalent H a-bonds H


orbital•.is termed as hybridization.
Shapes of simple organic moleeules
To explain the structures of organic molecules, the
electronic theory of valency and the concept of hybridization
was introduced.
. There are three types of hybridization encountered in H H
carbon atom. These are sp3. sp2 and sp-hybridization.
(i) Sp3 -hybridIZation: . sp3 -hybridization occurs when H H
one a-orbital and three p-orbitals mix together to form four H H
equivalent hybrid orbitals directed towards the corners of a
regular tetrahedron. o
o~ 1.54A
,~ C
H H
Carbon in excited state
H H
Fig. 1.3 Bonding In ethane
(ii) sp:% -hybridization: sp 2 -hybridization occurs when
one &-orbital and two p -orbitals mix together to form three
equivalent hybrid orbitals directed towards the corners of an
equilateral triangle, i. e., the three hybrid orbitals lie in the
same plane. The third 2pz-orbital is left unhybridized. This
Flg.1.1 Orientation of four sp3.hybrld orbitals (tetrahedron) orbital is oriented along an axis perpendicular to the plane of
hybrid sp2 -orbitals. Each sp2 -hybrid orbital and
Each sp3 -hybrid orbital contains one electron. It has 25% 2pz-unhybridized orbital contains one electron.
a-charact~r and 75% p-character. An the four hybrid orbitals
are identical (same energy and shape) but differ only in their
orientation in space with respect to. each, other. The angle Carbon in excited state
between any two hybrid orbitals is 109"28' (or 109S).
When.ever earbon is bonded to four other atoms or 2s
group~.lt uses sp3 -hybrid orbitals. The best examples are IT]
methane and ethane. In methane, four hybrid orbitals of Sp2 -hybridization
carbon overlap with la-orbital of each of the four hydrogen
atoms. The bonds formed are sigma bonds. The bond angles in
methane are also 109°28' (or 109.5°) as the C-H bonds are
also directed towards the corners of a tetrahedron with carbon Fig. 1A Orientation of three Sp2.hybrld orbitals
at the centre. Whenever carbon is bonded to three other atoms or
H H groups, it always uses sp 2-hybrid orbitals and .a p z-orbital
to form its bonds. The best example is ethylene molecule.
In ethylene molecule, each carbon atom is attached to
three other atoms. Each carbon atom is sp2 -hybridized. One
Sp2 -hybrid orbital of one carbon atom overlaps coaxially with
H
that of another carbon atom to form a sigma bond. The
H . H remaining sp2.hybrid orbitals of two carbon. atoms overlap
with l&-orbital of different hydrogen atoms and form four
a-bonds H .H sigma bonds. The two J::arbon atoms and four hydrogen atoms
fig. 1.2 Bonding In. methane lie in the same plane. The H--.:..c-H bond angle is 120°. The

Iil ethane, there are six C-H sigma bonds and one C--.:..c
sigma bond. Each C-H bond is formed by th~ overlap of an
. spJ -hybrid orbital of carbon and la-orbital of hydrogen. The
. C--.:..c bond results from the. oveilap of two sp3 -hybrid
Orbitals, one from .eachcarbon atom: This has been shown in
fig. 1.3. The bond angle is ;again 109~8~ as two tetrahedrons-
o have linked together. . .
Fig. 1.5 Bonding In ~lene
. Introduction to Organic Chemistry 5

unhybridized 2p=-orbii~1sof the two carbon atoms overlap The three types of ~ybridization of carbon can, thus, be

...
laterally to form a n-bond. For the proper sidewise overlap of summarised in the following manner:
these 2p-orbitals, tHe formation of 1t-bond restricts the
ethylene molecule into a planar: shape. Therefore, ethylene is a ~G#.
..~
flat or trigonal planar molecule. The double bond between ~, ....".. ~.
T~ .~.
two carbon atoms (C=C), thus, consists of one sigma and one
1t-bond. .
~
~'.
~~
(iii) sp-bybridization: sp-hybridization occurs when il Tetrahedral 109°28" 0 25~0 75.0
.one s-orbital and one p-orbital' mix together to form two (109.5°)
equivalent hybrid orbitals. The other two 2 p-orbitals are left si 'Trigonal 120° 1 33.3 66.6
planar
unhybridized. Each sp-orbital and unhybridized p-orbital
sp Linear 180° 2 50.0 50.0
contain an unpaired electron. Each hybrid orbital p~ssesses
same energy and shape. Two sp-hybrid orbitals lie in a straight Relative slze$ of sp, sp 1. and sp 3 .-orbitals t s-orbital
line, i.e., the angle between. them is 180°. The unhybridized
,character, in the three hybrid orbitals varies in the following
Qrbitals are at right. at;lgles. to tile line of sp-hybrid orbitalS-. manner: .
Whenever a carbon atom is bonded to two other atoms Sp>Sp2 >sp3
or groups, it always uses sp-hybrid orbitals and two
Since, &-orbitals are closer to the nucleus than p-orbitals,
2p-unhybridized orbitals to form its. bonds. The best
it is, thus, expected that greater the s-ebaracter of tbe
example is the acetylene molecule. One sp-hybrid orbital of a bybrid orbitaltbe smaller is its size. Therefore, the order of
Py the size of the three hybrid orbitals is:
sp3 >sp2 >sp
Carbon in excited state On the basis of the sizes, sp-orbital forms shortest and
2s 2p sp3 -orbital longest bonds with other atoms.
OJ I i i. i
~
i 1---+ ~pl~ .t.., Indicate the number of0'- and 1t-bonds in
sp-hybridization the following· molecules:
(i) CH 3-CH==CH 2 (ii) CH 3-CH 2--CH 2--CH 3

Fig. 1.6 Orientation of two sp-hybrld orbitals and


unhybrldlzed Py and Pz-orbltals
(ii.) CH,--C==C - CH, (iv) 0
~#on; For finding out the number of0'- and 1t-bonds .
carbon atom overlaps coaxially with that of another carbon ill a molecule, the following points should be kept in mind.:
atom to form. a sigma bond. The remaining sp-hybrid orbitals 1. All ,single bonds are sigma bonds.
of two carbon atoms overlap with Is-orbital Of two different 2. All double bonds consist of one 0'- and one 1t-bond.
hydrogen atoms to form two sigma bonds. The unhybridized _ 3. All triple bonds consist of otie 0'- andtwo n;-bonds.
p-orbitals of two carbon atoms overlap laterally to form two (i) ,This molecule consists of seven single bonqsand one
Jr-'bonds; Thus, the triple bond between two carbon atoms double bond. Thus, number of O'~bonds =8 and number of
(C==C) consists of.one sigma and two 1t.,.bonds. Two carb9n 1t-bQnd =1.
atoms and two hydrogen atoms of acetylene molecule lie in a _ (ii) This molecule consists of 13 single bonds.
. straight line~ Thus, number of a-bonds =13.
(iii) This molecule consists of 8 _single bonds and one
triple bond. Thus,. number of O'-bonds =9 and nUmber of
It-bonds
1t-bonds 2 = .
(iv) The molecule of benzene consists of nine single bonds
and three double bonds.
=
Thus,·number ofcs-bonds 12 and number of1t-bonds = 3.
H ,-,,_-.r _ijjppLe2.,. Indicate the type of hybridization of each
carbon atom in the following molecules: .
(i) CH r -C==C-CH 3 (ii) H 2C==C=CH 2
(iii) CH r --,-CH---:CH---:CH 3 (iv) CH 3-CH 2...:...cH 3
..... ',. 1 2 3 4
_ d O l l ~ . (i) CH3--C~--CH3 .
-, _. Carbon-l is liilked with four atoms =sp3 -hybridization
Fig. 1•., Bonding In aeetylene
Carbon-2 is linked .with two atoms =sp-hybridization
6 G.R.B. Organic Chemistry for Competitions

Carbon-3 is linked with two atoms =sp-hybridization bond length, greater is the bond energy, i. e., greater is the
Carbon-4 is linked with four ator;ns == sp 3 -hybridization strength of the bond. The carbon-carbon bonds, single, double
•• 1 2, 3 , 2 2 and triple, are not of equal strength, i.e., with the shortening of
(u) H 2 C=C=CH 2 C.sP, C 2 == sp and C 3 == sp
1 2 3 4
bond length, bond strength increases. It is in the following
(iii) CH 3 -CH=CH-CH 3 order:
C1 =Sp3, C 2 == sp2, C 3 =.sp2 and C 4 Sp3 Triple bond> Double bond> Single bond
.23 The value of a bond energy of a. 'particular bond may
(iv) CH 3-CH 2 -CH 3 sp 3 , C 2 == sp 3 , C'3 == sp 3 slightly change in different molecules depending on structural
enviromnent of the bond. Bond energies are determined
Bond Length
experimentally as heats of chemical reactions (calorimetry)
The average distance between the centres of the nuclei of and by spectroscopic methods. The unit of bond energy is
the two bonded atoms in a molecule i~called the bond length. kcallmol. Bond energies of some common bonds are listed
The length of a ¢ovalent bond between two given atoms below:
depends on whether it is a sigma bond or combination of a
sigma and n-bond or n-bonds, i.e., it is a single, double or aoj,dffteJ'ay
triple bond. It also depends Ot:! the type of hybridization and (kcarIDOI":l)
the resonance. The bond length i~ :
c-C 83 C~l 81
Single bond > Double bond > Triple bond
C=C 146 C-Br 68
The bond length of the sigma bond in, different types of
C_C 192 e-:-I 51
hybridization follows the following order:
,a-bond (sp 3) > a-bond (sp2) > a-bond (sp) C-H(si-s) 97 H-H 103
Bond length between two given atoms is approximately C-H(sp2~s) 104 O-H III
constant in different molecules depending upon the ,above ' N-H
e-:-H (sp"'s) 120 93
conditions unless it is not affected by inductive effect and
C-O 86 C-F [07
mesomerism. The bond length is expressed in angstrom units
(A) or picometre (pm), (lA 10- 10 m, 1 pm 10-12 m). The C=O 179 H-F - 136
bond lengths are measured by X-ray crystallography and by C==O 256 ' ~. ~ c:
H~l
, . ' '
103
:"< ',;
-'I" I:'" . '1, " '.~ ''':,".:
microwave llpectroscopy. For most of the bonds the values are 0-0 35" ~£ ", H';7""Bf "., 88
1 to 2 A. It may be noted that the values of bond lengths are 0=;0 119 H-I 7f
subject 'to small changes, depending on the 'structural
N-N 39 F-F 38
enviromnent of the bond and the experimental method used to
measure it. N N 98 Cl~l 58
"The bond lengths of some common covalent bonds are N N 226 Br-Br 46

....
listed below:

C--,-C
.... __ <A)
1.54
....
C-N' 1.47
C-N 73

1.1 REPRESENTATION OF ORGANIC


I-I 36

C=C 1.34 C-':'F 1.42 MOLECULES


C;r;;i;C 1.20 C~l 1.77 An organic compound can be represented either by molecular
e-:-H (Sp3_S) 1.112 C-Br , 1.91 formula or structural formula. The structural formula is more
informative as it shows the arrangement of various atoms in a
C~H (sp2-s) . 1,103 C-I 2.12
molecule. A single covalent bond is shown as a line (-)
C-H(sp:'s) 1.08 C-'S 1.82 joining ,the two atoms. Double line (=) represents a double
C~ 1.40 O-H 0.96 bond while triple line (=) a triple bond. Organic molecules
C=O 1.20 possess a three dimensional structure but these are represented
in tpe plane of paper (two-dimensional) and the bond angles
Bond Energies or Bond Strengths between valencies of carbon are shown at right angles in open
chain compounds for the sake of convenience. The structural
Bond energy or bond strength is defined as the amount of formula written on paper simply indicates the order in which
energy required to break a bond in a molecule. Each bond the various atoms are found and does not give any idea of
has a characteristic 'value of this energy and is a measure of the their disposition in space. For ,example, ethane and ethyl
strength of the bond. It is generally,'observed that shorter the alcohol may be written as:

lYe
Introduction to Organic Chemistry 7

H H Condensed fonnula is a short hand method of


I I representing the structural fonnula. In a condensed fonnula,
H-C-C-H all atoms bonded to a carbon atom are written after 'C' in the
I I same line but their bonds are not shown. The atoms or groups
H H other than hydrogen are written after the hydrogen atom. In a

Ethane
.
Structural fonnula
condensed structural fonnula double and triple bonds are
shown by double line (=) and triple line (==) respectively.
H H Some examples are given in the following table:
I I
H-C-C-O--H
C 2 H sOH
I I
H H
Molecular fonnula
. Structural fonnula

..
Ethyl alcohol

0...••• ... i• • •~
..... ! , .'"".,.'
@~
(o~
01.1...... .......
IJlWM.II •. .~

H H
..
H H I I
Isopropyl alcohol C3HsO H-C-C-O-H
II
Ethane' ·H-C-C-=-H
II kI
H-C-H
H H
I
H
H H
Ethyl chl()ride
I I
H-C-C-Cl
y W··.
H-C-C-O-H
. I I '1
H"H H

H H
I I, H-I_~_N<H
Ethylene' R-C=C-H I H
H

o
H H
I I
,.~!
H-C--':""C=O
;.,' . ,I CH 3 f=O Cyclohexane
H H
';..·v.,"\.:~.r~~_~ ~!-:!i7:~~.\ . .·~o.,·~~ '~~" ~,r .;·;:"~N: ~;. ;::_",~ .-

o
H H 0 H
I . I III
Ethyl methyl H-C-C-C-C~H Benzene
. ketone I II
H H H

1.7 'POLAR AND NON';POlARBONDS When two identical atoms are joined by a sigma bond,
both· attract the cr-electrons equally. For example in C---C,
The nature of the covalent bond can be predicted on the basis
H-H and F-F, the electrons involved in the sigma bond are
of the values of electronegativities of the two atoms forming
the bond. Electronegativity of an atom is a measure of its shared equally, i. e., electron density in the molecular orbital
power to attract electrons that it is sharing ina covalent binding the two atoms together is same around each atom.
bond. The decreasing order of electronegativity of some There is no development of charge on any of the two atoms.
commOn atoms which are generally encountered in organic Such a bond is known as nonpolar bond.
chemistry is: When two atoms of different electronegativities are .
bonded by a sigma bond, the electrons involved are not shared
F >0> CI= N > Br > C> H
n

equally. The more electronegative atom attracts the bonded

.. -
. nsf
8 G.R.B. Organic Chemistry for Competitions
. .
electrons more closely than the less electronegative atom, i. e., measure the total moment of the molecule which is a vectorial
the electron density in. the molecular' orbital will be more sum of the individual bond moments. Dipole moment of a .
around the atoin with higher electronegativity. As a result ~e molecule does not depend only on the polarity ofthe bond but
more electronegative atom will acquire a small negative also depends on the directions of the bond, i.e., the shape'of
charge, syrubolised by£)- and less electronegative atom a the molecule.
small positive charge, symbolised by £) +. Such a bond which (i) Dipole moment of symmetrical compound is always
appears to have a positive and a negative end, is said to be a' zero (J.1 = 0). ,
polar bond. The bonds such asC-Cl, C-Br, C-N, C-O, For example H 2, 02' N 2' C1 2, Br2' CH 4 , CCI 4 , BH 3 , BF3 ,
etc., are polar in nature. . CO 2, CS 2, H 2C=CH 2 and HC=:i=CH, etc.
The· polarity of bonds can lead to polarity of molecules (ii) Dipole moment. of . unsymmetrical compound is
always greater than zero.
and affect melting point, boiling point and solubility. A
. molecule is said to be polar if it contains one or more polar
.. ..
bonds and the polar bonds are so directed that there are .. ..
For example H2 0; H2 S ,HCI, CHCI 3 , CH 3 CI, NH3 and ,

separate centres of positive and negative charges in the HF,etc.


molecule. A symmetrical molecule is nonpolar even thougb . (iii) Dipole moment increases with· increaSe of
it contains polar bonds. For example, molecules like carbon electronegativity. Thus, the dipole moment of
dioxide and carbon tetrachloride possess polar bonds but these HF > HCI > HBr > HI and
are nonpolar molecules as they have symmetrical structures, .. . CHF3 >CHCI 3 >CHBr3 >CHI 3
i.e., the centre of the positive and negative charges is the same (iv) Dipole moment of cis is greater than trans in
in the molecule. geometrical isomers and dipole moment of trans derivative of
0- the compound C (a) (b) = C (a) (b) will only be zero ifboth (a)
CI and (b) will be in the form of atom (or groups having linear
0- 0+ 0- o 10+ 0- . moment). For example
O=C=O CI '. C--:-CI
1
Centre of the positive
and negative charge
7
.. I
CI
0-
Centre of the positive
~C><;:/CI
'II
c~'
H",,-C:..;:/CI

