ALKYNE

Intro duct ion :

A triple bond gives an alkyne four fewer hydrogen atoms than the corresponding alkane. Therefore, the triple
bond contribute two degree of unsaturation (DU).
Alkynes are not as common in nature as alkenes, but some plants do use alkynes to protect themselves against
disease or predators. Acetylene is by far the most important commercial alkyne. Acetylene is an important
industrial feedstock, but its largest use is as the fuel for the oxyacetylene welding torch.
Str ucture a nd bondi ng i n Alkyne s
(a) Alkynes are hydrocarbons that contain carbon-carbon triple bond.
(b) Alkynes are also called acetylenes because they are derivatives of acetylene
(c) The general formula is : C nH 2n-2. (one triple bond)
(d) In alkyne C C bond length is 1.20
(e) Its bond energy is 192 kcal. mol1
(f) The hybridization of carbon atoms having triple bond (C C) in alkynes is sp.
(g) Overlapping of these sp hybrid orbitals with each other and with the hydrogen orbitals gives the sigma
bond framework which is linear (180) structure.
(h) Two bonds result form overlap of the two remaining unhybridized p orbitals on each carbon atom.these
orbitals overlap at right angles (90) to each other, forming one bond with electron density above
and below the C-C sigma bond, and the other with electron density in front and in back of the sigma
bond. This result in a cylindrical electron cloud around bonded structure.

1.20 1.06
180
H H H C C H

Note : Any type of stereoisomerism does not arise in acetylenic bond due to linearity of C C bond.

IUPAC Nomenclature of Alkyne s :

SN. Compound Name
1. CH CH Ethyne
2. CH 3 C CH Propyne
3. HC C CH 2 CH 3 But-1-yne
4. CH 3 C C CH 3 But-2-yne
CH3 Br
5. CH3CHC CCH2CHCH3 6-Bromo-2-methylhept-3-yne

Isomerism in Alkynes

Typ e Categary Examples

(i) Chain isomerism CH3CH2CH2C CH & CH3CHC CH

CH3

Structural (ii) Positional isomerism CH 3 CH 2CH 2 C CH & CH 3CH 2 CCCH 3

Isomerism

(iii) Functional group isomerism CH 3 CH 2 CCCH 3 & CH 3 CH=C=CHCH 3 &

E x . Cis-trans isomerism is not possible in alkynes because of :-
S o l . 180 bond-angle at the carbon-carbon triple bond.
E x . Draw the geometrical isomers of hept-2-en-5-yne ?
Sol. MeC CCH2 H , MeCCCH2 Me
C= C C= C
H Me H H
(trans) (Cis)

General Met ho ds of Preparat ion :

1. From Gem dihalides ( by dehydrohalogenat ion) : Dehydrohalogenation agents are : NaNH 2 (Sodamide)
or Alc. KOH or ROH + RONa.
H X X
alc. KOH NaNH
R C CH
HX
R C CH
2
RC CH + NaX + NH3

H X H
(Stable by resonance)
(Vinyl halide)
(a) Due to stability of vinyl halide by resonance there is partial double bond in which elimination does not
take place by alc. KOH so stronger base NaNH2 is used.

(b) Basic strength : N H 2 is stronger base then RO
(c) Trans elimination takes place in forming of alkynes.
2. From Vici nal dihalide s (by dehydrohalogenat ion) :
H H H
alc. KOH NaNH 2
R C C H
HX R C C H
HX RC CH
X X X
(a) Elimination of Vic. dihalides gives also alkadiene (1, 2 and 1, 3 alkadienes) but the major product is alkyne.
H H H
NaNH 2
Example : CH C C H CH2 C CH2

H X X
+ CH3C CH
(Major)
(b) Non terminal gem dihalide gives 2-Alkyne in presence of alc. KOH while gives 1-alkyne in presence of
NaNH 2 .

H X H Alc. KOH
CH3 C C CH3 (major)
Example : CH3 C C CH
NaNH2
H X H CH3 CH2 C CH (major)

3. Dehalogenation of tetrahalo alkane : By heating 1, 1, 2, 2 - tetra halo alkane with Zn dust.

X X
2Zn
R C C H RC CH + 2ZnX 2

X X
4. From Kolbe's electrolysis : By the electrolysis of aqueous solution of sodium or potassium fumarate or
maleate, acetylene is formed at anode.

