3.

Acid Base Equilibria

Bronsted-Lowry Definition of acid Base behaviour

A Bronsted-Lowry acid is defined as a substance that can donate a proton.

A Bronsted-Lowry base is defined as a substance that can accept a proton.

HCl (g) + H2O (l) H3O+ (aq) + Cl- (aq)

Each acid is linked to a conjugate base on
acid base acid base the other side of the equation.

Calculating pH
pH = - log [H+] Where [H+] is the concentration of hydrogen ions in the solution.

Calculating pH of strong acids

The concentration of hydrogen ions in a monoprotic strong acid
Strong acids completely dissociate
will be the same as the concentration of the acid.

For HCl and HNO3 the [H+(aq)] will be the same as the
original concentration of the acid. Always give pH values to 2d.p. In the exam
For 0.1M HCl the pH will be –log[0.1] =1.00

Finding [H+] from pH

On most calculators this is Example 1
[H+] = 1 x 10-pH done by pressing What is the concentration of HCl with a pH of
Inv (or 2nd function) log 1.35?
- number(pH) [H+] = 1 x 10-1.35 = 0.045M

Ionic Product for water

In all aqueous solutions and pure water the following equilibrium occurs: H2O (l) H+ (aq) + OH- (aq)

This equilibrium has the following Because [H2O (l)] is much bigger than the
equilibrium expression concentrations of the ions, we assume its
Rearrange to value is constant and make a new constant Kw
[H+ ][OH- (aq)]
Kc= (aq) Kc x [H2O (l)] = [H+ (aq) ][OH- (aq)]
Kw = [H+ (aq) ][OH- (aq) ]
[H2O(l)]
Learn this expression

At 25oC the value of Kw for all aqueous solutions is 1x10-14 mol2dm-6 The Kw expression can be used to
calculate [H+ (aq)] ions if we know
the [OH- (aq)] ions and vice versa.
Finding pH of pure water

Pure water/ neutral solutions are neutral because the [H+ (aq) ] = [OH-(aq)]
Using Kw = [H+ (aq) ][OH- (aq) ] then when neutral Kw = [H+ (aq) ]2
and [H+(aq) ] = √ Kw
At 25oC [H+(aq) ] = √ 1x10-14 = 1x10-7 so pH = 7

At different temperatures to 25oC the pH of

Example 2 : Calculate the pH of water at 50ºC given that Kw = pure water changes. Le Chatelier’s principle
5.476 x 10-14 mol2 dm-6 at 50ºC can predict the change. The dissociation of
[H+(aq) ] = √ Kw = √ 5.476 x 10-14 =2.34 x 10-7 mol dm-3 water is endothermic so increasing the
pH = - log 2.34 x 10-7 = 6.6 temperature would push the equilibrium to
It is still neutral though as [H+ (aq) ] = [OH- (aq)] the right giving a bigger concentration of H+
ions and a lower pH.

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Calculating pH of Strong Base

For bases we are normally given the Example 3: What is the pH of the strong base 0.1M NaOH
concentration of the hydroxide ion.
Assume complete dissociation.
To work out the pH we need to work out [H+(aq)]
Kw = [H+ (aq)][OH- (aq)] = 1x10-14
using the kw expression.
[H+(aq)] = kw/ [OH- (aq)] = 1x10-14 / 0.1 = 1x10-13 M
Strong bases completely dissociate into their ions. pH = - log[1x10-13 ] =13.00
NaOH Na+ + OH-

Weak Acids
Weak acids only slightly dissociate when dissolved in water, giving an equilibrium mixture.

