Vidyalankar: Ch.13C: General Organic Chemistry

IIT-2023 : Chemistry
Ch.13C : General Organic Chemistry

MODULE 4A
Acidic Nature :
+
(1) Arrhenius Acid : The compounds which furnish H ion in aqueous solution are
called Arrhenius acids. Ex. H2SO4, HNO3, HCl, HClO4 etc.
+
(2) Bronsted Acids : The species which are H ion donors are called Bronsted acids.
Ex. NH4 ,H3O , etc. All Arrhenius acids are Bronsted acids.
r
(3) Lewis Acids : The lone pair acceptors are known as lewis acids. They have vacant
p or d orbitals. Ex BX3, AlX3, ZnX2 etc.
ka
Scale of Measurement of Acid Strength (Arrhenius or Bronsted acids).
R  COOH R  COO H
RCOO  H 
Ka     Where Ka  acid dissociation constant.
RCOOH
pKa   logKa
an 1.
2.
HI
HBr
+
A strong acid is defined as the acid which furnish more number of H ion in aqueous
solution OR the acid which is more ionised in aqueous solution.
So, a stronger acid has higher value of Ka, or its has lower value of pKa
[Note: Ar- Indicates 3. HCl

4. PhSO3H
al
Aryl/phenyl group]
5. RSO3H
Experimetal order of Ka:
i. Inorganic acids : The 6. HF
mineral acids are inorganic 7. ArCOOH
acids. These are considered 8. RCOOH
H2CO3 (for lab test)
dy
as completely ionised in
aqueous solution and are 9. NH4
described as strong acids. 10. PhOH
11. CH3OH
[H2SO4 > HCl > HNO3]. 12. H2O Decreasing order of Ka
ii. Organic acids : They are R

 SO3H > R  COOH > Ph  13.
Vi
OH > ROH
They are weakly ionised in 14. ROH

water, so these are weaker 15. RCCH
acids then mineral acids. 16. Ar3CH
17. NH3
18. R  CH = CH2
19. R  CH2  CH3
IIT/Booklets/Chem/Ch.13C/Pg.50
Notes on General Organic Chemistry (51)
Prediction of Acid Strength :
r
A stronger acid has more stable anion, so a stronger acid forms a more stable conjugate
base.
ka
Factors affecting stability of conjugate base/anion :
(I) Presence of EWG in the alkyl (R) part of the acid increase stability of anion, and
hence increases acidic strength.
an
al
Periodicity in Acid Strength of Hydrides :
(1) Along the period from left to right : As electronegativity increase, Ka 
(i) CH4 < NH3 < H2O < HF (Ka)
Conjugate base/Anion :
dy
E.N. dominates over size decrease.

(2) Along the group from up to down : As size increases, Acid strength 
(i) HF < HCl < HBr < HI
Order of Acidity
Vi
i. HCOOH > CH3COOH > CH3CH2COOH ……….

ii. Cl3C. COOH  Cl2 CHCOOH  ClCH2COOH  HCOOH  CH2  CH  COOH
PKa0.65 1.25 2.86 3.77
iii. FCH2COOH  ClCH2COOH  BrCH2COOH  ICH2COOH....
iv. HCOOH  PhCOOH  CH3COOH COOH

v. (COOH)2  CH2 (COOH)2  (CH2 )2
COOH
0719/IIT/Booklets/Chem/Ch.13C/Pg.51
(52) Vidyalankar : JEE(Advanced) – Chemistry
vi. MalicacidFumaric
Compounds ka  105
CH3COOH 1.75
CH2 = CH  COOH 5.6
C6H5COOH 6.3
HCOOH 17.7
r
ICH2CO2H 67
ka
Br CH2COOH 125
Cl CH2COOH 136
F CH2COOH 260
3. Basic Strength of Amines :
..
N
+
an
H/H2O
H
N
al
Degree of solvation
+
NH3 + H2O NH4 + OH
(NH4 )(OH )
Kb 
(NH3 )
dy
PKb =  log kb
H OH 2 H OH 2
+
R N H OH2 R N H OH2 R3 N H OH 2
H OH2 R
Vi

