CLS Aipmt 18 19 XI Che Study Package 4 SET 1 Chapter 13

Chapter 13
Hydrocarbons
Solutions
SECTION - A
School/Board Exam. Type Questions
Very Short Answer Type Questions :
1. What are paraffins?
Sol. The word paraffin has a Latin origin meaning parum, little; affinis, affinity. Those saturated hydrocarbons which
are inert under normal conditions and do not react with acids, bases and other reagents are known as paraffins.
2. What do you understand by homologus series?
Sol. Those consecutive alkanes which differ by —CH2 group or by molecular mass 14 are known as homologus
series.
3. During decarboxylation of sodium salts of carboxylic acid is there any change in the length of the carbon chain.
Sol. Decarboxylation of sodium salts of carboxylic acids gives alkanes containing one carbon atom less than the
number of carbon atoms in the carboxylic acid. Example,
CaO
CH3 COO – Na+ + NaOH ⎯⎯⎯
Δ
→ CH4 + Na2CO3
Sodium ethanoate
4. Name two reagents which can be used to test unsaturation.

Sol. Bromine water and alkaline KMnO4 can be used to test for the presence of unsaturation.
5. What happens when acetylene is passed through dil. H2SO4 in presence of HgSO4?
Sol. Ethanal is obtained.
H OH
H2SO4, H2O Rearrangement
HC CH HgSO4
HC CH CH3 CHO
Ethanal
6. Name any two cacinogenic hydrocarbons.
Sol. 1,2-Benzanthracene
1,2-Benzpyrene
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22 Hydrocarbons Solutions of Assignment (Set-1)
7. In the sulphonation of benzene whats acts as an electrophile?

Sol. Sulphur trioxide acts as an electrophile.
8. Of all the conformations in ethane molecule, which one has the greatest and least torsional strain?
Sol. Eclipsed form has the maximum and staggered form has the least torsional strain.
9. Complete the following
COOH
NaOH
+ NaOH (A) CaO
(B)
COONa
Sol. (A) = (B) =
10. Which concept was given by Kekule to explain the formation of only one ortho disubstituted product?
Sol. The concept of oscillating nature of double bonds in benzene was given by Kekule.
Short Answer Type Questions :

11. Draw the cis- and trans- structure of hex-2-ene. Which isomer will have higher boiling point and why?
Sol. CH3 CH2 CH2 CH3 CH3 CH2 CH2 H

C C C C
H H H CH3
cis-hex-2-ene trans-hex-2-ene
cis-hex-2-ene will have higher boiling point because cis form of alkene is found to be more polar than the trans
form as a consequence of greater dipole moment.
12. Convert propene into 2,3-dimethylbutane.
H3C H3C H3C CH3

HBr Na/ether
Sol. CH 2 CH Br Wurtz reaction CH CH
H2C H3C H3C CH3
13. What do you understand by aromatization?

Sol. n-Alkanes having six or more carbon atoms on heating to 773 K at 10-20 atmospheric pressure in presence
of oxides of vanadium, molybdenum or chromium supported over alumina get dehydrogenated and cyclised to
benzene and its homologues. This reaction is known as aromatization or reforming.
CH3
Cr2O3 or H2O5
CH2 CH2 or Mo2O3
773 K, 10-20 atm
CH2 CH2
CH2 Benzene
14. CH3 CH3 CH3 H

C C C C
H H H CH3
cis-But-2-ene trans-But-2-ene
Which form of geometric isomer has a higher boiling point and why?
Solutions of Assignment (Set-1) Hydrocarbons 23
Sol. cis-isomer has a greater boiling point than the trans-isomer due to greater polarity and consequent stronger
interparticle forces.
15. What is polymerisation? Give an example.
Sol. Polymerisation is the process in which small monomers conglomerates to form large molecules called polymers.
For example, alkenes undergoes polymerisation at high temperature and pressure to form polymer in presence
of catalyst.
High temp/Pressure
n(CH2 CH2) Catalyst
( CH2 CH2 )n
Polyethene
High temp/Pressure
n(CH3 CH CH2) Catalyst
( CH CH2 )n
CH3
Polypropene
16. How can you obtain butan-2-one from acetylene?
OH
NaNH2 C2H5Br H2SO4
Sol. HC CH HC C.Na HC C CH2CH3 H2O, HgSO4
H2C C CH2 CH3
–NH3 –NaBr
O
Rearrangement
H3C C CH2 CH3
Butan-2-one
17. Compare the C–H bond lengths and bond dissociation enthalpies of an alkyne, alkene and alkane.
Sol. As a generalised rule, the more is the s-character in the hybrid orbitals used by an atom, the closer are the
bonding electrons to the atom, and the shorter and stronger is the sigma bonds. The decreasing order of
C—H bond length is
sp3 > sp2 > sp
The decreasing order of bond enthalpies is,
H
H
C H C C H
H
H
sp sp2 sp3
18. What is isomerisation reaction? Give an example.

Sol. The process of conversion of one isomer into another isomer is called isomerisation reaction. For example,
when butane is heated in presence of anhydrous aluminium chloride and concentrated hydrochloric acid at about
200°C under a pressure of 35 atmospheres, is converted into Isobutane.
CH 3
AlCl3 + HCl (conc.)
CH3 CH2 CH2 CH3 200°C, 35 atm
CH3 CH CH3
Butane Isobutane
19. How can benzene be prepared from sodium benzoate?

