General Physics AISM-09/C/ALK

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SUBJECT: CHEMISTRY TOPIC: ALKENES & ALKYNES COURSE CODE: AISM-09/C/ALK

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General Physics AISM-09/C/ALK

Contents- ALKENES AND ALKYNES

Alkenes ................................................................................................................................................... 3 General methods of preparation of alkenes ......................................................................................... 6 Physical Properties of Alkenes : ........................................................................................................... 9 Addition reactions of Alkenes: ........................................................................................................... 10 Ozonolysis of alkenes : .......................................................................................................................... 16 Oxidation of Alkenes: ............................................................................................................................ 18 Following are the miscellaneous reactions of alkenes: ....................................................................... 20 Dienes or Diolefins or Alkadienes....................................................................................................... 23 Physical Properties of Alkenes : ............................................................................................................. 30 Chemical nature of Alkynes: .............................................................................................................. 31 Addition reactions of Alkynes : .......................................................................................................... 32 Oxidation of Alkenes: ............................................................................................................................ 38 Miscellaneous Reactions shown by alkynes: .......................................................................................... 40 Test for unsaturation ............................................................................................................................. 43

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Alkenes
(i) (ii) (iii) General formula CnH2n Also known as olefins (olefiant = oil forming) because their first member C2H4 forms oily product with chlorine or bromine Carbon atoms involved in double bond are sp2 hybridized having trigonal planar structure with an angle of 120oC. CH2==CH2 3 3

The coplanar structure of C=C has been described below, e.g. C2H4 CH3==CH3 I II I C Ground state II C Ground state

C Excited state (sp2)1(sp2)1(sp2)1p1

II

C Excited state (sp2)1(sp2)1(sp2)1p1

(iv)

Alkenes have the following characteristic bond lengths and bond energy. C=C =CH 2sp2( ) Bond length sp sp21s ( )

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Bond energy (v)

1.34 A 143.1 kcal mol1

1.108 A 98.69 kcal mol1

In ethylene the C=C involves one bond formed by head on overlapping of sp2sp2 orbitals having bond energy 91.60 kcal as well as one bond formed by lateral overlapping of pp orbitals of bond energy 51.5 kcal & thereby producing total bond energy of 143.1 kcal. That is why C=C (143.1 kcal) is more stronger than CC (83 kcal) bond. It is important to note that propylene has two types of carbon atoms: CH3CH=CH2 4 3 3 3 2 sp sp sp2 Thus it has bond lengths Also it has bond energy CC = 1.50 A and C=C = 1.34 A sp3sp2 sp2sp2 1 and C=C 143.1 kcal mol1 CC 84.48 kcal mol sp3sp2 sp2sp2

(vi)

(vii)

IUPAC nomenclature : (a) The IUPAC name is derived from the IUPAC name of alkanes by replacing ending ane by ene alongwith the position of double bonds. (e.g. alkane ane + ene = alkene). CH3CH=CHCH3 is known as but-2ene or butene2 or 2butene. (b) In case of two double or two triple bonds, the ending ne of alkanes is suitably replaced by diene or triene accordingly. CH3CH=C=CH2 : buta-1, 2-diene; CH2=CHCH=CH2: buta-1. 3-diene (viii) Alkenyl groups : Residual part left after the removal of one H atom from alkene is known as alkenyl group. According to IUPAC nomenclature, these groups are named by replacing terminal e of alkene by yl e.g.

Group 2 1 CH2=CH 3 2 1 CH2=CHCH2 1 2 3 CH=CHCH3 1 2 3 4 CH2CH=CHCH3

Trivial name vinyl allyl crotyl

IUPAC name ethenyl prop-2-enyl prop-1-enyl but-2-enyl

The numbering in alkenyl group is started from the carbon with free valencies.

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(ix)

Isomerism in alkenes : Alkenes show following isomerisms (i) C3H6 : CH3CH=CH2 & CH2CH2 Ring chain isomerism CH2 Cyclopropane (ii) C4H8 (a) (b) CH3CH2CH=CH2 but-1-ene CH3CH=CHCH3 but-2-ene

(c)

H3C C=CH2 H3 C H2CCH2 H3CCH2 (a) and (b) show position isomerism (a) and (c) show chain isomerism (a) and (d) show ringchain isomerism (b) also shows Geometrical isomerism CH3CH and CH3CH 2-methylpropene

(d)

cyclobutane

CH3CH HCCH3

The number of isomers increase with increase in carbon atoms more rapidly than corresponding alkanes. (pentane has only 3 isomers) C3H6 C4H8 C6H10 Possible structural isomers 2 4 5 Possible Geometrical isomers 2 2

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General methods of preparation of alkenes

(i) By cracking : CH3CH2CH3 (ii) C2H4 + CH4

By dehydration of alcohols : (a) Removal of H2O from a substrate molecule by a suitable dehydrating agent e.g. conc. H2SO4, AI2O3, H3PO4, P2O5. Some other dehydrating agents are KHSO4, BF3, dry HCI, CaCI2 etc. (b) This involves elimination. (c) e.g. RCH = CH2

RCH2CH2OH

RCH=CH2 RCH = CH2

CH3CH2CHCH3 CH3CH2CH=CH2

CH3CH=CHCH3

(d) (iii)

Major Minor OH (Cf. Saytzeff rule) The case of dehydration shows the order : tertiary > secondary > primary alcohols.

