Alkanes
Alkanes
Alkanes
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INTRODUCTION
The term ‘hydrocarbon’ is self-explanatory which means compounds of carbon and hydrogen only.
Hydrocarbons play a key role in our daily life. You must be familiar with the terms ‘LPG’ and ‘CNG’ used as
fuels.
LPG is the abbreviated form of liquified petrolieum gas whereas CNG stands for compressed natural gas.
Another term ‘LNG’(liquified natural gas) is also in news these days. This is also a fuel and is obtained by
liquifaction of natural gas. Petrol, diesel and kerosene oil are obtained by the fractional distillation of petroleum
found under the earth’s crust. Coal gas is obtained by the destructive distillation of coal.
Natural gas is found in upper strata during drilling of oil wells. The gas after compression is known as compressed
natural gas. LPG is used as a domestic fuel with the least pollution. Kerosene oil is also used as a domestic
fuel but it causes some pollution.Automobiles need fuels like petrol, diesel and CNG. Petrol and CNG operated
automobiles cause less pollution. All these fuels contain mixture of hydrocarbons, which are sources of energy.
Hydrocarbons are also used for the manufacture of polymers like polythene, polypropene, polysterene etc.
Higher hydrocarbons are used as solvents for paints. They are also used as the starting materials for manufacture
of many dyes and drugs. Thus, you can well understand the importance of hydrocarbons in your daily life. In
this unit, you will learn more about hydrocarbons.
CLASSIFICATION
Hydrocarbons are of different types. Depending upon the type of carbon-carbon bonds present, they can be
classified into three main categories - (i) saturated (ii) unsaturated and (iii) aromatic hydrocarbons.
Saturated hydrocarbons contain carbon-carbon and carbon-hydrogen single bonds. If different carbon atoms
are joined together to form open chain of carbon atoms with single bonds, they are termed as alkanes.
On the other hand, if carbon atoms form a closed chain or a ring, they are termed as cycloalkanes. Unsaturated
hydrocarbons contain carbon-carbon multiple bonds - double bonds, triple bonds or both. Aromatic
hydrocarbons are a special type of cyclic compounds.
HYDROCARBON
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H-C-H bond angles are of 109.50. As per hybridasation and 109.281 as per V.B.T.
C
H H
In alkanes, tetrahedra are joined together in which C-C and C-H bond lengths are 154 pm and 112 pm
respectively. The C-C and C-H bonds are formed by head - on overlapping of sp 3 hybrid orbitals of
carbon and 1s orbitals of hydrogen atoms.
Occurrence ( Natural Sources)
Petroleum = presence of large quantities of liquid hydrocarbons
Natural gas = presence of mainly lower alkanes
= contains 80% CH4, 10% C2H6, 10% mixture of higher alkanes and traces of H2, N2, CO2
etc.
Bee’s wax (Myricyl palmitate) = also contains small quantities of C27H56 and C31H64
Fuel gas = Obtained from coal contains about 32 % CH4
General Methods of Preparation of Alkanes
1. Decarboxylation of carboxylic acids ( Laboratory preparation)
An alkane is prepared by heating strongly the anhydrous sodium or potassium salt of a carboxylic acid
contain C-atoms 1 more than the number of C-atom required with sodalime (NaOH + CaO).
R – COONa + NaOH R – H + Na2CO3
CaO
Ex. CH 3CH 2COONa + NaOH CH3CH3 + Na2CO3
Sodium propionate CaO Ethane
N.B. : (i) The alkane prepared contains one carbon atom less than that of the original acid.
(ii) CaO increases the porosity of the mixture and acts as a dehydrating agent and catalyst.
2. Sabatier-Senderen’s Reaction
Alkane may be obtained by the catalytic hydrogenation of alkenes or alkynes in presence of Ni catalyst at
200oC – 300o C.
Ni
R CH CH 2 H 2 R CH 2CH 3
Alkene Alkane
Ni/
Ex. (a) CH 3 CH CH 2 H 2 CH 3CH 2CH 3
Pr opene Pr opane
Ni /
(b) CH 3C CH 2 H 2 CH 3CH 2CH 3
Pr opyne Pr opane
N.B. : (i) Platinum or Palladium may also be used as catalyst at ordinary temperature.
(ii) Methane cannot be prepared by this method.
