ALLEN
CHEMISTRY ALLEN Study Package For – JEE (Advanced)
JEE-Chemistry
HYDROCARBON ALKANE
Intro duct ion (i)
:
Branched and unbranched aliphatic saturated hydro carbons are called member of alkane. The structural formula of alkane have only single bonds or all bonds in alkane is only bonds.
(ii)
Alkanes does not reacts with chemical reagants such as dil. and conc. HCl, dil. & conc. H 2SO 4 , dil. & conc. HNO 3 , Caustic soda, acidic & basic K 2 Cr 2 O 7 , KMnO 4 etc. That is why alkanes are called paraffins. (Parum=little, affins = reactivity).
Prop er t y
Characteristics of
Prop er t y
Characteristics
alkane
of
alkane
General formula
C nH 2n+2
C—C Bond length
1.54 A°
C—C Bond energy
82.67 kcal/mole
C—H Bond length
1.112 A°
C—H Bond energy
98.67 kcal/mole
Hybridisation on C
sp 3
Bond angle
109°.28 '
shape
Tetrahedral
General Met ho ds of Preparat ions :
1.
From alkene s a nd alkyne s (Sabat ier a nd Sa ndrens react ion) or (By hy drogenat ion of alkene s
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and alkynes) : Alkenes and alkynes on catalytic hydrogenation gives alkanes. R—CH
CH—R + H 2
Catalyst R — C H 2— C H 2— R
Alkene R—C
Alkane Catalyst R — C H 2— C H 2— R
C—R + 2H 2 Alkyne
Catalyst
2.
:
(a)
Pd/Pt at ordinary temp. and pressure
(b)
Ni, 200–300° C (sabatier)
(c)
Raney Nicker at room temp.
(d)
Raney nickel is obtained by boiling Ni/Al with NaOH. Al dissolved & Ni obtained in finally divided state.
(e)
Methane can not be prepared by this method (From unsaturated hydrocarbon).
From alkyl Halide s (By reduct ion) : 2H
R—X Catalyst
(Nascent Hydrogen )
R—H + HX
:
(i) Zn + HCl
(ii) Zn + CH 3 COOH
(iv) Red P + HI
(v) Al + Hg + ethanol
Mechanism
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: Zn Zn +2 + 2e –
+
(iii) Zn—Cu couple in C 2 H 5 OH
2e R — X R+ X
–
–
R + H Cl R—H + Cl
Zn +2 + 2Cl ZnCl 2 .
Product
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JEE-Chemistry (a)
Alkyl halides can also be reduced to alkane by H 2 /Pd or LiAlH 4 or H 2 /Ni.
(b)
Reduction is due to the electron transfer from the metal to the substrate (R- X)
(c)
If any alkyl halide is asked, the H-atom of any carbon atom of given alkane is removed by halogen atom.
3.
From alkyl halide (By Wur tz react ion): A solution of alkyl halide in ether on heating with sodium gives alkane. R — X 2Na
(a)
Dry R— R
X— R
2NaX
ether
Two moles of alkyl halide treated with Na in presence of dry ether. If ether is wet then we obtain alcohol. 2Na +
H 2O
2NaOH + H 2
C H 3I +
NaOH
CH 3 OH + NaI
(b)
Methane can not be prepared by this method. The alkane produced is higher and symmetrical i.e. it contains double the number of carbon atoms present in the alkyl halide taken.
(c)
Two different alkyl halides, on wur tz raction give all possible alkanes.
(d)
The seperation of mixture in to individual members is not easy because their B.P. are near to each other and thus wurtz reaction is not suitable for the synthesis of alkanes containing odd number of carbon atom.
(e)
This reaction generally fails with tertiary alkyl halide.
Mecha nism : Two mechanism have been proposed for this react ion. (a)
Ionic
Mechanism:
2Na 2Na + 2e
2e R — X R+ X
R — X + R R — R + X–
2Na + 2X 2NaX
Product Example
: 2 C 2H 5— I
+
2 N a
C 2 H 5 —C 2 H 5 + 2NaI n–butane
(b)
Free radical mecha nism :
Na Na + e
.
e R — X R+ X
Na X NaX
R R R — R Product
Free radicals also undergo Disproportionation i.e. one radical gains hydrogen at the expense of the other which loss hydrogen. H .
.
.
.
