CHAPTER -6 HYDROCARBON Q 1:Explain Classification of Hydrocarbons [3 mark] The simplest organic compound containing carbon and hydrogen only

y are called hydrocarbons. Hydrocarbons are obtained from natural sources e.g. coal, natural gas and petroleum. Based on the types of the bonds between the carbon atoms they are classified in to four types (i) alkane (ii) alkene (iii) alkyne and (iv) arene Alkanes are saturated hydrocarbons; contain all C-C single bonds. Alkanes further classify into acyclic and cyclic. Alkenes are unsaturated hydrocarbons; contain at least one C=C double bond. Alkenes further classify into acyclic and cyclic. Alkynes are unsaturated hydrocarbons; contain atleast one carbon- carbon triple bond. Arenes are unsaturated hydrocarbons. They have cyclic structure and contain mainly carbon-carbon double bonds. Acyclic alkane General Bond Shape Example Structural Formula formula CnH2n+2 CC Three Methane CH4 single bond dimensional Ethane CH3CH3 Propane CH3CH2CH3 Cyclic alkane General Formula CnH2n

Bond C C single bond

Shape Three dimensional planar

Example Cyclo Propane

Structural formula
CH 2 H 2C CH 2

Cyclo butane

C H 2 C H 2

CH2 CH2

Acyclic alkene General Formula CnH2n

Bond C=C double bond

Shape Planar

Example Ethene (ethylene) Propene (propylene) 1-Butene (- butylenes) Example Cyclo Propene

Structural formula CH2=CH2 CH3CH=CH2 CH3CH2 CH=CH2 Structural formula

CH 2 HC
H 2C

Cyclic alkene General Formula CnH2n-2

Bond C C & C=C

Shape Planar

Cyclo Butene

CH
CH2

HC

CH

Alkyne General Formula

Bond

Shape

Example

Structural formula

CnH2n-2

CHAPTER -6 HYDROCARBON linear Ethyne Propyne 1-Butyne 2- Butyne

HC CH
CH3 C CH

triple bond

CH3 CH 2 C CH
CH3 C C CH3

Arene General Formula CnH2n-6

Bond C C & C=C

Shape plannar

Example benzene

Structural formula

Q 2 Describe general properties of alkanes [2 mark] The hydrocarbons which contain single bond between carbon-carbon are called alkanes. They are saturated compounds and known as parafins. {parum = little affins = affinity} In alkanes sp3 hybrid orbitals of carbon and 1s orbitals of four hydrogen atoms form tetrahedral structure of hydrocarbon. In tetrahedral structure of alkane C C and C H possesses a bond. The bond lengths of C C is 154 pm and C H bond length is 112 pm. All H C H bond angles are of 10928. The shape of methane molecule is represented in Figure
H

sp3

112 pm

109 28
H H

109028

Q 3 Describe general properties of alkenes [2 mark] Acyclic unsaturated compound containing a carbon carbon double bond are called alkenes. They are also called olefins (olefiant = oil forming ) [ lower member of this class such as ethane, propene etc. produce oily products on reaction with halogens.] Alkene compounds have at least one C=C in their structural formula. C=C bond length is 133pm in ethene. They are more reactive than alkane due to presence of C=C.
bond

C
H

134pm 121 7
0

2p z
sp
2

116 06

120

bond

sp2 120 0

bond

Q 4 Describe general properties of alkynes [2 mark] Acyclic unsaturated hydrocarbons containing a carbon-carbon triple bonds are called alkynes or acetylenes. Acetylene is the first member of alkyne series in which two sp hybridized carbon combine through triple bond. It has H-C-H bond angle 1800. In acetylene C-H bond length is 106pm and C-C bond length is 120pm.
2

CHAPTER -6 HYDROCARBON Alkynes are more reactive than alkene and alkynes.
bond 2py 2p y bond
sp

sp

180

180
bond
bond

2p z

2p z

bond Explain Isomerism and Nomenclature in Alkanes with example.[4mark] The compounds having same molecular formula but different physical and chemical properties are called isomers and this phenomenon is called isomerism. Compounds which have same molecular formula, but their structural formulas are different, are called structural isomers. The study of isomerism can be done very well in alkane chains. In the first three hydrocarbons methane, ethane and propane isomerism is not observed. Isomers are observed in the successive members having more than three carbon atoms. In common nomenclature method, all the isomers of alkane have same fundamental name, e.g., both the isomers having C4H10 molecular formula are known as butane, but the name of each isomer is separated by its prefix. The prefix is known according to the branch in the molecule. (1) Prefix 'n' is used for such alkanes in which all the carbon atoms are combined in same long chain. Here, n-means normal, e.g., CH3 CH2 CH2 CH3 (n-butane) (2) Prefix 'iso' is used in such alkanes in which an alkyl group like methyl group (-CH3) is attached to carbon second from last carbon e.g. Prefix 'neo' is used in such alkanes in which two alkyl groups like methyl groups are combined with the carbon second from left of the long chain of carbon. Prefix 'neo' applicable to pentane and nonane only. This type of nomenclature is convenient for simple hydrocarbons, but for more complex hydrocarbons IUPAC nomenclature is more convenient. Sr no. Molecular Structural formula Common IUPAC formula name name CH4 C2H6 C3H8 C4H10 CH3 (CH2)2-CH3 n-butane butane
Iso-butane 2-methyl propane pentane 2-methyl butane 2,2-di methyl propane hexane 2-methyl pentane