3. Sabatier Method :
Catalytic reaction of hydrogen with oxides of carbon ( like CO and CO2) in the presence of Nickel at
300o– 350oC, produces methane
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CO 3H 2
Ni
CH 4 H 2 O
Methane
CO2 4H 2
Ni
CH 4 2H 2 O
Methane
N.B.: Only for the preparation of methane, it is not used for preparation of higher alkanes like, Ethane,
Propane, Butane, etc...
4. By the Reduction of Alkyl Halides :
Alkyl halides are directly reduced by nascent hydrogen (H) to form alkanes. Nascent hydrogen is obtained
from any of the following reagents.
(a) Zn/Cu + (C2H5OH) (b) Al-Mg + C2H5OH
(c) Zn + HCl (d) Zn + Acetic acid (CH3COOH)
(e) LiAlH4 -ether ( except 30 R-X) (f) Red phosphorous and hydrogen iodide
(g) H2 + nickel or palladium or platinum (h) TPH (Triphenyltin hydride, Ph3SnH)
Zn Cu
RX 2H RH HX
Alkyl C 2 H 5OH (i) NaBH 4 ( except 10 R-X)
halide
5. Wurtz Reaction :
An etherial solution of alkyl halide when treated with sodium metal forms alkane.
R X 2Na X R
dry Ether
R-R 2NaX
N.B. :(i) Wurtz Reaction is useful only for the preparation of symmetrical alkanes containing even
number of carbon atoms.
(ii) When a mixture of two different alkyl halides are used a mixture of three alkanes are obtained.
Example : (a) CH3Cl 2Na ClC2 H5
Ether
CH3 C2 H5 2NaCl
Chlorormethane Chloroethane Propane
It is difficult to separate the three alkanes (C2H6, C3H8 and C4H10) from the mixture as they are in
gaseous state, their boiling points are very close to each other.
(iii) Methane cannot be prepared
(iv) This reaction fails when tertiary alkyl halides are used. 30 R-X Alkene
Mechanism
Two mechanisms have been proposed
I. Free-Radical Mechanism
Step 1 : Generation of free-Radical __ R NaBr
R Br + Na
Step 2 : Coupling between two free Radicals R R
R R
Side Reaction :
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. .CH
CH2 – CH2 – H +.CH2 – CH3 2 . 2
– CH CH2 = CH2 + CH3 – CH3
–
e
+ –
NaR + R – Br R – R + NaBr
6. Kolbe’s Electrolytic Method:
By the electrolysis of a concentrated aqueous solution of an alkali (Na or K) salt of a saturated monocarboxylic
acid using Pt electrodes alkanes can be prepared.
Alkanes with even number of carbons are obtained at anode.
2RCOONa + 2H 2 O R R 2 CO2 2 NaOH H 2
Mechanism
At Cathode :
1
H 2O e H 2 OH
2
Na OH NaOH
At Anode :
2e
2CH 3COO 2 CH 3CO O 2 e
2 CH 3CO O
2 C H 3 2 CO 2
. C 2 H 6 (Major)
2 C H 3
Bi Products:
CH 3COO CH 3 CH 3COOCH 3
CH3COO OOCCH3 CH3CO O O OCH3
It is free radical reaction.
N.B: Methane cannot be prepared by this method. In this method alkanes of even no. of carbon atoms
can be prepared.
Conformations:
Alkanes contain carbon-carbon sigma( ) bonds. Electron distribution of the sigma molecular orbital is
symmetrical around the internuclear axis of the C-C bond which is not disturbed due to rotation about its axis.
This permits free rotation about C-C single spatial arrangements of atoms in space which can change into one
another. Such spatial arrangements of atoms which can be converted into one another by rotation around a
C-C single bond are called conformations or conformers or rotamers. Alkanes can thus have infinite number
of conformations by rotation around C-C single bonds. However it may be remembered that rotation around
a C-C single bond is not completely free. It is hindered by a small energy barrier of 1-20 kJ mol 1 due to
weak repulsive interaction between the adjacent bonds. Such interaction between the adjacent bonds. Such
a type of repulsive interaction is called torsional strain.
