ALKYNE

Total No.of questions in Alkyne are -

In Chapter Examples.............................................................. 16
Solved Examples ................................................................... 36

Total No. of questions .......................................................... 52

 2.2 From Vicinal Dihalides
1. GENERAL INTRODUCTION
(Dehydrohalogenation) :
(a) These are the acyclic hydrocarbons which
contains carbon-carbon triple bond are called
alkyne. + Alc. KOH  

HX
(b) Hybridisation state of triply bonded carbon in
alkyne is sp or also called as diagonal
hybridisation.
NaNH
 2
(c) Geometry of carbon is linear in alkynes. R– C  C–H
 HX
(d) Bond angle in alkyne is 180º.
(e) Their general formula is CnH2n–2 Note : In the above reaction if the reactant
secondary butylene chloride is taken then the
(f) C – C triple bond length is 1.20 Å.
products are 2-butyne, 1, 2-butadiene and
(g) C – H bond length is 1.08 Å. 1, 3- butadiene in which 2-butyne is the chief
(h) C – C triple bond energy is 190 kcal./mol. product.
(i) C – H bond energy is 102.38 kcal./mol. 2.3 From Tetrahaloalkanes (Dehalogenation) :
(j) Alkyne shows chain, position and functional
isomerism. They are functional isomer with 
cycloalkene and alkadiene. + Zn(dust)  

300ºC
(i) C1 – C 4 compound do not show chain
isomerism.

  R – C  C–H
(ii) Functional isomer of C4H6 Zn dust
eg In the above reaction it is necessary that the four
CH3 – CH2 – C CH CH3 – CH=C = CH2 halogen atoms must be attached at vicinal
1 - Butyne 1,2 -Butadiene carbons. If they are attached at the two ends
then the product cyclo alkene is obtained.
CH2 = CH –CH = CH2 2.4 From Kolbe's Synthesis :

1,3-Butadiene Cyclobutene O O
||  || 

HCC O K H C C O
2. METHODS OF PREPARATION ||  + 2K+
||  
2.1 From Gem Dihalides (Dehydrohalogenation) : HCC O K H C C O
|| ||
O O
H X
| |
R  C  C  H + alc. KOH.   Potassium Malaete
| | HX At Anode :
H X
X
| NaNH
2
R  CH  C  H    R– C C– H
HX – 2e – 
Note:Alc.KOH is not used for elimination in
second step because in this case elimination
takes place from doubly bonded carbon atom H–C
which is stable due to resonance so strong base 
 ||| + 2CO
H–C
2 A
NaNH2 is used for elimination of HX.
At Cathode :
2K+ + 2e–  2K•
2K• + 2H2O  2KOH + H2 A
2.5 Laboratory method of preparation of
Acetylene : Methods of Preparation of alkyne
(a) In laboratory acetylene is prepared by
hydrolysis of calcium carbide. Ex.1 On dehydrohalogenation of isopropylidene
chloride the product would be -
(A) Propyne
(B) Propyne+ Isopropyne
(C) Allene + Allyliene
  + (D) Propyne + 2, 3 - dimethyl-2- butene
(Ans.C)
(b) It can also be prepared from CHCl3 with Ag
dust.
alc.KOH
Sol.  
HCl

NaNH2
  H–C  C – H    CH –C  CH
 AgCl HCl
3
Allyliene
2.6 From Alkynes : (To form higher Alkynes)
2.6.1 With Na : When acetylene or 1- alkyne react
with Na in presence of liq. NH 3 then an
intermediate compound sodium acetylide or
sodium alkynide is formed which gives higher alc.KOH
 
alkyne with alkyl halide. HCl
liq.NH3 
2H – C  C – H + 2 Na    2 H – C  C Na
H
2
NaNH2
X –R    CH = C=CH
   H – C  C – R 2 2
HCl
liqNH
. 3 
2R – C C – H + 2Na  
H2
 2R – C C Na
X –R Ex.2 What is the chief product of reaction between
  R – C C –R -butylene chloride and alc. KOH/NaNH2
2.6.2 With GR : When acetyline or 1- alkyne react (A) 1,2-butadiene (B) 1,3-butadiene
with GR then alkane and unsaturated GR is (C) 2-butyne (D) 1-butyne
formed which further react with alkyl halide and (Ans.C)
form higher alkyne. Sol. 2-butyne is the chief product according to
Saytzeff's rule -
H –C CH + R – Mg-X    H  C – MgX
 RH
acetylene Ex.3 Acetylene magnesium chloride is react with
XR ethyl bromide, what will be the product -
  H – C  C – R
 MgX 2 (A) 1-butyne (B) 2-butyne
R– C  C–H + R – Mg – X    (C) 1,2-butadiene (D) 1,3-butadiene
 RH (Ans.A)
R X Sol. This is the method of preparation of higher
R –C  C – MgX   R–C  C–R' alkyne.
HC  C - MgCl + C2H5 Br 
HCC–C2H5 + Mg (Cl) Br
Ex.4 When sodium fumarate is electrolysed, which 4. CHEMICAL PROPERTIES
alkyne is formed at anode -
Like alkene, alkyne also shows electrophilic
(A) propyne (B) butyne addition reaction but alkynes are less reactive
(C) Ethyne (D) None towards electrophilic addition than alkene.
(Ans.C) Of course alkyne is more reactive towards
Sol. In Kolbe's synthesis, sodium or potassium hydrogenations as it is expected due to greater
salt of maleic acid or fumaric acid on unsaturacy. Lower reactivity of alkyne towards
electrolysis gives acetylene or ethyne at electophilic addition probably caused by greter
anode. activation energy due to less stable intermediate