By dehydrohalogenation of monohalides: (a) Removal of HX from a substrate by alcoholic KOH or NaNH 2 (b) This too is elimination (c) RCH2CH2X CH3CH2CHCH3 X (d) RCH=CH2 CH3CH = CHCH3 + CH3CH2CH=CH2 Major Minor (Cf. Saytzeff rule)

The case of dehydrohalogenation shows the order: For alkyl halides: tertiary > secondary > primary alkyl halides For halogens in halides : iodide > bromide > chloride

(iv)

By halogenations of dihalides:

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(a)

Removal of X2 from a substrate Zn dust/CH3OH or ZnCu couple in alcoholic solution.

(b)

e.g.

CH3CHX2
gem dihalide

CH2=CH2

CH2XCH2X
vicinal dihalide

CH2=CH2

Note : Metallic sodium can also be used in place of zinc. (v) By Kolbes electrolysis : (a) Electrolysis of aqueous solutions of sodium or potassium salts of saturated dicarboxylic acids gives alkene. Anode Cathode (b) e.g. CH2COONa CH2 + 2CO2 + 2NaOH + H2 CH2COONa
Disodium succinate

CH2

(vi)

By partial hydrogenation of alkynes: (a) Hydrogenation of alkynes in presence of Lindlar catalyst gives alkenes. CH CH RC CH (b) (c) CH2=CH2 RCH=CH2

Lindlar catalyst is Pd on CaCO3 deactivated by lead acetate which prevents further hydrogenation. Use of Pd or Pd-charcoal poisoned by BaSO4 and quinoline give better results. (Cram et. Al)

(vii)

By heating quaternary ammonium compounds : (C2H5)4 N+ OH tetraethyl ammonium hydroxide (C2H5)4 N+ X (C2H5)3 N tertiary ethylamine + C2H4 + H2O

(C2H5)3N + C2H4 + HX

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(CH3CH2CH2CH2)4 N+ X
4N +

CH3CH2CH=CH2 + (C4H9)3N + HX X =CH2 +

3N

+HX

(viii) By Grignard reagents : R Mg + XCH=CH2 R (ix)

RCH=CH2 + MgX2

Action of Copper alkyl on Vinyl Chlorides : Vinyl chloride on alkylation with copper alkyl form higher alkenes. 2H2C = CHCI 2H2C=CHR + CuCI2
alkene

2H2C = CHCI

2H2C=CHR propene

+ CuCI2

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Physical Properties of Alkenes :

(a) (b) (c)

(d) (e) (f)

All are colourless & have no characteristic odour. Ethene has pleasant smell. Lower members (C2 to C4) are gases, middle one (C3 to C17) are liquids, higher are solids. The boiling points, melting points, and specific gravities show a regular increase with increase in molecular weight, however less volatile than corresponding alkanes. A cis isomer has high boiling and melting point than trans isomer because of more polar nature. Like alkanes, these too are soluble in non polar solvents. Alkenes are weak polar. The polarity of cis isomer is more than trans which are either non polar or less polar. (e.g. trans butene-2 is non polar; trans pentene-2 is weak polar).

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Addition reactions of Alkenes:

Following are addition reactions shown by alkenes. (a) Addiion of H2 or hydrogenation : (i) The mechanism reveals the free radical addition. The process is used to obtained vegetable ghee from hydrogenation of oil. CH2=CH2 + H2 (ii) CH3CH3

(iii)

In presence of Ni as catalyst, reaction occurs at 200 300oC whereas in presence of Pt or Pd, the hydrogenation of alkenes takes place even at room temperature. Hydrogenation of alkene is exothermic in nature. The heat of hydrogenation for alkenes are nearly 30 kcal/mol and their value is most commonly used as a scale for the stability of alkene. The lower the heat of hydrogenation of an alkene, the more is stability e.g. trans-2-butene ( Hh = 27.6 k cal/mol) is more stable then cis-2-butene ( Hh = 28.6 k cal/mol) and 1-butene ( Hh = 30.3 kcal/mol)

(b)

Addition of halogens : (i) Addition of CI2 on alkene is free radical addition, whereas addition of Br2 sows electrophilic addition. CH2=CH2 + CI2 CH2CICHCI CH2=CH2 + Br2 (in solvent) CH2BrCH2Br

The mechanism CH2=CH2 CH2 CH2 CH2=CH2 CH2+ CH2

Br CH2+ CH2

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Br

Br+

Br+ Br

Br Br

Br
(Br2 gets polarized due to electron cloud of alkene)

Br

Explained in terms of steric hinderance of bromine atom on carbonium ion or in terms of cyclic bromonium ion as intermediate i.e.

