Chapter 2

Acids and Bases

BrnstedLowry Acids and Bases

An acid is a proton donor A base is a proton acceptor
HBr + H2O Br + H3O

acid

base
NH4 + OH

NH3 + H2O base acid

Note that water can act as an acid or a base

BrnstedLowry Acids and Bases

HBr + H2O Br + H3O

HBr

Br

O H H

acid

base

conjugate base

conjugate acid

The remaining species after the proton has been donated is the conjugate base.

The resulting species after the proton has been accepted is the conjugate acid.
Every acidbase reaction involving proton transfer has two conjugate acidbase pairs.

Lewis Acids and Bases

A Lewis acid is an electron pair acceptor.
(think empty orbital)

A Lewis base is an electron pair donor.

(think filled orbital)

The result of a Lewis acidbase reaction is often called an adduct.

Lewis Acids and Bases

O
H

Lewis acid Electron deficient

Lewis base Electron rich

Adduct New covalent bond

Lewis Acids and Bases

Lewis acids dont have to donate a proton, as long as they can accept a share in an electron pair.
F F B F + CH3CH2 O CH2CH3
Lewis base Electron rich

F F F

CH2CH3 CH2CH3

B O
Adduct New covalent bond

Lewis acid Electron deficient

Lewis Acids and Bases

Examples of Lewis Acids: Fe3+ AlCl3 H3O+ Examples of Lewis Bases:
NH3 H2O Cl

pH
The concentration of hydrogen ions is used as a measure of acidity This concentration is expressed as pH pH = log[H3O+] The higher the concentration, the more acidic the solution and the lower the pH

pH
H2O + H2O OH + H3O

Neutral water: [H3O+] = 1.0 107 M pH = log[H3O+] = 7 pH < 7.00 pH = 7.00 pH > 7.00 Acidic solution Neutral solution Basic solution

The Acidity Constant, Ka

The strength of an acid is represented by its ionization constant (acidity constant), Ka
Ka=
product of concentrations of ionized species concentration of intact acid

HA + H2O

A + H3O
A
H3O
HA

Ka =

The Acidity Constant, Ka

The Ka implies the concentrations of the acid and the ions
Ka > 1 Ka < 1 Ka >> 1
(e.g., > 103)

Ionized products greater than intact acid. Ionized products less than intact acid. Ionization goes to completion (strong acid). Ionization does not occur to an appreciable amount.

Ka << 1

(e.g., < 103)

The Acidity Constant, Ka

Since the Ka values for various acids have such a wide range, a more manageable way to discuss this measure of acidity is to use
pKa = log (Ka)

Compare pKa and Ka Values

strong acids weak acids

pKa

-2 102

2 10-2

6 10-6

10 10-10

12

14 10-14

Ka

The smaller the value of the pKa the stronger the acid.

Acid Strength
HA + H2O H 3O + + A The difference between a strong acid and a weak acid can be described by the stability of the conjugate base. - WEAK ACID
A
E N E R G Y Has a strong conj. base (higher energy)

AHA
ionization easier

STRONG ACID Has a weak conj. base (lower energy)

Acid Strength
A more stable conjugate base means a stronger acid. Astabilization A-

E N E R G Y

HA

Acid Strength
Factors that influence stability of the conjugate base include:
Resonance Electronegativity Atomic Size Hybridization Inductive Effects

Acid Strength
Factors that influence stability of the conjugate base include:
Resonance Electronegativity Atomic Size Hybridization Inductive Effects

Acid Strength
Factors that influence stability of the conjugate base include:
Resonance Electronegativity Atomic Size Hybridization Inductive Effects

Acid Strength
Factors that influence stability of the conjugate base include:
Resonance Electronegativity Atomic Size Hybridization Inductive Effects

Acid Strength
Factors that influence stability of the conjugate base include:
Resonance Electronegativity Atomic Size Hybridization Inductive Effects

Resonance Effects
More or better resonance structures of the conjugate base lead to a stronger acid.