Ex.5 Chloroform is heated with Ag powder in

laboratory what will be the product - E
(i) –CC –  

(1) Acetylene (2) Ag2O
Less stable due to
(C) CH2Cl 2 (D) CH4
(Ans.A) shorter – C =C – bond


 E
Sol. 6 AgCl (ii) C C 

HC  CH More stable due to longer

acetylene
5. CHEMICAL REACTIONS

5.1 With Hydrogen :

3. PHYSICAL PROPERTIES

(a) Alkynes are colourless, odourless and tasteless. H

Ni, Pd, Pt |
(b) Lower alkynes are partially soluble in H 2O. R–CC –H + H2   R  C  CH
High Temp. |
(It is due to its polarisibility).
H
(c) Higher alkynes are insoluble in water due to more
H H
% of covalent character. | |
(d) Completely soluble in organic solvents.  R  C  C  H

| |
(e) Melting point and boiling point increases with H H
molecular mass and decreases with number of The above reaction is called as Sabatier
branches. Senderson's reaction.
(f) Upto C4 alkynes are gaseous.C5–C11 are liquid, 5.1.1 Hydrogenation in the presence of lindelar's
C12 & above are solids. Catalyst :
(g) Pure acetylene is odourless and impure acetylene Addition up to alkene takes place in cis manner.
has odour like garlic. It is due to impurities of
Arsene (AsH3) & Phosphine (PH3). PdBaSO
4
(i) H–CC–H + H2  

(h) Acetylene & 1- alkyne are acidic in nature. It is
due to greater electronegativity of sp hybridised (ii) CH3 –C C – CH3 + H2
'C'.
(i) Acetylene has two acidic hydrogen atoms. It can PdBaSO4
  
neutralise two equivalents of base at the same
time. So it is also called as dibasic acid. But
the base should be very stronger as – NH2 or
– CH etc.
3
5.1.2 Hydrogenation by Na + NH3 (liq.) :
Addition upto alkene takes place in trans manner X
HX |
  R  C  CH3
Na
(i) CHCH    |
NH3 (liq.) X
gem dihalide
(ii) R–CC –R Na /NH3liq.
  Mechanism : The reaction takes place in the
Mechanism : presence of Hg2+ ion.

Hg2+
NaNH3
R – C  C – R    Hg2 HX
–
e /  Na R –C C – R   R– C C –R

R Hg H R H
C= C  2
 C=C
2 NH2 H X  Hg
Na/NH3     R X R
   
e  2 NH2

HX
 

5.1.3 Hydrogenation by LiAlH4 :-

Note :- (i) First step is faster than the second
Addition upto alkene takes place in trans manner step among addition of two HX on alkyne.
by LiAlH4 also.
X H
LiAlH4 HX / Hg2 | |
R – CC–R    R – C  CH    R — C — CH
Faster
5.1.4 Reduction with the help of B2H6 : X H
2 | |
Alkyne is first reacted with B2H6 and is follwed HX / Hg
   R — C — C — H
by acidic hydrolysis, cis alkene is obtained. slower | |
X H
1. B2H6 Slower rate of addition of 2nd molecule is caused
R–CC–R   

2.H2O / H by lower electron cloud density on C = C, due to
5.2 Halogenation : – I effect of 'Cl'.
In presence of Lewis acid as a catalyst alkyne (ii) peroxide give same effect as in alkene
form tetrahaloderivative with halogen. H Br
HBr | | HBr
FeX 3 R–CCH    R — C — CH  
Peroxide

Peroxide
R–C  C–H + X–X   
X  F,ClBr
,

X X X H Br
| | | | |
R  C  C  H x 
2  R C  C H R—C —C —H
| | | | |
X X X H Br
5.3 Reaction with HX/Hydrohalogenation: 5.4 Reaction with Hypochlorous acid or
Chlorine water :
Alkyne form gem dihalide with HX because
reaction follows markownikoff's Ist and IInd rule Hypochlorous acid is broken into OH Cl&
both. ions & give addb. according to markonicoff's
X rule.
| OH
R – C  C – H + H – X     R  C  CH2
2 |
Hg
RC RC
  ||   
||| + HO  Cl  H O  Cl
H C H  C  
|
Cl
 olefinic ether
OH O  R'
| RC O
| |
R  C  OH R  C  O  R'
  H  C  Cl
|  H2O |
H  C  Cl | 
 

