pH calculations

A guide for A level students

KNOCKHARDY PUBLISHING

pH calculations
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pH calculations
CONTENTS
What is pH? - a reminder

Calculating the pH of strong acids and bases

Calculating the pH of weak acids Calculating the pH of mixtures - strong acid and strong alkali Calculating the pH of mixtures - weak acid and excess strong alkali

Calculating the pH of mixtures - strong alkali and excess weak acid

Check list

pH calculations
Before you start it would be helpful to
know the differences between strong and weak acid and bases be able to calculate pH from hydrogen ion concentration be able to calculate hydrogen ion concentration from pH know the formula for the ionic product of water and its value at 25C

What is pH?

pH = - log10 [H+(aq)]
where [H+] is the concentration of hydrogen ions in mol dm-3

to convert pH into hydrogen ion concentration

[H+(aq)] = antilog (-pH)

IONIC PRODUCT OF WATER

Kw = =

[H+(aq)] [OH(aq)] mol2 dm-6 1 x 10-14 mol2 dm-6 (at 25C)

Calculating pH - strong acids and alkalis

WORKED EXAMPLE

Strong acids and alkalis completely dissociate in aqueous solution

It is easy to calculate the pH; you only need to know the concentration.

Calculate the pH of 0.02M HCl

HCl completely dissociates in aqueous solution One H+ is produced for each HCl dissociating so

HCl [H+] pH

H+ + Cl = 0.02M = - log [H+] = 2 x 10-2 mol dm-3 = 1.7

Calculating pH - strong acids and alkalis

WORKED EXAMPLE

Strong acids and alkalis completely dissociate in aqueous solution

It is easy to calculate the pH; you only need to know the concentration.

Calculate the pH of 0.02M HCl

HCl completely dissociates in aqueous solution One H+ is produced for each HCl dissociating so

HCl [H+] pH

H+ + Cl = 0.02M = - log [H+] = 2 x 10-2 mol dm-3 = 1.7

Calculate the pH of 0.1M NaOH

NaOH completely dissociates in aqueous solution One OH is produced for each NaOH dissociating The ionic product of water (at 25C) therefore

NaOH

Na+ + OH = 1 x 10-1 mol dm-3 = 1 x 10-14 mol2 dm-6

[OH] = 0.1M Kw = [H+][OH]

[H+] = Kw / [OH] = 1 x 10-13 mol dm-3 pH = - log [H+] = 13

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)

Calculating pH - weak acids

A weak acid is one which only partially dissociates in aqueous solution
A weak acid, HA, dissociates as follows Applying the Equilibrium Law HA(aq) Ka = H+(aq) + A(aq) [H+(aq)] [A(aq)] [HA(aq)] mol dm-3 (1) (2)

Calculating pH - weak acids

A weak acid is one which only partially dissociates in aqueous solution
A weak acid, HA, dissociates as follows Applying the Equilibrium Law HA(aq) Ka = H+(aq) + A(aq) [H+(aq)] [A(aq)] [HA(aq)] The ions are formed in equal amounts, so therefore [H+(aq)] = [A(aq)] [H+(aq)]2 [HA(aq)] (3) mol dm-3 (1) (2)

Ka =

Calculating pH - weak acids

A weak acid is one which only partially dissociates in aqueous solution
A weak acid, HA, dissociates as follows Applying the Equilibrium Law HA(aq) Ka = H+(aq) + A(aq) [H+(aq)] [A(aq)] [HA(aq)] The ions are formed in equal amounts, so therefore [H+(aq)] = [A(aq)] [H+(aq)]2 [HA(aq)] Rearranging (3) gives [H+(aq)]2 = [HA(aq)] Ka (3) mol dm-3 (1) (2)

Ka =

therefore

[H+(aq)]

[HA(aq)] Ka

Calculating pH - weak acids

A weak acid is one which only partially dissociates in aqueous solution
A weak acid, HA, dissociates as follows Applying the Equilibrium Law HA(aq) Ka = H+(aq) + A(aq) [H+(aq)] [A(aq)] [HA(aq)] The ions are formed in equal amounts, so therefore [H+(aq)] = [A(aq)] [H+(aq)]2 [HA(aq)] Rearranging (3) gives [H+(aq)]2 = [HA(aq)] Ka (3) mol dm-3 (1) (2)

