HALOALKANES AND HALOARENES

INTRODUCTION, NOMENCLATURE AND PREPARATION

Aliphatic halogen derivatives are called alkyl halides. They have general formula,
Cn H2n+1X. Haloalkanes and Haloarenes are obtained by the replacement of a hydrogen atom of
an alkane and arene respectively by a halogen atom (F, Cl, Br, I). Aromatic halogen derivatives
are called aryl halides or haloarenes. Haloalkanes contain halogen atoms attached to the SP3 –
hybridised carbon atoms of an alkyl group, whereas haloarenes contain halogen atoms attached
SP2 – hybridised carbon atoms of an aryl group.

USES
1. They are used as solvents for relatively non-polar compounds
2. Chloramphenicol used for typhoid fever.
3. Thyroxine used to treat goiter.
4. Chloroquine used for the treatment of malaria.
5. Halothane used as an anaesthetic agent during surgery.

CLASSIFICATION
a. On the basis of no. of halogen atoms attached.

b. Based on compound containing hybridisation of ‘C’ in C—X Bond, CX attach to sp3/ sp2/sp
‘C’ atom.

sp3 hybridised sp2 hybridised sp hybridised

C–X bond C–X bond C–X bond

a. Alkyl halide Vinylic halide CH ≡ C – X

sp
‘C’ atom

sp2 ‘X’ attached sp ‘C’ atom

‘C’
Allylic halide Aryl halide
b.
c. Benzylic halide

‘X’ attached sp3 ‘C’ atom ‘X’ attached sp2 ‘C’ atom

NATURE OF C—X BOND

Since halogen atoms are more electronegative than carbon, the carbon-halogen bond of alkyl
halide is polarised; the carbon atom bears a partial positive charge whereas the halogen atom
bears a partial negative charge.

From F to I, atomic size increases so bond length between C—X. From F to I

bond length increases and bond strength decreases.
Bond dissociation energy order: C—I < C—Br < C—Cl < C—F
Order of dipole moment: C—Cl > C—F > C—Br > C—I

PREPARATION METHOD OF HALOALKANES

a. FROM ALCOHOLS
HCl
R—Cl + H2O
ZnCl2

PCl5
R—Cl + POCl3 + HCl

SOCl2
R—Cl + SO2 (g) + HCl (g)

PX3
R—X + H3PO3
(X = Cl, Br)
R—OH
NaBr
R—Br + NaHSO4 + H2O
H2SO4

HBr (40%)
R—Br + H2O

red P, X2
R—X
(X2 = Br2, I2)

KI/ NaI (90%)

R—I + NaOH or KOH
H3PO4

Thionyl chloride (SOCl2) is preferred for preparation of chloroalkanes because the other
two products (SO2, HCl) are escapable gases. Hence the reaction gives pure alkyl
chloride.
[ZnCl2 / HCl  Lucas reagent which is used for distinguish test of 10 and 20 and 30
alcohols.]
Reactivity order of alcohols with haloacid 30 > 20 > 10, more the number of e-
withdrawing group,in R-OH less is reactivity.
Above methods are not applicable for preparation of aryl halides as C—O bond in phenols
has a partial double bond character and is difficult to break being stronger than a single
bond.
b. FROM ALKANES
Haloalkanes can be prepared from free radical halogenation of alkanes. It gives mixture
of isomeric mono and polyalkanes which is difficult to separate as pure compounds.
Therefore, this method is not preferable.
Cl
Cl2 / UV light
CH3 CH2 CH2 CH3 CH3 CH2 – CH2 – CH2 Cl + CH3 – CH2 – CH – CH2Cl
Or

Reactivity Order F2 > Cl2 > Br2 > I2

| |
Violent reaction Slow reaction

c. FROM ALKENES
1. Addition of halogen acids

HX = HCl, HBr, HI

RCH = CH2 + HX R – CHX –CH3

(MR - Markovnikov’s addition)

peroxide
RCH = CH2 + HX R – CH2 – CH2 – X
(AMR - Anti-Markovnikov’s addition) Not for HCl and HI only for
HBr
2. Addition of halogens

(Reddish brown) (Colourless)

This is used for presence double bond test.