We can simplify this to

HA + H2O (l) H3O+ (aq) + A- (aq) HA (aq) H+ (aq) + A- (aq)

Weak acids dissociation expression Example 4 Write an equation for dissociation of propanoic acid and
its ka expression
[H+ (aq)][A- (aq)]
Ka= CH3CH2CO2H(aq) H+ (aq) + CH3CH2CO2- (aq)
[HA (aq)]
[H+ (aq)][CH3CH2CO2-(aq)]
Ka=
The Ka for ethanoic acid is 1.7 x 10-5 mol dm-3. [CH3CH2CO2H(aq)]
The larger ka the stronger the acid.
pKa
Sometimes Ka values are quoted as pKa values
pKa = -log Ka so Ka = 10-pKa
Calculating pH of a Weak Acid

To make the calculation easier two assumptions are made to [H+ (aq)][A- (aq)]
simplify the Ka expression: Ka=
[HA (aq)]
1) [H+ (aq)]eqm = [A- (aq)] eqm because they have dissociated
according to a 1:1 ratio. Simplifies to
2) As the amount of dissociation is small we assume that the initial [H+ (aq)]2
concentration of the undissociated acid has remained constant. Ka=
[HA (aq)]initial
So [HA (aq) ] eqm = [HA(aq) ] initial

Example 5 What is the pH of a solution of 0.01M ethanoic acid (ka is 1.7 x 10-5 mol dm-3)?
CH3CO2H(aq) H+ (aq) + CH3CO2- (aq)

[H+ (aq)]2 [H+ (aq)]2

[H+ (aq)][CH3CO2-(aq)]
Ka= Ka= 1.7x 10-5 =
[CH3CO2H(aq)]initial 0.01
[CH3CO2H(aq)]

[H+ (aq)]2 = 1.7 x 10-5 x 0.01 pH = - log [H+] = -log (4.12 x10-4)
pH =3.38
[H+ (aq)] = √ 1.7 x 10-7 = 4.12 x 10-4

Example 6 What is the concentration of propanoic acid with a pH of 3.52 (ka is 1.35 x 10-5 mol dm-3)?

CH3CH2CO2H(aq) H+ (aq) + CH3CH2CO2- (aq)

[H+] = 1 x 10-3.52 = 0.000302M

[H+ (aq)]2 [0.000302]2
[H+ (aq)][CH3CH2CO2-(aq)]
Ka= Ka= 1.35 x 10-5 =
[CH3CH2CO2H(aq)]initial [CH3CH2CO2H(aq)]initial
[CH3CH2CO2H(aq)]

[CH3CH2CO2H(aq)] = 9.12 x 10-8 /1.35 x 10-5 [CH3CH2CO2H(aq)] = 6.75 x 10-3 M

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pH Calculations involving Neutralisation Reactions
These can be quite complex calculations working out the pH of a partially neutralised acid or the pH of the solution if too
much alkali has been added and has gone past neutralisation. The method differs if the acid is strong or weak for the
partially neutralised case.

Strong Acid and Strong Base Neutralisations Work out new concentration of excess H+ ions
[H+] = moles excess H+
If excess
total volume (dm3)
acid
Total volume =
Work out moles of original acid pH = – log [H+] vol of acid + vol
Work out moles of base added of base added
Work out which one is in excess
Work out new concentration of excess OH- ions
[OH-] = moles excess OH-
If excess total volume (dm3)
alkali
H+] = Kw /[OH– ] Total volume =
vol of acid + vol
Example 7 15cm3 of 0.5M HCl is reacted with 35cm3 of pH = – log [H+] of base added
0.55M NaOH. What will be the pH of the resulting mixture?
Example 8 45cm3 of 1M HCl is reacted with 30cm3 of
Moles HCl = conc x vol = 0.5 x 0.015 = 0.0075mol
0.65M NaOH. What will be the pH of the resulting mixture?
Moles NaOH = conc x vol = 0.55 x 0.035 = 0.01925
HCl + NaOH NaCl + H2O
Moles of NaOH in excess = 0.01925 – 0.0075= 0.01175 (as Moles HCl = conc x vol = 1 x 0.045 = 0.045mol
1:1 ratio) Moles NaOH = conc x vol = 0.65 x 0.030 = 0.0195
[OH-] = moles excess OH- HCl + NaOH NaCl + H2O
total volume (dm3) Moles of HCl in excess = 0.045-0.0195 = 0.0255 (as 1:1 ratio)
[H+] = moles excess H+
= 0.01175/ 0.05 = 0.235M total volume (dm3)
H+] = Kw /[OH– ]
= 0.0255/ 0.075 = 0.34M
= 1x10-14 / 0.235 = 4.25x10-14
pH = – log [H+]
pH = – log [H+]
= -log 0.34
= -log 4.25x10-14
= 0.47
= 13.37