Ka =

therefore

[H+(aq)]
pH

[HA(aq)] Ka

= [H+(aq)]

Calculating pH - weak acids

A weak acid is one which only partially dissociates in aqueous solution
A weak acid, HA, dissociates as follows Applying the Equilibrium Law HA(aq) Ka = H+(aq) + A(aq) [H+(aq)] [A(aq)] [HA(aq)] The ions are formed in equal amounts, so therefore [H+(aq)] = [A(aq)] [H+(aq)]2 [HA(aq)] Rearranging (3) gives [H+(aq)]2 = [HA(aq)] Ka (3) mol dm-3 (1) (2)

Ka =

therefore

[H+(aq)]
pH

[HA(aq)] Ka

= [H+(aq)]

ASSUMPTION

HA is a weak acid so it will not have dissociated very much. You can assume that its equilibrium concentration is approximately that of the original concentration.

Calculating pH - weak acids

WORKED EXAMPLE

Calculate the pH of a weak acid HX of concentration 0.1M ( Ka = 4x10-5 mol dm-3 ) HX dissociates as follows HX(aq) H+(aq) + X(aq)

Calculating pH - weak acids

WORKED EXAMPLE

Calculate the pH of a weak acid HX of concentration 0.1M ( Ka = 4x10-5 mol dm-3 ) HX dissociates as follows Dissociation constant for a weak acid HX(aq) Ka = H+(aq) + X(aq)

[H+(aq)] [X(aq)] mol dm-3

[HX(aq)]

Calculating pH - weak acids

WORKED EXAMPLE

Calculate the pH of a weak acid HX of concentration 0.1M ( Ka = 4x10-5 mol dm-3 ) HX dissociates as follows Dissociation constant for a weak acid HX(aq) Ka = H+(aq) + X(aq)

[H+(aq)] [X(aq)] mol dm-3

[HX(aq)]
Substitute for X as ions are formed in equal amounts and then rearrange equation [H+(aq)] = [HX(aq)] Ka mol dm-3

Calculating pH - weak acids

WORKED EXAMPLE

Calculate the pH of a weak acid HX of concentration 0.1M ( Ka = 4x10-5 mol dm-3 ) HX dissociates as follows Dissociation constant for a weak acid HX(aq) Ka = H+(aq) + X(aq)

[H+(aq)] [X(aq)] mol dm-3

[HX(aq)]
Substitute for X as ions are formed in equal amounts and the rearrange equation [H+(aq)] = [HX(aq)] Ka mol dm-3

ASSUMPTION HA is a weak acid so it will not have dissociated very much. You can assume that its equilibrium concentration is approximately that of the original concentration

Calculating pH - weak acids

WORKED EXAMPLE

Calculate the pH of a weak acid HX of concentration 0.1M ( Ka = 4x10-5 mol dm-3 ) HX dissociates as follows Dissociation constant for a weak acid HX(aq) Ka = H+(aq) + X(aq)

[H+(aq)] [X(aq)] mol dm-3

[HX(aq)]
Substitute for X as ions are formed in equal amounts and the rearrange equation [H+(aq)] = [HX(aq)] Ka mol dm-3

ASSUMPTION HA is a weak acid so it will not have dissociated very much. You can assume that its equilibrium concentration is approximately that of the original concentration
[H+(aq)] 0.1 x 4 x 10-5 mol dm-3 4.00 x 10-6 2.00 x 10-3 = mol dm-3 mol dm-3 2.699

= = =

ANSWER

pH = - log [H+(aq)]

CALCULATING THE pH OF MIXTURES

The method used to calculate the pH of a mixture of an acid and an alkali depends on...

whether the acids and alkalis are STRONG or WEAK which substance is present in excess

