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Alkane: General Methods of Preparation: (1) by Catalytic Reduction of Alkenes and Alkynes
Alkane: General Methods of Preparation: (1) by Catalytic Reduction of Alkenes and Alkynes
Alkane
General methods of preparation :
(1) By catalytic reduction of alkenes and alkynes :
H , 25 C
R – C C – R 2
R – CH2 – CH2 – R
Ni, Pt or Pd
2 H , 25C
R – CH = CH – R
R – CH2 – CH2 – R
Ni, Pt or Pd
Hydrogenation Addition of H2 to unsaturated bond.
Hydrogenation is of two kinds
(a) Heterogeneous (b) Homogeneous
(a) Heterogeneous : It is two phase hydrogenation the catalyst is finely devided metal like Ni, Pt or Pd and
a solution of alkene.
(b) Homogeneous : It is one phase hydrogenation both catalyst and alkenes are in solution. In this
hydrogenation catalyst are organic complex of transition metal like Rh or Ir.
Hydrogenation is exothermic, quantitative and during the hydrogenation, total heat evolved to hydrogenate
one mole of unsaturated compound is called heat of hydrogenation. Heat of hydrogenation is the measurment
of stability of isomeric alkenes.
1
stability of alkene Heat of hydrogenat ion
Note : Hydrogenation of alkene or alkyne in presence of metal catalyst is syn addition
Pd Pd
(a) + H2
(b) + H2
CH3 COOH CH3 COOH
R X + 2e¯
(1 , 2)
S 2 R–R
N
NaX
(b) Free radical mechanism
Na
R–X + R +
R + R R – R
JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 343
Note : The alkyl halide should be 1° or 2°, with 3° R – X SN2 and free radical coupling is not possible due to
steric hinderence so in that case elimination or disproportionation is possible.
In the ionic mechanism alkyl sodium gives strong base as well as nucleophile which gives SN2
with R – X, ether should be dry otherwise if moisture is present than forms R – H instead of R – R with H2O.
Na
(a) CH3 – CH2 – Br CH3 – CH2 – CH2 – CH3
Na
(b) CH3 – Cl + CH3 – CH2 – Cl CH3 – CH3 + CH3 – CH2 – CH3 + CH3 – CH2 – CH2 – CH3
(ii) By reduction of alkyl halides :
(A) with metal-acid
RX R – H + HX
1
Reducing agent
Zn / HCl , Zn – Cu / H2O or Zn – Cu + CH3COOH
Zn – Cu / C2H5OH, Na – Hg / HCl, Al – Hg / H2O etc.
(B) With metal hydrides
(a) TPH (Ph3SnH) Triphenyltin hydride : It reduces 1°, 2° & 3° R – X
3Ph SnH
R–X R – H
1º / 2º / 3º
4 NaBH
(b) NaBH4 : R X R – H
2 & 3
4 LiAlH 4 LiAlH
(c) LiAlH4 : R X R–H ; R X Alkene
1 & 2 3
all active
RMgX + H containg R – H
compound
H2O
R–H + Mg (OH) X
ROH
R–H + Mg (OR) X
RMgX NH3
R–H + Mg (NH2) X
R – C CH
R–H + Mg (C CR) X
RSH
R–H + Mg (SR) X
R – COOH
R–H + Mg (OCOR) X
R – R
Mechanism
R CO2K R CO2– + K+
At Anode: - R CO2– R CO 2 + e– (oxidation)
(I)
R CO 2 R + CO2
(II)
R + R R – R
If n is the number of carbon atoms in the salt of carboxylic acid, the alkane formed has 2(n–1) carbon atoms.
Electrolysis
e.g. 2CH3 – COOK + 2H2O
CH3CH3 + 2CO2 + H2 + 2KOH.