II
H3C~C/H

I
C .
'~C~CH3
. I
. /,C;::-....
and negative charge H / ~CI CI"?"- H H/Sf"~CH3 H Sf" '-:;;: CH
.~ sp3 3
The molecules such as H-F, H 20, NH 3 , CH 3CI, CHCI 3 , (cis) (trans) (trans) .(cis)
1l=1.85D \.1=0 1l=0 \.1=0.33 D
etc., are polar molecules. Polar molecules behave as small
dipoles and possess a dipole moment. The dipole moment (J.t) ~C~CH3 ~~CH3 H"&,COOH EtOOC~C/H
of a bond X -.:.. Y is the product of the magnitude of the
.charges and the distance between the charges. It is roughly I I I . I
equal to the difference in the electronegativities of X and Y in
debye.
H/C~CI CI"?"- H HOOc:?'"C""- H EtOOC-?""-H
(cis) (trans) (trans) (cis)
Jl exd \.I = 0.27 D Il = 0.93 D =
\.I 2.38 D Il =2.54 D

Where, J.1 = dipole moment (in debye unit) Fig. 1.9


e magnitude of separated charges (in esu) (v) Dipole moment of disubstituted benzene
d = distance between the centre of charges (in cm) (a) When both groups X and Yare electron donating or
The dipole moment of an individual bond cannot be both groups are electron withdrawing then
measured in polyatomic molecules but it is possible to
. Jl =~Jlf .+ J..l~ +2JlIJ.12 cose
•• CI
where, J.11 =dipole moment of bond C-X
H::!::::!::CI
11
NO
11 11 Jl2 dipole moment of bond C-Y
. Hydrogen chloride
Il = 1.03 D .
~I 1~ ~ \~.
\
e =angle between X and Y
dipole moment of ottho-di > meta-di > para-di(Jl = O}
H . . H
. Ammonia Water Methyl chloride
For example, Dimethyl benzenes: 0- > m- > p- (Ii 0)
. J.l= 1.46 D il=1.84 D Il = 1.87 D Dichloro benzenes: 0- > m- > P- (Jl 0)

.. H CI
Some exceptions are:
OH ·COOR
11 I 11
~. ~
N ·~C~ ~
:7\~F.
/< C
CIY\~CI C(/\\~CI
F CI CI
Nitrogen trifluorjde Chloroform Carbon tetrachlOride
OH COOR
Il = 0:?4 0 J.l = 1.02 D J.l=0.0
(Il *0, but Il 0.83 D) (Il '* 0, but J.L = 0.27 D)
Fig. 1.8

fmd
Introduction to Organic Chemistry . 9

(b) Wh~n one group is electron withdrawing and the other in them. Examples of H-bonding in between the .two
group is electron donating then molecules of same compounds are:
~ =~r~-t=-+-~-~---2j.t-I~-2-C-O-s-6 H-F---H-F; H-O,---H-O, ;
Hydrogen fluoride
Hence, dipole moment is as follows: (associated) H H
p-disubstituted > m-disubstituied > o-disubstituted Water
(associated)
For example, chlorotoluenes: p- > m- > 0-

1.8 HYDROGEN BONDING IN ORGANIC .,H H


, R
,
R
I
COMPOUNDS H-N-":-H-N' 0- H- - -O---.:H
, I' Alcohol·
(associated)
In 1920 Latimer and Rodebush introduced the idea of H H
. "hydrogen bond" to explain the nature of association in Ammonia
(associated)
liquid state of substances like water, hydrogen fluoride,
ammonia and formic acid, etc. In a hydrogen compound, when Examples of H-bonding in between the two moles of
a hydrogen atom lies between two atpms having high electro- different
.. compounds are: .
negativities, it shows a unique property of forming a bond or a R H H O-H
bridge between them, holding one of the atoms by a covalent I , , I
bond and other by purely electrostatic forces (dipole-dipole O-H--":O-H; H-N---H
attraction). This chemical combination between highly Alcohol and water I
°
electronegative atoms of small atomic radius, such as F, arid H
Ammonia and water·
N through a hydrogen bond is referred to as Hydrogen bond
or Hydrogen bridge.
Conditions for Hydrogen Bonding
For example, hydrogen fluoride has a great tendency to
(i) Hydrogen atom should be linked to. a highly electro-
polymerise at temperature below 90°C, hence it occurs as
H 2 F2 · molecule. In H-F, the hydrogen is attached to a negative atoms such as F, or N. °
(ii) The size of electronegative atom should be small.
strongly electronegative element,. fluorine. As a result, the
Further larger the electronegativity and smaller the size of
fluorine acquires a partial negative charge and hydrogen the atom (F, 0, N), the strongest is the hydrogm bond which is
acquires a partial positive charge [H1)+ -' F1)-]. evident from the relative order of energies of hydrogen bonds
The .positive charge on hydrogen in a· molecule of in the three elements. For example, electronegativities
hydrogen fluoride will be attracted electrostatically by a . decrease as F >0 > N. Consequently, strength of hydrogen
negative charge on the fluorine atom in another molecule of . bond decreases as:
hydrogen fluoride.' This electrostatic attraction (dipole-dipole H-F---H > H-O---H > H-N ---H
10 kca1/mol 7 kcal/mol 2 kcal/mol
attraction) between different molecules of hydrogen fluoride
continues resulting in the formation of large molecular Although Cl has the same electronegativity as nitrogen
aggregate. but no hydrogen bonds are formed in case of H--CI because
1)+ 1)- 1)+ 1)- 1)+ 1)- 1)+ 1)- of the larger size of Cl atom. Similarly, sulphur forms a very
H-F---H-F---H-F---H-F--- weak: hydrogen bond due to its low elec1ronegativity, although
\/
(Covalent bond)
~/
(Hydrogen bond)
oxygen present in the same group forms a strong hydrogen
bond.

. So~ the linkage between hydrogen and the other fluorine is Types 01 Hydrogen Bonding
simply due to electrostatic forces of attraction, which results a Generally speaking, the hydrogen bonds can be classified
weak: bond, commonly known as Hydrogen bond and. . into two categories:
represented by dotted lines (- - -). 1. Intermolecular hydrogen bonding: This type of
Thus, hydrogen bond is defined as "an electrostatic bonding is between two or more same or different molecules
attractive force between the. covalent bonded hydrogen when combine together to form a dimer or polymer respec-
atom of one molecule and an electronegative atom (such as tively and leads to a phenomenon called association.
F, 0, N) of the 'other molecule'" The resultant bond . Examples are:
(hydrogen bond) is weaker (strength about 2-10 kcallmol or
8.4-42 kJ/mol) as compare to a covalent bond (strength about t.55A/F l.o9A , >F H H H
50-100 kcallmol or 209-418.4 kJ/mol). Liquids in which
, H' "H It I. I I
"F/ -"F/ ---N---II---N~II--~N---II---
molecules are held together by hydrogen bonds are said to be I I I
Hydrofluoric acid
associated. Such liquids have high boiling points due to the H H H
greater energy required to break: the hydrogen bonds present Ammonia molecule
10 . G.R.B.~ Or:ganic Chemistz.for Commtitions

H H H isomers of hydroxy, nitro, carbonyl compounds than their


I I I corresponding m- and p-isomers.
O-H---O-H---O-H
I I I Intramolecular hydrogen bonds are also considered to
I I I
I I I

H H H influence the acidity of certain acids. Thus, o-hydroxy benzoic


I I I acid is about 18 times more acidic than benzoic acid, whereas
O-H---O-H---O-H p-hydroxy benzoic acid is half as acidic as benzoic acid, i. e.,
Water molecule

"0',· . "
..... COOR
«'''~'t··O·'
"'' 1 '\?'.«,}"',
. , COOl! . .. COOH

<
• '9;; <.:; ·AI:J'I1i:'-p,'.
.j '!on.)."''' .•'';';
O-H---O> .
H-C,- C-H, ~., ..... ~ . .
O---H-O OH

o Fonnic acid (Dimer) Benzoic acid Salicylic acid p-hydroxy benzoic acid
6.2 x 10-5 105 X 10-5 t9 x IO-s ..
~ The large acidity is due to the intramolecular hydrogen
---CI~O-H---CI~O-H--- bonding which is capable of stabilizing the salicylate ion.
m-Chlorophenol
Thus, intramolecular H-bonding is weaker than
intennolecular H-bonding.

Nature and Importance of Hydrogen Bonding


(i) Hydrogen bond is merely an electrostatic force rather
than a chemical bond.
(ii) Hydrogen bond never involves more than .two atoms.
(iii) Bond energy of hydrogen bond is in the range of 3 to
10 kcaVmol or to to 40 kJ/moI, i. e., about IIIOth the energy of
a covalent bond. .
p-Nitrophenol and water (iv) With the increase of electronegativity of the atom to
which hydrogen is covalently linked,the strength of' the
This type of hydrogen bonding increases the boiling hydrogen bond increases.
point of the compound and also its solubility in water. The (v) All the three atoms in X -H- - -X lie in a straight line.
increase in boiling point is due to association of' several

molecules of the compound. Effects of Hydrogen Bonding 'on Physical Properties
2. lntr.amoleeularhydrogen'bondlng:: This type of Almost all physico-chemical properties (such as boiling
bonding occurs within two atoms of the same molecule and and melting points, solubility, spectra, acidic strength and
leads to a phenomenon called chelation. This type of basic strength of amines, etc.) are affected by hydrogen
hydrogen bonding frequently occurs in organic compounds bonding. Some of them are discussed below.
and results in the cyclisation (six or five membered ring) of (a) BOiling point and melting point: The boiling point
the molecule. Examples are: of a liquid is the temperature where its kinetic energy is
sufficient to overcome the intennolecular attractive forces.
Thus, heavier the molecule and stronger the intennolecular,
O-H forces, higher will be the boiling point of the compound and

6-~
so the boiling and melting points generally increase with
increase in number of carbon atoms in most of the
homologues series. Examples are:
(i) Water: The boiling point of covalent compounds
o-Fluorophenol. 0- Nitrophenol 2,6-Dihydroxy increases with increase in molecular weight and thus H 20
t':);;" :hbenzeie: acid
(mol. wt. =18) should have low boiling point than H2S(mol.
This type of hydrogen bonding decreases the boiling wt. = 34). But H 20 is liquid (high boiling point) and H 2S is
point of the compound and also its solubility In water. The gas. Beclil-use in water molecule, qydrogen bonding is presept
chelation between the orrho substituted groups restricts the and so become more compact and requires more energy to get
possibility of intermolecular hydrogen bonding and thus them separated during evaporation, while sulphur is less
prevents association of the molecules which would have electronegative nature than oxygen and give S-H bond, a
. raised the melting point or boiling point. In m- and p-isomers smaller ionic character than the O-H bond and thus H 2 S
chelation does not take'place because the two groups (atoms) fonns very weak hydrogen bond. Hence, it is the H-bonding
are far away from each other and hence in such cases which leads for the facts that: ..
intennolecular hydrogen bonding occurs. Thus, we can (ii) Boiling point of HF (liquid) is greater than boiling
explain the low melting and boiling points of the ortho . point of HCI (gas) .
Introduction to Organic Chemistry 11

(iii) NH3 has high boiling point than PH 3 . (b) Solubility in water: A hydrogen-bonded organic
(iv) Alcohols: (R-OH) have high boiling point than compound is usually soluble in another hydrogen-bonded
those of corresponding thioalcohols (R-SH, mercaptans) and substance. So, compounds whose molecule can form H-bonds
ethers (R-O-R). But the b.pt. of water (100°C) is higher with water molecule are soluble in water. Because of this
than ethyl alcohol (78°C) because greater number of water reason lower members of alcohols, acids, primary and
molecules are associated (through H-bonding) than the ethyl secondary amines, phenols and carbonyl compounds ate more
alcohol. soluble in water, whereas alkanes, ethers and thiols are
(v) Polyhydric alcohols have higher boiling points than insoluble in water.
their ethers, inspite of increase in the molecular masses of R HR··
ethers. For example: I I I-
CH 2OCH 3 - - - 0 -H- - -0-H- - -0-H- - -
CH 20H CH 2OCH 3
I I I
CH 2OCH 3
However, as the hydrocarbon chain (R-) in organic
CH 20H CH 20H compounds increases, the hydrophobic character of alkyl
. 85°C
chain predominates over H-bonding with' the result the
b.pt. 197°C 125°C
solubility of alcohols in water decreases. with .increase in
CHzOH CH ZOC 2 H s CH ZOC 2 H s CH 2OC 2 H s molecular mass and alcohols become almost insoluble when
I I I I alkyl groups of more than seven carbon atoms are present,
CHOH CHOH CHOH CHOCzH s while methyl, ethyl and propyl alcohols are very much soluble
I I I I in water. .. .... .
CHzOH CHzOH CHzOCzH s CH 2OC 2 H s When the compound has a large ratio of ~H groups to
b.pt. 290°C 230°C 191°C 185°C hydrocarbon groups, the compound wiH have a significant
solubility in water. For example. spgars~ ce$in ,starches and
Glycerol (CH 20H CHOH CH 20H) having three polyvinyl alcohols are fairly soluble ill water. .
-OH groups per molecwe (b.pt. 290°C) can· form more
It is important to note that while the intermolecular
hydrogen bonds per molecule than that of water. So, glycerol is
hydrogen bonding increases solubility of the compound in
more viscous than alcohol because of more binding sites available
for H~bonding. water, th,e intramolecular hydrogen bonding decreases and
(vi) Boiling points of aldehydes and ketones are lower therefore the solubility of o-nitrophenol is lower (because of
than alcohols. chelation) than m- and p-nitrophenois.
(vii) Andnes:' The boiling points of primary (R-NH2) (c) Stereo isomerism: Intramolecular H-60nding have
a strong influence on the spatial configuration of a molecule
and secondary amines (~NH) are higher than the isomeric and inhibits isomerisation of one form to another. For
tertiary ~nes (R3N) because like water and alcohols, the example, the trans-isomer of indigo is so stabilised by
primary and secondary amines are capable of forming H-bonding that it resists photochemical isomerisation to the
intermolecular hydrogen bonding but tertiary amine does not. cis-isomer,
Hence, in general the boiling point is increased due to
(d) Adsorption: Intermolecular H-bonding plays a
intermolecular hydrogen bonding but there are certain
very important role in the process of dyeing of textiles.
cases where the boiling point is decreased _due to
(e) Miscellaneous effects: Besides 'these' many other
intramolecular hydrogen bonding. For example, the ortho
properties such as colour, dipole moments, heat of mixing,
isomers of hydroxy -nitro, -carbonyl, -carboxylic or -chloro
heat of vaporisation, viscosity and refractive index, etc., are
compounds have lower melting and boiling points than the
also affected by H-bonding.
respective meta or para isomers. Example (given inibe table):
In fact, H-bonding is likely to affect most of the physical
Compound ortho-isomer pa",~somer properties.
m.pt. m.pt. (t) Effect of hydrogen bonding on chemical
Nitrophenol 44°C 114°C properties: The presence of H-bonding also affects the
Nitrobenzaldehyde 44°C 106°C chemical property of certain- compouuds. For example, the
Nitrobenzoic acid 144°C 241°C dibenzoyl methane does not give the nonnal reactions of
carbonyl group, i.e., it does not add HCN or NaHS0 3 , etc.
So, intermolecular H-bonding is more stronger than intra-
This is due to the formation of H-bonding which ties up the
molecular H-bonding. That is why m- or p-nitrophenol has
carbonyl group (enolic form).
high boiling point than o-nitrophenol (which is steam volatile) /H-,_
and 0- substituted compound leads to chelation which decreases o 0
boiling point. Chelation also explains the low boiling poiDt of I ~ .
enolic form of acetoacetic ester than the ketonic form of the
same.
O-H---O
V
~C
~CH'
/C~
V
(Enol fonn) I
I I
CH 3 -C=CH-C-OC zH s Dibenzoyl methane
(enol form) chelation
12 G.R.B. Organic Chemistry (or Competitions

Moreover the -OH group formed is also not free and is The actual structure of benzene, which can explain all the
neither acetylated by acetic anhydride nor does it give observed properties, lies somewhere in between these two
methane with methyl magnesium iodide. Similarly 0- hydroxy structures.
azo-compounds unlike p-isomers, do not give the normal
reactions of hydroxyl group.
(g) Hydrogen bonding In biologiea. systems:
H-bonding iri biological systems also plays an important role
and stabilizes usual structure of proteins and nucleic acids.
O· · 0
(i) (ii)

So, it was found in certain compounds, that no structural


1.9 INTERMOLECULAR FORCES formula (electron ic picture) could satisfactorily explain all the
propc'rties, For example, the electronic structure of carbon
In non-ionic compounds such as organic compounds, the
dioxide may be represented by at least three electronic
structural units are molecules. The forces holding these
arrangements given as follows:
molecules together are generally very \\cak and are. of three
types: O~C=O ~ -O-C==a+ ~
(i) Dipole-dipole attraction: In polar molecules, the or
positive end of one molecule is attracted by the. negative end .' ..0: :C::O. ~
. .(O:C::O+:
. ..
of another molecule. As a result of this dipole-dipole
attraction, polar molecules arc held to each other.
.. .. '.... .. ..
~ :+O::C :0-:

