(Hi) As the distance between the electron-withdrawing substituentfrom the COOHgroup increases,

the strength of the acid decreases. This is due to the reason that inductive effect decreases rapidly with
distance. For example,
CI

CI

I
CH3CH2CHCOOH

>

I
CH3CHCH2COOH

a-Chlorobutyric acid

>

CICH 2 CH 2 CH 2 COOH

P-Chlorobutyric acid

(pKfl = 2-84)

y-Chlorobutyric acid

(pK a = 4 0 6 )

(pK a - 4-52)

3. Comparison of relative strength of alkynes. The relative acid strength of alkynes follows
the order :
HC s CH > C H 3 ^ - C = CH > CH 3 CH 2 ->C = CH
Explanation. The + I-effect of the alkyl groups decreases in the order CH 3 CH 2 > CH 3 > H. Thus
as we move from H to CH 3 to CH 3 CH 2 , the electron density in the CH bond increases and thus the
m CH bond becomes stronger. In other words, it becomes more and more difficult to release a proton
and hence the acidity decreases in the order :
CH = CH > C H 3 - > C ^ C H

> CH 3 CH 2 ->C = CH

3. Comparison of relative strength of bases. All the aliphatic amines (1, 2 or 3), like ammonia,
possess a pair of electrons on the nitrogen atom which they can easily donate to a proton. As a result,
all the amines, like ammonia, are basic in nature. Further, greater the tendency of an amine to donate its
lone pair of electrons, stronger is the base. The strength of an amine in aqueous solution is usually
expressed in terms of dissociation constant Kb or pKb
[KNH 3 ][OH-]
Kfe

[RNH 2 ]

_
or

1 0

^"

From the above expressions, it is evident that higher the value of Kb or lower the value
stronger is the base.

ofpKb,

Let us now discuss the effect of electron-donating and electron-withdrawing substituents on the
basicity of amines.
(/) Effect of electron-donating groups. Aliphatic 1, 2 and 3 amines contain one, two and three
alkyl groups attached to the nitrogen atom respectively. These alkyl groups because of their + I-effect
tend to increase the electron-density on the nitrogen atom. Consequently, all the amines can donate a
pair of electrons more readily than ammonia and thus are stronger bases than ammonia.
HNH
I
H
Ammonia

NH
I
, H

R -NH
+
R

Primary amine

Secondary amine

<-R

+
R

Tertiary amine

On the basis of + I-effect of the alkyl groups alone, the expected order of basicity should be : 3
amine > 2 amine > 1 amine.
However, the actual order of basicity of amines in aqueous solution is : 2 amine > 1 amine > 3
amine. This is supported by the pKb values of these three classes of amines :
(CH 3 ) 2 NH >
CH 3 NH 2
>
(CH 3 ) 3 N
Dimethylamine
( p K j = 3-23)

STRUCTURE AND BONDING

Methylamine

(pKb = 3-36)

Trimethylamine
(pK 6 = 4-20)

Explanation. The reason why the actual order is different from the expected order may be explained as follows :
The basicity ofan amine in aqueous solution does not entirely depend upon the electron density on the N-atom but also
depends upon the stability of the conjugate acid formed by accepting a proton from the solution. The stability of the
conjugate acid, in turn, depends upon the extent of H-bonding. Obviously, greater the number of H-atoms on the N-atom.
more stable is the conjugate acid. Thus, the conjugate acid of 1 amine is the most stable since it has three H-atoms which
can form H-bonds ; the conjugate acid of 2 amine is less stable since it has two H-atoms while that of 3 amine is the least
stable since it has only one H-atom which can form H-bond as shown below :

H
RNH 2 + H1"
1 Amine

>

OH2

RNH
H

OH2
OH2

(Most stable)
R\

) N H + H+

2 Amine

R\+/H

OH22

r/

oh 2

(Less stable)

R\
RN + H

>

R \ +
R NH

OH,

R^
(Least stable)

Thus, on the basis of stability of the conjugate acids alone, the basic strength of amines should follow the order :
RNH 2 > R 2 NH > R 3 N.
In actual practice, these two opposing factors balance each other in case of 2 amine. This makes 2 amine to be the
strongest. 3Amines are weaker bases than 2 amines since their conjugate acids are less stable than those of 2 amines
while 10 amines are less basic than 2 amines since the electron density on the N-atom is less and hence the lone pair of
electrons on nitrogen is less easily available for protonation.

