SplitPDFFile 5 to 41
SplitPDFFile 5 to 41
·INTRODUCTION. TO
ORGANIC CHEMISTRY
·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 .
. 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
-- ;:
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
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
lYe
Introduction to Organic Chemistry 7
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
.. -
. 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 ,
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
.. 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-
. 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
"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.
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)
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
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:
••
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
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~ . , , ?
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
:~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. '
(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
(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
o
[UGET (Med.) 1006)
(b) C2 H4
o (d) C2H2Br2
0
0
X*x'S: X
[JEE (WB) 1010)
, (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
, _______________________________________________ ~~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 []
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)
~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
#
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
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
'~ .. "