CH2 — CH2 + C2H5 C2H6
+
Ethane
C2H4
Ethylene
This explains the presence of ethylene and ethane in the butane obtained by Wur tz reaction.
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Methanol
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JEE-Chemistry Ex.
If two moles of Isopropyl chloride reacts with Na in presence of dr y ether. Which alkane is obtained.
S o l . 2, 3-Dimethyl butane. Ex.
If isopropyl chloride and ethyl chloride both react with Na in presence of dry ether which alkanes are obtained.
S o l . n-Butane, 2-Methyl butane and 2, 3-Dimethyl butane. Ex.
Which of the following compound can not obtained from wurtz reaction. (A) ethane
(B) butane
(C) isobutane
(D) hexane
Sol.
(C) [Hint : In wurtz reaction unsymmetrical alkane can not be obtained.
Ex.
When ethyl chloride and n-propyl chloride undergoes wur tz reaction which is not obtained. (A) n–butane
(B) n–pentane
(C) n–hexane
(D) isobutane
S o l . (D) C 2 H 5 —Cl + C 3 H 7 Cl
Na C H —C H + C H —C H + C H —C H 2 5 2 5 3 7 3 7 2 5 3 7 dry ether
4.
:
Core y-House
Synt he sis
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This method is suitable for the preparation of unsymmetrical alkanes i.e. those of type R—R' (i)
RX + Li RLi + LiX
(ii)
2RLi + CuX R 2 CuLi + LiX
(iii)
R 2 CuLi + R ' X R—R' + RCu + LiX (1 or2 )
Note : In Corey-house reaction symmetrical and unsymmetrical alkane both can be formed. 5.
From Frankland Reagent:
If Zn is used in place of Na, the reaction is named as Frankland reaction.
R—X + 2Zn +RX R 2 Zn + ZnX 2 Frankland reagent R 2 Zn + R—X R—R + RZnX 6.
From Carboxylic Acid (By decarboxylation) : Saturated monocarboxylic acid salt of sodium or potassium on dry distillation with soda lime give alkane. RCOONa + NaOH R—H + Na 2 CO 3 Cao
Soda Lime (a)
The process of elimination of Carbon-di-oxide from Carboxylic acid called decarboxylation.
(b)
Replacement of -COOH by hydrogen is known as decarboxylation. The alkane formed always contains one carbon atom less than the original acid.
(c)
This reaction is employed for stepping down a homologous series.
(d)
Soda lime is prepared by soaking quick lime CaO with NaOH solution and then drying the products.
(e)
Decarboxylat ion of sodium formate gives H 2 HCOONa + NaOH (CaO) H 2 + Na 2 CO 3 CH 3 COONa + NaOH + CaO CH 4 + Na 2 CO 3
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JEE-Chemistry
Mecha nisim : Decarboxylation proceeds via. the formation of carbanion i ntermediate as follows.
OH
CH3 C O + OH(NaOH)
CH3
C
O
ONa
ONa OH CH3
O
C
CH3 + HO C O (NaHCO3)
ONa(Acidic)
ONa
CH O C 3 + H
ONa
CH3 H +O C ONa Product O
Na 2 C O 3
O
O Na + Na
O C O
(a)
If in a compound two carboxylic groups are present and they are attached to same carbon atom then also decarboxylation of one of the carboxylic groups takes place simply on heating.
Ex.
COOH COOH
CH 3 COOH + CO 2
(b)
CH 4 can be prepared by CH 3 COOH.
(c)
C 2 H 6 can be prepared by CH 3 CH 2 COOH.
(d)
CH 3 —CH 2 —CH 3 can be prepared by Butanoic acid and 2–Methyl propanoic acid.
How many acids can be taken to obtain isobutane from decarboxylation ? (A) 4
S o l . (C)
(B) 3
(C) 2
(D) 5
To obtain isobutane the acids are (i)
CH3 CH CH2 COOH CH3 CH CH2 H CH3
CH3
COOH (ii)
CH3
C
H
CH3 CH3
CH3
C
CH3
CH3
So two acids can be taken.
