Hydrocarbons (Synopsis)

Alkanes or Paraffins. They have the general formula CnH2n+2. These can be prepared
(a) By hydrogenation of unsaturated hydrocarbons with Ni at 473K or Raney Ni at room temperature.
(b) By the reduction of alkyl halides with Zn/HCI or Zn/CH3COOH or Red P/HI, etc.
(c) By Wurtz reaction (RX and Na in ether)
 All hydrocarbons prepared by this method contain small amount of olefins as by-product.Formation of alkene is due to
disproportionation reaction. 3o-alkyl halide do not give this reaction. This reaction is suitable for symmetrical alkyl
halides. Crossed Wurtz reaction gives mixture of hydrocarbon
 When this reaction is carried out in presence of zinc is known as Frankland's reaction. It is not given by 1o alkyl halide.
(d) By decarboxylation of carboxylic acids with soda lime.( RCOONa+NaOH/CaO RH+Na2CO3)
(e) By electrolysis of Na or K salts of fatty acids (Kolbe's electrolytic reaction).
(f) From Grignard reagents: By decomposition of Grignard’s reagent with compounds containing active hydrogen atom like
HOH, R—OH, NH3, R—NH2, R2NH, CH3CCH, CH3COOH ... etc.
(g) By reduction of alcohols, aldehydes, ketones, carboxylic acids & their derivatives with hot conc. HI & red P
(h) By Corey-House synthesis: An alkyl halide is first converted into lithium alkyl which reacts with cuprous iodide to
form lithium dialkyl cuprate (LiR2Cu). It is then treated with an alkyl halide to give an alkane.
Physical Properties: Straight chain alkanes have higher boiling points than branched chain alkanes having same number
of carbon atoms. Branching decreases the surface area & thus magnitude of van der waal’s forces
Chemical Properties: Both C—C & C—H bonds of alkanes are non-polar and strong sigma bonds cannot break under
ordinary conditions, hence alkanes are quite inert towards acids, alkalies, oxidising & reducing agents. Important reactions
of alkanes are
(a) Halogenation: Alkanes react with halogens in presence of UV or diffused sunlight at high temperature (523-673K), the
hydrogen atoms of alkane are successively replaced by halogen atoms. The extent of halogenation depends upon the
amount of halogen used. (Reactivity order of halogens is F 2 > C12 > Br2 > I2).
(b) Chlorination and bromination proceeds in almost identical manner. Reaction with fluorine is very violent but the
reaction with iodine is very slow and reversible, so iodination occurs in presence of an oxidizing agent. Halogenation of
alkanes is a substitution reaction and occurs by a free radical chain mechanism. Bromination is more selective than
chlorination Ease of abstraction of hydrogen atom is 3o>2o>1o. It is in ratio of 5:3.8:1 for chlorination & 1600:5:1 for
bromination
Combustion: Alkanes readily burn in excess of air or oxygen to form CO 2, H2O and heat. Hence used as fuels
Chemical oxidation: Alkanes containing tert. hydrogen atoms are oxidised to tert. alcohols by KMnO4.
Isomerisation: The process of conversion of one isomer into another is called isomerisation. The straight chain (n-alkanes)
alkanes on treatment with Lewis acid catalyst, e.g., anhydrous A1C13, and conc. HCI, are converted into branched chain
alkanes. Isomerization involves 1,2 methyl or hydride shift.
Aromatisation: The conversion of aliphatic compounds into aromatic compounds is known as aromatisation. It occurs at
high temperature in the presence of Pt, Pd, Ni, Cr2O3-Al2O3.
Alkenes
Unsaturated hydrocarbons with one double bond are called Alkenes or Olefins and represented by the general formula
CnH2n. Heats of hydrogenation can be used to estimate the relative stability of alkenes.