RNH3 H2O RNH2  H3O
(RNH2 ) (H3O )
Ka 
(RNH3 )
pKa   log Ka
Kb  Basicity ; or pKa  Basicity
1
pKb 
Basicity
Order of Basic Strength of Alkyl Amines

a. In Aqueous medium, order of basicity is :
 (CH3 )2 NH  CH3NH2  (CH3 )3 N  NH3

pKa (10.72) (10.64) (9.7) (9.26)
 (C2H5 )2 NH  (C2H5 )3 N  C2H5NH2

pka 10.98 10.76 10.70
r
 (C2H5)3N
ka
N pKa : 10.75
pKa : 10.95
O

N
H
pKa (11.2)
anN
H
pyrididine
(11.1)
 R  CH2NH2  RCH  NH  RCN

NH2
(10.64)
N (morpholine)
H
(8.2)
al
 RNH2  ArNH2
b. In nonaqueous or gaseous medium = 3 > 2 > 1 > NH3

dy
Vi
r
ka
an
al
dy
Vi
r
ka
an
al
dy
Vi
r
ka
an
al
dy
Vi
sterichindriance
MODULE 4B
Inductive Effect
During polarization, the bonding electron pairs are polarized towards more
electronegative part developing particle negative () charge on the negative component
+
while partial positive ( ) charge on positive past of the molecule.
 
+
 
+ +
 
+
r
C X ; C C C X
I
ka
+I
All alkyl substituents attached to C  atom of C X bond are considered as +I groups

while all electronegative atoms or groups attached to C  atom are I groups. Order of
+I effect is 3 > 2 > 1 > CH3 group.
Application
1. Reactivity of alkyl halides :
an
 order of reactivity : 3 > 2 > 1 > CH3 X
 order wrto halogen atoms : C I C Br C Cl C F

al
2. Acidity of carboxylic acid :
O O O
O
.. more stable
-H+ C
C .O. H C O C O
dy
due to resonance
O
+
HA + H 2O H 3O + A
(H 3O+) (A )
Ka =
HA
Vi
EWG C O H more acidic

(electron with drawing group)
EDG C O H less acidic
O
(electrondonating group)
Order of Basicity of N is the Compound
O
II
C NH CH3
I
HN III
N
r
CH3
 III > I > II
ka
 Basic strength of Substituted Anilines :
NH2 ( Kb  1010 )
When X  CH3  ; p   m   phNH2  o 
12 5.6 4.2 2.6
X X  OCH3 ; p  phNH2  o  m 
(20) (3.2) (2.0)
an (140)
(4.2)
X  NH2 ; p  m  phNH2  o 
(10)
X  NO2 ; phNH2  m   p   o 
4.2 .03
4.2
.001
3.0
.00006
N N
al
(Basic strength)

dy
N N
 Structure II is more basic than I. Since in II, the

withdrawing power of NO2 is decreased due to
steric hindrance.
NO2 NO2
Vi
 NH2 C NH2 H2N CH2 NH2 CH3CH2 NH2
NH
NH2

CH3
N N
o,m,p
H
Solved Examples
1. Explain acidic nature of vinyl alcohol.
Solution
CH2  CH  OH CH2  CH  OH
less stable due to charge separation
CH2  CH  O CH2  CH  O
r
More stable due to absence of charge separation
ka
+
After loss of H ion vinyl alcohol stabilizes by resonance, hence it will favour loss of
+
H and hence acidic in nature.
2. Explain the order of basicity of alkylamines and how solvation relates to basicity.
Solution :
a) (CH3)2NH
an
Basicity  (+I) power of the group, base on which the order of alkylamines would
have been 3amine > 2amine > 1amine > NH3 However it is found that
> CH3NH2 > (CH3)3 N > NH3
b) (C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3
However, Basicity  degree of solvation.

al
Degree of solvation of ammonia, 1amine and 2amine is almost same but
degree of solvation of 3amine is zero.
This makes 3amine least basic.
dy
Solvation of amines :
H
H
O
H H O R
H H H H R
+ H H
+
H +
O H N H O ; R N H O R N H O +
R N H O
H H H
H H H
Vi
H H
H O H O R
O (NH 3) H H
H H (1amine) (2amine) (3amine)
3. Compare the acidity of

a. Maleic acid with fumaric acid
b. Monomaloate anion with mono fumarate anion
Solution :
a. Acidity order ; O O
H C O H H C OH
C C
C C
H C O H HO C H
O O
Maleic acid Fumaric acid
r
-H+
-H+
ka
O
O
H C O H+
H C O
C
C
H C
C H
HO C
H C O
O
O
an
more stable
(monomaleate anion)
less stable
(monofumarate anion)
b. Acidity order of monofumarate anion > monomaleate anion, Because