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Conformation of ethane: Ethane molecule( C2 H 6 ) contains a carbon - carbon single bond with each carbon
atom attached to three hydrogen atoms. Considering the ball and stick model to ethane, keep one carbon
atom stationary and rotate the other carbon atom around the C-C axis. This rotation results into infinite
number of spatial arrangements of hydrogen atoms attached to other carbon atom. These are called
conformational isomers(conformers). Thus there are infinite number of conformations of ethane. However,
there are two extreme cases. One such conformation in which hydrogen atoms attached to two carbons are
as closed together as possible is called eclipsed conformation and the other in which hydrogens are as far
apart as possible is known as the staggered conformation. Any other intermediate conformation is called a
skew conformation. It may be remembered that in all the conformations, the bond angles and the bond lengths
remain the same. Eclipsed and the staggered conformations can be represented by Sawhorse and Newman
projections.
1. Sawhorse projections:
In this projection, the molecule is viewed along the molecular axis. It is then projected on paper by drawing
the central C-C bond as a somewhat longer straight line. Upper end of the line is slightly tilted towards right
or left hand side.The front carbon is shown at the lower end of the line, whereas the rear carbon is shown at
the upper end. Each carbon has three lines attached to it corresponding to three hydrogen atoms. The lines
are inclined at an angle of 1200 to each other. Sawhorse projections of eclipsed and staggered conformations
of ethane are depicted in Fig.
2. Newman projections:
In this projection, the molecule is viewed at the C-C bond head on. The carbon atom nearer to the eye is
represented by a point. Three hydrogen atoms attached to the front carbon atom are shown by three lines
drawn at an angle of 1200 to each other. The rear carbon atom ( the carbon atom away from the eye) is
represented by a circle and the three hydrogen atoms are shown attached to it by the shorter lines drawn at an
angle of 1200 to each other. The Newman’s projections are depicted in Fig.
Relative stability of conformations: As mentioned earlier, in staggered form of ethane, the electron clouds of
carbon-hydrogen bonds are as far apart as possible. Thus, there are minimum repulsive forces, minimum
energy and maximum stability of the molecule. On the other hand, when the staggered form changes into the
eclipsed form, the electron clouds of the carbon-hydrogen bonds come closer to each other resulting in
increase in electron cloud repulsions. To check the increased repulsive forces, molecule will have to possess
more energy and thus has lesser stability. As already mentioned, the repulsive interaction between the electron
clouds, which affects stability of a conformation, is called torsional strain. Magnitude of torsional strain depends
upon the angle of rotation about C-C bond. This angle is also called dihedral angle or torsional angle. Of all
the conformations of ethane, the staggered form has the least torsional strain and the eclipsed form, the
maximum torsional strain. Thus it may be inferred that rotation around C-C bond in ethane is not completely
free.
The energy difference between the two extreme forms is of the order of 12.5kJ 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 12.5kJ mol 1 through intermolecular collisions. Thus, it can be said that rotation about
carbon-carbon single bond in ethane is almost free for all practical purposes. It has not been possible to
separate and isolate different conformational isomers of ethane.
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Ethane Conformations
Potential Energy
12.6 kJ/mol
(3.0 kcal/mol)
0 60 120 180
0 Dihedral angle
HH H 60 HH H
120
H H H H
180
H H H H
H H H H H H H H
H H
Eclipsed Staggered Eclipsed Staggered
The torsional energy of ethane is lowest in the staggered conformation. The eclipsed confirmation is about 3.0
kcal/mol (12.5kj/mol) higher in energy. At room temperature. This barrier is easily overcome, and the molecules
rotate constatntly
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OH H
H H H H
H H H OH
OH OH
Staggered, anti Staggered, Gauch
In above forms gauche is more stable than staggered because of intramolecular hydrogen
bonding of gauche form.
A. PHYSICAL PROPERTIES :
First four members are gases, next 13 members are colourless liquids and rest are solids.
The alkanes are insoluble in water but soluble in organic solvents like ether, carbon tetrachloride, benzene
etc.
The density and boiling points increase with the increase of molecular weights. The boiling points of
isomeric branched chain alkanes, are generally lower than those of straight chain alkanes.
Boiling point(b.p.)of different alkanes are given in Table from which it is clear that there is a steady increase in
boiling point with increase in molecular mass. This is due to the fact that the intermolecular van der Waals
forces increase with increase of the molecular size or the surface area of the molecule.
You can make an interesting observation by having a look on the boiling points of three isomeric pentanes
viz.,(pentane, 2-methylbutane and 2,2-dimethylpropane). It is observed that pentane having a continuous
chain of five carbon atoms has the highest boiling point(309.1K) whereas 2,2-dimethylpropane boils at 282.5K.
With increase in number of branched chains, the molecule attains the shape of a sphere. This results in smaller
area of contact and therefore weak intermolecular forces between molecule attains the shape of a sphere.