Reactivity of acid stability of carbanion Presence of electron attracting group (–I) in the hydrocarbon part of the fatty acid increases the decarboxylation. If – I is more effective group then weak base may be taken. Example
:
(i)
3 R CH CH2COOH
CH CH2 H
OH
OH
NaHCO
R
NaHCO
(ii)
R
3 CH CH2COOH R
CH CH2 H
NO2
NO2
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CH2
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JEE-Chemistry (iii)
-Keto acids are decarboxylated readily simply on heating (soda lime is not required)
R
Ex.
C CH2COOH R
C CH3
O
O
Give reactivity order for decarboxylation ? C H 3— C H 2— C O O H
CH2
CH—COOH
I
II
(A) I > II > III S o l . (B)
CH
C —COOH III
(B) III > II > I
(C) III > I > II
(D) None is correct
In decarboxylation intermediate s are,
CH 3 — CH 2
CH
CH 2
I
CH
II
C
III
The stability order of carbanion – III > II > I So reactivity order for acid is – III > II > I 7.
From carboxylic acid (By Kolbe's proce ss) : Alkanes are formed on electrolysis of concentrated aqueous solution of sodium or potassium salt of saturated monocarboxylic acids. Electrolysis — R 2CO 2NaOH H 2 2RCOONa + 2H 2 O R 2
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At Anode
At Cathode
Electrolysis of Sodium propionate solution give n-butane, ethylene, ethane and ethyl propionate as followselectro. 2C 2 H 5 — COONa C 2 H 5 — C 2 H 5 2CO 2 2NaOH H 2
Mechanism
:
—COO + N a
electro. C 2 H 5 —C OON a C 2H 5 H2O
(Ionization) – e
C 2 H 5 — COO C 2 H 5 —COO
At Anode :
C2H5
Fragmentation . C 2 H 5 + CO 2 C O
O
C 2 H 5 + C 2 H 5 C 2 H 5 —C 2 H 5 Product H
..
.
.
CH2 — CH2 + C2H5 CH 3 —CH 2 —H + CH 2
CH 2
(minor products) An ester is also formed.
C 2 H 5 — CO O + C H 5 C 2 H 5 —COOC 2 H 5 2 (minor products) At cathode :
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Na + e Na Na + H 2 O
NaOH +
1
2
H2
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JEE-Chemistry (a) (b)
Methane can not be prepared by this method. Electrolysis of an acid salt gives symmetrical alkane, However in case of a mixture of Carboxylic acid salts, all probable alkanes are formed. Electrolysis
R'COOK + R"COOK (R'—R" + R'—R' + R"—R") +2CO 2 + H 2 +2NaOH
8.
- position decrease the yield of alkanes.
(c)
Presence of alkyl groups in
(d) (e) (f) (g)
Tr ue aromatic acids do not undergo Kolbe's electroly tic reaction. Free radical mechanism has been suggested for Kolbe reaction. At anode alkane (major) and CO 2 gas is formed while at cathode NaOH and H 2 gas is formed. The concentration of NaOH in solution is increased with time so pH of solution is also increased.
From alka nol, alka nals, Alka none a nd alka noic acid (By reduct ion) : The reduction of either of the above in presence of red P and HI gives corresponding alkane. R—OH
+2HI
Re d P R—H+H 2 O+ I 2 150 C
R—CHO + 4HI
Re d P RCH 3 +H 2 O + 2I 2 150 C
R—CO—R+4HI
Re d P R—CH 2 —R+H 2 O + 2I 2 150 C
RCOOH + 6HI
Re d P R—CH 2 —R+H 2 O + 3I 2 150 C
R—CH 3 + I 2 2P + 3I 2 9.
From
alka none s
R—CH 2 —I + HI 2PI 3
(By
Clemmensen's
met ho d)
:
Carbonyl compound (Preferably ketones) may also be reduced with Zinc amalgam and concentrated HCl (Zn—Hg/HCl), this reaction is called Clemmensen reduction. R—CO—R'+4H
Zn / Hg R—CH —R'+H O 2 2 con. HCl
CH 4 , CH 3 —CH 3 , isobutane and neopentane are not obtained from Ketones because these alkane do not contain 10.
CH 2 group.