CH3 CH CH3

C5H12

CH3 (CH2)3CH3
CH3 CH CH2 CH3 CH3 CH3
CH3 C CH3

CH3

n-pentane Iso-pentane Neo-pentane

C6H14

CH3 (CH2)4CH3
CH3

CH3

CH3 CH CH2 CH 2 CH3

n-hexane Iso -hexane

CH3 CH 2 CH CH2 CH 3
CH3

CHAPTER -6 HYDROCARBON
CH 3

3-methyl pentane 2,2 di-methyl butane

CH3 C CH 2 CH 3 CH3 CH3 CH CH CH 3

CH 3

CH 3

2,3 di-methyl butane

Q 5 Explain preparation of alkane by various methods [4 mark] Explain preparation of alkane from unsaturated hydrocarbons: [2-mark] Alkane compounds are obtained by addition reaction of unsaturated hydrocarbons like alkene and alkyne compounds with dihydrogen in presence of catalyst like Pt or Pd at normal temperature. This reaction is known as hydrogenation. If this reaction is carried out in presence of Ni catalyst, it requires high temperatures and pressure.

CH2 = CH2 + H2 ethene

C CH3 + 2 H2 CH3 C but-2-yne
CH2 = CH2 ethene + H2

[Pt / Pd ]

CH3 CH3 ethane

CH3 CH2 CH2 CH3 butane
CH3 CH3 ethane CH3 CH2 CH2 CH3 butane

[Pt / Pd ]

[Ni ] pressure [Ni ] C CH3 + 2 H2 CH3 C but-2-yne pressure

Explain preparation of alkane from alkyl halide. [2-mark] Alkanes obtained by reduction of alkyl halide with zinc metal and hydrochloric acid.

CH3CH2Cl + H2 ethyl chloride

CH3CH2CH2Cl 1-chloro propane

[Zn + HCl]

di hydrogen
H2

CH3 CH3 + HCl ethane [Zn + HCl] CH3 CH2 CH3 + HCl di hydrogen propane

Explain preparation alkane from carboxylic acids. [2-mark] Sodium salts of carboxylic acid are first obtained by reaction of carboxylic acid with sodalime (solid NaOH + CaO). When these sodium salts are allowed to react with sodalime at high temperature, they give alkanes containing one carbon less than the carbon atoms in original carboxylic acid. This reaction is known as decarboxylation reaction because carbon dioxide is released from carboxylic acid during this process.
(NaOH + CaO) CH3COOH sodalime 573 K
(NaOH + CaO) CH3CH2COOH propanoic acid sodalime

(NaOH + CaO)
CH3COONa sodium acetate

CH3COONa

CH4 methane
CH3

sodalime

Na2CO3 sodium carbonate

3

(NaOH + CaO)
CH3CH2COONa CH3CH2COONa sodium sodium propanotate propanotate

sodalime

- CH

ethane

Na2CO3 sodium carbonate

Chemical properties (Chemical reactions): Alkane compounds are saturated compounds and so give only substitution reactions.
4

CHAPTER -6 HYDROCARBON Write a note on halogenations of alkane: At very high temperature or in presence of ultraviolet radiation of sunlight, alkane reacts with halogen to form alkyl halide. This phenomenon is called halogenations. The order of reactivity of halogens for halogenation reaction is as follows. F 2 > Cl2 > Br2 > I2 Explain fluorination of methane [2mark] As fluorine molecule is highly active, according to free radical mechanism, this reaction does not need a catalyst.
CH4

F2

CH3F + fluoro methane

HF

Explain chlorination of methane [3mark] Chlorination: In chlorination of alkane, in presence of sunlight or high temp (573 673 K) alkanes react with chlorine Cl2, e.g. in presence of uv radiation or at 573 K methane reacts with chlorine and chloro methane is obtained.
CH4

Cl2

hv or 573K

CH3Cl chloro methane

HCl

As the reaction proceeds continuously the substitution of remaining three hydrogen atoms takes place by chlorine and, finally, tetra chloromethane is obtained. hv or HCl + CH3Cl + Cl2 CH2Cl2 520-670K di chloro methane
CH2Cl2