+
monomalate anion does not furnish H ion easily due to intra molecular
+
association while monofumarate ion can easily give up H ion.
al
Classwork Problems
Subjectives
1. Inductive effect on the acid strength of some carboxylic acid is given below.
Comment in one line for each case. (Comment for case (a)) is given for hint.
dy
Acid Ka Comment
O (reference case)
|| 1.8  105
CH3 COH
O CH3 is a weak electron
1.3  10
5
|| donating group, acid
(a) CH3CH2 C OH strength decreases slightly.
Vi
O
|| 1.4  103 ………
(b) ClCH2 C OH
O
|| 2.2  103 ………
(c) FCH2 C OH
O
|| 7.6  104 ………
(d) ICH2 C OH
Acid Ka Comment
O
|| 1.05  104 ………
(e) ClCH2CH2 COH
O
|| 2.24  101 ………
(f) Cl3C C OH
OO
|| || 1.5  103 ………
(g) HO C C OH
r
OO
|| || 2.0  106 ………
ka
ⓛ
(h) O C C OH
2. Record the following sets of compounds according to increasing pK a (=  log Ka) :

(a) cyclohexanol, phenol, cyclohexane carboxylic acid
(b) 1-butyne, 1-butene, butane
(c) propanoic acid, 3-bromopropanoic acid, 2-nitropropanoic acid
an
(d) phenol, o-nitrophenol, o-cresol
(e) hexylamine, aniline, methylamine
Objectives
Single Correct Answer Type

al
1. The correct order of acidity for HCOOH, CH3COOH, C6H5COOH is
(A) HCOOH > CH3COOH > C6H5COOH
(B) C6H5COOH > HCOOH > CH3COOH
(C) HCOOH > C6H5COOH > CH3COOH
(D) CH3COOH > HCOOH > C6H5COOH
dy
2. The correct order of acidity for
COOH COOH COOH COOH

CH3 Cl NO2 is
Vi
1 2 3 4
(A) 1 > 3 > 4 > 2 (B) 4 > 3 > 2 > 1 (C) 4 > 3 > 1 > 2 (D) 4 > 1 > 3 > 2
3. The correct order of basic strength is

(A) C2H5NH2  (C2H5 )2 NH  (C2H5 )3 N (B) (C2H5 )3 N  (C2H5 )2 NH  C2H5NH2
(C) (C2H5 )2 NH  C2H5NH2  (C2H5 )3 N (D) (C2H5 )2 NH  (C2H5 )3 N  C2H5NH2
Multiple Correct Answer Type
1. Which of the following are less acidic than benzoic acid?

(A) HCOOH (B) CH3COOH
(C) ClCH2COOH (D) H3C COOH
2. Which of the following are less acidic than

HO O
r
ka
HO O
OH CH3
COOH COOH
NO2 Cl
(A) (B) (C) (D)
an
3. Which of the following are stronger base than
NO2
?
Cl
N
NH2
al
N
N
(A) (B) (C) (D)
N N
H N H
dy
Paragraph Type
Using the following Paragraph, Solve Q. 1 and 2

The acidic nature of carboxylic acids, phenol and basic nature of amines can be decided
by considering the magnitudes of inductive and mesomeric effects caused by atoms or
group attached to these species. Electron withdrawing groups (I, M) increase acidic
Vi
nature but reduces basic nature while electron releasing groups (+I, +M) have just
opposite trends.
1. Which of the following is the correct decreasing order of acidic strength for following ?
(1) (2) (3) (4) (5)
(A) 3 > 4 > 2 > 1 > 5 (B) 3 > 2 > 4 > 1 > 5
(C) 3 > 4 > 1 > 2 > 5 (D) 3 > 5 > 4 > 2 > 1
2. Which of the following order is not correct for basic nature ?
(A) (B)
(C) (D)
r
Numerical Type
ka
1. From the given compounds how many of them are more acidic than benzoic acid ?
COOH COOH
COOH COOH COOH OH
CH3 NH2 Cl NO2
NH 2 CH 3
Matrix Match Type

1. Match the Ka values
a)
b)
Benzoic acid
O 2N
anCOOH
Ka
3.3  10
10.2  10
–5
–5
al
–5
c) Cl COOH 30.6  10
–5
d) H3CO COOH 6.4  10
dy
–5
e) H3C COOH 4.2  10
2. Column I (compounds) Column II (Pkb value)
(A) (p) 13.6

Vi
(B) (q) 6.21

N
..
(C) N (r) 3.35

..
(D) N (s) 8.80

H
Homework Problems
Subjectives
1. Explain the following : CHCl3 is more acidic than CHF3.
2. Arrange n-butane, n-butanol, n-butyl chloride, isobutane in the increasing order of boiling
point.
3. Which is the stronger acid in each pair ?
I II
r
(a) CH3COOH ………
ka
(b) CH3OH
………
(c) CH3COOH ………
(d)
an ………
al
4. Arrange in increasing acid-strength.
dy
5. Compare the basicity for and

N
N
H
6. Explain, which compound is a stronger acid :
Vi
(a) CH3CH3 or CH3NO2
(b) or
(c) or
(d) or
(e) or
r
7. Arrange the following in incorrect acid strength :
ka
(a)
an
(b)
al
(c)
dy
+ +
Vi
8. (CH3OH2) is .............. acidic than (CH3NH3) .
9. Which of the following is more acidic and why ?