Cl H OR HC H
| |
Cl H
unstable
acetal / ketal
5.7 Addition of carboxylic acid :
5.5 Hydration :
In the presence of Hg2+ unioxylation of carboxylic
Addition of water takes place in the presence acid takes place.
of Hg2+ (HgSO 4 + H2SO 4)
O
H OH ||
Hg2 | | H–C  C – H + H – O – C – CH3
(i) R—CC—H H  OH
 R— C = C — R O
Hg2 ||
unstable  CH2 = CH – O – C – CH3
 
O
||
                       R—CH2 — C — R 5.8 Hydroboration :
HO H Carboxyl compound is obtained by hydroboration
Hg2 | | followed by treatment with
(ii) R – C  C – H H  R – C  CH
 OH H
B2H6 R
unstable R—C CH     C =C
O H–BH2 H BH2
||
                                R– C –CH3 syn addition
Mechanism : O —H O
Hg+ | ||
H2O 2 R – CH = CH  R–CH – C –H
  2
Hg2
R–CCH   R– C CR  —H
:O 5.9 Addition of HCN :
|
H Addition takes place in the presence of CuCl
CuCl
Hg H – C  C – H + H – CN   CH2 = CH – CN
|
770º
 H
  R — C — CH
5.10 Addition of AsCl3 :
|
OH Lewisite is obtained
H
| R– CC – H R—C  C—H
H | |
 R — C — C — H  R– C – CH3

| || Cl AsCl2
OH O
Lewisite
unstable
5.6 Addition of alcohol 5.11 Oxidation :
O  R' 5.11.1 With acidic or alkaline KMnO4 alkyne break
| into two parts from triply bonded carbon and every
RC
|| part forms respective acid.
RC  
   C H
||| + H O  R NaO —R R – CC –H + [O]  Acidic / Alk.KMnO 4
 
H C |
H R  C  OH + H  C  OH
|| ||
O O

H–CC–H + [O]  Acidic


KMnO4

 2H  C  OH   2R–C  CNa
NH3
||
O H– C C – H + Na  NaC CNa
CH3 – C C – H + [O]  Acidic / Alk.KMnO 4
 
disodium acetylide
Note : Where this alkynide is treat with alkyl
CH3  C  OH + H  C  OH halide higher alkyne is obtained.
|| ||
O O R–CCNa + X–R  R–CC–R' + NaX
Na – C  CNa + 2R – X  R'C  C – R' + 2NaX
CH3 –CC–CH3 + [O]  Acidic / Alk.KMnO 4
 
5.12.2 Reaction with Ammonical Silver Nitrate
2CH3  C  OH solution : (Tollen's Reagent)
||
O 2R – C C – H + AgNO3 + NH4OH
Exception : Acetylene forms oxalic acid with
  2R–CCAg
alkaline KMnO4 exceptionally.  H2O
COOH silver alkynide (white ppt)
H –C C–H + [O]  Alk .KMnO4
  |
COOH H–C C – H + AgNO3 + NH4OH
5.11.2 Oxidation with Ozone:   AgC  CAg
 H2O
O
||
silver acetylide (white ppt)
 R–C–C–H
R–C C –H + O3 
| |
O O 5.12.3 Reaction with Ammoniacal Cuprous
Ozonide Chloride solution :
HOH, Zndust
  R C  C H 2R – C C – H + Cu2Cl 2 + NH4OH
|| ||
O O   2R– CCCu
 2HCl
R  C  C  H + H2O2 

|| || cuprous alkynide (red ppt.)
O O H –CC – H + Cu2Cl 2 + NH4OH
R  C  OH + HO  C  H    CuC   CCu
|| ||  2 HCl
O O
dicuprous acetylide (red ppt.)
5.12 Acidic nature of 1- Alkyne or Acetylene
5.12.4 Reaction with NaOCl :
In 1- alkyne or acetylene, the H which is linked
with sp hybridised carbon is called as acidic or Acidic hydrogen is substituted by 'Cl'
active H. It can easily be substituted by metal or
alkaline species. Hence 1- alkyne or acetylene (i) H – CC–H NaOCl
 Cl – CC– Cl
are acidic in nature. eg.
5.12.1 Reaction with Na : (ii) R – CC–H NaOCl
 R– C C–Cl
2R – CC–H + Na Mechanism :
LiqNH
. 3
   2R – C  CNa
 H2

