Organic Chemistry Principles and Techniques

Level-I
Chapter 12
Organic Chemistry : Some Basic
Principles and Techniques
Solutions (Set-1)
Very Short Answer Type Questions :

1. Give the IUPAC name of the saturated hydrocarbon having the following carbon skeleton.
C—C—C—C—C—C—C
C—C—C C C C
5 4 3 2 1
Sol. C — C — C — C — C — C — C
C—C—C C C C
8 7 6
5-Ethyl, 2, 3, 4-trimethyl octane
– –
2. CH2 = CH is more basic than CH  C . Why?
–
Sol. sp-carbon is more electronegative than sp2-carbon, therefore, CH  C is less willing to donate a pair of
–
electrons than CH2 = CH .
3. How will you purify a liquid having non-volatile impurities?
Sol. Simple distillation will give us the pure liquid while the non-volatile impurities will remain in the flask as residue.
4. Will sodium cyanide give a positive Lassaigne’s test for nitrogen?
Sol. Yes, during fusion with Na metal, the N of the organic compound is actually converted into NaCN which is
the primary requirement for Lassaigne’s test for nitrogen.
5. Name the organic compounds which contain nitrogen atom but cannot kjeldahlised.
Sol. (i) Compound containing nitrogen atom in the ring.
(ii) — NO2 (nitro) compounds
(iii) — N = N — (azo) compounds
6. What are isomers?

Sol. Compounds having same molecular formula but different properties are called isomers.
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
2 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Level-I) (Set-1)
7. Write the metamers of diethyl ether. What is its IUPAC name?

Sol. CH3 — O — CH2 — CH2 — CH3
Methoxy propane
8. Will you get any precipitate if you add silver nitrate solution to chloromethane? If not, why?
Sol. No, because chloromethane is a covalent compound and hence does not ionise to give Cl– ions to react with
AgNO3.
CH3 — Cl + AgNO3 
 No reaction
9. Give one example of functional isomerism.

O
Sol. CH3 — C — CH3 CH3 — CH2 — CHO
Propanone Propanal
10. Write the IUPAC name of

CH3 — CH — CH2 — CH — COOH
CHO CH3
Sol. 4-Formyl-2-methyl pentanoic acid.
Short Answer Type Questions :
11. Draw the structure of 3-methylhex-3-enol and select the word Root, 1° and 2° suffix and prefix.
1 2 3 4 5 6 1 2 3 4 5 6
Sol. HO — C — C — C = C — C — C or OH — CH2 — CH2 — C = CH — CH2 — CH3
CH3 CH3
Word Root — Hex
1° suffix — ene
2° suffix — ol
Prefix — Methyl
12. Explain the heterolytic fission of covalent bond.
Sol. When a covalent bond joining two atoms A and B breaks in such a way that both the electrons of the covalent
bond are taken away by one of the atom, the mode of bond cleavage is called heterolytic fission.
Heterolytic
A: B fission
A+ + B– (When electronegativity of B > A)
Heterolytic – +
A:B fission
: A + B (when electronegativity of A > B)
Heterolytic fission results in the formation of charged species i.e., cations and anions.
13. Define functional isomers with suitable examples.
Sol. The compound which have same molecular formula but have different functional groups are called functional
isomers.
Example :
O
(i) CH3 — CH2 — CHO CH3 — C — CH3
Propanal Propanone
CH3 — CH2 — OH CH3 — O — CH3

(ii) Ethyl alcohol Dimethyl ether
Solutions of Assignment (Level-I) (Set-1) Organic Chemistry : Some Basic Principles and Techniques 3
14. Give its IUPAC name
O
(i) C6H5 — CH2 — C — CH3
O
(ii) CH3 — CH — CH = C — C — H
NH2 C2H5
(iii) HOOC — CH = CH — COOH

Sol. (i) 1-Phenyl propanone
(ii) 4-Amino 2-ethyl pent-2-enal
(iii) But-2-en-1, 4-dioic acid
15. Calculate the hyperconjugated bond and arrange the given alkenes in its stability order.
(i) CH3 — CH = CH2
(ii) CH3 — CH = CH — CH3
H
Sol. (i) H — C — CH = CH2 (There are three hyperconjugated bond)
H
H H

(ii) H — C— CH = CH — C — H (There are six hyperconjugated bond).
H H
Its stability order is CH3 — CH = CH — CH3 > CH3 — CH = CH2

16. How many structural isomers are possible for C6H5C2H5 compound? Draw it.
Sol.
Ethyl benzene 1, 2-Dimethyl 1, 3-Dimethyl
benzene benzene 1, 4-Dimethyl
benzene
Three structural isomers are possible.

17. Give the structures and IUPAC name of all the isomeric monochlorobutane.
Sol. Monochlorobutane (C4H9Cl)
CH3 — CH2 — CH2 —CH2 —Cl CH3 — CH2 — CH — CH3

1-Chlorobutane 2-Chlorobutane |
Cl
Cl
CH3 — CH — CH2 — Cl
CH3 — C — CH3
CH3 CH3
1-choro-2-methyl propane
1-Chloro-1-methyl propane
18. How you detect the halogens with silver nitrate test?
Sol. For the detection of halogens the sodium extract is boiled with dilute nitric acid upon cooling a few drops of
silver nitrate solution are added when
(i) A white ppt is formed and if it is soluble in ammonium hydroxide indicates the presence of chlorine in
organic compound (O.C).
NaCl + AgNO3 
 AgCl + NaNO3
From O.C. White ppt
(ii) A pale yellow ppt is formed, which is slightly soluble in NH4OH solution, indicates the presence of Br in
organic compound.
NaBr + AgNO3 
 AgBr  + NaNO3
From O.C Pale yellow ppt
(iii) A yellow ppt is formed, which is insoluble in NH4OH solution indicates the presence of iodine in organic
compound.
NaI + AgNO3 
 AgI  + NaNO3
Yellow ppt
19. What is the type of hybridisation of each carbon in the following?