 The more substituted alkenes are more stable and has lesser heat of hydrogenation, i.e., the stability order is
R2 C = C R 2 > R 2 C = C H R > R 2 C = C H 2 > R C H = C H R > RCH=CH2 > CH2=CH2
 Trans but-2-ene is more stable than cis-but-2-ene
General Methods of Preparation:
(i) By dehydration of alcohols: By heating with conc. H2SO4 at 443K or Al2O3 at 523K or H3PO4 at 473K, with P2O5 etc.
 The ease of dehydration is Tert. (3°) > Sec. (2°) > Primary (1°).
(ii) By dehydrohalogenation of alkyl halides: On heating at high temperature with alcoholic KOH. Stronger bases like
NaNH2 or C2H5ONa or Et3N can also be used for dehydrohalogenation.
 When two alkenes may be formed; the alkene which is most substituted one predominates (Saytzeff's rule). The
formation of less substituted alkene in an elimination reaction is called as a Hofmann Elimination. The ease of
dehydrogenation is 3°>2°>1o.
(iii) By dehalogenation of dihaloalkanes (vic- and gem-) on heating with zinc dust and methanol.
(iv) By electrolysis of salts of dicarboxylic acids (Kolbe's method)
(v) By controlled partial hydrogenation of alkynes: Hydrogenation of alk ynes with Pd -CaCO 3 (Lindlar's catalyst)
or a nickel boride (called P-2) catalyst yields cis-alkene.
 Sodamide (Na/liq. NH3) yields predominantly trans-alkene (Birch reduction). Reduction with Na/C 2 H 5 O H gives
trans-alk ene.
Physical Properties The b.pts. increases with increasing chain length, while m.pts. of highly substituted alkenes are
higher than straight chain alkenes. cis-isomers has higher dipole moment than trans isomer
Chemical Properties:
(i) Alkenes are reactive due to the presence of double bond &t important reactions of alkenes are the addition reactions.
(ii) Addition of hydrogen (Hydrogenation): In presence of catalyst Ni (473-523K) or finely divided Pt or Pd
(Sabatier-Senderen's reaction) or Raney Ni at room temperature.,alkenes form alkanes .
(iii) Addition of halogens: With C1 2 and Br 2 in prese n c e o f a n i n e r t s o l v e n t l i k e C C 1 4 . , a l k e n e s f o rm
v i c i n a l d i h a l i d e s B r 2 w a t e r i s decolourised by unsaturated hydrocarbons (hence the test of unsaturation).
 Addition of halogens is usually predominantly trans. Thus with trans-but-2-ene, the product is meso. With cis-
but-2-ene,the product is racemic mixture.
 A more substituted alkene is more reactive towards Br 2 or C12, as carbocation is the intermediate. Thus the order
of reactivity is H2C=CH2 < RCH=CH2 < RCH=CHR < R2C=CH2 < R2C=CHR < R2C=CR2
(iv) Addition of halogen acids: The order of reactivity is HI > HBr > HCI > HF Addition of HX to symmetrical
alkenes give only one product and addition of HX to unsymmetrical alkenes, give two different products. Under normal
conditions, the addition takes place in accordance with Markownikoff's rule.
 It is an electrophilic addition and is favoured by most stable carbocation intermediate. There may be 1,2-hydride or
1,2-methyl shift and stability order being 1°<2o<3°.
(v) Peroxide effect: Kharasch observed that the addition of HBr only to unsymmetrical alkenes in the presence of
organic peroxides, i.e., benzoyl peroxide (C 6 H 5 COO) 2 follows anti-Markownikoff's addition and is called as Peroxide
effect . It is a free radical addition reaction.
(vi) Addition of hypohalous acid (HOX)or Cl 2 or B r 2 i n p r e s e n c e o f w a t e r : H a l o h y d r i n s a r e f o r m e d .
( v i i ) Addition of sulphuric acid: Cold and concentrated H2SO4 readily adds to alkenes and form alkyl hydrogen
sulphate which on boiling with H 2 O (hydrolysis) yields alcohol. So, this reaction is called Indirect hydration of alkenes.