CH COOK CH
Electrolysis +CO2


CH COOK CH
Mechanism :

CH COOK CH COO
lonization

+2K+
CH COOK CH COO
at anode (Alkyl and CO 2 gas is formed)
.
CH COO 2e CH COO

.
CH COO CH COO
(Oxygen free radical)

O
CH . C O.
. CH
2CO2


CH. C O
. . CH

at cathode (KOH and H 2 gas is formed)

2K + + 2e 2K
2K + 2H2O 2KOH + H2
Ex. Is PH of solution changed in Kolbe's electrolysis.
S o l . The concentration of NaOH solution increased so pH of solution is increased with time.
5. Preparat ion of higher alkyne s by Grignard reagent : By this method lower alkyne is converted in to
higher alkyne

C MgBr Br
RI
CH C H CH 3 Mg Br + CH4 Mg + R C CH
CH I

Br
C MgBr
RC CH + CH3MgBr + CH4 R 'I
R' C CR + Mg
C R I

6. Preparat ion of Et hyne or Acet ylene:

(a) From Metal carbide [ Laborator y method] : Acetylene is prepared in the laboratory by the action
of water on calcium carbide.
CaC2 + 2H2O CH CH + Ca(OH)2

Ca+2 + C C + 2H+ + 2OH CH CH + Ca(OH)2
(b) Manufacture : Acetylene is manufactured by heating methane or natural gas at 15000C in an electric arc
2CH 4 Electric arc CH CH + 3H2

(c) Berthelot's process : Acetylene is synthesized by striking an electric arc between carbon electrodes in
presence of hydrogen. 2C + H2 1200 C
CH CH
 (d) From haloform [CHI 3 , CHCl 3 ] : Pure acetylene is obtained when iodoform or chloroform is heated
with Silver powder
CHI3 + 6Ag + I3CH CH CH + 6AgI
(e) Partial oxidation of methane : A recent method for manufacturing of acetylene is the controlled
partial oxidation of methane at high temperature.
1500 C
4CH4 + 3O2 2CH CH + 6H2O

Physical Proper t ie s :
(a) Alkynes are relatively nonopolar (w.r.t. alkyl halides and alcohols) and nearly insoluble in water (but they
are more polar than alkenes and alkanes). They are quite soluble in most organic solvents, (acetone,
ether, emthylene chloride, chloroform and alcohols).
(b) Acetylene, propyne, and the butynes are gases at room temperature, just like the corresponding alkanes
and alkanes. In fact, the boiling points of alkynes are nearly the same as those of alkanes and alkenes
with same number of carbon atoms.
Chemical Proper t ie s :
The chemical properties of alkynes are due to two factors
(a) Presence of electrons : Due to presence of loosely bonded electrons, alkynes like alkenes, undergo
easily electrophilic addition reaction.
Carbon-carbon triple bond is less reactive than the carbon-carbon double bond
towards electrophilic addition reactions.
In addition to electrophilic additons, alkynes also undergo nucleophilic addition with nucleophiles
(b) Presence of acidic hydrogen atom : The hydrogen atom attached to the triple bonded carbon can
be easily removed by a strong base and hence acetylene and 1-alkynes are considered as weak acids.
Explanation : The amounts of s-character in various types of CH bonds is as-
CH CH CH
50% 33% 25%
Since s electrons are closer to the nucleus than the p electrons, the electrons present in a bond having more s-
character will be more closer to nucleus. Due to high s-character of the CH bond in alkyne (s 50%) the
electrons constituting this bond are more strongly held by the carbon nucleus, with the result the H present on
CH can be easily removed as proton.

The acidic nature of the three types of CH bonds as

CH > CH > CH
sp sp2 sp3

Relative acidic order

H2O > ROH > HC CH > HNH2 > CH2 CH2 > CH3CH3

Addition Reaction :
(1) Electrophilic addition : Addition reactions where the addition is initiated by electrophile (positive group).The
characteristic reaction of alkynes is electrophilic addition but the reactivity of alkynes towards electrophilic
addition is less than alkenes because in C C, the electrons are tightly held by carbon nuclei and so they are
less easily available for reaction with electrophiles.

