Water undergoes Self Ionisation

H2O(l) ⇄ H+(aq) + OH-(aq)

or
-
H2O(l) + H2O(l) ⇄ H3O
+
(aq) + OH (aq)

The concentration of H+ ions and OH- ions

is extremely small.

Because the equilibrium lies very much on the left hand

Ionisation Strong/weak acids
Ionic Product Strong/Weak bases
pH pH Curve
Logarithm End-Point
Kw Dissociation Constant
Indicator
pH scale
 H2O(l) ⇄ H+(aq) + OH-(aq)

Kc =
In the above expression, the value of [H2O] may be taken as having a
constant value because the degree of ionisation is so small.

Kc =

Kc [H2O] = [H+] [OH-]

Both Kc and [H2O] are constant values so

Kw = Kc [H2O] = [H+] [OH-]

 T (°C) Kw (mol2/litre2)

0 0.114 x 10-14
10 0.293 x 10-14
20 0.681 x 10-14
25 1.008 x 10-14
30 1.471 x 10-14
40 2.916 x 10-14
50 5.476 x 10-14

Kw of pure water decreases as the temperature increases

Acid–Base Concentrations in Solutions
Acid–Base Concentrations in Solutions
10-1
concentration (moles/L)

H+ OH-

10-7
H+ OH-

OH- H+

10-14
[H+] > [OH-] [H+] = [OH-] [H+] < [OH-]
acidic neutral basic
solution solution solution
 Soren Sorensen
(1868 - 1939)

The pH scale was invented by the Danish chemist

Soren Sorensen to measure the acidity of beer in a
brewery. The pH scale measured the concentration of
hydrogen ions in solution. The more hydrogen ions,
the stronger the acid.
1 2 3 4 5 6 7 8 9 10 11 12 13 14

Strong Weak Neutral Weak Strong

Acid Acid Alkali Alkali
The quantity of hydrogen ions in
solution can affect the color of
certain dyes found in nature. These
dyes can be used as indicators to
test for acids and alkalis. An
indicator such as litmus (obtained
from lichen) is red in acid. If base is
slowly added, the litmus will turn
blue when the acid has been
neutralized, at about 6-7 on the pH
scale. Other indicators will change
color at different pH’s. A
combination of indicators is used to
make a universal indicator.
Measuring pH
Universal Indicator Paper

Universal Indicator Solution

pH meter
Measuring pH

pH can be measured in several ways

 Usually it is measured with a coloured acid-base

indicator or a pH meter

 Coloured indicators are a crude measure of pH, but

are useful in certain applications

 pH meters are more accurate, but they must be

calibrated prior to use with a solution of known pH
Limitations of pH Scale
The pH scale ranges from 0 to 14

Values outside this range are possible but do not

tend to be accurate because even strong acids and
bases do not dissociate completely in highly
concentrated solutions.

pH is confined to dilute aqueous solutions

At 250C
Kw = 1 x 10-14 mol2/litre2

[H+ ] x [OH- ] = 1 x 10-14 mol2/litre2

This equilibrium constant is very important because it

applies to all aqueous solutions - acids, bases, salts,
and non-electrolytes - not just to pure water.
For H2O(l) ⇄ H+(aq) + OH-(aq)

→ [H+ ] = [OH- ]

[H+ ] x [OH- ] = 1 x 10-14 = [1 x 10-7 ] x [1 x 10-7 ]

[H+ ] of water is at 250C is 1 x 10-7 mol/litre

Replacing [H+ ] with pH to indicate acidity of solutions

pH 7 replaces [H+ ] of 1 x 10-7 mol/litre

where pH = - Log10 [H+ ]

 T (°C) pH

0 7.12
10 7.06
20 7.02
25 7
30 6.99
40 6.97

pH of pure water decreases as the temperature increases

A word of warning!
If the pH falls as temperature increases, does this mean that water
becomes more acidic at higher temperatures? NO!
Remember a solution is acidic if there is an excess of hydrogen ions over hydroxide ions.
In the case of pure water, there are always the same number of hydrogen ions and hydroxide
ions. This means that the water is always neutral - even if its pH change
•define pH

•describe the use of the pH scale as a measure of the degree of

acidity/alkalinity

•discuss the limitations of the pH scale

•explain self-ionisation of water

•write an expression for Kw

Acid – Base Concentrations and pH
10-1
pH = 3 pH = 11
concentration (moles/L)

H+ OH-

pH = 7
10-7
H+ OH-

OH- H+

10-14
[H3O+] > [OH-] [H3O+] = [OH-] [H3O+] < [OH-]

acidic neutral basic

solution solution solution
pH describes both [H+ ] and [OH- ]