sodium alkynide
OR
2R – C C – H + NaNH2
R–C  R – CC–Cl
 Note : These (5.12.2) and (5.12.3) both reactions mesitylene (having 3-1º, 3-2º & 3-3º carbons)
are used in the test of terminal alkynyl hydrogen. Important : Mesitylene can also be obtained
These ppt or metal acetylide or alkynide are f rom acetone by condensation
polymerisation.
insoluble in solution and in dry condication
(c) Tetramerisation : According to the name
explode, therefore they are destroyed with HNO3
four moles of acetylene are heated with nickel
before dryness (they form same compound again)
tetra cyanide, then acetylene forms a cyclic
5.13 Polymerisation Reactions : Alkyne mainly tetramer cyclo octa tetraene.
shows addition polymerisation reactions.
5.13.1 Dimerisation and Cyclysation CH  CH
(a) Dimerisation : CH CH
Two mole acetylene reacts with Cu2Cl 2 & ||| |||
CH CH
NH4Cl and forms vinyl acetylene. CH  CH
Note : If acetylene would be in excess then
product would be divinyl acetylene and the CH=CH
reaction is called trimerisation. CH CH
H Ni(CN)4
|   CH CH
H  C  C + H–C  C–H H H CH=CH
| |
Cu2Cl2  NH4Cl H  C  C  C  C  H
   cyclooctatetraene
vinyl acetylene or butenyne (Nonaromatic)
H H H 5.13.2 Coupling:-
| | |
H C  C  C  C H + C  C H (a) Alkyne form respective cuprous alkynide with
H H H H ammonical cuprous chloride solution. When
| | | | cuprous alkynide is reacted with pottasium
           H  C  C  C  C  C  C  H
divinyl acetylene ferri cyanide [K3Fe(CN)6] they converted into
(b) Trimerisation : conjugated diyne.
If three mole of acetylene is passed into red
hot iron or Cu or quartz tube, then a cyclic R – C  CH + Cu (NH3)2Cl  R–C C.Cu
trimer is formed which is called benzene. cuprous alkynide
CH
CH 2R – C C.Cu O
2  R–CC– CC–R
CH Re d hot Fe / Cu / Quartz

  diyne
CH Co(CO)8  Br2
CH

(Octa Carbonyl cobalt (b) Coupling is also done easily by 1-alkyne in

CH

with bromine) the presence of Cu2Cl 2 (cuprous compound)

and amine (ie. pyridine + air) cuprous
alkynide is formed (this coupling is known as
oxidative coupling or glaser coupling)

benzene 1 Cu2Cl2 /NH3

2R – C  CH + O   
2 2
CH3
| CH3 R – C C – C  C – R + H2O
|
CH C
||| \\\ C 2 CH3 – CCH + ½ O2  Cu2Cl2 /NH
3

CH3  C CH CH CH
CH3 – C C– C  C – CH3 + H2O
C  CH3 
 CH3 –C C– CH3
/// 2,4–Hexadiyne.
CH
HC
5.14 Formation of heterocyclic compounds :
Chemical reactions of alkyne

Ex.6 What happens when 2- butyne reacts with

CH CH Al2O3 H2 in presence of LiAlH4 -
(a) ||| + NH3 + |||   
CH CH  (A) CH3  C  H
||
CH3  C  H

Pyrrole (B) CH3  C  H

||
H  C  CH3
CH CH Al2O3 (C) CH3 – CH2– CH2– CH3
(b) ||| + + |||  
CH CH  (D) CH2  CH Ans.[B]
|
Thiophene CH  CH2

5.15 Reaction with Formaldehyde Sol. 2-butyne mainly forms trans-2-butene on

hydrogenation with LiAlH4.
1– Alkyne in the presence of copper react with
methanal to form alkynol. Ex.7 What happens when 2- butyne reacts with
H Na + Liq. NH3
|
H  C  C + CH2 = O 
 CH  C – CH2OH (A) CH3  C  H
||
CH3  C  H
prop-2-yne-1-ol
Note : Acetylene react with two mole of HCHO (B) CH3  C  H
||
(methanal) to give 2–butyne–1,4–diol. This H  C  CH3
reaction is used in the formation of 1,3 butadine. (C) CH3 – CH2– CH2– CH3
Which is used in the formation of buna rubber. (D) CH2  CH Ans.[D]
|
5.16 Isomerisation :– CH  CH2
(a) When 1-alkyne is treated with alcoholic KOH Sol. Reaction is called as 'Birch- Reduction'.
2-alkyne is formed.
Ex.8 What happens when 2- butyne reacts with
Alco.KOH H2 in presence of Nickle Boride or lindlar's
R–CH2–CCH    R–C  C – CH3
 catalyst (Pd/CaCO3–PbO) -
(A) CH3  C  H
1 – alkyne 2 – alkyne ||
CH3  C  H
(b) When 2-alkyne is treated with sodamide then
it is converted into 1-alkyne. (B) CH  C  H
3
||
NaNH2 H  C  CH3
CH3 –C C – CH3   
NH3
(C) CH3 – CH2– CH2– CH3
 H2O
CH3 –CH2 –CCNa    CH3 –CH2 –CCH
NaOH (D) CH2  CH Ans.[A]
|
CH  CH2
Sol. 2-butyne forms cis-2-butene with lindlar's
OH
catalyst. |
H C   HC
||| + HO  Cl  ||
 
HO  Cl
Ex.9 Write down the products when propyne reacts H C H  C  
|
with HBr in the following conditions given in Cl
the sketch below-
OH
A B | H C  O
Peroxide
CH3 – C  CH + HBr 
 C D H  C  OH |
Peroxide |  H  C  Cl
E F H  C  Cl H2 O |
| Cl
Cl