Reactivity order of hydrocarbons for electrophilic addition Alkenes > Alkynes > Alkanes .
Another reasons is : The intermediates when an electrophile attack on alkene and alkynes are :
H
+
H+
(i) RC CR
R C C R
+ +
H
(ii) RCH CHR R CH CH R

H
Stabi lit y of i ntermediate s :

RCH C R < R C H 2 CH R
(+) ve on more EN more stable
atoms is less stable
So we can say that alkenes are more reactive towards electrophilic addition reaction.
(a) Addition of hydrogen : Alkynes reacts with hydrogen in presence of a catalyst.In presence of Pt., Pd
or Ni alkynes give alkanes with H2
Ni, H 2 Ni, H 2
RC CH 300 C RCH
CH 2
300 C R C H 2 C H 3

In presence of Lindlar's catalyst [ Pd / CaCO 3 + quinoline or Nickle boride] alkynes give cis alkene

Lindlar 's catalyst

R R'
RC CR' H2 C C (Stereo specific reaction)
H H
cis - alkene
In presence of Na/NH 3 alkynes give trans-alkene. (Birch Re-cuction)

Na / NH 3
R H
RC CR'
H2 C C (Stereo specific reaction)
H R'
trans-alkene

(b) Addition of Halogens : Reactivity order of Halogens Cl 2 > Br 2 > I 2

Alkynes react with Cl2 or Br2 in dark in presence of metal halide and form di and tetra halo derrivatives.
Cl Cl
2 Cl 2
RC CH
FeCl 3 R C C H
Cl Cl
Mechanism :
Cl 2 + FeCl 3 Cl+ + FeCl 4

Cl
+ [FeCl4]
Cl
R C CH R C CH R C CH R C CH + FeCl3
+
:Cl Cl Cl
.. :

less stable More stable FeCl3 Cl2

(Incomplete octet) (Complete octet)
of (+) ve Catom) of (+) ve Clatom)
(Cyclic cation is intermediate) Cl Cl

R C C H
Cl Cl
(Product)
(Tetrachloride)
 Acetylene tetrachloride is also called as westron.
When westron is treated with Ca(OH)2 then we get westrosol
Cl Cl
CHCl
HCl
H C C H + Ca(OH)2
CCl2
Cl Cl Westrosol or triclene
Both westron and westrosol are used as solvents in cloth industries

React ion w it h di lute Br 2 or bromi ne water:

CH CH + Br2 H2 O Br C H C H B r

H H
CH CH + Br2 liquid Br
C CBr
Br Br

Reaction with Iodine :

ethanol
CH CH + I2 CHI CHI (addition reaction)
NH 3
CH CH + I2 IC CI + NH 4I (substitution reaction)
Di iodoacetylene
(c) Addition of halogen acids (H X) : Addition according to Markowni-Koff's Rule.

Reactivity order of H X : HI > HBr > HCl > HF

X H
H X
RC CH R C C H
X H
(Gem dihalides major product)
Mechanism :
+
H
RC CH
[H X ] R C C H
H
(Intermediate is carbocation)
X

X
R C CH 2
R C CH2
Further
X X
X

H +

R C CH2 R C CH2
R C CH2
H H
(more stable (only I of X)
due to +M of X)
so
X X
X
R C CH3 R C CH3
+
X
(Major Product)
(d) Addition of HOX : Alkynes react with hypohalous acids according to markownikoff's rule and form
gem diol, which are unstable, lose a molecule of water and form halo aldehyde or halo ketones.

Reactivity order HOCl > HOBr > HOI

R C CH + HOCl R C CHCl2
O
Mechanism :
+
Cl
RC CH
[HOCl] R C CH R C CH
+
:Cl Cl
.. :
(Cyclic cation)
OH

OH
R C CH R C CH
+
Cl Cl
Further
OH Cl Cl
Cl
R C CH R C CH + R C CH
Cl OH Cl OH Cl
(more stable due (less + M of Cl - Atom)
to +M of OH group)
so
Cl OH

+ OH H2O
R C CH R C CHCl2 R C CHCl2

OH Cl OH O
(Unstable) (Dichloro ketones)

(e) Addition of BH 3 / THF or B 2 H 6 (Hydroboration) : THF - Tetrahydrofurane is used as solvent.

BH 3
3RC CR
THF (R C C )3B
H R
Since BH3 is not available as monomer so a solvent THF is used for the stability of BH3.

