Equilibria: Acids and bases - pH, Ka, pKa and Kw

Strong and Weak Acids

 Strong acids fully dissociate in solution – all molecules of the acid split, releasing
the maximum number of protons, H+(aq), possible.

 Weak acids partially dissociate in solution – some acid molecules that have
released a proton re-gain a proton to form a molecule of the acid again.

 A strong acid fully dissociates in solution. This means all molecules of the acid in the
solution release all the possible H+(aq) ions that they can. For example, hydrochloric
acid.

The number of moles of HCl(aq) that we start with is the same as the number of moles
of H+(aq) that are released. The concentration of H+(aq) ions in solution is the same as
the original concentration of acid.

 Weak acids do not fully dissociate in solution, they partially dissociate. This means
the concentration of H+(aq) ions in solution is not the same as the original
concentration of acid.
 Ethanoic acid is a weak acid:
 when ethanoic acid (CH3COOH) is placed in water, some of the acid
molecules will lose a proton (H+) to become negatively charged ethanoate ions
(CH3COO-). Ethanoate ions are the conjugate base of ethanoic acid.

 Some ethanoate ions will then recombine with a proton, to reform the acid
molecule. Meanwhile, more acid molecules will lose protons to become
ethanoate ions. This means an equilibrium is formed. There will still always be
acid molecules present in the solution, as well as protons and conjugate base
ions.

 Summary: By saying weak acids do not fully dissociate, it means there is a constant
exchange of protons between acid molecules and their conjugate base ions. This
constant exchange leads to an equilibrium being formed, where the overall
concentrations of acid and conjugate base molecules do not change, but individual
acids and bases are still exchanging protons.

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Equilibria: Acids and bases - pH, Ka, pKa and Kw

Monoprotic and Diprotic Acids

 Monoprotic acids release one H+(aq) ion for every one molecule of acid.

 Diprotic acids release two H+(aq) ions for every one molecule of acid.

 The concentration of a strong, monoprotic acid solution is the same as the

concentration of H+(aq) ions present in the solution.

 An example of a monoprotic acid, the HCl(aq) releases one H+(aq) ion for every
molecule of HCl.
 Mono means one, protic means proton. A monoprotic acid releases only one
H+(aq) ion for every molecule of acid.
 Diprotic acids can release two H+(aq) ions per molecule, for example Sulfuric acid
(H2SO4).

 One mole of a diprotic acid can release two moles of H+(aq) ions.

Acid Dissociation Constant, Ka

 Weak acids only partially dissociate in solution, forming an equilibrium between

the acid and its conjugate base.

 Acid dissociation constants, Ka, are used to show how much either the forward or
reverse reaction is favoured and to give an indication of the acid’s strength.

 The stronger the acid, the more the position of equilibrium will favour the forward
reaction (dissociation of the acid), so the concentration of H+(aq) ions in the
solution will be higher.

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Equilibria: Acids and bases - pH, Ka, pKa and Kw

-
 If a weak acid is shown as HA and its conjugate base as A , then the Ka for that acid
can be found using:

 The greater the concentration of H+(aq) ions, the stronger the acid and the larger the
value of Ka
 The smaller the value of Ka, the weaker the acid.

 the value of Ka is temperature dependant. If the temperature is changed, then the

Ka value will also be different for a particular acid.

 Since Ka values of many weak acids are very low, pKa values are used instead to
compare the strengths of weak acids with each other

pKa = -log10 Ka
 The less positive the pKa value the more acidic the acid is

pH Calculations

 pH (potential of hydrogen) is a scale used to show how acidic or alkaline a solution

is.

 Acidity is determined by the concentration of H+(aq)ions in a solution, meaning pH is a

way of describing the H+(aq)concentration in a solution.

 pH refers to the concentration of H+(aq) ions present in a solution.

 The larger the value of pH, the less acidic the solution.

 It can be calculated using:

pH = - log10[H+]
[H+] = 10-pH
 The pH scale is logarithmic, meaning a change in pH value of one refers to a change
in concentration of H+(aq) ions by a factor of 10.

 The pH scale starts at zero and this refers to a solution with a [H+(aq)] = 1 mol dm-3.