0b) Effect of electron-withdrawing groups. Electron-wididrawing groups because of their -Ieffect tend to decrease the electron density on the N-atom thereby making the lone pair of electrons less
readily available for protonation. Thus, the presence of electron-withdrawing groups on the N-atom
decreases the basicity of amines. For example, tris (trifluomethyl) amine is virtually non basic due to
F3C<N > CF3

powerful -I-effect of the three CF 3 groups.

+
CF

1.10.4. FIELD EFFECTS*

We have discussed above that inductive effect operates through bonds. There is another effect which
does not operate through bonds but occurs directly through space or solvent molecules. This is called field
effect. Although it is very difficult to separate inductive effect from field effect, it has been done in a
number of cases generally by taking advantage of the fact the field effect depends upon the geometry of the
molecule but the inductive effect depends upon the nature of bonds. For example, in isomers I and II, die
inductive effect of the chlorine atoms on the position of electrons in the COOH group should be the same
since the same bonds intervene. In odier words, acidity of die two acids should be die same.
C1WH
HwCI
Hv A - C I
CkA-H

COOH

COOH
pK a = 6-07

pK a = 5-67

* Not included in K.U. and M.D.U. syllabi.

P r o d e e p ' s O R G A N I C C H E M I S T R Y V O L . I.

RCOOH + H 2 O

RC00- + H30+

The strength of an acid is usually expressed in terms of its dissociation or acidity constant K a .
[RCOO ] [ H 3 0 + ]

K a =

[RCOOH]

0r

gKa

Since K a is directly proportional to the concentration of H 3 0 , therefore, higher the value ofKa or
lower the value of pKa, stronger is the acid. Alternatively, the value of K a depends upon the concentration
of carboxylate anion ( R C O O ) which, in turn, depends upon its stability. In other words, any factor
which stabilizes the RCOO" anion relative to RCOOH, should increase the acidity while any factor
which destabilizes the RCOO" anion relative to RCOOH decreases the acidity of the carboxylic acid.
In the light of these arguments, it is expected that electron donating groups (EDG) because
of their + I-effect would destabilize the carboxylate anion relative to carboxylic acid by intensifying
the negative charge and hence should decrease the acidity of the carboxylic acid. Conversely,
electron-withdrawing groups (EWG) because of their -I-effect would stabilize the carboxylate
anion relative to carboxylic acid by dispersing its negative charge and hence should increase the
acidity of the carboxylic acid
EWG

Ct

>0
0_J

E W G disperses - v e charge by withdrawing

electrons, stabilizes the carboxylate ion,
increases the acid strength

EDG*

Ct

>0
Oj

EDG intensifies the-ve charge by donating electrons,

destabilizes the carboxylate ion, decreases the acid
strength

In nutshell it may be stated that electron-withdrawing groups increase the acidity while electrondonating groups decrease the acidity of carboxylic acids.
Let us now briefly discuss the effect of various substituents on the acidity of carboxylic acids.
(/) Effect of electron-donating substituentsalkyl groups. Let us compare the relative strength
of formic acid (HCOOH) and acetic acid (CH 3 COOH)
O
II

O
II

HCOH

CH 3

Formic acid (pKa = 3-75)

C->O-* H

Acetic acid {pKa = 4-76)

Methyl group present in acetic acid due to its + I-effect increases the electron-density in the
OH bond. As a result, release of H + ions from acetic acid will be more difficult as compared to
formic acid. Hence, formic acid is a stronger acid than acetic acid.
Alternatively,

CH 3 group because of its + I-effect intensifies the negative charge on acetate ion

and thus destabilizes it relative to formate ion. Hence, formic acid is a stronger acid that acetic acid.