Br Ex.11 CH3 - C  CH + dil. H2SO 4 (Hg+2)  X,

| what is the 'X'
Sol. A = CH3  C  C  H (A) Acetal (B) Acetone
|
H (C) Butanone
(D) Propeledine hydrogen sulphate
Ans.[B]
Br
Sol. In dil H2SO 4 alkyne is hydrolyses to form
|
B = CH3  C  CH3 ketone here acetone will be the main product.
|
Br Ex.12 Product formed by the oxidation of acetylene
in the presence of alkaline KMnO4
C = CH3  C  C  H (A) Glyoxal (B) Oxyrane
| | (C) CO2 + H2O (D) Oxalic acid
H Br Ans.[D]
Sol. This is the exceptional case of oxidation in
H Br which triple bonded carbon is not separated.
| | The product is oxalic acid.
D = CH3  C  C  H
| |
H Br Ex.13 Terminal alkynyl hydrogen is tested by
reacting it with -
Br (A) Ammoniacal cuprous chloride
| (B) Ammoniacal silver nitrate
E = CH3  C  C  H (C) Both of the above
| (D) None of these Ans.[C]
H
Sol. Terminal hydrogen is acidic therefore with
Br H ammonical cuprous chloride and ammoniacal
| | silver nitrate respectively precipitate is formed
F = CH3  C  C  H (Red and white)
| |
H Br
Ex.14 When acetylene and sulphur react in the
Ex.10 What will be the product of chlorine water presence of hot iron pyrite, product formed -
and acetylene - (A) Pyrrole (B) Benzene
(A) Dichloro propanol (B) Dichloroethanal (C) Toluene (D) Thiophene
(C) Propanol (D) 2-Chloro ethanol Ans.[D]
Ans.[B]
Sol. In the presence of hot iron pyrite thiophene
Sol. Chlorine water (HO O  Cl ) when react with is formed as a product when NH3 is taken at
the place of sulphur pyrrole is formed.
acetylene dichloro ethanal is formed
Ex.15 The product of reaction between one mole of (7) Alkyne with organic acid alkylidine acetate is
acetylene and two mole of HCHO in the formed in the presence of Hg2+ ion.
presence of Cu is -
(8) Ethyne is used in oxy-acetylene f lame
(A) HOCH2 - C  C - CH2OH
(B) H2C = CH - C  C - CH2OH (2800-3200ºC) for cutting and welding of metal.
(C) HC  C - CH2OH (9) Ethyne is used in carbide lamps for lightning
(D) None of these Ans.[A]
(is a illuminating agent in hawker's lamp)

Sol. CH2=O + H-CC-H + CH2=O  Cu (10) When hydrogen is passed in atmosphere of


electric arc between. carbon electrode, a mixture
HOCH2-CC-CH2OH
2-butyne-1,4 diol. of H2 & ethyne is formed (Berthelot Method).
(11) Mixture of ethyne and nitrogen in electric spark
Ex.16 PMMA polymer is formed by methyl acrylate, converted into HCN .
which is prepared as follows - (12) Ethyne burns with sooty flame due to presence
CO  ROH of high % of carbon.
(A) R - C  CH   
(13) Acetylene is used in artificial ripening of fruits.
CO  CH OH
3 
(B) HC  CH Ni
 
(CO) 4

CO  H O
2
(C) HC  CH   
Ni(CO )4

(D) None of these Ans.[B]

Sol. By carbonylation of acetylene by
(CO + CH3OH) in the presence of Ni (CO)4
gives methyl propenoate which is known as
methyl acrylate.

6. IMPORTANT – POINTS

(1) Alkyne with conc. H2SO 4, alkyledene hydrogen

sulphate is formed.
(2) Alkyne with dil. H2SO 4 and Hg+2, carbonyl
compound is formed.
(3) With hypohalous acid dihalo carbonyls is formed.
With ethyne dihalo aldehyde & with other alkynes
dihalo ketones are formed.
(4) With aqueous solution of sodium hypochlorite
(NaOCl) acidic hydrogen of 1-alkyne is substituted
by Cl (subtitution reaction)
(5) Product formed by reaction of 1-alkyne and dialkyl
borane, when treated with (H 2O 2 / NaOH)
(oxidation)– carbonyl compound is formed.
When treated with 3CH3COOH - alkene is formed.
(6) Alkyne f orm bicyclo compound with
diazomethane in the presence of sunlight.
 SOLVED EXAMPLES
Ex.1 The triple bonded carbon atoms –
(a) Are sp hybridised CH3–CH2– –CC– –CH2–CH3
(b) Are sp3 hybridised       CH3–CH2–CC–CH2–CH3
(c) Forms three sigma bonds and one pi bond
(d) Forms two pi bonds and two sigma bonds Ex.5 Acetylene can be prepared from –
The correct answer is – (A) Potassium fumarate
(A) a, c (B) a, d (B) Calcium carbide
(C) a, b (D) b, d (C) Ethylene bromide
Ans. (B) (D) All Ans. (D)