This result in smaller area of contact and therefore weak intermolecular forces between spherical molecules,
which are overcome at relatively lower temperatures.
* Table : Variation of Melting Point and Boiling Point in Alkanes
M o le cu la r Nam e M o le cu la r b .p ./ (K ) m .p ./ (K )
fo rm u la m a ss/ u
CH4 M ethan e 16 11 1.0 9 0.5
C 2H 6 E tha n e 30 18 4.4 1 01 .0
C 3H 8 P ro p an e 44 23 0.9 8 5.3
C 4H 10 B utan e 58 27 2.4 1 34 .6
C 4H 10 2 -M eth ylp ro p an e 58 26 1.0 1 14 .7
C 5H 12 P en tan e 72 30 9.1 1 43 .3
C 5H 12 2 -M eth ylb u tan e 72 30 0.9 1 13 .1
C 5H 12 2 ,2-D im ethylp rop an e 72 28 2.5 2 56 .4
C 6H 14 H e xan e 86 34 1.9 1 78 .5
C 7H 16 H e p tan e 1 00 37 1.4 1 82 .4
C 8H 18 O cta n e 1 14 39 8.7 2 16 .2
C 9H 20 N o n an e 1 28 42 3.8 2 22 .0
C 10H 22 D eca n e 1 42 44 7.1 2 43 .3
B. CHEMICAL PROPERTIES
Alkanes are generally stable and chemically inert.
The C — H and C — C bonds in alkanes are almost non-polar, attacking reagents find no reaction sites to
which they could be attacked.
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CH 4 Cl2
hv
CH 3Cl HCl
CH 3Cl Cl2
hv
CH 2Cl2 HCl
CH 2Cl2 Cl2
hv
CHCl3 HCl
CHCl3 Cl2
hv
CCl4 HCl
CH 3 CH 3 Cl2
hv
CH 3 CH 2Cl HCl
It is found that the rate of reaction of alkanes with halogens is F2 > Cl2 > Br2 > I2. Rate of replacement of
hydrogens of alkanes is : 3° > 2° > 1°.
N.B.: Methyl Chloride is the major product if an excess of methane is used.
Halogenation is supposed to proceed via free radical chain mechanism involving three steps namely initiation,
propagation and termination as given below:
Mechanism
(i) Initiation : The reaction is initiated by homolysis of chlorine molecule in the presence of light or heat. The
Cl–Cl bond is weaker than the C–C and C–H bond and hence, is easiest to break.
Cl Cl hv
homolysis
C l Cl
Chlorine free radicals
(ii) Propagation : Chlorine free radical attacks the methane molecule and takes the reaction in the forward
direction by breaking the C-H bond to generate methyl free radical with the formation of H-Cl.
(a) CH 4 C l
hv
C H 3 H Cl
The methyl radical thus obtained attacks the second molecule of chlorine to form CH3 – Cl with the
liberation of another chlorine free radical by homolysis of chlorine molecule.
C H 3 Cl Cl
hv
CH 3 Cl C l
(b)
Chlorine free radical
The chlorine and methyl free radicals generated above repeat steps (a) and (b) respectively and thereby
setup a chain of reactions. The propagation steps (a) and (b) are those which directly give principal
products, but many other propagation steps are possible and may occur. Two such steps given below
explain how more highly halogenated products are formed.
CH 3Cl C l C H 2Cl HCl
C H 2Cl Cl Cl CH 2Cl2 C l
(iii)Termination: The reaction stops after some time due to consumption of reactants and / or due to the
following side reactions :
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The possible chain terminating steps are :
(a) C l C l Cl Cl
(b) H 3 C C H 3 H 3C CH 3
(c) H 3 C C l H 3C Cl
Though in (c), CH3 – Cl, the one of the products is formed but free radicals are consumed and the chain is
terminated. The above mechanism helps us to understand the reason for the formation of ethane as a
byproduct during chlorination of methane.
Bromination : Bromine reacts with alkanes in a similar manner but less vigorously.
Iodination : The reaction between iodine and alkane is reversible. Iodination can be done in the presence
of an oxidising agent such as HIO3 (or HNO3) which removes the hydroiodic acid (HI).
CH 4 I 2
CH 3 I HI
HIO3 5HI 3I 2 3H 2O
Fluorination : Fluorine reacts with alkanes at ordinary temperature explosively. So fluorination can be
done by diluting fluorine with an inert gas or indirectly.