+ +
NH 3 NH 3
COOH COOH
10. Compare the acidity of and
NO2 NO2
I II
11. Arrange the following in increasing order of acid strength :
ClCH2COOH(I), CH3CH2COOH(II), ClCH2CH2COOH(III), (CH3 )2 CHCOOH(IV) ,
r
CH3COOH (V)
ka
12. Compare the basicity of alkyl amines with arylamines?
13. Parahydroxy benzoic acid is less acidic than benzoic acid. Explain why ?
14. Rank the following amines in increasing basic nature :
(a)
(b)
an
al
(c)
dy
(d)
Vi
15. Arrange the following as stated:

(i) increasing order of acid strength :
ClCH2COOH, CH3CH2COOH, ClCH2CH2COOH, (CH3 )2 CHCOOH,CH3COOH
(ii) increasing order of acidity HClO,HClO2,HClO3,HClO4.
(iii) increasing strength of Hbonding (X   HX)
O, S, F, Cl, N.
Objectives
1. In the following compounds phenol (I), pcresol (II), mnitrophenol (III) and
pnitrophenol (IV) the order of acidicity is
(A) III > IV > I > II (B) I >IV >III > II
(C) II > I > III > IV (D) IV > III > I > II
2. Arrange given acid in increasing order of acid strength
r
FCH2COOH CH3COOH CH3  CH2COOH
(I) (II) (III)
ka
(A) I > II > III (B) II > III > I (C) III > I > II (D) III > II > I
3. Which compound is most acidic ?
(A) CH3COOH (B) C6H5COOH
(C) O2NC6H4COOH (D) H3CC6H4COOH
4. Which one is least basic ?

(A) NH3 (B) CH3NH2
an (C) (CH3 )2 NH
5. The arrangement of (CH3 )3 C,(CH3 )2 CH,CH3CH2  when attached a benzene or

an unsaturated group in increasing order of inductive effect is :
(D) H2N  CH2  NH2
(A) (CH3 )3 C  (CH3 )2 CH  CH3CH2 

(B) CH3CH2   (CH3 )2 CH  (CH3 )3 CH2
al
(C) (CH3 )2 CH  (CH3 )3 C  CH3CH2 
(D) (CH3 )3 C  CH3CH2   (CH3 )2 CH 
6. Which of the following acids has the smallest dissociation constant ?
(A) CH3CHFCOOH (B) FCH2CH2COOH
dy
(C) BrCH2CH2COOH (D) CH3CHBrCOOH
7. Which of the following compound is least acidic ?

COOH COOH COOH COOH
CH 3 NH 2 NO2 Cl
Vi
(A) (B) (C) (D)
8. Which of the following is least basic ?

O
(A) (B) (C) (D)

N
N N N
H
H H
9. Order of basic strength of the leveled N-atom in the given compound is

b
a CONHCH 3
HN
c
N
CH 3
(A) a > b > c (B) b > a > c (C) c > a > b (D) c > b > a
r
10. Which of the following is most acidic ?
COOH
ka
OH
O HO O NO2
(A) (B) (C) (D)
O HO O
11. Arrange the following in the increasing order of acidity ?

H2O, H2S, NH3, CH  CH
(A) CH  CH < NH3 < H2O < H2S

(C) H2O < H2S < NH3 < CH  CH
an (B) NH3 < CH  CH < H2O < H2S
(D) H2S < H2O < CH  CH < NH3
12. Which one of the following is correct?

Formic acid has lower pKa than that of CH3COOH because :
al
(A) formic acid does not dissociate
(B) formic acid does not have an alkyl group
(C) formic acid is smaller in size than acetic acid
(D) formic acid is a strong reducing agent
dy
13. In the following compounds,
OH OH OH OH
Vi
NO2
CH3 NO2
(I) (II) (III) (IV)

the order of acidity is :
(A) III > IV > I > II (B) I > IV > III > II
(C) II > I > III > IV (D) IV > III > I > II
14. Which of the following has the most acidic hydrogen ?