Cl2

hv or 520-670K

CHCl3 tri chloro methane

HCl

CCl4 HCl + tetra chloro methane 520-670K (b) Bromination: Bromine reacts with alkane which is similar to chlorination reaction but it is slow. Explain iodination of methane [2mark] Iodination: Alkane with iodine gives reversible reaction. CH3I + HI CH4 + I2 iodo methane Explain cyclization reaction of alkane.[2mark] By Cyclization normal alkane having 6 or more carbon atoms heated at 773 K temperature and 10-20 atmosphere pressure in the presence of catalyst benzene and its derivatives are obtained. This reaction is known as cyclization or dehydrogenation. e.g. n-hexane at 773 K temperature and 10-20 atmosphere pressure in the presence of V2O5 or Cr2O3 or Mo2O3 as catalyst, dehydrogenation takes place and benzene is formed. CHCl3 Cl2
CrO3 / V2O3 / Mo2O3 773K 10-20 atm

hv or

CH3

(CH2)4

CH3

4H2O

Describe Reaction of alkane with water (vapour) [2 mark] Reaction of alkane in presence of Ni catalyst with water vapour at higher temperature, dihydrogen gas is released. This process is used in industries to obtain dihydrogen gas. Likewise, reaction of methane with water vapour in presence of Ni catalyst at higher temperature, a mixture of CO and H2 called water gas is obtained. [Ni] CH4 + H2O CO + 3H2 Explain preparation of alkene compounds by any two methods [4 mark] Explain preparation of alkene From alkyne: [2 mark] Alkene is obtained by the addition reaction of alkyne with H2 gas in presence of mixture of palladium (Pd) and charcoal as catalyst. This catalyst mixture of palladium and charcoal is known as 'Lindlars' catalyst. Thus, addition reaction of hydrogen in group is called hydrogenation reaction.
5

CHAPTER -6 HYDROCARBON
[Pd/C] CH CH ethyne
CH3 C CH

+
+

H2

Lindlar's catalyst
[Pd/C]

CH2 = CH2 ethene

CH3CH = CH2 propene

H2

Lindlar's catalyst

Explain preparation of alkene From alkyl halide: [2 mark] Alkene is obtained by reacting with potassium hydroxide dissolved in ethanol (Ethanolic KOH) with alkyl chloride at higher temperature. During this reaction, removal of halogen from -carbon and hydrogen from carbon of alkyl halide takes place hence this reaction is known as -elimination or de hydro halogenation reaction. ethanolic KOH CH2 = CH2 + KCl + H2O CH3CH2Cl ethyl chloride ethene Explain preparation of alkene From vicinal dihalide (From dihalogen alkane) : [2 mark] Dihalides in which two halogen atoms are attached to two adjacent carbon atoms are known as vicinal dihalides. Vicinal dihalides on treatment with zinc metal gives a molecule of ZnX2 (X = halogen) and forms an alkene. This reaction is known as dehalogenation.
CH2 CH2

Zn

Br Br 1,2 di bromo ethane

CH3CH Br CH2 Br

CH2 = CH2 ethene

ZnBr2

Zn

CH3CH = CH2 propene

ZnBr2

1,2 di bromo propane

Explain preparation of alkene from alcohol: [2 mark] Alkene is obtained by reacting alcohol with cone H2SO4 at 443 K temperature. During this process water molecule is released. This process is called dehydration. It is also known as acidic dehydration of alcohols. [ Conc. H2SO4] CH2 = CH2 + H2O CH3CH2OH 443k ethene ethanol Describe physical properties of alkenes: [3 marks] (i) Variation is observed in physical properties of alkene due to polar nature. Isomerism is also observed in alkene. (ii) Alkene containing two, three or four carbon atoms are in gaseous form, C5 to C15 members are in liquid form and those with more number of carbons are obtained in solid form. Ethene is colourless gas with a fruity sweet smell. (iv) Except ethene all other alkenes are odourless and tasteless. (v) Except ethene all alkene are insoluble in polar solvent like water, but it is soluble in non-polar organic solvents like petrol, benzene, ether and carbon tetrachloride. (vi) Alkenes have higher melting points and boiling points than alkanes, and these increase with the increase in the molecular mass. Write a note on Isomerism in Alkene [4 mark] Alkenecompounds give two types of isomerism : (i) Structural isomerism (ii) Geometrical isomerism (i) Structural isomerism : The alkene compounds containing two or three carbon atoms do not show structural isomerism, but the alkene compounds containing four or more carbon atoms show structural isomerism. For example, the alkene having molecular formula C4H8 shows structural isomerism and the isomers can be shown as under :
6

CHAPTER -6 HYDROCARBON
CH3 C CH3 CH2

CH3

CH2

CH

CH2

CH3

CH

CH

CH3

But-1-ene

but-2-ene

2-methyl propene

Explain geometrical isomerism. [ 3 mark] Although some alkene compounds have same structural formula and molecular formula, their functional group and/or spatial arrangement of atoms is in different directions. Here, due to the presence of - C = C - the molecular structure is planar. This type of isomerism is known as geometrical isomerism. Usually, geometrical isomers are known as cis and trans isomers. For example,
CH3 C H C H
H