This led to the idea that such compounds exist in a state


(Ii) 'Hyd,rogen bonding: Intermolecular hydrogen'
bonding brings association of the molecules and thus, which is some combination. of tWo or more structures and each
increases the melting and boiling points of the compound. . one· oJ which makes sOme contribution to itS structure,· but
(iii) van der Waals'forces: In'non-polar compounds,. none of them describes allthe properties of the molecule or an
there .is a very weak intermolecular attraction due to ion. Ingold, (1933) called this phenomenon as mesomerism
electrostatjc attraction between the nuclei of one molecule and (between the parts, Le., an intermediate structure).
the electrons of the other. This attraction is llirgely This phenomenon in which two or more structures can be
. compensated by the repulsion between the electrons of written for a compound, but none of them represents it
neighbouring molecules as well as the repulsion between the . accurately, is referred'to as resonance. The actual structure of
nuclei o(neighbouring molecules. The van der Waals' forces the compound is said to be a resonance hybrid of various
are very weak and are significant only when the molecules 'are possible alternative structures which themselves are known as
very close to each other. van der Waals '. forces are stronger in resonatirig structures or canonical structures. In canonical
the compounds of high molecular masses. structures, there is only delocalization of· electrons
The relative order of these intermolecular forces is: (1t-electrons and unshared electrons) without sh~fting any
Hydrogen bond > dipole-dipole attraction> van der Waals' atom. The resonance hybrid is a definite form which cannot be
represented. It does not oscillate between various structures Of
attr:action
it is not the mixture of various canonical forms. Its properties

0
1.10 RESONANCE are fixed and these are the pr-operties of the actual hybrid
structure. Thus, resonance is hybridization of resonating
An organic molecule is generally represented by an structures and takes place in conjugated. compounds
electronic structure and it is expected that this .1. ~ (containing alternate single bond·and multiple bond).
structure satisfactorily explains all the observed //
Conditions of Resonance
properties of the compound. But very often single
.electronic structure cannot explain all the observed properties. (i) Structures contributing towards the hybrid must
For' example, bepzene is ordinarily represented as inside conform to real Lewis structures.
figure. ' (ii) The arrangement of atoms must be identical or almost
the same in every contributing structure, i. e., canonical form.
This structure has two types of carbon-carbon bonds.
(iii) Resonance involves delocalization of only 1t-electrons.
Three carbon-carbon bonds are single bonds and three
(iv) All canonical forms must have same number of
carbon~ca:rbcin bonds are double bonds. However, it has been
unpaired electrons.
observed experimentally that all carbon-carbon bonds are (v) The energy contents of all the canonical forms must'
identical and have the same bond length (1.39 A). The normal be nearly the same.
carbon-carbon single bond length is 1.54 A and .normal (vi) All resonance structures (canonical forms) do not
carbon-carbon double bond length is 1.34 A. Actually contribute equally to the hybrid. Structures with more
benzene can be represented by the given two alternative covalent bonds are more stable than those with lesser number
structures but none is able to explain fully all the observed of covalent bonds. The non-polar form of butadiene (I) is most
properties of benzene. These two structures differ only in the stable of all its canonical forms (II and III).
position of electrons.

it
Introduction to Organic Chemistry 13

+ Examples of Some Molecules or Ions Showing Resonance


CH 2=CH-CH=CH 2 ~ CH 2-CH=CH-CH 2 '
(I) (II) (1) Benzene, C6H6
. . +
~ CH2-CH=CH~CH2
(III)
(vii) Resonance structures having like charges on
adjacent atoms contribute very little towards resonance hybrid (ii) Acetate, CH 3COO-
as these structures possess high energy and thus are less
stable. . 0- /
(viii) Structures with isolated unlike charges have less CH 3- C ( ~ CH 3-C-(
contribution than those in which they are close to each other. ~O '0-
Thus, structure (II) of phenol has more contribution than
stru~ture (III) to its resonance hybrid. (ill) Carbonate ion, CO~-
ED ED
(D--H O-H O-H. o 0-· ~-
-o-e£ ~ ~O-C,~
0-6 -6
(n (fl)'
9

e
(III)
. . "'0-
(Iv) Sulphur trioxide, S03

/0
O=C< f-'-'7
. 0-

/0
"0

/0
(ix) Structures with negative. formal charge on the most O=S~ ~O~S~ ~O~S,
electronegative atom. and positive charge on the least o 0 0
electronegative atom have significant contribution. Structures
(v) Diazo methane,CH 2 N 2
with negative formal charge on the electropositive atom and
positive ch~ge on the electronegative atom have least' +.. .. +
contribution to the resonance hybrid. The structure (II) is more H 2C=N=N: ~ H 2 C-N::sN:
contributing than structure (III) to the resonance hybrid of (vi) Vinyl chloride, H2C == CHCI
acrolein [acrylic aldehyde, an Il, ~unsaturated aldehyde (I)].
•• •• +
o Oe H 2C=CH-CI: ~ H 2C-CH=CI: ~
~ a II ED I •• ••
CH2=CH-C-H ~ CH 2-CH=C-H (a) (b)
ex, ~-unsaturated (II) + ••
aldehyde (1) H 2C-CH=CI- :
••
+ (c)
:0 (The order of stability (a) > (b) > (c), i.e., structure (a) is
e I more stable because it has no formal charge and (c) is least
~ CH 2-CH=C-H
(III) stable having an electron deficient carbon.)
(x) Structures with electron deficient atom (i.e., (vii) Carboxylic acld, R--COOH
••
possessing less than eight electrons in its outermost shell)
have high energy, i.e., low stability, hence they contribute less
than those structures in which octet rule is not violated. Thus,
R-C~~.
0
2
"'-O.:.........H
~ R-C,+
/
0:
••

structure (I)' contributes more .than structure (II) to the •• O-H


••
resonance hybrid of diazomethane (CH 2 N 2)'
ED ~. •• ••
CH 2=N=N ~ CH2=N-N
•• ••
(I) (II)
(xi) Resonating structures are more important in
conjugated system than those in isolated system.
(xii) Resonating structures must be planar.
·14 G.R.B. Organic Chemistry (or CompetitiQns
\ " '

greater is the stability of the molecule. The resonance hybrid


is represented by a double headed arrow ( ~ )~

ILLUSTRATIONS OF OBJECTIVE QUESTIONS


1. Which of the following has maximum bond energy?
(a) C1 2 (b) F2
(c) Br2 (d) 12
[Ans. (a)]
2. Which one of the following does not have
sp2 -hybridized carbon?
(a) CH3COCH 3 (b) CH 3COOH
(c) CH 3 -C=N (d) CH 3CONH 2
[ADS. (c)]
Effects of Resonance spJ sp2 spJ sp3 sp2 sp3 sp
(i) Resonance is responsible for the greater stability of [lila. : (a) CH3COCH3 (b) CH3 -COOH (c) CH3-C==N
the molecule. acetone acetic acid acetonitrile
spJ sp2
(ii) In a resonance hybrid, the bond length is smaller
(d) CH3CONH2]
than in canonical forms. . . . . ;,<" , . " acetamide
(iii) Heat of formation of a resonance hybritl is abnormal 3. Which bond is not polar?
in comparison to canonical forms. (a) O-F (b) C-CI
(iv) On account of greater stability of the resonance (c) C-F (d) C-N
hybrid, the reactivity of the molecule decreases. [ADS. (a)]'
Resonance Energy ,, [111ft. : O-F bond is non-polar due to very much less difference
One of the most important effect of resonance is that in electronegativities of oxygen and fluorine.]
resonance hybrid (the real molecule) has much lower energy 4. Number of H-bonds formed by a water molecule is:
than the energy calculated for any of the canonical forms. The (a) 2 (b) 8
difference between the actualen~ ofilie iholecule (the'energy (c) I (d) 4
of resonance hybrid) and the energy calculated for the most [ADS. (d)]
stable of the canonical form, i. e., having the lowest energy
among the canonical forms is called the resonance energy.
[Experimental heat of formation (observed) - Theoretical
heat of formation (calculated)]
[II11l.:
The resonance energy is calculated from the difference
between the theoretical and experimental heats of hydrogenation
of the compound. For example, it is possible to determine the

o
resonance energy of benzene from the following data:

+ H,
Cyclohexene
GaIaIy~ • 0 +28.6

Cyclohexane
~cM!niol
5. The electronegativity follows the order :
(a) F>CI> Br>O
(c) 0> F>CI> Br
[Ans. (b)]
(b) F>O>CI> Br
(d) CI> F>O> Br

[IIlat: Electronegativity decreases from F to I and 0 is next to F


Accordingly,

0
~ .
1
Catalyst
+ 3H2 --"-+~ 0 ,'" +3 x'28.6='85.8'kcaVmol
in order of decreasing electronegativity.]
6. In which of the following compounds, delocalized
bonding is not possible?
(a) 1,3-Butadiene . (b) 1,4-Pentadiene
Cyclohexatriene Cyclohexane (c) 1,3,S-Hexatriene (d) Benzene
(hypothetical) [Ans. (b)]
But, however, the experimentalvalue of heat of hydrogenation [Hlot; (b) is not a conjugated system.]
of benzene is·49.8 kcaVmol. 7. The carbonyl group has following resonating structures,
Therefore, benzene is having 36 kcaVmol (8S.g..... 49.8) (i) )C=O (ii) )C-O (iii) )C+-O-
less energy than, expected for a typical compound which is
The correct order of stability of these structures is:
having three double bonds. Hence, resonance energy of
(a) (i»(ii»(iii) (b) (iii»(i»(ii)
benzene molecule is 36 kcaVmol by which the benzene
(c) (i) > (iii) > (ii) (d) (iii) > (ii) > (i)
molecule gets stabilized. The greater the resonance energy, the
[Ans. (c)]
Introduction
__ ..... ' ... z .. __ to
.. _. Organic
t
Chemistrv
_ ,... " .. _, __ .', ,- .,~Z
15
!.Hlat: The reS()nat;ng sp,-ucng:e with minimum or no charge is when the less soluble component crystallises out earlier than
more stable. Thus; the stahility of structure (i) is maximum. As the the more soluble component. The various fractions are
, negative charge is present on more electronegative oxygen atom
. {as in structure (iii)}. (iii) i~ more stable than structure (ii).] separated from time to time. These fractions are now sepa-
8.. The ratio of 0' and rc-bonds in mesitylene is: rately" ,put" to:, ,~rystallisation. ,cA., series~; ';ot ii rep,eated
(a) 3 (b) 5 crystallisations separate the two compounds in pure;fQrrn,
(c) 6 (d) 7 (il) SubUmation: Certain organic substances pass
[Ans. (d)] directly from so1id to vapour state on heating and vice-versa '.
tHlat: The structure of mesitylene is on cooling. This is called sublimation and the process is very
H
useful for separation of substances which sublime on heating
I from non-volatile impurities. The organic compounds such as
H-C-H benzoic acid, naphthalene, anthracene,· camphor, indigo.
CI ' , anthraquinone, etc., are purified by this process.
H HC-P 'CH H Heat
I I II I Solid .-----'" Vapours
H-C--C~ .......C--C-H Cool
I CH I,
a H, . The process of sublimation requires no solvent and is
Total number of a-bonds = 21 completed in a short time but it can be applied to only a
Total number of tt-bonds 3 = limited number of organic subs~c~~ .which possess high
So, ratio .of 0' and 1t~"9Pds
. .. .' '" ::: .isj:,l]
- -. . "", ' , ~ ~
vapour pressure at normal atmospheric'pressure~ . , , ?

1.11 PURIFICATION' OF ORGANIC COMPOUNDS Methods Employed for.purlfication of Liquids


(i) Distillation: Distillation is the most important
The organic compounds derived from natural sources or
prepared in the laboratory are seldom pure. They are usually method for purifying the organic liquids. Several methods of
contaminated with other substances. Purification means the distillation, such as simple distillation. fractional distillation,
removal of undesirable impurities associated with a vacuum distillation. steam distillation, etc., are used. The type
particular organic compound, i.e., to obtain tbe organic of distillation depends mainly oti''the"liatUre' of ' impurities
eompound in pure state. The' methods commonly used for present in the organic compound.
the separation and purification of organic compounds are:
Distillation is a process which involves two steps:
(i) Crystallisation:
1. Vaporisation: Liquid is converted into vapours.
(a) Simple crystallisation
(b) Fractional crystallisation 2. Condensation: Vapours are condensed again' into
(ii) Sublimation liquid.
(iii) Distillation: (a) Simple distillation: Simpld distiUationjis 'applied
(a) Simple distillation only for' volatile liquids which boil without decomposition at
(b) Fractional distillation atmospheric pressure and contains non-volatile impurities.
(c) Vacuum distillation This method can also be used for separating liquids
(d) Steam distillation having sufficient difference in their boiling points. For
(iv) Solvent extraction example.
(v) Chromatography. (i) benzene (b.pt. 80°C) and aniline (b.pt. 184°C)
~ n'~~F~-; ~\vi-~:;'~":'f.:i;~;~-' <:.·H'·~ :l,~;··~:·j:~'
Methods Employed for PurifieatioD of Solids (ii) chloroform (b.pt. 61°C) and aniline (b.pt. 184°C)
(a) Simple crystallisation : It involves the preparation (iii) ether (b.pt. 35°C) and toluene (b.pt. no°C)
of saturated solution of the impure organic'compound in a Nitrobenzene prepared in the laboratory can also be purified
suitable solvent at a higher temperature, i.e.• near its boiling by distillation.
point. The solution so formed is filtered while hot to remove (b) Fractio.oat distillation: This method is used for
insoluble impurities. The clear solution is cooled when the the separation and purification of organic liquids from
solid organic compound separates out in the form of fine non-volatile impurities or for separating two or more volatile
crystals. The solid is filtered and dried. liquids from a liquid mixture which have boiling points close
Examples: (i) Sugar mixed with common salt can be to each other.
purified with ethan0ln, ".~"". t"" ;"'" ,; Since, in this process, the distillate is coUeetedin
(ii) Phthalic acid mixed with naphthalene can be purified fractions under difi'erent temperatures, it is known as
with hot-water. fractional distillation.
(b) Fractional crystalUsation: The method is used for Liquids forming constant boiling mixture (azeotropic
the separation of a mixture of two compounds which are mixture) cannot be separated by this method. Fractional
soluble in the same solvent but their solubilities are different. distillation is used these days in' industry, especially. in the
The hot saturated solution of the mixture is allowed to cool distillation of petroleum, coal-tar and crude alcohol. A
16 G.R.B. Organic Chemistry for Competitions