Sol. Lime is heated with coke at very high temperature at which it reacts to form calcium carbide (CaC2).
Δ
CaO + 3C ⎯⎯ → CaC2 + CO
Lime Coke
The produced calcium carbide when hydrolysed produces acetylene which is passed through hot iron tube to
produce benzene.
CaC2 + 2H2O ⎯→ Ca(OH)2 + C2H2
Fe tube
3C2H2 ⎯⎯⎯⎯
873 K
→ C6H6
20. How will you obtain? Give equation only

(i) Ethane from methane
(ii) Ethane from acetic acid
hν
Sol. (i) CH4 + Cl2 ⎯⎯ ⎯→ CH3Cl + HCl
CH3Cl + 2Na + ClCH3 ⎯⎯→ CH3 – CH3 + 2NaCl

Ethane
(ii) CH3COOH + NaOH ⎯→ CH3COO–Na+ + H2O
Electrolysis
2CH3 COO −Na + ⎯⎯⎯⎯⎯
H O
→ CH3 – CH3 + 2CO2 ↑ + 2NaOH + H2 ↑
2
Ethane
21. What is Markovnikov rule? Illustrate with an example.

Sol. Markovnikov rule states that the negative part of the adding molecule adds to that carbon atom which contains
less number of hydrogen atoms.
+ ⊕
H
CH3 CH CH2 + HBr CH3 CH CH3
Contains less number

of hydrogen atoms
+
CH3 CH CH3 + Br– CH3 CH CH3
(Negative part
of the molecule) Br
22. Can conformational isomers of ethane be separated? Why?

Sol. No, the conformational isomers of ethane can not be separated. The energy difference between the two extreme
forms i.e., staggered and eclipsed form is very small to the order of 12.5 kJ/mol. Even at ordinary temperatures,
the ethane molecule gains the thermal or kinetic energy sufficient enough to overcome this energy barrier of
12.5 kJ/mol through intermolecular collisions. So, it can be said that rotation about carbon-carbon single bond
in ethane is almost free for all practical purposes and becomes almost impossible to isolate the different
conformational isomers of ethane.
23. With an example briefly explain pyrolysis.
Sol. Higher alkanes on heating to high temperatures decompose to lower alkanes or alkenes. Such a decomposition
reaction into smaller fragments by the application of heat is called pyrolysis or cracking.
Example :
C6H12 + H2
773 K
C6H14 C4H8 + C2H6
C3H6 + C2H4 + CH4
24. How many monochlorinated products are possible for
(i) neo pentane?
(ii) n-pentane?
CH3 CH3
hν
Sol. (i) H3C C CH3 + Cl2 Cl CH2 C CH3
CH3 CH3
Only one product 2,2-Dimethylchloropropane can be obtained by monochlorination of neopentane.
Cl
(ii) H3 C — CH2 — CH2 — CH2 — CH3 ⎯⎯⎯
2
hν
→
Three products or three monochloro isomeric n-pentane can be obtained i.e.,

(a) Cl—CH2 —CH2 —CH2 —CH2 —CH3; 1-chloropentane
(b) H 3C CH CH2 CH2 CH3; 2-chloropentane
Cl
(c) H 3C CH 2 CH CH2 CH3; 3-chloropentane
Cl
25. Draw the structure of ethene showing orbital picture of it to exhibit π-bond, σ-bonds, bond angles and bond
length.
Sol. Carbon-carbon bond in alkenes consists of one strong sigma bond formed by the head on overlapping of sp2
hybridized orbitals and a weak pi-bond obtained by the sideways overlapping of the two 2p-orbitals of the two
carbon atoms.
π-bond H
1s
π-cloud
σ
σ σ-bond H H
H 1s C C 1s H C C
σ
σ
H H
1s
H π
(a) π-bond (b) π-cloud of electrons
H 121.7° H
116.6° C C 110 pm
H 134 pm H
(c) Bond angles and bond lengths
26. Find the product obtained in the following cases

(i) C3H8 undergoes combustion
(ii) Methane undergoes partial oxidation at high pressure in presence of molybdenum oxide.
(iii) 2-Methylpropane is subjected to oxidation by KMnO4
Sol. (i) C3H8 + 5O2 ⎯⎯→ 3CO2 + 4H2O

Propane Carbon dioxide
(ii) Methane forms methanal on partial oxidation at high pressure in presence of molybdenum oxide as catalyst.
Mo O , Δ
CH4 + O2 ⎯⎯⎯⎯⎯⎯2 3
High pressure
→ HCHO + H2 O
Methane Methanal
(iii) Corresponding alcohol is obtained when oxidised by KMnO4.
CH3 CH3
KMnO4
H3C C H Oxidation
H3C C OH
CH3 CH3
2-Methylpropane 2-Methylpropan-2-ol
27. What is Saytzeff rule? Give example.

Sol. Saytzeff rule states that greater is the number of attached alkyl groups, greater is the alkene stability. It shows
greater number of hyperconjugative structures raising its stability. Example, the stability order of the alkenes
can be given as follows :
CH3 H CH3 H CH3 CH3 CH3 CH3