(ii) (iii)

(iv)

The reactivity order of halogens : CI2 > Br2 > I2 The addition of Br2 on alkenes provide a useful test for unsaturation in molecule. The brown colour of the bromine being rapidly discharged. Thus decolorization of 5% Br2 in CCI4 by a compound suggests unsaturation in it. Additionof bromine on ethylene in aqueous sodium chloride solution gives ethylene dibromide and 1-bromo, 2-chloroethane. CH2=CH2 + Br2 Similarly BrCH2CH2Br + BrCH2CH2I CH2=CH2 + Br2 BrCH2CH2Br BrCH2CH2ONO2 + BrCH2CH2Br + BrCH2CH2CI

(c)

Addition of halogen acids : (i) (ii) (iii) Electrophilic addition e.g. CH2=CH2 + HX CH3CH2X The reactivity order for halogen acids is:

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HI > HBr > HCI > HF (iv) chapter 1. (d) Addition of hypohalous acids : (i) Electrophilic addition (ii) The reactivity order for oxyacids is: Follow mechanism of reaction & Markownikoff rule in

HOCI > HOBr >

HOI CH2=CH2 + HOX halo hydrin) (iii) (iv) In place of HOX, (halogen + water) may be used to get above reaction. For addition of HOX on unsymmetrical alkene Markownikoff rule is followed. CH3CH=CH2 + HO X+ (e) CH3CHOHCH2X CH2OH CH2X (ethylene

Addition of H2O : (i) Alkenes show addition of H2SO4 which on hydrolysis yield alcohols. CH2=CH2 CH3CHOHCH3 (ii) (iii) + H2SO4 CH3CH2HSO4

This too is electrophilic & addition on unsymmetrical alkenes obeys Markownikoff rule. The reaction is used to separate alkenes from a mixture of alkane and alkenes. CH3CH=CH2 CH3CHOHCH3 CH3CHCH3

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HSO4 Note : (i) Alkene1 on addition of H2O gives alkanol2. To obtain alkanol1, hydroboration of alkene1 followed with its reaction with H2O2 is made. 6RCH=CH2+B2H6 2(RCH2CH2)3B 6RCH2CH2OH+2H3BO3

(ii)

Alkene1 may also be converted to alkanol1 as: RCH=CH2+HBr RCH2CH2OH

Kharasch effect

RCH2CH2Br

(f)

Addition of NOCI : CH2 = CH2 + NO+ CI CH2CICH2NO ethylene nitrosochloride

Note :

NO

The addition of NOCI on alkene gives CC . This product is stable only when the carbon atom bearing. CI NO R NO group does not contain hydrogen e.g. CC . If H atom is present on the carbon atom, the product. R CI Undergoes rearrangement to form more stable oxime. NO

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H CC CI CC=NOH CI oxime RCHCH2

Ag catalyst

(g)

Addition of O2 : RCH=CH2 + O2
lower alkenes

O
epoxy alkane (or oximes, a class of compounds)

Alkane epoxides are cyclic ethers which on hydrolysis give diols or glycols. (h) Addition of HNO3 :
+

CH2=CH2 + HO NO2
(fuming)

HOCH2 CH2NO2
2nitroethanol

(i)

Addition of Acetyl Chloride :

+

CH2=CH2 + CH3COCI

CH2CI 4chlorobutan-2-one
ketones

CH2COCH3
or methyl-chloroethyl

(j)

Addition of isoalkanes or alkylation : CH3C=CH2 + CH3CHCH3 CH3CCH2

CHCH3
HF

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CH3 CH3

CH3

0 to 10^C

CH3
Isooctane

(k)

Polymerization : (i) Alkenes on heating in presence of catalyst (O 2, HF or peroxides) at high P undergo addition polymerization i.e. self addition. Polymerization is reversible reaction and the strength of polymer depends upon experimental conditions. nCH2 = CH2
high P,T

(ii)

(H2CCH2)a
polyethene

nCH2 = CH2
polyethene

Note : The derivatives of alkenes of the type CH2=CHX (where X may be halogen, N, OH etc.) also undergo polymerization to form useful polymers such as poly vinyl cyanide ,

polyvinyl

chloride

and

polyvinyl

alcohol

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Ozonolysis of alkenes :
A test for unsaturation in molecule. (a) On passing ozone through a solution of alkenes in inert solvent i.e. CHCI3 or CCI4 or ether, addition of ozone takes place round double bond of alkene to form ozonides. The mono ozonides are highly explosive in nature and are generally decomposed during hydrolysis or by reduction with hydrogen in presence of catalyst to give two molecules of carbonyl compounds. The complete process of ozonide formation (step a) and then their decomposition to give carbonyl compounds (step b) is known as ozonolysis. The ozonolysis thus involves the replacement of an olefinic bond C=C by two carbonyl groups C =O. The total number of carbon atoms in two carbonyl compound is equal to total number of carbon atoms in alkene. The ozonolysis is used to detect the position and nature of unsaturation in a molecule. For this purpose first ozonides are formed. The solution is evaporated to get the ozonides as viscous oil which are then either hydrolysed directly with water using Zn dust as reducing agent or reduced by H2 is presence of Pd or Pt. The Zn dust used during hydrolysis checks the formation of H 2O2 which can otherwise oxidize the products (carbonyl compounds) to respective acids. Identification of aldehydes & ketones formed during ozonolysis suggests the nature & position of unsaturation in molecule. A symmetrical alkene give rise to two molecules of same carbonyl compound. e.g.CH3CH2CH=CH2 CH3CH2CHO CH2 CH3CH2CHO + HCHO

(b)

(c)

(d)

(e)

(f) (g)

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OO CH3CH2CHO + HCHO
Zn dust

CH3CH=CHCH3 2CH3CHO

CH3CHOCHCH2
above

OO H3C C=CH2 C=O + HCHO H3C H3C H3C COCH2 H3C OO (h) (i) An alkene of the type RCH=CHR gives two aldehydes RCHO & RCHO (ii) An alkene of the type R2C = CHR gives R2C = O + RCHO (iii) An alkene of the type R2C=CR2 gives ketones only R2C=O&R2C=O Reduction of ozonide can also be made by Zn/Acid, H2Raney Ni or triphenyl phosphine to carbonyl compounds. Reduction of ozonide by LiAIH4 or sodium borohydride gives corresponding alcohols. RCHOCHR OO RCH2OH + RCH2OH
above