Weak Acid and Strong Base Neutralisations Work out new concentration of excess HA
[HA] = initial moles HA – moles OH-
If excess
total volume (dm3)
acid
Work out moles of original acid
Work out moles of base added Work out concentration of salt formed [A-]
[A-] = moles OH- added
Work out which one is in excess
total volume (dm3)
Rearrange ka = [H+] [A-] to get [H+]
If excess alkali use the same method [HA]
with excess alkali and strong acid above pH = – log [H+]

Example 9 55cm3 of 0.5M CH3CO2H is reacted with 25cm3 of 0.35M NaOH. What will be the pH of the resulting mixture?

CH3CO2H+ NaOH CH3CO2Na + H2O

Moles CH3CO2H = conc x vol =0.5x 0.055 = 0.0275mol
ka is 1.7 x 10-5 mol dm-3
Moles NaOH = conc x vol = 0.35 x 0.025 = 0.00875

Moles of CH3CO2H in excess = 0.0275-0.00875 = 0.01875 (as 1:1 ratio)

[CH3CO2H ] = moles excess CH3CO2H [CH3CO2- ] = moles OH- added

total volume (dm3) total volume (dm3)
= 0.01875/ 0.08 = 0.234M = 0.00875/ 0.08 = 0.109M

ka = [H+] [CH3CO2- ]
[H+] = ka x[ CH3CO2H ] / [CH3CO2- ]
[ CH3CO2H ] pH = – log [H+]
= 1.7 x 10-5x 0.234 / 0.109 = -log 3.64 x 10-5
= 3.64 x 10-5 = 4.44

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Working out pH of a weak acid at half equivalence
Example 10
When a weak acid has been reacted with exactly half the
What is the pH of the resulting solution when
neutralisation volume of alkali, the above calculation can be simplified
25cm3 of 0.1M NaOH is added to 50cm3 of 0.1M
considerably.
CH3COOH (ka 1.7 x 10-5 )
ka = [H+] [CH3CO2- ] At half neutralisation we can make the
[ CH3CO2H ] assumption that [HA] = [A-] From the volumes and concentrations spot it is half
neutralisation (or calculate)
So [H+(aq)] = ka And pH = pka pH = pka = -log (1.7 x 10-5 ) = 4.77

Diluting an acid or alkali pH of diluted base

pH of diluted strong acid [OH–] = [OH–]old x old volume
new volume
[H+] = [H+]old x old volume
[H+] = Kw
new volume [OH– ]
pH = – log [H+] pH = – log [H+]

Example 11 Calculate the new pH when 50.0 cm3 of 0.150 mol dm-3 HCl is mixed with 500 cm3 of water.
H+] = [H+]old x old volume 0.05 [H+(aq)] = 0.0136
[H+(aq)] = 0.150 x
new volume 0.55 pH = – log [H+]
= -log 0.0136
= 1.87

Buffer Solutions

A Buffer solution is one where the pH does not change

significantly if small amounts of acid or alkali are added to it. A basic buffer solution is made from a weak
base and a salt of that weak base ( made
An acidic buffer solution is made from a weak acid and a salt from reacting the weak base with a strong
of that weak acid ( made from reacting the weak acid with a acid).
strong base). Example :ammonia and ammonium chloride
Example : ethanoic acid and sodium ethanoate NH3 and NH4+Cl-

CH3CO2H (aq) and CH3CO2- Na+

How Buffer solutions work

In an ethanoic acid buffer
In a buffer solution there is a much
CH3CO2H (aq) CH3CO2- (aq) + H+ (aq) higher concentration of the salt
CH3CO2- ion than in the pure acid.
Acid conjugate base

The buffer contains a reservoir of HA and A - ions

If small amounts of acid is added to the buffer: Then the above equilibrium
will shift to the left removing nearly all the H+ ions added, [CH3CO2H (aq)]
[H+(aq)] = Ka
CH3CO2- (aq) + H+ (aq) CH3CO2H (aq) [CH3CO2-(aq) ]
As there is a large concentration of the salt ion in the buffer the ratio
[CH3CO2H]/ [CH3CO2-] stays almost constant, so the pH stays fairly
constant.