3. Allylic halogenations
773 k
CH3 – CH = CH2 + X2 CH2 – CH = CH2 + HX
X2, hϑ/sunlight
X
d. HALOALKANES BY HALOGEN EXCHANGE METHOD
1. Swarts Reaction
Fluoroalkanes are prepared by treating alkyl chloride bromide in the presence of a
metallic fluoride such as AgF, Hg2F2, CoF2, or SbF3. This reaction is known as Swarts
reaction.
CH3 - Br + AgF CH3 - F + AgBr
(Methyl bromide) (Silver fluoride) (Fluoromethane) (Silver bromide)
2. Finkelstein Reaction
Alkyl iodides are often prepared by the reaction of alkyl chlorides / bromides with NaI
in dry acetone. This reaction is known as Finkelstein reaction.
Dry Acetone
R – X + NaI R – I + NaX

where, X = Cl, Br
Nacl / NaBr formed is precipitated in dry acetone it facilitates forward reaction
according to Le Chatelier’s Principle.

PREPARATION METHOD OF HALOARENES

a. BY ELECTROPHILIC SUBSTITUTION
CH3 CH3
Cl, FeCl3
dark +
Cl Cl

‘O’ ‘P’

CH3

Br, FeBr3 CH3

dark +
Br

Br
‘O’ ‘P’
Aryl chloride and bromide prepared in presence of Lewis acid FeCl3. In this ‘O’ and ‘P’
isomer can be formed which can be easily separated due to difference in their melting
points.
Reaction with I2 is reversible so here use oxidising agent HNO3 / HIO4 which oxidise
the HI formed during iodination.
Fluoro compounds are not formed by this method due to high reactivity of fluorine.
b. SANDMEYER’S REACTION

(CU2Cl2)
PHYSICAL PROPERTIES
1. For a given halogen atom, the boiling point of alkyl halides increases with increase in size
of alkyl group.
The B.P. of haloalkanes decreases with increase in branching because as branching in
haloalkanes increases its surface area decreases due to which intermolecular force of
attraction decreases.
2. a) Halogen compounds have higher B.P. than the corresponding HCs. This is because
the greater polarity as well as higher molecular mass as compared to the parent HCs
causes intermolecular force of attraction (dipole-dipole and van der Waals) to be stronger
in the halogen derivatives.
b) Increase in size and mass of halogen atom the magnitude of van der Waal forces
increases.
B.P. order R – I > R – Br > R – Cl > R – F
3. Boiling points of isomeric dihalobenzenes are very nearly the same. However, the para-
isomers are high melting as compared to their ortho and meta-isomers. It is due to
symmetry of para-isomers that fits in crystal lattice better as compared to ortho- and meta-
isomers.
4. Alkyl halides are slightly soluble in water though they are polar because they do not form
H – bonds with water.
5. The stability of haloalkanes decreases as the strength of C – X bond decreases, (RF >
RCl > RI) due to increase in size of halogen atom down the group.
Alternatively, bond dissociation enthalpy for C – X bond decreases down the group.
6. C – X bond in aryl halides is shorter (due to partial double bond character acquired by C
–X bond due to resonance), stronger and less polar than alkyl halides.
7. The density increases with increasing no. and the atomic mass of halogen.

CHEMICAL PROPERTIES OF HALOALKANES

Reactions of Haloalkanes –
1. Nucleophilic substitution
2. Elimination reactions
3. Reaction with metals
a. NUCLEOPHILIC SUBSTITUTION
Due to partial positive charge on the carbon bonded to halogen (due to electronegativity
difference between them) nucleophile substitutes halide ions and form bond with the
carbon.

 KCN and AgCN, KNO2 and AgNO2 these are called Ambident nuclophile.

 A nucleophile species which is capable of attacking a molecule through more than one
site is called ambident nucleophile.
 Cyanide group is nucleophile in two different ways as it is a hybrid of two contributing
structures. [ΘC ≡ N ↔ :C = NΘ] i.e. it can link through ‘C’ atom resulting in alkyl cyanide
and through ‘N’ atom leading to isocyanide ion.
..
 Nitrite ion has two different point of linkage [-O – N = O]. The linkage through oxygen
results in alkyl nitrites while through nitrogen atom it leads to nitroalkanes.