(A) 3Hexanone (B) 2,4Hexanedione
(C) 2,5Hexanedione (D) 2,3Hexanedione
16. Arrange substituted aromatic amines according to decrease in basic character
NH 2 NH 2 NH 2 NH 2
Me
(I) (II) (III) (IV)
r
Me
ka
Me
(A) IV > II > III > I (B) IV > III > I > II
(C) II > IV > III > I (D) III > IV > I > II
17. Out of the following pairs, which one is not correct according to their acidic property.
NH2 NH2
(A)
O 2N
C
NO2
an
>
O 2N
NO2
NO2
N
al
OH OH
Me Me
(B) >
dy
Me Me
NO2 NO2
OH OH
Me Me
Vi
>
(C)
Me Me
C C
N N
COOH COOH
Me
Me Me
C Me
(D) >
Me
18. Among the following, the correct order of basicity is :

(A) NH2 OH RO RCOO (B) NH2 RO OH RCOO
(C) RCOO > NH2 > RO > OH (D) RCOO > RO > NH2 > OH
19. Which of the following is a Lewis acid?

(A) AlCl3 (B) Cl (C) CO (D) C2H2
20. What is the decreasing order of strength of the bases :

OH, NH2 ,H  C  C and CH3  CH2 ?
r
(A) CH3  CH2  NH2  H  C  C  OH
ka
(B) H  C  C  CH3  CH2  NH2  OH
(C) OH  NH2  H  C  C  CH3  CH2
(D) NH2  H  C  C  OH  CH3  CH2
21. Among the following compounds, the strongest acid is

(A) HC  CH (B) C6H6 (C) C2H6 (D) CH3OH
compounds?
an
22. Which of the following presents the correct order of the acidity in the given
(A) BrCH2COOH > ClCH2COOH > FCH2COOH > CH3COOH

(B) FCH2COOH > ClCH2COOH > BrCH2COOH > CH3COOH
al
(C) CH3COOH > BrCH2COOH> ClCH2COOH > FCH2COOH
(D) FCH2COOH > CH3COOH > BrCH2COOH > ClCH2COOH
23. The correct order of basic strength of the compounds

dy
NH2 N
Is
N
II H III
I
(A) I > II > III (B) II > I > III (C) III > II > I (D) II > III > I
Vi
24. Which of the following is having most acidic H?

O
(A) (B) CH3CH2NO2 (C) CH2  (NO2 )2 (D) CH2Cl2
25. Which of the following has least pKb value

H 3C CH 3
NH 2
N
(A) (B)
..
H3C CH3 NH 2
N H 3C CH 3
r
(C) H3C CH3 (D)
ka
26. Which of the following has most acidic hydrogen?
O O O
(A) (B)
(C) H
O
O
an (D)
O
O
H
al
27. The correct order of basicity of three compounds
NH2 NH2 NH2
dy
CH3 NO2
(I) (II) (III)
(A) I > II > III (B) III > I > II (C) II > III > I (D) II > I > III
Vi
28. Which is the strongest acid ?

(A) pKa = 15.88 (B) pKa =9.93 (C) pKa = 5.63 (D) pKa =1.67
29. Among the following, the strongest base is :

(A) C6H5NH2 (B) p  NO2C6H4NH2
(C) m  NO2C6H4NH2 (D) C6H5CH2NH2
30. The correct order of basicities of the following compounds is :

NH O
CH3 C ,CH3CH2NH2 ,(CH3 )2 NH, CH3 C NH2
NH2
1 2 3 4
(A) 2 > 1 > 3 > 4 (B) 1 > 3 > 2 > 4

(C) 3 > 1 > 2 > 4 (D) 1 > 2 > 3 > 4
r
31. In the anion HCOO , the two carbonoxygen bonds are found to be equal length.
What is the reason for it ?
ka
(A) the C = O bond is weaker than the C  O bond
(B) the anion HCOO has two resonating structures
(C) the electronic orbitals of carbon atom are hybridized
(D) the anion obtained by removal of a proton from the acid molecule
32. Which of the following is least basic ?
NH 2 NH 2 NH2 NH2
(A) (B)
an (C) (D)
CH3
CH 3 NH 2 OCH3 CH
al
CH3
33. Arrange according to decrease in acidic character of the monoanion of the following
Dibasic acid.
O O O O O
dy
OCCOH OC(CH2 )3 COOH OC(CH2 )2 COOH OCCH2 COOH

(I) (II) (III) (IV)
Oxalic Gutaric Succinic Malonic
(A) I > IV > III > II (B) I > II > III > IV (C) IV > I > II > III (D) I > IV > II > III
34. Arrange the following according to decrease in Acidic Character.
Vi
OH OH OH OH OH
I) II) III) IV) V)
NO2 Cl Me OMe
(A) II > III > I > IV > V (B) II > III > I > V > IV
(C) III > II > I > IV >V (D) V > IV > I > III > II
35. Out of following structure which structure doesn’t contain ‘Ortho effect’.
COOH NH 2 OH
COOH
Me Me Me
NO2
(A) (B) (C) (D)
36. Which of the following groups has (+M) effect.
r
O
O
ka
S OH H
(A) (B)
O
H
CH3
(C)
N
CH 3 an (D)
al
38. Arrange the following according to decrease in acidic strength.
COOH COOH COOH COOH

dy
Me
(I) (II) (III) (IV)
Me
Me
(A) I > II >III > IV (B) I > III > IV > II (C) I > II > IV > III (D) II > I > III > IV
Vi
39. The correct order of decreasing basicity of the following compounds is :
(A) I > II > III > IV (B) II > I > III > IV
(C) III > IV > I > II (D) II > I > IV > III
40. Which of the following compounds is a weaker acid as compared to benzoic acid?
(A) (B) (C) (D)
41. In the following compounds,

