Equilibrium calculationsinvolving

weak acids The acid dissociation constant, Ka The equilibrium law can be
applied to aqueous solutions of weak acids. The equation for the partial ionisation of ethanoic
acid in water is: CH3COOH(aq) + H2O(l) Y CH3COO (aq) + H3O+(aq) Because water is
present at a very high concentration, we can assume that its concentration is constant and we
can simplify this equation to: CH3COOH(aq) Y CH3COO (aq) + H+(aq) The equilibrium
expression for this reaction is: Ka = [CH3COO ][H+ _______________] [CH3COOH] Ka is the
acid dissociation constant. For a monobasic weak acid such as ethanoic acid, the units of Ka
are moldm−3 A high value for Ka e.g. 40moldm−3 indicates that the position of equilibrium is
well over to the right. The acid is almost completely ionised. A low value for Ka e.g. 1.3 ×
10−5moldm−3 indicates that the position of equilibrium is well over to the left. The acid is only
very slightly ionised. We can also use pKa values to compare the strengths of acids. pKa =
−log10 [Ka ]. The general equilibrium expression for Ka We can write a general equilibrium
expression for all monobasic acid based on the general reaction: HA Y H+ + A HA represents
the unionised acid. A represents the conjugate base of the acid. The general equilibrium
expression is therefore: Ka = [H+ ____]_[A___] [HA] Since the concentration of H+ and A must
be equal, we can simplify this further: Ka = [H+]2 _____ [HA] In calculations involving Ka we
make two assumptions. If the Ka value for the weak acid is very small, we can assume that the
concentration of acid molecules remaining at equilibrium is the same as the concentration of
undissociated acid molecules in the original acid. We can ignore the hydrogen ions which arise
from the ionisation of water. For most work this is acceptable because the ionic product for
water, Kw, is very small. Learning outcomes On completion of this section, you should be able
to: understand the term ‘acid dissociation constant, Ka ’ perform calculations involving the use
of Ka , pH and [H+ ]. 109 Chapter 9 Acid–base equilibria Calculations involving Ka We can
calculate the value of Ka for a weak acid if we know: the concentration of acid the pH of the
solution. We can calculate the pH of a solution of a weak acid if we know the value of Ka the
concentration of the acid. Worked example 1 Deduce the pH of a solution of 0.05moldm−3
ethanoic acid. Ka for ethanoic acid = 1.74 × 10−5moldm−3 Step 1: Write the equilibrium
expression. Ka = [H+]2 ____________ [CH3COOH] or Ka = [H+]2 _____ [HA] Step 2:
Rearrange the equation to make [H+]2 the subject: [H+]2 = Ka × [CH3COOH] Step 3: Substitute
the values: [H+]2 = (1.74 × 10−5 ) × 0.05 = 8.7 × 10−7 Step 4: Find [H+] by taking the square
root: √8.7 × 10−7 = 9.33 × 10−4moldm−3 Step 5: Convert [H+] to pH: pH = − log10 [H+] = −
log10 (9.33 × 10−4 ) pH = 3.03 Worked example 2 The pH of a 0.01moldm−3 of methanoic acid
is 2.9. Deduce the value of Ka Stage 1: Convert pH to [H+]: [H+] = 10−2.9 = 1.26 ×
10−3moldm−3 Stage 2: Write the equilibrium expression. Ka = [H+]2 __________ [HCOOH] or
Ka = [H+]2 _____ [HA] Stage 3: Substitute into the equilibrium expression: Ka = (1.26 × 10−3 )2
______________________ 0.01 Ka = 1.59 × 10−4moldm−3 Exam tips n calculations involving
Ka , remember that hydrogen ion concentration can be converted to pH and pH to hydrogen ion
concentration. Key points For a weak acid, [H+ ] and pH can be calculated using the
expression: Ka = [H+ ][A − ] _______ [HA] Where [A − ] is the concentration of ionised acid and
[HA] is the concentration of unionised acid. 110 9.4 Acid and base dissociation constants Using
pKa values We can use pKa values to compare the acidity of weak acids. pKa = −log10 [Ka ].
