chemistry

hYDROCARBONS
Sakshi Vora

IIT - Roorkee

10th, 12th CBSE State Topper

7+ Years of Teaching Experience

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SAKSHI SAKSHI
[Adv. 2020 ]
[Adv. 2020 ]
HYDROCARBONS
Hydrocarbon
Compounds containing carbon and hydrogen only
 Are these compounds hydrocarbon?

C3H4D2

C3H4Cl2

O
||
C

H3C CH3
 Alkanes

(i) The alkanes or the paraffins are the saturated hydrocarbons.

(ii) These are also called as “Paraffins' (Parum + Affinis i.e. less reactive).
(iii) General formula is CnH2n+2·
(iv) Hybridisation state of carbon is sp3.
(vi) Bond angle is 109° 28.
Alkene

A. General formula : CnH2n.

B. The doubly bonded carbon atoms are sp2 hybridized.
C. Geometry of unsaturated 'C' carbon is trigonal planar.
D. C = C bond length is 1.34 Å.
E. C = C bond energy is 143.1 Kcal mol-1.
Alkynes

A. Alkynes are also called acetylenes because they are derivatives of

acetylene, the simplest alkyne.
A. Bond angle in alkyne is 180º.
B. Their general formula is Cn H2n-2.
C. C - C triple bond length is 1.20 Å.
Cycloalkane

CnH2n n ≥ 3
Preparation
of alkanes
 From ALKENES

By catalytic hydrogenation : Addition of H2 on alkene takes in

cis manner in the presence of Pt or Ni or Pd to give alkane.
Heterogeneous Catalysis

(i) Ravey Ni
(ii) Ni
(iii) Pt
(v) PtO2
(vi) Pd
(vii) Pd-C
(viii) Ru
(ix) Rh
Mechanism of Hydrogenation

1. Syn addition occurs

2. Hydrogenation is a surface phenomenon
3. Rate of hydrogenation is inversely proportional to steric crowding
Predict the total number of products of hydrogenation
Stereochemistry of addition reactions

Type of Addition PRODUCT PRODUCT

Alkene Unsymmetrical Symmetrical

Cis Syn (cis) Erythro Erythro

土 (Meso)

Trans Anti (Trans) Erythro Erythro

土 (Meso)

Cis Anti ( Trans) Threo Threo

土 土

Trans Syn (Cis) Threo Threo

土 土
PRACTICE
QUESTIONS
Predict the total number of products of hydrogenation
[Adv.
2015]
1 eq H2/Pd
 1, 4 addition reactions on alkenes

● 1, 4 addition takes place in conjugated dienes if diene is

present in s-cis form
● A 6 membered cyclic transition state is formed
● Always cis alkene will be formed
PRACTICE
QUESTIONS
Important
note
Note :

In conjugated dienes, 1,4 addition occurs if the double bonds are in s cis
form or if they can be converted to s cis form

If diene is not in s cis form, then simply 1,2 addition takes place at a less
crowded form
PRACTICE
QUESTIONS
PREDICT the product of hydrogenation
 From ALKYNES

Lindlar’s catalyst : Pd/ BaSO4 Quinoline

PRACTICE
QUESTIONS
 H2/Pd
R - CH = CH - R ?
BaSO4
Arrange the following in the order of rate of hydrogenation
Which of the following compounds produces an optically inactive
compound on hydrogenation ?

A.

B.

[Sep. 03, 2020 (I)]

C.

D.
Kolbe's Electrolysis :
Wherever sodium or potassium salt of a carboxylic acid
undergoes electrolysis, hydrocarbon is obtained as a product.

2 RCOONa + 2H2O electro R - R + 2CO2 + 2NaOH + H2

 Mechanism
Anode:

Cathode:
IMPORTANT
POINTS
Note

(i) CO2 gas is evolved at anode

(ii) H2 is evolved at cathode

(iii) As NaOH is produced, the pH increases

(iv) CH4 can not be obtained

PRACTICE
QUESTIONS
 Kolbe’s Electrolysis
COONa
 COONa
Kolbe’s Electrolysis

COONa
 Kolbe’s Electrolysis
COONa

COONa
COONa
kolbe’s

COONa
PRACTICE
QUESTIONS
Wurtz reaction
When alkyl halide reacts with sodium in presence of dry
ether then we get higher alkane.

dry
R - X + 2Na + X - R R-R
ether
Free Radical Mechanism
Ionic Mechanism
IMPORTANT
POINTS
 Important Points

1. Breaking of C-X bond is RDS

2. Used for preparation of alkanes with even number of carbon atoms
3. Preparation of alkanes with odd number of carbon atoms/ unsymmetrical
alkanes is tough.
4. Order of rate of reaction

C-I > C - Br > C - Cl

PRACTICE
QUESTIONS
Cl
Na

dry ether

Cl
Cl
Na

dry ether

Cl
Frankland Reaction
If alkyl halide is treated with Zn dust in closed tube then
higher symmetrical alkanes will be formed.