STRONG ACID and STRONG BASE - EITHER IN EXCESS WEAK ACID and EXCESS STRONG BASE STRONG BASE and EXCESS WEAK ACID

pH of mixtures
Strong acids and strong alkalis (either in excess)
1. Calculate the initial number of moles of H+ and OH ions in the solutions 2. As H+ and OH ions react in a 1:1 ratio; calculate unreacted moles species in excess 3. Calculate the volume of solution by adding the two original volumes 4. Convert volume to dm3 (divide cm3 by 1000) 5. Divide moles by volume to find concentration of excess the ion in mol dm-3 6. Convert concentration to pH If the excess is H+ pH = - log[H+]

If the excess is

OH

pOH = - log[OH]
pH + pOH = 14

then

or use Kw = [H+] [OH] = 1 x 10-14 at 25C [H+] = Kw / [OH] pH = - log[H+] then

therefore

pH of mixtures
Strong acids and alkalis (either in excess)

WORKED EXAMPLE

Calculate the pH of a mixture of 25cm3 of 0.1M NaOH is added to 20cm3 of 0.1M HCl

pH of mixtures
Strong acids and alkalis (either in excess)

WORKED EXAMPLE

Calculate the pH of a mixture of 25cm3 of 0.1M NaOH is added to 20cm3 of 0.1M HCl
1. Calculate the number of moles of H+ and OH ions present

25cm3 of 0.1M NaOH 2.5 x 10-3 moles

20cm3 of 0.1M HCl 2.0 x 10-3 moles

moles of OH = 0.1 x 25/1000 = 2.5 x 10-3

moles of H+ = 20 x 20/1000 = 2.0 x 10-3

pH of mixtures
Strong acids and alkalis (either in excess)

WORKED EXAMPLE

Calculate the pH of a mixture of 25cm3 of 0.1M NaOH is added to 20cm3 of 0.1M HCl
1. Calculate the number of moles of H+ and OH ions present 2. As the ions react in a 1:1 ratio, calculate the unreacted moles of the excess species

25cm3 of 0.1M NaOH 2.5 x 10-3 moles

20cm3 of 0.1M HCl 2.0 x 10-3 moles

The reaction taking place is

or in its ionic form

HCl + NaOH
H+ + OH

NaCl
H2O

H2O

(1:1 molar ratio)

pH of mixtures
Strong acids and alkalis (either in excess)

WORKED EXAMPLE

Calculate the pH of a mixture of 25cm3 of 0.1M NaOH is added to 20cm3 of 0.1M HCl
1. Calculate the number of moles of H+ and OH ions present 2. As the ions react in a 1:1 ratio, calculate the unreacted moles of the excess species

25cm3 of 0.1M NaOH 2.5 x 10-3 moles

20cm3 of 0.1M HCl 2.0 x 10-3 moles 5.0 x 10-4 moles of OH UNREACTED

The reaction taking place is

or in its ionic form

HCl + NaOH
H+ + OH

NaCl
H2O

H2O

(1:1 molar ratio)

2.0 x 10-3 moles of H+ will react with the same number of moles of OH this leaves 2.5 x 10-3

2.0 x 10-3 = 5.0 x 10-4 moles of OH in excess

pH of mixtures
Strong acids and alkalis (either in excess)

WORKED EXAMPLE

Calculate the pH of a mixture of 25cm3 of 0.1M NaOH is added to 20cm3 of 0.1M HCl
1. Calculate the number of moles of H+ and OH ions present 2. As the ions react in a 1:1 ratio, calculate the unreacted moles of the excess species

3. Calculate the volume of the solution by adding the two individual volumes

the volume of the solution is 25 + 20 = 45cm3

pH of mixtures
Strong acids and alkalis (either in excess)

WORKED EXAMPLE

Calculate the pH of a mixture of 25cm3 of 0.1M NaOH is added to 20cm3 of 0.1M HCl
1. Calculate the number of moles of H+ and OH ions present 2. As the ions react in a 1:1 ratio, calculate the unreacted moles of the excess species

3. Calculate the volume of the solution by adding the two individual volumes
4. Convert volume to dm3 (divide cm3 by 1000)

the volume of the solution is 25 + 20 = 45cm3

there are 1000 cm3 in 1 dm3 volume = 45/1000 = 0.045dm3

pH of mixtures
Strong acids and alkalis (either in excess)