(5) By Reduction :
(i) By Clemmensen’s reduction (Zn – Hg / conc. HCl):
Zn Hg / conc . HCl
R – CHO RCH3 + H2O
O
||
Zn Hg / conc . HCl
R C R RCH2R + H2O
Zn Hg / conc . HCl
e.g. CH3 – CHO
CH3CH3 + H2O
O
||
Zn Hg / conc . HCl
CH3 C C 2H5 + 4[H] CH3CH2C2H5 + H2O
Clemmensen reduction is not used for compounds which have acid sensitive group.
Wolff-kishner reduction is not used for compounds which have base sensitive groups.
Zn Hg / conc . HCl
eg.
Among the isomeric alkanes, the branched chain isomers have relatively low boiling points as compared to
their corresponding straight chain isomers. Greater the branching of the chain, lower is the boiling point. This
is due to the fact that branching of the chain makes the molecule more compact and brings it close to a
sphere, so the magnitude of vander wall forces decreases.
Melting Point :
It is evident that the increase in melting point is
relatively more in moving from an alkane having odd
number of carbon atoms to the higher alkane with
even no. of ‘C’ while it is relatively less in moving
from an alkane with even number of carbon atoms
to the higher alkane.
• •
(iii) C H3 + X2 CH3X + X – 70 – 26 – 24 – 20
Reactivity of X2 : F2 > Cl2 > Br2 > I2
Reactivity of H : 3°H > 2°H > 1° H
With F2 alkanes react so vigorously that even in the dark and at room temperature, reactant is diluted with an
Inert gas. Iodination is reversible reaction, since HI formed as a by product and It is a strong reducing agent
and reduces alkyl iodide back to alkane. Hence iodination can be done only in presence of strong oxidising
agent like HIO3, HNO3 or HgO.
R – H + I2 R – I + HI
When equimolar amount of methane and Cl2 is taken, a mixture of four possible products are formed, but
when we take excess of CH4 then yield of CH3Cl will be high.
Each photon of light cleaves one chlorine molecule to form two chlorine radicals, each chlorine atom starts
a chain and on an average each chain contains 5000 repeatitions of the chain propagating cycle so about
10,000 molecules of CH3Cl are formed by one photon of light.
In a chain reaction following reagents are involved -
(i) Initiators they initiate the chain reaction, Initiators are peroxide (R2O2), Perester's etc.
•
h
R – O – O – R
R O
or
•
h
R C O O C R R C O
|| || or ||
O
O O
(ii) Inhibitors A substance that slows down or stops the reaction is known as inhibitors
For example O2 is a good inhibitor
• • •
R + O2 R O O + R R – O – O – R
all reactive alkyl free radicals are consumed so reaction stops for a period of time.
Relative reactivity of halogen towards methane
Order of reactivity is F2 > Cl2 > Br2 > I2 which can be explained by the value of H (enthalpy change)
2 Cl
(b) CH3 – CH2 – CH2 – CH3 CH3 CH2 CH CH3 + CH3 CH2 CH2 CH2 Cl
light , 25C |
Cl 28%
72%
CH3
Cl2 |
(c) CH3 CH CH3 CH3 CH CH2 Cl + CH3 C CH3
light , 25C
| | |
CH3 CH3 Cl
64% 36%
Br 2
(d) CH3 – CH2 – CH3 CH3 CH2 CH2 Br + CH3 CH CH3
heat, 127C
|
3% Br
97%
Relative amounts of the various isomers differ remarkably depending upon the halogen used. From the above
reaction, it is observed that chlorination gives mixture in which no isomer greatly dominates while, in bromination
gives a mixture in which one isomer dominates greatly (97% – 99%),
Factors affecting the relative yields :
Factors determining the relative yields of the isomeric products.
(i) Probability factor : This factor is based on the number of each kind of H atom in the molecule.
(ii) Reactivity of hydrogen : The order of reactivity is 3° > 2° > 1° the relative rate per hydrogen atom is
found to be
e.g.