CH2 CH2 C C C C C C C C
H H CH3 H CH3 H CH3 CH3
Increasing hyperconjugative structures, hence, higher stability
28. Draw the resonance structure of benzaldehyde and tell which position is more prone to electrophilic substitution.
– – –
H C O H C O H C O H C O H C O
Sol.
Since electron density decreases at the ortho and para positions, the meta position is having comparatively
higher electron density than the ortho and para positions, becoming more prone to electrophilic attack.
29. How do structural isomers differ from stereo isomers?
Sol. Structural isomers are the isomers having same molecular formula but different structures i.e., different
arrangement of atom or groups of atoms within the molecule. The structure differs due to difference in the
attachment positions. This is the reason they are also known as constitutional isomers.
Stereo isomers are the molecules which have same structural formula but have different relative arrangement
of atoms or groups of atoms in space. They have the same atomic connectivity but different orientation of
atoms or groups in space.
30. Why alkanes and alkynes does not show geometrical isomerism?
Sol. Alkanes : Alkanes do not show geometrical isomerism because :
(i) These do not possesses carbon-carbon double bond.
(ii) There is free rotation around C—C single bond.
Alkynes : These does not show geometrical isomerism because :
(i) The triply bonded carbon atoms are sp-hybridized where the bond angle is 180° confirming it to be a linear
molecule.
(ii) Since carbon atoms are triply bounded, only one atom or group can be attached to each carbon atom.
So, the different arrangements of atoms or groups in space are not possible.
Long Answer Type Questions :
31. Discuss the mechanism of halogenation of methane.
Sol. Halogenation of alkanes takes place either at high temperature or in the presence of diffused sunlight or ultra-
violet light. For example, methane undergoes complete replacement of hydrogen by the halogen when allowed
to react in excess of halogen.
hν
CH4 + Cl2 ⎯⎯ ⎯→ CH3 Cl + HCl
Chloromethane
hν
CH3 Cl + Cl2 ⎯⎯ ⎯→ CH2 Cl2 + HCl
Dichloromethane
hν
CH2Cl2 + Cl2 ⎯⎯ ⎯→ CHCl3 + HCl
Trichloromethane
hν
CHCl3 + Cl2 ⎯⎯ ⎯→ CCl4 + HCl
Tetrachloromethane
The halogenation process is supposed to proceed through the free radical mechanism which involves three
steps namely initiation, propagation and termination.
(i) Initiation : Chlorine molecule undergoes homolytic cleavage producing chlorine free radicals in presence
of sunlight.
hν
Cl − Cl ⎯⎯⎯⎯⎯
Homolysis
→ Cl• + Cl•
Chlorine free radical
(ii) Propagation : Chlorine free radicals are very reactive and attacks the methane molecule breaking the
C—H bond producing a methyl free radical and H—Cl.
• •
(a) CH4 + Cl ⎯⎯→ CH3 + HCl
The methyl radical attack second molecule of chlorine liberating another chlorine radical.
• •
(b) CH3 + Cl − Cl ⎯⎯→ CH3 − Cl + Cl
The free radicals produced in the reaction starts a chain reaction.
• •
CH3 Cl + Cl ⎯⎯→ CH2Cl + HCl
• •
CH2Cl + Cl − Cl ⎯⎯→ CH2Cl2 + Cl
(iii) Termination step : The free radicals are consumed and the reaction stops after sometime.
• •
(a) Cl + Cl ⎯⎯→ Cl2
• •
(b) Cl + CH3 ⎯⎯→ CH3 Cl
• •
(c) CH3 + CH3 ⎯⎯→ CH3 − CH3
32. Predict the major products of the following reactions with reason
(i) CH3 –CH=CH2 + HBr
(ii) 2-Methylpropene + HCl
Sol. The addition will follow the Markovnikov rule which states that negative part of the hydrogen halide will add to
the most alkynated carbon of the double bond and hydrogen adds to the less substituted or more hydrogenated
carbon atom.
(i) CH3 CH CH2 + HBr CH3 CH CH3 + CH3 CH2 CH2 Br
Br
2-Bromopropane 1-Bromopropane
(Major product) (Minor product)
Mechanism :
⊕
(a) CH3 CH CH3
2° carbocation
(More stable)
CH3 CH CH2 + H+
⊕
(b) CH3 CH2 CH2
(Less stable)
⊕ ⊕
(a) CH3 CH CH3 (b) CH3 CH2 CH2
Br – Br –
CH3 CH CH3 CH3 CH2 CH2 Br

1-Bromopropane
Br (Minor product)
2-Bromopropane
(Major product)
Cl H
(ii) CH2 C CH3 + HCl CH3 C CH3 + Cl CH2 C CH3
CH3 CH3 CH3
2-Methylpropene 2-Methyl- 2-Methyl-
2-chloropropane 1-chloropropane
(major) (minor)
Mechanism :
CH2 C CH3
CH3
+ +
H H
⊕ ⊕
(a) CH3 C CH3 (b) CH2 CH CH3
CH3 CH3
3° carbocation 1° carbocation
(Most stable) (Less stable)
– –
Cl Cl
Cl Cl CH2 CH CH3
CH3 C CH3 CH3
CH3 2-Methyl-1-chloropropane (minor)
2-Methyl-2-chloropropane (major)
33. (i) How will you convert ethanoic acid into benzene?
(ii) When 2-pentyne reacts with mercuric sulphate in dilute sulphuric acid, the product obtained is a mixture
of two ketone. Show by reaction.
Sol. (i) Ethanoic acid reacts with sodium hydroxide to form salt of sodium ethanoate which is further subjected
to decarboxylation method produces methane. Methane is chlorinated in limited quantity of chlorine in
presence of diffused sunlight or ultra-violet light which produces methyl chloride. Methyl chloride reacts
with sodium in presence of dry ether (Wurtz reaction) to yield ethane, which on limited chlorination gives
ethyl chloride. Ethyl chloride undergoes dehydrohalogenation reaction producing ethene which produces
vicinal dihalide on reaction to Bromine. The vicinal dihalide produces ethyne when allowed to react with
alcoholic KOH followed by reaction with sodamide. Ethyne when passed through red hot iron tube at
873 K undergo cyclisation process to produce benzene.
NaOH CaO, Δ hν Na/dry ether Cl2

CH3COOH –H2O
CH3COO–Na+ NaOH
CH4 Cl2
CH3Cl Wurtz reaction
C2H6 C2H5Cl
–KCl
alc. KOH
–H2O
Red hot iron tube NaNH2 alc. KOH

