Acid-Base Equilibrium

Chapter 18

Acids and Bases

Arrhenius
acids: generate H+ in water
bases: generate OH- in water
Brnsted-Lowry
acids: H+ donors
bases: H+ acceptors
HCl + H2O Cl + H3O+
acid
base

H3O+ =

H+(aq) = proton in water

Conjugate acid-base pairs

Conjugate base:
remains after H+ is lost
acid: HCl
conj. base: ClConjugate acid:
remains after H+ is gained
base: NH3
conj. acid: NH4+
Conjugate Pair
Acid

Base

Base

Conjugate Pair

Acid

Strong and Weak Acids

Strong:

100% dissociation
good H+ donor
equilibrium lies far to right (HNO3)
generates weak base (NO3-)

Weak:

<100% dissociation
not-as-good H+ donor
equilibrium lies far to left (CH3COOH)
generates strong base (CH3COO-)

Relative Acid
Strength

Relative Conj.
Base Strength

Very strong
Strong

Very weak

Weak
Weak
Strong
Very weak
Very strong

Acid Dissociation Constant

-

HA H 2 O

A H 3O
-

[H 3O ][A ] [H ][A ]
Ka

[HA]
[HA]

Ka Increases

Strength
vs. Ka

Water is amphoteric

Acid

Base

Conj. Acid

K w [H 3O ][OH ] 1 10

14

Conj. Base

at 25 C

Proton Transfer in Water

H

O H

O H

O H

O H

O H

H O H
+

O H

O H

O H

H
H O H

[H3O+] and [OH-]

K w [H 3O ][OH ] 1 10
Kw
[H 3O ]
[OH ]

[H3O+]
[OH-]

14

Kw
[OH ]

[H 3O ]
-

1x100 to 1x10-14
1x10-14 to 1x100

in water
in water

Finding [H3O+] and [OH-]

pH Scale

pH - log[H 3O ] - log[H ]
pH

to

14

in water

pOH - log[OH ] - log[OH ]

pOH

14

to

in water

K w [H 3O ][OH ] 1 10
pKw =

pH + pOH

14

14

pH and pOH
As [H3O+] rises, [OH-] falls

OH-

H
0

OH

1 2
Acidic

H
4

OH

7 8
Neutral

H+
9

10 11 12

As pH falls, pOH rises

13 14
Basic

Indicators

Polyprotic Acids
1. H3PO4 H2PO4- + H+
Ka1 = 7.2 x 10-3
2. H2PO4- HPO42- + H+
Ka2
= 6.3 x 10-8
3. HPO42PO43- + H+
Ka3
= 4.2 x 10-13
Ka1 > Ka2 > Ka3

Strength of Bases
Strong:
100% dissociation
OH- supplied to solution
NaOH(s) Na+(aq) + OH-(aq)
Weak:
<100% dissociation
OH- by reaction with water
CH3NH2(aq) + H2O(l)
CH3NH2(aq) + OH-(aq)

Base Dissociation Constant

-

B H 2O

BH OH
-

[BH][OH ]
Kb
[B ]

Kw, Ka and Kb

K w [H 3O ][OH ] 1 10
K w K a K b 1 10
Kw
Ka
Kb

Kw
Kb
Ka

14

14

Structure and Acid-Base Behavior

Binary hydrides:
1. Bond polarity (high acid strength)
2. Bond strength (low acid strength)

Structure and Acid-Base Behavior

Binary oxides:
1. Acidic oxides (acid anhydrides)
OX bond:
strong and polar
SO2, SO3, NO2, P4O10,
2. Basic oxides (basic anhydrides)
OX bond:
ionic
K2O, CaO,

Structure and Acid-Base Behavior

Oxoacids (HaXbOc):
1. Same number of O on different X
EN of X
2. Different number of O on same X
more O

Relative Strengths of Oxoacids

Cl

1O

Cl

4O

Electron density
O

3O

Electron density
O

2O

Cl

Electron density
O
O Cl
O

Electron density

Increasing Acid
Strength

Lewis Acids and Bases

Lewis Acid:
Lewis Base:

Al3+ + 6 O

electron pair acceptor

electron pair donor

Acid

H
Al

H
Base

3+

O
H