CHAPTER THREE

ACIDS AND BASES

(AN INTRODUCTION to ORGANIC CHEMISTRY)
 RELATIVE STRENGTH OF
SELECTED ACIDS AND

THEIR CONJUGATE BASES

 Acid pKa Conjugate Base

Strongest Acid HI -10 I Weakest Base

H2SO4 -9 HSO4
HBr -9 Br
HCl -7 Cl
H3O -1.8 H2O
HNO3 -1.4 NO3
CF3CO2H 0.18 CF3CO2
HF 3.2 F
Increasing acid strength

CH3CO2H 4.8 CH3CO2

H2CO3 6.5 HCO3
(CH3CO)2CH2 9 (CH3CO)2CH

Increasing base
NH4 9.2 NH3
C6H5OH 9.9 C6H5O

strength
2
HCO3 10.2 CO3
H2O 15.7 OH
CH3CH2OH 16 CH3CH2O
CH3COCH3 19.2 CH3COCH2
HC CH 25 HC C
H2 35 H
NH3 38 NH2
H2C CH2 44 H2C CH2
Weakest Acid H3C CH3 50 H3C CH2 Strongest Base
As thestability of the conjugate
base of an acid increases as its
acidity increases
 Important
Effects in Organic Chemistry

Inductive (Electronegativity) Effect

Polarizability (Size) Effect
Resonance Effect
Octet Rule
 The difference is cuz
of Size effect

H I H Br H Cl H F
pKa = -10 pKa = -9 pKa = -7 pKa = 3.2

_ _ _ _
I Br Cl F
+ + + +
+ H + H + H + H
_ _ _ _
I > Br > Cl > F

most stable least stable

H3CH2C H H2N H HO H H F
pKa = 50 pKa = 38 pKa = 15.7 pKa = 3.2

_ _ _ _
CH3CH2 NH2 HO F
+ + + +
+ H + H + H + H

_ _ _ _
F > HO > NH2 > CH3CH2

most stable least stable

 O H O
H
O CH3 C O H Cover pKa means it 's base
Ethanol Phenol Acetic acid will be more stable
pKa = 16 pKa = 10 pKa = 5

_
O O
_ _
+
O + H+ + H CH3 C O + H
+

Ethoxide Phenoxide Acetate

0 Resonance 3 Resonance 1 Resonance

_
O O _ O the
More
Stable Oxygen handles we

H >

CH3 C O charge better than C

_
H
_
O O
_ _
CH3 C O > > O
most stable least stable
 O O O
 
H3C C CH3 CH3 C CH2 C CH3
Acetone Acetylacetone
pKa = 20 pKa = 10

O _ O _ O
+ +
H3C C CH2 + H CH3 C CH C CH3 + H

_ _
_
O O O O O

H3C C CH2 CH3 C CH C CH3 CH3 C CH C CH3

O _ O O _
CH3 C CH C CH3 > H3C C CH2

more stable less stable

Alcohol pkaulb S character
✓
sp3 %s = 25 =
zp -100%
sp2 %s = 33.33 % sp %s = 50↑ More
electronegativity

CH3CH3 H2 C CH2 HC CH
pKa = 50 pKa = 44 pKa = 25
More
electronegativity
can stabilize the electrons
_ _ _↓ better
.

CH3CH2 H2C CH HC C
+ + +
+ H + H + H
_ _ _
HC C > H2C CH > CH3CH2
most stable least stable
Any system which has -

ve charge is rich in electrons To stabilize the

.

system put electronegative atoms

O O .

C C
H3C OH F3C OH
Acetic acid Trifluoroacetic acid
Hlf
pKa = 4.8 Electronegativity pKa = - 0.18

O O
_ _
+ C +
C + H F3C O + H
H3C O

O O
_ _
C C
F3C O > H3 C O

more stable less stable

 Acid
O Cl O O
C C C
OH OH OH
F Cl

Conjugate Base
O Cl O O
_ _ _
C C C
O O O
F + + Cl +
+ H Clisltbonbs + H Gibbons + H
Chess distance
away away
O O
_ Cl O
C _ _
C
O > O > C
O
F Cl
most stable least stable

Inductive Effect Decreases with Distance

This lone /
is
pair

busy stabilizing
the resonance

I
 Wherever you have 0 charge there should be a product . Higher pka attacks the lower pKa .

ÑHÑH
"

liq. NH3
a. CH3 C C H + NaNH2

conjugate
Water pka -15.7
Higher pKa ads as the base
 to C6H5C C D Isotope of
C6H5C C H ←

Hydrogen
 Good Luck
Dr. Imad A. Abu-Yousef