If small amounts of alkali is added to the buffer. The OH- ions will react with H+ ions to
form water.
Learn these
H+ + OH - H2O explanations carefully
and be able to write
The Equilibrium will then shift to the right to produce more H+ ions. the equilibrium to
illustrate your
CH3CO2H (aq) CH3CO2- (aq) + H+ (aq)
answer.
Some ethanoic acid molecules are changed to ethanoate ions but as there is a large
concentration of the salt ion in the buffer the ratio [CH3CO2H]/ [CH3CO2-] stays almost
constant, so the pH stays fairly constant.

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Calculating the pH of buffer solutions
We still use the weak acids dissociation expression
[HA(aq)]
But here we assume the [A-] Normally we [H+(aq)] = Ka
[H+ (aq)][A- (aq)] rearrange to
Ka= concentration is due to the added [A- (aq) ]
[HA (aq)] salt only
We also assume the Initial concentration of the
The salt content can be added in several ways: a salt solution could be acid has remained constant, because amount
added to the acid or some solid salt added. A buffer can also be made by that has dissociated or reacted is small.
partially neutralising a weak acid with alkali and therefore producing salt.

Example 12: making a buffer by adding a salt solution

We can enter moles of
What would be the pH of a buffer made from 45cm3 of 0.1M ethanoic acid acid and salt straight
and 50cm3 of 0.15 M sodium ethanoate (Ka = 1.7 x 10-5) ? into the equation as
they both have the
Work out the moles of both solutions same new final volume
Moles ethanoic = conc x vol = 0.1 x 0.045 = 0.0045mol [HA(aq)]
[H+(aq)] = Ka
Moles sodium ethanoate = conc x vol = 0.15 x 0.050 = 0.0075 [A- (aq) ]

0.0045
[H+(aq)] = 1.7 x 10-5 x [H+(aq)] = 1.02x 10-5 pH = – log [H+]
0.0075 = -log 1.02x 10-5
= 4.99

Example 13 : making a buffer by adding a solid salt

We can enter moles of
A buffer solution is made by adding 1.1g of sodium ethanoate into 100 cm3 acid and salt straight
of 0.4M ethanoic acid. What is its pH? Ka =1.7 x10-5 into the equation as
they both have the
Work out the moles of both solutions same new final volume
Moles ethanoic = conc x vol = 0.4 x 0.1 = 0.04mol [HA(aq)]
[H+(aq)] = Ka
Moles sodium ethanoate = mass/Mr= 1.1/82 = 0.0134 [A- (aq) ]

0.04
[H+(aq)] = 1.7 x 10-5 x [H+(aq)] = 5.07x 10-5 pH = – log [H+]
0.0134 = -log 5.07x 10-5
= 4.29

If a buffer is made by adding sodium hydroxide to partially neutralise a weak acid then follow the method below

Example 14 55cm3 of 0.5M CH3CO2H is reacted with 25cm3 of 0.35M NaOH. What will be the pH of the resulting buffer
solution?
CH3CO2H+ NaOH CH3CO2Na + H2O
Moles CH3CO2H = conc x vol =0.5x 0.055 = 0.0275mol
ka is 1.7 x 10-5 mol dm-3
Moles NaOH = conc x vol = 0.35 x 0.025 = 0.00875

Moles of CH3CO2H in excess = 0.0275-0.00875 = 0.01875 (as 1:1 ratio)