mixture of methanol (b.pt. 65°C) and propanone (b.pt. 57°C) Mobile pbase
or a mixture of benzene and toluene may be separated by I
fractional distillation. I
. (e) DlstlUation under reduetd pressure (VacuulD
I
Liquid Gas
dlstiUatiod): The compounds, which decompose at a
temperature below their normal boiling points, cannot be
I I
Liquid-solid Gas-solid
purified by distillation under ordinary atmospheric pressure. chromatography chromatography
Glycerine is one such compound which decomposes at its (LSC) (GSC)
,boiling point. I
The pressure is reduced by suction, pump and the
distillation is carried out at lower temperature as glycerine can
I
Adsorption column Adsorption
be distilled at 180°C (normal b.pt. 290°C) under a pressure of chromatography thin-layer
10-12 mm. Cane juice can also be concentrated by this (ACC) chromatography
method. This technique can be used to separate glycerol from (TLC)
spent lye in soap industry. (b) When stationary phase is liquid, the chromatography
Distillation under reduced pressure is not only useful in isknown as partition chromatography. Depending upon the
avoiding decomposition but also serves to economise fuel for natUre of mobile phase, partition chromatography is further
industrial concerns. classified as follows: .
(d) StealD dlstUlatlon: This type of distillation is
essentially a co-distillation With water and is carried out when Mobile phase
a solid or liquid, practically insoluble in water, is volatile with I
steam, possesses a vapour pressure of about 10-15 'mm of I I
mercury but the impurities are non-volatile. Liquid Gas
This process is used in the purification of compounds I I
such ,as chlorotoluenes, aniline and nitrobenzene. It is also Liquid-liquid Gas-liquid
empioyed in the isolation of essential oils from flowers. chromatography chromatography
(LLC) (GLC)
(il) Solvent extraetion: The process of separation of
an organic compound from its aqueous solution by Shaking
I
with a suitable organic solvent is termed solvent extraction. Partition Partition Paper Reverse phase
The solvent should be immiscible with water and the organic thin-layer column chromatography partition
compound to be separated (by using separating funnel) should chromatography chromatography (PC) chromatography
• (TLC) (PCC) (RPPC)
be highly soluble in it. .
(Hi) Cbr.omatograpby: It is a recent and most The most common ones are:
effIcient technique which was first used by Tswett, a botanist, (i) Column chromatography or adsorption chromato-
in 1906 for the separation of coloured substances into graphy,
(ii) Thin layer chromatography (TLC),
individual components. The name chromatography (Greek (iii) Paper chromatography,
word, chroma colour and graphy =writing) means colour (iv) Gas chromatography,
writing. The name is no longer accurate as the technique has (v) Ion-exchange chromatography.
undergone tremendous modifications and is now used to The first three techniques have been described as:
separate almost any given 'mixture, whether coloured or Column (Adsorption) ~hromatograpiay: This is
colourless, into its .constituents and to test the purity of these based on adsorption (or surface) phenomenon: The extent of
constituents. This technique is even applicable to micro adsorption of various constituents present in a mixture lIquid
quantities (even less than 50 mg or 1 mL). (mobile phase) varies with a given adsorbent (stationary
Chromatography. is based on selective distribution of the phase). The common adsorbents used are magnesium oxide,
vari,ous, constituents of a mixture between two phases, a alumina, cellulose powder, silica gel, active animal charcoal,
stationary phase ,and a moving (mobile) phase. ,Different etc.
constituents migrate, at different rates, through the stationary Column chromatography involves the
phase. The stationary phase can be a solid or a liquid, while the (i) preparation of adsorbent column,
mobile (moving) phase is a liquid or a gas. Based on the nature of (ii) adsorption and
the stationary phase and the mobile phase, different types of (iii) elution of components and recovery.
chromatographic techniques have been developed, ' Thin layer chromatography (TLC): It is a special
(a) When stationary phase is solid, the chromatography is technique of adsorption chromatography in which thin layers
,known as adsorption or column chromatography. of adsorbents such as silica gel are spread on glass plates. A
Depending upon the nature of mobile phase, adsorption slurry of the adsorbent in an organic solvent is prepared. The
chromatography i~ further classified as follows: ~lurrY is then, coated on the glass plate with the help of a
device called applicator. A spot of the selution of the mixture
Introduction to Organic Chemistry 17
. ..
to be separated is kept at a distance of 2 em frOIn'one; side of . mixture is.detennmed. Ifthe meltiQg point of the mixture is sharp
the· glass plate with th~.help 9f capillary. The siz~ of the spot . and comes out to be the same as that of pure compound, it is sure
should be as small as possible. The plate is then dried. The that the compound under test is pure. On the other hand, if the
glass plate is now placed vertically in a developing chamber melting point of the mixture is less than the melting point of the
(close jar) containing a suitable solvent or solvent mixture at pure compound, the compound in question is not pure.
the bottom (about 1 cm deep). The end which has the sample
Bolling point*: The boiling point of a liquid is defined
spot is dipped in the solvent. The chamber is closed and the
solvent is allowed to ascend. The solvent consequently as the temperature at which the vapour pressure of a liquid is
resolves the original spot of mixture into a series of spots, each equal to external pressure. Boiling points .are also normally
corresponding to a single component. The relative adsorption quoted for standard atmospheric pressure. A pure organic
of each component of the mixture is expressed in terms of its liquid boils at a fixed temperature which is characteristic' of
retardation factor, i.e., RJ value. that substance.
If enough liquid is available, it can be distilled in a
R = Distance moved by the substance from base line
distillation apparatus and the constant temperature recorded
f Distance moved by the solvent from base
by the thermometer is the bQiling point.
The plate is taken off and dried. Each spot is now eluted When the amount of the liquid is small, Siwololf's
separately. method (capillary tube method) is used. .
Paper chromatography: It is a type of partition
chromatography•. The process is similar to thin layer ILLUSTRATIONS OF OBJECTIVE QUESTIONS
chromatography, exc~t that a strip of paper acts as the
adsorbent. Paper chromatography is based on a mechanism 9•. Suggest a method to purity benzene containing non-volatile
which is partly partition and partly adsorption. The paper impurities:
consists of cellulose fibres having molecules of water strongly (a) steam distillation
adsorbed on them. This serves as the stationary pbase while a (b) distillation under reduced pressure
suitable organic solvent is used as a mobile phase. A drop of (c) simple distillation
the solution of a mixture to be separated is placed on a strip of (d) sublimation
chromatographic paper and the solvent is allowed to travel [Ans. (c)]
along the strip. When the eluting solvent moves upwards, it is 10. A substance has boiling point 563 K, but it starts
termed ascending paper chromatography and when the decomposing near this temperature. Which type of
eluting solvent moves downwards, it is termed f,lescending distillation process is suitable for its purification?
paper chromatograpby. (a) Distillation
Finally, the paper strip is taken out and dried in air. The (b) Fractional distillation
position of various components, on the paper, is determined (c) Steam distillation
by spraying some suitable reagent which makes the spots
(d) Distillation under reduced pressure
(components) visible. In the separation and identification of
[Ans. (d)]
amino acids, ninhydrin is used for developing the coloured
11. Petroleum refining involves:
spots.
·(a) vacuum distillation
1.12 CRITERIA OF PURITY OF ORGANIC (b) fractional distillation
COMPOUNDS ( c) steam distillation
(d) passing over activated charcoal
Melting point: A pure organic solid has a definite and [Ans. (b)]
sharp (sudden, rapid and complete) melting point, while an [HInt; Crude petroleum is subjected for fractional (iistillation to
impure substance has a lower and indefinite melting point. get different products.]
The melting point of a solid may be defined as the temperature U. In steam distillation of toluene, the pressure of toluene
at which the solid and liquid states of the compound are in vapour is:
equilibrium with each other at an external pressure of I (a) equal to the pressure of barometer
atmosphere. (b) less than the pressure of barometer
Mixed melting point: The melting point of two (c) equal to vapour pressure of toluene in simple
~oroughly mixed substances is called mixed melting point. distillation
This can also be used for ascertaining. the purity of a (d) more than the vapour pressure of toluene in
compound. simple distillation
[Ans. (b)]
The substance, whose purity is to be tested, is mixed with a
pure sample of the same compound. The melting point of the
"'Boiling point is not as reliable a test of purity as is the melting point for the solids. There are many liquids which are miscible with other liquids and
mixtures have fixed boiling points (azeotrQPe). Thus, other physical properties are being used fur deciding the purity.
11 G.R.B. Organic Chemistry tor Competitions

: ~';,." IMPORTANT POJNTS TO REMEMBER (SUII.ARY)~


a All ~rganic compounds contain carbon and hydrogen as identical and have the same bond length (1.39 A). The
essential constituents. normal C--C single bond length is 1.54 A and normal C--C
IJCarbon has the maximum tendency of catenation as it can double bond length is 1.34 A.
combine with other carbon, atoms bysiogle;, double or Typ~ ofResonan~e,:
triple covalent bonds. The bonding can be extended to ~i} lsoyalent: The different contributing structures
form long open chains (straight or branched) or closed
having same number of covalent bonds is called Isovalent
one. This leads to a large number of organic compounds.
IJ Organic compounds being covalent are generally resonance. For example, benzene have isovalent resonating
insoluble in water and other polar solvents but soluble in structures similarly in carboxylate anion, there is same
non-polar solvents. number of bonds.
IJ The nature of the covalent bonding in organic compounds (ii,~yalent: The different contributing structures
can be desCribed in terms of orbitals hybridization having different number of bonds is called Heterovalent
concept, according to which carbon can have sp3 , Sp2 and resonance. For example,
, sp-hybridized orbitals. The tetrahedral shape of methane, +
H 20=CH-'CH=CH 2 ~(--7) H 2 C-CH=CH-CH2
planar shape of ethene and linear shape of ethyne can be
(I) ,." ,~. ,(D) .. ,c
understood on the basis of this concept.
a A; ~pJ .ihybnd" 'OFDitar.' cim'; i()verlap~ lWith" 'l~orbitgl; .of ~
+
H 2 C-CH=CH-CH 2
hydrogen to give a carbon hydrogen (G-H) single bt?~d (III)
(sigma, 0' ,bond). The bond angle is 109°28' (or 109.5°). In buta-I,3-diene, there are eleven bonds in structure (I)
Overlap of a Sp2 -hybrid orbital of one carbon atom while ten bonds in structures (II) and (III) respectively.
coaxially with that of another carbon atom to form a ,eoBditiQllS ,of R-eso:nanee:
(C--C) sigma bond. The unhybridized 2pz -orbitals on
two adjacent carbon atoms overlap laterally (side-by-side)
IJ All contributing structures must have same number of
paired or unpaired electrons, same or nearly the same
to form a pi (1t) bond. The H--C-H bond angle is 120°.
energy contents, same atomic skeleton a planar structure
Similarly the triple bond between two carbon atoms
and involves delocalization of only 1t-electrons.
(C==C) consists of one sigma and two pi-bonds
(sp-hybridization) and the bond angle is 180°.
a Resonati'ng structures with more covalent bQnds are more
stable. They are more important in conjugated system than
IJ Greater the S'-Character of the hybrid orbital, the smaller is
those in isolated system and non-polar structures are more
its size. So, the order, of the size of the three hybrid orbitals
stable than the polar structures.
is:
Effects ,of Resonanee:
Sp3 > sp2 > sp.
IJ Resonance is responsible for the gre.ater stability of the
a The distance between the nuclei of the two atoms joined molecule.
by the bond is called Bond Length (Single bond> Double (J The bond lengths of hybrid form are different from any of
bond> Triple bond). The amount of energy required; ~o the resonating structures.
break a bond in a molecule is called Bond Energy or t:J The heat of hydrogenation determined experimentally an~
Bond Strength. It is in the following order: thatCaI~V!f1t~ ,tp.e9f~tic~Jfy tQ~ tb..e.:~p&t sta~le ~tn:~tm;e
(Triple bond> Double bond> Single bond). are different. This difference IS caI1eq R~sQrumceenergy.
t:J An electrostatic attractive force between the covalent IJPurification, Qualitative and Qtianiitati\,;e" 'analysis .of
bonded hydrogen atom of one molecule and, highly organic compoundS' are carried out for,. qetem,rln;n..g. their
electronegative atom of small atomic radius (suc~r:s F, 0, structures.
N) of the other molecule is referred to as Hydrogen bond. t:J Purification means the removal of undesirable impurities
The strength of hydrogen bond decreases as: "; associated with a particular organic, compound, i.e., to
H··· F> H·· ,0> H··· N obtain the organic compound in pure state. The methods
t:J Resonance: If a molecule or an ion can be shown by two employed for purification of solids are as follows: ,
or more structures, differing only in the qistribution of IJ Crystallisation is used to purify organic solids by dissolv~
electrons, but none of them truly explain all the properties ing them in suitable solvent f?~~owe4 by ,ijltra,tiB.~;9f the
of the molecule or an ion, these structures are called hot solution and crystallisation.
resonating or contributing or canonical, structures and IJ Fractional crystallisation isused to separate two or more
this phenomenon is called Resonance. organic solids with different solubilities in the same
t:J Benzene can be shown by two or more resonating solvent.
stnictures and each one makes some contribution to its t:J Sublimation is used for separation of certain organic
structure, ~l!t.none of them describe all the properties of substances which sublime (passes directly from solid to
benzene molecule and actual structure lies some where in vapour stafe "on~heatirig 'ana' viCe:'versa) 'on'1ieaHng'fro~
between, called resonance hybrid. non-volatile inipurities. Examples are camphor, benz(nc
t:J It has been proved experimentally that all C--C bonds are acid, naphthalene and anthracene, etc.
19
-a 'The lflethods empitryed f6t'{.lirification' ~' q, mt'" 9 Solvt(D~'t'\tractloinfteih.6d"Ts· Used'to 's'eparate'lf given
i follows:
, ' , ,;(:::;, 'j', ;: f orgru:ik~~poundfrom Its aqueous solution by shaking
,..0 .Simple ,distillation is. ,applied only .. for volatile "liquids.. ' ... with ,a~suitahJe,.organie·solvent"in-whieh-the·oompound is
which boil without decomposition at atmospheric pressure more soluble than water.

:~c~o~~~~::~:~~ti!~ff:P~~~~~:~
30-50 K.
:::! ~x:':a~ a. ~=fl:::~ri~~~' t~~~:t~~o~di~!01;f
available in very small amount.
[J Fractional distillation is applied for separating two' or [J'Adsorption (column) chromatography is based on the
more volatile liquids from a liquid mixture in which the differences in rates at which the components of a mixture
components differ in boiling points close to each other by ,liquid (moving phase) are adsorbed on an adsorbent
10 to 20 K. (stationary phase).
[J Vacuum distillation' is applied for liquids, which a Partition chromatography involves. continuous
decompose at a temperature below their normal boiling partitioning of the components of a mixture between
points.' stationary and mobile phases. Paper chromatography is a
[J Steam distillation is 'applied for separation and "type of partition chromatography.
purification of liquids which is appreciably volatile in a Criteria of purity, of an organic compound is best
steam, practically immiscible with water but the impurities determined by mixed melting point.
are non-volatile. '

mrt'lIlrr nn .,. '···W-: "1!'tr'


Introduction to Organic Chemistrz 21

(i) Resonance decreases the stability of the molecule and 6. Classify the following in~o polar and non-polar molecules:

,
increases its reactivity. (i) CO 2 , (ii) CHCI 3, (iii) CCI 4 , (iv) CH3 0CH 3 ,
G) With the shortening of bond le.n~, bond strength (v) C 2H s OH, (vi) C 2H 6 , (vii) CHzCl z, (viii). NH 3 ,
. ,~ ;.", '
increases. ~, (ix) HzO, (x) CH3 CL
(k) A symmetrical molecule is non-polar even though it 7. Indicate the type of hybridization of each carbon atom in the
contains polar bonds. following molecules:
t (I) CCI 4 has high value of dipole moment.
(m) Resonance involves movement of cr- and 1t-electrons.
I z 34
(i) CH3-CH=CH--'CH3 (ii) H-C==C-C==C-H
1234

[
I Z 3 4 1 Z 3
(n) The greater the resonance energy, the lower is the (iii) CH3 -C==C-CH 3 (iv) CH r -CHz-CH3
stability of the molecule.
(0) More is the number of canonical forms for a molecule,
more is the resonance energy of molecule.
I
(v) CH 3 -C==N
2 III°
(vi) H-C-NH2
(p) A carbon--carbon double bond is stronger than a I 2 3 4
carbon--carbon single bond. (vii) CH3 --CH CH-C==N
(q) A polar bond results when the atoms have same
electronegativity.
(r) Acetylene is a linear molecule.
I
(viii) CH3 -C-CH3
°
211 3

(s) The criterion of purity of a solid organic compound is


its molecular mass. (ix) H 2C=C=O
(t) Chromatography is a method to separate and purify
compounds when present in small amounts. .
(u) Naphthalene can be separated from ammonium
8. Indicate the number of cr- and 1t-bonds in the following
chloride by sublimation. molecules:
(v) Aniline is purified by steam distillation. (i) CH3-C-C-H (ii) CH3 -CH=CH z
(w) Benzene- and toluene can be separated by fractional (iii) H2C-C=CH~ (iv) CH 3 -CH z-CH 3
distillation. (v) H 2C=C=CH-CH3
(vi) HC=C-CH=CHCH3
(x) In organic compounds, carbon is always sp3 - hybridized.
(vii) H 2C=CH-C==N (viii) CH30H
(y) All bond length values in ethane are same.
(ix) CH3 --C==N (x) CH3NOi
(z) A triple bond consists one sigma and two pi bonds.
(xi) CH 2CI 2 (xii) C6 H1Z (Hexene)
..~ Match the following:
9. (a) How do bond length and bond strength vary in the
(a). (A) Vital force theory (i) Bond angle 1200
following cases?
(B) sp3 -hybridization . (ii) Kolbe C-C, C=C, C==C
(C) Hydrogen bonding (iii) Wohler (b) Arrange the sp,sp:;' - and sp 3-hybridization in increasing
(D) Resonance (iv) Onesigmatwopibonds order of:
(E) spz -hybridization (v) Sublimation (i) bond length (ii) bond allgk (iii) bonl energy
(F) Urea (vi) Vacuum distillation (iv) size of orbitals (v) s-charact?r
(G) Acetic acid (vii) CH 4 tO~ Which resonance form in each of the following s-:ts is the
(H) Naphthalene (viii) Berzelius major contributor to the real structure?
(I) Triple bond (ix) C6 H6 + -
(1) Glycerol (x) CzHsOH (i) CH z=C-CH=CH 2 ~ CH 2-C=CH-C'H,
(It) (A) Sublimation (i) Benzene + Toluene I I -
(B) Chromatography (ii) Tswett CH3 CH 3
(C) Steam distillation (iii) Camphor (A) (8)
(D) Fractional distillation (iv) Aniline 4-