Sol. H – C  C – H each carbon is sp hybridised Sol. These are methods of preparation of C2H2.
& forms 2 & 2 bonds. Potassium fumerate on electrolysis, CaC2 on
hydrolysis and ethylene bromide on
elimination gives acetylene.
Ex.2 In the given reaction
CH3 – C  C – CH3 Na/NH ( ) Ex.6 Which of the following acid is dibasic –
 3  [X]
(A) CH3–CH =CH–CH3 (B) (CH3)2C=CH2
[X] will be -
(C) CH3–CCH (D) CHCH
(A) Butane (B) trans-2-butene
Ans. (D)
(C) cis-2-butene (D) 1-Butene
(Ans. B) Sol. Acetylene contains two active hydrogen
Ex.3 Ethylene dibromide on treating with alcoholic atoms.
KOH gives –
(A) C2H6 (B) CH4 Ex.7 Order of acidity of H2O, NH3 and acetylene
(C) C2H4 (D) C2H2 is –
Ans. (D) (A) NH3 > CH  CH > H2O
Sol. Alkynes can be prepared by (B) H2O > NH3 > HC  CH
dehydrohalogenation of alkyl dihalides (C) H2O > HC  CH > NH3
KOH alc. CHBr (D) NH3 > H2O > HC  CH Ans. (C)
CH2Br  

| KBr
||
CH2Br H2 O CH2 Sol. The order of acidity of H 2 O, NH 3 and
acetylene depends upon the relative basicity
Ethylene dibromide Vinylbromide
of OH¯, NH2¯ and HC  C¯ the decreasing
KOH alc. CH nature of basic character is
 

KBr ||| NH2¯>HC C¯ > OH¯, hence the decreasing
H2 O CH
order of acidity is H2O > HC  CH > NH3.
Acetylene
Vinyl bromide being less reactive and thus to Ex.8 Alkynes can be reduced to alkenes by
get better yield a stronger base NaNH2 is hydrogenation in presence of –
used in second step. (A) Raney Ni (B) Anhy. AlCl 3
Ex.4 Reaction (C) Pd (D) Lindlar's catalyst
Ans. (D)
CH3CH2Br + A  CH3CH2–CC–CH2– CH3
here the compound. A will be – Lindlar
Sol. CH  CH Catalyst
 CH = CH . Lindlar
2 2
(A) CH3 COOAg (B) CH = CNa
(C) NaC = CNa (D) C2H5ONa catalyst prevents further reduction of ethene
Ans. (C) to ethane.
Sol.
Ex.9 Westrosol has the following formula –
(A) CH3 CH2 CH  Br
|
Cl Br
|
(A) H  C  Cl (B) H  C  Cl (B) CH2  CH2  CH2
|| | | |
H  C  Cl H  C  Cl Br Br
|
Cl (C) CH3 CH  Br
|
(C) Cl  C  Cl (D) Cl  C  Cl CH2Br
|| ||
Cl  C  Cl H  C  Cl (D) All above Ans. (C)
Ans.(D) Sol. The product formed by the addition of HBr to
propyne in the presence of H 2 O 2 is
Sol. Acetylene adds up two molecules of chlorine
CH3CH(Br)CH2Br. The addition is contrary to
to give tertachloroethane, known as westron Markownikoff's rule.
industrially. This on dehydrochlorination of
westron with lime water gives trichloro ethene, HBr
CH3 – C  CH   CH3 – CH = CH Br
commerically called westrosol Peroxide
HBr
Cl   CH – CHBr
| Peroxide 3
|
H  C  Cl
| CH2Br
H C H  C  Cl Ex.12 On passing vinyl acetylene into conc. HCl in
||| + 2Cl  | the presence of cuprous and ammonium
2
H C Cl chlorides, the following is produced-
Westron
(A) Neoprene (B) Isoprene
(C) Chloroprene (D) None of these
Cl  C  H Ans. (C)
Lime water ||
  Cl  C  Cl Sol. On passing vinyl acetylene into conc. HCl
HCl
Trichloroethene acid in the presence of cuprous and
( Westrosol) ammounium chlorides. There is a great deal
of evidences that chloroprene is formed and
the reaction proceeds by 1,4 addition
Ex.10 Acetylene on treating with HI gives – followed by rearrangement under the influence
(A) 1, 1-Diiodoethane (B) Ethylene of the catalyst.
(C) Iodoethane (D) Ethane CH2 = CH – C  CH + HCl  [CH2Cl –
Ans. (A)
CH=C = CH2]  [CH2 = C – CH = CH2]
|
Sol. Acetylene on treating with HI gi v es Cl
1,1-diiodoethane Chloroprene (2-chlorobuta-1, 3-diene)
CH2 Ex.13 The compounds A and B in the sequence
CH ||
||| + HI dark
 CHI dark
  H2SO 4 ,HgSO 4 [O]
CH vinyl iodide CH  CH + H2O   A  
 B
60 ºC
are ?
CH3 (A) Acetone and acetic acid respectively
|
CH  I2 (B) Acetaldehyde and acetic acid respectively
ethylidene diiodide (11
,  diiodoethane) (C)Acetaldehyde and ethyl alcohol
respectively
The reactivity of halogen acids is (D) Acetone and acetaldehyde respectively
HI > HBr >HCl Ans. (B)
Ex.11 The product formed by the addition of HBr to H SO ,HgSO
2 4 4
propyne in the presence of H2O2 is – Sol. CH  CH + H2O  
  CH CHO
360 º C