WORKED EXAMPLE

Calculate the pH of a mixture of 25cm3 of 0.1M NaOH is added to 20cm3 of 0.1M HCl
1. Calculate the number of moles of H+ and OH ions present 2. As the ions react in a 1:1 ratio, calculate the unreacted moles of the excess species

3. Calculate the volume of the solution by adding the two individual volumes
4. Convert volume to dm3 (divide cm3 by 1000) 5. Divide moles by volume to find concentration of excess ion in mol dm-3

[OH]

= 5.0 x 10-4 / 0.045

= 1.11 x 10-2 mol dm-3

pH of mixtures
Strong acids and alkalis (either in excess)

WORKED EXAMPLE

Calculate the pH of a mixture of 25cm3 of 0.1M NaOH is added to 20cm3 of 0.1M HCl
1. Calculate the number of moles of H+ and OH ions present 2. As the ions react in a 1:1 ratio, calculate the unreacted moles of the excess species

3. Calculate the volume of the solution by adding the two individual volumes
4. Convert volume to dm3 (divide cm3 by 1000) 5. Divide moles by volume to find concentration of excess ion in mol dm-3

6. As the excess is OH use

or

pOH = - log[OH]
Kw = [H+][OH]

then

pH + pOH = 14

so [H+] = Kw / [OH]

[OH] [H+] pH

= 5.0 x 10-4 / 0.045 = Kw / [OH] = - log[H+]

= 1.11 x 10-2 mol dm-3 = 9.00 x 10-13 mol dm-3 = 12.05

Kw = 1 x 10-14 mol2 dm-6 (at 25C)

pH of mixtures
Weak acid and EXCESS strong alkali
1. Calculate the initial number of moles of H+ and OH ions in the solutions 2. As H+ and OH ions react in a 1:1 ratio, calculate unreacted moles of the excess OH 3. Calculate the volume of solution by adding the two original volumes 4. Convert volume to dm3 (divide cm3 by 1000) 5. Divide moles by volume to find concentration of excess OH in mol dm-3 6. Convert concentration to pH either using Kw = [H+] [OH] = 1 x 10-14 at 25C therefore

[H+]

= Kw / [OH]
pH = - log[H+]

then

or

pOH

= - log[OH]

and

pH + pOH = 14

pH of mixtures
Weak acid and EXCESS strong alkali

WORKED EXAMPLE

Calculate the pH of a mixture of 25cm3 of 0.1M NaOH and 22cm3 of 0.1M CH3COOH
1. Calculate the number of moles of H+ and OH ions present

25cm3 of 0.1M NaOH 2.5 x 10-3 moles

22cm3 of 0.1M CH3COOH

2.2 x 10-3 moles

moles of OH = 0.1 x 25/1000 = 2.5 x 10-3

moles of H+ = 22 x 20/1000 = 2.2 x 10-3

pH of mixtures
Weak acid and EXCESS strong alkali

WORKED EXAMPLE

Calculate the pH of a mixture of 25cm3 of 0.1M NaOH and 22cm3 of 0.1M CH3COOH
1. Calculate the number of moles of H+ and OH ions present 2. As the ions react in a 1:1 ratio, calculate the unreacted moles of excess OH

25cm3 of 0.1M NaOH 2.5 x 10-3 moles

22cm3 of 0.1M CH3COOH 3.0 x 10-4 moles of OH UNREACTED

2.2 x 10-3 moles

The reaction taking place is or in its ionic form

CH3COOH + NaOH H+ + OH

CH3COONa H2O

H2O

(1:1 molar ratio)

2.2 x 10-3 moles of H+ will react with the same number of moles of OH
this leaves 2.5 x 10-3

2.2 x 10-3 = 3.0 x 10-4 moles of OH in excess

pH of mixtures
Weak acid and EXCESS strong alkali

WORKED EXAMPLE

Calculate the pH of a mixture of 25cm3 of 0.1M NaOH and 22cm3 of 0.1M CH3COOH
1. Calculate the number of moles of H+ and OH ions present 2. As the ions react in a 1:1 ratio, calculate the unreacted moles of excess OH