[CH3CO2H ] = moles excess CH3CO2H [CH3CO2- ] = moles OH- added

total volume (dm3) total volume (dm3)
= 0.01875/ 0.08 = 0.234M = 0.00875/ 0.08 = 0.109M

ka = [H+] [CH3CO2- ]
[H+] = ka x[ CH3CO2H ] / [CH3CO2- ]
[ CH3CO2H ] pH = – log [H+]
= 1.7 x10-5 x 0.234 / 0.109 = -log 3.64 x 10-5
= 3.64 x 10-5 = 4.44

Calculating change in pH of buffer on addition of alkali

If a small amount of alkali is added to a buffer then the moles of the acid would reduce by the number of
moles of alkali added and the moles of salt would increase by the same amount so a new calculation of
pH can be done with the new values

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 Titration curves
Constructing a PH curve Practical
•Measure initial pH of the acid Calibrate meter first by measuring known pH of a
• Add alkali in small amounts noting the volume added buffer solution. This is necessary because pH
• Stir mixture to equalise the pH meters can lose accuracy on storage
• Measure and record the pH to 1 dp
• When approaching endpoint add in smaller volumes of Can improve accuracy by maintaining
alkali constant temperature
•Add until alkali in excess

Strong acid – Strong base

e.g. HCl and NaOH There are 4 main types of curve
1. Strong acid and strong base
pH
2. Weak acid and strong base
13 3. Strong acid and weak base
Long vertical part 4. Weak acid and weak base
from around 3 to 9
7
pH at equivalence point = 7

3
25 cm of base

You may also have to work out the

neutralisation volume from titration
data given in the question. These
are done by standard titration The equivalence point lies at the
calculations from module 1. mid point of the extrapolated
vertical portion of the curve.

The Key points to sketching a curve:

Initial and final pH
Volume at neutralisation
General Shape (pH at neutralisation)

Weak acid – Strong base e.g. CH3CO2H and NaOH

Half neutralisation volume
pH
For weak acids
13
[H+ (aq)][A- (aq)]
Equivalence point >7 Ka=
[HA (aq)]
7
At ½ the neutralisation
Vertical part of curve >7 volume the [HA] = [A-]
(around 7 to 9)
pH So Ka= [H+] and pKa = pH
starts 1

near 3 25
3
cm of base If we know the Ka we can then work
out the pH at ½ V or vice versa
At the start the pH rises quickly and then
levels off. The flattened part is called the
buffer region and is formed because a buffer
solution is made

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 Weak acid – Weak base
Strong acid – Weak base
e.g. HCl and NH3
e.g. CH3CO2H and NH3
pH
pH
13
13
No vertical part of the curve

Vertical part of curve

7 7
<7 (around 4 to 7)

Equivalence point < 7

1
1
3
25 cm of base
3
25 cm of base

Choosing an Indicator
HIn (aq) In- (aq) + H+ (aq)
Indicators can be considered as weak acids. The acid colour A colour B
must have a different colour to its conjugate base
We can apply Le Chatelier to give us the
An indicator changes colour from HIn to In- over a colour.
narrow range. Different indicators change colours
In an acid solution the H+ ions present will
over a different ranges.
push this equilibrium towards the reactants.
Therefore colour A is the acidic colour.
The end-point of a titration is reached when [HIn] = In an alkaline solution the OH- ions will
[In-]. To choose a correct indicator for a titration one react and remove H+ ions causing the
should pick an indicator whose end-point coincides equilibrium to shift to the products. Colour B
with the equivalence point for the titration. is the alkaline colour.

An indicator will work if the pH range of the indicator lies on the vertical part of the titration curve. In this case
the indicator will change colour rapidly and the colour change will correspond to the neutralisation point.

pH
Only use phenolphthalein in titrations with strong strong base
13
bases but not weak bases-
Colour change: colourless acid pink alkali pH range for
weak base phenolphthalein
7

Use methyl orange with titrations with weak acid pH range for
strong acids but not weak acids methyl orange
Colour change: red acid yellow alkali 1
strong acid
(orange end point)
3
25 cm of base

7
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