[O]
 CH3COOH
Ex.14 CH  C–COOH HgSO
4 /H2 SO 4
 product
(A), A is-
Sol. CH3–C  CH + O3  CH3 –
(A) CH2 = C –COOH
|
OH
H O
3
(B) CH3– C –COOH    CH3  C  O H2O 2
H2O 2 |  
||
O H C  O
(C) OHC–CH2–COOH CH3COOH + HCOOH
(D) OH–CH=CH–COOH Ans. (C)
 
Sol. CHC–COOH H  OH
  Ex.18 Acetylene and ethylene react with alk KMnO4
to give –
CH = CH–COOHOHC–CH2–COOH
(A) Oxalic acid and formic acid
OH(Enol form) (Keto form)
(B) Acetic acid and ethylene glycol
Ex.15 When acetylene is passed into methanol at (C) Ethyl alcohol and ethylene glycol
160-200ºC in the presence of a small amount (D) None Ans. (A)
of potassium methoxide and under pressure,
the following is formed – Sol. Acetylene and ethylene react with alk.
(A) Polyvinyl alcohol KMnO4 to give oxalic acid and formic acid
(B) Divinyl ether respectively.
(C) Dimethyl ether CH COOH
||| + 4 [O]  |
alk. KMnO4
 
(D) Methyl vinyl ether Ans. (D)
CH COOH
Sol. When acetylene is passed into methanol at acetylene oxalic acid
160-200ºC in the presence of a small amount
(1-2%) of potassium methoxide and under CH2
|| + 4 [O] alk. KMnO4
pressure just high enough to prevent boiling, CH2   2HCOOH
methyl vinyl ether is formed.
ethylene formic acid
The mechanism is believed to involve
nucleophillic attack in the first step.
HC  CH + CH3 O¯ C¯H = CH OCH3 Ex.19 Acetic acid is the only product of ozonolysis of
CH3OH (A) 1- Butyne
  CH2 = CH2O CH3 + CH3O¯
(B) Dimethyl acetylene
Methyl vinyl ether
(C) Ethyl acetylene
(D) 2- Butene Ans. (B)
Ex.16 In the reaction
Sol. Acetic acid is the only product of ozonolysis
CH3 – CH2 – CBr3 Ag powder/ 
    [X] of dimethyl acetylene.
the product [X] is - CH3–CC–CH3+O3
(A) Propyne
(B) CH3 – C  C – Ag
(C) 3-Hexyne
(D) 3-Hexene (Ans. C)
HO
Ex.17 Propyne on ozonolysis forms, 
2

(a) Ethanoic acid (b) Methanoic acid
(c) Propanoic acid (d) None
The correct answer is – 2CH3COOH + H2O 2
(A) a, b (B) b, c ethanoic acid
(C) c, d (D) a, c
Ans. (A)
Ex.20 Acetylenic hydrocarbons are acidic because– Sol. CAg  CAg is white and CuC  CCu is red.
(A) Sigma electron density of C — H bond in
acetylene is nearer a carbon which has Ex.24 How can we distinguish between butyne-1
50% s-character and butyne-2 –
(B) Acetylene has only one hydrogen atom (A) By alkaline KMnO 4
at each carbon atom (B) By Br2 water
(C) Acetylene contains least number of (C) By ammoniacal cuprous chloride
hydrogen atoms among the possible (D) By Benedict reagent Ans. (C)
(D) Acetylene belongs to the class of alkynes
with formula Cn H2n – 2
Sol. Only terminal alkyne give red ppt. with
Ans. (A)
ammoniacal cuprous chloride sol.
Sol. The acidic character of H is,
F—H > O—H >  C—H > N—H; H atom Ex.25 Starting compound for P.V.C. preparation is–
attached on F, O, N and triply bonded carbon (A) Ethylene (B) Acetylene
is acidic. (C) Ethane (D) None
Ans. (B)
Ex.21 The basic character of OH¯ , NH2 , C2H¯ is:
Sol. HC  CH HCl CH 2 = CH–Cl


(A) C2H¯ > NH2 > OH¯
Cl
(B) C2H¯ > OH¯ > NH2 |
Polymerisation
   [–CH2– CH –]n PVC
(C) NH2 > C2H¯ > OH¯ (poly vinyl chloride)

(D) OH¯ > C2H¯ > NH2 Ans. (C) Ex.26 Acetylene trimerises to give benzene. The
Sol. The acidic nature is H2O > C2H2 > NH3; reaction occurs in the presence of –
Thus conjugate base order will be (A) Iron
OH¯ < C2H¯ < NH2 (B) Silica
(C) (C6H5)3 P + Ni(CO)4
Ex.22 Which is the most suitable reagent among
(D) Cr2O3 + P2O 5 Ans. (C)
the following to distinguish compound (c) from
the rest of the compounds: Sol. When ethyne is passed through a red hot
(a) CH3C  CCH3 iron tube, benzene is formed. This reaction
(b) CH3CH2–CH2CH3 was first discovered in 1870. When this
reaction is carried out in the presence of
(c) CH3CH2C  CH (d) CH3CH= CH2 nickel carbonyl and triphenyl phosphene in
(A) Br2 in CCl 4 (B) Br2 in CH3COOH benzene solution. 90% yield is obtained.
(C) Alkaline KMnO4 (D)Tollen's reagent
Ans. (D)