From alka nals a nd alka none s (By Wolf Kishner react ion) : C
O + NH 2 N H 2
C
Hydrazine
N.NH 2
Glycol / KOH
CH 2 + N 2
Hydrazone
From G.R. : (a) For mat ion of alka ne s w it h same number of C atoms : With same number of C-atoms as G.R. react with compound containing active hydrogen alkanes is obtained. R
Mg
X+ H
O
H R H + Mg (OH) X
+R
O
H R H + Mg (OR) X
+R
(b)
NH
H R H + Mg (NHR) X
This reaction is used to determine the number of active H-atoms in the compound this is known as Zerewitnoff's method. G.R. react w it h alkyl halide to give h igher alka ne s : RMgX + R'—X R—R' + MgX 2
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In the above reaction I 2 is formed which acts as reducing agent and may reduce alkane and form alkyl halide. So red P is added i n the react ion to remove I 2 formed in the react ion.
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JEE-Chemistry Ex.
Which of the following does not give alkane with R—Mg—X. (A) Ph—OH (B) Cl —NH 2 (C) CH 3 COOH (D) HCl S o l . (B) [Hint : Except Cl—NH 2 all have active hydrogen, but Cl—NH 2 when reacts with R—Mg—X the product is R—NH 2 .]
11.
From metal carbide (By hy drolysis) : Only CH 4 can be obtained by the hydrolysis of Be or Al carbides Al 4 C 3 12H 2 O
4 Al(OH ) 3 3CH 4
Be 2 C 4H 2 O
2Be(OH ) 2 CH 4
Physical
Prop er t ie s
(i)
C 1 to C 4 gases, Neopentane also gas but n-pentane and isopentane are low B.P. liquids.
(ii)
Next member s C 5 to C 17 are Colourless liquids and above C 17 are Wa xy solids.
(iii)
Density : The density of alkanes increases with increase in molecular weight and becomes constant at 0.8 g/mL. Thus all alkanes are lighter than water.
(iv)
Solubility : Alkanes being non polar and thus insoluble in water but soluble in non-polar solvents Example
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:
(v)
i.e.
: C 6 H 6 , CCl 4 ,ether etc.
The solubility of alkanes decreases with increase in molecular weight
Liquid alkanes are themselves good non-polar solvents.
Boiling point -
molecular weight (for n-alkanes)
Vanderwaals force of attraction molecular weight surface area of molecule. boiling point
Pentane < hexane < heptane
Also boiling point
1 number of side chain
because the shape approaches to spherical which results in decrease in Vanderwaals forces (as sur face area decreases) Thus boiling point n–Pentane > Isopentane > neopentane (vi)
Melt i ng Poi nt : M.P. of alkanes do not show regular trend. Alkanes with even number of carbon atoms have higher M.P. than their alkanes of odd number of carbon atoms. The abnormal trend in M.P. is due to the fact that alkanes with odd carbon atoms have their carbon atom on the same side of the molecule and in even carbon atom alkane the end Carbon atom on opposite side. Thus alkanes with even carbon atoms are packed closely in crystal lattice to permit greater intermolecular at tractions.
C C
C C
C C
C
C
<
C
Odd number of carbon
C C
C C
Even number of carbon
E x . Alkanes are inert is nature, why ? S o l . Alkanes are quite inert substances with highly stable nature. Their inactiveness has been explained as: (i) Alkanes have all the C—C and C—H bonds being stronger bonds and are not influenced by acid, oxidants under ordinary conditions. (ii) The C—C bond is completely non polar and C—H is weak polar. Thus polar species i.e. electrophiles or nucleophiles are unable to attack these bonds under ordinary conditions.
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JEE-Chemistry 12.
Chemical
Prop er t ie s
:
Oxidation : Complete oxidat ion or combust ion : Burn readily w ith non-luminous flame in pre sence of air or oxygen to give CO 2 and water with evolution of heat. Therefore, alkanes are used as fuels.
3n 1 O 2 nCO 2 + (n+1) H 2 O + Q; (H =–ve) 2
C n H 2 n 2
Incomplete oxidation : In limited supply of air gives carbon black and CO. 2CH 4 + 3O 2
2CO + 4H 2 O
CH 4 + O 2
C + 2H 2 O
C–black (used in printing)
(i)
Catalytic oxidation : Alkanes are easily converted to alcohols and aldehydes under controlled catalytic oxidation. Red hot Cu or Fe tube 2CH OH 2CH 4 + O 2 High P and T 3
Mo 2 O 3 HCHO + H O 2
CH 4 + O 2 (ii)
230 0 C,100 atm
Alkanes on oxidation in presence of manganese acetate give fatty acids. (CH COO ) Mn
(iii)
Ter tiar y alkanes are oxidized to give ter tiar y alcohols by KMnO 4 .