+
H
+

R C C R+ B H
R CH C BH2
H
R
R CH C BH2 + 2R C C R (R CH C )3B
R R
H2O2( OH)
(R C C OH + B(OH)3 R CH2 C R
Basic oxidation
H R O
(enol form) (Ketones)
(R C C )3B
H R R R
H+/ H2O
C C + B(OH)3
H H
(cis-Alkene)
Example :

BH 3 H2O2 / O H
CH3C CCH3
THF (CH3 C C )3B CH3 CH C OH CH3 CH2 C CH3
H CH3 CH3 O
(enol form (keto form
less stable) more stable)

(2) Nucleophilic addition reaction : In these reactions some heavy metal cation like Hg +2, Pb +2, Ba +2 are used.
These cation attracts the e of alkynes and decrease the e density and hence a nucleophile can attack an
alkynes.
(a) Addition of dil. H 2 SO 4 (Hydration) : The addition of water takes place in the presence of Hg +2 and
H2SO 4 [1% HgSO 4+40% H 2SO 4]. In this reaction carbonyl compounds are obtained .

CH CH + HOH CH 2 CH O H

C H 3 C H O
enol unstable
OH H
CH 3C CH + HOH CH3 C CH

CH3 C CH3
O
enol (unstable)
A structure in which OH group is attached to double bond carbon is called as enol (ene + ol).
This reaction is used for preparation of aldehyde and ketone.
dil. H 2 SO 4 (1% )
RC CH
dil. HgSO 4 (40% ) R C CH3
O
Mechanism :
2
Hg
RC CH R C CH R C CH
+2
:Hg+ Hg

+
H O H OH OH
..
H O
.. H + +
H H
R C CH R C CH R C CH R C CH R C CH3
+2 Hg+2
Hg Hg+ Hg+ H O
(enol) (Keto more stable)

OH O
H / H2 O
Example : CH 3 C CCH 3
Hg 2
CH3 C C CH3 CH3 C CH2 CH3
H

2-butanone
(b) Addition of HCN : The addition of HCN in presence of barium cyanide to form vinyl cyanide.
CH Ba(CN )2
CH + HCN CH2
CHCN
The vinyl cyanide is used for making polymers such as orlon and Buna-N rubber.
Polymerisation
CH 2 CHCN ( CH2 CH )n
CN
Orlon
 (c) Addition of acetic acid : Acetate acetylene combines with acetic acid in presence of murcuricsulphate.
It first forms vinyl acetate and then ethylidene acetate.

CH H CH2 CH3
+ Hg 2 CH 3 COOH

CH OOCCH3 CHOOCCH3 CH(OOCCH3)2

vinyl acetate Ethylidene acetate

Polymerisation Hydrolysis
CH2 CHOC CH3 ( CH2 CH )n ( CH2 CH )n + nCHCOOH
3

O O C CH3 OH
Vinyl Acetate O
(Monomer) Poly vinyl acetate Poly vinyl alcohol
(Polymer : adhesive compound)

When ethylidene acetate is heated it give acetaldehyde and acetic anhydride

O
OC CH3 CH3 C
CH3 CH
CH3 CHO +
O O
OC CH3 CH3 C
O O

(d) Addition of alcohols : In presence of BF3 and HgO alkynes react with alcohols and form acetal and ketal

BF3
CH 3 OH OCH3
CH CH + CH3OH HgO CH 2 CHOCH3 CH3 CH
OCH3

Methylal (acetal)

OCH3 OCH3
BF3 CH 3 OH
RC CH + CH3OH
HgO R C CH2 R C CH3
OCH3

Ketal
Acetylene forms acetal while other alkynes form ketal.
(3) Addition of AsCl 3 : In presence of AlCl3 or HgCl2 acetylene combines with AsCl3 to yield Lewisite gas. It is
four times poisonous than mustard gas.

CH CH + ClAsCl2 CH Cl

CHAsCl2

2-Chlorovinyl dichloro arsine (Lewisite gas)

The action of Lewsite may be checked by its antidote BAL (British Anti Lewisite). BAL combines with the
Lewisite to form a cyclic non toxic compound.