H3C

(i) (j)

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Oxidation of Alkenes:
(a) Combustion : The combustion of alkenes is also exothermic with high calorific values and thus used for welding purposes in oxy-ethylene welding. CH2=CH2 + 3O2 CnH2n + (3n/2)O2 (b) 2CO2 + 2H2O; H = ve nCO2 + nH2O; H = ve

Oxidation by Baeyers reagent or hydroxylation : A test for unsaturation Alkenes on passing through dilute alkaline, 1% cold KMnO 4 (i.e. Baeyers reagent) decolorize the pink colour of KMnO 4 and forms dihydroxy compounds (e.g. glycols) CH2 + H2O + [O] CH2
reagent

CH2OH CH2OH ethylene glycol

CH3CH=CH2 + H2O + [O]

CH3CHCH2 OH OH propylene glycol

(c)

Oxidation by alkaline KMnO4 : Oxidation of alkenes by hot alkaline KMnO4 gives two acid salts showing fission of C=C bond RCH=CHR
alk. KMnO 4

RCOOK + RCOOK

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(d)

Oxidation by acidic KMnO4 or K2Cr2O7 :

(i)

Oxidation of alkenes by acidic KMnO4 or K2Cr2O7 gives carboxylic acids. If HCOOH is acid, it is further oxidized to CO2 & H2O. HCCOH + HCOOH
4

CH2=CH2 HCOOH only

acidic KMnO

H2O + CO2 (for

CH3CH = CH2 RCH = CHR R C=C R (ii) (iii) R R

CH3COOH + HCOOH RCOOH + RCOOH R CO R

Same products are obtained if oxidation is made by per iodic acid or lead tetra acetate. The nature of acid formed decides the position of unsaturation in molecule.

Note : Alkenes on oxidation by osmium tetraxide gives an intermediate product which on refluxing with NaHSO 3 (alc.) gives glycols.

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Following are the miscellaneous reactions of alkenes:

1.Isomerization (i) (ii) Alkenes on heating to 500 to 700oC or on heating in presence of catalyst {AICI3 or AI2(SO4)3} undergo isomerization. The isomerisation involves migration of olefinic bond or alkyl group. CH3CH2CH = CH2 (CH3)2C=CH2
butene-1

CH3CH=CHCH3 or
butene-2 isobutene

2.

Allylic substitution (i) (ii) (iii) The alkyl group of the alkene (except C2H4) undergoes substitution at high temperature in presence of CI2 or Br2. It is free radical substitution The substitution occurs at carbon to the double bond. CH3CH=CH2 + CI2 CH3CH2CH=CH2 + CI2 HCI Note : At normal temperature halogens show addition reactions with alkenes. CH3CICH=CH2 + HCI CH3CHCICH = CH2 +

3.

Wohl-Ziegler bromination. (Allylic bromination with NBS) O CH2C HCH2CH=CH2 + O CH2C BrCH2CH=CH2 +

NBr

NH

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CH2C O
N-bromisuccinimide

ally bromide

CH2C O

4.

Oxy-mercuration-demercuration This method involves synthesis of alcohols from alkenes. Here addition occurs according to Markownikoffs rule H H RCHCH3 (ii) NaBH4, alkene CH3 CH3 CH3CH2CCH2
OH

RC==CH OH

OH alcohol CH3 CH3CH2

CH3CH2C=CH2 CCH3 + Hg
THF-H O 2

2-methylbutane-1 ol

MeCOO HgOOCMe OH 2-methylbutan-2-

Uses : (i) In plastic formation i.e., polyethene, polypropene etc. and synthetic rubber formation. (ii) (iii) (iv) In oxy-ethylene welding. As food preservatives (C2H4) and ripening of fruits. As general anaesthetic (C2H4 with 10% O2)

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(v)

In preparation of mustard gas An oily liquid having high vaporizing tendency. Its vapours have high penetrating power and penetrate even thick boots and causes painful blisters on skin as well as inside the body, causing death ultimately. It was used I world war. CH2 + S CH2
sulphur monochloride

CH2 S2CI2 + CH2

CH2CI

CH2CI +

CH2SCH2
mustard gas or

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Dienes or Diolefins or Alkadienes

Hydrocarbons having two double bonds ae known as alkadienes. Alkadienes are classified into three categories on the basis of location of two double bonds. (i) Cumulative dienes: Two double bonds are on adjacent carbon atoms e.g. CH2 = C = CH2 allene or 1, 2-propadiene (ii) Conjugated dienes: Molecules having alternate single & double bonds e.g. CH2 = CHCH = CH2 buta-1, 3-diene CH2 = CCH = CH2 2-methylbuta-1, 3-diene or isoprene CH3 (iii) Isolated diene : Molecules having two double bonds separated by more than one single bond. CH2=CHCH2 CH=CH2 CH=CHCH2CH2CH=CH2 1, 4-pentadiene 1, 5-hexadiene