(i) CH3Cl
(ii) (CH3)2CO
(iii) CH3 — C  N
(iv) HCONH2
H H O H
| |  || |
  
Sol. (i) H—
 C — Cl (ii) H —
 C — C —
 C — H
| sp3 hybridisation | | 
H H 3 H sp3 hybridisation
sp sp
2
H O
|  ||  H
 —
(iii) H—
 C—C— —  N (iv) H — C — N
   
| 
H
H
sp3 sp hybridisation 2
sp hybridisation
20. Write the bond line formula for
(i) CH3 — CH — CH2 — OH

CH3
OH
(ii) N  C — CH — C  N
(iii) CH3 (CH2)4 CH2 CH(Br) CH2CHO
(iv) CH3 CO CH2 CH2 CH2 — COOH
OH
OH
Sol. (i) (ii)
NC C N
H O O
(iii) (iv)
Br O OH
21. Write the bond line structural formula of

(i) Cyclohex-2-en-1-ol
(ii) 4-Ethyl-1-fluoro-2-nitrobenzene
(iii) 2, 3-Dibromo-1-phenylpentane
(iv) p-Nitroaniline
OH NO2
F
Sol. (i) (ii)
Br NH2
(iii) (iv)
Br
NO2
22. Write all structural isomers of molecular formula, C3H6O.
O
||
Sol. CH3 — C — CH3 , CH3 — CH2 — CHO
OH
|
OH, CH3 — C = CH2 , CH2 = CH — CH2 — OH,
HO — CH = CH — CH3
23. Write the resonance structure of
(i) CH3COO–
(ii) CH2 = CH — NH2
–
O O O
–
Sol. (i) CH3 — C CH3 — C  CH 3 — C

O
– O O
–  –
(ii) CH2 = CH — NH2 CH2 — CH = NH2  CH 2 — CH — NH 2
24. Draw the resonatic structure of C6H5NH2 compound.
NH2
Sol. or
 

NH2 NH2 NH2 NH2 NH2 +
|| NH2
– –
  –
–

–
25. Explain why (CH3)3C+ is more stable than CH3CH2 and CH3 is the least stable cation.
Sol. Stability of carbocation is explained on the basis of hyperconjugaion, more hyperconjugation more
hyperconjugated structure  stability.
H H
| |
H — C — C have only three hyperconjugation structure.
| |
H H
H
|
H—C—H
| |
H — C — C have nine hyperconjugation structure.
| |
H — C —H
|
H
CH+3 have no hyperconjugation structyure.
Hence,  CH3 3 C  CH3CH2  CH3 stability order.
26. Give IUPAC name of following.
(i)
O
(ii)
Cl Br COOH
(iii)
OH
O
(iv)
O
Sol. (i) 1-propyl benzene
(ii) 7-Bromo-7-chloro-4-keto nonanoic acid
(iii) 3-Ethyl-4-methyl pentanol
(iv) Propyl pentanoate
27. Write IUPAC nomenclature of the following.
(i) CH 3 — CH — CH — CH 2OH
C2H5 C2H5
O
(ii)
CH3 — C — CH2 — Cl
(iii) CH  C — CH = CH — CH = CH 2
OH
Br Br
(iv)
Br
Sol. (i) 2-Ethyl-3-methyl pentanol
(ii) 1-Chloro propanone
(iii) Hexa-1, 3-diene-5-yne
(iv) 2, 4, 6-tribromophenol
28. Classify the following transformations according to the reaction type.
(i) CH3 — CH = CH — CH3 + Br2 

 CH3 — CHBr — CHBr — CH3
(CH3)2C = C(CH3)2 + Br2  (CH3)2 C = C(CH3) CH2Br + HBr

h
(ii)
(iii) CH2 = CH — CH2CH3 

 CH3CH = CHCH3
(iv) C6H5CHO + CH3COCH3 

 C6H5CH(OH)CH2COCH3
(v) (CH3)3 CCl + HO– 

 (CH3)2 C = CH2 + H2O + Cl–
O
+
H3O
(vi) CH 3 — C = N — OH    CH3 — C — NHC6H5
C6H5
Sol. (i) Addition reaction
(ii) Substitution reaction
(iii) Rearrangement
(iv) Addition
(v) Elimination
(vi) Rearrangement
29. (i) What are carbocations? Give an example.
(ii) Indicate the sigma and Pi bonds in phenol.
Sol. (i) Positively charged carbon atoms in Heterolytic fission is known as carbocation.
Example : CH3 (Methyl carbocation)

O— H

H  
  H

 
13  -bond
(ii) 
3  -bond

 
 
H 
H
H
30. How does hyperconjugation effect explain the stability of alkenes?
Arrange CH3 — CH = CH — CH3, CH3 — C = CH — CH3 ,

CH 3
CH3 — C = C — CH3 in increasing order of stability.
CH3 CH3
Sol. Number of hyperconjugation structure  Stability

 
CH3 — CH = CH — CH3 have six hyperconjugated structure.
 