CH2Br Br2
873 K
CH CH CH2 CH Br CH2 CH2
CH2Br
Benzene
H H
2+ +
Hg , H
(ii) CH3 C C CH2 CH3 + H OH 333 K
CH3 C C CH2 CH3 + CH3 C C CH2 CH3
2-pentyne
OH OH
H OH O
Isomerisation
CH3 C C CH2 CH3 CH3 CH2 C CH2 CH3
3-pentanone
OH H O
Isomerisation
CH3 C C CH2 CH3 CH3 C CH2 CH2 CH3
2-pentanone
34. Write the possible isomeric structures of pentene and name them. What are the products obtained when each
of it is subjected to reductive ozonolysis?
Sol. The possible isomeric structures of pentene are :
(i) CH 2 CH CH2 CH2 CH3 Pent-1-ene
(ii) CH 3 CH CH2 CH2 CH3 Pent-2-ene
(iii) CH 3 CH C CH3 2-Methylbut-2-ene
CH3
(iv) CH2 CH CH CH3 3-Methylbut-1-ene
CH3
(v) CH 2 C CH2 CH3 2-Methylbut-1-ene
CH3
The products obtained when each of it is subjected to reductive ozonolysis are as follows.
O O
O3
H
(i) CH2 CH CH2 CH2 CH3 C C CH2 CH2 CH3
H O H
Zn/H2O
HCHO + CH3CH2 CH2 CHO
Formaldehyde Butanaldehyde
O O
O3
(ii) CH3 CH CH CH2 CH3 CH3 C C CH2 CH3
H O H
Zn/H2O
CH3CHO + CH3CH2CHO
Ethanaldehyde Propionaldehyde
O O
O3
(iii) CH3 CH C CH3 CH3 C C CH3
H O CH3
CH3
O
Zn/H2O
CH3CHO + CH3 C CH3
Ethanaldehyde Propanone
O O
O3
H H
(iv) CH2 CH CH CH3 C C CH CH3
H O
CH3 CH3
Zn/H2O
HCHO + CH3 CH CHO
CH3
Formaldehyde 2-Methylpropanal
O O
O3
H
(v) CH2 C CH2 CH3 C C CH2 CH3
H O CH3
CH3
O Zn/H2O
HCHO + CH3 C CH2 CH3

Formaldehyde Butanone
35. How can the structure of an alkene is determined by ozonolysis?

Sol. Ozonolysis serves one of the best methods to determine the position of double bond in an alkene. When an
alkene is treated with ozone in an inert solvent, forms ozonide, which when treated with Zn/H2O, carbonyl
compounds are obtained. The structure of carbonyl compound depends upon the structure of the alkene. Some
points should be kept in mind while deciding the structure of the alkene :
H H
(i) When formaldehyde O C H is obtained, it means the group is CH2 when O C R type of
aldehyde is obtained, it means the group is CHR .
R R
When a keto group, O C R is obtained, it means the group is C R.

(ii) When only one type of aldehyde or ketone is obtained, it means alkene is symmetrical with respect to
the double bond.
(iii) The structures of carbonyl compounds are written in a way that the carbonyl group faces each other.
R2 R4
R1 C O O C R3
[A] [B]
(iv) The ==O of both the compounds are removed and linked through a double bond. This is the structure of
unknown alkene.
R2 R4
R1 C C R3
R1, R2, R3 or R4 are either hydrogen atoms or alkyl groups or both.

36. What are the steps involved in an electrophilic substitution reaction? Discuss with a general mechanism.
Sol. Electrophilic substitution reactions proceed via three steps
(i) Generation of an electrophile
(ii) Attack of electrophile on benzene ring
(iii) Deprotonation.
(i) Generation of an electrophile, E⊕ : During chlorination, alkylation and acylation of benzene, anhydrous
FeCl3, AlCl3 or FeBr3, acting as a Lewis acid helps in generation of the electrophile Cl⊕, R⊕, RC⊕O
(acylium ion) respectively by combining with the attacking reagent.
E – Nu + AlCl3 ⎯→ E⊕ + [AlCl3Nu]–
Where E = Electrophile and Nu = Nucleophile and [AlCl3Nu]– is the intermediate complex.
(ii) Attack of electrophile on benzene ring (formation of arenium ion) : The attack of electrophile E⊕
results in the formation of a σ (sigma) complex or arenium ion in which one of the carbon is sp3
hybridized.
H
⊕
+E ⊕ E
H
Sigma complex
(arenium ion)
The arenium ion gets resonance stabilised.
H H ⊕ H H
⊕E E E ⊕ E
⊕
H H H H
Resonance
hybrid
(iii) Removal of proton : To restore the aromatic character, σ-complex releases proton from sp3 hybridised
carbon atom.
H E
⊕
E +H
+
H
[AlCl3N4]– + H+ AlCl3 + H-Nu
37. (i) Write the general formule of alkynes.
(ii) Write down the IUPAC name and structures of all alkynes having the molecular formula C5H8.
(iii) Give any two methods for preparing acetylene.
(iv) Discuss any three chemical properties of acetylene.
Sol. (i) The general formula of alkynes is Cn H2n – 2.
(ii) C5H8 has the following isomers :
(a) CH3 CH2 CH2 C CH

pent-1-yne
(b) CH3 CH2 C C CH3

pent-2-yne
(c) CH3 CH C CH
CH3
3-Methylbut-1-yne
(iii) Acetylene can be prepared by the following two methods :

(a) Hydrolysis of calcium carbide
CaC2 + 2H2O ⎯→ C2H2 + Ca(OH)2
(b) By dehydrohalogenation of vicinal dihalides of alkanes
CH 2 Br
+ 2KOH CH CH + 2KBr + 2H2O
CH 2 Br Alcoholic
1-2-dibromoethane
(iv) The three chemical properties of acetylene are as follows :