Sol. Terminal alkynes (  C–H) giv e white

precipitate with Tollen's reagent (ammoniacal
AgNO3) 

Ex.23 Acetylene gives –

(A) White ppt with AgNO3 and red ppt with
benzene
Cu2Cl2
(B) White ppt with Cu2Cl 2 and red ppt with
AgNO3
(C) White ppt with both
(D) Red ppt with both Ans. (A) or
Ex.27 Lewisite has the following structure – Sol. The compound which can be prepared from
acetylene by carbonylation is CH2 = CH –
(A) CH2  Cl (B) CH3 COOH
| |
BF
CH2  ASCl2 CH2  As Cl 2 H – C  C – H + CO + H2O
3
  
Ni( CO)4
(C) CH2 (D) CH  Cl acetylene
|| || CH2 = CH – COOH
CH  As Cl 2 CH  As Cl 2
acrylic acid
Ans. (D)
Ex.31 Which of the following compounds will give
Sol. Lewisite has the structure Cl–CH=CH–AsCl2.
only one ketone on hydration -
Arsenous chloride adds on acetylene to form
lewisite which is used as a poisonous war (A) CH3–CH2–CC–CH3
gas. (B) CH3–(CH2)2 –CC–CH3
(C) CH3–CC–CH3
CH  Cl CH  Cl (D) All of these (Ans. C)
||  ||
CH  As Cl2 CH  As Cl2
Lewisite Ex.32 HC  CH on treatment with NH3 in the
(–Chlorovinyl dichloro arsene) presence of Fe-pyrite produces the following
products.
Ex.28 Ethylene and acetylene may be distinguished (A) Pyridine (B) Ethyl amine
by using – (C) Methyl amine (D) Pyrolle
Ans. (D)
(A) Tollen's reagent (B) Baeyer's reagent
(C) Schiff's reagent (D) Bromine water Sol. HC  CH on treatment with NH3 in the
Ans. (A) presence of Fe-pyrite produces Pyrolle.
Sol. Acetylene reacts with tollen's reagent to form CH CH Fe Pyrite
a white precipitate of silver acetylide ||| + NH3 + |||  

CH CH 

Actylene
Ex.29 Acetylene reacts with CO and H2O to form
acrylic acid in the presence of the following–
(A) Hg+2 + H2SO 4 (B) Ni
(C) BF3 + HgO (D) Pd + BaSO4
Ans. (B)
|
Sol. Acetylene reacts with CO and water in the
presence of Nickel Catalyst to give acrylic H
acid, Ni(CO)4 is probably formed as an Pyrolle (Pyrolle is a hetrocyclic compound)
intermediate species which catalyses the
reaction Ex.33 Of the following the compound that will most
readily react with gaseous Br2 is –
CH H CH2
||| +CO+ | Ni || (A) C3H6 (B) C4H10
 (C) C2H2 (D) C6H6
CH OH CH  COOH
Ans. (A)

Ex.30 Which of the following compound can be

prepared from acetylene by carbonylation ? Sol. is more reactive than – C  C –
(A) CH3 – COOC2H5
(B) CH2 = CH – COOH
and
(C) CH3 – CH2 – COOH
(D) CH3 – CH2 – COOCH3 Ans. (B)
Ex.34 Acetylene reacts with HCN in the presence Ex.36 When 2-butyne reacts with sodamide in an inert
of Ba(CN)2 to yield:
solvent in the presence of dilute HCl, the product
(A) Vinyl cyanide
formed is:
(B) 1,1- dicyanoethane
(C) 1,2-dicyanoethene (A) n-Butane (B) 2-Butene
(D) None Ans. (A) (C) 1-Butyne (D) 1-Propyne
Ans. (C)
Sol. CH CH + HCN Ba( CN)2
  CH2 = CH (CN)
Sol. When 2-butyne is heated with NaNH2 in an
Vinyl Cyanide
inert solvent, the sodium derivative of but-1-
yne which is converted into but-1-yne by the
Ex.35 The addition of HOCl to CH3–C  CH in the
presence of mineral acids produces. action of dil HCl.

(A) CH3  C  CH CH3 – C  C – CH3 + NaNH2 Paraffin

| |  
OH Cl dil. HCl
NH3+CH3CH2C CNa 
(B) CH3  C  CH
| |
Cl OH CH3CH2CCH
1-butyne
(C) CH3  C  CH  Cl
|| |
O Cl

(D) CH2  C  CH2 Ans. (C)

| || |
Cl O Cl

Sol. The addition of hypochlorous acid (HOCl) on

propyne in the presence of mineral acids
produce dichloro ketones.

CH3 – C  C – H + HOCl 
H

OH Cl
| |
CH3 – C  C  H
 HOCl

O
||
  CH – C – CH – Cl
–H2O 3 2
1,1 dichloropropanone