ꝺ+ ꝺ- _ _
R – CH2 X + Nu R – CH2 – Nu + X

Nucleophilic substitution reaction takes place through SN1 and SN2 mechanism.
1. Unimolecular nucleophilic substitution SN1
Step 1: Formation of carbocation
Step 2: Nucleophilic attack on carbocation

CH3
|
Nu – C – CH3 +
|
CH3

Rate r = k [RX] (racemic mixture)

 Allylic and benzylic halides show high reactivity towards the SN1 reaction as the
formed carbocation gets stabilised through resonance.
Reactivity order of alkyl halide 30 > 20 > 10 (Note: 30 carbocations are more stable)

 In SN1, polar protic solvents used such H2O, K-OH, or aq. Organic solvent (acetic
acid) promotes stabilization of formed ions by solvation.

 As the rate of reaction depends upon the concentration of only one reactant it is SN1.
During SN1 reaction optically active alkyl halides gives racemic products. SN1 is
shown by 30 R–X.
2. Bimolecular nucleophilic substitution SN2

This SN2 reaction takes place in one step only. The incoming nucleophile interacts with
alkyl halide causing the C – X bond to break while forming a new
C – OH bond.
Rate of reaction depends on concentration of both reactants so it is called SN2. In case of
optically active R – X, SN2 results in the inversion of configuration.
Reactivity order of alkyl halide 10 > 20 > 30
(Note: In 30 alkyl halide, steric hinderance is more)
R – I > R – Br > R –Cl > R – F (Note: As ‘I–’ (Iodide ion) is a good leaving group)

Difference between SN1 and SN2

SN1 SN2
1. Unimolecular nucleophilic substitution Bimolecular nucleophilic substitution
reaction. reaction.
2. This is two step reaction involves This is one step reaction, it involves
formation of carbocation intermediate. direct attack of NuΘ
3. Reactivity order in R –X 30 > 20 > 10 as Reactivity order 10 > 20 > 30
tertiary carbocation is more stable.
4. Racemic mixture in the product is Inversion of configuration in the
obtained which is optically inactive. product is obtained.
Retention of configuration takes place.

SOME STEREOCHEMICAL ASPECTS

 If all the substituents attached to that carbon are different, such a carbon is called
asymmetric carbon or stereocentre.
This asymmetry of the molecule is responsible for the optical activity.
The angle by which the plane polarised light is rotated measured by an instrument
called polarimeter.
 If PPL rotates right hand side or clockwise direction when it is passed through
organic solution is called dextrorotatory.
Vice versa for laevorotatory.
 The stereoisomers which are non-super imposable mirror images are called
enantiomers.
 Enantiomers possess identical physical properties namely, melting point,
boiling point, refractive index, etc. They only differ with respect to the rotation of
plane polarised light.
 The light whose vibrations occur only in one plane is termed plane polarised light.
 Molecules which are non-superimposable on its mirror image are said to be chiral
molecule. The property of a compound being chiral is called chirality.
 Optical Isomerism - Two compounds having same molecular formula and
structural formula but differ in the direction of rotation of the plane of plane
polarised light. Ex: Lactic acid
 A mixture containing two enantiomers in equal proportions which is optically
inactive called racemic mixture.

b. ELIMINATION REACTION
When a haloalkane with β – ‘H’ atom is heated with alcoholic KOH, there is elimination of
‘H’ atom from β carbon atom and halogen atom from α-carbon atom resulting in the
formation of alkene.
This reaction follows Saytzeff rule Saytzeff rule – The preferred product
H H major product is that alkene which has
| | alcoholic KOH the greater number of alkyl groups
attached to the doubly bonded carbon
H–C–C–H H2C = CH2
atoms.
| |
H X

Reactivity order - R – X 30 > 20 > 10

Br
| alcoholic KOH
H3C – CH2 – CH2 – CH – CH3 H3C – CH2 – CH2 – CH = CH2
Hofmann (19%) minor