CH3

CH3 C C

H CH3

Cis but -2-ene trans-but-2-ene In cis isomer, two carbon atoms having double bonds are attached to the similar atom or group of atoms present on same side of C = C. While in trans isomer, similar groups are found in diagonal position of C = C. If double bond containing carbons have same functional groups on same side, it does not show geometrical isomerism. The polarity in cis and trans isomers as under.
CH3

CH3

CH3

CH3

cis but -2-ene( = 0.33D)

trans-but-2-ene

From the above figure, it becomes clear that cis isomer is polar while trans isomer is non-polar, because in trans isomer both methyl groups are in opposite directions due to which resulting value of dipole moment is zero. What kind of reactions is given by alkene? Why? [ 1mark] In alkene with- C = C -; -bond of carbon breaks and the addition of atom or functional group (group of atoms) of reactants on carbon atom takes place. This addition reaction is known as electrophilic addition reaction. Explain reaction of alkene with halogen acid with mechanism [4 mark] Alkyl halide is obtained by the reaction of alkene with halogen acid. This is known as hydro halogenation reaction. Reaction of symmetrical alkene is as under CH2 = CH2 + HCl CH3 CH2 chloro ethene ethane Cl Reaction of asymmetrical alkene with (CH3CH=CH2) with halogen acid and Markovnikov rule
CH3CH = CH2 propene

HCl

CH3 CH CH3 Cl 2- chloro propane (I)

CH3 CH2CH2Cl 1- chloro propane (II)

In the reaction of propene with hydrochloric acid, two products I and II are obtained. It is necessary to know the Markovnikov rule to understand the stability of products obtained. In 1869, Russian scientist Markovnikov proposed the rule as under: "In the addition reaction of compounds having asymmetric ethylinic double bond the electronegative part of asymmetric reagent attaches with the ethylinic carbon having less number of hydrogens." This principle can be understood by the following reaction mechanism: Reaction Mechanism
7

CHAPTER -6 HYDROCARBON Initially, electrophilic H+ ion of hydrochloric acid (HCI) is attached with carbon containing ethylinic double bond and forms carbocation as under.
CH3 CH CH2 H+

+ H-Cl

CH3

+ Cl 0 stable 2 carbocation
CH+ CH3

CH3

+ Cl unstable 1 carbocation
0

CH2

CH2+

Primary carbocation is more stable than secondary carbocation. Due to this CI- ion of HCI attaches rapidly to the carbon of secondary carbocation. When carbon has positive charge in its molecule, it is called carbocation.

CH3

20 carbocation

CH+

CH3

+ Cl

CH3

CH Cl

CH3

iso propyl chloride

Thus, Cl ion attaches to the ethylinic carbon containing less hydrogen. The product obtained is stable. H.W. Explain hydro chlorination of propene gives iso propyl chloride [3 mark] H.W. Explain reaction mechanism for the hydro chlorination of propene. [3 mark] Explain reaction of asymmetric alkene with halogen acid in presence of peroxide with reaction mechnism. [4 mark] If the reaction occurs between asymmetric alkene with halogen acid like HBr in presence of hydrogen peroxide then the product obtained is against the Markovnikov's rule. HCl and HI do not show this type of reaction. Only HBr shows this reaction. In 1933, M.S Kharsh and M.P. Mayo studied this reaction mechanism which is known as Kharsh effect, peroxide effect or anti-Markovnikov rule. e.g
CH3 CH CH2

+ HBr

(C6H5CO)2O2

CH3

CH2

CH2Br

HBr

According to peroxide effect, free radical addition reaction mechnism is shown as under. Free radical is obtained by the hemolytic covalent bond fission.
C6H5 C O O O C O
C6H 5 + HBr free radical

C6H5

2C6H5

C O

2C6H5

+ 2CO2

C6H 6 + Br free radical

CH3

CH

CH2

+ Br

CH3

CH
0

CH2Br

CH3

CH Br

CH2

stable 2 free radical

unstable 10 free radical

CH3 CH CH2Br

+ HBr

CH3

CH2

CH2Br

Br

1- bromo propane major product

CHAPTER -6 HYDROCARBON
CH3 CH Br CH2

HBr

CH3

CH Br

CH3

Br

2- bromo propane minor product

Explain reaction of alkene with dihydrogen. [2 mark] At normal temperature alkane is obtained by addition reaction of alkene with dihydrogen in presence of catalyst like Pt or Pd. This reaction is called hydrogenation. If this reaction is carried out in presence of Ni catalyst, then higher temperature and pressure are required. [Ni ] [Pt / Pd ] CH2 = CH2 + H2 CH2 = CH2 + H2 CH3 CH3 CH3 CH3 pressure ethane ethene ethane ethene Describe Reaction of alkene with halogen : [2 mark] Alkane with di-halogen is obtained when alkene reacts with halogen where the bond of ethylinic double bond breaks. This reaction is known as halogenation reaction. The halogen molecule is chlorine, the reaction is known as chlorination.