2C 2 H 5 Br HgF2
2C 2 H 5 F HgBr2
2. Nitration : A mixture of an alkane and nitric acid vapours is heated at 400°C –500oC, one hydrogen atom
of the alkane is replaced by a nitro group. This reaction is also free radical substitution.
R H HO NO 2
R NO 2 H 2 O
Nitric Acid Nitroalkane
o o
C 500 C
CH 4 HNO3 400
CH 3 NO 2 H 2O
Vapour phase Nitration Nitromethane
N.B.:This temperature (400°C-500°C) is sufficient to break C–H as well as C–C bond homolytically and
thus mixture of products are obtained.
o o
C 500 C
CH 3CH 3 HONO2 400
CH 3CH 2 NO 2 CH 3 NO 2 H 2O
Nitroethan e Nitrometha ne
3n 1
N.B.: Cn H 2n 2 O 2
Flame
nCO 2 n 1 H 2 O Heat
2
2CH 3CH 3 7 O 2
4CO 2 6 H 2O 745 .6Kcal / mole
(ii) Incomplete Combustion :
2CH4 + 3O2 2CO + 4H2O
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CH 4 O 2
C 2H 2 O
Carbon black
Methanal
CH COO Mn
2CH 3CH 3 3O2
3
2
2CH 3COOH 2 H 2O
Ethanoic acid
Ordinarily alkanes resist oxidation but alkanes having tertiary H atom can be oxidized to corresponding
alcohols by potassium permanganate
CH 3 3 CH
KMnO
Oxidation
CH 3 3 COH
4
2-Methylpropane 2-Methylpropan-2-ol
5. Isomerisation : Normal alkanes are converted to their branched chain isomers in the presence of aluminium
chloride and HCl at 25oC.
Ex.
CH3
AlCl3
a) CH3 – CH2 – CH2 – CH3 HCl
CH3 – CH – CH3
n – Butane Isobutane
(2 – Mehtypropane)
b)
c) C12 H 26
Pt / Pd / Ni
973 K
C7 H16 C5 H10 Other products
Dodecane Heptane Pentene
N.B.: In the presence of finely divided silica-alumina as catalyst, this reaction can be carried at less high
temperature. This is called catalytic cracking.
7. Aromatisation : n-Alkanes having six or more carbon atoms on heating to 773K at 10-20 atmospheric
pressure in the 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.
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(ii) (CH 3 ) 2 C C2 H 5 2
(iii) tetra - tert - butylmethane
Solution
(i) 2,2,4,4 -Tetramethylpentane
(ii) 3, 3 - Dimethyl pentane
(iii) 3,3-Di-tert-butyl -2,2,4,4- tetra methylpentane.
If it is important to write the correct IUPAC name
for a given structure, it is equally important to write
the correct structures from the given IUPAC name.
To do this, first of all, the longest chain of carbon
atoms corresponding to the parent alkane is written.
Then after numbering it, the substituents are attached
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1) Enantiomers
31. C2 H 2 can not be formed in pyrolysis of Hexane.
2) Diastereomers
32. Byeproduct in the chlorination of methane is ethane 3) Structural isomers
4) Two molecules of the same compound
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21. How many chiral compounds are possible on of ‘A’ is (The relative reactivities of 10 , 20 ,30 -
monochlorination of 2-methyl butane
hydrogens are 1 : 3.8 : 5)
1) 8 2) 3 3) 4 4) 6
1) 36% 2) 64% 3) 72% 4) 28%
Na NaOH CaO
X
1 Y Z, CH3
22. H2 if Z is the first
2
homologue of alkane series, then X 28. X NaOH + CaO CH3 – C – CH3
1) Methanoic acid 2) Bromo ethane CH3
3) Ethyl alcohol 4) Ethanoic acid
23. The volume of CH4 at NTP is formed when X
Kolbe's electrolysis
y ‘y’ is
20.5 g of CH3COONa is treated with soda lime
1) CH3 CH3
1) 4.4 l 2) 2.2 l
3) 3.2 l 4) 5.6 l CH3 – C – CH2 – C – CH3
24. For the given reaction how many products will CH3 CH3
obtain (all isomers on monobromination)?
2) CH3 CH3
Br2/hv
Products CH – C – CH – CH – C – CH
3 2 2 3
1) 1 2) 6 CH3 CH3
3) 4 4) 3
25. Which of the following reactions has zero 3) CH3CH3 4) CH3
activation energy?