SH SH OH
2, 3Dimercapto1propanol [BAL]
CH2 CH CH2
(4) Carbonylation : Reaction of alkynes with CO in presence of Ni(CO) 4

Alkyne + CO + H2O Ni(CO) 4 Olefinic acid

Alkyne + CO + ROH Ni(CO) 4 Olefinic ester

CH CH2
+ CO + H2O Ni(CO) 4

CH CHCOOH

Acrylic acid

CH H CH2
+ CO + Ni(CO) 4

CH O R CHCOOR

Alkyl acrylate
Oxidat ion react ions :
(a) Combustion :

3n 1
CnH2n-2 + O2 nCO2 + (n-1) H 2O + Heat
2

2HC CH + 5O 2 4CO 2 + 2H 2O + 312 K.cal

The combustion of acetylene is used for welding and cutting of metals in which oxy-acetylene flame having high
temp (30000C) is produced.
(b) Oxidation with alkaline KMnO 4 : Oxidation with alkaline KMnO 4 gives carboxylic acids.

CH COOH
+ 4[O] alk.KMnO 4

CH COOH

Acetylene Oxalic acid

CH 3C CH + 4[O] alk.KMnO 4 CH 3 COOH + HCOOH

(c) Oxidation with acidic KMnO 4 or K 2 Cr 2 O 7 : In presence of acidic KMnO 4 or acidic K 2Cr 2O7. Alkynes
are oxidised to monocarboxylic acids.

RC CR' + 2[O] R C H 2 O [O]

C R' RCOOH + R'COOH
O O

CH CHO
+ 2[O] H 2 O [O] 2HCOOH

CH CHO

glyoxal
H 2 O [O]
CH3C CH + 2[O] CH3 C O CH3COOH + HCOOH

CHO

Ex. An alkyne on oxidation with acidic KMnO4, only acetic acid is obtained what is given alkynes ?
S o l . In Oxidation of alkynes two moles of mono carboxylic acids are obtained.

CH3 C OH + HO C CH3 CH 3 C C CH 3
2 Butyne
O O

 (d) Oxidation with selenium dioxide : Selenium dioxide oxidises alkynes to the dicarbonyl compounds.

CH CHO
2[O ]

SeO 2

CH CHO
Glyoxal

CH3 C CH3 CO
2[O ]

SeO 2

CH3 C CH3 CO

2Butyne Butane - 2, 3 -dione

(e) Oxidation with ozone (O 3 ) : In the ozonolysis both sp-C-atoms are converted into C C group.
O O

O
R C C R + O3 R C C R R C C R + H2O2 R C OH+ R C OH

O O O O O O

Ozonide (Addition of ozone) (Acids)

In this reaction H2O2 is oxidant which oxidise R C C R into acids.
O O
But if we use some amount of Zn as reductant with H2O then it reduce H2O2 so oxidation does not take place
H2O2 + Zn ZnO + H2O

(i) O3
CH3 C C H+ H2O2 CH3 C OH + HCOOH
(ii) H2O
O O O
Example : CH3 C CH
(i) O3
CH3 C C H+ ZnO
(ii) H2O/Zn
O O

Subst itut ion React ion : (Format ion of metal lic derivat ive s)

Only 1-alkynes give substitution reaction and show acidic characters C H

Acetylene is dibasic acid where as propyne is monobasic means acetylene can give two H+ where as propyne

can give one H+.

(a) Formation of sodium acetylides : Acetylene and 1-alkynes react with sodamide to form acetylides
NaNH 2 NaNH 2
HC CH NaC C H NaC CNa

Mono sodium Disodium acetylide

acetylide
Dry alkynides are generally unstable and explosive. These are easily converted in to original alkynes when
heated with dilute acids.
NaC CNa + 2HNO3 HC CH + 2NaNO3
This reaction can be used for the purification, seperation and identification of 1-alkynes.
 (b) Formation of copper and silver acetylides : Copper and silver acetylides are obtained by passing
1-alkynes in the ammonical solution of cuprous chloride and silver nitrate (Tollen's reagent) respectivley.
RC CH + Cu2Cl 2 + NH4OH RC CCu + NH4Cl + H2O
ammonical cuprous- copper acetylide
chloride [Red ppt.]
RC CH + AgNO 3 + NH 4OH RC CAg + NH 4NO 3 + H 2O
Tollen's reagent White ppt.
These reactions are used for detecting the presence of acetylenic hydrogen.These are test for distinguish
alkenes and alkynes or 1-alkynes and 2-alkynes.