5~ In each case, select the property which is typical of organic ~ CHz-C=CH-C11.,


rather than inorganic compounds:
I -
A. (i) Water soluble CH 3
. (ii) Water insoluble ,C)
_ B. (i) Low melting point
(ii) High melting point
C. (i) Flammable
r
(ii) CH3 -C-CH=CHz ~
0-
I
CH3 -C-CH=CH2
+
(ii) Non-flainmable (A)
(8)
D. (i) Ionic bonding
(ii) Covalent bo~ding 0-
E. (i) Chemical reactions are slow ! +
(ii) Chemical reactions are fast <:----7 ell 3-C=CH-CH2
(C)
22 G.R.B. Organic Ch~mistry for Competitions
+.
(iii) CH 2 =CH-CH=CH 2 ~ CH 2 -CH=CH-CH2 (i) a-dichlorobenzene, m-dichlorobenzene,
(A) (B) p-dichlorobenzene
+ ~ SHORT ANSWER TYPE
~ CH 2-CH=CH-CH 2
(C) 13. Explain the following:
(i) Why is ethylene a planar molecule and acetylene a
R)+
(iv) R C-O ~ R
R)_ +~ R)C=O
C-O
R linear molecule?
(ii) Why does bond length decrease in the order?
C-C>C=C>C==C
(A) (B). (C) (iii) The boiling point of methanol is 66°C and that of
11. Answer of the following: methyl mercaptan is 6°C, whereas the boiling points
(i) The type of hybridiZation' which carbon atoms of diethyl ether and diethyl sulphide are 35°C and
undergo in the formation of ethane molecule is. 92°C respectively.
(ii) The type of hybridization which carbon atoms (iv) Ethanol boils at higher temperature than ethylamine
undergo in the formation of ethene molecule inspite of the fact that both have nearly' same molecu-
lar masses.
(H2 C=CH2 ) is.
(v) What effect should the following resonance of vinyl
(iii) The type of hybridization which carbon atoms undergo
chloride have on its dipole moment?
in the formation of ethyne molecule (HC==CH) is. - +
(iv) Carbon-carbon bond distance in benzene is CH2 =CH-CI ~ CH2 -CH=CI
intermediate between the C-C bond distances in (vi) The central carbon-carbon bond in 1,3-butadiene is
ethene and ethane. shorter than that of n-butane.
(v) Alcohols have higher boiling points than the (vii) What property of carbon accounts for the occurrence
corresponding isomeric ethers. of large number of its compounds?
(vi) CH30Hhas higher boiling point than CH3 SH. (viii) The C-CI bond is polar while CCl 4 is non-polar.
(vii) The 0- and p-chlorophenols have different boiling (ix) Explain the factor on which polarity of bond depends? .
points. (x) The CI atom has same electronegativity as nitrogen
(viii) The three carbon-oxygen bonds are equal in carbonate but it does not form effective hydrogen bonding.
ion. 14. Explain how the following mixtures may be s~parated:
(ix) Carbon-oxygen bond lengths in formic acid are (i) A mixture of two miscible liquids.
1.23 A and 1.36 A and both the carbon-oxygen bonds (ii) A mixture of benzoic acid and sodium chloride (solid
in sodium formate have same value, i. e., 1.27 A.
mixture).
(x) A mixture of plant pigments is separated by which (iii) A mixture of plant pigments.
method?
(iv) Ether and water.
(xi) The purity of an organic solid is tested by which (v) Benzoic acid-water mixture.
physical property?
15. (i) Discuss orbital structure of methane.
(xii) C-C bond lengths in ethane,< ethylene and acetylene (ii) Discuss orbital structure of ethylene.
are. (iii) Discuss orbital structure of acetylene.
(xiii) What are the bond angles in sp3 ::'sp2 - and sp-hybrid (iv) Discuss the hybridization of carbon atoms in allene
orbitals? (C 3 H 4 ) and show the 1t-orbital overlaps.
(xiv) Chloral hydrate, CCI 3 CH(OH)2 is stable although it 16. (A) Write the resonance structures of the following species:
has two hydroxyl groups attached to the same carbon
atom. (i) :CH 2 -C==N:
(xv) C=C hond length is shorter than the C-:-C bond +
length.
+ -
(xvi) Why o-hydroxy benzaldehyde is a Hquid at room (iii)· CH 2-CH =CH-CH 2
temperature while p-hydroxy benzaldehyde is a high
melting solid? :0:
12. Arrange the followings in increasing order of a dipole II -
moment. (iv) CH3-C-CH2
(a) HF, HCI, HBr, HI
••
(B) Write resonance structures for the intermediate
(b) CH3Cl. (,'H,Br, CH3I, CH3F
carbocation in the aromatic chlorination of benzene.
(c) CHF). 011 3 , CHBr3' CHCl 3
(C) Write the main resonance structures of the conjugate
(d) CH4 , CH3CI, CH 2CI 2 , CHCl 3
base of a 1,3-diketone.
(e) NH 3 , SbH3 , AsH 3 , PH 3
(D) Write the resonance structures of CH 2 =CH-CHo.
(t) S03, Si02 , P20 S , Cl 20 7
Indicate relative stability of the contributing structures.
(g) o-chlorotoluene, m-chlorotoluene, p-chlorotoluene
17. Write short notes on the following:
(h) o-nitrophenol, m-nitrophenol, p-nitrophenol
(i) Vital force theory.
Introduction to Organic Chemistry 23

(ii) General characteristics of organic compounds. (vii)C 1 =sp3, C 2 =Sp2, C 3 =Sp2, C4 =sp
(iii) Hybridization. (viii) C 1 = sp3, C 2 = Sp2, C 3 = sp3
(iv) Polar and non-polar bonds. (ix) Sp2, sp (x) sp3, Sp2
(v) Hydrogen bonding. (xi) sp3, sp3 (xii) sp3, sp3
(vi) Resonance. 8. (i) a-bonds = 6, x-bonds = 2
(vii) Fractional crystallisation. (ii) a-bonds = 8, x-bond = I
(viii) Vacuum distillation. (iii) a-bonds = 6, x-bonds = 2
(ix) Mixed melting point. (iv) a-bonds = 10
(x) Purity of an organic compound. (v) a-bonds = 9, x-bonds = 2
(vi) a-bonds = 10, x-bonds = 3
(vii) a-bonds = 6, x-bonds = 3
(viii) a-bonds = 5, x-bonds = Nil
1. (a) hydrocarbons; (b) catenation; (c) Berzelius; (d) ammonium
(ix) a-bonds = 5, x-bonds = 2
cyanate; (e) acetic acid; (t) covalent, molecular, slow; (g) carbon
(x) a-bonds = 6, x-bond = I
dioxide; (h) synthetic; (i) three; G) sp3; (Ie) Sp2; (I) sp3; (m) sigma,
(xi) a-bonds = 4
two pi; (n) sp3, 109°28'; (0) smallest, longest; (P) 146; (q) higher; (xii) a-bonds = 17, x-bond = I
(r) 1.20 A; (s) sp; (t) Sp2; (u) hydrogen; (v) lower, less; (w) more; 9. (a) Bond length order C-C > C=C > C=C
(x) three; (y) non-polar; (z) CH 3-C=CH-C-CH 3. Bond strength order C=C > C=C > C-C
I I (b) (i) sp-s < Sp2 -s <·sp3 -s (ii) sp3 < Sp2 < sp
0, /0 (iii) sl < Sp2 < sp (iv) sp < Sp2 < sp3
'H'
2. (i) vacuum distillation; (ii) fractional distillation; (iii) sublimation; (v) sl < Sp2 < sp
(iv) steam volatile, sparingly soluble; (v) alumina or silica gel; 10.• Form A in (i), (ii), (iii) and form C in (iv) is the major contributor
(vi) rapidly; (vii) crystallisation· from solution in ethanol; because in these structures each atom has octet and no formal
(viii) melting point; (ix) boiling point; (x) less; (xi) steam charge is present.
distillation; (xii) elution; (xiii) sublimation; (xiv) steam distillation; 11. (i) sl; (ii) Sp2; (iii) sp; (iv) resonance in benzene molecule;
(xv) vacuum distillation; (xvi) fulctional distillation; (xvii) steam (v) hydrogen bonding is present in alcohols; (vi) oxygen is more
distillation; (xviii) fractional distillation; (xix) separating funnel; (xx) electronegative than sulphur. Thus, hydrogen bonding is present in
vacuum distillation. CH 30H; (vii) o-chlorophenol involves intramolecular hydrogen
J. (a) True; (b) False-organic compounds have low melting and bonding while p-chlorophenol involves intermolecular hydrogen
boiling points. These are bad conductors and insoluble in water; bonding; (viii) due to resonance; (ix) no resonance is present in
(c) True; (d) True; (e) False-More than 90% of organic formic acid molecule but in formate ion resonance exists;
compounds have been prepared by synthetic methods; (t) False- (x) chromatography; (xi) melting point; (xii) C-C ... 1.54 A,
s-character 33%, p-character 66%; (g) True; (h) True; (i) False- C=C ... 1.34 A. C=C ... 1.20 A:, (xiii) sp3 ... 109°28', Sp2 ... 120°,
Resonance increases the stability of a molecule and decreases its sp ... 1800; (xiv) Chloral hydrate is stable due to intramolecular
reactivity; G) True; (k) True; (I) False-CCl4 being symmetrical hydrogen bonding between hydrogen and chlorine atom; (xv) With
has zero dipole moment; (m) False-resonance involves only increase in s-character, the size of hybridized orbital decreases
x-electrons; (n) False-The greater the resonance energy, the which leads to more overlapping and shortening of bond length in
greater is the stability of the molecule; (0) True; (P) True; C=C; (xvi) o-hydroxy benzaldehyde has intramolecular
(q) False-Polar bond results when atoms have different H-bonding (so low melting point and is a liquid at room
electronegativity; (r) True; (s) False-criterion of purity ofa solid temperature), while p-hydroxy benzaldehyde have interinolecular
organic compound is its melting point; (t) True; (u) False-With
H-bonding (so high melting point).
the help of water; (v) True; (w) True; (x) False-Carbon
12. (a) HI < HBr < HCI < HF
undergoes sl-s/- or sp-hybridization; (y) False-All bond lengths
(b) CH3I < CH3Br < CH 3CI < CH3F
are same except between carbon and carbon atoms; (z) True. (c) CHI 3 < CHBr3 < CHCI 3 < CHF3
4. (a) (A-viii); (B-vii); (C-x); (D--ix); (E-i); (F-iii); (G-ii); (d) CH 4 < CH 3CI < CH 2CI 2 < CHCl 3
(H-v); (I-iv); (J-vi). (e) SbH 3 < AsH3 < PH 3 < NH3
(b) (A-iii); (B-ii); (C-iv); (D--i). (t) CI 20 7 < S03 < P20 S < Si0 2
5. A. (ii); B. (i); C. (i); D. (ii); E. (i). (g) o-chlorotoluene < m-chlorotoluene < p-chlorotoluene
6. CO 2 , CCI 4, C2I-4 are non-polar molecules while rest are polar (h) p-nitrophenol < m-nitrophenol < o-nitrophenol
molecules. (i) p-dichlorobenzene < m-dichlorobenzene < o-dichlorobenzene
7. (i)C 1 =sp3, C 2 =Sp2, C 3 =Sp2, c 4 =sl . 13. (i) In ethylene each carbon atom undergoes sp2-hybridization
(ii) C 1 = sp, C 2 = sp, C 3 = sp, C 4 = sp while in acetylene each carbon undergoes sp-hybridization; (ii) As
(iii) C 1 =sp3, C 2 =sp, C 3 =sp, C 4 =sp3 the s-character increases in the hybridized orbitals, greater
overlapping occurs with the shortening of bond length; (iii)
(iv) All carbon atoms are sp3-hybridized.
CH 30H has higher boiling point than CH 3SH due to hydrogen
(v) C 1 = sp3, C 2 = sp bonding. Diethyl sulphide has higher boiling point than diethyl
(vi) C 1 = Sp2 ether due to larger molecular mass; (iv) Oxygen being mere
electronegative than nitrogen forms stronger hydrogen bond than
24 G.R.B. Organic Chemistry for Competitions
I Z 3
the latter; (v) Resonance decreases the dipole moment of vinyl
15. (iv) Allene are cummuJative dienes, CHz=C=CHz (Propa-I,2-
chloride as the positive charge on chlorine and a negative charge on
diene). In allene C 1 and C3 are sl-hybridized and C2 is
carbon oppose each other; (vi) 1,3-butadiene has si
_Sp2 C-C
sp-hybridized. The two 7r-bonds are present in the central carbon,
bond length, while n-butane has si
_Sp3 C-C bond length. More is
one each from Py- and pz-orbitals thus, overlapping planes in C 1 and
's' character in hybridization, lesser is bond length; (vii) (a) C3 are also different.
catenation, (b) carbon can link with other carbon atom with single,
double and triple bonds. It can form bonds with other atoms also,
(c) isomerism; (viii) The dipole moment ofCCI 4 is zero inspite of
four similar polar (C-CI) bonds on account of symmetrical
structure; (ix) The polarity of bond depends upon electronegativity
• difference of two atoms involved in covalence; (x) The size of CI
atom is large as compared to nitrogen and so it pulls the shared pair
of electron from hydrogen atom less effectively and thus it does not
possess appreciable partial charge to show hydrogen bonding.
14. (i) By fractional distillation; (ii) By sublimation; (iii) By
chromatography; (iv) By simple distillation; (v) By distilling of
water.

.......
.+
GfHaH
..
();;:::
CI.......
~ +
Cl
r!::l<H
0 CI

Base
---""
~

. :~:
(D) CHz=CH-C-H ~ +CHz-CH=C-H ~ :CHz-CH=C-H
:?: ~ :r +

I IT m
Stability I > II > III
Structure I: More stable, because it has more number of covalent bonds and have no formal charge. Each carbon and oxygen atom has an
Octet.
Structure II: Less stable, because it has negative charge on more electronegative atom and positive charge on more electropositive atom.
Structure III: Least stable, beca~se it does not contribute as oxygen has positive charge and carbon has negative charge .
Introduction to Organic Chemistry 25

OIJtCllvt IS
SET I: This set contains questions with single correct answer.
1.' The propertY of catenation is strongest in carbon because: TH 3

(a) its ionisation potential is low 0 12. In the compound HC=:::C--C-CH2, the hybridization of
(b) its electronegativity is low 0 C 2 and C 3 carbons are respectively: [JEE (WB) 2009)
(c) the C-Cbond energy is high 0 (a) Sp3 and sp2. 0 (b) sp2 and sp3 0
(d) its atomic radius is small 0 (c) sp3 and sp 0 (d) sp2 and sp 0
1.. The main source of organic compounds is: 13. The CI-C-CI angle in 1,1,2,2-tetrachloroethene and
(a) vegetable kingdom 0 (b) synthetic reactions 0 tetrachloromethane will be about:
(c) animal kingdom 0 (d) petroleum 0 (a) 9()0 and 109S' 0 (b) 109.50 and 900 0
3. The ftrst organic compound prepared from inorganic 0
(c) 109.5 and 120 0
o
compounds was:
14. Which of the following molecules does not have net dipole
(a) acetic acid 0 (b) methane 0 moment? IAMU (Engg. 2010»)
(c) urea 0 (d) ethyl alcohol 0 (a) CH 3 -Br 0 (b) CH2Cl 2 0
4. The flfSt organic compound synthesised in the laboratory
from its elements: t (c) H)e=c<H 0 (d) HCOOH o
(a) urea 0 (b) methane o H H
(c) ethylene 0 (d) acetic acid X
5. The bond between carbon atom (I) and carbon atom (2) in
I 2
compound N=G-CH=CH 2 , involves hybridization:
(a) sp 2 and sp2 0 (b) sp3 and sp o
15. Dipole moment Of© is 1.5 D. The dipole mo..... of

(c) spand sp2 0 (d) spand sp o


6. The C-H bond distance is the longest in:

o
[UGET (Med.) 1006)
(b) C2 H4
o (d) C2H2Br2
0
0
X*x'S: X
[JEE (WB) 1010)

7. The enotic form of acetone contains: (a) 1 D 0 (b) 1.5 D o


(a) 9 sigma bonds, I pi bond and 2 lone pairs of electrons (c) 2.25 D 0 (d) 3 D o
o
r (b) 8 sigma bonds, 2 pi bonds and 2 lone pairs of electrons
16. The shape of acetylene molecule is:
(a) linear 0 (b) planar 0
, o (c) pyramidal 0 (d) tetrahedral 0
(c) 10 sigma bonds, I pi bond and I lone pair of electrons
t o 17. The compound in which carbon uses only its sp3-hybrid
(d) 9 sigma bonds, 2 pi bonds and I lone pair of electrons orbitals for bond formation is:
o (a) HCOOH 0 (b) (CH 3 )3 COH 0
8. The number of sigma and pi bonds in but-l-ene-3-yne are: (c) NH2CONH 2 0 (d) (CH~hC-CHO 0
(a) 5 sigma and 5 pi 0 (b) 7 sigma and 3 pi 0 18. The bond energy (in k cal mol-I) of-a C-C single bond is
(c) 8 sigma and 2 pi 0 (d) 6 sigma and 4 pi 0 approximately: [lIT 2010)
9. How many sigma and pi bonds are there in tetracyano (a) 1000 0 (b) 100 . 0
ethylene molecule'? (BUU (Mains) 2008)
(c) 10 0 . (d) 1 0
(a) 90 and 9Jt 0 (b) 90 and 7Jt 0 19. Which of the following bonds is strongest?
(c) 50 and 9Jt, 0 (d) 50 and 71t 0
10. In benzene molecule, there are 3 pi bonds and: (a) ~C-C~ o (b) )C=C< o
(a) 3 sigma bonds 0 (b) 6 sigma bonds 0 (c) --C-G- o (d) None of these o
(c) 10 sigma bonds 0 (d) 12 sigma bonds 0 10. In which case, the carbon-carbon bond length is same?
11. The compound buta-I,2-diene has: IUGET (Med.) 2006) (a) 2-butene 0 (b) benzene 0
(a) only sp-hybridized carbon atom . 0 (c) I-butene 0 (d) I-propyne 0
(b) only sp2-hybridized carbon atom 0 21. All carbon atoms are sp2-hybridised in :
(c) both sp-and sp2-hybridized carbon atoms 0 [PET (Kerala) 1010)
. (d) sp, sp2-and sp3-hybridized carbon atoms ·0 (a) HC=:::C--C==CH 0 (b) H 2C . C=CH 2 0
[Hint: The structure ofbuta-I ,2-diene is HlC-HC=C=CHiI (c) 2-butene o (d) 1,3-butadine 0
(e) cyclohexane o
26, G.R.B. Organic Chemistry for Competitions

12. Resonance is due to: ,:/'


~ ~ ~,
;.r~,:i.:· " J.:"
'{r}.~~JiJ~.
j.'