CH3 – C – C – CH3 CH3 – C – CH3
1) CH 4 Cl C H 3 HCl CH3CH3 CH3
2) Cl Cl
hv
2Cl 29. 2-Methylbutane on reacting with Br 2 in
presence of sunlight mainly gives:
3) CH 3 CH 3 CH 3 CH 3 1) 1-bromo-2-methylbutane
4) CH 3 Cl Cl CH 3 Cl Cl 2) 2-bromo-2-methylbutane
26. Which of the following can produce a racemic 3) 2-bromo-3-methylbutane
mixture on monobromination? 4) 1-bromo-3-methylbutane
30. Which of the following is not obtained when
propyl chloride and methyl chloride react with
1) 3) sodium in dry ether?
1) C2 H 6 2) C4 H10 3) C3 H 8 4) C6 H14
31. The volume of methane at N.T.P formed from
3) 4) CH3 CH3 8.2g of sodium acetate by fusion with soda
lime is
1) 10 l 2)11.2 l 3) 5.6 l 4) 2.24 l
CH3 CH3 – Br
27. 32. Reaction of ROH with R ' MgX produces
CH3 – C – CH3 + CH3 – CH – CH3 '
1) RH 2) R H 3) R-R 4) R ' R '
Br 33. In Wurtz reaction, n-hexane is obtained from
(A) (B) 1) n- propyl chloride 2) n-butyl chloride
CH3 3) Ethyl chloride 4) Isopropyl chloride
Br2
CH3 – CH – CH3 the percentage yeild
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16. Propane has two different types of hydrogen 39. (CH3 )2 CH - CH (CH3 )2
17. Unsaturated compounds can be hydrogenated 40. Corey-House synthesis
18. CH3OH , HCHO 41. CH 3I ¾ Mg
¾ ® CH 3 MgI ¾ EtOH
¾ ¾® CH 4
19. Complete oxidation gives CO2 , H2O one mole one mole one mole
0
400 475 C 0 42. Hydrolysis
20. Al4C3
Hydrolysis
CH 4 CH 3 NO2
HNO 3
43. Even number of carbon atom pack closely
21. It has two chiral carbons h
44. CH 4 Br
/ 2
CH 3 Br w
Na / dry ether
urtz reaction
CH 3 CH 3
CH 3COOH Na CH 3COONa
22. NaoH
CaO /
CH 4 Na2CO3 EXERCISE - II
1. The correct statement regarding the
23.
CH 3COONa NaOH
CaO comparison of staggered and eclipsed
conformations of ethane is:
CH 4 Na2 CO3 1) The staggered conformation of ethane is less
stable than eclipsed conformation, because
staggered conformation has torsional strain.
24. 6 isomers (including optical isomers) 2) The eclipsed conformation of ethane is more
25. Chain termination has zero activation energy. stable than staggered conformation, because
CH3 CH3H eclipsed conformation has no torsional strain.
Br2
3) The eclipsed conformation of ethane is more
26.CH3 – C – CH2 – CH3 CCl4
CH3 – C – C– CH3 stable than staggered conformation even though the
CH3 CH3Br eclipsed conformation has torsional strain.
4) The staggered conformation of ethane is more
1 5 stable than eclipsed conformation, because
27. % of A = 1 5 9 1 100 36%
staggered conformation has no torsional strain.
2. Arrange the following in decreasing order of
28. x = (CH3 )3 C - CH 2 - COONa their boiling points
29. Brominations is highly selective (A) n - butane (B) 2 - methylbutane
30. Crossed Wurtz reaction (C) n - pentane (D) 2 , 2-dimethylpropane
(E) Propane
31. 2CH 3COONa ¾ Electrolysis
¾ ¾ ¾ ® CH 3 - CH3
1) A B C D > E 2) B C D A > E
32. ROH + R 'MgX ® R 'H + Mg (OR ) X 3) D C B A > E 4) C B D A > E
33. 2C3H7 X ® C6 H14 3. Marsh gas is
34. I is good leaving group 1) CH 4 2) C2 H 6 3) C2 H 2 4) C2 H 4
35. Nitration occurs at high T 4. Less reactivity of alkanes is due to
36. Grignard reagent on decomposition with water or 1) Less bond energy 2) More bond energy
other compounds having active hydrogen give 3) Low activation energy 4) Less availabilities
alkane. 5. Which of the following reactions of methane is
37. Grignard reagent on decomposition with water or incomplete combustion
other compounds having active hydrogen give
1) 2CH 4 O2
Cu /523 K /100 atm
2CH 3OH
alkane.