(a) Addition of hydrogen :
Ni/Pd/Pt
HC CH + 2H2 H 3C CH 3
(b) Addition of halogens :
Br Br
Br2
HC CH + Br2 HC CH H C C H
Br Br Br Br
1,1,2,2-Tetrabromopropane
(c) Cyclic polymerisation : When acetylene is passed through red hot iron tube at 873 K. Cyclic
polymerisation takes place forming benzene.
Fe tube, 873 K
3HC CH
Benzene
38. Predict the major product in the following reactions. Give mechanism as well.
H SO
(i) C6H6 + CH3CH2CH2 —OH ⎯⎯⎯⎯
2 4
→?
Cl
Δ
(ii) C6H6 + CH3 C CH3 + AlCl3 ?
CH3
Sol. (i) In the presence of H2SO4 propanol first gives 1° carbocation which then rearranges by hydride shift to
give 2°carbocation. The carbocation then reacts with benzene to form Isopropyl benzene.
H H
+ –H2O
H
CH3 CH2 CH2 O H CH3 CH2 CH2 O+ H H3C C C⊕
H H H
Protonated alcohol 1° carbocation
(Less stable)
H H
Hydride shift
H3C C C H
⊕
H
2° carbocation
(More stable)
CH3 CH CH3
H CH3
+ H3C CH CH3 ⊕
CH
⊕
CH3
Benzene Loss of proton Isopropyl benzene
CH3 CH3
(ii) CH3 C Cl + AlCl3 CH3 C⊕ + [AlCl4]–
CH3 CH3
CH3
CH3 C CH3
CH3 H CH3
–
[AlCl4]
+ ⊕C CH3 C CH3 + HCl + AlCl3
⊕
CH3 CH3 Tertiary

Benzene Loss of proton Butylbenzene
39. Explain the following
(i) Why alkenes are more reactive than alkanes?
(ii) Acetylene reacts with Sodamide to form an acetylide while ethylene does not?
(iii) But-2-ene shows geometrical isomerism but but-1-ene does not?
Sol. (i) Alkenes contains π-bond which is weaker than sigma bond and can be easily broken. Whereas in
alkanes, all the bonds are strong σ (sigma) bonds which are difficult to break. So alkenes show greater
reactivity in comparison to alkanes.
(ii) Acetylene reacts with sodamide (NaNH2) that is a strong base, due to its acidic nature. It contains acidic
hydrogen in it.
H C C H + NaNH2 H C C–Na+ + NH 3
Sodium acetylide
H H
C C + NaNH2 No reaction
H H
(iii) In but-1-ene, the carbon atom is linked by double bond which is attached with two hydrogen atoms and
thus it will not show geometrical isomerism.
CH3 H2C H
C C Two hydrogen on the same side of the C C plane.
H H
But-1-ene
While But-2-yne can show geometrical isomerism being the doubly bonded carbon atom is linked by
different groups.
H3C CH3 H3C H

C C C C
H H H CH3
cis-but-2-ene trans-but-2-ene
40. How will you synthesise?

(i) Vinyl chloride from acetylene
(ii) Propane from isopropyl alcohol
(iii) 2,3-Dimethylbutane from propene
(iv) Cyclohexene from cyclohexane
(v) But-2-yne from propyne
2HCl alc. KOH

Sol. (i) H C C H H3C CHCl2 Elimination
H2C CHCl
Markovnikov's
Acetylene addition –HCl Vinyl chloride
H3C H2SO4
H3C H2, Ni
(ii) CHOH CH Δ
CH3 CH2 CH3
(conc.)
H3C H2C Propane
Isopropyl alcohol
H3C CH3
Na/ether
(iii) H3C CH CH2 HCl
H3C CH CH3 (Wurtz reaction)
HC CH
Propene H3C CH3
Cl
2,3-Dimethylbutane
Cl
Cl2 alc. KOH
(iv) hν
Cyclohexane Cyclohexene
NaNH2 CH3Cl
(v) H 3C C CH H 3C C C–Na+ H 3C C C CH 3
Propyne But-2-yne
41. Give the structural formulae for the seven alkynes of the formula C6H10. Which of these isomers are terminal
alkynes? Which of these on partial hydrogenation followed by reductive ozonolysis will produce only one type
of compound?
Sol. HC C CH2CH2CH2CH3 CH3 C C CH2 CH2 CH3 CH3 CH2 C C CH2 CH3
Hex-1-yne Hex-2-yne Hex-3-yne
(A) (B) (C)
CH3
CH3 CH C C CH3 CH3 CH CH2 C CH CH3 CH2 CH C CH CH3 C C CH
CH3 CH3 CH3 CH3

4-Methylpent-2-yne 4-Methylpent-1-yne 3-Methylpent-1-yne 3,3-Dimethylbut-1-yne
(D) (E) (F) (G)
Terminal alkynes are those which have a triple bond at the end of the carbon chain. Here in the isomers given
(A), (E), (F) and (G) are the terminal alkynes.
Hex-3-yne when subjected to partial hydrogenation followed by reductive ozonolysis will produce same carbonyl
compound.
H2, Ni, Δ
CH3 CH2 C C CH2 CH3 CH3 CH2 CH CH CH2 CH3
Hex-3-ene
O
Zn/H2O O3
2CH3CH2CHO CH3 CH2 C–H H–C CH2 CH3
Propanal
O O
42. What are the conditions necessary for exhbibting geometric isomerism in open chain compounds? Why cis-
isomer is more polar than trans-isomer?
Sol. (i) The conditions necessary for geometric isomerism

(a) There should be a double bond in the molecule.
(b) The two atoms or groups attached to each doubly bonded carbon atom should be different. If one
of the two double bonded carbon atoms carries two identical groups or atoms then the molecule does
not exhibit geometrical isomerism. For example :
H CH3 CH3 CH3

C C C C
H H CH3 H
Propene 2-methylbut-2-ene
No geometrical isomerism
CH3 CH3 CH3 H