6 15.2
% yield A = × 100 = 28.3 % ; % yield B = × 100 = 71.%
21.2 21.2
Sulphonation :
Lower alkanes are not easily sulphonated but hexane & higher members are sulphonated on heating with
oleum (conc. H2SO4 + SO3) at 400°C
400C
C6H14 + H2SO4 C6H13SO3H + H2O
Isomerisation :
Anhyd . AlCl / HCl
3
CH3CH2CH2CH3
CH3 CH CH3
300C
|
CH3
Isobu tan e
CH3
|
AlCl3 / HCl
CH3 – (CH2)3 – CH3 300
CH3 C CH3
C
|
CH3
Neopentane
CH3 CH3
| |
CH3 C H + H C C CH conc. H SO4
2 3 2 CH3 C CH2 CH CH3
| | | |
CH3 CH CH3 CH3
3
Isobu tane Isooc tan e
Isobutene
Aromatisation :
Alkanes containing 6 or more number of C atoms are oxidised (dehydrogenate & cyclised) in presence of
oxidising agent at higher temparature and form benzene or its derivatives.
Cr O Al O
CH3 – (CH2)4 – CH3 23
2 3
+ 4H2
600C
High P
Cr O Al O
CH3 – (CH2)5 – CH3 23
2 3
600C
High P
Cr O Al O
CH3(CH2)6CH3 23
2 3
+
600C
High P
CH3
| Cr O Al O
CH3 (CH 2 ) 4 CH CH3 23
2 3
600C
High P
CH3
| Cr O Al O
CH3 (CH 2 )3 CH CH2 CH3 23
2 3
600C
High P
Pyrolysis / Cracking :
CH3 – CH2 – CH3 CH3CH3 + CH3CH = CH2 + CH2 = CH2+ CH4 + H2
Higher alkanes are heated in absence of air so these compounds break down into smaller alkanes which are
better fuel. Mixture of products contains all lower alkanes, alkenes & hydrogens.
Combustion :
3n 1 combustion
CnH2n+2 + O nCO2 + (n + 1) H2O (Hcombustion = -ve)
2 2
exothermic reaction
y combustion y
CxHy + x O2 xCO2 + HO
4 2 2
combustion
C5H12 + 8O2 5CO2 + 6H2O
CH3
|
e.g. CH3 – CH2 – CH2 – CH3 CH3 C CH3
|
I H
II
Hcomb. : I > II
Stability : II > I
Points to remember for H of combustion :
Homologes : Higher homologes have higher heat of combustion.
CH4 < C2H6 < C3H8
Isomers : Branched isomer has lower heat of combustion.More branched alkane has more no. of primary
C – H bonds. (therefore it has more bond energy).
> >
Cyclo-alkanes : More strained ring has higher heat of combustion per – CH2 – unit.
Octane Number :
It is a scale of fuel efficiency when the fuel burns during combustion, more branched alkanes have lower
knocking (cracking sound). so are better fuels. On commercial scale iso-octane has been alotted a rating
i.e. octane no. of Isooctane is 100 & n-heptane is - ‘0’
If the octane no. of a fuel is 80, it means that the efficiency of the fuel is equivalent to the efficiency of mixture
of 80% isoctane and 20% n-heptane.
1.
Sol. R2C=CR2 > R2C = CHR >R2C = CH2 > R CH CH R > RCH CHR > R – CH = CH2 > CH2 = CH2
trans cis
CH3
|
CH3 CH CH CH2 , CH2 C CH2 CH3 , CH3 C CH CH3
| |
CH3 II CH3
I III
Ans. III > II > I
Sol. Stability of alkene Hyperconjugative Structure.
Na
4. C2H5Cl products
Ether
Write all possible product
disproportion
CH3 – CH3 + CH2 = CH2
Li CuI Y
6. CH3 – Br A B C
if C is CH3 – CH2 – (CH2)5 – CH3, than what is Y.
Ans. CH3 – (CH2)6 – Br
Li CuI
CH3 – (CH2 )5 – CH2 – X
Sol. CH3 – Br CH3Li (CH3)2CuLi CH3 – CH2 – (CH2)5 – CH3
NaOH
7. A B
CaO /
Sol. A is , B is