CH3 — C = CH — CH3 have nine hyperconjugated structure.
|
CH3
 
CH3 — C = C — CH3 have twelve hyperconjugated structure.
 
CH3 CH3
So, CH3 — C = C — CH3 > CH3 — C = CH — CH3 > CH3 — CH = CH — CH3 Stability order.
CH3 CH3 CH3
Long Answer Type Questions :

31. Calculate the amount of CaCO3 formed when CO2 produced by complete combustion of 94 g of phenol (C6H6OH)
is passed through lime water.
Sol. C6H5 OH + 7O2  air   6 CO2  3H2 O
12 × 6 + 6 + 16
78 + 16 = 94 g phenol gives = 6 mole of CO2 gas.
Ca  OH 2  CO2  CaCO3  H2O

lime water 1mole 1mole
1mole
1 mole CO2 gives 1 mole of CaCO3

6 mole CO2 gives 6 mole of CaCO3
Number of mole of CaCO3 = 6
1 mole = 100 g
6 mole = 600 g
32. Give its IUPAC name
(i)
O
C—O—H
(ii)
O
(iii) O
(iv)
(v) CH 3 — CH — CH = CH — CH — CH 3
OCH 3 CH3
Sol. (i) 6, 7-dimethyl octa-1, 3-diene
(ii) Cyclobutane carboxylic acid or cyclobutanoic acid
(iii) Isopropyl hexanoate
(iv) 1, 2-diethyl -4, 5-dipropyl cyclohexane
(v) 2-Methoxy-5-methyl hex-3-ene
33. Give structures of the following :
(i) Ethyl benzoate
(ii) 2-Phenyl propanal
(iii) 4-Ethyl hept-2-yne
(iv) 3-Ethyl-4-methyl pent-2-ene
(v) 5-Oxohexanoic acid
O
||
C — O — CH2 — CH3
Sol. (i)
(ii) CH3 — CH — CHO
CH2 — CH2
(iii) CH3 — CH2 — CH CH3
C  C — CH3
(iv) CH3 — CH = C — CH2 — CH3
CH — CH3
CH3
O O
(v) CH3 — C — CH2 — CH2 — CH2 — C — OH
34. 0.395 g of an organic compound by carius method for the estimation of sulphur gave 0.582 g of BaSO4.
Calculate the % of S in the compound.
 At. mass of Ba = 137 

 C = 32

Sol. Wt. of organic compound = 0.395 g

Wt. of BaSO4 = 0.582 g
Formula used,
32 Wt. of BaSO4 formed

Percentage of S = 
233 Wt. of organic compound
32 0.582
Percentage of S =   100 = 20.22%
233 0.395
35. (i) Discuss the chemistry of Lassaigne’s test for nitrogen and sulphur.
(ii) How will you separate a mixture of ammonium chloride and common salt?
Sol. (i) Nitrogen and sulphur in organic compounds are covalently bonded in organic compounds and have to be
first converted into ionic forms with sodium metal in fusion process.
Na + C + N 
 NaCN
Sodium cyanide
Na + S + C + N 
 NaSCN
Sodium thiocyanide
Test for Nitrogen (N) : To the Lassaigne’s extract add FeSO4 crystal then acidity with dil. H2SO4.
If Prussian blue colour is obtained, presence of nitrogen is confirmed. If blood red colour is obtained then
presence of N and S both are confirmed.

 Na 4 Fe  CN 6 + Na2SO 4
6NaCN + FeSO 4  
Na 4 Fe  CN6  + Fe2 SO4 
 Fe 4 Fe  CN6 
Prussian blue
Ferric ferrocyanide 
 Fe  SCN3
3NaSCN + Fe+3 
Blood red colour
 ferricthiocyanate
(ii) Sublimation
36. (i) Electromeric effect is a temporary effect. Assign reason.
(ii) How will you separate a mixture of benzoic acid and naphthalene?
Sol. (i) The electronic effect is noticed in the organic compounds containing multiple bond i.e., double bond
(> C = C < or > C = O) or triple bond (— C  N, — C  C —) under the influence of the attacking
reagent at the moment the attacking reagent is removed pi() electron pair comes back to its original
position forming multiple bond again. Therefore, electromeric effect is a temporary effect.
(ii) Both these solids sublime on heating. Therefore, there cannot be separated by sublimation. The mixture
is heated with water when only benzoic acid will dissolve. Upon filtration, naphthalene is separated and
the solution upon cooling gives crystals of benzoic acid.
Alternatively the mixture is reacted with strong aqueous sodium hydroxide when benzoic acid is converted
to soluble sodium benzoate while napthalene is unaffected. It can be separated by filtration. The filtrate
is then treated with dil. HCl to regenerate benzoic acid.
C6H5COOH  s  NaOH  aq 

 C6H5COONa  aq  H2O
Benzoic acid Sodium benzoate
C6H5COONa  aq + HCl  aq 

 C6H5COOH  s  NaCl  aq
 White ppt.
37. Write bond line notation formulae for
(i) Tert . butylcyclohexane
(ii) Hexan-3-one
(iii) Isopropyl chloride
(iv) 2-Methylcyclopentanone
(v) 3, 3-Dimethylpentan-2-one
(vi) Cyclobuta-1, 3-diene
(vii) 2-Amino ethan-1-ol
(viii) But-2-enoic acid
(ix) 3, 4, 4-trimethyl hex-1-yne
(x) Benzophenone
Sol. (i) (ii) ||