Isomerisation : When alkyne-1 is heated with alc. KOH alkyne-2 is obtained.

alc. KOH
C H 3 C H 2 C CH
C H 3 C CCH3
1Butyne 2Butyne
When alkyne -2 is heated with NaNH2 alkyne -1 is obtained
NaNH 2
C H 3 C CCH3
C H 3 C H 2 C CH
2Butyne 1Butyne

Polymerisation :
(a) Linear polymerisation :
Dimerisation : When two molecules of acetylene passed through a solution of Cu 2Cl 2 and NH 4Cl a
vinyl acetylene is obtained.
Cu2 Cl2
2HC CH
NH 4 Cl CH 2 CHC CH
mono vinyl acetylene
When vinyl acetylene react with HCl then chloroprene is obtained.
HCl
CH 2 CHC CH CH2 Polymerisation
CH C CH2 Neoprene
prene (Synthetic rubber)

Cl
2- chloro-1,3-butadiene
[chloroprene]
Trimerisation : 3 molecules of acetylene.
Cu2 Cl2
3CH CH
NH 4 Cl CH 2 CHC CCH CH 2
Divinyl acetylene
(b) Cyclic polymerisation : When alkyne is passed through red hot metallic tube, cyclic polymerisation
takes place with the formation of aromatic compound
Re d hot
3CH CH
iron tube

Benzene
CH3
Re d hot
3 CH 3 C CH
iron tube

H3C CH3
Mesitylene
CH3
CH3 CH3
Re d hot
3 CH 3 C CCH 3
iron tube
CH3 CH3
CH3
Hexa methyl benzene
 Ni(CO )4
3 HC CH
( C 6 H 5 )3 P

benzene (90% yield)
(triphenyl1phosphene)

CH CH
HC CH
4CH CH Ni(CN )2
HC CH
CH CH
1,3,5,7cyclooctatetraene
Ot her react ions of acet ylene :

NH3
2HCN
Electric spark

NH3
HC CH CH CH
High temp.
CH.. CH
N

H Pyrole

HCN
Red hot Fe ..
N Pyridine
CH2
CH2N2, CH N
CH
2 2
CH N CHCH
N2 2

CH2 CH2
Cyclo propene Bicyclo (1,1,0) butane

CH2N2
CH CH CH2 CH
cold ether solution H2

CH N CH2 N
.. ..
NH NH
Pyrazoline
S
CH CH
Al2O3, 400C

CH CH
..
S
..
Thiophene

(vi) Reaction with HCHO : This reaction is called ethynylation.

OH OH
CH Cu
CH + HCHO HCHO
HC CCH 2OH CH2 C C CH2
propargyl alcohol
(vii) React ion w it h NaOCl : (Subst itut ion react ion)
0C
H C CH + NaOCl
absence of air and light
HC CCl + NaOH

0C
HC CCl + NaOCl
absence of air and light
ClC CCl + NaOH
Dichloro acetylene
 Uses of Acetylene :
(i) Oxyacetylene flame used in welding and cutting
(ii) Acetylene is used as an illuminant
(iii) Acetylene is used for artificial ripenning of fruits
(iv) Used for manufacture of acetaldehyde, acetic acid, ethyl alcohol, westron, westrosol, PVC, PVA,
Chloroprene, butadiene, Lewisite etc.
(v) It is used as a general anaesthetic.

L aborator y Te st for alkyne s :

Functional Reagent Observation Reaction Remarks

Group
alk.KMnO 4
(1) Bayer's Pink Colour CH 2 =CH 2 +H 2 O+O
Reagent disappears CH2CH2 Hydroxylation
alk.dil.Cold KMnO 4 OH OH

CC (2) Br 2/H 2O Red Colour CH2CH2

decolourises Br 2+CH 2=CH 2 Br Br Bromination
White ppt

O3
(3) O3 (ozone) Acid Formed RCCR' RCOOH+R'COOH Ozonolysis

L aborator y te st of termi nal alkyne s :

When triple bond comes at the end of a carbon chain. The alkyne is called a terminal alkyne.

acetylenic hydrogen

H C CCH2CH3
1-Butyne, a terminal alkyne

Funct ional Group Reagent Observation Reaction

(1) Cuprous chloride Red ppt. RCCH+CuCl NH4OH

RC C Cu (red)
+ NH4OH

RCCH (2) AgNO 3 +NH 4 OH White ppt. RCCH+Ag' RC C Ag (white)

(3) Na in ether Colourless gas HC CH + 2Na Na C C Na + H2

(i) Decolourization of Br2 in CCl4 solution.