CH3 CH3 C
CH3 [O]
CH3 H
CH3 Ex.
OH
CH3
How many litre of Oxygen required for complete conbustion of 6.0 g ethane at NTP ?
2C 2 H 6 7O 2 4CO 2 6H 2O
Sol.
60 g ethane required O 2 (at NTP) = 7 ×
C
KMnO 4
22.4 litre
1 g ethane required O 2 (at NTP) =
7 22.4 litre 2 30
6 g ethane required O 2 (at NTP) =
7 22.4 6 15.68 litre 2 30
Substitution Reactions : Substitution reaction in alkanes shows free radical mechanism. They give following substitution reaction. (a) Halogenation : Replacement of H-atom by halogen atom R—H + X 2 R—X + HX Halogenation is made on exposure to (halogen + alkane) mixture to UV or at elevated temp. The reactivity order for halogens shows the order. F2 > Cl 2 > Br2 > I 2
Tertiary C – H > Sec. C – H > primary C – H
Reactivity order of hydrogen atom in alkane is (i)
Fluorination : Reacts explosively even in dark. Fluorination can be achieved without violence when alkane is treated with F 2 diluted with an inert gas (like N 2 ) By the action of HgF 2 on bromo or iodo derivatives. C 2 H 5 I + HgF 2 C 2 H 5 F + HgI 2
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3 2 CH 3 (CH 2 ) n CH 3 CH 3 (CH 2 ) n COOH high Temp
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JEE-Chemistry (ii)
Chlorination
:
Cl
Cl
Cl
Cl
2 2 2 2 CH 4 CH 3 Cl CH 2 Cl 2 CHCl 3 CCl 4
The monochloro derivative of alkane is obtained by taking alkane in large excess. When chlorine is in excess, a mixture of mono, di, tri, tetra and perchloro derivatives is obtained. Explosively CH 4 + Cl 2 C + HCl
Mechanism
UV for CH 4 + Cl 2
Step I
Chain
initiation
step
Step II
Chai n
propagat ion
CH 3 Cl + HCl UV
Cl Cl Cl : Cl or
:
step
. . : Cl + H : CH3 H: Cl + CH3 Methane
Methyl radical
. . CH3 + Cl : Cl CH3Cl + Cl Step III
Chai n
ter mi nat ion
step
: Cl Cl Cl 2 , CH 3 Cl CH 3 Cl ,
CH 3 CH 3 CH 3 CH 3 A
Cl
can also at tack CH 3 Cl to form chloromethyl ( CH 2 Cl ) free radical. T his free radical
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participates further in the chain reaction to yield methylene chloride (dichloromethane).
H . Cl + H: C
Cl
Cl
and
H
H . C + Cl : Cl H
Simi larly, chloroform and CCl 4 are obtained by fur ther chain reaction. (iii) Bromi nat ion : Br 2 reacts with alkane s in a simi lar manner but le ss vigorously. (iv) Iodination : Iodine reacts with alkanes reversibly. HI formed as the by product is a power ful reducing agent and is capable of reducing the CH 3 I to CH 4 . Iodination may be carried out in the presence of an oxidising agent such as HIO 3 , HIO 4 , HNO 3 , HgO etc. Which destroy HI,
CH 4 I 2
CH 3 I HI
5HI + HIO 3 3I 2 + 3H 2 O Iodination is ver y slow because energy of activation of the reaction is ver y large
CH 4 I HI + C H 3 Note
: Halogenation is inhibited in presence of oxygen because oxygen reacts with alkyl free radicals to form less react ive peroxy alkyl radical R–O–O • which can not propagate the chain.
Reactivity (i)
selectivity
Principle
:
Probability factor : The factor is based on the number of each kind of H atom in the molecule. For example is CH 3—CH 2 —CH 2 —CH 3 there are six equivalent 1° H's and four equivalent 2° H's. The probability of abstracting 1° H's to 2° H's is 6 to 4. i.e., 3 to 2.