(viii) H y d r o b o r a t i o n o x i d a t i o n : I t i s a n t i Markownikoff's addition of water (hydration) to a double
bond. It involves addition of borane (B 2 H 6 ) to double bond followed by hydrolysis to give alcohol. Hydroborating
agent is borane-tetrahydrofuran complex. Diglyme or ether can also be used in place of THF. It is a syn addition.
(ix) Addition of water: In presence of acid or catalyst BF 3 alkenes yields alcohol in accordance with Markownikoff's
rule. Rearrangement can take place.
(x) Oxymercuration-demercuration: With mercuric acetate (in THF) followed by reduction with NaBH4/NaOH is also
an example of hydration of alkene according to M.R. It is a better process than catalytic hydration by dil. H 2SO4, because
it avoids rearrangement.
(xi) Diels-Alder reaction: It is a diene-dienophile addition reaction and forms cyclic compounds.
(xii) Addition of ozone: When O 3 or ozonised oxygen is passed through a solution of alkene in an inert solvent, addition
takes place across the double bond to form an ozonide. Ozonides are easily decomposed on warming with Zn/H2O or reduction
with H2/Pd catalyst breaking C=C < to produce two carbonyl compounds.. From the ozonolysis product, the position of the
double bonds can be determined.
 An alkene of the type RCH=CHR' gives two aldehydes (same or different).
 An alkene of the type R2C=CHR' gives one aldehyde and one ketone.
 An alkene of the type R2C=CR' gives two ketones (same or different).
 Addition of ozone followed by oxidation or absence of reducing agent gives carboxylic acid instead of
aldehydes. It is called oxidative ozonolysis.
Oxidation reactions: (i) Oxidation with cold, dilute, alkaline KMnO 4 (Baeyer's reagent): Glycols are formed
 This reaction is used for the detection of unsaturation and is called Baeyer's test. Hydroxylation by KMnO4 is
always syn-addition Hydroxylation using OsO4 followed by Na2SO3 also gives cis-glycol.
 H y d r o x y l a t i o n c a n a l s o b e d o n e w i t h peroxy acids (HCO3H or a mixture of H2O2 and HCOOH) followed
by hydrolysis. It gives trans-glycol.
(ii) O x i d a t i o n w i t h a c i d i c K M n O 4 o r a c i d i c K2Cr2O7 (Strong oxidising agent): They break the double bond and
give ketones and carboxylic acids
(iii) Per i od ic ac i d ( H IO 4 ) or l e a d te tr a - ac e ta t e (CH 3 COO) 4 Pb oxidises alkene into glycols and finally gives
aldehydes or ketones depending upon the nature of alkene.
(vi) Oxidation of alkenes by SeO 2 affects the allylic position and not the double bond.
(vii) Substitution reaction (Halogenation): NBS (N-Bromo succinimide) is a reagent used for the bromination of
alkenes at the allylic position, i.e., replacement of H-atom of the alpha carbon atom with respect to double bond of alkyl
group by the halogen atom at about 773K . This is known as allylic substitution. It takes place by free radical mechanism.
Alkynes
Unsaturated hydrocarbons with one triple bond are known as Alkynes or Acetylenes and represented by the
& general formula CnH2n-2. Mono substituted acetylenes or 1-alkynes are called terminal alkynes and the H-atom attached
to CC is called acetylenic (acidic) hydrogen (R—CC—H).
General Methods of Preparation:
(a) By dehydrohalogenation (—HX) of dihalides: On heating dihalides (vic- and gem-) with alc. KOH or sodamide, NaNH2
(in liquid NH3 or solid KOH or KNH2, etc.
(b) By dehalogenation (—X) of tetrahalides: On heating with Zn dust in alcohol. (c) By heating iodoform with silver powder.
(d) By the electrolysis of Na/K salts of unsaturated dicarboxylic acids (Kolbe's method).
(e) By the action of water on calcium carbide (Lab method). (f) By the hydrolysis of magnesium carbide, propyne is formed.