O
O
||
(iii) Cl (iv)
O
||
(v) (vi)
O
OH ||
(vii) (viii)
NH2 OH
O
O ||
||
(ix) (x) C or
38. Write the IUPAC names of the following compounds.
(i) C6H5 CH2 CH2 OH
(ii) (CH3)2 CHC  CH
(iii) (CH3)2 CH CH2 CHO
(iv) Br CH2 CH2 CH2 Cl
CH3
(v) CH3 — CH2 — C — CH — CH2 — Cl
Br Br
(vi) CH2 = CH — C  N
(vii) CH3 CH = CH CH2 NH2
(viii) CH3 CH = CHCOOH
(ix) CH3O CH(CH3)2
(x) (C2H5)2 CH CH2 OH
Sol. (i) 2-Phenyl ethan-1-ol
(ii) 3-Methyl but-1-yne
(iii) 3-Methyl butanal
(iv) 1-Bromo-3-chloropropane
(v) 2, 3-Dibromo-1-chloro-3-methylpentane
(vi) Prop-2-enenitrile
(vii) But-2-en-1-amine
(viii) But-2-enoic acid
(ix) 2-Methoxy propane
(x) 2-Ethyl butan-1-ol
39. Write the structures of the following compounds.
(i) But-2-en-1-ol
(ii) 2-Amino ethan-1-ol
(iii) 2, 4-Dimethyl hexan-3-one
(iv) 1, 3-Diaminopropane
(v) 4-Ethyl-2, 4-dimethyl hexane

Sol. (i) CH3 — CH = CH — CH2 — OH
(ii) NH2 — CH2 — CH2 — OH
O
||
(iii) CH3 — CH — C — CH — CH2 — CH3
| |
CH3 CH3
(iv) NH2 — CH2 — CH2 — CH2 — NH2
C2H5
|
CH3 — CH — CH2 — C — CH2 — CH3
(v) | |
CH3 CH3
N
40. 0.35 g of an organic acid was Kjeldahlised and the ammonia obtained was passed into 100 cm3 of H SO .
5 2 4
N
The excess of the acid required 154 cm3 of NaOH for neutralisation. Calculate the percentage of nitrogen
10
in the compound.
Sol. Volume of unused acid
N1V1 = N2V2
Acid Base
1 1
×V=  154
5 10
 V = 77 cm3
Volume of acid used = 100 – 77 = 23 cm3
1.4 × Normality of acid used × Volume of acid used

Percentage of N =
Mass of compound
1.4  0.2  23
= = 18.4%
0.35
41. What is the principle of Kjeldahl’s method? Discuss the method in detail.
Sol. Kjeldahl’s method: A known mass of the organic compound is digested with conc. H2SO4 in presence of
potassium sulphate and a little copper sulphate in a long necked flask. The nitrogen in the compound is
quantitatively converted into ammonium sulphate.
N  NH4  2 SO4
+ Conc.H2SO4 
From organic compound
The resulting liquid is then distilled with excess of sodium hydroxide solution and ammonia evolved is passed
into a known but excess volume of the standard acid (HCl or H2SO4).
NH4 2 SO4 + 2NaOH  Na2SO4 + 2H2O + 2NH3
 NH4  2 SO 4
2NH3 + H2SO 4 
The acid left unused is estimated by titration with some standard alkali.
2NaOH + H2SO4 
 Na2SO4 + 2H2O
The amount of acid used against ammonia can be known and from this, the percentage of nitrogen in the
compound can be calculated.
42. Discuss the Liebig’s method for the estimation of C, H in given organic compound.
Sol. (i) Estimation of Carbon and Hydrogen (Liebig’s Method) : In this method, carbon and hydrogen are
estimated simultaneously.
Principle : A known mass of the given dry organic compounds is heated strongly with dry cupric oxide
in an atmosphere of air or oxygen free from CO2. The carbon and hydrogen of the organic compound are
oxidised to CO2 and water vapour as :
C + 2CuO 
 CO2  2Cu
From organic
compound
2H + CuO 
 H2O  Cu
From organic
compound
 y y
In general : CxHy +  x +
  O2 
 xCO2 + H2O
4 2
The mass of water produced is absorbed in a U-tube containing anhydrous CaCl2 (Calcium chloride) or
anhydrous magnesium perchlorate while CO2 produced is absorbed in another U-tube containing a strong
solution of KOH. The tubes are weighed before and after the combustion. The increase in the mass of
CaCl2 in U-tube gives the mass of water produced while increase in the mass of KOH in U-tube gives
the mass of CO2 produced.
The apparatus used for estimation of carbon and hydrogen is shown in the following figure.
Sample in
Platinum Boat
CuO pallets
Combustion
tube
Excess
O2
Pure dry
oxygen
Anhydrous CaCl2 KOH solution
Calculations : Suppose the mass of the organic compound taken = w g
Increase in the mass of calcium chloride tube = a g
= Mass of water formed
Increase in the mass of potash bulbs = b g
= mass of CO2 gas liberated
(a) Calculation of % of H : One mole of water contains two mole of hydrogen atom
∵ 18 g of water contains 2 g hydrogen
 2 
 a g of water contains   a g hydrogen
 18 
2
a
Thus, The % of H  18  100
w
(b) Calculation of % of C : One mole of CO2 contains one mole of carbon atom.
∵ 44 g of CO2 contains carbon = 12 g
 12 
 b g of CO2 contains carbon =   bg
 44 
12
b
Hence , The % of carbon = 44  100
w
43. What is isomerism? Give its different types with examples if required.
Sol. Such organic compounds which have the same molecular formula but differ from each other in their properties
are called as isomers and the phenomenon is called as isomerism.
It is of two types :
1. Structural isomerism
2. Stereoisomerism
1. Structural Isomerism : Compounds having the same molecular formula but different structure are called
structural isomers and the phenomenon is called structural isomerism.
It is of the following types :
(i) Chain isomerism : The compounds having same molecular formula but different chain of carbon atom.
For example : Butane and 2-methyl propane are chain isomers.
CH3 — CH2 — CH2 — CH3 CH3 — CH — CH3