H3C – CH2 – CH = CH – CH3

Saytzeff product (83%) major
c. REACTION WITH METAL
Alkyl halide reacts with Mg in the presence of dry ether to form corresponding alkyl
magnesium halide which is known as Grignard reagent.
dry ꝺ- ꝺ+
R – X + Mg R – Mg – X
ether Organometallic compound
(Grignard reagent)
dry
CH3 – Cl + Mg CH3 – Mg – Cl (G. R.)
ether
H | OH
ꝺ- | ꝺ+
CH3 – Mg – Cl + H2O CH4 + Mg(OH) Br
| alkane
G. R. are highly reactive and react with any source of proton (e.g. H2O) so it is
necessary to avoid traces of moisture from G. R. It should prepare in anhydrous
condition.
1. Wurtz Reaction
Alkyl halides react with Na in dry ether to give hydrocarbons containing double the
number of carbon atoms present in the halide. This reaction is known as Wurtz
reaction. (Free radical and carbanion intermediate formed.)
dry
2RX + 2Na R – R + 2NaX
ether

dry
2CH3 X + 2Na C2H6 + 2NaX
ether

REACTIONS OF HALOARENES
a. NUCLEOPHILIC SUBSTITUTION REACTION
Alkyl halides are more reactive than aryl halides towards nucleophilic substitution
reaction. It is due to as following reason:
a. In haloalkanes, there is single bond between R – X which needs less bond dissociation
energy hence they are more reactive towards nucleophiles. In haloarenes, there is
double bond character between C – X bond due to resonance. Therefore, has more
bond dissociation energy.
b. Carbon attached to halogen is sp3-hybridised in haloalkane and sp2-hybridised in
haloarenes. sp3-hybridised carbon is less electronegative than sp2-hybridised carbon
due to less percent of ‘S’ character. Thus, C – X bond length is shorter in haloarenes
than in haloalkanes.
c. It is difficult for the electron rich nucleophiles to approach electron rich benzene ring
in haloarenes. There is no such thing in haloalkanes.
d. The phenyl cation formed cation formed as a result of self-ionisation in haloarenes is
not stabilised by resonance. Thus, it doesn’t undergo SN1 mechnism.
Low reactivity of aryl halides is attributed due to the following reason
a. Due to resonance, C – X bond has partial double bond character.
b. Stabilisation of the molecule by delocalisation of ēs.
c. In stability of phenyl carbocation.
d. Repulsion between nucleophile and electron rich benzene ring in haloarenes.
Presence of ē withdrawing group (like – NO2, – SO3H, etc.) at ‘O’ and ‘P’ positions of aryl
halide undergo nucleophilic substitution reaction easily.

Dows reaction

The presence of nitro group at ‘O’ and ‘P’ positions withdraws ē density from the benzene
ring and thus facilitates the attack of nucleophile on haloarenes.
b. ELECTROPHILIC SUBSTITUTION REACTION

This reaction takes place slowly and require more drastic conditions compared to benzene
because halogen atom show –I effect has some tendency to withdraws ēs from the
benzene ring. As a result, ring gets somewhat deactivated as compared to benzene.
Halogen atoms is O-, P- directing in the electrophilic substitution reactions since, electron
density increases at O and P position due to the +R effect.

Halogenation

Nitration
Sulphonation

Friedel-Crafts reaction - Alkylation

Friedel-Crafts reaction - Acylation

[Here ‘P’ product is more and ‘O’ is less because in ‘O’ product there is more steric
hinderance.]
[Reactivity is controlled by the stronger –I effect (Inducke effect) and orientation is
controlled by +R effect (resonance effect).
c. REACTION WITH METALS
1. Wurtz-Fitting reaction
When aryl halide is heated with alkyl halide in the presence of sodium in dry ether,
halogen atom is replaced by alkyl group and alkyl arene is formed. This reaction is
called Wurtz-Fitting reaction.
dry
Cl + 2Na + Cl CH3 CH3 + 2NaCl
ether
Toluene

2. Fitting reaction
When aryl halides react with sodium in the presence of dry ether, two aryl group are
joined together and diphenyl is formed. This reaction is called Fitting reaction.
dry
Cl + 2Na + Cl + 2NaCl
ether
Diphenyl
SOME IMPORTANT EXTRA REACTIONS
 FROM PHENOL
OH
|

+ PCl5 C6H5Cl + HCl + POCl3

Due to resonance in chlorobenzene C – Cl bond is shorter hence its dipole moment is less
than that of cyclohexyl chloride.