Chemical Properties:
1. Acidic nature: The H-atoms of 1-alkynes are more acidic than those of alkenes. The decreasing or d er of
ac id i t y is : H —CC —H > H 2 C = CH 2 > CH 3 -CH 3 . The group —CCH (1-alk ynes) is acidic in nature due to
more s-character (50%) of CC which is sp-hybridised. Hence proton release in —CCH takes place more readily.
On account of acidic nature, Terminal alkynes give the following reactions .
( a) Formation of sodium acet ylides: Acetyl ene reacts with NaNH 2 or Na/liq. NH 3 forms sod. alkynides
which is utilized for the preparation of higher alkynes with 1° alkyl halide ( 2° & 3° R—X gives mainly alkenes).
(b) Formation of copper acetylides: Acetylene when passed through an ammoniacal cuprous chloride solution, a red
precipitate of cuprous acetylide is formed.
(c) Formation of silver acetylides: Acetylene when passed through an ammoniacal solution of silver nitrate (Tollen's
reagent), a white precipitate of silver acetylide is formed.
2 Electrophilic Addition Reactions (i) Addition of hydrogen (Hydrogenation): Alkynes on treatment with hydrogen in
presence of a catalyst (Ni, Pt or Pd) form first alkenes and finally alkanes.
(ii) Addition of halogens: Alkynes add two molecule halogens and decolourises Br2 water (Test of unsaturation). The
reactivity order of halogens is as follows: F2 >Cl2>Br2 >I2. Iodine reacts slowly in alcohol to form di-iodo derivative
(predominantly trans-isomer). Alkynes are less reactive than alkenes towards electrophilic addition because alkynes
form less stable carbocations
(iii) Acetylene reacts with Cl2 in the presence of catalyst SbCl5 to give W estronCl 2 CH-CHCl 2 . W hich on heating with
BaCl2 or lime or alc. KOH gives Westrosol (ClCH=CCl2)
(iv) Addition of water (Hydration): Alkynes add on one molecule of water when passed into dil.H2SO 4 , at 333K in
presence of HgSO 4 catalyst to form aldehydes or ketones through keto-enol tautomerism.
v) Addition of HCN: Ethyne adds HCN in presence of Ba(CN) 2 or NaCN,catalyst to form vinyl cyanide (acrylonitrile)
which is a monomer for the polymer polyacrylonitrile (PAN).It is a nucleophilic addition reaction
(vi) Addition of CH3COOH: Ethyne adds two moles acetic acid in presence Hg 2+ or BF3 catalyst gives ethylidene acetate
which on heating gives acetaldehyde and acetic anhydride It is a nucleophilic addition reaction.
(vii) Addition of alcohol: In presence of NaOH or KOH or mercury salt, acetylene reacts with alcohol to form
alkyl vinyl ether (vinylation) which on hydrolysis gives acetaldehyde and alkanol. It is a nucleophilic addition reaction
OXIDATION REACTIONS (i) Addition of O 3 and subsequent hydrolysis: Acetylene and its homologues form
ozonides with O3 and these compounds are decomposed by water to form diketones, which are then oxidi sed
by H2O2 (formed in the reaction) to carboxylic acids (Oxidative ozonolysis).
(ii) Oxidation with alk. KMnO4 solution: Acetylene is finally converted into oxalic acid with Baeyer's reagent and pink
colour of the solution is discharged. Higher alkyne under similar conditions gives diketones. At higher temperature 383K
the final products are carboxylic acids, CO2 and ketones.
(iii) Oxidation with acidified KMnO 4 : Acetylene is converted into formic acid with acidic KMn O 4 on heating,
while higher alkynes, give R—COOH. Symmetrical alkynes give a single product while unsymmetrical alkynes give a
mixture of two products. Oxidation with chromic acid (K 2 Cr 2 O 7 + H 2 SO 4 ) : Acetylene is converted into acetic acid
and the orange colour changes to light green.
(iv) Oxidation with SeO 2 : Acetylene is oxidised to glyoxal while propyne gives keto propanal.