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JEE-Chemistry (ii)
(iii)
Reactivity of halogen free radical : the more reactive chlorine free radical is less selective and more influenced by the probability factor. On the other hand, the less reactive Br radical is more selective and less influenced by the probability factor (Reactivity selectivity principle). Reactivity of alkanes (ease of abstration of 'H' atoms) : Since the rate determining step in halogenations is abstraction of hydrogen by a halogen atom be the formation of alkyl radical, halogenation of alkanes follows order of stability of free radical is 3° > 2° > 1° > CH 3 . Reactivity ratio of H atom for Chlorination (1° : 2° : 3° H) 1 : 3.8 : 5 Reactivity ratio of H atom for bromination (1 : 82 : 1600) T he above order of stabi lity of radicals is due to the ease of their format ion from the cor responding alkane which in turn is due to difference in the value of H. CH 3 —H •CH 3 H •
H 1
C H 3 — C H 2 — H •CH 3 — CH 2 H •
H 2
• • CH3—CH—CH3 CH —CH—CH +H
H 3
3
3
H CH3
CH3 •
CH3—C—CH3 CH3—C—CH 3+H •
H 4
Ex.
Reactivity of any H-atom number of H atoms of that kind × reactivity of that H. Thus the amount of energy required to form the various classes of radicals decreases in the order CH 3 > 1° > 2° > 3° (H 1 >H 2 >H 3 >H 4 ). Therefore, it easie st to form 3° radical and it is most difficult to form CH 3. We can also interpret this in an alternative way the case of abstraction of H atoms from hydrocarbon fallows the sequence 3° > 2° > 1° CH 4 which should also be the case of formation of free radicals. The above order of stability is in accordance with the stability of free radicals on the basis of delocalization of odd electron. Order of stability of free radical is : Allyl, benzyl > 3° > 2° > 1° > methyl, vinyl. What is the percentage of products obtained from monobromination of isobutane ?
Br S o l . CH3 CH CH3 + Br2 CH3 C
CH3 (I)
CH3
Pr oduct (I) = Pr oduct (II)
CH3 + CH3 CH CH2 Br
No.of primary H × No.of tertiary H
reactivity of primary H reactivity of tertiary H
% of product (I) =
9 100 0.56% 1600 9
% of product (II) =
1600 100 99.44% 1600 9
(b)
Nitrat ion
CH3 (II)
=
9 1 9 1 1600 1600
: (Vapour phase nitration) This involve s the substitut ion of a hydrogen atom of
alkane with -NO 2 group.
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JEE-Chemistry At ordinary temperature, alkanes do not react with HNO 3 . But reacts with vapours of Conc. HNO 3 at 450 ° C. 0
400 500 C R — H HO — NO 2 R — NO 2 H 2 O
Since the reaction is carried at high temp. the C—C bonds of alkanes break during the reaction and a mixture of nitroalkane s is formed. Example
450 0 C : CH 3 —CH 3 + HNO 3 CH 3 CH 2 NO 2 + CH 3 NO 2 + H 2 O
450°C
CH3CH2CH3 + HNO3
1–Nitro propane 2–Nitro propane Nitro ethane Nitromethane
25% 40% 10% 25%
Mechanism : (Free Radical substitution)
OH NO HO NO 2 2
Step – I
– R
H + OH R + H2O
R + HO – NO 2 R – NO 2 + OH
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(Pr oduct )
Step – III
R + NO2 R – NO 2
R + O R – OH (minor)
OH + N HONO 2 (c)
Sulphonation : Replacement of H atom of alkane by –SO 3 H is known sulphonation. Alkane react with fuming H 2 SO 4 or oleum (H 2 S 2 O 7 ). The branched lower alkanes and higher alkanes react to give alkane sulphonic acid. Example
:
CH3 CH3
CH3 H + HO SO3H CH3 C
C CH3
CH3
2–Methyl propane
2–methyl propane–2–sulphonic acid
The reactivity order for sulphonation is
SO3H + H2O
tert. H > Sec. H > prim. H
Mechanism : (Free Radical substitution)
400 C HOSO 3 H HO SO 3 H
C 6 H 13 H OH C 6 H 13 H 2 O
C 6 H 13 S O 3 H C 6 H 13 SO 3 H
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JEE-Chemistry Lower members such as propane, butane, pentane etc. react with SO 3 in vapour phase to form sulphonic acids. C 3 H 8 + SO 3 C 3 H 7 – SO 3 H (d)
Chlorosulphonat ion (Reed react ion) : Reaction with a mixture of SO 2 and Cl 2 at ordinar y temp. in the presence of UV light is called chlorosulphonation. UV
C 3 H 8 SO 2 Cl 2
C 3 H 7 SO 2 Cl HCl Propane sulphonyl Chloride
Further hydrolysis of alkane sulphonyl chloride gives alkane sulphonic acid. H O
2
C 3 H 7 SO 2 Cl
C 3 H 7 SO 3 H HCl
propane sulphonic acid C 3 H 7 SO 3 H NaCl
C 3 H 7 SO 3 Na HCl
Sodium salt of sulphonic acid (used as detergent)
Isomerization
:
Unbranched chain alkanes on heating with AlCl 3 + HCl / 200 0 C are converted in to branched chain alkanes
CH 3 — CH 2 — CH 2 — C H 3
3
CH3 CH CH3
n-butane
Isobutane
Branched chain alkanes converted to more branched alkane.
