Calculations involving buffer solutions
Equilibrium aspects Consider a buffer solution consisting of a weak acid and its conjugate base:
CH3COOH(aq) Y CH3COO (aq) + H+(aq) weak acid conjugate base We can write an
equilibrium expression for this reaction in terms of hydrogen ions: Ka = [CH3COO ][H+
_______________] [CH3COOH] So [H+] = Ka × _[C__H_3_C__O_O__H__] [CH3COO ] or
more generally [H+] = Ka × _[H__A__] [A ] Since Ka is constant, the ratio of the concentration of
acid to conjugate base (salt) controls the H+ ion concentration (and thus the pH). Dilution of the
buffer has no effect on its pH since A− and HA are diluted equally. Deducing the pH of a buffer
solution We can calculate the pH of a buffer solution if we know: the value of Ka of the weak
acid the equilibrium concentrations of the weak acid and conjugate base. Worked example 1
Deduce the pH of a buffer solution made by adding 0.20mol of sodium ethanoate to 500cm3 of
0.10moldm−3 ethanoic acid. Ka of ethanoic acid = 1.7 × 10−5moldm−3 Step 1: Calculate the
concentrations of the acid and its conjugate base: [CH3COOH] = 0.10moldm−3 [CH3COO ] =
0.2 × _1_0_0_0_ 500 = 0.40moldm−3 Step 2: Rearrange the equilibrium expression in terms of
[H+] ions: [H+] = Ka × _[C__H__3C__O_O__H__] [CH3COO ] Step 3: Substitute the values:
[H+] = 1.7 × 10−5 × _0_._1_0_ 0.40 = 4.25 × 10−6moldm−3 Step 4: Calculate pH: pH = −log10
[H+] = −log10 (4.25 × 10−6 ) pH = 5.4 (to 2 s.f.) We can make buffer solution calculations easier
to deal with if we use the expression: pH = pKa + log10 _[s_a_l_t_] [acid] So if we are given the
pKa or calculate it from Ka , we can do the calculation much more simply. Step 1: Convert Ka to
pKa : −log10 (1.7 × 10−5 ) pKa = 4.77 Learning outcomes On completion of this section, you
should be able to: know how to calculate the pH of a buffer solution from appropriate data
know how to calculate the acid/ base ratio required to make a buffer solution with a particular pH
know how to conduct an experiment to determine the pH of a buffer solution. 119 Chapter 9
Acid–base equilibria Step 2: Substitute into the equation: pH = 4.77 + log10 _____(0__.4__0_)
(0.10) pH = 4.77 + 0.6 pH = 5.4 (to 2 s.f.) Calculating the acid–conjugate base ratio For an
acidic buffer solution, the higher the acid–conjugate base ratio, the lower is the pH of the buffer.
But in order to make a buffer solution with a particular pH, we need to know exactly how much
base to add to an acid or in what volumes to mix solutions of the acid and salt of known
concentrations. The example below shows how to do this. Remember that [salt] is the same as
[conjugate base]. Worked example 2 How many moles of sodium propanoate must be added to
250cm3 of solution containing 0.10mol of propanoic acid to make a buffer solution of pH 5.30?
Ka of propanoic acid = 1.35 × 10−5moldm−3 Step 1: Calculate the concentration of the
propanoic acid: [acid] = 0.10 × _1_0_0_0_ 250 = 0.40moldm−3 Step 2: Calculate [H+] from pH:
[H+] = 10−5.30 = 5.01 × 10−5moldm−3 Step 3: Rearrange the equilibrium expression with [salt]
as the subject: [salt] = Ka × _[a_c_i_d_] [H+] Step 4: Substitute the values: [salt] = (1.35 × 10−5
____________)_×___0_.4_ 5.01 × 10− 5 = 1.08moldm−3 Step 5: Calculate number of moles:
1.08 × _2_5__0_ 1000 = 0.27mol Determining the pH of a buffer solution We can nd the pH of a
buffer solution experimentally by using a glass pH electrode connected to a pH meter. The glass
pH electrode is dipped into the buffer solution and the value of the pH found by direct reading
from the meter. The functioning of the glass electrode is based on the fact that the potential
difference (voltage) between the surface of the glass and the solution varies linearly with the pH.
A hydrogen electrode (see section 10.1) can also be used to determine pH. Exam tips n buffer
solution calculations, do not fall into the trap of thinking that the concentration of hydrogen ions
is the same as the concentration of conjugate base. Remember that hardly any of the conjugate
base comes from ionisation of the acid. t is added as a salt. Key points The pH of a buffer
solution can be calculated using the equilibrium concentrations of the weak acid and its
conjugate base together with the Ka value for the weak acid. The acid/ base ratio of a buffer
solution can be calculated using the values of pH of the solution and the Ka value of the weak
acid. The pH of a buffer solution can be determined experimentally using a glass electrode
connected to a pH meter