0 Acidic [H+ ] = 100 [OH- ] =10-14

pH = 0 pOH = 14

 Neutral [H+ ] = 10-7 [OH- ] =10-7

pH = 7 pOH = 7

 Basic [H+ ] = 10-14 [OH- ] = 100

pH = 14 pOH = 0

pH of Common Substances

Acidic Neutral Basic

 pH [H+] [OH-] pOH

14 1 x 10-14 1 x 10-0 0
NaOH, 0.1 M 13 1 x 10-13 1 x 10-1 1
Household bleach
12 1 x 10-12 1 x 10-2 2
More basic

Household ammonia

Lime water 11 1 x 10-11 1 x 10-3 3

Milk of magnesia
10 1 x 10-10 1 x 10-4 4
Borax
9 1 x 10-9 1 x 10-5 5
Baking soda
Egg white, seawater 8 1 x 10-8 1 x 10-6 6
Human blood, tears
Milk 7 1 x 10-7 1 x 10-7 7
Saliva
Rain 6 1 x 10-6 1 x 10-8 8
More acidic

Black coffee 5 1 x 10-5 1 x 10-9 9

Banana
Tomatoes 4 1 x 10-4 1 x 10-10 10
Wine
Cola, vinegar 3 1 x 10-3 1 x 10-11 11
Lemon juice
2 1 x 10-2 1 x 10-12 12
Gastric juice
1 1 x 10-1 1 x 10-13 13
0 1 x 100 1 x 10-14 14
Calculations and practice
• You will need to memorize the following:

[H+] = 10–pH
[OH–] = 10–pOH

pH = – log10[H+]
pOH = – log10[OH–]

pH + pOH = 14
pH Calculations
pH = -log10[H+]
pH [H+]
[H+] = 10-pH

pH + pOH = 14 [H+] [OH-] = 1 x10-14

pOH = -log10[OH-]
pOH [OH-]
[OH-] = 10-pOH
 pH for Strong Acids
 Strong acids dissociate completely in solution

Strong alkalis (bases) also dissociate completely in

solution.
 It is easy to calculate the pH of strong acids and strong bases; you
only need to know the concentration.
concentration
pH Exercises
a) pH of 0.02M HCl c) pH of solution where [H +]
pH = – log10 [H+] is 7.2x10-8M
= – log10 [0.020] pH = – log10 [H+]
= 1.6989 = – log10 [7.2x10-8]
= 1.70 = 7.14
b) pH of 0.0050M NaOH
(slightly basic)
pOH = – log10 [OH–]
= – log10 [0.0050]
= 2.3
pH = 14 – pOH
= 14 – 2.3
=11.7
 pH = ?
HA(aq) H1+(aq) + A1-(aq) pH = - log10 [H+]
monoprotic
e.g. HCl, HNO3 0.3 M 0.3 M 0.3 M pH = - log10[0.3M]
pH = 0.48

H2A(aq) 2 H1+(aq) + A2-(aq) pH = - log10[H+]

diprotic
e.g. H2SO4 0.3 M 0.6 M 0.3 M pH = - log10[0.6M]
pH = 0.78
 Given: pH = 4.6 determine the [hydrogen ion]

pH = - log10 [H+] choose proper equation

4.6 = - log10 [H+] substitute pH value in equation

- 4.6 = log10[H+] multiply both sides by -1

2nd log - 4.6 = antilog [H+] take antilog of both sides

[H+] = 2.51x10-5 M
10x

antilog

You can check your answer by working backwards.

pH = - log10[H+]
pH = - log10[2.51x10-5 M]
pH = 4.6
Most substances that are acidic in water are actually weak acids.
Because weak acids dissociate only partially in aqueous solution,
an equilibrium is formed between the acid and its ions.
The ionization equilibrium is given by:
HX(aq) H+(aq) + X-(aq)
where X- is the conjugate base.
For Weak Acids

pH = -Log10

For Weak Bases

pOH = Log10

pH = 14 - pOH
 Calculating pH - weak acids

A weak acid is one which only partially dissociates in aqueous solution

A weak acid, HA, dissociates as follows HA(aq) H+(aq) + A¯(aq) (1)

Applying the Equilibrium Law Ka = [H+(aq)] [A¯(aq)] mol dm-3 (2)

[HA(aq)]

The ions are formed in equal amounts, so [H+(aq)] = [A¯(aq)]

therefore Ka = [H+(aq)]2 (3)

[HA(aq)]

Rearranging (3) gives [H+(aq)]2 = [HA(aq)] Ka

therefore [H+(aq)] = [HA(aq)] Ka

 pH of solutions of weak concentrations
Weak Acid

pH of a 1M solution of ethanoic acid with a Ka value of 1.8 x 10 -5

pH = -Log10

pH = -Log10

pH = 2.3723
 pH of solutions of weak concentrations
Weak Base

pH of a 0.2M solution of ammonia with a Kb value of 1.8 x 10-5

pOH = -log10

pOH = -log10
pOH = 2.7319

pH = 14 – 2.7319

pH = 11.2681
 Theory of Acid Base Indicators
Acid-base titration indicators are quite often weak acids.