OH OH OH OH
r
ka
NO2
CH3 NO2
(I) (II) (III) (IV)
the order of acidity is :

(A) III > IV > I > II
(C) II > I > III > IV
an (B) I > IV > III > II
(D) IV > III > I > II
42. Which of the following has lowest pKa value?

al
(A) (B) (C) (D)
43. Which of the following carbocation is most stable?

dy
+
+
(A) Ph3C (B) CH
2


(C)  CH3 2 CH (D) C
3
Vi
1. Which of the following are more acidic than benzoic acid?
COOH COOH COOH COOH
(A) (B) (C) (D)
OH CH3 Cl NO2
2. Which of the following are more acidic than C2H5OH?

(A) CH3OH (B) (CH3 )2 CHOH (C) C2H5SH (D) H2O
3. Which of the following are less basic than, ?
N
NH 2 NH2
NH 2
CH 3
r
(A) (B) (C) (D)
N
ka
CH3 H
4. Which of the following statements are correct ?

..
(A) is more basic than N
N an
(B) (CH3)2 NH is more basic than (CH3)3N is nonaqueous solvent
(C) (CH3)2NH is more basic than (CH3)3N is aqueous medium

O
(D) is more basic than

al
N N
H H
5. Which of the following are less basic than CH2 = NH ?
dy
(A) CH3  C  N (B)

N
H
(C) CH3CONH2 (D) C6H5CONH2
Vi
6. In which of the following NO2 group is not coplanar with phenyl ring ?
NO2 NO2 NO2 NO2

H3C CH3 I I
(A) (B) (C) (D)
H3C CH3
7. Which of the following more acidic than benzoic acid

COOH COOH COOH COOH
(A) (B) (C) (D)
CH 3 NH 2 NO2 Cl
8. Correct order of basicity is ……
r
(A) CH3CH2NH2 > CH3CH = NH > CH3C  N
ka
(B) (CH3)2NH > CH3NH2 > (CH3)3N
H
NH2 NH CH3
N
(C) < <
(D) H2S > H2O > NH3

an
9. Which of the following are more acidity than + ?
NH2
Cl Cl
al
(A) + (B) +
NH2 NH2
Cl
CH3
CH CH 3
dy
CH3
(C) (D)
+ +
NH2 NH 2
10. Choose the correct statements :
(A) o-hydroxy benzoic acid is more acidic than m, p-isomers
(B) p-hydroxy acid is more acidic than benzoic acid
Vi
(C) m-hydroxy acid is more acidic than p-hydroxy acid

(D) Benzoic acid is more acidic than p-hydroxy acid
11. Which of the following statements are correct ?

(A) Hydration effect stabilize dimelhyl ammonium ion more than trimethyl ammonium
ion
(B) RCONH2 is more acidic than RCOOH
(C) CH3  NH2 OH; Nucleophillicity order in DMSO
(D) Phenol is less acidic than CH3OH
12. In which of the following pairs the first one is the stronger base than second ?
(A) CH3COO ,HCOO (B) OH,NH2
(C) CH2  CH,CHC (D) CH3NH2 ,CH3OH
Numerical Type
1. Among the following, how many of them are more basic than aniline :
r
ka
an
2. How many acidic Hydrogen present in this structure ?
OH O
C
H
al
H
H 2C C C C H
dy
3. How many of the following compounds are more acidic than phenol ?
Vi
4. How many of the following are the stronger acid than benzoic acid ?
5. How many of the following have more acidic hydrogen than ethanol ?
CH3COCH3(I) CH3COOCH3(II) 2,5pentanedione(III)
CH3  CH = CH  CHO (IV) 1,3cyclohexanedione(V) CH3CONH2(VI)
6. How many of the following are more acidic than 2fluorobutanoic acid ?
r
ka
7. How many are more acidic than phenol ?
OH OH OH OH OH
OH OH
Br CH3 OMe
, , , , ,
,
Matrix Match Type

1.
II
Column I (Compound)
an III
OMe
IV
CH3
V
NO2
VI
Column II (Character)
Cl
VII
(A) NH2 (p) Ortho effect

al
OMe
(B) COOH (q) Intra molecular hydrogen bonding
dy
OMe
(C) COOH (r) +I effect

Vi
CH3
(D) OH (s) I effect
NO2
(t) +R effect
(u) R effect
(v) Hyper conjugation
2.
Column I Column II
Compounds Pkb value
(A) NH2 (p) Pkb  9.61
(B) NH2 (q) Pkb  12.98
r
NO2
ka
(C) NH 2 (r) Pkb  14.29
NO2
(D) NH2
OMe
an
(s) Pkb  9.42
(E) NH2 (t) Pkb  9.80

al
Me
dy
3. Match the Column I and Column II.