 FROM BENZENE DIAZONIUM SALT

CuCl / HCl
C6H5Cl + N2
+ - Sandmeyer reaction
N2Cl CuBr / HBr
C6H5Br + N2

Cu / Hcl
C6H5Cl + N2
Gattermann reaction
Cu / HBr
C6H5Br + N2

HBF4 +
C6H5N2BF4 C6H5F
273 K (Balz schiemann reaction)

Flow chart for some chemical properties of Alkyl halides

Flow chart for some chemical properties of Aryl halides
REASONING QUESTIONS
1. Why are halo alkanes more reactive than haloarenes?
In haloarenes, there is double bond character between carbon and halogen due to
resonance effect which makes it less reactive. In benzene, carbon atom is sp2 hybridised
which is shorter than sp3 present in halo alkanes. Hence C – Cl bond in aryl halides is
shorter and stronger.
2. Why do halo alkanes undergo nucleophilic substitution whereas haloarenes undergo
electrophilic substitution.
Due to more electro negative nature of halogen atom in halo alkanes carbon atom
becomes slightly positive and is easily attacked by nucleophilic reagents. While in
haloarenes due to resonance, carbon atom becomes slightly negative and attacked by
electrophilic reagents.
3. When an alkyl halide is treated with ethanolic solution of KCN, the major product is
alkylcyanide where as if alkyl halide is treated with AgCN, the major product is alkyl
isocyanide.
KCN is ionic they can attach through C or N but C – C bond is stronger than C – N bond
so RCN is major product. AgCN is covalent in nature so nitrogen is free to donate
electron pair to ‘C’ and forms isocyanide.
4. Aryl halides cannot be prepared by the action of sodium halide on phenol in the
presence of H2SO4. Why? OR Arylhalide cannot be prepared by the reaction of phenols
with HX.
Due to resonance the carbon-oxygen bond in phenol has partial double bond character
and it is stronger than carbon oxygen single bond.
5. Grignard reagent should be prepared under anhydrous conditions. Why?
Grignard reagent reacts with H2O (moisture) to form alkanes, therefore they are
prepared under anhydrous condition.
X
R – Mg – X + H2O R – H + Mg
OH
6. Why is Sulphuric acid not used during the reactions of alcohols with KI?
It is because HI formed will get oxidized to I2 by concentrated Sulphuric acid which is an
oxidizing agent.
7. p-dichloro benzene has higher m. p. than those of ortho and m-isomers?
p-dichloro benzene is symmetrical., fits into crystal lattice more readily and has higher
melting point.
8. Although chlorine is an electron-with drawing group, it is ortho and para directing in
electrophilic aromatic substitution reactions. Why?
Chlorobenzene is resonance hybrid, there is –ve charge at ortho and para positions,
electrophilic substitution reaction will take place at ortho and para position due to +R
effect which dominating over the –I effect.
9. Reaction of Halogen acids with alcohols to form alkyl halides follow the order
HI > HBr > HCl.
This is because as the size of the halogen atom increases the bond dissociation
energies of H – X bond decreases. The bond dissociation energy of HI is less than that
of HBr which is in turn less than that of HCl.
10. Reactivity of alcohols with halogen acids to form alkyl halides follow the order
30 > 20 > 10.
This is because greater the number of electron releasing groups on the α-carbon atom of
the alcohol, more is the polarity of C – OH. As a result, the cleavage of C – O bond
becomes easy and the reactivity increases.
11. Iodination of alkanes require the presence of an oxidizing agent like HNO 3 or HIO3.
Iodination of alkanes is reversible and is done by heating with iodine in the presence of
oxidizing agent which oxidize the HI formed during the reaction to Iodine, and hence shift
the equilibrium to the forward direction.
CH4 + I2 CH3I + HI
5HI + HIO3 I2 + 3H2O
12. Alkyl halides, though polar are immiscible with water.
Because energy required to overcome attraction between haloalkane molecules and
break the H-bonds between H2O molecule is much higher than energy released by water
alkyl halide interaction.
13. CH3Cl when reacted with KNO2 gives nitrite and with AgNO2 gives nitro compounds.
On treating haloalkanes with KNO2, nitrite is formed as the major product, it is due to the
reason that bond between K – O is ionic nature. Therefore, negative charge on oxygen
serves as attacking site.
On treating ethanolic solution of alkyl halides with silvernitrite, nitroalkane is formed, it is
due to the reason that the bond between Ag – O being covalent, the lone pair on
nitrogen acts as attacking site for nucleophilic substitution.
14. Explain why the dipole moment of chlorobenzene is lower than that of cyclohexyl
chloride.
There are two reasons: 1. In case of chlorobenzene, carbon to which chlorine is
attached is sp2-hybridised and is more electronegative than the corresponding carbon in
cyclohexyl chloride which is sp3-hybridised. So the net dipole moment is lower in
chlorobenzene. 2. In chlorobenzene C – Cl bond has some double bond character so its
bond length is smaller. Hence dipole moment is smaller than cyclohexyl chloride which
has a longer C – Cl single bond.