CH2=CH2

+ Cl2

CH2-CH2 Cl Cl 1,2 dichloro ethane

Explain isomerism of Alkyne compounds. [2 mark] The carbon containing compounds having same molecular formula but different structural formulae are called structural isomers. This phenomenon is known as structural isomerism. Alkyne compounds containing two or three carbon atoms having same structural formulas do not give structural isomers. In alkyne compounds the compounds with five carbon atoms shows isomerism.
CH3 CH CH3 C CH

CH3

CH2

CH3

HC

CH2
CH3

CH2

CH3

3-methyl but-1-yne

pent-2 yne

pent-1-yne

CH3

CH CH3

CH3

HC

C CH3

CH3

4-methyl pent-2-yne

3,3 dimethyl but-1 yne

Describe preparation of Alkyne Compounds by any two methods [4 mark] Explain preparation of Alkyne From calcium carbide[3 mark] Ethyne is prepared by the industrial process in which carbide reacts with water. Initially, calcium carbonate is heated at higher temperature from which calcium oxide (lime) is obtained by decomposition.
CaO CO2 + lime On heating calcium oxide with coke, calcium carbide and carbon monoxide are obtained. CaCO3 1373K
CaC2 + calcium carbide By reaction of calcium carbide with water ethyne is obtained as follows. CaO + 3C 2273K CO

CaC2

2H2O

Ca(OH)2

CH HC ethyne

Explain preparation of Alkyne From vicinal dihalides [2 mark]

CHAPTER -6 HYDROCARBON Alkyl halide is obtained by reaction of vicinal dihalide with alcoholic potassium hydroxide reaction and this alkyl halide on reaction with sodamide (NaNH2) gives alkyne. This reaction is called dehydro-halogenation reaction.
CH2 Br CH2 + Br 1,2 di bromo ethane KOH alcohol - KBr - H2O CH2 CH Br bromo ethene + Na NH2 - NaBr - NH3 HC CH ethyne

Write a note on Physical properties[2 mark] (i) The first three members of alkyne series are in gaseous form, then after upto C 8 are in liquid form and alkynes containing more than 8 carbons are obtained in solid form. (ii) All alkyne compounds are colourless. The smell of ethyne is specific. Except ethyne all alkynes are odourless. (iii) Alkynes are weak polar compounds. (iv) Alkynes are lighter than water, and are insoluble in polar solvents like water. They are soluble in non-polar organic solvents like ether, carbon, tetrachloride, benzene. (v) With the increase in molecular mass of alkynes, melting point, boiling point, and density also increase. In the following Table 6.8 the melting points and boiling points of some alkyne compounds Write a note on chemical properties (Chemical Reactions) of Alkynes: Explain acidic properties of Alkynes. [ 2 mark] Only ethyne possesses acidic properties. Ethyne is a weak acid, it reacts with strong base like sodium or sodamide to give mono sodium ethanide ( sodium acetylide)
HC CH ethyne + Na+ HC C Na+ mono sodium ethanide + 1/2 H2

HC CH + NaNH2 ethyne

HC C Na+ + sodium acetylide

NH3

If the alkyl does not have terminal hydrogen, it will not possess acidic property e.g. 2-butyne is not acidic. Terminal alkynes are showing acidic character because compare to sp 3 and sp2 hybridized carbon sp hybridized carbon has highest electro negativity. Explain Addition Reaction (Electrophilic addition reaction with dihydrogen) [2 mark] Alkyne on heating with dihydrogen reacts in presence of catalysts like Pt, Pd or Ni and gives alkene by addition reaction, which further on reacting with more hydrogen gives alkane by addition reaction. This realtion is known as hydrogenation reaction.
Pt / Pd HC CH ethyne + H2 CH2 CH2 ethene Pt / Pd + H2 CH3 CH3 ethane

[Ni] HC CH ethyne + H2 pressure CH2 CH2 ethene

[Ni]

+ H2

pressure

CH3 CH3 ethane

Reaction of alkyne with dihalogen: When alkyne reacts with dihalogen the -bond breaks and alkene dihalide is formed. Further reacting with more dihalogen, this gives tetra halide alkane by addition reaction. This reaction is known as halogenation reaction. Explain Addition Reaction With hydrogenhalide ': [2 mark] By addition reaction of alkyne with hydrogen halides like HCI, HBr, HI, it gives alkene halide. On reacting with more hydrogen halide, this gives dihalide of alkane. This reaction is known as hydrohalogenation reaction.
10

CHAPTER -6 HYDROCARBON
Pt / Pd HC CH ethyne + HBr CH2 CHBr bromo ethene HBr CH3 CH Br

Br 1,1 di bromo ethane

Explain Addition Reaction With water : [2 mark] Alkyne does not react with water at normal temperature, but in presence of mercuric sulphate and dilute sulphuric acid at 333 K temperature it gives carbonyl compounds.
HC CH ethyne + H2O H2SO4 dil HgSO4 333K CH2 CH rearrangement CH3 C O ethanal H