For the indicator HIn

The equilibrium can be simply expressed as

HIn(aq, colour 1) H+(aq) + In-(aq, colour 2)

The un-ionised form (HIn) is a different colour to the anionic

form (In¯).
 Theory of Acid Base Indicators
Applying Le Chatelier's equilibrium principle:

Addition of acid
• favours the formation of more HIn (colour 1)

HIn(aq) H+(aq) + In-(aq)

because an increase on the right of [H+]

causes a shift to left

increasing [HIn] (colour 1)

to minimise 'enforced' rise in [H+].

 Theory of Acid Base Indicators
Applying Le Chatelier's equilibrium principle:

Addition of base
• favours the formation of more In- (colour 2)
HIn(aq) H+(aq) + In-(aq)
The increase in [OH-] causes a shift to right
because the reaction
H+(aq) + OH-(aq) ==> H2O(l)

Reducing the [H+] on the right

so more HIn ionises to replace the [H+]

and so increasing In- (colour 2)

to minimise 'enforced' rise in [OH-]
 Theory of Acid Base Indicators
Summary
 In acidic solution

HIn(aq) H+(aq) + In¯(aq)

 In alkaline solution
 Theory of Acid Base Indicators
Acid-base titration indicators are also often weak bases.

For the indicator MOH

The equilibrium can be simply expressed as

MOH(aq, colour 1) OH-(aq) + M+(aq, colour 2)

 Theory of Acid Base Indicators
Applying Le Chatelier's equilibrium principle:

Addition of base
• favours the formation of more MOH (colour 1)

MOH(aq) M+(aq) + OH-(aq)

because an increase on the right of [OH-]

causes a shift to left

increasing [MOH] (colour 1)

-
to minimise 'enforced' rise in [OH ].
 Theory of Acid Base Indicators
Applying Le Chatelier's equilibrium principle:

Addition of acid
• favours the formation of more M+ (colour 2)
MOH(aq) M+(aq) + OH-(aq)
The increase in [H+] causes a shift to right
because the reaction
H+(aq) + OH-(aq) ==> H2O(l)

Reducing the [OH-] on the right

so more MOH ionises to replace the [OH-]

and so increasing M+ (colour 2)

+
Acid Base Titration Curves
Strong Acid – Strong Base Strong Acid – Weak Base

Weak Acid – Strong Base Weak Acid – Weak Base

 Choice of Indicator for Titration
Indicator must have a complete colour change in
the vertical part of the pH titration curve

Indicator must have a distinct colour change

Indicator must have a sharp colour change

Indicators for Strong Acid Strong Base Titration

Both phenolphthalein
and methyl orange
have a complete
colour change in the
vertical section of the
pH titration curve
Indicators for Strong Acid Weak Base Titration
Methyl Orange is
used as indicator for
this titration

Only methyl orange

has a complete
colour change in the
vertical section of the
pH titration curve
Phenolphthalein has
not a complete colour
change in the vertical
section on the pH
titration curve.
Indicators for Weak Acid Strong Base Titration
Phenolphthalein is
used as indicator for
this titration

Only phenolphthalein
has a complete
colour change in the
vertical section of the
pH titration curve
Methyl has not a
complete colour
change in the vertical
section on the pH
titration curve.
Indicators for Weak Acid Weak Base Titration
No indicator suitable
for this titration
because no vertical
section

Neither phenolphthalein
nor methyl orange have
completely change colour
in the vertical section on
the pH titration curve
 indicator pH range

litmus 5-8

methyl orange 3.1 - 4.4

phenolphthalein 8.3 - 10.0

Colour Changes and pH ranges
Methyl Orange
Phenolphthalein
 Universal indicator components

Indicator Low pH color Transition pH range High pH color

Thymol blue (first transition) red 1.2–2.8 orange

Methyl Orange red 4.4–6.2 yellow
Bromothymol blue yellow 6.0–7.6 blue

Thymol blue (second transition) yellow 8.0–9.6 blue

Phenolphthalein colourless 8.3–10.0 purple

Students should be able to:
• calculate the pH of dilute aqueous solutions of strong acids and bases
 
• distinguish between the terms weak, strong, concentrated and dilute
in relation to acids and bases
 
• calculate the pH of weak acids and bases (approximate method of
calculation to be used – assuming that ionisation does not alter the
total concentration of the non-ionised form)
 
• define acid-base indicator
 
• explain the theory of acid-base indicators
 
• justify the selection of an indicator for acid base titrations