Among the three types of dienes, conjugated alkadienes have some characteristic nature and undergo addition reactions in a peculiar manner. The simplest conjugated alkadiene is buta-1, 3-diene. It has following note worthy features. (i) (ii) All carbon atoms in CH2=CHCH=CH2 (buta-1, 3-diene) are sp2 hybridized The delocalization of electrons results in resonance in molecule to show extra stable nature than corresponding non conjugated alkadienes (Resonance energy of buta-1, 3-diene is 3 kcal mol1) CH2=CHCH=CH2 (iii) CH2+ CH=CHCH2 CH2CH=CHCH2

The addition of H2, Br2 or HBr .. etc on conjugated alkadienes takes place in two ways either 1, 2 or 1, 4-addition. 1, 2-addition 1, 4-addition

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CH2=CHCH=CH2 CH3 CH2=CHCH=CH2 + Br2

CH3CH2CH=CH2

CH3CH=CH

CH2CHBrCH=CH2 + CH2CH=CHCH2 Br Br + Br CH3

CH2=CHCH=CH2 + HBr CH=CHCH2Br (iv)

CH3CHBrCH=CH2

(v)

Non ionizing solvent favours 1, 2-addition whereas ionizing solvent favours 1, 4-addition. However in each case mixture of both type of addition products are formed, the one predominating on the other as the case may be. It undergoes polymerization in presence of peroxides to give polybutadiene (Buna Rubber). nCH2=CHCH=CH2 (CH2CH=CHCH2)n
Buna rubber

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Alkenes (i) General formula CnH2n (ii) Also known as olefins (olefiant = oil forming) because their first member C2H4 forms oily product with chlorine or bromine (iii) Carbon atoms involved in double bond are sp2 hybridized having trigonal planar structure with an angle of 120oC. CH2==CH2 3 3

The coplanar structure of C=C has been described below, e.g. C2H4 CH3==CH3 I II I C Ground state II C Ground state

C Excited state (sp2)1(sp2)1(sp2)1p1

II

C Excited state (sp2)1(sp2)1(sp2)1p1

(iv)

Alkenes have the following characteristic bond lengths and bond energy. C=C =CH Bond length sp2sp2( ) sp21s ( ) 1.34 A 1.108 A 1 Bond energy 143.1 kcal mol 98.69 kcal mol1

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(v)

In ethylene the C=C involves one bond formed by head on overlapping of sp2sp2 orbitals having bond energy 91.60 kcal as well as one bond formed by lateral overlapping of pp orbitals of bond energy 51.5 kcal & thereby producing total bond energy of 143.1 kcal. That is why C=C (143.1 kcal) is more stronger than CC (83 kcal) bond. It is important to note that propylene has two types of carbon atoms: CH3CH=CH2 4 3 3 3 2 sp sp sp2 Thus it has bond lengths Also it has bond energy CC = 1.50 A and C=C = 1.34 A sp3sp2 sp2sp2 CC 84.48 kcal mol1 and C=C 143.1 kcal mol1 sp3sp2 sp2sp2

(vi)

(vii)

IUPAC nomenclature : (a) The IUPAC name is derived from the IUPAC name of alkanes by replacing ending ane by ene alongwith the position of double bonds. (e.g. alkane ane + ene = alkene). CH3CH=CHCH3 is known as but-2ene or butene2 or 2butene. (b) In case of two double or two triple bonds, the ending ne of alkanes is suitably replaced by diene or triene accordingly. CH3CH=C=CH2 : buta-1, 2-diene; CH2=CHCH=CH2: buta-1. 3-diene (viii) Alkenyl groups : Residual part left after the removal of one H atom from alkene is known as alkenyl group. According to IUPAC nomenclature, these groups are named by replacing terminal e of alkene by yl e.g.

Group 2 1 CH2=CH 3 2 1 CH2=CHCH2 1 2 3 CH=CHCH3 1 2 3 4 CH2CH=CHCH3

Trivial name vinyl allyl crotyl

IUPAC name ethenyl prop-2-enyl prop-1-enyl but-2-enyl

The numbering in alkenyl group is started from the carbon with free valencies. (ix) Isomerism in alkenes : Alkenes show following isomerisms

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(i)

C3H6 : CH3CH=CH2

&

CH2CH2

Ring chain isomerism

CH2 Cyclopropane (ii) C4H8 (a) (b) CH3CH2CH=CH2 but-1-ene CH3CH=CHCH3 but-2-ene

(c)

H3C C=CH2 H3 C (d) H2CCH2 2-methylpropene

H3CCH2

cyclobutane

(a) and (b) show position isomerism (a) and (c) show chain isomerism (a) and (d) show ringchain isomerism (b) also shows Geometrical isomerism CH3CH and CH3CH HCCH3 CH3CH

The number of isomers increase with increase in carbon atoms more rapidly than corresponding alkanes. (pentane has only 3 isomers) C3H6 C4H8 C6H10

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Possible structural isomers Possible Geometrical isomers Preparation of Alkynes (i) By dehydrohalogenation of dihalides : CH3 or CHX2 CH2X CH2X

4 2

5 2

CHX
HX

CH
HX

CH2
vinyl halide

CH
acetylene

Vinyl halide being less reactive & thus to get better yield a stronger base sodalime NaNH2 is used in II step. (ii) By dehalogenation of tetrahalides : CHX2 CH CH CHX2
or strong electro positive metals

(iii)

By haloform : only for acetylene CHX3 + 6Ag + X3HC

Powder

CH CH + 6AgX

(iv)

By Kolbes electrolytic method : CHCOOK CHX(aq)

pot fumarate or maleiate

Anode

Cathode

CH CH + 2CO2 + 2KOH + H2

(v)