3. Calculate the volume of solution by adding the two individual volumes

the volume of the solution is 25 + 22 = 47cm3

pH of mixtures
Weak acid and EXCESS strong alkali

WORKED EXAMPLE

Calculate the pH of a mixture of 25cm3 of 0.1M NaOH and 22cm3 of 0.1M CH3COOH
1. Calculate the number of moles of H+ and OH ions present 2. As the ions react in a 1:1 ratio, calculate the unreacted moles of excess OH

3. Calculate the volume of solution by adding the two individual volumes

4. Convert volume to dm3 (divide cm3 by 1000)

the volume of the solution is 25 + 22 = 47cm3 there are 1000 cm3 in 1 dm3 volume = 47/1000 = 0.047dm3

pH of mixtures
Weak acid and EXCESS strong alkali

WORKED EXAMPLE

Calculate the pH of a mixture of 25cm3 of 0.1M NaOH and 22cm3 of 0.1M CH3COOH
1. Calculate the number of moles of H+ and OH ions present 2. As the ions react in a 1:1 ratio, calculate the unreacted moles of excess OH

3. Calculate the volume of solution by adding the two individual volumes

4. Convert volume to dm3 (divide cm3 by 1000) 5. Divide moles by volume to find concentration of excess ion in mol dm-3

the volume of the solution is 25 + 22 = 47cm3 there are 1000 cm3 in 1 dm3 volume = 47/1000 = 0.047dm3

[OH]

= 3.0 x 10-4 / 0.047

6.38 x 10-3 mol dm-3

pH of mixtures
Weak acid and EXCESS strong alkali

WORKED EXAMPLE

Calculate the pH of a mixture of 25cm3 of 0.1M NaOH and 22cm3 of 0.1M CH3COOH
1. Calculate the number of moles of H+ and OH ions present 2. As the ions react in a 1:1 ratio, calculate the unreacted moles of excess OH

3. Calculate the volume of solution by adding the two individual volumes

4. Convert volume to dm3 (divide cm3 by 1000) 5. Divide moles by volume to find concentration of excess ion in mol dm-3

6. As the excess is OH use

or

pOH = - log[OH]
Kw = [H+][OH]

then

pH + pOH = 14

so [H+] = Kw / [OH]

[OH] [H+] pH

= 3x 10-4 / 0.045 = Kw / [OH] = - log[H+]

= = =

6.38 x 10-3 mol dm-3 1.57 x 10-12 mol dm-3 11.8

pH of mixtures
EXCESS Weak monoprotic acid and strong alkali This method differs from the others because the excess substance is weak and as such is only PARTIALLY DISSOCIATED into ions. It is probably the hardest calculation to understand.
1. Calculate the initial number of moles of acid and OH ions in the solutions 2. As H+ and OH ions react in a 1:1 ratio, calculate unreacted moles of the excess acid 3. Calculate moles of salt anion formed; 1 mol of anion is formed for every H+ removed 4. Obtain the value of Ka for the weak acid and substitute the other values 5. Re-arrange the expression and calculate the value of [H+] 6. Convert concentration to pH using pH = - log[H+]

The following example shows you how to calculate the pH of the solution produced by adding 20cm3 of 0.1M NaOH to 25cm3 of 0.1M CH3COOH

pH of mixtures
EXCESS Weak monoprotic acid and strong alkali
1. Calculate the initial number of moles of acid and OH ions in the solutions

WORKED EXAMPLE

20cm3 of 0.1M NaOH 2.0 x 10-3 moles

25cm3 of 0.1M CH3COOH 2.5 x 10-3 moles

moles of OH = 0.1 x 20/1000 = 2.0 x 10-3

moles of H+ = 25 x 20/1000 = 2.5 x 10-3

pH of mixtures
EXCESS Weak monoprotic acid and strong alkali
1. Calculate the initial number of moles of acid and OH ions in the solutions

WORKED EXAMPLE

2. As H+ and OH ions react in a 1:1 ratio, calculate unreacted moles of excess acid

20cm3 of 0.1M NaOH 2.0 x 10-3 moles

25cm3 of 0.1M CH3COOH 2.5 x 10-3 moles

unreacted CH3COOH 5.0 x 10-4 moles

The reaction taking place is

CH3COOH + NaOH

CH3COONa

H2O

2.0 x 10-3 moles of H+ will react with the same number of H+; this leaves 2.5 x 10-3