n-Butane
CH3
2-Methyl Butane
or Isobutane
Similarly, n-pentane, isopentane and neo-pentane are chain isomers.
CH3 CH3
| |
CH3 — CH2 — CH2 — CH2 — CH3 CH3 — CH — CH2 — CH3 CH3 — C — CH3
n-Pentane 2-Methyl butane |
or CH3
Isopentane Neo pentane
or
2, 2-Dimethyl propane
(ii) Position Isomerism : Compounds having the same molecular formula but different in position
substituents, C = C, C  C or functional group are called position isomers.
Examples :
(a) C4H8 : CH3 — CH2 — CH = CH2 CH3 — CH = CH — CH3

But-1-ene But-2-ene
OH
(b) C3H8O : CH3 — CH2 — CH2 — OH CH3 — CH — CH3
Propan-1-ol Propan-2-ol
OH OH OH
(c) C6H6O2 : OH
Benzene-1, 2-diol OH
Benzene-1, 3-diol OH
Benzene-1, 4-diol
Cl
(d) C3H7Cl : CH3 — CH2 — CH2 — Cl CH3 — CH — CH3
1-Chloroprapane 2-Chloropropane
(iii) Functional isomerism : The compounds having same molecular formula but different functional groups
in the molecule are called functional isomers.
Examples
(a) Alcohols and ethers (C2H6O) : CH3 — CH2 — OH CH3 — O — CH3

Ethanol Methoxy methane
(Alcoholic functional group) (-O-ether functional group)
(b) Aldehyde and ketone (C3H6O) : CH3 — CH2 — CHO CH3 — C — CH3
Propanal Propanone
(Aldehydic functional group) (Ketonic functional group)
(c) Carboxylic Acids and Esters (C2H4O2) : CH3 — COOH CH3 — O — C — H

Ethanoic acid Methyl methanoate

(d) Cyanides & Isocyanids (CH3NC) : CH3 — C  N CH3 — N  C
Methyl cyanide Methyl isocyanide
(iv) Metamerism : The compounds having same molecular formula but different alkyl group on either side
of the functional group, are called metamers.
Examples :
(a) C4H10O : CH3 — CH2 — O — CH2 — CH3 CH3 — CH2 — CH2 — O — CH3
Ethoxy ethane Methoxy propane
(b) C4H11N : CH3 — CH2 — NH — CH2 — CH3 CH3 — CH2 — CH2 — NH — CH3
N-ethyl ethanamine N-methyl propanamine
O O
(c) C5H10O : CH3 — CH2 — C — CH2 — CH3 CH3 — CH2 — CH2 — C — CH3
Pentanone or Pentane-3-one Pentane-2-one
Note : Ketones show position isomerism as well as metamerism but preferentially we consider
position isomerism.
2. Stereoisomerism : Isomers which have the same structural formula but have different relative arrange-
ment of atoms or groups in space are called stereioisomers and the phenomenon is called stereoisom-
erism. It has two types:
(i) Geometrical Isomerism
(ii) Optical Isomerism
44. Discuss the resonance or mesomeric effect. How it effect the reacting species?
Sol. Resonance or Mesomeric Effect (R-effect) : Sometimes all the properties of certain molecules are not
explained by a single structure, therefore to explain all the properties of these compounds more than one
structures are depicted but these all are imaginary. The actual structure of molecule is in between these
structures. The structures drawn to explain properties of molecules are called as resonating or canonical or
contributing structures and actual structure is called as resonance hybrid.
The phenomenon of exhibiting more than one possible structure is called as resonance. The resonance can
be explained clearly on the basis of structure of benzene. The benzene can be represented by following two
canonical form.
Resonance
I II
hybrid
The I and II structures are resonating structures. Any one of these structures cannot satisfy the properties of
benzene, such as the C — C bond length should be 1.34 Å (C = C) and 1.54 Å (C – C) but all the
C – C bonds present in benzene are identical having bond length 1.39 Å. The actual structural of benzene is
represented by resonance hybrid. The resonance hybrid is always more stable than any one of the resonating
structures. The stability of resonance hybrid is explained on the basis of resonance stabilisation energy.
Resonance effect it decrease the charge density of reaction intermediate it stabilize the intermediate.

