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

Each acid is linked to a conjugate

base on the other side of the
equation.

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

Acid 1 Base 2 Base 1 Acid 2 CH3(CH2)2COOH2+
Acid 1 Base 2 Base 1
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 strong acid will be the same as the concentration of
water 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 Example 1
[H+] = 10 -pH is
done by pressing What is the concentration of HCl
with a pH of 1.35?
Inv (or 2nd function) 
[H+] = 1 x 10-1.35 = 0.045M
log  - number(pH)

Ionic Product for Water

In all aqueous solutions and pure water the following equilibrium occurs: H 2O (l)  H+(aq)
+ OH-(aq)

Because [H2O(l)] is much

bigger than the concentrations
of the ions, we assume its
value is constant and make a
new constant Kw
ACID BASE NOTES MISS CHOHAN 12/23/2015

This equilibrium has the

following equilibrium
expression

The Kw expression can be

At 25oC the value of Kw for all aqueous solutions is 1x10-14 used to calculate [H+(aq)]
mol2dm-6 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
Calculate the pH of water at 50ºC given that Kw =
Chatelier’s principle can predict the
5.476 x 10-14 mol2 dm-6 at 50ºC [H+(aq)] = √Kw =
change. The dissociation of water is
√5.476 x 10-14 =2.34 x 10-7 mol dm-3 pH = - log 2.34
endothermic so increasing the
x 10-7 = 6.6
temperature would push the
It is still neutral though as [H+ (aq) ] = [OH- (aq)] 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 0.1M NaOH
concentration 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
[H+(aq)] = kw/ [OH- (aq)] = 1x10-14 / 0.1 = 1x10-
ions. NaOH 13
M

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 Example 4 Write an equation for dissociation of

expression 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 = -log Ka so Ka = 10-pKa
The larger ka the stronger the acid

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)

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)

 ACID BASE NOTES MISS CHOHAN 12/23/2015

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 What is the pH of the resulting
can be simplified considerably solution when 25cm3 of 0.1M
NaOH is added to 50cm3 of 0.1M
At half neutralisation we can CH3COOH (ka 1.7 x 10-5)
make the assumption that [HA] From the volumes and
= [A-] 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

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
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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 from reacting the weak base with
An acidic buffer solution is made from a weak acid
a strong acid).
and a salt of that weak acid ( made from
reacting the weak acid with a strong base). Example : ammonia and ammonium
chloride NH3 and NH4+Cl
Example : ethanoic acid and sodium ethanoate
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 salt CH3CO2- ion than in
CH3CO2H (aq) ⇌ CH3CO2- (aq) + H+ (aq) the pure acid i.e there is a
Acid conjugate base
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.

If small amounts of alkali is added to the buffer. The OH- ions will react with H+
ions to form water.

H+ + OH H2O Learn these

explanations carefully
The Equilibrium will then shift to the right to produce more H + ions. and be able to write the
equilibrium to illustrate
CH3CO2H (aq) ⇌ CH3CO2- (aq) + H+ (aq) your 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 [CH 3CO2H]/ [CH3CO2-] stays almost
constant, so the pH stays fairly constant.
ACID BASE NOTES MISS CHOHAN 12/23/2015

Calculating the pH of buffer solution

We still use the weak acids dissociation expression

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 We also assume the Initial
can also be made by partially neutralising a weak acid with concentration of the acid has
alkali and 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

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?
ACID BASE NOTES MISS CHOHAN 12/23/2015

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 H2CO3 ⇌ H+ + HCO3–
blood pH

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

Titration Curves

Constructing a pH curve

 Measure initial pH of the acid Calibrate meter first by measuring

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

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
ACID BASE NOTES MISS CHOHAN 12/23/2015

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

Strong Acid – Weak Base

Weak Acid – Weak Base

e.g. CH3CO2H and NH3

ACID BASE NOTES MISS CHOHAN 12/23/2015

Choosing An Indicator

Indicators can be considered as weak

acids. The acid must have a different HIn (aq) ⇌ In- (aq) + H+ (aq)
colour to its 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
change colours over a different ranges this equilibrium towards the reactants.
Therefore colour A is the acidic colour.

In an alkaline solution the OH- ions will react

The end-point of a titration is reached and remove H+ ions causing the equilibrium to
when [HIn] = [In-]. To choose a correct shift to the products. Colour B is the alkaline
indicator for a titration one should pick an colour.
indicator 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)
ACID BASE NOTES MISS CHOHAN 12/23/2015