38. CH3 - CH 2 - CH3 2) CH 4 O2
Mo2O3
HCHO H 2O
6 ´ 1 = 6,2 ´ 1 = 2 3) CH 4 O2 C s 2 H 2O l
100 ´ 6 / 8 = 75,100 ´ 2 / 8 = 25
4) CH 4 2O2 CO2 g 2 H 2O l
NARAYANAGROUP 141
HYDROCARBONS - 1 CHEMISTRY NEET -VOL-III
SR-MAIN-CHEM-VOL-II
6. Some oxidation reactions of methane are given 2) S-I & II are correct, S-II is not correct
below. Which of them is/are controlled explanation of S-I
oxidation reactions? 3) S-I is true but S-II is false
i) CH 4 g 2O2 g CO2 g 2 H 2O l 4) S-I is false but S-II is true
1. Statement-I(S-I) : Iodination of alkane is slow and
ii) CH 4 g O2 g C s 2 H 2O l reversible in nature.
Statement-II(S-II) : Iodination of alkane is
iii) CH 4 g O2 g
Mo2O3
HCHO H 2O performed in presence of strong oxidising agent like
HIO3which consumes the byproduct and recycles
iv) 2CH 4 g O2 g
Cu /523/100 atm
2CH 3OH
into reactants I2 .
1) iii and iv 2) i and ii 2. S-I: When n-butane is heated in presence of
3) ii and iv 4) i and iv
AlCl3 / HCl it will be converted to propane
7. Match the hydrocarbons in Column I with the
boiling points given in Column II. S-II: In presence of AlCl3 / HCl if any alkane
Column I Column II having four carbon is heated, it under goes
i) n–Pentane (a) 282.5 K isomerisation to give isomer of reactant alkane
ii) iso-Pentane (b) 309 K 3. S-I: Branched alkanes have lower boiling point than
iii) neo-Pentane (c) 301 K their unbranched isomers
1) i-b, ii-c, iii-a 2) i-a, ii-b, iii-c S-II: Branched chain alkanes have relatively small
3) i-c, ii-a, iii-b 4) i-a, ii-c,iii-b surface area , so less london forces operate in
8. The boiling points of four saturated molecules.
hydrocarbons are given below. Which boiling 4. S-I: Alkanes float on surface of water.
point suggests maximum number of carbon S-II: Density of alkanes is in the range of 0.6-0.9
atoms in its molecule? g/ml which is lower than water.
1) -1620C 2) -88.60C 5. S-I: Raney ‘Ni’ is used as catalyst in Sabatier-
3) -0.50C 4) -42.20C Senderen’s reaction.
KEY S-II: Due to large surface area Raney ‘Ni’ has high
1) 4 2) 4 3) 1 4) 2 catalytic activity.
5) 3 6) 1 7) 1 8) 3 6. S-I: CH3I and C2H5I with ‘Na’ in presence of dry
ether forms three types of alkanes.
HINTS & EXPLANATIONS
S-II: In wurtz reaction ‘Na’ is reducing agent.
1. Stability of conformation of ethane : staggered >
7. S-I: Chlorination in alkane is more reactive than
Eclipsed
selective.
2. B.P of alkane depends on mol.wt. and surface area
S-II: Bromination is more selective and less
3. CH 4 is known as marsh gas reactive.
4. Less reactivity of alkane is due to more bond energy 8. S-I: Methane is called Marsh gas.
5. Incomplete combustion of methane gives C, CO.... S-II: Methane is bubbled from marshy places.
6. Controlled oxidation of methane gives HCHO, 9. S-I: During free radical chlorination of butane, some
CH3OH ethane is also formed as by product.
7. B. P of n - pentane > isopentane > neo-pentane S-II: Disproportionation is a characteristic of a free
8. The heavier the molecule, greater is the boiling point. radical intermediate.
So molecule with boiling point -0.50C will have EXERCISE - III-KEY
maximum number of carbon atoms. 01) 2 02) 4 03) 1
EXERCISE - III 04) 1 05) 1 06) 2
Statement Type Questions 07) 2 08) 1 09) 4
1) S-I & II are correct, S-II is correct explanation
of S-I
142 NARAYANAGROUP