CH3 CH3 CH CH2
CH3 CH3 AlCl HCl
3 CH2 CH3 CH3 CH CH CH3
Isomerisation of alkanes is of great importance in petroleum industry to increase the octane number of petrol (gasoline).
Pyrolysis
or
Cracki ng
or
t her mal
decomposit ion
:
When alkanes are heated to 500-700 0 C they are decomposed in to lower hydrocarbon. This decomposition is called pyrolysis. In petroleum industry it is also termed as cracking.Cracking is used for the manufacture of petrol, petrol gas/oil gas etc. Example
1000 C : CH 4 C H2
500 C CH 3 CH 3 CH 2 CH 2 H 2 absence of air
CH3CH2CH3
CH2 CH3
CH2 + CH4 CH CH2 + H2
Cracking n-Butane 1-Butene + 2–Butene + Ethane + Ethene + Propene + CH 4 + H 2
The mechanism of pyrolysis occurs via free radicals.
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CH3 AlCl HCl
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JEE-Chemistry
Hydroforming or dehydrogenat ion or cyclisat ion or cataly t ic reforming or aromat izat ion : Unbranched higher alkanes (from 6 to 10 carbon atoms) when heated in presence of oxides of Cr, Mo, V on Al 2 O 3 suppor t at 500 0 C aromat ic hydrocarbons are formed. Cr O / Al O
2 3 2 3 n hexane 500 C
+
4H2
CH3 Cr O / Al O
2 3 2 3 CH 3 (CH 2 ) 5 CH 3
500 C
n-heptane
+ 4H2 Toluene
Cr O / Al O
2 3 2 3 CH 3 (CH 2 ) 6 – CH 3 500 C
CH3 CH3
n-octane o-xylene It provides an excellent method of passing from aliphatic to aromatic series. Chlorinolysis
:
0
300 400 C CH 3 CH 2 CH 3 Cl 2 C 2 Cl 6 CCl 4 HCl Pr essure (g) (s) ( )
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JEE-Chemistry SOLVED
Which of the following reactions can be employed for getting unsymmetrical alkanes in good yield ? (A) Wurtz reaction
(B) Corey–House reaction
(C) Both
(D) None of these
Sol.
Wurtz reaction is suitable for symmetrical alkanes
Ex.2
Sodium propionate on decarboxylation with sodalime gives (A) Propane
(B) Ethane
Ans.(B)
(C) Butane
(D) Pentane
Ans.(B)
Sol.
Decarboxylation with soda lime results in the formation of alkane with one carbon less than the starting compounds
Ex.3
Which of the following alkanes cannot be produced by Kolbe electrolysis of sodium or potassium salts of carboxylic acids ? (A) Methane
(B) Ethane
(C) Butane
(D) Hexane
Ans.(A)
Sol.
In Kolbe electrolysis, the alkane is formed by union of two alkyl groups. The alkane formed has, thus, two or more carbon atoms.
Ex.4
The homolytic fission of hydrocarbon results in the formation of (A) Free radicals
(B) Carbocations
(C) Carbanions
(D) Carbenes.
Ans.(A)
Sol.
Homolytic fission results in the formation of free radicals.
Ex.5
n-Heptane when heated to a temperature of about 800 K under high pressure in the presence of Cr 2O3/Al2O3 catalyst gives (A) 1-heptene
Sol.
(B) 2-Methylhexane
4H 2 CH 3 —(CH 2 ) 5 —CH 3
(C) Toluene
(D) Xylene.