C C C C
H H H CH3
Geometrical isomerism
(ii) Cis-isomer is more polar than the trans-isomer because in it the individual bond dipoles do not cancel
out each other. For example, dipole moment of cis-but-2-ene is 0.33 D whereas that of trans-but-2-ene
is almost zero.
CH3 CH3 CH3 H

C C C C
H H H CH3
(μ = 0.33 D) (μ = 0)
43. (i) What is Huckel rule? Give example to explain.
(ii) Why benzene prefer to undergo substituion reaction rather than addition reaction?
Sol. (i) Huckel rule defines the aromaticity of a compound. If a following set of characteristics are followed, the
compound will be aromatic.
(a) It should be planar.
(b) It should have complete delocalisation of π-electrons in the ring.
(c) It should have (4n + 2)π electrons in the ring where ‘n’ is whole number 0, 1, 2, 3, ........
Example :
Benzene has six π-electrons and behaves as an aromatic compound.
Benzene
(n = 1)
(ii) Despite of being highly unsaturated, benzene prefer to undergo substitution rather than addition because
in addition reaction, the resonance stabilised benzene ring is destroyed, destroying its aromatic character.
On the other hand, aromaticity is maintained during substitution since delocalisation of electron remains
intact.
H X
H
X
X2 )
ion Delocalisation of
ddit electrons destroyed
(A
Su
X X
bs
titu
tio
n
Delocalisation of
electrons intact
44. Explain the orbital structure of benzene with the reason for its extra stability.
Sol. According to the orbital structure, each carbon atom in benzene is sp2 hybridized with three orbitals lying in
one plane at an angle of 120°. There is one unhybrid orbital lying perpendicular to the hybrid orbitals plane.
Each carbon atom uses two hybrid orbitals for axial overlaing with the two other carbon atom orbitals on the
either side, whereas the third one is used to overlap axially with 1s orbital of hydrogen forming six C–H sigma
bonds. From given figure C–C and C–H sigma bonds can be depicted.
H 1s
σ
120°
C
H 1s σ σ 1s H
σ σ
C C
σ σ
sp2 hybridised
C C
σ σ
H 1s σ σ 1s H
σ
H 1s
The unhybridized p-orbital undergoes sideways overlapping forming weak π-bonds.
(a) (b) (c)

The molecular orbital containing π-electrons spreads uniformly over the entire carbon skeleton forming a doughnut
structure. This delocalisation of π-electrons, results in decrease of energy and hence accounts for its extra
stability of benzene.
H H
C C
H C C H
C C
H H
Orbital picture of benzene
45. With a suitable mechanism show how benzene can be converted to Styrene (C6H5 —CH==CH2).
Sol. Benzene undergo Friedel Craft’s reaction to be alkylated.
C2H5
anhyd AlCl3
+ C2H5Cl + HCl
Mechanism :
Δ
C2H5 Cl + AlCl3 ⎯⎯→ C2H⊕
5 + (AlCl4 )
−
H
+
+ C2H 5 C2H5
⊕
Attack of
electrophile
H H ⊕ H H
C2H5 C2H5 C2H5 ⊕ C2H5
⊕ ⊕
Resonance stabilised Resonance

hybrid
H C2H5
–
⊕ C2H5 + [AlCl4] + HCl + AlCl3
Proton loss
CH3
CH2 CH3 CH Cl
+ Cl2 hν
+ HCl
Mechanism :
Homolytic
Cl Cl fission
2Cl
H H
C CH3 + Cl –HCl
C CH3
H 2° free radical
(more stable
than primary)
H H
C CH3 + Cl C CH3
Cl
H H H H
α β β-elimination
C C H + alc. KOH C C H + KCl + H2O
Cl H Styrene
SECTION - B
Model Test Paper
Very Short Answer Type Questions :
1. What is the bond angle in methane molecule?
Sol. 109°28′
2. Write the IUPAC name of the following compound
CH2 CH3
H3C CH2 CH2 CH CH C CH2 CH3
CH3 CH CH3 CH2 CH3
CH3
Sol. 3,3-Diethyl-5-isopropyl-4-methyloctane.
3. CH3 CH CH2 CH2 CH3 Cl CH2 CH2 CH2 CH2 CH3 CH3 CH2 CH CH2 CH3
Cl Cl
(I) (II) (III)
What is the relation between the given three structures?
Sol. They are positional isomers.

4. What is the order of rate of reaction for halogens in dehydrohalogenation relations?
Sol. The order of rate of reaction for halogens is as follows :

Iodine > Bromine > Chlorine
5. Draw the proposed Kekule structure for benzene.
Sol.
6. What is the product obtained when ethyne undergoes cyclic polymerization? Give the reaction.
Sol. When acetylene is passed through heated iron tube at 873 K, benzene is obtained as the product of cyclic
polymerization.
CH
CH
HC CH Fe tube, 873 K CH CH
HC CH CH CH
CH
CH
Acetylene Benzene
7. Give two examples of carcinogenic substances and how do they causes cancer?
Sol. Carcinogenic substances are polynuclear hydrocarbons, which enters the human body and undergoing through
various biochemical reactions finally damage DNA and causes cancer. Example of carcinogenic
hydrocarbons are
1,2-Benzanthracene 1,2-Benzpyrene
8. Give an example of dehalogenation reaction for the preparation of an alkene from vicinal dihalides.
Sol. Vicinal dihalides on treatment with zinc metal loses a molecule of ZnX2 to form an alkene.
CH3CHBr – CH2Br + Zn ⎯→ CH3CH==CH2 + ZnBr2
9. Draw cis and trans isomer of the following compounds. Also write their IUPAC names :
(i) CHCl==CHCl
(ii) C2H5CCH3 ==CCH3C2H5
Sol. (i) H H H Cl
C C C C
Cl Cl Cl H
cis-1,2-Dichloroethene trans-1,2-Dichloroethene
(ii) CH3 CH3 CH3 C2H5