Some examples are shown in the table. Acid Equilibrium in aqueous solution Ka /moldm−3 pKa
sulphuric(IV) H2 SO3 Y H+ + HSO3 1.5 × 10 −2 1.82 hydrofluoric HF Y H+ + F 5.6 × 10 −4 3.25
methanoic acid HCOOH Y H+ + HCOO 1.6 ×10 −4 3.80 ‘carbonic acid’ CO2 + H2O Y H+ +
HCO3 4.5 × 10 −7 6.35 The higher the pKa value, the weaker the acid. We can use pKa values
in calculations rather than Ka values. Worked example 1 Deduce the pH of a solution of
0.001moldm−3 benzoic acid. pKa benzoic acid = 4.2. Step 1: Convert pKa to Ka : pKa = − log10
[Ka ] So Ka = 10−pKa Ka = 10−4.2 Ka = 6.3 × 10−5moldm−3 Step 2: Write the equilibrium
expression: Ka = [H+]2 _____ [HA] Step 3: Rearrange the equation to make [H+]2 the subject:
[H+]2 = Ka × [HA] Step 4: Substitute the values: [H+]2 = (6.3 × 10−5 ) × 0.001 = 6.3 × 10−8
Step 5: Find [H+] by taking the square root: √6.3 × 10−8 = 2.51 × 10−4moldm−3 Step 6: Convert
[H+] to pH: pH = −log10 [H+] = −log10 (2.51 × 10−4 ) pH = 3.6 The basic dissociation constant,
Kb For calculations involving a weak alkali, we can use the basic dissociation constant, Kb . For
example, in the reaction: NH3 (g) + H2O(l) Y NH4+(aq) + OH (aq) We can write the equilibrium
expression: Kb = [NH4+ ______]_[_O_H___] [NH3 ] or more generally Kb = [BH+
_____]_[O__H___] [B] Where [B] is the weak base and [BH+] is the conjugate acid. We make
similar assumptions to those for a weak acid in applying this expression (see Section 9.1). Since
[BH+] = [OH ] we can simplify the expression further to: Kb = [OH ]2 _______ [B] Learning
outcomes On completion of this section, you should be able to: describe pKa , Kb and pKb
perform calculations involving pKa , Kb and pKb and pKw Exam tips We can calculate the
approximate pH for a dibasic acid such as H2 S in a similar way as for a monobasic acid. This is
because the value of Ka1 is much greater than Ka2 . e.g. H2 S(aq) Y HS – (aq) + H+ (aq) Ka1 =
8.9 × 10 –8 mol dm–3 HS – (aq) Y S2–aq) + H+ (aq) Ka2 = 1.2 × 10 –13 mol dm–3 We can
ignore the H+ ions arising from the second ionisation because their concentration is insignificant
compared with those arising form the first ionisation. 111 Chapter 9 Acid–base equilibria Worked
example 2 Calculate the pH of a 0.01moldm−3 solution of ethylamine. Kb (ethylamine) = 6.5 ×
10−4moldm−3 Kw = 1.0 × 10−14moldm−3 Step 1: Write the equilibrium expression: Kb = [OH ]2
_______ [B] Step 2: Rearrange the equation to make [OH ]2 the subject: [OH ]2 = Kb × [B] Step
4: Substitute the values: [OH ]2 = (6.5 × 10−4 ) × 0.01 = 6.5 × 10−6 Step 5: Find [OH ] by taking
the square root: √6.5 × 10−6 = 2.55 × 10−3moldm−3 Step 6: Use Kw = [H+][OH ] to calculate
[H+]: [H+] = __K__w__ [OH ] = 1.0 ×10−14 ___________ 2.55 × 10−3 = 3.92 × 10−12moldm−3
Step 7: Calculate pH: pH = −log10 [H+] = −log10 (3.92 × 10−12 ) pH = 11.4 Using pKa and pKb
values A useful expression which relates Kw to Ka and Kb is pKa + pKb = pKw This can also be
written as: −log10Ka − log10Kb = 14 (the 14 derives from −log10 (1.0 × 10−14 )) Worked
example 3 Deduce the value of Ka for a 0.01moldm−3 solution of aqueous ammonia. pKb for
ammonia = 4.7 Step 1: Apply the relationship pKa + pKb = pKw to calculate pKa : pKa + 4.7 =
14 So pKa = 14 – 4.7 = 9.3 Step 2: Convert pKa to Ka : pKa = −log10Ka = −log10 (9.3) Ka = 5.0
× 10−10moldm−3 Exam tips A quick way to get an answer to a question such as ‘calculate the
pH of a solution of a strong base of concentration 0.1moldm−3 ’ is to use the expression 14
–log10 [OH ]. This works because − log10 [H+ ] − log10 [OH ] = 14 Key points For a weak base
the concentration of hydroxide ions can be calculated using the general expression: Kb = [BH+
][OH− ] __________ [B] where [BH+ ] is the concentration of the protonated base (salt) and [B]
is the concentration of unionised base. pKa = −logKa and pKb = −logKb