Laboratory method : Acetylene is prepared in laboratory by the action of water on calcium carbide. CaC2 + 2H2O Ca(OH)2 + C2H2 (Wohler reaction)

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The air of the flask in which acetylene is to be prepared is displaced with oil gas as acetylene forms an explosive mixture with air. Acetylene evolved is collected over water. The acetylene so prepared is contaminated with small amounts of impurities such as PH3, H2S, AsH3 and NH3 which are removed by passing the mixture through CuSO4 solution before its collection over water. (vi) Manufacture : old method : Modern method : or (vii) 2C + H2 6CH4 + O2 2CH4 C2H2 (Bertholots reaction) 2CH CH + 2CO + 10H2 CH CH + 3H2

Preparation of higher alkynes : Higher alkynes may be obtained b acetylene. (a) CH CH + Na CH CNa + RX (b) CH CH + RMgX CH CNa + H2 CH CR + NaX XMgC CH RC CH + MgX2

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Physical Properties of Alkenes :

(a) (b) (c) All are colourless & have no characteristic odour. Ethene has pleasant smell. Lower members (C2 to C4) are gases, middle one (C3 to C17) are liquids, higher are solids. The boiling points, melting points, and specific gravities show a regular increase with increase in molecular weight, however less volatile than corresponding alkanes. A cis isomer has high boiling and melting point than trans isomer because of more polar nature. Like alkanes, these too are soluble in non polar solvents. Alkenes are weak polar. The polarity of cis isomer is more than trans which are either non polar or less polar. (e.g. trans butene-2 is non polar; trans pentene-2 is weak polar).

(d) (e) (f)

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Chemical nature of Alkynes:

An alkyne molecule (except ethyne) has three parts R C C H Alkyl part Alkyne Acidic H Part (i) (ii) Alkyl part : The alkyl part being inert in alkyne & thus does not show substitution reaction. Alkyne part : It consists of one & 2 bonds. Due to more strain than alkene, bonds are highly reactive and less stable. The polarization of bonds in alkynes leads to addition reaction. Unlike alkene, alkyne reacts with two molecules of additive to form saturated molecule. Acidic hydrogen part : H atom attached to sp hybridized carbon or triply bonded carbon atom is acidic in nature. The acidic character is due to the fact than an increase in s character of carbon atom give rise to higher electonegativity to it and thus H atom attached on sp hybridized carbon acquires polarity to show acidic nature. Type of bond s character Thus CH 50% or =CH 33.3% or CH 25% or RC C + HBase

(iii)

RC CH+ + Base

The hybridized carbon atom being more electronegative, is best able to accommodate the electron pair in the anion left after the removal of proton. Relative acidic nature : Relative basic nature : HOH HOR > HC CR > HNH2 > H2C=CH2 > CH3CH3 OH OR < C CR < NH2 < CH=CH2 < CH2CH3

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Addition reactions of Alkynes :

(a) Addition of H2 : Addition of two molecules of H2 takes place on alkyne. CH CH + H2 CH2=CH2 CH3CH3

However the addition of 2nd H2 molecule can be checked if Lindlar catalyst is used. Dialkyl acetylenes may be catalytically reduced to a mixture of cis and trans alkenes, the former is formed predominantly if Lindlar catalyst is used. R C C R R (cis) R C C H R (trans) H R C C H H

However reduction with sodium in liq. NH3 or by LiAIH4 produces trans alkene. (b) Electrophilic addition : Acetylenic bond in alkyne is a combination of one sigma bond and two bonds. Like alkenes, alkynes also show characteristic electrophilic addition reactions which take place in two stages involving the formation of olefinic intermediate. Thus alkynes shows addition of two molecules of addendum.

C C + ENu

C C E Nu olefinic intermediate

CC E Nu

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General Physics AISM-09/C/ALK

However the rate of electrophilic addition in acetylene is rather show than that of ethene inspite of the fact that alkynes has excess of electron. This fact is also supported than in many of electrophilic addition reaction, presence of catalyst such as Hg2+ ions is needed. The low reactivity of acetylene is not yet clear. (ii)

Addition of Halogens :
CH CH + CI2(g) or CICH=CHCI
Acetylene dichloride

CHCI2CHCI2
Acetylene

tetrachloride

Br2

(or western)

lime or BaCI2

CHCI CCI2 Westrosol (a) (b) (c) Western and westrosol are good industrial solvents for rubber, fats and varnishes. Western also have some insecticidal action. The rate of reaction increases in presence of light. The reactivity order for halogens is : CI2 > Br2 > I2 CH CH + Br2 water CHBr = CHBr (only)

CH

CH + Br2 CHBr2CHBr2 in CCI4 CHI=CHI

CH CH + I2 in alcohol (d)

(e)

Direct combination of acetylene with chlorine may be accompanied with explosions, but it is prevented by the presence of metallic chloride as catalyst. The predominant product during addition of one molecule of halogen on alkyne ins trans isomer.

(iii)

Addition of halogen acids :

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General Physics AISM-09/C/ALK

CH CH + HX

CH2=CHX vinyl halide

CH3CHX2 ethylidene dihalide

The reactivity order is : HI > HBr > HCI Acetylene reacts with dil HCI in presence of Hg 2+ at 65oC to give vinyl chloride, used in preparation of poly vinyl chloride, a synthetic polymer. CH CH + dil. HCI CH2=CHCI

Note : (i) (ii)

Peroxides have the same effect on the addition of HBr to unsymmetrical alkynes as they have on alkenes. Because of I effect of the bromine atom, the availability of the electrons during the second molecule addition becomes much slower than ethylene.