C C C C
C2H5 C2H5 C2H5 CH3
cis-3,4-Dimethylhex-3-ene trans-3,4-Dimethylhex-3-ene
10. Draw Newman’s projections of ethane and tell which one is more stable.
Sol. There are two main projections of ethane molecule eclipsed and staggered.
H
H H
H H
H
H HH H H
H
(i) Eclipsed (ii) Staggered
Staggered conformation of ethane molecule is more stable due to less torsional strain.
11. What are the products obtained when but-2-yne undergoes partial hydrogenation in presence of palladised
charcoal and in presence of Lindlar’s catalyst?
Sol. When but-2-yne is subjected to partial hydrogenation in presence of palladised charcoal cis-2-butene is
produced.
CH3 CH3
Pd/C
CH3 C C CH3 H2
C C
Lindlar's H H
Catalyst cis-but-2-ene
when but-2-yne undergoes hydrogen addition in presence of Na and liq. NH3 trans but-2-ene is formed.
CH3 H
Na/liq. NH3
CH3 C C CH3 Birch
C C
Reduction H CH3
trans-but-2-ene
12. What is Wurtz reaction? Give an example of reaction in support of your answer.
Sol. Alkyl halide on treatment with sodium metal in ethereal solution gives higher alkanes. This reaction is known as
Wurtz reaction. This method is employed for the preparation of higher alkanes with even number of carbon atoms.
Dry ether
CH3CH2Br + 2Na + BrCH2CH3 ⎯⎯⎯⎯→ CH3 CH2 CH2 CH3 + 2NaBr
n-Butane

13. (i) Sodium salt of which acid will be needed for the preparation of propane? Write chemical equation for the
reaction.
(ii) How can BHC (Benzene Hexachloride) be prepared?
Sol. (i) Butanoic acid
CaO
CH3CH2CH2COO–Na+ + NaOH ⎯⎯⎯ → CH3CH2CH3 + Na2CO3
(ii) Three chlorine molecules adds to the benzene in presence of ultraviolet light to produce benzene
hexachloride.
Cl
Cl Cl
UV
+ 3Cl2 500 K
Cl Cl
Cl
Benzene Benzene
hexachloride
14. With a suitable mechanism explain how an alkane can be produced through Kolbe’s electrolytic method?
Sol. An aqueous solution of sodium or potassium salt of a carboxylic acid on electrolysis gives alkane containing
even number of carbon atoms at the anode.
2CH3 COO −Na + + 2H2 O ⎯⎯⎯⎯⎯

Electrolysis
→ CH3 – CH3 + 2CO2 + H2 + 2NaOH
Sodium acetate
The possible mechanism is as follows :
(i) 2CH3COO–Na+ 2CH3COO– + 2Na+
(ii) At anode :
O O
–
– –2e
2CH3 C O 2CH3 C O 2CH3 + 2CO2↑
Acetate ion Acetate free Methyl free
radical radical
(iii) H3C + CH3 H3C — CH3↑

Ethane
(iv) At cathode :
H 2O + e – –
OH + H
2H H2
15. What is the product obtained when isomers of butene are subjected to reductive ozonolysis?
Sol. Isomers of butene are
CH3 CH CH CH3 CH2 CH CH2 CH3

But-2-ene But-1-ene
(I) (II)
When but-2-ene is subjected to reductive ozonolysis, the product obtained is
H O
O3
O H Zn/H2O
CH3 CH CH CH3 CH3 C C CH3 2CH3 C H
Ethanal
O O
Ozonide
The product obtained on reductive ozonolysis of but-1-ene are
O O
H
O3
H O H Zn/H2O
C CH CH2 CH3 C C CH2 CH3 H C H + CH3 CH2 C H
H H Methanal Propanal
O O
Ozonide
16. With few example define aromaticity.

Sol. Those ring system hydrocarbons which possesse benzene ring or not but possesses certain characteristics
are known as aromatic compounds. The characteristics which must be possessed by aromatic compounds
are as follows :
(i) Molecule should be planar
(ii) π electrons in the ring should be completely delocalised
(iii) Presence of (4n + 2)π electrons in the ring where n is the whole number (n = 0, 1, 2, .....). This is also
known as Huckel Rule.
Few examples of aromatic compounds are
Benzene Naphthalene Anthracene

(n = 1) (n = 2) (n = 3)
17. How will you bring conversion of

(i) Benzoic acid to benzene
(ii) Cyclohexane to cyclohexane 1,2-diol
COOH COO–Na+
NaOH
Sol. (i) + NaOH CaO
+ Na2CO3
Benzene
Br 1% cold and OH
Br2 alc. KOH alkaline KMnO4
(ii) Δ –KBr
–HBr –H2O OH
Cyclohexane Hexan-1,2-diol
Long Answer Type Questions :
18. What is Anti-Markovnikov addition? With a suitable mechanism tell how propene reacts with hydrogen bromide?
Sol. Anti-Markovnikov addition is also known by the other names like peroxide effect or Kharasch effect. This rule
is in contrary to the Markovnikov rule where the negative part of the molecule undergoing addition to the carbon-
carbon double bond, attaches to the less substituted or more hydrogenated carbon atom. This reaction occurs
in the presence of a peroxide. Propene reacts with HBr in presence of benzoylperoxide through free radical
mechanism to form 1-Bromopropane
Peroxide
CH 3 CH CH2 + HBr CH3 CH2 CH2 Br
Mechanism : Peroxide effect proceeds via free radical mechanism.
O O O
Homolysis
(i) C O O C 2 C O
Benzoyl peroxide
O O
Homolysis
(ii) — C — O + H — Br — C — OH + Br
CH3 CH CH2 (Less stable primary free radical)
(iii) CH3 CH CH2