15. n-Butyl bromide has higher boiling point that t-butyl bromide.
n-Butyl bromide, being a straight chain molecule have strong intermolecular forces
whereas t-Butyl bromide being a branched chain molecule have weaker intermolecular
forces due to smaller surface area.
Hence, boiling point of n-Butyl bromide is higher than that of t-Butyl bromide.
16. Haloalkanes easily dissolve in organic solvents, why?
The intermolecular attractions between haloalkanes and organic solvent molecules have
the same strength as in the separate haloalkanes and solvent molecules.
17. The presence of –NO2 group at ortho and para position increases the reactivity of
haloarenes towards nucleophilic substitution reactions.
The presence of nitro group at o-and p-positions withdraws electrons from the benzene
ring and thus, facilitates the attack of the nucleophile on haloarenes. The carbanion thus
formed is further stabilised by resonance.
18. Out of 2-bromopentane, 2-bromo-2-methylbutane, and 1-bromopentane, which
compound is most reactive towards elimination reaction and why?
2-Bromo-2methylbutane will give fastest elimination reaction because it is a tert-halide
and tert-halides prefer elimination reaction.
19. Out of chlorobenzene and benzyl chloride, which one gets easily hydrolysed by aqueous
NaOH and why?
Benzyl chloride gets easily hydrolysed by aqueous NaOH due to formation of stable
benzyl carbocation. But due to partial double bond character of C – Cl bond in
chlorobenzene, it does not hydrolyse.
20. Why is (±)-butan-2-ol is optically inactive?
The two enantiomeric forms are present in equal amounts therefore, it does not rotate
the plane of polarized light and is optically inactive.

21. C – Cl bond length in chlorobenzene is shorter than C – Cl bond length in CH3 – Cl.
In halobenzene C – X bond has partial double bond character due to resonance while
CH3 – X bond is single bond. Thus, bond length of C – X bond in halobenzene is smaller
than that in CH3 – X.

22. SN1 reactions are accompanied by racemization in optically active alkyl halides. OR
Racemisation occurs in SN1 reactions. Why?
In SN1 reaction carbocation intermediate is formed which is a planar molecule so, an
incoming nucleophile can attack from either side and a equimolar mixture of two
components are formed and resulting mixture is optically inactive.
23. Racemic mixture is optically inactive.
Racemic mixture contains equal amount of d- and l-forms, hence rotation due to one
enantiomer is cancelled by another.
24. Although chlorine is and electron withdrawing group, yet it is ortho-para-directing in
electrophilic aromatic substitution reactions. Why?
Although Cl is electron withdrawing (-I effect) but still o- and p- directing as due to +R
effect, electron density is maximum at o- and p- positions.
25. Chloroform is stored in closed dark brown bottles.
Chloroform when exposed to air and sunlight changes to phosgene which is poisonous
gas.
CHCl3 + ½ O2 COCl2 + HCl
(Phosgene)

26. Chlorobenzene is extremely less reactive towards a nucleophilic substitution reaction.

Haloarenes are much less reactive than haloalkanes towards nucleophilic substitution
reactions due to the following reasons.
1) Resonance effect: in haloarenes the electron pairs on halogen atom are in
conjugation with π-electrons of the ring and the following reasoning structure are
possible.