2RX + Zn R - R + ZnX2
 Reed’s Reaction
RH + SO2Cl2 ----------------> RCl + HCl + SO2
From Alkyl Halides
RX + Zn/HCl ----------------> RH
Soda Lime Decarboxylation

Whenever sodium salt of carboxylic acid is treated with soda lime,

it gets decarboxylated and corresponding hydrocarbon is formed
Mechanism
IMPORTANT
POINTS
Soda Lime Decarboxylation

● It is decarboxylation reaction
● Intermediate is CARBOANION
● Formation of carboanion is RDS
● Rate of reaction depends upon stability of carboanion
PRACTICE
QUESTIONS
Which will show faster decarboxylation
Which will show faster decarboxylation

o o o

COOH COOH
Which of the following reactions produce(s) propane as a major
product ?

A.

B.

[Adv .2019]
C.

D.
PHYSICAL
PROPERTIES OF
ALKANES
Physical Properties

1. Alkanes are non polar.

2. Boiling point depends on the extent of vanderwaal forces of
attraction which depends on surface area
3. Boiling point decreases on branching
Physical Properties

1. Alkanes are lighter than water, so it floats over water.

2. Physical state:

C1 - C4 Gaseous state
C5 - C17 Liquid state
(except neo pentane)
C18 & above Solid like wax
Physical Properties

Melting and boiling points increase with molecular mass and

decreases with branches
the alkane having even carbons have more M.P. than odd
carbons,
For e.g.
Isomers of hexane, based on their branching, can be divided into
three distinct classes as shown in the figure. The correct order of
their boiling points is

[Adv. 2014]

A. I > II > III

B. III > II > I
C. II > III > I
D. III > I > II
chemICAL
PROPERTIES OF
ALKANES
Combustion Reactions
At 300 K and 1 atmospheric pressure, 10 mL of a hydrocarbon
required 55 mL of O2 for complete combustion, and 40 mL of CO2
is formed. The formula of the hydrocarbon is :

A. C4H10

B. C4H6

C. C4H7Cl
[April 10, 2019 (I)]
D. C4H8
 NBS

NBS oxidises allylic/benzylic position by substituting Br

Practice
questions
[2016]
Halogenation
Alkanes react with bromine or chlorine in the presence of
sunlight or UV light or in dark at high temperatures
(250°C - 400°C) forming a mixture of substituted products.
For example,
Mechanism of Halogenation :
Important
points
Important points
❖ Free radical intermediate is formed
❖ It is a substitution and an oxidation reaction
❖ RDS is the formation of free radical
❖ Rate of reaction for alkanes:
Tertiary > secondary > primary
❖ Rate of reaction for halogens:
F2 >> Cl2 >Br2 >I2
Practice
questions
On monochlorination of 2 - methylbutane, the total number of
chiral compounds formed is

A. 2
B. 4
C. 6
D. 8

[2004 S]
The major product obtained in the photo catalysed bromination
of 2 - methylbutane is:

A. 1-bromo-2-methylbutane
B. 1-bromo-3-methylbutane
C. 2-bromo-3-methylbutane
D. 2-bromo-2-methylbutane
The total number of stereoisomers that can exist for M is

[Adv .2015]
 fractional distillation M (isomeric products)

Identify N and M

[2006 - 5M, -1]

A. 6, 4
B. 6, 6
C. 4, 4
D. 3, 3
Important
notes
Direct fluorination is explosive and can be achieved by the action of
inorganic fluorides on bromo or iodo derivatives.

2C2H5Br + HgF2 → 2C2H5F + HgBr2

Chlorination is highly reactive and less selective
Bromination is less reactive but more selective

Relative Reactivity of Chlorination towards tertiary, secondary and

primary:

1: 3.8 : 4.5

Relative Reactivity of Bromination towards tertiary, secondary and

primary:

1 : 80 : 1600
lodination is reversible and can be carried out sufficiently in the
presence of strong oxidising agents like iodic acid (HIO3) or nitric
acid that destroys hydroiodic acid (HI) and shifts the equilibrium
towards the right.