Level-I
Chapter 12
Organic Chemistry : Some Basic
Principles and Techniques
Solutions (Set-2)
Structure, Classification, Nomenclature of Organic Compounds

1. The IUPAC name of the compound
CH3 CH3
CH
CH3
CH3—CH—C—CH
CH3
CH3 CH
CH3 CH3
(1) 3-diisopropyl-2,4-dimethylpentane (2) 2, 4-dimethyl-3-diisopropylbutane

(3) 2, 4-dimethyl-3-3-bis(1-methylethyl) pentane (4) None of these
Sol. Answer (3)
5 carbon in longest chain.
Me
2. The IUPAC name of the compound
Et
(1) 3-methyl-6-ethylcyclohexene (2) 6-ethyl-3-methyl cyclohexene
(3) 3-ethyl-6-methyl cyclohexene (4) 6-methyl-3-ethyl cyclohexene
Sol. Answer (3)
Priority of Et is alphabetically higher.
Isomerism
3. Compound having molecular formula C5H12O cannot show
(1) Tautomerism (2) Position isomerism
(3) Metamerism (4) Functional isomerism
Sol. Answer (1)
Factual
4. Which will have the highest melting point?
(1) (2) (3) (4)
Sol. Answer (3)

Due to symmetrical structure neopentane will have most efficient stacking and hence highest melting point.
5. Three dimensional arrangements which can be interconverted into one another due to rotation along a single
bond are known as
(1) Conformers (2) Diastereomers (3) Chain isomers (4) Positional isomers
Sol. Answer (1)
Conformers are formed due to rotation about single bond.
O
6. The compounds and are
O
(1) Chain isomers (2) Metamers (3) Position isomers (4) Both (1) & (2)
Sol. Answer (4)
Both have different carbon chain length.
7. What is the index of hydrogen deficiency in the molecule C12H17NO?
(1) 4 (2) 5 (3) 6 (4) 7
Sol. Answer (2)
17  1
Index of hydrogen deficiency  (12  1) 
2
= 13 – 8 = 5
8. Which of the following compound cannot have a  bond?
(1) C10H21N (2) C7H12 (3) C20H40Cl2O (4) C30H50Br2O2
Sol. Answer (3)
Degrees of unsaturation in compound C 20 H 40 Cl 2O is zero, therefore the compound cannot have a
 bond.
9. Which of the following compounds will have highest enolic content?
(1) (2) CH3COCH2CHO (3) CH3CHO (4) CH3COCH3
Sol. Answer (1)
O O H
H
mos t stable enol

form s tabilized by
Aromatic character
10. The total number of structural monochloroderivatives possible in C5H12 is

(1) 6 (2) 7 (3) 8 (4) 5
Sol. Answer (3)

n-pentane, isopentane and neopentane form 3, 4 & 1 structural monohaloderivatives respectively.
Electronic displacement, Resonance, Aromaticity

11. In which of the following all electronic effects namely inductive, mesomeric and hyperconjugative effects are
present?
O O
CH3
(1) (2) (3) (4)
H3C CH3
O
Sol. Answer (4)

In (1), (2) and (3) hyperconjugate effect is absent.
12. At conjugated position – NO2 imparts

(1) + M and + I effect (2) – M and – I effect (3) + M and – I effect (4) – M and + I effect
Sol. Answer (2)
–NO2 show – M and – I effect.
13. In the given anion, –ve charge is delocalized on
(1) One atom (2) Three atom (3) Four atom (4) Five atom
Sol. Answer (3)
(2)
– (1)
(3)
(4)
14. Which of the following group will have the strongest electron donating mesomeric effect?
H
 O Me N O
(1) N (2) N (3) C=O (4) O–C
O Me H3C R
Sol. Answer (2)

Electron donating mesomeric effect of a group depends upon size, electronegativity and lone pair availability
of key atom.
15. Which of the following organic molecule cannot form hydrogen bond in pure state but can form the same in
water?
O
(1) (CH3CH2)2NH (2) CH3CHO (3) CH3CH2COOH (4) CH 3–C –NH 2
Sol. Answer (2)
H 3C
–   – H
C = O ----- H — O
H
16. Which of the following is correct order of dipole moment of o, m and p-methyl benzonitrile?
CH3 CH3 CH3 CH3 CH3 CH3

CN CN
(1) > > (2) > >
CN CN
CN CN
CH3 CH3 CH3 CH3 CH3 CH3

CN CN
(3) > > (4) > >
CN CN
CN CN
Sol. Answer (2)
CH3– is electron donating group and –CN is electron withdrawing group   12  22 + 21 2cosθ
17. Among the following, the most stable carbocation is

(1) CH3  CH CH3 (2) (3) (4)
Sol. Answer (2)

+
is an aromatic cation.
18. Resonance is not possible in
(1) (2) NH3 (3) NO2 (4) BH2

O
Sol. Answer (2)
Nitrogen cannot form five bonds due to absence of vacant low energy d orbital.
19. Which of the following hydrocarbon is most acidic?
(1) (2) (3) (4)
Sol. Answer (1)
is most acidic because it generates most stable aromatic conjugate base.
20. Which of the following represents the correct order of stability of the given carbocations?
CH2
I
II III
(1) III > I > II (2) I > III > II (3) III > II > I (4) II > III > I
Sol. Answer (1)

IIIrd is aromatic (most stable) and IInd is antiaromatic (least stable).
21. In which of the following molecules positive charge is not delocalized because of resonance?

NH NH2

Me 
Me
(1)  C (2) (3) C—N (4) C
H3N NH2 Me Me NH2 NH2
Sol. Answer (1)
Nitrogen atom cannot form five bonds due to absence of vacant d-orbitals.
22. The number of sp2 hybridised carbon in one benzyne is

(1) 4 (2) 5 (3) 6 (4) 3
Sol. Answer (3)

All carbon atoms are sp2 hybridised.