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Equilibria: Acids and bases - pH, Ka, pKa and Kw

 If H+ ion concentration is increasing by a factor of ten, the pH will decrease by one. If

H+ ion concentration is decreasing by a factor of ten, the pH will increase by one.
 For example:
 pH of 0 means a solution has a H+(aq) ion concentration of 1 mol dm-3.
 pH of 1 means a solution has a H+(aq) ion concentration of 0.1 mol dm-3

Worked Example

Calculating the Ka & pKa of weak acids

Calculate the Ka and pKa values of 0.100 mol dm-3 ethanoic acid at 298K which forms
1.32 x 10-3 of H+ ions in solution.

Answer

 Step 1: Write down the equation for the partial dissociation of ethanoic acid:

-
CH3COOH (aq) ⇌ H+ (aq) + CH3COO (aq)

 Step 2: Write down the equilibrium expression to find Ka:

Ka =

 Step 3: Simplify the expression:

 The ratio of H+ to CH3COO- is 1:1
 The concentration of H+ and CH3COO- is, therefore, the same
 The equilibrium expression can be simplified to:
 Ka =

 Step 4: Substitute the values into the expression to find Ka:

 Ka =

 Ka = 1.74 x 10-5

 Step 5: Determine the units of Ka:

 Ka = = mol dm-3

 Therefore, Ka is 1.74 x 10-5 mol dm-3

 Step 6: Find pKa:

 pKa = - log10 Ka
 pKa = - log10 (1.74 x 10-5)
 pKa = 4.76

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Equilibria: Acids and bases - pH, Ka, pKa and Kw

Kw
 The Kw is the ionic product of water

o It is the equilibrium constant for the dissociation of water at 298 K

o Its value is 1.00 x 10-14 mol2 dm-6
 For the ionisation of water, the equilibrium expression to find Kw is:

H2O (l) ⇌ H+ (aq) + OH- (aq)

Kw =

-
 As the extent of ionisation is very low, only small amounts of H+ and OH ions are
formed

 The concentration of H2O can therefore be regarded as constant and removed

from the Kw expression

 The equilibrium expression therefore becomes:

Kw = [H+] [OH-]

 As the [H+] = [OH+] in pure water, the equilibrium expression can be further
simplified to:

Kw = [H+]2

Worked Example 3: Calculating the concentration of H+ of pure water

Calculate the concentration of H+ in pure water, using the ionic product of water

Answer

 Step 1: Write down the equation for the partial dissociation of water:

o In pure water, the following equilibrium exists:

H2O (l) ⇌ H+ (aq) + OH- (aq)

 Step 2: Write down the equilibrium expression to find Kw:

o Kw =

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Equilibria: Acids and bases - pH, Ka, pKa and Kw

 Step 3: Simplify the expression:

o Since the concentration of H2O is constant, this expression can be

simplified to:

o Kw = [H+] [OH-]

 Step 4: Further simplify the expression:

o The ratio of H+ to OH- is 1:1

o The concentration of H+ and OH- is, therefore, the same and the
equilibrium expression can be further simplified to:

o Kw = [H+]2

 Step 5: Rearrange the equation to find [H+]:

o [H+] =

 Step 6: Substitute the values into the expression to find Kw:

o [H+] =

o [H+] = 1.00 x 10-7 mol dm-3

Worked Example 3: pH calculations of weak acids

Question: Calculate the pH of 0.100 mol dm-3 ethanoic acid at 298K with a Ka value of
1.74 x 10-5 mol dm-3.

Answer

 Ethanoic acid is a weak acid which ionises as follows:

CH3COOH (aq) ⇌ H+ (aq) + CH3COO- (aq)

 Step 1: Write down the equilibrium expression to find Ka:

o Ka =

 Step 2: Simplify the expression:

o The ratio of H+ to CH3COO- ions is 1:1

o Therefore the concentration of H+ and CH3COO- ions are the same

o So, the expression can be simplified to:

o Ka =

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Equilibria: Acids and bases - pH, Ka, pKa and Kw

 Step 3: Rearrange the expression to find [H+]:

o [H+] =

 Step 4: Substitute the values into the expression to find [H+]:

o [H+] =

o [H+] = 1.32 x 10-3 mol dm-3

 Step 5: Find the pH:

o pH = -log10 [H+]

o pH = -log10 1.32 x 10-3

o pH = 2.88

Homework questions

Question 1

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Equilibria: Acids and bases - pH, Ka, pKa and Kw

Question 2