(iv)

Addition of hypohalous acids : CH CH + HOCI CHOH=CHCI CH(OH)2CHCI2 CHOCHCI2 unstable dichloro acetaldehyde

OH CH3C CH+HOCI CH3COCHCI2 CH3C=CHCI CH3CCHCI2 dichloro acetaldehyde OH OH Unstable

Note : (i)

Presence of two or more OH gp on one carbon atom makes it unstable and the molecules loses H2O molecule. However two exceptions to this rule; one is chloral hydrate CCI3CH(OH)2 and the other is carbonic acid HOCOH. Chloral O hydrate is extra stable inspite of two OH gp on one carbon atom due to H-bonding.

(ii)

(v)

Addition of H2SO4 :

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CH CH + H2SO4 (cold & conc.)

CH2=CHHSO4 vinyl hydrogen sulphate CH3CH(OH)2

H2SO4

CH3CH(HSO4)2 Ethylidine dihydrogen sulphate CH3CHO

CH3CH(HSO4)2

The above reaction can also be made as: H CH CH

60%

CH2=CC OH H O

HCCH (or CH3CHO)

Vinl alcohol CH2=CHOH, which is rapidly converted into an equilibrium mixture that is almost CH3CHO is an example of keto-enol tautomerism. CH3C CH
60%

CH3COCH3

Note : Only C2H2 on addition of H2O gives aldehyde and rest all alkynes give ketone. (vi)

Addition of AsCI3 :
CH CH + AsCI3 CHCI=CHAsCI2
chlorovinyl dichloroarsenic (Lewsite), A poisonous gas, more poisonous than mustard gas

(vii)

Addition of HCN :
CH CH + HCN CH2=CHCN
vinyl cyanide or acrylonitrile used for preparation of (i) Buna-N rubber

a copolymer of vinyl cyanide & butadiene and (ii) synthetic fibre orlon.

(viii) Addition of acetic acid :

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CH CH+CH3COOH CH2=CH(OOCCH3) CH3CH(OOCCH3)2 (CH3CO)2O+CH3CHO

vinyl acetate used in preparation of polymer polyvinyl acetate ethylidene diacetate

(ix)

Addition of CO and H2O :

CH CH + CO + H2O CH2=CHCOOH acrylic acid

(x)

Polymerisation or self addition : Alkynes undergo polymerization yielding

different types of polymeric compounds under different conditions. (a) Cyclic polymerization : (i) 3CH CH(g)
metal tube benzene

CHCH CH (ii) 4CH CH

Tetra hydro furan (solvent for C2H2) High P

CH CH CHCH Cyclooctatetraene CH

(iii)

CH3C CH
mesitylene

(b)

Linear Polymerisation : CH2=CHC CH

monovinyl acetylene

CH CH+CH CH CH=CH2

CH2=CHC C
divinyl acetylene

Vinyl acetylene on reaction with HCI forms 2-chloro, 1, 3-butadiene (or chloroprene) which on exposure to air polymerizes to give synthetic rubber neoprene

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CH2=CHC CH+HCI C=CH2

CH2=CH

CI chlorprene

neoprene (rubber)

Note : Acetylene on heating with spongy copper or its oxide gives a cork like substance, used in manufacture of linoleum. Ozonolysis : O CH CH+O3 CH3CCH CH3COOH+HCOOH O-O
Acetylene monoozonide

CH3CO

CHO+H2O2

CH3C CH+O3 CH

O CH3C CH3COOH+HCOOH O-O O

CH3COCHO+H2O2

RC CR

RCCR O-O

TCCR + H2O2 O O

RCOOH + RCOOH

(i)

(ii)

Addition of O3 on alkynes gives their monoozonides which on hydrolysis forms dicarbonyl compounds which are further oxidized to carboxylic acids. In alkenes two molecules of carbonyl compounds are formed during ozonolysis and in alkyne one molecule of dicarbonyl compound is formed which is further oxidized to two acids.

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Oxidation of Alkenes:
(a) Combustion : The combustion of alkenes is also exothermic with high calorific values and thus used for welding purposes in oxy-ethylene welding. CH2=CH2 + 3O2 CnH2n + (3n/2)O2 (b) 2CO2 + 2H2O; H = ve nCO2 + nH2O; H = ve

Oxidation by Baeyers reagent or hydroxylation : A test for unsaturation Alkenes on passing through dilute alkaline, 1% cold KMnO 4 (i.e. Baeyers reagent) decolorize the pink colour of KMnO 4 and forms dihydroxy compounds (e.g. glycols) CH2 + H2O + [O] CH2
reagent

CH2OH CH2OH ethylene glycol

CH3CH=CH2 + H2O + [O]

CH3CHCH2 OH OH propylene glycol

(c)

Oxidation by alkaline KMnO4 : Oxidation of alkenes by hot alkaline KMnO4 gives two acid salts showing fission of C=C bond RCH=CHR RCOOK + RCOOK

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alk. KMnO 4

(d)

Oxidation by acidic KMnO4 or K2Cr2O7 :

(i)

Oxidation of alkenes by acidic KMnO 4 or K2Cr2O7 gives carboxylic acids. If HCOOH is acid, it is further oxidized to CO2 & H2O. HCCOH + HCOOH
4

CH2=CH2 HCOOH only

acidic KMnO

H2O + CO2 (for

CH3CH = CH2 RCH = CHR R C=C R (ii) (iii) R R

CH3COOH + HCOOH RCOOH + RCOOH R CO R

Same products are obtained if oxidation is made by per iodic acid or lead tetra acetate. The nature of acid formed decides the position of unsaturation in molecule.

