ACID BASE NOTES MISS CHOHAN 12/23/2015

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.

Each acid is linked to a conjugate base

on the other side of the equation.

HNO3 + HNO2 ⇌ NO3– + H2NO2+ HCOOH + CH3(CH2)2COOH ⇌ HCOO– + CH3(CH2)2COOH2+

Acid 1 Base 2 Base 1 Acid 2 Acid 1 Base 2 Base 1 Acid 2

In these reactions the substance with bigger Ka will act

as the acid

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 acids completely dissociate in water strong acid 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
done by pressing
[H+] = 10 -pH
What is the concentration of HCl with
a pH of 1.35?
Inv (or 2nd function) 
log  - 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: H 2O (l)  H+(aq) + OH-
(aq)
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This equilibrium has the Because [H2O(l)] is much bigger

following equilibrium expression than the concentrations of the
ions, we assume its value is
constant and make a new constant
Kw

The Kw expression can be used

At 25oC the value of Kw for all aqueous solutions is 1x10 -14 mol2dm-6
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

Example 2 : At different temperatures to 25oC the

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

Calculating pH of Strong Base

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

pH = - log[1x10-13] =13.00
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Weak Acids

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

Weak acids dissociation expression Example 4 Write an equation for dissociation of

propanoic acid and its ka expression

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

pKa
The Ka for ethanoic acid is 1.7 x 10-5 mol dm-3.
Sometimes Ka values are quoted as pKa values pKa
The larger ka the stronger the acid = -log Ka so Ka = 10-pKa

Calculating pH of A Weak Acid

To make the calculation easier two assumptions are made to simplify

the Ka expression:

1) [H+(aq)]eqm = [A-(aq)] eqm because they have dissociated

according to a 1:1 ratio.

2) As the amount of dissociation is small we assume that the initial

concentration of the undissociated acid has remained constant.

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)

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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)

Working out pH of a weak acid at half equivalence

When a weak acid has been reacted with exactly half the Example 7
neutralisation volume of alkali, the above calculation can be What is the pH of the resulting
simplified considerably solution when 25cm3 of 0.1M NaOH
is added to 50cm3 of 0.1M
At half neutralisation we can make
CH3COOH (ka 1.7 x 10-5)
the assumption that [HA] = [A ]
-

From the volumes and

concentrations spot it is half
neutralisation (or calculate)

pH = pka = -log (1.7 x 10-5 ) = 4.77

Diluting An Acid or Alkali

pH of diluted base
pH of diluted strong acid

Example 8 Calculate the new pH when 50.0 cm3 of 0.150 mol dm-3 HCl is mixed with 500 cm3 of water
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Comparing The pH of a Strong Acid and A weak Acid After Dilution 10, 100 and
1000 Times

Because pH is a logarithmic scale, diluting a strong acid 10 times will increase its pH by one unit,
and diluting it 100 times would increase its pH by two units

Weak acids would not change in the same way as when they are diluted. They increase by less
than 1 unit CH3CH2CO2H +H2O ⇌ H3O+ + CH3CH2CO2

Diluting the weak acid pushes the equilibrium to the right so the degree of dissociation
increases and more H+ ions are produced meaning pH increases less than expected

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 from reacting the weak base with a strong
a salt of that weak acid ( made from reacting the acid).
weak acid with a strong base).
Example : ammonia and ammonium chloride
Example : ethanoic acid and sodium ethanoate NH3 and NH4+Cl
CH3CO2H and CH3CO2- Na+

How Buffer Solutions Work

In a buffer solution there is a

In an ethanoic acid buffer much higher concentration of the
CH3CO2H (aq) ⇌ CH3CO2 (aq) + H (aq)
- + salt CH3CO2- ion than in the pure
Acid conjugate base acid i.e there is a large reservoir
of the salt anions A-

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, CH3CO2- (aq) + H+(aq) ⇌ CH3CO2H
(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.
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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
CH3CO2H (aq) ⇌ CH3CO2 (aq) + H (aq)
- + illustrate your answer.

Calculating
Some ethanoic acid the pH ofare
molecules buffer solution
changed to ethanoate ions but as there is a large
concentration of the salt ion in the buffer the ratio [CH 3CO2H]/ [CH3CO2-] stays almost
We still use the weak acids dissociation expression
constant, so the pH stays fairly constant.

But here we assume the

[A-] concentration is due
to the added salt only

The salt content can be added in several ways: a salt solution

could be added to the acid or some solid salt added. A buffer can We also assume the Initial
also be made by partially neutralising a weak acid with alkali and concentration of the acid has
therefore producing salt remained constant, because
amount that has dissociated or
reacted is small

Example 9: making a buffer by adding a salt solution

What would be the pH of a buffer made from 45cm3 of 0.1M ethanoic acid and 50cm3 of 0.15M sodium
ethanoate (Ka = 1.7 x 10-5) ?

Example 10 : making a buffer by adding a solid salt

A buffer solution is made by adding 1.1g of sodium ethanoate into 100 cm 3 of 0.4M ethanoic acid. What is
its pH? Ka =1.7 x10-5
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If a buffer is made by adding sodium hydroxide to partially neutralise a weak acid then follow the method
below

Example 11 55cm3 of 0.5M CH3CO2H is reacted with 25cm3 of 0.35M NaOH. What will be the pH of the
resulting buffer solution?

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

Buffering Action in Blood

A carbonic acid– hydrogencarbonate equilibrium Equilibrium

acts as a buffer in the control of blood pH H2CO3 ⇌ H+ + HCO3–

The H2CO3/HCO3– buffer is present in blood Adding alkali reacts with H+ so the above
plasma, maintaining a pH between 7.35 and 7.45. Equilibrium would shift right forming new
H+ and more HCO3 –

Titration Curves

Constructing a pH curve

Calibrate meter first by measuring known

 Measure initial pH of the acid
pH of a buffer solution. This is necessary
 Add alkali in small amounts noting the
because pH meters can lose accuracy on
volume added
storage
 Stir mixture to equalise the pH
 Measure and record the pH to 1 dp
 When approaching endpoint add in smaller Can improve accuracy by maintaining
volumes of alkali constant temperature
 Add until alkali in excess
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Strong Acid – Strong Base

There are 4 main types of curve

1. Strong acid and strong

base
2. Weak acid and strong base
3. Strong acid and weak base
4. Weak acid and weak base

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

At ½ the neutralisation volume the

[HA] = [A-]

So Ka= [H+] and pKa = pH

If we know the Ka we can then work

out the pH at ½ V or vice versa
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Strong Acid – Weak Base

Weak Acid – Weak Base

e.g. CH3CO2H and NH3

Choosing An Indicator

Indicators can be considered as weak acids.

The acid must have a different colour to its HIn (aq) ⇌ In- (aq) + H+ (aq)
conjugate base colour A colour B
We can apply Le Chatelier to give us the colour.
An indicator changes colour from HIn to In-
over a narrow range. Different indicators In an acid solution the H+ ions present will push this
change colours over a different ranges equilibrium towards the reactants. Therefore
colour A is the acidic colour.

The end-point of a titration is reached when In an alkaline solution the OH- ions will react and
[HIn] = [In-]. To choose a correct indicator remove H+ ions causing the equilibrium to shift to
for a titration one should pick an indicator the products. Colour B is the alkaline colour.
whose end-point coincides with the
equivalence point for the titration

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.

Only use phenolphthalein in titrations with strong

bases but not weak bases

Colour change: colourless acid  pink alkali

Use methyl orange with titrations with strong

acids but not weak acids Colour change:
red acid  yellow alkali
(orange end point)
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