Column I Column II
(A) NaHCO3 (p)
Vi
(B) Na will react with (q)
(C) NaOH will react with (r)
(D) NaNH2 will react with (s)
Classwork Problems
Subjectives
1. (a) given
(b) Cl is an electron-withdrawing group ; acid strength increases.
(c) F is a stronger electron-withdrawing group than Cl because it is more
r
electronegative.
(d) I is less electronegative and a weaker electron-withdrawing group than Cl.
ka
(e) Cl is farther from the reaction site ; the inductive effect decreases rapidly with
increasing distance.
(f) Three Cl atoms have a stronger inductive effect than one.
(g) COOH group is electronwithdrawing.
(h) CO2 group is electron-donating, this is a weaker acid than CH3COOH.
2. (a) cyclohexane carboxylic acid < phenol < cyclohexanol

(b)
(c)
(d)
(e)
an
1-butyne < 1-butene < butane
2-nitropropanoic acid < 3-bromopropanoic acid < propanoic acid
o-nitrophenol < phenol < o-cresol
aniline < methyl amine < hexyl amine
Objectives

al
1. (C) 2. (B) 3. (D)
1. (B), (D) 2. (A), (B), (C), (D) 3. (B), (C), (D)
dy
Paragraph Type
1. (B) 2. (D)
Numeric Type
1. [3]
Vi
Matrix Match Type

1. Ka value
–5
a) Benzoic acid 6.4  10
–5
b) pNO2  C6H4  COOH 30.6  10
–5
c) pCl  C6H4  COOH 10.2  10
–5
d) pCH3 C6H4 – COOH 4.2  10
–5
e) pOCH3 – C6H4 – COOH 3.3  10
2. (A)  (q) ; (B)  (r) ; (C)  (s) ; (D)  (p)
Homework Problems
Subjectives
1. Cl3 C : is less basic than F3 C : because fluorine can disperse charge only by an
inductive effect, while Cl (having empty 3d orbitals) disperses charge by inductive
effect as well as by p-d bonding delocalization. Fluorine is a second period
element with no 2d-orbital.
2. Isobutane < nbutane < nbutyl chloride < nbutanol.
3. (a) II (b) II (c) II (d) I
r
4. III < II < I
ka
5. more basic than
N N
H
an
is a cyclic secondary amine with pka value 11.2 while
N
is a bicyclic
Tertiary amine with comparatively more sterric effect than the former one and has the
pka value of 10.95
6. (a) CH3NO2 (NO2 is electron-withdrawing group : EWG)

al
O O
|| ||
(b) CH3 C CH2CN (CH3 C and  CN both are EWG)
dy
(c) (d) (e)