',,~ 1; •. ~.:')WfiK~b0tl~ i$th~:~tnallest? .


..t'J«-:
" (A)Aelac.alisatiQI) of sigma~elec:trOris' '
Oft '( I¥ 1';~1
•• " ".:" ':; , : ~":il '. r'o ", .
(b) -delocalisatiori ofpi:electrons' ,. o (a) -C=C- '0 (b) ) C = O ' O
(c) migration of H~atoms o I I
(d) migration of protons
23. Resonance structures of a molecule do not have:
o (c) -f N- 0 (d) -f-y- 0

, (a) identical arrangement of atoms 0 33. Maximum hydrogen bonding would be observed in the
(b) nearly the same energy content 0 compound:
(c) the same number of paired electrons 0 (a) methanol 0 (b) glycol 0
(d) identical bonding 0 (c) diethylamine 0 (d) diethyl ether 0
24. Which of the following statements is false about resonance? 34. . ..... bond is the most polar.
(a) It increases stability of the molecule (a) C-O 0 (b) C-Br 0
(b) It leads to similar type of bonding 0 (c) C-S 0 (d) C-F 0
(c) It increases reactivity of the molecule D 35. Examine the following two structures for the anilinium ion
, (d) It decreases reactivity of the molecule 0 and choose the correct statement from the ones given below.
, +

o ~·6
25. How many sigma and pi-bonds are there in the molecule of
dicyanoethene (CN-CH CH-CN)?
(a) 3 sigma and 3 pi 0 (b) 5 sigma and 2 pi Of
(c) 7 sigma and 5 pi 0 (d) 2 sigma and 3 pi 0
26-. Which of the following compounds shows evidence of the I II
strongest hydrogen bonding? (SEE (WB) ZO.O) (a) II is not an acceptable canonical structure because
(a) Propane-I,2,3-triol 0 (b) Propane-l,2-diol 0 carbonium ions are less stable than ammonium ions 0
(c) Propan-I-ol 0 (d) Propan-2-01 0 (b) II is not an acceptable canonical structure because it is
27. The hydrogen bond is strongest in which one of the non-aromatic 0
following? IDPMT ZOO6; AilEE %007] (c) II is not an acceptable canonical structure because
(a) F~H-:'-F 0 (b) O-H---O 0 nitrogen has 10 valence electrons 0
(c) S-H - - - F 0 (d) F-H - - - 0 0 (d) II is acceptable canonical structure 0
28. C-C bond length would be minimum in: 36. s-character of sp-sp2 -and sp3 -hybrid orbitals follows the
I I I
(a) ==c-y- 0 (b) =C-
y- o decreasing order:
(a) sp3 > Sp2 > sp o
(b) sp> sp2 > sp3 o
(c) =y-y= 0 (d) ==C-C== o (c) sp2 > sp3 > sp o (d) sp2 > sp> Sp3

29. C-H bond energy in ethane, ethene and ethyne is:


(a) equal in all the three compounds 0
37. A straight chain hydrocarbon has the molecular formula,
CgHIO' The hybridization for the carbon atoms from one
end of the chain to the other are sp3, sp2, Sp2, Sp3, Sp2, sp2,
,
(b) maximum in ethane 0 sp and sp respectively. The structural formula of the
(c) maximum in ethene 0 hydrocarbon would be:
(d) maximum in ethyne 0 (a) CH 3 -C=C-CH2-CH=CH-CH=CH2 0
30. Hybridized carbon atoms used in the formation of the (b) CH 3 -CH=CH-CH2-CH=CH-C==CH 0
compound, CH 3-CH-CH-CH2 -CH 3 are: (c) CH3 -CH=CH-CH2-C=C-CH=CH 2
(a) sp and sp3 0 (b) sp and sp2 0 (d) CH3 -C' C-CH2-C==C-CH=CH2 0
(c) only sp 0 (d) sp2 and Sp3 0 38. Which one of the followin,g does not have Sp2 -hybridized
31. The state of hybridization of C2 , C3 , C 5 and C6 of the carbon? rSCECE (Med.) Z-1
hydrocarbon, (CBSE (Med.) ZOO9) (a) Acetone 0 (b) Acetic acid 0
yH 3 yH 3
(c) Acetonitrile 0 (d) Acetamide
39~ Number of pi bonds in H 2 C=CH-CH=CH-C==CHis::
0
CH3 -:,<;::-CH=CH-CH-C==CHis: .
7 61 5 4 3 2 I (a) 2 0 (b) 3 0
CH3 (c) 4 0 (d) 5 0
(a) Sp,sp3 ,sp2 and Sp3 0 (b) sp,sp2 ,sp2 and Sp3 0 40. Number of pi~electrons present in naphthalene is:
(a) 4 0 (b) 6 o
(c) sp,Sp2 ,Sp3 andsp2 0 (d) Sp3 ,sp2 ,Sp2 and sp 0
(c) 10 0 (d) 14 o

, _______________________________________________ ~~t_.~~!=1Z.r~
.
Introduction to .Organic Chemistry 27

41. In a resonance hybrid, the bond length: (b) C-I> C-Cl > C-Br t)'
(a) is smaller than in canonical structure 0 (c) C-Br> C-CI > C-I 0
(b) is greater than in canonical structure 0 (d) C-I > C-Br > C-CI 0
(c) is the same as in canonical structure 0 54. Arrange the following compounds in order of increasing
(d) none of the above 0 dipole moment:
42. Resonance energy of benzene is about so much kcallmol: (i) toluene (ii) m-dichloro benzene
(a) 35 0 (b) 58 0 (iii) o-dichloro benzene (iv) p-dichloro benzene
00100 0 OOI~ 0 (a) (i) < (iv) < (ii) < (iii) o
43. Resonance in a molecule results in: (b) (iv) < (i) < (ii) < (iii) o
(a) destabilisation 0 (c) (iv) < (i) < (iii) < (ii) o
(b) stabilisation 0 (d) (iv) < (ii) < (1) < (iii) o
(c) increase in bond length 0 55. Sublimation is a process in which a solid:
(d) none of the above 0 (a) changes into another allotropic fonn o
44. In which of the compounds below is there more than one (b) changes into liquid form o
kind of hybridization (sp, sp 2 , sp 3 ) for carbon? (c) changes into vapour form o
(i) CH3 CH2 CH2 CH3 (ii) CH 3-CH=CH-CH3 (d) none of the above o
(iii) H 2 C=CH-CH=CH2 (iv) H-O=G-H 56. Naphthalene is a volatile solid. It is best purified by:
(a) (i) and (iv) 0 (b) (ii) and (iii) 0 (a) crystallisation 0 (b) distillation o
(c) (ii) 0 (d) (iii) and (iv) 0 (c) steam distillation 0 (d) sublimation o
45. Which of the following has a bond fonned by overlap of 57. Methanol and acetone can be separated by:
Sp3 -sp-hybrid orbitals? (a) fractional distillation 0 (b) distillation 0
(a) CH3-C=C-CH 3 [J (c) steam distillation 0 (d) vacuum distillation O.
(b) CH 3 -CH=CH-CH 3 0 58. Separation of two substances by fractional crystallisation
depends upon their differences in:
(c) CH2 =CH-CH=CH 2 0
J . (d) HC=CH 0
(a) densities 0 (b) volatility o
I
(c) solubility 0 (d) crystalline shape o
46•. Maximum amount of hydrogen bonding occurs in case of: 5'. Aniline is separated from a mixture by:
(a) HOH 0 (b) HF 0: . (a):tra.ctiQnal crystallisation . tJ
~ (c) C2 H 5 0H 0 (d) NH3 0 (b) fractional distillation 0
47. Intramolecular hydrogen bonding is exhibited by: (c) vacuum distillation 0
(a) o-nitrophenol 0 (b) catechol 0 (d) steam distillation 0
(c) salicylic acid 0 (d) all of these 0' 60. Glycerol is purified by: IPMT (Kefala) 10101
48. The maximum possible number of hydrogen bonds, a water (a) steam distillation 0 (b) vacuum distillation 0
molecule can form is: tCET (Karnataka) 1088] (c) sublimation 0 (d) simple distillation 0
(a) 4 .0 (b) 3 0 61. Two inuniscible liquids are separated by:
(c) 2 0 (d) 1 0 (a) separating funnel 0 (b) fractional distillation 0
49. Which of the following explanations accounts for o-nitro- (c) chromatography 0 (d) sublimation 0
phenol to be more volatile than p-nitrophenol? 62. Latest technique for purification, isolation and separation of
(a) Intermolecular hydrogen bonding· 0 organic compounds is: rPMT (Kerala) 2007;
Punjab CET (En. .) 20081
(b) Resonance 0
(a) chromatography 0 (b) steam distillation 0
(c) Intramolecular hydrogen bonding 0 (c) crystallisation 0 (d) vacuum distillation 0
(d) Inductive effect 0 63. Steam distillation is applied to those organic compounds
so. Bond energy is maximum in: which are steam volatile and:
(a) 0-{) 0 (b) O=C 0 (a) soluble in water 0
(c) C~N 0 (d) N N 0 (b) insoluble in water 0
51. The bond energy: of C-C bond in kcallmol is: (c) sparingly soluble in water 0
(a) 58 0 (b) 83 0 . (d); insoluble in all solvents 0
(c) 145 0 (d) 192 0 64. There are several criteria for purity of organic compounds.
51. The maximum bond energy is present in: Out of these which one is considered best?
(a) C-H o (b) C-C (a) Melting point o
[]
(c) C-N 0 (d) G-O 0 (b) Microscopic examination
(c) Mixed melting point []
53. Among the C-X bonds, the correct bond energy order is:
(a) C-CI > C-Br> C-I 0 (d) Colour []