+
 Acidity and Basicity

23. In which of the following reactions equilibrium will shift towards right?
+ NaHCO3
(1) (2) C C—H + NaOH
H H
O
OH
C
(3) + NaHCO3 (4) OH
+ NaHCO3
Sol. Answer (4)

NaHCO3 a weak base can deprotonate a very strong benzoic acid. Other acids are very less acidic, hence
cannot be deprotonated by NaHCO3.
O O
O
C H C
O C ONa
+ NaO OH
+ .
O
CO2 + H2O C
HO OH
24. Strongest and weakest acid among the following is

CH3 — NO2 CH3 — CHO CH3 — F CH3 — CN
I II III IV
(1) I and II (2) III and IV (3) III and II (4) I and III
Sol. Answer (4)
Conjugate base of nitromethane (CH3—NO2) is stabilized by very strong – I and – M effect of – NO2 group
O O O
H—CH2—N CH2—N CH2—N
O O O
B
Very stable
conjugate base
Conjugate base of CH3—F is only stabilized by – I effect of F atom hence it is less stable and CH3F is
least acidic.
25. Correct order of acidic strength for the given species
CH3—C N—H CH3—CH2—CH3 CH3—C C—H CH2—H
I II III IV
(1) I > II > IV > III (2) II > IV > III > I (3) III > I > IV > II (4) I > III > IV > II
Sol. Answer (4)
CH3—C — CH3—C —
B
— N—H —N
highly unstable More stable
due to presence
of positive charge
on highly en. sp—N
26. Which of the following will have weakest indicated C—H bond?
CH3
H3C C
H3C
(1) O2N CH2—H (2) CH2—H
H3C
H3C C
H3C
CH3
CH3
C
CH3
(3) CH2—H (4) CH3—H
CH3
C
CH3
CH3
Sol. Answer (3)
CH3
CH3
C
CH3
CH2—H
CH3
C
CH3
CH3
Therefore, indicated C—H bond in (3) is weakest.
27. Which of the following compounds will not dissolve in aqueous NaOH?
R O
O H
O S
H C H
(1) (2) OH (3) (4)
OH OH
HO
Sol. Answer (3)
OH is least acidic.
28. Most acidic species among the following is
O O S S O O
(1) (2) (3) (4)
O S O O
Sol. Answer (2)
Because its conjugate base is stabilized by p-d back bonding.
29. Which of the following is the strongest base in water?
(1) (2) NH2 (3) (4)

N
Sol. Answer (4)

In this compound lone pair of N is nondelocalized. Above all, the N atom is sp3-hybridized and hence, this
N is most basic.
N
3
sp
H
30. Which of the following is most acidic?
NH2 OH NH2
(1) (2) NH2 (3) CH3 – O – H (4) C
N
H H2N NH2
Sol. Answer (2)

It forms most stable conjugate base.
31. Most acidic species among the following is

O
(1) CH3 – C – CH3 (2) CH3 – O – H (3) CH3 – C  C – H (4) H
Sol. Answer (2)
—O—H bond is most polar due to maximum electronegativity difference.
Reaction Intermediates
32. Which of the following experimental techniques can be used to detect carbon free radicals in a reaction mixture?
(1) Magnetic susceptibility method (2) Polarimetry
(3) NMR-spectroscopy (4) IR-spectroscopy
Sol. Answer (1)
This method indirectly gives some information about the presence of unpaired electrons.
33. Which of the following reactions will not generate a carbanion?
(1) NaOEt NH 2
(1) (2)
Et-OH NO 2
O
SbF5
(3) (4) CH3 — C C — H 
NaNH2 /NH3

F
Sol. Answer (3)
O O
H SbF5 + [SbF6]
–
H NaOEt +
F
O O
NH2
CH3—C C—H CH3—C C
34. Out of the given reactive intermediates which will be attracted towards the magnetic field?
(1) Carbocation (2) Carbanion (3) Carbon free radial (4) Nitrene
Sol. Answer (3)
Carbon free radicals will have unpaired electrons and hence it will be attracted towards the magnetic field.
35. Which of the following species cannot behave as electrophile?

(1) BCl3 (2) AlCl3 (3) NH4+ (4) SO3
Sol. Answer (3)

NH4 does not have vacant orbital of appropriate energy.
36. Least stable carbocation among the following is

CH3
H3C – C – CH3 CH3
(1) (2) (3) CH3 – C – CH3 (4) CH

H2C CH2
CH3
CH2 CH2
Sol. Answer (4)
It has less number of resonating structures and less hyperconjugation effect.
37. The most stable free radical is
CH
(1) (2) (3) (4)
Sol. Answer (2)

Due to resonance and hyperconjugation both.
38. Which of the following double bond in the given molecule is most reactive towards a strong protic acid?
Me A C
Me
B D
Me
(1) A (2) B (3) C (4) D
Sol. Answer (1)
Attack of H+ on double bond (A) gives most stable carbocation.
CH 3
+ CH3
CH3
39. Among the following,
Cl Cl Cl
I II III
the correct order of reactivity of chloride is
(1) I > II > III (2) III > II > I (3) II > I > III (4) II > III > I
Sol. Answer (4)
Stability order is
+ + +
(Antiaromatic)
40. Correct stability order of the given free radicals is
CH3 CH3
(1) CH2 > > CH3— C > (CH3)2CH (2) > CH2 > CH3–C– > (CH3)2CH
CH3 CH3
CH3 CH3
(3) > CH3–C– > CH2 > (CH3)2CH (4) CH2 > CH3–C– > (CH3)2CH >
CH3 CH3
Sol. Answer (2)
Allyl C—H bond has lesser bond dissociation energy than benzylic C—H bond and hence corresponding allyl
free radical is more stable.
41. In which of the following homolytic bond fission takes place?
(1) Alkaline hydrolysis of ethylchloride (2) Addition of HBr to double bond
(3) Photochlorination of methane (4) Nitration of benzene
Sol. Answer (3)
Halogenation of methane proceeds through free radical mechanism. In the initiation step of this reaction. Free
radicals are generated through homolysis of a bond.
Initiation
 or h
Cl — Cl Cl + Cl
 Purification, Separation, Quantitative and 