Vi
7. (a) I < III < II (Intramolecular H-bonding in III makes it less acidic than p-isomer)
(b) II < I < III (c) I < III < II
8. Stronger 9. II > I
10. I is more acidic than II. In structure I NO2 group retains its withdrawing ability while
in case of II the withdrawing ability of NO2 group is sterically hindered. Less, the
withdrawing effect, less is the acidity.
12. Order of basicity : alkyl amine > Aryl amine
R NH2 > NH2
+Igr -Igr
In arylamine, the lone pair on Natom is not freely available due to conjugation effect,
.. + + +
NH 2 NH 2 NH 2 NH 2
r
ka
and Ncarries a positive charge on it which does not allow the proton to attack into it easily.
13. In p-hydroxy benzoic acid  OHgr acts as a strong +M group and electron donating
group decreases acidity. Thus in p-hydroxy benzoic acid the hydroxy phenyl
15. (i)
an
substituent as a whole acts as a electron supply substituent to COOH group.
14. (a) IV < II < III < I (b) III < II < I < IV (c) I < II < III < IV (d) I < III < II
(CH3 )2 CHCOOH  CH3CH2COOH  CH3COOH  ClCH2CH2COOH  ClCH2COOH
(ii) HClO  HClO2  HClO3  HClO4.
(iii) S < Cl < N < O < F.
al
Objectives
1. (D) 2. (A) 3. (C) 4. (A) 5. (A) 6. (C)
7. (B) 8. (C) 9. (C) 10. (C) 11. (B) 12. (B)
13. (D) 14. (B) 15. (C) 16. (B) 17. (C) 18. (B)
dy
19. (A) 20. (A) 21. (D) 22. (B) 23. (B) 24. (C)
25. (C) 26. (A) 27. (D) 28. (D) 29. (D) 30. (B)
31. (B) 32. (D) 33. (B) 34. (A) 35. (C) 36. (A)
37. (C) 38. (D) 39. (C) 40. (C) 41. (D) 42. (A)
43. (B)
Vi
1. (C), (D) 2. (A), (C), (D) 3. (A), (B), (C) 4. (A), (C)
5. (A), (B), (C), (D) 6. (C), (D) 7. (C), (D) 8. (A), (B), (C)
9. (A), (B) 10. (A), (C), (D) 11. (A), (C) 12. (A), (C), (D)
Numerical Type
1. [4] 2. [4] 3. [5] 4. [6] 5. [3] 6. [3] 7. [4]
Matrix Match Type
1. (A)  (s), (t) ; (B)  (p), (s), (u) ; (C)  (t) ; (D)  (q), (s), (u)
2. (A)  (s) ; (B)  (r) ; (C)  (q) ; (D)  (t) ; (E)  (p)
3. (A)  (p), (q), (s) ; (B)  (p), (q),(r), (s) ; (C)  (p), (q), (r), (s) ; (D)  (p), (q), (r), (s)

Vidyalankar: Ch.13C: General Organic Chemistry

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Vidyalankar: Ch.13C: General Organic Chemistry

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IIT-2023 : Chemistry

Ch.13C : General Organic Chemistry

[Note: Ar- Indicates 3. HCl

ii. Organic acids : They are R

They are weakly ionised in 14. ROH

Prediction of Acid Strength :

E.N. dominates over size decrease.

i. HCOOH > CH3COOH > CH3CH2COOH ……….

iii. FCH2COOH  ClCH2COOH  BrCH2COOH  ICH2COOH....

iv. HCOOH  PhCOOH  CH3COOH COOH

CH2 = CH  COOH 5.6

3. Basic Strength of Amines :

Order of Basic Strength of Alkyl Amines

 (CH3 )2 NH  CH3NH2  (CH3 )3 N  NH3

 (C2H5 )2 NH  (C2H5 )3 N  C2H5NH2

 R  CH2NH2  RCH  NH  RCN

b. In nonaqueous or gaseous medium = 3 > 2 > 1 > NH3

All alkyl substituents attached to C  atom of C X bond are considered as +I groups

+I effect is 3 > 2 > 1 > CH3 group.

 order wrto halogen atoms : C I C Br C Cl C F

EWG C O H more acidic

EDG C O H less acidic

Order of Basicity of N is the Compound

 Structure II is more basic than I. Since in II, the

 NH2 C NH2 H2N CH2 NH2 CH3CH2 NH2

1. Explain acidic nature of vinyl alcohol.

However, Basicity  degree of solvation.

H H (1amine) (2amine) (3amine)

3. Compare the acidity of

b. Acidity order of monofumarate anion > monomaleate anion, Because

2. Record the following sets of compounds according to increasing pK a (=  log Ka) :

Single Correct Answer Type

2. The correct order of acidity for

COOH COOH COOH COOH

3. The correct order of basic strength is

Multiple Correct Answer Type

1. Which of the following are less acidic than benzoic acid?

(C) ClCH2COOH (D) H3C COOH

2. Which of the following are less acidic than

Using the following Paragraph, Solve Q. 1 and 2

(1) (2) (3) (4) (5)

2. Which of the following order is not correct for basic nature ?

Matrix Match Type

2. Column I (compounds) Column II (Pkb value)

(A) (p) 13.6

(B) (q) 6.21

(C) N (r) 3.35

(D) N (s) 8.80

(c) CH3COOH ………

5. Compare the basicity for and

(a) CH3CH3 or CH3NO2

8. (CH3OH2) is .............. acidic than (CH3NH3) .

9. Which of the following is more acidic and why ?

10. Compare the acidity of and

15. Arrange the following as stated:

Single Correct Answer Type

4. Which one is least basic ?

5. The arrangement of (CH3 )3 C,(CH3 )2 CH,CH3CH2  when attached a benzene or

(A) (CH3 )3 C  (CH3 )2 CH  CH3CH2 

(C) BrCH2CH2COOH (D) CH3CHBrCOOH

7. Which of the following compound is least acidic ?

(A) (B) (C) (D)

8. Which of the following is least basic ?