OH ethen-1-ol

Explain Polymerizations reaction of alkyne : [3 mark] The reaction of ethyne with HCl and HCN gives vinyl chloride and vinyl cyanide (acrylonitrile) respectively. Large number molecules of vinyl chloride join with each other by chemical bond forming large molecule of polyvinyl chloride polymer. This reaction is known as polymerisation.
n CH2 CHC l polymerization CH2 CH Cl PVC n

HC CH ethyne

HCl

HgCl2

CH2 CHCl vinyl chloride

In the same way polyacrylonitrile is obtained from vinyl cyanide.

n CH2
HC CH ethyne + HCN CH2 CHCN vinyl cynide

CHCN

polymerization

CH2

CH CN PAN n

Describe general properties of aromatic Hydrocarbons[2 mark] Aromatic hydrocarbons are also known as arene compounds. Most of these compounds possess characteristic fragrance (aroma) due to which they are known as aromatic compounds, for example, the components of organic compounds present in bitter almond, clove, bishop's seed etc, have specific smell (aroma) in the essential oils alvailable from them and so they are called aromatic compounds. Organic compounds containing carbon and hydrogen showing aromatic characteristics are called Aromatic Hydrocarbons. "the first member of aromatic hydrocarbon is benzene, other members of aromatic hydrocarbon forming homologous series have general formula CnH2n-6m where m = number of rings in cyclic structure. Cyclic hydrocarbons containing benzene ring are known as benzenoids and when cyclic hydrocarbons do not contain benzene ring they are known as non-benzenoids. Some examples of aromatic hydrocarbons are given below .
CH3

benzene

toluene

bi phenyl

naphthalene

anthracene

phenanthrene

napthacene

Explain Nomenclature and Isomerism in aromatic hydrocarbon [4 mark] Benzene contains 6 carbon and 6 hydrogen atoms which are identical and thus does not have isomers. When any carbon of benzene substitutes its hydrogen it gives monosubstituted benzene it also does not have any isomer. In the IUPAC nomenclature of monosubstituted benzene, the displaced group is indicated, and then word benzene is expressed. e.g

11

CHAPTER -6 HYDROCARBON
Cl
NO2

CH3

CH2CH3

When two hydrogens of two carbons in benzene are substituted, then the obtained disubstituted benzenes have three isomers.e.g. ortho, meta and para. If the substituted groups on carbon in benzene are on 1-2 position, 1-3 position and 1-4 position, then their nomenclatures are indicated by the prefixes ortho(o), meta (m) and para (p) respectively. e.g.
CH3
CH3 CH3

CH3

CH3

CH3

For the nomenclature of benzene, with the substitution of more than two positions, the reactivity of substituted groups on carbon are taken into consideration and numbering of carbon in benzene is done as 1,2,3 ... The remaining groups are indicated by considering the alphabetical order.
CH3 O2N NO2

1,2 di methyl benzene

1,3 di methyl benzene

1,4 di methyl benzene

2,4,6 tri nitro toluene Sources of Aromatic Hydrocarbons [ 2 mark] The scientist Michael Faraday for the first-time obtained benzene from illuminating gases, in 1825. In 1845, the scientist August Hofmann obtained benzene from coal tar. Destructive distillation of coal gives coal gas, coaltar and coke. Coaltar has large amount of aromatic hydrocarbons. Destructive distillation of coaltar gives toluene, xylene, naphthalene etc. Whereas the alkanes obtained as a result of fractional distillation of petroleum, when heated in presence of catalyst at higher pressure benzene, xylene, toluene can be obtained.
NO2

Explain structure of benzene based on chemical properties[ 4 mark] From the qualitative and quantitative analysis of benzene, ratio of carbon and hydrogen atoms is found to be 1:1. Thus, the empirical formula is found to be CH and empirical formula weight = 13. Molecular mass of benzene is 78 g/mol, hence, the molecular formula of benzene is confirmed as C 6H6. Structure of benzene is proved by the following chemical reactions : (i) On reacting one mole of benzene with three moles of dihydrogen at high temperature and pressure in presence of Ni catalyst, cyclohexane is obtaine
CH
2

C6H6

+ 3H2

Ni

HC
2

CH

catalyst high temperature

HC
2

CH CH
2

(ii)

In reaction with one mole of benzene with three moles of chlorine in presence of ultraviolet light, hexachloro cyclohexane is obtained. hv C6H6Cl6 CH + 3Cl
6 6 2

ultra violate light

hexa chloro cyclo hexane

(iii)

On reacting one mole of benzene with three moles of ozone, unstable benzene triozonide is obtained. On hydrolysis in presence of zinc it gives three moles of glyoxal. {this reaction indicates the alternate positions of C-C and C=C in benzene ring
C6H6 + 3O 3

benzene tri ozonide

12

C6H6(O3)3

hydrolysis Zn + 3 H2O

CHO

CHO glyoxal

+ 3H O 2 2

CHAPTER -6 HYDROCARBON From the above reactions (i), (ii) and (iii), it can be proved that benzene contains hexagonal cyclic structure and in the ring three single bond between C - C and three double bond between C = C are present. In 1865, scientist August Kekule suggested the following structure of benzene
H C H C C H C H C H