... lett #'1


28 G.R.B. Organic Chemistry for Competitions

65. Two volatile and miscible liquids can be separated by 75. Anthracene is purified by:
fractiorial distillation into pure components under the (a) filtration 0 (b) distillation
conditions when: (c) crystallisation 0 (d) sublimation 0
(a) they have low boiling points 0 76. Which of the following is useful for making pure water
(b) the differcmce in their boiling points is large 0 from a solution of salt in water?
(c) the boiling points of the liquids are close to each other (a) Filtration 0 (b) Simple distillation 0
o (c) Steam distillation 0 (d) Chromatography 0
(d) they do not form azeotropic mixture 0 77. Water and alcohol can be separated from a mixture by:
66. The boiling points of two miscible liquids, which do not (a) fractional distillation 0 (b) sublimation 0
form azeotropic mixture, are close to each other. Their (c) decantation 0 (d) evaporation 0
separation is best carried out by: 78. A mixture of water and NaCI can be separated by:
(a) vacuum distillation 0 (b) fractional distillation 0 (a) sublimation 0 (b) evaporation 0
(c) steam distillation 0 (d) redistillation 0 (c) decantation 0 (d) filtration 0
67. In paper chromatography: 79. In laboratory, solvent can be separated from solute by the
(a) the moving phase is a liquid and stationary phase is a process:
solid 0 (a) decantation 0 (b) sedimentation 0
(b) the moving phase is a solid and stationary phase is a (c) distillation 0 (d) filtration 0
liquid 0 80. In simple distillation of liquids, it involves simultaneously:
(c) both the phases are liquids 0 (a) vaporisation and condensation 0
(d) both the phases are solids 0 (b) heating and sublimation 0
68. Oils are purified by: (c) vaporisation and sublimation 0
(a) fractional distillation 0 (b) steam distillation 0 (d) boiling and filtration 0
(c) vacuum distillation 0 (d) simple distillation 0 81. Distillation under reduced pressure is used to purity liquids
69. Chromatography technique is used for the separation of: which:
(a) small samples of mixtures 0 (a) are highly volatile 0
(b) plant pigments 0 (b) have high boiling points 0
(c) dye stuffs 0 (c) are explosives 0
(d) all of the above 0 (d) decomposes below their boiling points - 0
70. A mixture of naphthalene and benzoic acid can be separated 12. which one of the following reagents is useful for separating
by: [JIPMER 2007) aniline from nitrobenzene?
(a) chromatography· 0 (a) Aq. NaHC0 3 p (b) Aq. NaHS0 3 0
(b) sublimation 0 (c) Aq. HCI 0 (d) Dilute H2 S04 0
(c) fractional crystallisation 0 83. A mixture of phenol and benzoic acid will completely
(d) distillation 0 dissolve in an aqueous solution of:
71. In column chromatography, the moving phase is: (a) HCI 0 (b) NaCI 0
(a) the substances which are to be separated 0 (c) NaHC0 3 0 (d) NaOH 0
(b) eluent 0
84. Silica gel is used for keeping away the moisture because it:
~~~~ 0 (a) adsorbs water molecule 0
(d) mixture of eluent and substances to be separated 0 . (b) absorbs water molecule 0
72. Azeotropic mixtures: (c) reacts with water 0
(a) boil at different temperatures 0 (d) none of the above 0
(b) are mixtures of solids 0 85. Anhydrous CaCl 2 is used as drying agent, because it:
(c) are constant boiling mixtures 0
(d) none of the above 0 (a) adsorbs water molecule 0
73. Which is useful for the separating benzoic acid from methyl (b) absorbs water molecule 0
benzoate? (c) both adsorbs and absorbs water molecule 0
(a) Aq. NaHC0 3 0 (b) Oil. HCI 0 (d) none of the above 0
86. The function of fractionating column is:
(c) Aq. NaHS0 3 0 (d) Oil. H 2 S04 0 (a) to separate the two components 0
74. A mixture of camphor and benzoic acid can be easily (b) to provide greater.cooling surface to the vapours 0
separated by: [BBU 2005) (c) to kept the vapour pressure constant . 0
(a) sublimation 0 (d) to avoid mixing of the vapours of two components 0
(b) fractional distillation 0 87. One having high vapour pressure at temperature below its
(c) chemical method 0 melting point is:
(d) extraction with solvents 0 (a) benzoic acid 0 (b) salicylic acid 0
(c) citric acid 0 (d) all of these 0
Introduction to Organic Chemistry 29

II. Osazone formation is used to separate and identifY: (c) 8 sigma, 3 pi and 4 non-bonded electrons 0
(a) alcohols 0 (b) carboxylic acids 0 (d) <} sigma, 3 pi and 2 non-bonded electrons 0
(c) carbohydrates 0 (d) starch 0 100. In th~ compound CH 2 =CH-CH 2 -CH z-C==CH, the
89. Fractional distillation is used to separate liquids which C 2-C 3 bond is of the type:
differ in their boiling points by: (a) sp_sp2 0 (b) sp3_sp 3 o
(a) 0-100 C 0 (b) 10- 20° C 0 (c) sp_sp3 0 (d) sp2_sp 3 .0
(c) 20~ 40" C 0 (d) 40- 800 C 0
101. p-nitrophenol and o-nitrophenol are separated by:
90. Which of the substance is purified by subliinaflion?oo
[D<!E (Engg.) 2007) IDPMT 2003; PMET (Punjab) 2008]
(a) Naphthalene 0 (b) Benzoic acid 0 (a) crystallisation 0 (b) fractional distillation 0
. (c) Catl!phor 0 (d) All of these 0 (c) distillation 0 (d) steam distillation 0
91. A mixture of oil and water is separated by: 102. Intermolecular hydrogen bonding is strongest in:
(a) filtration 0 [ADMS 2003]
(b) using separating funnel 0 (a) methylamine o (b) phenol o
(c) sublimation 0 (c) formaldehyde o (d) methanol o
l 2 3 4
(d) fractional distillation 0 103. In the compound H2 C=C=CH-CH3 ,the hybridization of
92. Styrene can be purified by: iJIPMER 2008]
1st and 2nd carbon atom is: IBHU 2003)
(a) simple distillation 0 (b) fractional distillation 0 (a) sp3_sp 0 (b) sp2_sp3 0
(c) vacuum distillation 0 (d) steam distillation 0
'3~(A) is a higller phenol and (B) is an aromatic carboxylic
(c) sp2_sp 0 (d) SpZ_sp2 0
.. acid~ Separation of a mixture of (A) and (B) can be carried 104. Camphor is often used in molecular mass determination
out easily by using a solution of: because: feBSE (Med.) 2004)
(a) NaOH 0 (b) lime 0 (a) it is readily available 0
(c) NaHC0 3 0 (d) Na zC0 3 . .0 (b) it has very high cryoscopic constant 0 .
94~ Which IS correct statement about azeotropic mixture? (c) it is volatile 0
(a) It boils at constant temperature (d) it is a solvent for organic substances 0
(b) It does not obey Raoult's law 0 lOS. How will you separate a solution (miscible) of benzene +
(c) It cannot be separated by fractional distillation 0 . CHCI 3 ? -IAFMe 2005)
(d) All of the above 0 (a) Distillation 0 (b) Sublimation 0
95. Separation of organic compounds by column (c) Filtration 0 (d) Crystallisation 0
chromatography is due to: 106. Allyl cyanide contains 0' and n-bonds: [PMT (MP) 2004)
(a) selective absorption. 0 (a) 50',7n 0 (b) 90',3n 0
(b) selective adsorption 0
(c) both absorption and adsorption 0 (c) 30',411: 0 (d) 90',911: 0
(d) solubilities 0 .107. Which of the following gives correct arrangement of
96. The technique of gas liquid chromatography is suitable for compounds involved based on their bond strength?
compounds which are: . IBHU 2005)
(8) soluble in water 0 (a) HF>HCl>HBr>HI 0 (b) HI > HBr >HCI >HF 0
(b) highly volatile 0 (c) HF>HBr>HCI>HI 0 (d) HCI>HF>HBr>HI 0
(c) vaporise without decomposition 0
(d) liquids
97. Two substances when separated out on the basis of their
0 .11. How many bonds are there in~ ?
extent of adsorption, by one material, the phenomenon is . . . IDeE 2005)
called: (a) 140',811: 0 (b) ·180',811: 0
(a) chiomatography 0 (b) paper chromatography 0 , (c) 190',411: 0 (d) 140',2n 0
(c) steam distillation 0 (d) sublimation 0 109. The correct order regarding the eleetronegativity of hybrid
98. When a hybridization state of carbon atom changes from orbitals of carbon is: leBSE (Med.) 2006)
sp3 to spz and finally to sp, the angle between the (a) sp< sp2 > sp3 0 (b) sp< spz < sp3 0
hybridized orbitals:
(c) sp>spZ<sp3 0 (d) Sp>Sp2>sp3 0
(a) is not affected 0
(b) increases progressively 0 110. Among the following mixtures, dipole-dipole as the major
(c) decreases gradually 0 interaction is present in: rAIEEE 2006)
<I'
(d) decreases considerably 0 (a) benzene and ethanol 0
99. Allyl isocyanide has: (b) acetonitrile and acetone
(a) 9 sigma and 4 pi bonds 0 (c) KCI and water o
(b) 8 sigma and 5 pi bonds 0 (d) .benzene and carbon tetrachloride o
30 G.R.B. Organic Chemistry for Competitions

Ill. Consider the following compounds: (b) F2 > Cl z > Br2> 12 : Electronegativity ,0
(A) chloroethene (B) benzene (c) F2 > Cl 2 > Br2> 12 : Oxidising power o
(C) buta-l,3-diene (D) 1,3,5-hexatriene (d) F2 > Cl 2 > Br2> 12 : Electron gain enthalpy o
All the carbon atoms are Sp2 -hybridized in: U9. In the hydrocarbon,
(PET (Kera.l) 1006] H3 C-CH=CH-CH2 -C==CH
6 5 4 3 2 I
(a) A, C, D only 0 (b) A, B only 0 'The state of hybridization of carbons 1,3,5 are in the
(c) B, C, D only 0 (d) C, D only 0 following sequence: ICPMT (Med.) 1008]
(e) A, B, C, D 0 (a) sp,Sp2,sp3 . 0 (b) sp3,Sp2,SpO
112., The d~creasing order· of bond. dissociation energies of
(c). spz ,sp,sp3 0 (d) sp,sp3,sp2 0
C----C, C-H and H-H bonds is:
(EAMCET (EnS8-) 10071 120. The enolic form of butanone contains: '
(a) H-H > ----C-H > ----C----C- ,0 tPMT (Kerala) 1008)
. (b) .----C----C- > ----C-H > H-H 0 (a) 121.1 bonds, Ix bond and 2 lone pairs of electrons I. '0
(c) ----C-H > ----C----C- > H-H 0 (b) 111.1 bonds, Ix bond and 2 lone pairs of electrons 0
(d) ----C----C- > H-H > ----C-H 0 (c) 121.1 bonds, Ix bond and I lone pair of electrons []
113. Number ofl.1 and x-bonds in C6 H sCOOH is: . (d) I (b bonds, 2x bonds and 2 lone pairs of electrons 0

©
(e) 131.1 bonds, Ix bond and 2 lone pairs of electrons 0
(DPMT 10071
'(a) 131.1,4x 0 (b) 14G,4x 0
121. Hybridization of nitrogen atom in pyridine [ liS:
(c) 151.1,4x 0 (d) 16o',4x 0
114. Compare List I and List II and choose the correct matching
codes from the choices given: . '" (BOU (Main.) 1001]
List I List D (a) sp3 0 (b) spz 0
(A) Glycerol (i) Sublimation. (c) sp 0 (d) sp 3d 0
(B) o-nitrophenol (ii) Beilstein's test 122. The number of x-bonds in the following compound
(C) Anthracene (iii) Victor-Meyer's method OzN---C==C-NO z is: (DPMT 2008]
(D) Halogens (iv) Steam distillation (a) 2 0 (b) 3 0
(E) Molecular weight (v) Vacuum distillation (c) 4 0 (d) I 0
(vi) Eudiometry , Ill. The compound in which underlined carbon uses only its
Copes: [PET (Kerala) 20071
sp3 -hybrid orbitals for bond formation is:
(a) (A-v), (B-iv), (C-i), (D-ii), (E-iii) 0
(b) (A-iv), (B-v), (C-i), (D-vi), (E-ii) 0 (BelCE (Med.) 200S]
(c) (A-vi), (B-iv), (C-i), (D-iii), (E-ii) 0 (a) CH3 gOOH o (b) CH3 gONH2 0
, (d) :(A-'-v), (B-iv), (C-vi), (D-ii), (E-Ui) 0 ' (c) CH3 CHzOH o (d) CH3 CH=CH2 0
(e) (A-iv), (B-vi), (C-ii), (D-iii), (E-v) 0 124. Match the following:
11S. Which one of the following can be purified by sublimation? (A) Simple distillation (i) to separate the liquids
(MOCET (Med.) 10M! which are steam volatile,
(a) F2 0 (b) Cl z 0 insoluble in water arid
(c) Br2 0 (d) 12 0 contains non-volatile
116. What is the percentage of p-character of hybrid orbits of impurities
carbon in methane, ethene and ethyne respectively?
(B) Fractional distillation (ii) to separate liquids which
(SCRA (Med.) 10071 decomposes at a tempera-
(a) 75,66,50 0 (b) 50,66,75 ,0
ture below their normal
(c) 25, 33, 50 0 (d) 50, 33,25 'D boiling points
. 1t7. In the following the least stable resonance structure is:
, . (UT 1007] (C) Vacuum distillation (iii) to separate two or more
liquids which have boiling
~ @ -?,O ~.®-?,O
(a) e N (b) ® N points close to each other.
I I "',;1
(D) Steam distillation (iv) to separate liquid fr,Qm
o 0
e non-volatile impuritieS
e ABC D
(c) ~~-?,O (d) ~~/O (a) (i) (ii) (iii) (iv)
I @ I • ?i (b) (iv) '(iii) (ii) (i)
oe 0
e (c) (iii) (i) (iv) (ii)
(d) (ii) (iv) (i) (iii)
US. Which one of the following arrangements does not give the •
US. Match the following:
correct picture of the trends indicated against is?
(A) Sublimation (i) Ether + toluene
(CPMT (Med.) 2oo8J
(a) F2 > Cl 2 > Brz > 12 : Bond dissociation energy 0 (B) Distillation (ii) o-Nitrophenol + p-nitrophenol
Introduction to Organic Chemistry 31

(C) Vacuum distillation (iii) Benzoic acid + benzaldehyde IlS. Mixed melting point is determined to check:
(D) Steam distillation (iv) Glycerol from spent lye (a) the purity of organic compound o
ABC D (b) whether the two compounds are same o
(a) (iv) (iii) (ii) (i) (c) whether the two compounds are different o
(b) (i) (ii) (iii). (iv) (d) whether the two compounds can be separated by
(c) (iii) (i) (iv) (ii) fractional crystallisation method 0
(d) (ii) (iv) (i) (iii) 129. Which of the following compounds can be purified by
SET II: This set contains the questions having one or more, correct vacuum distillation?
answers. ',~ { "" (a) Glycerine 0 (b) Glycerol 0
(c) Propane-l,2,3-triol 0 (d) Ethanol 0
126. Which resonance form in each of the fdtlowing sets is the 130. Which of the following compounds can be purified by
major contributor to the real structure? . 'I" steam distillation? ',
•• •• +
(i) H2C=CH-CI: ~ H2 C-CH=CI: (a) Salicylaldehyde o
•• •• (b) Bromobenzene :0
(a) (b)
+ • •• - (c) p-Hydroxy benzaldehyde o
~ H 2 C-CH. CI:
,- +
00 (d) Nitrobenzene o
(ii) H2 C-CH=NH2 ~ H 2 C=CH-NH 2 (e) 131. Mixture of benzene and aniline can be separated by:
(a) (b)
(a) distillation 0 (b) steam distillation o
(c) dil. HCI 0 (d) dil. NaOH
132. Absolute alcohol can be prepared from rectified spirit by:
(a) azeotropic distillation with benzene 0
(b) fractional distillation 0
(c) keeping over fresh CaO for few hours and then

O l-O~ -(1)-~
(iv) distilling o
~ '. # llJ)J V, " _ (d) distillation under reduced pressure o
(a) (b) (e) (d)
, 113. Select the wrong statements about chromatography.
(a) Moving phase is liquid and stationary phase is solid 0
+ (b) Moving phase is liquid and stationary phase is liquid 0
0- :0
+ '. 1 _I (c) Moving phase is solid and stationary phase is solid 0
(v) H 2 C-CH=C-H ~ H 2 C-CH C-H (d) Moving phase is solid and stationary phase is liquid'
'W' 00 -0
134. A substance which decomposes at or below its boiling point

6 -6:
}, Ell Ell_
H cannot be purified by:
'(a) steam dit>tillation '0
(b) simple distillation []
(Vi1 o
(c) fractionaJ distillation . '
e
(a) (b)
(d) distillation under reduced pressure o
135. Refining of petroleum does,not involve:
·127. Chromatography technique is used in the sepafl:!,tion of: (a) simple distillation o
(a) volatile liquids 0'(1» amino acids (b) steam distillation o
(q) plant pigments o (d) sugars o '(c) fractional distillation ' ,0
," .'
,
(d) distillation
,
under reduced pressure o
ASSERrI9N·RE~ON TYp(~~:i~9~~s~I~~"j~;;:;~;= i.'~ ~~,~-:::::I,:i:::f::::::::::=:~::I: I
.: ' . "
i Instiructiom: Each question contains statement-l (Assertion,
•A) and statement-2 (Reason, R). Of these statement,. 'Irk ;(c) Statement~ r (A) is true; ~tatement-i (R) is false. ' {
: Co !Teet choice i f : ; ,' ,(d) StatemeI):t.l (A) is false,! statement-2 (R) is true.... ,. -
(a) Statement-l (A) and statement-2 (R) are true and I. (A) Oils are purified by steam distillation.
statement-2 (R) is the correct explanation for (R) The compounds which decompose at their boiling
statement-l (A). . points can be purified by steam distillation. .
(b) Statement-I, (A) and statement-2 (R) are true and - . IAIIMB--.
; ....... statement-2 (R)is not the correct explanation for 2. (A) Mixture of glucose andm-dinitrobenzene can-be
statement-l (A). separated by shaking it with ether,
32 G.R.B. Organic Chemistry {Or Competitions

(R) Glucose is soluble in water. (R) Fractional distillation helps in -separating two liquids
3. (A) Thiophene present in benzene as impurity can be from their mixture when their boiling points differ by
removed by shaking the mixture with cold cone. lOoC.
H 2 S04 , 7. (A) Aniline has odd molecular mass, i.e., 93.
(R) Thiophene is a heterocyclic aromatic compound. (R) All nitrogenous compounds containing odd no. of
4. (A) A mixture of camphor and benzoic acid cannot be nitrogen has odd molecular mass.
separated by sublimation. 8. (A) Molecular nitrogen is less reactive than molecular