+ Br Br
(a)
CH3 CH CH2 Br (More stable secondary free radical)

(b)
• •
Homolysis
(iv) CH3 — CH — CH2Br + H — Br ⎯⎯⎯⎯⎯
→ CH3 — CH2 — CH2 — Br + Br
(Major product)
Homolysis
(v) CH3 CH CH2 + H Br CH3 CH CH3 + Br
Br Br
(Minor product)
The secondary free radical obtained in the above mechanism is more stable than the primary thus explaining
the formation of 1-bromopropane as the major product.
19. Draw all the possible confirmations of butane and arrange them in the order of their stability.
Sol. CH3–CH2–CH2–CH3
CH3 CH3 CH3
CH3 H
CH3
H CH3 H H
H H H CH3 H H
H H
H H H H CH3
H
Fully eclipsed Skew Partially eclipsed Anti
Order of stability
Anti > Skew > Partially eclipsed > Fully eclipsed.
20. (i) Even though benzene has a high degree of unsaturation, it does not favour addition reaction whereas it
favours substitution reactions. Why?
(ii) Is it possible to isolate and separate conformational isomers of ethane? Why?
Sol. (i) Benzene contains three double bonds showing a high degree of unsaturation but it does not undergo easy
addition reactions as in case of alkenes. This is because the addition reaction distorts the shape of the
molecule causing it to lose its planarity and aromatic character. On the other hand substitution reaction
does not brings about any change in the planar or aromatic character.
X
X2
(Addition)
X
Aromatic character
destroyed
X
X2
(Substitution)
+ HX
Aromatic character
maintained
(ii) No, it is not possible to isolate and separate conformational isomers of ethane because the energy
difference between extreme forms of ethane i.e., eclipsed and staggered is of only 12.5 kJ mol–1, which
is very small. Even at ordinary temperatures, the ethane molecule gains thermal or kinetic energy
sufficient enough to overcome this energy barrier of 12.5 kJ mol–1 through intermolecular collisions. Thus,
we can say that rotation about carbon-carbon single bond in ethane is almost free making it impossible
to separate and isolate different conformational isomers of ethane.


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Chapter 13

4. Name two reagents which can be used to test unsaturation.

7. In the sulphonation of benzene whats acts as an electrophile?

Sol. (A) = (B) =

Short Answer Type Questions :

Sol. CH3 CH2 CH2 CH3 CH3 CH2 CH2 H

H3C H3C H3C CH3

13. What do you understand by aromatization?

14. CH3 CH3 CH3 H

16. How can you obtain butan-2-one from acetylene?

18. What is isomerisation reaction? Give an example.

19. How can benzene be prepared from sodium benzoate?

20. How will you obtain? Give equation only

CH3Cl + 2Na + ClCH3 ⎯⎯→ CH3 – CH3 + 2NaCl

(ii) CH3COOH + NaOH ⎯→ CH3COO–Na+ + H2O

21. What is Markovnikov rule? Illustrate with an example.

Contains less number

22. Can conformational isomers of ethane be separated? Why?

C3H6 + C2H4 + CH4

Only one product 2,2-Dimethylchloropropane can be obtained by monochlorination of neopentane.

Three products or three monochloro isomeric n-pentane can be obtained i.e.,

(b) H 3C CH CH2 CH2 CH3; 2-chloropentane

(c) H 3C CH 2 CH CH2 CH3; 3-chloropentane

(a) π-bond (b) π-cloud of electrons

26. Find the product obtained in the following cases

Sol. (i) C3H8 + 5O2 ⎯⎯→ 3CO2 + 4H2O

(iii) Corresponding alcohol is obtained when oxidised by KMnO4.

27. What is Saytzeff rule? Give example.

CH3 H CH3 H CH3 CH3 CH3 CH3

Increasing hyperconjugative structures, hence, higher stability

The free radicals produced in the reaction starts a chain reaction.

(i) CH3 CH CH2 + HBr CH3 CH CH3 + CH3 CH2 CH2 Br

CH3 CH CH3 CH3 CH2 CH2 Br

NaOH CaO, Δ hν Na/dry ether Cl2

Red hot iron tube NaNH2 alc. KOH

(ii) CH 3 CH CH2 CH2 CH3 Pent-2-ene

(iii) CH 3 CH C CH3 2-Methylbut-2-ene

(iv) CH2 CH CH CH3 3-Methylbut-1-ene

(v) CH 2 C CH2 CH3 2-Methylbut-1-ene

HCHO + CH3 C CH2 CH3

35. How can the structure of an alkene is determined by ozonolysis?

When a keto group, O C R is obtained, it means the group is C R.

R1, R2, R3 or R4 are either hydrogen atoms or alkyl groups or both.

The arenium ion gets resonance stabilised.

(a) CH3 CH2 CH2 C CH

(b) CH3 CH2 C C CH3

(iii) Acetylene can be prepared by the following two methods :

(iv) The three chemical properties of acetylene are as follows :

CH3 CH3 Tertiary

39. Explain the following

(i) Why alkenes are more reactive than alkanes?

H3C CH3 H3C H

40. How will you synthesise?

2HCl alc. KOH

(A) (B) (C)

CH3 CH C C CH3 CH3 CH CH2 C CH CH3 CH2 CH C CH CH3 C C CH

CH3 CH3 CH3 CH3

(D) (E) (F) (G)

Sol. (i) The conditions necessary for geometric isomerism

H CH3 CH3 CH3

CH3 CH3 CH3 H

CH3 CH3 CH3 H

43. (i) What is Huckel rule? Give example to explain.