CHEM1907/8

Lecture 12. Introduction to Acids and Bases

Acids and Bases (Classical)

Acids and Bases

Learning Objectives

Lecture Slides (04/04/03)

(Silberberg; 18.1-18.5)

Become familiar with common acids and bases

Equilibrium

An acid is a substance that contains hydrogen and dissociates

in water to yield a H+ (H3O+) hydronium ion

For the balanced reaction

aA + bB

Calculate pH values
Understand the relationship between pH and pKa values

The reaction quotient,

An acid and a base react to form salt and water (Eq 1).

Definitions of Acids and Bases

HCl + NaOH

Classical (Arrhenius) !
!

Lewis

not yet

H +(aq)

Water is a weak electrolyte

H3O (aq)

= Kw = [H3

= 1.0

HA + H2O
Qc =

Qc [H2O] = Ka =

The ion-product for water, Kw:

O+][OH]

1014

(at 25C)

For pure water the concentration of hydroxyl and

hydronium ions is equal

Other quantities are expressed as the p values

pH = log[H+]
pOH = log[OH]

pKa = log[Ka]

H2O(l)

.. (Eq 2)

[C] c [D] d
[A]a [B]b

where the PRODUCT terms go in the numerator and the

REACTANT terms go in the denominator multiplied by each other
and each term is raised to the power of its balancing coefficient.

At equilibrium, Q = K, the equilibrium constant

The p Convention

H 3O+ + A

pH = log[H+]

[A ] [H + ]
[H2O] [HA]

[A ] [H+ ]
[HA]

Ka is the acid dissociation constant.

If Ka is large, then [HA] is small and the acid is strong
If Ka is small, then [HA] is large and the acid is weak

The p Convention

The p Convention

pKw = log[Kw]

OH (aq)

OH (aq)

Kc = [H3O+][OH]
[H2O]2
Kc[H2O]2

Qc =

.. (Eq 1)

The Acid Dissociation Constant

Autoionisation of Water
+

NaCl + H2O

Neutralisation (Eq 2) is the reaction of an H+ (H3O+) ion from

the acid and the OH ion from the base to form water (the ionic
equation of Eq 1)

Brnsted-Lowry

2H2O(l)

cC + dD

A base is a substance that contains the hydroxyl group and

dissociates in water to yield OH

Kw = [H3O+][OH] = 1.0 1014 (at 25C)

The pH scale (and other p scales) are logarithmic

A change of one unit in pH represents a ten-fold

difference in [H+] concentration
A HCl solution of 1 103 M has a pH of 3
A HCl solution of 1 104 M has a pH of 4

The relationship between Ka and pKa

Acid Name (Formula)

Ka at 25oC

pKa

hydrogen sulfate ion (HSO4)

1.02 102

1.991

nitrous acid (HNO2)

7.1

104

3.15

acetic acid (CH3COOH)

1.8

105

4.74

hypobromous acid (HBrO)

2.3 109

8.64

phenol (C6H5OH)

1.0 1010

10.00

Taking the log

logKw = log[H+] + log[OH] = 14

Dividing by 1

logKw = (log[H+]) + (log[OH]) = 14

Since log[H+] = pH
log[OH] = pOH and
log[Kw] = pKw

pKw = pH + pOH = 14
1

Brnsted-Lowry Acid-Base Definition

Brnsted-Lowry Acid-Base Reaction

An acid is a proton donor; any species that donates an H+ ion.

eg; HNO3; H2PO4

A conjugate acid-base pair is a pair of chemical molecules

whose formulae differ by H+

H
H
H

A base is a proton acceptor; any species that accepts an H+ ion.

A base must contain a lone pair of electrons to bind the H+ ion;
eg; NH3, CO32, F , OH .

Conjugate Acid - Conjugate Base Pairs

O
H

H
base
H+ acceptor

NH4+ is the conjugate acid of NH3

acid
H+ donor

In the Brnsted-Lowry definition of acids and bases:

one species donates a proton and another species accepts it
an acid-base reaction is a proton transfer process.

NH3 is the conjugate base of NH4+

NH3 + H+

NH4+

H
H

Acids donate a proton to water

A conjugate base has one less proton than the corresponding

conjugate acid

H
Bases accept a proton from water

conjugate acid of NH3

Relative Strengths of Conjugate

Acid-Base Pairs

PROBLEM

Give conjugate bases for the following acids

HI

HNO3

conjugate base of H2O

PH4+

A Brnsted-Lowry acid base equilibrium can be

considered a competition for protons

HSO4

Strength of Conjugate Acid-Base Pairs

stronger acid
100% ionised
in water

Strongest acids lose their protons easily

Strongest bases hold onto their protons strongly

Give conjugate acids for the following bases

HSO4

H2O

NH2

Relation Between pKa and pKb and pKw

HA + H2O

H3O+ + A

A + H2O

OH + HA

Ka =

Ka

[A ] [H+ ]
[HA]

Kb =

[OH ] [HA]
[A ]

Kb = Kw = 1014

Values of pKa and pKb are used to

predict the direction of a reaction
HSO3

conjugate acid

NH3
conjugate base

Ka = 107.36

stronger acid

Kb = 104.76

+ stronger base

SO32

conjugate base

NH4+

ACID

BASE

HClO4
HCl
H2SO4
HNO3
H3O+
CH3CO2H
H2CO3
H2S
NH4+
HCO3
H2O
OH
H2

ClO4
Cl
HSO4
NO3
H2O
CH3CO2
HCO3
HS
NH3
CO32
OH
O2
H

stronger base
100% protonated
in water

Polyprotic Acids Dissociate in Steps

Phosphoric acid is a weak acid, and normally only looses one
proton in solution, but it will loose all three when reacted with a
strong base with heat.

conjugate acid

Kb = 106.64

Ka = 109.24

weaker acid +

weaker base

H3PO4

H+ +

H2PO4

Ka (1) = 7.2 103

H2PO4

H+ +

HPO42

Ka (2) = 6.3 108

HPO42

H+ +

PO43

Ka (3) = 4.2 1013

The reaction proceeds to the right and the

products are favoured