C H

- ^ - c ^
Acetate ion

STRUCTURE AND BONDING

>0

(;/') Effect of electron-withdrawing groups. Let us consider the relative acid strength of acetic
acid and chloroacetic acid.
O
II
CH3 ->C-0->H

O
II
C1^<-CH2<-C<-H

Acetic acid (pKa = 4-76)

Chloroacetic acid (pK.a = 2-86)

The chlorine atom present in chloroacetic acid because of its -I-effect withdraws electrons from
the OH bond. As a result, the electron density in the OH bond decreases. In other words,
the OH bond weakens and thus the release of H + ions from chloroacetic acid is facilitated relative to
acetic acid. Hence, chloroacetic acid is a stronger acid than acetic acid.
CH3

CL
>0
N > J

Cl-^-CH2-cf

>0
J

>

CH 3 group donates electrons and

Cl-atom withdraws electrons and

thus destabilizes the acetate ion

thus stabilizes the chloroacetate ion

Alternatively, Cl-atom because of its -I-effect tends to disperse the negative charge on chloroacetate
ion while CH 3 group because of its + I-effect tends to intensify the negative charge on acetate ion. As
a result, chloroacetate ion is more stable than acetate ion and hence chloroacetic acid is a stronger acid
that acetic acid.
Important conclusions. From the above discussion following conclusions can be drawn :
(i) The stronger the + I-effect of the substituent, or greater the number of electron-donating
groups, the weaker is the acid. For example,
CH3
CHj-s.

CH,3 - M - COOH > C H3X H2, ->COOH >

Ethanoic acid

Propanoic acid

' ^ CHCOOH > CH,>~C

>-COOH
3
C H3, ^
A
t
, ,,
,
/

2-Methylpropanoic
acid

3
2, 2-Dimethylpropanoic
acid

(/;) The stronger the -I-effect of the substituent, stronger is the acid. For example,
02N*-CH2<-COOH
>
NC <- CH 2 <- COOH > F <- CH 2 C O O H
Nitroacetic acid

Cyanoacetic acid

(pK a - 1 - 6 8 )

CI <- CH 2 - COOH
Chloroacetic acid
(pK-a = 2-86)

(/>K= 2-47)

>

Br C H

Fluoroacetic acid
(pKa - 2-57)

<- COOH > I C H

Bromoacetic acid
(pKa = 2-90)

<- COOH

Iodoacetic acid
(pK fl = 3-16)

This is due to the reason that -I-effect decreases in the order :

- N 0 2 > - C N > - F > -CI > -Br > -I.
Further, large the number of electron withdrawing substituents, stronger is the acid. For example,
CI
CI
+
I
CIC<COOH
>
CI< CH < COOH
> CI C H 2 C O O H

CI
CI

Trichloroacetic
acid
roac

Dichloroacetic acid
(pK0-l-25)

Chloroacetic acid
(pK a = 2-86)

(PK = 0-65)

W M S 3 S E X o r g a n i c c h e m i s t r y VOL.1.

However, the acidity of the two acids has been found to be different. This is obviously due to the
field effect which is different for the two isomers. In isomer I, the two chlorine atoms being closer to
the -COOH group, exert greater field effect as compared to that in isomer II. Consequently, isomer II
is a stronger acid than isomer I. This is supported by their pKa values. From die above example, it
appears that sometimes field effects are even more pronounced tiian inductive effects.
An example of field effect which occurs through solvent molecules is provided by comparison of
first and second dissociation constants of dicarboxylic acids (Table 1.5).
TABLE 1.5. Dissociation constants of some dicarboxylic acids
Acid

K\!K

PKJ

Oxalic
Malonic acid
Succinic acid
Glutaric acid
Adipic acid

'1

1-271
2-86
4-21
4-34
4-41

4-266
5-70
5-64
5-27
5-28

989
692
26-9
8-51
7-41

Since these acids contain two carboxyl groups, ionization can occur in two stages :
H0 2 C(CH 2 )C0 2 H + H 2 0
H02C(CH2)co-+H20

N
n

H0 2 C(CH 2 )C0 2 + H 3 0 +
-02C(CH2)mC02+H30

...(/)

...(H)