C – Cl bond acquires a partial double bond character due to resonance. As a result,

the bond cleavage in haloarene is difficult than haloalkane and therefore, are less
reactive towards nucleophilic substitution reaction.
2) In haloarenes, halogen is attached to sp2-hybridised carbon while in halolakanes,
halogen is attached to sp3-hybridised carbon.
27. Ethyl iodide undergoes SN2 reaction faster than ethyl bromide.
Since I-- is a better leaving group than Br--, thus CH3CH2I undergoes SN2 reaction faster
than CH3CH2Br.
28. Why dextro and laevo-rotatory isomers of Butane-2-ol are difficult to separate by
fractional distillation?
Dextro and laevo-rotatory isomers of butane-2-ol are difficult to separate by fractional
distillation because they have almost same boiling point.
29. Which is better nucleophile, a bromide ion or iodide ion?
Because of bigger size and lower electronegativity, iodide ion can donate a pair of
electrons more easily than bromide ion hence iodide ion is better nucleophile than iodide
ion.
30. Why the boiling point of halides are higher than hydrocarbons of comparable molecular
mass.
Because of greater polarity as well as higher molecular mass as compared to the parent
hydrocarbon, the inter molecular forces of attraction are stronger in the halogen
derivatives.
31. Why haloalkanes undergoes nucleophilic substitution reaction?
In halolakanes due to difference in electronegativity of carbon and halogen, carbon
bears partial positive charge and attracts nucleophile and halogen atom departs as
halide ion.
32. Vinyl chloride is less reactive than ethyl chloride?
In vinyl chloride chlorine atom is directly attached to C = C, the electron pair on chlorine
atom conjugates with the π electron pair of the double bond.
– +
..
CH2 ═ HC – Cl CH2 – CH ═ Cl
As a result, there is partial double bond character in C – Cl and its bond strength
increases.
Consequently, it become difficult to cleave C – Cl bond as compared to the bond in
ethylchloride when no such conjugation is possible.
33. Allyl chloride is more reactive than n-propyl chloride towards nucleophilic substitution
reaction. Why?
Greater stabilization of allylic carbocation intermediate is formed by resonance.
–Cl–
H3C – CH2 – CH2 – Cl CH3 – CH2 – CH2 + CH2 ═ CH – CH2 – Cl
n-propyl chloride propyl carbocation allyl chloride

–Cl– + +
CH2 = CH – CH2 CH2 – CH = CH2
allylic carbocations
34. Explain the physical properties of arylhalides (haloarenes).
1. Boiling point: The boiling point of monohalogen derivatives of benzene, which are
all liquids, follow the order-iodo > bromo > chloro.
The boiling point of isomeric dihalobenzenes are nearly the same. However, their
melting points are quite different.
2. Solubility: they are soluble in organic solvents like alcohol and ether but insoluble in
water as they cannot form H-bonding with water molecules.
3. Density: These compounds are heavier than water. Their densities follow the order –
Iodo > Bromo > Chloro.
35. Cyanide ion acts as an ambident nucleophile. From which end it acts as a stronger
nucleophile in aqueous medium?
C ≡ N: is an ambident nucleophile since it can react either through C or through N. since
C – C bond is stronger than C – N bond, cyanide ion will preferentially attack through
carbon to form alkyl cyanides.
36. Explain Isomerism In Haloalkanes:
Haloalkane exhibits following type of isomerism.
Chain Isomerism:
The halolakanes having four or more carbon atoms show chain isomerism. For example,
CH3
|
CH3CH2CH2CH2Cl H3C ─ CH ─ CH2 ─ Cl
1-chlorobutane 1-chloro-2-methyl propane
Position Isomerism:
The haloalkanes with three or more carbon atoms show position isomerism. For
example, C3H7Br has two isomers.
Br
|
CH3-CH2-CH2-Br H3C ─ CH ─ CH3
1-bromopropane 2-bromopropane
(n-propyl bromide) (iso-propyl bromide)

37. The treatment of alkyl chloride with aqueous KOH leads to the formation of alcohols in
the presence of alc KOH alkanes are major products. Explain OR Aqueous KOH shows
SN reaction with R – X but alc KOH shows elimination reaction with R – X. Why?
In aq KOH, KOH is completely ionized to give OH— ions which acts as strong nucleophile
resulting in nucleophilic substitution reaction on alkyl chloride to form alcohols. On the
other hand, alc KOH contains alkoxide (RO— ions) which being stronger base than OH—
ions preferentially eliminates HCl molecule from an alkyl chloride to form alkene.
38. Halogens are deactiving but ortho and para directive.
The negative I effect of halogens withdraws electron from the benzene as a result the
ring gets somewhat deactivated conversely halogen donates its lone electron pair to the
benzene ring (+R effect) and hence increase the electron density at ‘O’ and ‘P’ position
makes benzene ring ‘O’ and ‘P’ directive for electrophilic substitution reaction.