Ans.(C)
CH3 Toluene
Ex.6
The reaction conditions leading to the best yield of C2H5Cl are Dark
UV light (A) C2H6 (excess) + Cl2
(B) C2H6 + Cl2 room temperature
UV light (C) C2H6 + Cl2 (excess)
UV light (D) C2H6 + Cl2
Ans.(D)
Sol.
C2H6 should be used in excess, otherwise polychlorination will take place
Ex.7
Number of isomer which can be theoretically obtained on monochlorination of 2-methylbutane is (A) 1 1
Sol.
(B) 2 2
3
(C) 3
(D) 4
(C) Ethanal
(D) CO2 and H2O
Ans.(D)
4
CH3—CH—CH2—CH3 1
CH3 Ex.8
Complete oxidation of ethane yields (A) Ethanol
(B) Ethanoic acid
Ans.(D) Sol.
2C 2H6 + 7O 2 4CO 2 + 6H 2O
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Ex.1
EXA MPLES
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JEE-Chemistry Ex. 9
In iso-pentane, the H atom that can be most easily substituted is on 1
2
3
4
CH3—CH—CH2—CH3 CH3 (A) C—1
(B) C—2
(C) C—3
(D) C—4
Ans.(B)
Sol.
Ease of substitution of various types of H atoms is 30 > 20 > 10.
Ex.10
8 c.c. of gaseous hydrocarbon requires 40 c.c. of O 2 for complete combustion. Identify hydrocarbon.
Sol.
Volume of hydrocarbon = 8 c.c. ;
8 2 = 40 3n+ 1
Formula No. 1,
1 2 = 5 3n+ 1
or
Volume of O 2
3n + 1 = 10 or
= 40 c.c.
(For alkane)
3n = 10 - 1 = 9
,
n= 3
The value of n comes in whole number from 1st formula it means hydrocarbon is Alkane and it is of 3C atom.
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Hydrocarbon is C 3 H 8 (Propane)
Ex.11
10 mL of a mixture of CH 4 and C 3 H 8 requires 41 mL of oxygen for complete combustion. What is the volume of CH 4 and C 3 H 8 in the mixture.
Sol.
Suppose the volume of CH 4 in (CH 4 + C 3 H 8 ) mix = x c.c. = Volume of C 3 H 8 w ill be = 10 – x c.c. For CH 4 CH 4 2O 2 CO 2 2H 2 O
For C 3 H 8
1 Vol. of CH 4 requires 2 vol. of O 2 for complete combustion x c.c. of CH 4 , 2x c.c. of O 2 C 3 H 8 +5O 2
3CO 2 + 4H 2 O
1 volume of C 3 H 8 requires 5 ml of O 2 for complete combustion (10 – x) c.c. of C 3 H 8 requires 5(10 – x) c.c. of O 2
Total Volume of O 2 = 2x + 5 (10 – x) it is equivalent to 41 (according to question)
2x + 5 (10 – x) = 41 x = 3 c.c.
Volume of CH 4 is 3 c.c. a nd volume of C 3 H 8 is 7 c.c. Ex.12
If 5 g C 2H 5I reacts with Na (Metallic) in presence of ether, and the yield is 60% then how many grams of n-butane will you get.
Sol.
2C 2 H 5 I 2Na C 4 H 10 2NaI Molecular weight of 2C 2 H 5 I = 24 + 5 + 127 = 156 Molecular weight of C 4 H 10 = 48 + 10 = 58 Two molecule of C 2 H 5 I are taking par t in above reaction.
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JEE-Chemistry
We get 58 g of C 4 H 10 from 2 x 156 g of C 2 H 5 I
We get
58 2x156
g C 4 H 10 from 1 g of C 2 H 5 I
We get
58 x5 2x156
g C 4 H 10 from 5 g of C 2 H 5 I
yield is 60% So the quantity of C 4 H 10 will be
58 x5 60 x 2x156 100
g = 0.55 g
Ex.13
The density of one hydrocarbon at N.T.P. is 1.964 g/litre. Identify the hydrocarbon.
Sol.
Molecular weight of Hydrocarbon = density of 1 lit. x 22.4 = 1.964 x 22.4 = 44 So Molecular weight of hydrocarbon = 44
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So the hydrocarbon is C 3 H 8 (Propane).
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