Note : Alkenes on oxidation by osmium tetraxide gives an intermediate product which on refluxing with NaHSO 3 (alc.) gives glycols.

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Miscellaneous Reactions shown by alkynes:

1. Isomerization : CH3CH2C CH
but-1-yne Triple bond shifts from corner to centre

CH3C CCH3

NaNH2,
Triple bond shifts from centre to corner

2.

Action of N2 : CH CH + N2 2HCN

3.

Formation of heterolytic compounds : CH + NH3 + CH CH CH N H Pyrrole CH +S+ CH CH

Fe Pyrite

CH

CHCH CH

CH

CHCH CH CH

S Thiophene 4. Nucleophilic addition : Acetylene undergoes nucleophilic addition with CH 3OH in presence of CH3ONa. CH CH + CH3OH CH2=CHOCH3 vinyl mehyl ether CH==CH CH=CH2

CH CH

CH+ = CH

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General Physics AISM-09/C/ALK

H+

H+ OCH3

H+ OCH3

OCH3 5.

OCH3

OCH3

Substitution reaction : Acetylene on passing through sodium hypochlorite solution at 0oC in absence of light shows substitution of H by chlorine atom. (a) Formation of sodium acetylide or alkynides : CH CH
liq. NH3

CH CNa + H2 mono sod. acetylide CH CNa NaC CNa di. sod. acetylide

CH CH + Na

(b)

Formation of Acetylenic Grignard reagent : CH CH + R MgX CH CMgX

(c)

Formation of copper alkynides : on passing alkynes through ammoniacal cuprous chlorides solution, a red precipitate of cuprous alkynide is obtained. CH CH + Cu2CI2 + 2NH4OH CuC CCu + 2NH4CI + 2H2O cuprous acetylide red ppt. 2RC CH + Cu2CI2 + 2NH4OH 2RC CCu + 2NH4CI 2H2O red ppt.

(d)

Formation of silver alkynides : On passing alkynes through ammoniacal silver nitrate solution (Tollens reagent) a white precipitate of silver alkynides is obtained CH CH + 2AgNO3 + 2NH4OH AgC CAg + 2NH4NO3 + 2H2O silver acetylide (while ppt.)

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RC CH + AgNO3 + NH3OH Note : (i) (ii) (iii)

RC CAg + NH4NO3 + H2O

These alkynides are ionic in nature Alkynides are generally explosive and unstable when dry. Copper and silver alkynides are very sensitive to shock when dry & may explode

(iv)

These alkynides are easily converted to original alkynes when treated with dilute acids.

NaC CNa + 2HNO3

HC CH + 2NaNO3

(v)

Acidic nature of alkyne can be utilized to separate, purify and identify alkyne-1 from other hydrocarbons.

Uses : Among alkynes, acetylene has got wide applications in industries. (i) (ii) (iii) (iv) As oxy-acetylene flame for welding. As illuminating agent in hawkers lamps and light houses. In artificial ripening of fruits. In preparation of monomeric unit (vinyl chloride, vinyl cyanide, vinyl cyanide, vinyl acetate, vinyl acetylene, etc.) to get polymers (PVC, PVA, chloroprene, Buna-S etc.) widely used in textile, plastic, shoe and rubber industries. In preparation of poisonous gas, Lewiste. In preparation of solvents such as westron, westrosol and other useful chemicals e.g., C6H6, acetaldehyde, acetone etc. It is used as general anaesthetic under the name Naracylene

(v) (vi) (vii)

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Test for unsaturation

(i) (ii) By Br2 in CCI4 : The decolorization of 5% Br2 in CCI4 by a compound confirms the presence of unsaturation in molecule. By Baeyers reagent : The decolorization of pink colour of 1% cold alkaline KMnO4 by a compound confirms the presence of unsaturation in molecule. Alkenes without any hydrogen atom on olefinic bond do not show these tests e.g. Aldehydes, primary and secondary alcohols which are readily oxidized by alk. KMnO4 and thus decolorize alk. KMnO4

Note : (i) (ii)

To locate the position of unsaturation : By ozonolysis To distinguish (i) (ii) (iii) (iv) Alkane and alkene : By Br2 in CCI4 or By Baeyers reagent Alkane and alkyne : As above Alkene-1 and alkene-2 : By ozonolysis Alkyne-1 and alkyne-2 : By Amm. AgNO4 or Amm. Cu2CI2

To separation a mixture of alkane, alkene and alkyne-1 The mixture is passed through amm. Cu2CI2 or amm. AgNO3 where alkyne-1 are retained in it and alkane, alkene mixture comes out. The mixture is then passed through conc. H2SO4 which absorbs alkene and alkane comes out. RC CH + AgNO3 + NH4OH RC CAg + NH4NO3 + H2O white ppt RC CH
by dil acid Alkyne-1

RCH=CH2 + H2SO4

RCH2CH2
on heating to 170^oC

RCH=CH2
Alkene-1

HSO4

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