CH4 + I2 ⟶ CH3 I + HI
5 HI + HIO3 ⟶ 3I2 + 3H2O
Preparation
of alkenes
From Alkynes :

Poison of catalyst such as BaSO4, CaCO3 are used to stop the reaction
after the formation of alkene, otherwise alkanes are formed.
(i) The reaction takes place at the surface of Pd, that is why it is cis
addition and the product is cis from eg.
 From ALKYNES

BIRCH REDUCTION: Na/Liq ammonia

1. Birch reduction can not reduce ALKENES

2. Na/liq ammonia shows acid base reaction with terminal alkynes.
3. Birch reduction gives trans alkenes exclusively.
From ALKYNES
Mechanism of Birch
Reduction
[April 15, 2018 (II)]
[Main 2018]
[April 11, 2014 ]
Electrophilic
addition on
alkenes
Electrophilic Addition
Arrange the following in the order of electrophilic attack
Electrophilic Addition

1. Check the nucleophilicity of alkene

2. If nucleophilicity is same, check the stability of carbocation
3. If the stability of carbocation is same, check the stability of
alkene
4. More stable the alkene, less reactive it will be.
Practice
questions
Arrange the following in the order of electrophilic attack
Types of Electrophilic Addition
Types of Electrophilic Addition
Hydrohalogenation Reaction
[Adv. 2017]
Markovnikov Addition

The negative part of attacking species goes to that carbon which

has less number of hydrogens attached to it.
Practice
questions
Find the major product of the following reaction
Hydration of alkenes
Practice
questions
The major product of the following reaction is :

[Sep. 06, 2020 (I)]

Which of the following has the shortest C - Cl bond ?

A. Cl - CH = CH2
B. Cl - CH = CH - NO2
C. Cl - CH = CH - CH3
D. Cl - CH = CH - OCH3
[Jan. 09, 2020 (II)]
[April 10, 2016]
[Adv.
2015]
The major product formed in the following reaction is :

A. CH3CH(Br)CH2CH(CH3)2
B. CH3CH2CH(Br)CH(CH3)2
C. Br(CH2)3CH(CH3)2
D. CH3CH2CH2C(Br)(CH3)2 [Sep. 05, 2020 (II)]
[Main 2016]
Practice
questions
 Which of the following reactions will not produce a racemic
product ?

B.
A.

[Jan. 09, 2020 (II)]

C. D.
[Main 2018]
The major products of the following addition reaction is

A. B.
[Jan. 08, 2020 (I)]

C. D.
Anti Markovnikov Addition/ Peroxide effect/ Kharasch effect
Mechanism of Anti Markovnikov Addition
Important points

1. Intermediate: Free Radical

2. No rearrangement is possible
3. Out of all HX only HBr can show anti markovnikov effect
since its both propagation steps are exothermic
4. HCl and HI do not show anti markovnikov since in HI, the
first propagation step is endothermic and for HCl the second
step is endothermic
Find the major product of the following reaction
Find the major product of the following reaction
Practice
questions
The increasing order of the boiling point of the major products A,
B and C of the following reactions will be :

[Sep. 06, 2020 (II)]

A. B<C<A
B. C<A<B
C. A<B<C
D. A<C<B
The major products A and B in the following reactions are :

[Jan. 08, 2020 (I)]

A.

B.

C.

D.
[April. 08, 2019 (II)]
A. Six
B. Zero
C. Two
D. Four [Main 2017]
[April 9, 2013]
OXIDATION OF
ALKENES
Oxidation of alkenes
Bayer’s reagent for oxidation of alkenes
Oxidation of alkenes by peracid
Oxidation of alkenes by peracid
Practice
questions
But-ene on treatment with alkaline Potassium permanganate at
elevated temperature followed by acidification gives
A.

B. one molecule of CH3CHO and one molecule of CH3COOH

C. 2 molecules of CH3COOH

D. 2 molecules of CH3CHO
[April. 12, 2019 (I)]
Ozonolysis of alkenes
Ozonolysis of alkenes
Find the major product of the following reaction
[2012]
Electrophilic
addition on
alkynes
Find the major product of the following reaction
Hydration of alkynes/ Kuchrov’s Reaction
Mechanism of hydration of alkynes
Find the major product of the following reaction
[Sep. 06, 2020 (I)]
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Bratin Mondal Top Amaiya singhal
100 %ile 100 %ile
Results
 11th / 9, 10

12th / Drop

SAKSHI SAKSHI
SAKSHI