C H

According to Kekule's proposed benzene structure, the following reactions show that it has two structures : On reacting one mole of benzene with one mole of bromine in presence of FeBr 3 catalyst, one isomer bromobenzene is obtained by substitution reaction. As the rate of the reaction is slow, higher temperature is necessary.
bromo benzene From the above reaction, it can be proved that 6 carbons and 6 hydrogens of benzene are equivalent in position and in reactivity. {Give reason for 2 mark} On second substitution of benzene with bromine in presence of FeBr3 catalyst, a mixture of o and p-isomers of dibromobenzene in different proportions are obtained.
6 5 bromo benzene

C6H6

+ Br 2

[FeBr3]

C6H5Br +

HBr

C H Br

Br

[FeBr3]
2

C H Br
6 4

di bromo benzene From the above reaction it can be said that during second substitution 6 carbon atoms of benzene are not equivalent. From this result, Kekule gave following structures of benzene in which three double bonds are arranged alternately and these bonds continuously and very rapidly interconvert so that they resonate between structure (I) and (II)

HBr

(I)

(II)

Limitations of Kekules structure The structures proposed by Kekule do not resemble with the chemical properties. Though three double bonds are present in benzene, but it gives substitution reaction like saturated alkane. In normal conditions, like alkenes benzene dose not react with bromine water and cold KMnO 4 to give addition reaction. [Ethene decolourise both these reagents solution but benzene does not] Ethene gives polymerization but it does not occur in benzene. Hence, it can be said that although benzene contains three double bonds, it possesses stability. Stability and Resonance structure of benzene: On the basis of the chemical properties and stability of benzene, Kelkule gave two resonating structures A and B for benzene. So that the intermediate position, structure C is represented. Position of alternate double bond is different.

Structure of Benzene based on the physical properties : Structure of benzene based on lewis dot structure: [2 mark] After 70 years Lewis in 1937 represented Kekule structure of benzene which was based on the information obtained about covalent bonding of organic compound and the electronic configuration of their atom. This can be shown in Fig

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.. C. . . C . . ..C. .. . . ... C C. .. .... C ..

H H

CHAPTER -6 HYDROCARBON
H H H

.. . C . . . C . . .C . . . . .. .. C C. .... C .. ..
H

This structure also indicates the resonance between two different structure of benzene with different position of double bonds. Explain Structure of benzene based on hybridization concept [2 mark] Benzene has 6 carbon atoms containing sp2 hybridization. Any of its a-bond between C C and C - H remain in one single plane. Bond angle between C - C - C and C - C - H is 120. Moreover each C atom in benzene has Pz orbital which is perpendicular to the plane of molecule which is represented in Fig.

Those Pz orbitals do not take part in hybridizationremain perpendicular from the main axis and form -bond by sharing electrons. As a result structure of benzene is obtained in which alternate double bond is present. This supports the two structures (A) and (B) of benzene proposed by Kekule.

By the X-ray analysis of benzene, it was found that each C - C bond length is 139 pm. The bond length of - C - C - single bond in alkane is 154 pm and bond length of - C = C double bond in alkene is 133 pm. Bond length 139 pm shows intermediate value. This phenomenon represents the resonance between structures A and B of benzene that means very rapid and continuous inter conversion between these two structures. Based upon the resonance, it can be said that the structure of benzene should be between A and B. Structure of benzene based on resonance energy [3 mark] Explain In spite of three double bonds in benzene, it is much less reactive than ethene hence it does not give addition reaction but gives substitution reactions. [3 mark] Proof regarding resonating structures of benzene can be by value of heat of hydrogenation. Cyclohexene, containing one double bond has hydrogenation enthalphy 119.66 k Jmol1. Therefore, benzene having three double bond should have hydrogenation enthalpy of 119.66 x 3 = 358.9 k J mol1. But the experimental hydrogenation enthalpy of benzene is 208.36 k Jmol1. Thus, benzene has 358.9 - 208.36 = 150.63 k Jmol1 enthalpy less. The amount of heat of hydrogenation is less by 150.63 k J1. This value is known as resonance energy of benzene. This resonance energy indicates its stability and also less chemical reactivity. This is known as aromaticity or aromatic character. The difference between the theoretical and experimental values of heat of hydrogenation is known as resonance energy. Due to the resonance energy, its resonance structure contains less molecular energy, this indicates its excessive stability and also less chemical reactivity Aromatic character of benzene is based on the following facts :
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CHAPTER -6 HYDROCARBON (i) Resonance bond energy 150.63 k J mol1 of benzene (ii) sp2hybridization of carbon in benzene (iii) Continuous transformation of the three -bonds among 6 carbons in benzene. Kekule's represented structure (C) of benzene is known as aromatic or resonance structure. Its ring shape of molecular orbitals and charge clouds (electron clouds) are represented in the following figure