(R) Camphor on heating sublimes but benzoic acid does oxygen.
not. (R) The bond length ofN2 is shorter than that of oxygen.
5. (A) A mixture of o-nitrophenol and p-nitrophenol can be 9. (A) p-hydroxy benzoic acid has a lower boiling point than
. separated by steam distillation. o-hydroxy benzoic acid.
(R) o-nitrophenol is steam volatile but p-nitrophenol is not (R) o-hydroxy benzoic acid has intramolecular hydrogen
though both are water soluble. bonding. (lIT 1007)
6. (A) Acetone (b.pt. 329K) and methyl alcohol (b.pt. 338 K) 10. (A) Chlorine has higher electron affinity than fluorine.
are separated by fractional distillation. (R) Chlorine is a poor oxidising agent than fluorine.
(AIIMS 1007)

ANSWERS
OBJECTIVE QUESTIONS

1. (c) 2. (b) 3. (c) 4. (d) 5, (c) 6. (c) 7. (a) 8. (b) 9. (a) 10. (d)
11. (d) 12. (d) 13. (d) 14. (c) 15. (b) 16. (a) 17. (b) 18. (b) 19. (c) 20. (b)

21. (d) 22. (b) 23. (d) 24. (c) 25. (c) 26. (a) 27. (a) 28. (d) 29. (d) 30. (d)
31. (a) 32. (b) 33. (a) 34. (d) 35. (c) 36. (b) 37. (b) 38. (c) 39. (c) 40. (c)
41. (a) 42. (a) 43. (b) 44. (c) 45. (a) 46. (b) 47. (d) 48. (a) 49. (c) 50. (d)
51. (b) 52. (a) 53. (a) 54. (b) 55. (c) 56. (d) 57. (a) 58. (c) 59. (d) 60. (b)

61" (a). 62. (a) 63. (b) 64. (c) 65. (d) 66. (b) 67. (c) 68. (b) 69. (d) 70. (a)
71. (d) 72. (c) 73. (a) 74. (c) 75. (d) 76. (b) 77. (a) 78. (b) 79. (c) SO. (a)
81. (d) 82. (c) 83. (d) 84. (a) 85. (b) 86. (b) 87. (a) 88. (c) 89. (a) 90. (d)
91. (b) 92. (d) 93. (c) 94. (d) 95. (b) 96. (c) 97. (a:) 98. (b) 99. (d) 100. (d)
101. (d) 102. (d) 103. (c) 104. (c) lOS; (ay , ; l06.)(b) , . lQ7. (a) -',:iOS: (c),' 109.-(dj 110. (b)
11:t (e) 112. (a) 113. (c) 114. (a) '115. (d) 116. (a) 117. (a) 118. (a) 119. (d) 120. (a)
121. (b) , 122. (c) 123. (c) 124. (b) 125. (c) 126. (i) (a) (ii) (b) (iii) (c) (iv) (a,b) (v) (a) (vi) (b)
127. (b,c,d) J128. (a,b,c) 129. (a,b,c) 130. (a,b,d) 131. (a,c) 131. (a,c) 13J. (a,c,d) 134. (a,b,c) 135. (a,c,d)

ASSERTION-REASON TYPE QUESTIONS


1. (e) 1. (b) 3. (b) 4. (c) 5. (a) 6. (a) 7. (a) 8. (a) 9. (d) 10. (c)
Introduction to Organic Chemistry 33

[BRAIN STORMING PROBLEMS Z


1. \ , This hydrocarbon has hybridization on CH3 CI
C-atoms:
(a) sp,sp2,sp3
(c) sp2,sp3
0 (b) Sp,Sp2
0 (d) sp,sp3
2. 1°,2°,3° and 4° carbon atoms are present in:
0
0 (il 6 (ii)
6:::::::....
I CI

~CI
¢
CI
(a) 2,2,3-trirnethyl pentane 0
(b) 2,3,4-trirnethyl pentane 0
(c) both (a) and (b)
(d) none of the above
3. Two molecules indicated below are capable to intra-
0
0
(iii)
U (iVl

CI
moiecular H-bonding. Which is likely to form more stable
hydrogen bonds? (a) (i) < (iv) < (ii) < (iii) 0 (b) (iv) < (i) < (ii) «iii)
0
H (c) (iv)«i)«iii)«ii) 0 (d) (iv) < (ii) «i) «iii) 0
I
10. H-C ~
yO H-C
.>-0
~ , c-o bond lengths.
CH3'-...C"""C'::::::::'C,..,.,CH3
p a-.:-H I) o·
~ 6
H ....--
designated by u, Il, y and 0 are in order:
(a) u=y<ll=o 0 (b) u<ll<y=o 0
(I)
(c) u< y =0< Il 0 (d) all are equal 0
WI 0 [HInt: Length of 'Y and /) will be same due to the resonance.
(b) II 0 o o· r 01
( c) Both are equally capable
(d) Cannot be predicted
0
0
H-c(O. ~ H-C(O = lH-:X~OJ}
4. Which one of the underlined carbons is sp 3 -hybridized?
11. Which one ofthe following compounds is an allylic halide?
(a) CH39i=CHz 0 (b) CH 3 9iZNHZ 0 Br
(c) CH 3 §ONHZ 0 (d) CH 3 CH2QN 0
(a) CH3-@--cH=t-CH3 0
s. The hybridization of iodine in iodosobenzene is :
(a) sp 0 (b) sp2 0
(c) sp3 0 (d) sp 3d . 0 (b) BrCH2--@-cH=CHCH3 0
6•. Carboxylic acids do not give the characteristic reactions of
> C= 0 group because of:
(a) p()lar nature 0 (b) resonance 0 (c) CH3-@--cH=CHCHzBr . o
(c) symmetrical structure 0 (d) attached alkyl group 0

(d)CH~~HCH' .
7. Which among the following has highest boiling point?
(a)CH3 CH 2CH zCH2CI D. o
(b) (CH3)2CHCH2CI 0
(c) (CH3 h C-CI 0 [Hint: (a) is vinylic (b) is benzylic
(d) None of the above 0 (c) is allylic (d) is arylic]
8. Which among the following has highest melting point? ll. The compound in which all carbon atoms use only sp3 -
(a) (CH3CO)20 0 (b) CH3CN 0 hybrid orbitals for bond formation is:
(c) CH3CONHZ 0 (d) CH3 COCI 0 (a) CH3 CHO 0 (b) CH 3 COCH 3 0
[Hint: (c) Amide has highest melting point due to fonnation of . (c) (CH3)3COH 0 (d) HCOOH· O.
intennolecular hydrogen bonding.) 13. Which of the following is unacceptable resonating structure
9. Order of arrangement of the following compounds with of buta-l ,2,3-triene?
increasing dipole moment is : ~
(a) CHz-C==C-CHz 0
~
(b) CH z =C-:-C=CH2
0
34 G.R.B. Organic Chemistry for Competitions

14. The resonating structures of cyanate ion are, the hybridization state of marked carbon atom changes
O=C==N- ~ -O-C55N ~ +Q==C-N 2-" from:
(i) (il) (iii) (a) Sp2 to sp (b) Sp3 to spo. o
The correct set of oxidation states of 0, C, and N (c) Sp3 to sp2 o (d) Sp2 to sp3 o
respectively with the most stable structure out of the above 19. Which of the following structures have resonance stability?
is: .
(a) (i) -3, +4,-2 o
(b) (ii)-2,+4,-3 o CH3-C "'" ~ CH 3-C
/0 <'H
+ ~
(c) (iii) -1,+4,-3 o
(d) (i) 0,+4,-5 o OH OH
(a) (b)
IS. Arrange the following molecules in increasing order ofcs to
o
(1)0
1t bond ratio: 0-

(2) 'CO~
. ". I
CH - C.<0(-) ~ CH -C( 0
3 3 + H+
~ ~ (e) (d) .
20. Arrange the following resonating structures of formic acid
in order of decreasing stability :

(3) 000(4)00
~ ~ ~ ~ ~ H-C-OH
o
~
~
6
I +
H-C=OH ~ H-C-OH
0-
I
(a) 2<3<4<1 0 (b) 2<4<3<1 0 (I) (II) (~II)
(c) 3<2<1<4 0 (d) 2<3<1<4 0 0+
I
[HiDt:O

120,31t
CO
~ ~
190,51t , (a) II>I>III>IV o (b) I>III>I1>IV
~ H---,C-OH
(IV)
0
o 4 o 19
i' .. 1'=4 i' .. '5=3.8 (c) I1I>II>IV>1 0 (d) IV>III>!>11 0
21. Arrange the following resonating structures of vinyl

000
~

0
~.-9

260',71t .
2;=3.71
co
.~

0'
250,61t
25
#

i' = 6" =4:166]


chloride in order of decreasing stability :

CH 2 =CH-Cl
(I)
(a) I > II > III
(c) II> I > III
~
-
CH 2 -CH=O

o
(II)
(b) III> II > I
o
(d) I> 11= III
+

.
~
+
CH 2-CH=Cl
(III)
-

o
o
i' 22. Among the following four structures, one is not a
16. Whicb one of the following ions is the most resonance permissible resonance form. Identify the wrong structure.
stabilized? [PMT (Kerala) 2010] + •••• + ••
(a) Ethoxide' 0 (b) iso-Propoxide 0 (a) CH 2 -N-0: o (b)CH2 N---,O:
I •• o
.1 ••
, (c) n-Butoxide 0 (d) tert. Butoxide 0 .CH3 'CH3
(e) Phenoxide 0
17. Arrange the following C- H bonds (a, p, y) in decreasing (c) CH
2
N=O:
I •• ' o (d): CH2 -:N=0: o
order of bond energy :
I -
CH3 CH3

H-~-H
f H-C55C-H
(r) 23. Which of the following compounds has (have) sp-
hybridized carbon atom?
1(<<)
(a) CH2=C=0 0 (b) CH2=CH-CN 0
H
(a) a>p>y (b) y>p>a o (c) CH3 -CH=CH2 0 (d) H 2C=0 0
(c) p>a>y . o (d) y> Cl > p o ,24. Identify the weakestC-Hbond among the following:
18. In the reaction, H R R
o I I I
H-C-H R-CH2-H R-CH-H ' R-C-H
I Ia ' ll' I Y' I I)
CH3-C~NH2
• H R
Introduction to Organic che;"i~try-'-'--' 35
(a) a (b) ~
0 0 (c) Four carbons are in sp2 and two in Sp3 -hybrid state 0
(c) y 0 (d) 0 0 (d) Four carbons are in Sp3 and two in sp2-hybrid state 0
lS. Which of the following is the correct sequence of the bond 31. The pair of structures that are resonance hybrid is :
.length? •• + +
(a) S-H>C-H>N-H>O-H 0
(a) HO-CHCH3 and HO=CHCH3
•• ••
o
(b)C-H>~H>O-H>N-H 0
(e) O-H>N-H>C-H>~H 0 o
(d) ~H>O-a>N-H>C-H 0
16. Arrange the following bonds in decreasing order of bond
length: :-0: O-H
••
CI H H II I

a4LOJ IHf;al
CI CI
CH:?, 01
H
H-+.OI
H
(c) CH3-C-H and CH2=C-H
+
(d) CH 3 CH 2 and CHzCH3
+
o
'31. The correct decreasing order of stability of I, II and III
(a) } > 2 > 3 > 4 0 (b) 4 > 3 > 2 > I 0 carbocations is:
(c) 2 > 3 >.1 > 4 [J (d) 4 > I > 2 > 3 0 (I) CH 3 - r n -CH3 (II) CH3-rn-COCH3
17. Which of the following compounds has weakest C-X +
(III) CH3 -CH-OCH 3
. bond?
(a) CH3F 0 (b) CH 3 C} 0 (a) I> II > III ' 0 (b) II >. III > I 0
(c) III> I > II 0 (d) II> I > III 0
(c) CH3 Br 0 (d) CH31 0 B A
18. How many electrons are present in the p-orbitals of a methyl 33. The hybrid states of carbon atoins in (CN)4 C 2 are A and B
cation? and number of x bonds in compound is C. Then: '
(a) 2 0 (b) 3 .D (a)A=sp,B=sp2 andC=9 0
(c) 4 D. (d) None of these 0 (b) A =sp2 ,B =sp, and C = 9 CI
19. In which of the following, delocalisation of x-electrons (c) A =sp3 ,B=sp and C= 9 0
is/are possible?
(d) A =sp2 ,B =sp2 and C =9 D
(a) CH 2 =CH2 0
+ • .. -
(b) CH3-CH2-CH=CH2 0 34. -C- C - C -C- Select the correct state of
(c) CH 2=CH-CH=CH2 0
XI I X2 X3 I X4 '
(d) CHi =CH-:-CH 2-CH=CH2 0 hybridization at X I , X Z ,X 3 and X 4'
XI Xi X3 X4
H
(a) sp2 sp sp2 sp3 0
, H,e-b-C/H
(b)sp3 sp2 sp sp CJ
30. II I II
C (c) sp2 sp2, " :sJr .• sp3 0
H/ 4-C'H
(d) Sp3 Sp2 Sp2 sp·
H
In the given Dewar structure of benzene, which of the 3S. Resonating structures of a molecule have :
following statement(s) is/are correct? (a) identical bondmg 0
(a) All the carbOns are in sp2-hybridstate 0, (b) different bonding CJ
(c) identical arrangement of atoms and nearly same
(b) All the carbons are in Sp3 -hybrid state Cl energies CJ
(d) the same number of paired and unpaired electrons

ANSWERS: BRAIN STORMING PROBLEMS I'


1. (b) 1. (a) 3. (a) 4. (b) S. (c) 6. (b) 7. (a) 8.;(c) 9. (b) 10. (c)
t
11. (c) n. (c) 13. (d) 14. (b) IS. (c) 16. (e) 17. (b) 18. (a) 19. (c,d) 10. (b)
11. (a) 22. (c) 13. (a, b) 14. (d) 2S. (a) 26. (b) 27. (d). 1& (d) 19~ (c) 30. (c)
31. (a) 31. (c) 33. (b) 34. (a) , jS. (b, c, d)
G.R.B. Organic Chemistry for Competitions

LINKED COMPREHENSION TYPE QUESTIONS

2) ¢
Passage 1
A polar covalent bond is fonned between the two elements of
different electronegativities. The polarity of a bond depends on
the electronegativity ditlcrence, the bonding atoms and also on
the shape of the molecule.
>
QCF3
>

CF3
A-B , True (a) False (b)
Let X:,4 and.xa are the eiectronegativities of bonding atoms A
and B then, percentage ionic character of the bond can be Passage 2
calculated as,
. Geometry of organic compound is often described in tenns
% ionic character =211 x A - Xo I +3.51 x A - xal 2 of the valence shell electron pair repUlsion theory. The VSEPR
Dipole moment of the bond ( J1) depends on the bond length model rests on the premise that an electron pair, either bonded
and the polarity of the bond. pair or an unshared pair, assOCiated with a particular atom will be
as far away from the atom's other electron pairs as possible.
}l=qxd The tricoordinate carbon atoms of an alkene or carbonyl
Here, q =charge of the dipoles group also fonn bonds with angles near 1200 • In these
d = bond length compounds, unsaturated double bonds have two electron
pairs-those of the sigma and pi bonds. RePulsion by these two
It is observed that the dipole moment increases with increase
pairs are some what greater than those between single bonds, so
in the inductive effect.
that deviation from exact '1200 trigonal geometry is observed.
Answer the following questions as indicated:
Another factor which has important influence on shapes is
Select code (a)ifthe statement is true and code (b) if the non bonded repulsion between the atoms within the molecule.
statement is false. Such repulsion is also referred to as sterle effects.
1. The dipole moment of CH 3 -X bond lies in the Answer the following questions:
following sequence: l,~ ~
CH3 -1 < CH3-Br < CH3-CI • HuH H ~ 'CH3
True (a) False (b)
2. Dipole moment of methanol is less than ethanol: CH3~
y CH 3 (CH3)3C ~
li qCH3)3
True (a) False (b) Select the correct sequence of bond angles indicated in the
3. pipole moment of C-Cl bond is greater than C-Fpond : above molecules.
True (a) False (b) (a) a<13<'Y<6 (b) a:~ 'Y 0
, . /0"", (c) a>~>'Y>o (d) a<~dk'Y
4. Dipole moment of methyl alcohol (CH3 H) is less
F~ Cl~ H~
than that of water : 2. F/C-O Cl/C-O H/ C - O
True (a) False (b)
5. Dipole moment of trans-2-butenai is greater than butanal : Select the correct sequence of indicated bond angles.
o (a) a<~<'Y (b) a>~>'Y
(c) a ~='Y (d) a<~>'Y
I
/CH~ /C",
CH 3 CH 2 H
butanal
o Select the correct sequence of indicated bond angles.
(a) a>~>'Y (b) a=~='Y
H II, ' (c) a<~<'Y (d) a>~<'Y

tH/
""'C = ~I / "'H ~H
4. Cl---l.(,;(,tU
3 H • "q'H
trans-2-butenal H
True (a) False (b) Which amo~g the following is correet about the indicated
..6. Dipole moment of para-nitlUphenol is greater than phenol: bOnd angles?
" True (a) '. False (b) (a)a= ~ (b) a> ~
7. ,pipole moment of anilin,e, trifluoromethyl benzene and (c) a<~ (d) , Can not be predicted
p-trifluoromethyl aniline lies in the following sequence:

~-"--j
,P('>' .. 'ief
Introduction to Organic Chemistry 37
S. Which compound has bond angles nearest to 120°?
(a) O=C=S (b) CHI 3
(c) H 2 C=0 (d) H-C=C-H
(e) CH4

Passage 3 CH3
Double bond equivalents help in search for structure of a
compound. It involves following .steps:
• Calculate the expected number of hydroge!1 atoms in the
[Hint: Tertiary arnines (CH 3-,I N) are· not involved in

CH 3
saturated structure. intennolecular hydrogen bondhig, hence their boiling
(a) For C n there would be : (2n + 2) hydrogens if point is lowest as compared to corresponding primary
compound contains C, H, 0 only. . and secondary arnines.]
(b) For CnN m, there would be (2n + 2+ m)hydrogens. 2. Which of the following molecules is dimerised' when
• Subtract the actual number of hydrogen and divide by 2. dissolved in nonpolar or organic solvent?
This gives the double bond equivalents.
• rung is considered to possess single DBE. COOH
Answer the following questions on DBE: (a) R-COOH (b) I
1. Double bond equivalent of compound C 7 H 12 0 is: COOH
(a) 2
(c) 4

(a) 2
(c) 4
(b) 3
(d) 1
2. Double bond equivalent of benzene will be:
(b) 3
(d) 1
(c) R-OH (d) 0
3. Which of the following compounds is (are) stablised by
3. Which of the following is not correct? intramolecular hydrogen bonding? .
Compound DBE
(a) C7 HlO O 2 CI OH
(b) C 7 H g O 4 .. - 1 I
(c) C 7 H17 N
(d) C7H'3NO
3
2
(a) Cl-f-f-H
4. Double bond equivalent ofC7H 16 0wouid be ...
CI OH
(a) 0
(c) 2
(b) 1
(d) 3
fH
(c) CH3-C==CH-C-OC2Hs
V
Passage 4 CH 20H
The hydrogen bond is an electrostatic attractive force
(d) I
CH2 0H
between covalently bonded hydrogen atom of one molecule and
an electronegative atom like (F, 0, N) of other molecule. 4. Select the compound which involves intramolecular
Hydrogen bond is nearly an electrostatic attractive force and not a hydrogen bonding.
normal chemical bond. It is very weak (2-lOkcaJ/mol) as (a) HCOOH (b) CH3COOH
compared to a covalent bond (strength 50-100kcal/mol). (c) C6 Hs COOH (d) CH3 COOOH
In intramolecular hydrogen bonding, the two or more than [Hint: Per acids fonn intramolecular hydrogen bond.
two molecules of the same or different substances are linked to r-
form polymeric aggregate. Intermolecular hydrogen bonding
increases the boiling point ofthe compound and also its solubility
in water. Intramolecular hydrogen bonding occurs within two
Cfl3-C("',f,+ ]
0-0
atoms of the same molecule. Intramolecular hydrogen bonding is
also calied chelation, since it. involves· . ring ~ormation. 9. . 9. . OH P.
Intramolecular hydrogen bonding decreases the boiling point of II ' II . I .II
the compound and also its solubility in water. S. CH3 -C-CH 2-C-CH 3..----'" CH3-C=CH-C-CH3
Answer the ·following questions: 2,4-pentadione 4-hydroxypent-3-en-2-one
. (.4) . (B)
1. Which among the following has lowest boiling point?
Select the correct statement about above tautomers.
(a) Form (A) is· more stable due' to formation of

6
. NH2
intramolecular hydrogen bond
(b) Form (B) is more stable due to formation of
(a) intermolecular hydrogen bond
· 38·· G.R.B. Organic Chemistry (or Competitions

(c) Form (B) is more stable due to the formation of (d) Form (A) is more stable due to the formation of
intramolecular hydrogen bond intermolecular hydrogen bond

'~ .. "

ANSWERS: LINKED COMPREHENSION TYPE QUESnONSI-- 1--------------,


Passage I I.. (a) 2. (b) 3. (il) 4. (a) s. (a) 6. (a) 7. (b)
passage 2 I. (a) Z. (b) 3. (a) 4. (b) S. (c)
Passage 3 I. (a) l. (c) 3. (c) 4. (a)
Passage 4 I. (d)%. (a) 3. (a, b, c) 4. (d) S. (c)

You might also like