Resonance Effects
increasing quality of resonance

pKa Values 18
R CH3

R OH

45

R NH2

28

CH3 OH 10
O CH3O C CH3 O
5

30

NH2 25
25

O R C OH

O
20

R C CH3
O O

R C NH2

15

R C CH2 C R 9

 The Acetate Ion

O CH3 C OH

Resonance Effects
O
-H+
Base

CH3

C O

acetic acid

O CH3 C O

acetate ion Resonance Stabilized Equivalent structures (charges on oxygens)

 The Phenolate Ion

O

Resonance Effects
O
O

More resonance structures, but not more stable than acetate Nonequivalent structures (note charges on carbon and oxygen)

Electronegativity
Placing the negative charge on a more electronegative element (from the same period) in the conjugate base leads to a stronger acid.

increasing electronegativity

Electronegativity
pKa Values

O
CH4
NH3 H2O HF

>45
34 16 3.5

RCH3 RNH2 ROH

45 35

R C CH3 20 O

18

R C NH2 15

O R C OH
5

Consider the conjugate bases

increasing electronegativity

Electronegativity
pKa Values

CH4
NH3 H2O HF

> 45
34 16 3.5

H H C H

O
RCH3 RNH2 ROH 45 35

R C CH3 20 O

H N H

18

R C NH2 15

O
H O

R C OH

F Consider the conjugate bases

Atomic Size
Placing the negative charge on a larger atom (from the same group) in the conjugate base leads to a stronger acid.

increasing size

Atomic Size
pKa Values

HF
HCl

3.5
7 9

H2O H2S H2Se H2Te

16 7

O R C OH O

4 3

R C SH
S R C SH

HBr

HI

10

Consider the ionic radii

increasing size

Electronegativity
pKa Values

O
HF
HCl

3.5
7 9

F
Cl

1.36
1.81

H2O H2S H2Se H2Te

16 7 4 3

R C OH O R C SH
S R C SH

HBr

Br 1.95 I

HI

10

2.16

Consider the ionic radii

Hybridization
More s character in the orbital bearing the negative charge in the conjugate base leads to a stronger acid.

Hybridization
H
pKa pKa

sp3

H C H H
H H C C H H

C
> 45

H O H H
-1.74

sp2

35

R R C O H
-7

sp H C C H

25

As electrons in hybrid orbitals become closer to the nucleus, they are lower in energy

Inductive Effects
Electron-withdrawing effects due to differences in electronegativity pull electron density away from the negatively charged end of the conjugate base, lowering the energy and stabilizing the conjugate base, making the acid stronger.
O R C O C O O

O
O

S O O

Inductive Effects
Electron-donating effects due to differences in electronegativity push electron density toward the negatively charged end of the conjugate base, increasing the energy and destabilizing the conjugate base, making the acid weaker.
O R C O C O O

O
O

S O O

Inductive Effects
Electron-withdrawing Groups Electron-donating Groups

Cl

CH3

F, Cl, Br, O, N

R, CH3, B, Si

electronegative elements alkyl groups and elements less electronegative than carbon pull electron density push electron density toward carbon away from carbon
Remember, the electron-withdrawing and -donating groups work through the s bond system, while resonance groups work through the p system.

Inductive Effects
Chlorine helps to stabilize CO2 by withdrawing electrons

O Cl C O
O O

This effect diminishes with distanceit extends for about 3 bonds

Cl C C C

increasing electronegativity

Inductive Effects
pKa Values 3.13
CH3
Cl

increasing substitution

I Br

CH2COOH

COOH

4.75

CH2COOH 2.87

CH2

COOH 2.81

Cl

CH2COOH 2.81
CH2COOH

Cl Cl CH COOH

1.29

Cl
F

2.66

Cl

C Cl

COOH

0.65

Inductive Effects
Increasing substitution

O CH3 C OH Cl CH2
2.81

O C OH
Cl

Cl O C Cl C OH

pKa: 4.75

0.65