Chapter 2

Acids and
Bases:
Central to
Understanding Organic
Chemistry

Paula Yurkanis Bruice

University of California,
Acid rain have devastated the Norway Santa Barbara
Spruce trees

1
2.1 AN INTRODUCTION TO ACIDS AND BASES
Brø nsted–Lowry definition: proton (H+)

Acid: proton donor (HX)

Base: proton acceptor (B:)

Amphoteric H2O

2
the stronger the acid, the weaker its conjugate base.
2.2 pKa AND pH

Ka = acid dissociation constant

= acidity constant
= degree of ioniz’n of acid in water

In dilute solution, [H2O] is constant (= 55.5 M)

The stronger the acid, the larger the Ka.

The stronger the acid, the smaller the pKa.

The concentration of protons in a solution is indicated by pH. This concentration can be

written as either [H+] or, because a proton in water is solvated, as [H3O+]. 3
4
 Statue of George Washington in Washington Square Park,
in Greenwich Village, New York.

Acid rain is formed where sulfur dioxide and nitrogen oxides are
produced, because when water reacts with these gases, strong acids
such as sulfuric acid and nitric acid are formed.

Marble, a form of calcium carbonate, decays because

5
2.3 ORGANIC ACIDS AND BASES

Protonated alcohols and protonated carboxylic acids are very strong acids.
6
An Alcohol Can Behave as an Acid and as a Base

• A curved arrow
points from the
electron donor to the
electron acceptor.

• An arrow with two

barbs ~ two e’s
move

A Carboxylic Acid Can Behave as an Acid and as a Base

7
An Amine Can Behave as an Acid or as a Base

8
 HX RNH2
inorg 16 amines
–2
acids 35-40
–10 10
–6 5
15.74 RH
hydrocarbons
phenol 25-60
conj
weaker HA
–1.74
weaker B:
Rϴ
Xϴ RCOOϴ ROϴ, HOϴ carbanion
halide ion carboxy anion alkoxide ion RNHϴ
hydroxide ion amide ion
9
2.4 HOW TO PREDICT THE OUTCOME OF
AN ACID-BASE REACTION

Acid is the one with the lower pKa.

10
2.5 HOW TO DETERMINE THE POSITION OF
EQUILIBRIUM

• The equilibrium favors formation of the weaker acid.

• The weaker the base, the stronger is its conjugate acid
• Stable bases are weak bases

11
Calculating the Equilibrium Constant

The equilibrium constant for the reaction of

acetic acid with ammonia:

The equilibrium constant for the reaction of

ethyl alcohol with methylamine:

12
2.6 HOW THE STRUCTURE OF AN ACID AFFECTS
ITS pKa VALUE
Electronegativity

When atoms are the same size,

the strongest acid has its hydrogen attached
to the most electronegative atom.

EN  ~ weaken Y−H bond

~ proton leaves better

13
The Strength of an Acid is Determined by the
Stability of Its Conjugate Base
The more stable the conjugate base, the stronger the acid.

Stable bases are weak bases.

EN  ~ accommodates
(−) charge better, and
accepts H+ less well

14
Why are Alcohols Stronger Acids
than Amines?

Oxygen is more electronegative than nitrogen.

15
Hybridization

s  ~ closer to nucleus

e- closer to nucleus
C more EN
stable, hard to give e-

The strongest acid has the most 16

stable (weakest) conjugate base.
Size
The stronger acid will have its proton attached to the largest atom.

Stability
Its negative charge is
Hybrid orbital volume 2sp3 < 3sp3 < 4sp3 < 5sp3 spread over a larger volume
of valence e-

period ~ EN governs
size overrides electronegativity group ~ size wins
17
18
 2.7 HOW SUBSTITUENTS AFFECT
THE STRENGTH OF AN ACID
• EN ~ H < Br < Cl < F

• EWG closer ~ stronger acid

Inductive electron withdrawal increases the acidity of a conjugate acid

19
 2.8 AN INTRODUCTION TO
DELOCALIZED ELECTRONS
Why is a Carboxylic Acid a Stronger Acid than an Alcohol?

1. Inductive electron withdrawal 2. Delocalized electrons: resonance

• e--withdrawing through s bonds

• inductive effect of C=O

20
 2.9 A SUMMARY OF THE FACTORS THAT
DETERMINE ACID STRENGTH
1. Size: As the atom attached to the hydrogen increases in size, the
strength of the acid increases

2. Electronegativity

3. Hybridization

21
4. Inductive effect

5. Electron delocalization

22
2.10 HOW pH AFFECTS THE STRUCTURE OF AN
ORGANIC COMPOUND

Compounds exist primarily in their acidic forms (with its proton) in solutions
that are more acidic than their pKa values and primarily in their basic forms
(without its proton) in solutions that are more basic than their pKa values.

23
The relative amounts of a compound with a pKa of 5.2 in the acidic
and basic forms at different pH values.

24
Is a Compound Neutral or Charged?

A carboxylic acid is
neutral in its acidic form and charged in its basic form.

An alcohol is
neutral in its acidic form and charged in its basic form.

An amine is
charged in its acidic form and neutral in its basic form.
25
The separation of carboxylic acid (RCOOH) with a pKa of
5.0 and a protonated amine (RNH3+) with a pKa of 10.0,
dissolved in a mixture of water and diethyl ether.

pKa = 5

pKa = 10

 at pH = 2, both in acidic form

 RCOOH to ether, RNH3+ to water
 charged [ionic] to (polar) water;
neutral [organic] to (organic) ether.
 |pH – pKa| > 2 for better separation
(< 1/100)

Q. pH for amine in ether and acid in water?

 Do Problem 44 – 46. 26
 Aspirin must be in its basic form to be
physiologically active !

In the stomach (pH = 1 – 2.5) it is in the acidic form, then it can pass easily
through membranes, while the charged basic form cannot.

In the cell (pH = 7.4), it is in the basic form, then it can carry out the reactions
to reduce fever, pain, and inflammation.

27
 2.11 BUFFER SOLUTIONS
A buffer solution contains an acid and its (salt of) conjugate
base.

A buffer solution maintains nearly constant pH when small

amounts of acid or base are added to it.

28
 2.12 LEWIS ACIDS AND BASES
Lewis acid: a species that accepts (a share in) an electron pair
Lewis base: a species that donates (a share in) an electron pair

All Brø nsted acids are Lewis acids.

All Brø nsted bases are Lewis bases.

29
 How Chemists Use the Terms

“acid” = a proton-donating acid

“Lewis acid” = a non-proton-donating acid
Example: AlBr3, BF3, FeCl3, BH3, etc.
LA accepts e pair with empty orbital

All bases are Lewis bases

because they have a pair of electrons they can share.

30