2.0 x 10-3 = 5.0 x 10-4 moles of CH3COOH in excess

pH of mixtures
EXCESS Weak monoprotic acid and strong alkali
1. Calculate the initial number of moles of acid and OH ions in the solutions

WORKED EXAMPLE

2. As H+ and OH ions react in a 1:1 ratio, calculate unreacted moles of excess acid 3. Calculate moles of salt anion formed; 1 mol of anion is formed for every H+ removed

20cm3 of 0.1M NaOH 2.0 x 10-3 moles

25cm3 of 0.1M CH3COOH 2.5 x 10-3 moles

CH3COONa produced 2.0 x 10-3 moles

The reaction taking place is

CH3COOH + NaOH

CH3COONa

H2O

2.0 x 10-3 moles of H+ will produce the same number of CH3COONa this produces 2.0 x 10-3 moles of the anion CH3COO

pH of mixtures
EXCESS Weak monoprotic acid and strong alkali
1. Calculate the initial number of moles of acid and OH ions in the solutions

WORKED EXAMPLE

2. As H+ and OH ions react in a 1:1 ratio, calculate unreacted moles of excess acid 3. Calculate moles of salt anion formed; 1 mol of anion is formed for every H+ removed

4. Obtain the value of Ka for the weak acid and substitute the other values
Substitute the number of moles of anion produced here... it will be the same as the number of moles of H+ used up

Ka
Substitute the Ka value

[H+(aq)] [CH3COO(aq)] [CH3COOH(aq)]

mol dm-3

Substitute the number of moles of unreacted acid here

pH of mixtures
EXCESS Weak monoprotic acid and strong alkali
1. Calculate the initial number of moles of acid and OH ions in the solutions

WORKED EXAMPLE

2. As H+ and OH ions react in a 1:1 ratio, calculate unreacted moles of excess acid 3. Calculate moles of salt anion formed; 1 mol of anion is formed for every H+ removed

4. Obtain the value of Ka for the weak acid and substitute the other values
Substitute the number of moles of anion produced here... it will be the same as the number of moles of H+ used up

1.7 x 10-5 =
Substitute the Ka value

[H+(aq)] x (2 x 10-3) (5 x 10-4)

mol dm-3

Substitute the number of moles of unreacted acid here

pH of mixtures
EXCESS Weak monoprotic acid and strong alkali
1. Calculate the initial number of moles of acid and OH ions in the solutions

WORKED EXAMPLE

2. As H+ and OH ions react in a 1:1 ratio, calculate unreacted moles of excess acid 3. Calculate moles of salt anion formed; 1 mol of anion is formed for every H+ removed

4. Obtain the value of Ka for the weak acid and substitute the other values
5. Re-arrange the expression and calculate the value of [H+]

[H+(aq)]

= 1.7 x 10-5 x 5 x 10-4 2 x 10-3 = 4.25 x 10-6 mol dm-3

mol dm-3

pH of mixtures
EXCESS Weak monoprotic acid and strong alkali
1. Calculate the initial number of moles of acid and OH ions in the solutions

WORKED EXAMPLE

2. As H+ and OH ions react in a 1:1 ratio, calculate unreacted moles of excess acid 3. Calculate moles of salt anion formed; 1 mol of anion is formed for every H+ removed

4. Obtain the value of Ka for the weak acid and substitute the other values
5. Re-arrange the expression and calculate the value of [H+] 6. Convert concentration to pH using pH = - log[H+]

[H+(aq)]

= 1.7 x 10-5 x 5 x 10-4 2 x 10-3 = 4.25 x 10-6 mol dm-3

mol dm-3

pH

= - log10[H+(aq)] = 5.37

REVISION CHECK

What should you be able to do?

Calculate pH from hydrogen ion concentration Calculate hydrogen ion concentration from pH Write equations to show the ionisation in strong and weak acids

Calculate the pH of strong acids and bases knowing their molar concentration
Calculate the pH of weak acids knowing their Ka and molar concentration Calculate the pH of mixtures of acids and bases

CAN YOU DO ALL OF THESE?

YES

NO

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pH calculations
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