IChO 2003 · Theory problem 6

Preparing a phosphate buffer

How many \(\mathrm{cm^3}\) of 1.00 M \(\ce{NaOH}\) solution must be added to 100.0 \(\mathrm{cm^3}\) of 0.100 M \(\ce{H3PO4}\) solution to obtain a phosphate buffer solution with \(pH\) of about 7.2? (The \(pK\) values for \(\ce{H3PO4}\) are \(pK_1 = 2.1\), \(pK_2 = 7.2\), \(pK_3 = 12.0\))

(a) 5.0 \(\mathrm{cm^3}\) ( )

(b) 10.0 \(\mathrm{cm^3}\) ( )

(c) 15.0 mL ( )

(d) 20.0 mL ( )

Official English text of the problem.

Answers

  • 6. (c): Add \(\boxed{15.0\ \mathrm{cm^3}=15.0\ \mathrm{mL}}\) of 1.00 M sodium hydroxide solution.

Solution

6. The buffer pair associated with \(pK_2=7.2\) is:

  • Dihydrogen phosphate, \(\ce{H2PO4^-}\): O=P(O)(O)[O-].
  • Hydrogen phosphate, \(\ce{HPO4^2-}\): O=P(O)([O-])[O-].

The Henderson–Hasselbalch equation is \[ pH=pK_2+\log_{10}\frac{[\ce{HPO4^2-}]}{[\ce{H2PO4^-}]}. \] Thus, \(pH=pK_2=7.2\) requires equal concentrations, and therefore equal amounts, of these two ions. The widely separated \(pK_1\) and \(pK_3\) justify neglecting the other phosphate forms at this pH.

Initially, the amount of phosphoric acid, \(\ce{H3PO4}\) (O=P(O)(O)O), is \[ n_0=(0.100\ \mathrm{mol\,L^{-1}})(0.1000\ \mathrm{L}) =0.0100\ \mathrm{mol}. \]

Sodium hydroxide ([Na+].[OH-]) supplies hydroxide ions, \(\ce{OH^-}\) ([OH-]). First, one equivalent neutralizes phosphoric acid to dihydrogen phosphate: \[ \ce{H3PO4 + OH^- -> H2PO4^- + H2O}. \] This consumes \(0.0100\ \mathrm{mol}\) of hydroxide.

Next, half of the dihydrogen phosphate must be converted to hydrogen phosphate: \[ \ce{H2PO4^- + OH^- -> HPO4^2- + H2O}. \] This consumes another \[ \frac{0.0100}{2}=0.00500\ \mathrm{mol} \] of hydroxide, leaving \(0.00500\ \mathrm{mol}\) of each buffer component.

In these equations, \(\ce{H2O}\) is water (O); the sodium ion, \(\ce{Na+}\) ([Na+]), is a spectator.

The total amount of sodium hydroxide required is therefore \[ n(\ce{NaOH})=0.0100+0.00500=0.0150\ \mathrm{mol}, \] giving \[ V=\frac{0.0150\ \mathrm{mol}}{1.00\ \mathrm{mol\,L^{-1}}} =0.0150\ \mathrm{L} =\boxed{15.0\ \mathrm{cm^3}}. \]

Hence, select (c).

The answers were checked against the official answers published by the organisers.