During the first stage of ionization, i.e., equilibrium (/'), the acid can lose a proton from two
positions but the half ion (conjugate base, CBj) can add a proton to only one position. If no other
factors operate, it is reasonable to assume that the acid in equilibrium (/), should be twice as strong as
a monocarboxylic acid, i.e., K' = 2 x Kfl of RC0 2 H.
During the second stage of ionization, i.e., equilibrium (//), the half ion can lose a proton from only
one position but the dianion (CB2) can add a proton to two positions. Therefore, for equilibrium (if), K^
= 1/2 K a of RC0 2 H. Thus, equilibrium (/') is satistically four times as favoured as equilibrium (//). Thus,
on the basis of above assumption that no other factors operate, the value of K* is expected to be four
times K^. In practice, the two constants widely differ from the factor 4 (Table 1.5).
To explain the above experimental results, it has been suggested that electrostatic effect of the
negatively charged carboxylate ion, CBj, would require additional energy to separate the proton from
the carboxyl group. In other words, a field effect occurs through the solvent and this increases the ratio
K* / K^ above 4. Further as the chain length increases, i.e., as ^-increases, both the field effect and the
+ I-effect would decrease and so the ratio would approach 4.
| 0 | ELECTROMERIC EFFECT*
Unlike inductive effect, electromeric effect is a temporary effect and operates in unsaturated
compounds only at the demand of the attacking reagent. It involves complete transfer of %-eleclrons of
a multiple (double or triple) bond to one of the bonded atoms. Consider, for example, the attack of a
nucleophile (i.e. ~CN) to a carbonyl group. In the presence of a nucleophile, the 7i-electrons of the
carbon-oxygen double bond are completely transferred to the mote electronegative oxygen atom :
Nucleophile added

>c =o

* = = = f e . i
Nucleophile removed

* Included in Panjab and J a m m u University Syllabi

STRUCTURE AND BONDING

-,

>c-rO
"

As a result of this electron displacement, the positive charge on the carbon atom of the carbonyl
group increases and this facilitates the attack of the nucleophile on it. Such a complete transfer of the
electrons of a multiple bond to one of the bonded atoms (usually more electronegative) in the presence
of an attacking reagent is called the electromeric effect or simply the E-effect.
I
If, however, the attacking reagent is removed without the reaction being allowed to take place, the
molecule reverts back to the original state. Thus, electromeric effect is only temporary in nature.
1.11.1. TYPES OF ELECTROMERIC EFFECT
Like inductive effect, electromeric effect is also of two types, i.e., + E-effect and -E-effect.
If the %-electrons are transferred to that atom of the double bond to which the attacking reagent
gets finally attached, the effect is called + E-effect. For example, the addition of acids to alkenes.
>C

>CC<

(+ E-effect)

H
I f , on the other hand, %-electrons are transferred to an atom of the double bond other than the one
to which the attacking reagent gets finally attached, the effect is called -E-effect. For example, the
addition of cyanide ion to the carbonyl group.
>C*=0^+XCN

>CO-

(-E-effect)

CN
Significance of electromeric effect. It may be noted that so far, it has not been possible to
distinguish experimentally between I- and E-effects. But the fact that the reactivity of a molecule
increases considerably upon the close approach of the reagent definitely suggests the involvement of
some electronic effect such as electromeric effect. In certain molecules both I- and E-effects operate
together. Sometimes they assist or reinforce each other and sometimes they oppose, Whenever they
oppose each other, it is always the E-effect which dominates over the I-effect.
1.11.2. COMPARISON OF INDUCTIVE AND ELECTROMERIC EFFECTS
INDUCTIVE EFFECT
1. It operates only in saturated compounds
containing at least one polar cr-bond.
2. It is a permanent effect and involves the mere
displacement of a-electrons.

3. It does not require any outside attacking reagent

for its operation.
4. The displaced electron pair does not leave its
molecular orbital but due to inductive effect,
there occurs a slight distortion in the shape of
the molecular orbital of the polar a-bond.
5. Due to inductive effect only a partial separation
of positive and negative charges occurs but ions
are not formed.

ELECTROMERIC EFFECT
1. It occurs in unsaturated compounds containing
at least one double or a triple bond which mayor may not be polar in nature.
2. It is a temporary effect and involves the
cleavage of a multiple bond with complete
transfer of a shared pair of electrons to one of
the bonded atoms.
1 3. It takes place only in the presence of an attacking
reagent.
4. The electron pair which gets transferred
completely during electromeric effect leaves its
original molecular orbital and gets transferred
to a new molecular orbital.
5. Due to electromeric effect, there occurs a
complete transfer of electrons from the reagent
:
to the substrate or vice-versa and hence ions
are always formed.
mmmmmmwm*

org

mmMm&x-.mmssm <tm M

v o l . i.