qualitative analysis of organic compounds 
 
42. Which of the following reagents can be used to separate benzoic acid from a mixture of Benzoic acid, Phenol,
Benzaldehyde and Toluene?
(1) aq. HCl (2) aq. NaHCO3 (3) Diethyl ether (4) NaOH
Sol. Answer (2)
When benzoic acid reacts with NaHCO3 it forms water soluble sodium benzoate and hence through extraction.
It can be separated.
43. A mixture contains four solid organic compounds A, B, C and D. On heating, only C changes from solid to vapour
state. The compound (C) can be separated from the mixture by
(1) Distillation (2) Kinetic resolution (3) Crystallization (4) Sublimation
Sol. Answer (4)
Solid is directly converted to vapour.
44. Which of the following compound will give blood red colour while doing the Lassaigne’s test for N?
NH2
(1) (NH2)2 C O (2) H2N (C6H4) SO3H (3) C6H5SO3H (4)

Cl
Sol. Answer (2)

When both N and S is present in a compound, it gives blood red precipitate in Lassaigne’s test.
45. Which of the following compounds will give negative Lassaigne’s test for Nitrogen?
(1) NH2 (2) N N
NO2
(3) N (4)
Sol. Answer (2)

It is azo compound. Azo compound gives negative Lassaigne’s test.


Organic Chemistry Principles and Techniques

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Organic Chemistry Principles and Techniques

Uploaded by

Copyright:

Available Formats

Level-I

Very Short Answer Type Questions :

3. How will you purify a liquid having non-volatile impurities?

4. Will sodium cyanide give a positive Lassaigne’s test for nitrogen?

Sol. (i) Compound containing nitrogen atom in the ring.

(ii) — NO2 (nitro) compounds

(iii) — N = N — (azo) compounds

6. What are isomers?

7. Write the metamers of diethyl ether. What is its IUPAC name?

9. Give one example of functional isomerism.

10. Write the IUPAC name of

CH3 — CH2 — OH CH3 — O — CH3

(iii) HOOC — CH = CH — COOH

Its stability order is CH3 — CH = CH — CH3 > CH3 — CH = CH2

Three structural isomers are possible.

CH3 — CH2 — CH2 —CH2 —Cl CH3 — CH2 — CH — CH3

19. What is the type of hybridisation of each carbon in the following?

20. Write the bond line formula for

(i) CH3 — CH — CH2 — OH

21. Write the bond line structural formula of

22. Write all structural isomers of molecular formula, C3H6O.

Sol. (i) CH3 — C CH3 — C  CH 3 — C

24. Draw the resonatic structure of C6H5NH2 compound.

CH+3 have no hyperconjugation structyure.

Hence,  CH3 3 C  CH3CH2  CH3 stability order.

26. Give IUPAC name of following.

Sol. (i) 2-Ethyl-3-methyl pentanol

(ii) 1-Chloro propanone

(iii) Hexa-1, 3-diene-5-yne

28. Classify the following transformations according to the reaction type.

(i) CH3 — CH = CH — CH3 + Br2 

(CH3)2C = C(CH3)2 + Br2  (CH3)2 C = C(CH3) CH2Br + HBr

(iii) CH2 = CH — CH2CH3 

(iv) C6H5CHO + CH3COCH3 

(v) (CH3)3 CCl + HO– 

Sol. (i) Addition reaction

(ii) Substitution reaction

29. (i) What are carbocations? Give an example.

(ii) Indicate the sigma and Pi bonds in phenol.

Arrange CH3 — CH = CH — CH3, CH3 — C = CH — CH3 ,

CH3 — C = C — CH3 in increasing order of stability.

Sol. Number of hyperconjugation structure  Stability

CH3 CH3 CH3

Long Answer Type Questions :

Sol. C6H5 OH + 7O2  air   6 CO2  3H2 O

Ca  OH 2  CO2  CaCO3  H2O

1 mole CO2 gives 1 mole of CaCO3

Sol. (i) 6, 7-dimethyl octa-1, 3-diene

(ii) Cyclobutane carboxylic acid or cyclobutanoic acid

(iii) Isopropyl hexanoate

(iv) 1, 2-diethyl -4, 5-dipropyl cyclohexane

(v) 2-Methoxy-5-methyl hex-3-ene

33. Give structures of the following :

(i) Ethyl benzoate

(ii) 2-Phenyl propanal

(iii) 4-Ethyl hept-2-yne

(iv) 3-Ethyl-4-methyl pent-2-ene

(v) 5-Oxohexanoic acid

(ii) CH3 — CH — CHO

(iii) CH3 — CH2 — CH CH3

(iv) CH3 — CH = C — CH2 — CH3

 At. mass of Ba = 137 

Sol. Wt. of organic compound = 0.395 g