(ii) Decolourisation of 1% alkaline KMnO 4 solution.
(iii) 1- alkynes give white ppt. with ammonical AgNO 3 and red ppt with ammonical cuprous chloride
solution.
Note : (i) and (ii) tests are used for determination of unsaturation (i.e, presence of double or triple bond in any
compound)
(iii) Test is used for distinguish between alkenes and 1-alkynes or 1-alkyne and 2-alkyne.

Seperation of ethane, ethene and ethyne :

[C2H2 + C2H4 + C2H6]

Passed through ammonical Cu2Cl2

red ppt Gaseous mixture

CuC CCu (C2H6 + C2H4)
KCN solution conc. H2SO4

Ethyne
Ethyl sulphate Ethane (Gas)

Ethene
 SOLVED EXA MPLES

Ex. RCH 2CCl 2R RC CR. The reagent is -

Re agent

(A) Na (B) HCl in H2O (C) KOH in C2H5OH (D) Zn in alcohol.
Ans.(C)
Sol. Alcoholic KOH brings about dehyrohalogenation
Ex. Acetylene when treated with dilute HCl at 600C (333 K) in presence of HgCl2 produces -
(A) Methyl chloride (B) Vinyl chloride (C) Acetaldehyde (D) Formaldehyde
Ans.(B)
HgCl2
Sol. (B) HC C H + HCl
60
CH2 = CH Cl

Vinyl chloride
Ex. When propyne is treated with aqueous H2SO4 in the presence of HgSO4, the major product is -
(A) Acetaldehyde (B) Propanal (C) 2-Propanol (D) Propanone Ans.(D)

Sol. CH3 C CH + H2O CH3 C CH2 CH3 C CH3

OH O
Ex. Alkaline KMnO4, oxidizes acetylene to -
(A) Acetic acid (B) Glyoxal (C) Oxalic acid (D) Ethylene glycol
Ans.(C)

COOH
Sol. H C C H + 4[O]
COOH

Ex. Which of the following is most acidic -

(A) Ethyne (B) Propyne (C) 1-Butyne (D) 2-Butyne Ans.(A)
Sol. Because ethyne gives most stable anion.
Ex. Ozonolysis of acetylene gives -
(A) Oxalic acid (B) Ethylene glycol (C) Glyoxal (D) CH 3CHO Ans.(C)

(i)O3
Sol. HC CH
(ii) H2 O / Zn
H C C H
O O
Glyoxal

Ex. Propyne on reaction with aqueous chlorine gives -

(A) 1, 1, 2, 2-Tetrachloropropane (B) 1, 2-Dichloropropene
(C) 1, 1-Dichloropropanone (D) 2, 2-Dichloropropanone Ans.(C)

OH
O
Sol. CH3C CH + 2HOCl CH3 C CHCl2 H2 O
CH3CCHCl2
OH

Ex. Mesitylene can be obtained by polymerization of -

(A) Ethyne (B) Ethene (C) Propene (D) Propyne Ans.(D)
 H3C CH3
Sol. Propyne on trimerization yields mesitylene 3CH3C CH

CH3
Mesitylene

Ex. Excess of CH3COOH is reacted with CH CH in presence of Hg2+, the product is -

(A) CH 3 CH(OOCCH 3) 2 (B) CH 2 = CH(OOCCH 3 )
(C) (CH 3 COO)CH 2 CH 2 (OOCCH 3 ) (D) None of these
Ans.(A)

Sol. HC CH + 2CH3COOH
CH3 CH(OCOCH3) 2
Both the protons go to same carbon atom
Ex. A compound is treated with NaNH2 to give sodium salt. Identify the compound -
(A) C 2H 2 (B) C6H6 (C) C2H6 (D) C 2H 4
Ans.(A)
Sol. Ethyne is acidic in character

1
HC CH + NaNH2
H C CNa+ + H
2 2