Describe aromatic Structure of benzene. (i) The aromatic structure of benzene is represented on the basis of the molecular orbital theory. (ii) This structure is accepted on the basis of information obtained from X-ray spectrum. (ill) Each carbon atom of benzene possesses sp2hybridisation. (iv) In benzene 6 carbon atoms, 6 hydrogen atoms, 6 (C-C) Carbon-Carbon, s-bond and 6 (C-H) CarbonHydrogen s-bond lie in a same plane. (v) In benzene, 6 carbon atoms have perpendicular Pz orbitals. Each contains one 6 electron, which takes part in the formation of 3-bonds. (vi) The six Pz orbitals overlap with each other and form a huge rc-electron cloud above or below the molecular plane, in which 6 electrons revolve over the carbon atom. (vii) The nature of all the 6 carbon atoms inbenzene is the same. (viii) Bond lengths between all C - C bond in benzene are equal. (ix) Electron clouds of 6 electrons in benzene support the less potential energy or the presence of resonance energy in it. Huckels Law The scientist Huckel in year 1931 A. D. showed that when, the number of electrons in planar cyclic compounds equals (4n + 2) these compounds possess aromaticity. In planar cyclic aromatic compounds like benzene, naphthalene, anthracene etc. when we put n = 1 , 2, 3, the number of electrons in benzene, 6, naphthalene, 10, and anthracene, 14. As shown in the figure of structure of benzene , naphthalene and anthracene , it can be seem that the number of electrons are respectively 6, 10 and 14. This obeys Huckel's law. Hence, on the basis of Huckel's law, it can be said that cyclic compounds like benzene, naphthalene and anthracene are aromatic.

benzene n= 1

napthalene n= 2

anthracene n= 3

Write Characteristics of Aromatic Benzene: (i) At normal temperature, just like alkanes, benzene resists oxidation with KMnO 4 and addition reaction with H2, Cl2, Br2. (ii) Like alkane, benzene also gives electrophilic substitution reactions like nitration, sulphonation, chlorination, bromination, alkylation, acylation etc. under suitable but vigorous conditions. (ill) Just like alkenes, benzene also gives reaction with hydrogen (H2), chlorine (CI2) and ozone (O3) in suitable but vigorous reaction conditions. (iv) Benzene has much more stability than alkene compounds. (v) Like alkene, benzene does not undergo polyrnerisation. (vi) There is only one isomer of monosubstituted benzene but there are three isomers of disubstituted benzene. (vii) Aromatic or resonating structure is the modem structure of benzene. (viii) The C - C bond length is less than C - C bond length of alkane and more than that of C = C double bond in alkene. (ix) The electron clould of 6p electrons moves around in ring shape on both the sides of its plane.
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(x) Benzene obeys Huckel's rule.

CHAPTER -6 HYDROCARBON

Inductive Groups and Its Directive Effect The quality of 6 carbons of benzene is same hence the functional group entering the molecule attaches to any of the carbon and gives only one isomer. Once the functional group is introduced in benzene, mono substituted derivative has unequal carbons. When second time substitution reaction is carried out on mono substituted benzene, the second group enters and di substituted benzene derivative is obtained. But where the second group will join the mono substituted benzene depends on the characteristic of the functional group attached to the monosubstituted benzene. Thus the group already present in mono substituted benzene is the inductive group for the entering second group. In this way the first group directly affects where the second entering group will attach at which position in benzene. This directive effect is of two types: (i) Ortho-para directing effect (ii) meta directing effect Ortho-para directing effect If the functional group attached to phenyl ring in mono substituted benzene is amino (-NH2) hydroxyl (-OH), methyl (-CH3) halogen (-F, - CI, - Br, - I) etc. due to their effect the second entering functional group will attach to the ortho and/or para position. Usually, functional groups of this type tend to pass on electron towards the phenyl ring and hence they are known aselectron donating or +ve. [As they are passing electon pair towards benzene ring hence electron density increases at ortho and para positions.] Hence, these type of electron donating functional groups are known as ortho-para directing groups. In the presence of such directing functional groups the second substitution occurs at ortho and para position and therefore the disubstituted derivative will be a two component (ortho and para) mixture. Normally these groups are ring activating groups. Meta Directing Effect : If the functional group attached to the phenyl ring is nitro (-N02) aldehyde (-CHO), carboxyl (-COOH), nitrile (CN) etc. due to their effect, the second entering functional group will be attached to the meta position. Usually such type of functional groups is getting electrons from the phenyl ring towards themselves hence they are known as electron loving or - ve groups. [As they are attracting electron pair from benzene ring hence electron density increases at meta positions.] This type of electron attracting groups are known as meta directing) In this type of directing functional group the second substitution occurs at meta position and only one isomer is obtained for such disubstituted benzene. Explain nitration of bromo benzene gives o & p bromo nitro benzene while bromination of nitrobenzene gives m- bromo nitro benzene. (H.W.)

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