IChO 2003 · Theory problem 2

Exact hydrogen ion concentration of hydrochloric acid

Which one of the following equations must be used for the exact calculation of \([\ce{H+}]\) of an aqueous \(\ce{HCl}\) solution at any concentration \(c_{\ce{HCl}}\)? \((K_w = 1\times10^{-14})\).

(a) \([\ce{H+}] = c_{\ce{HCl}}\) ( )

(b) \([\ce{H+}] = c_{\ce{HCl}} + K_w/[\ce{H+}]\) ( )

(c) \([\ce{H+}] = c_{\ce{HCl}} + K_w\) ( )

(d) \([\ce{H+}] = c_{\ce{HCl}} - K_w/[\ce{H+}]\) ( )

Official English text of the problem.

Answers

  • 2: (b). Mark only the box beside \[ \boxed{[\ce{H+}]=c_{\ce{HCl}}+\frac{K_w}{[\ce{H+}]}}. \]

Solution

2. In the model assumed by the problem, hydrogen chloride Cl dissociates completely into hydrogen ions (protons) [H+] and chloride ions [Cl-]. Using the problem’s aqueous \(\ce{H+}\) notation, \[ \ce{HCl -> H+ + Cl-}, \qquad [\ce{Cl-}]=c_{\ce{HCl}}. \]

Water O also undergoes autoionization, producing hydrogen ions and hydroxide ions [OH-]: \[ \ce{H2O <=> H+ + OH-}. \] Thus, \[ K_w=[\ce{H+}][\ce{OH-}], \qquad [\ce{OH-}]=\frac{K_w}{[\ce{H+}]}. \]

Electrical neutrality requires the total positive and negative charge concentrations to be equal: \[ [\ce{H+}]=[\ce{Cl-}]+[\ce{OH-}]. \] Substitution gives \[ \boxed{[\ce{H+}]=c_{\ce{HCl}}+\frac{K_w}{[\ce{H+}]}}, \] which is option (b).

Equivalently, setting \(h=[\ce{H+}]\), \[ h^2-c_{\ce{HCl}}h-K_w=0. \] The physically admissible, positive root is \[ \boxed{ [\ce{H+}] =\frac{c_{\ce{HCl}}+\sqrt{c_{\ce{HCl}}^2+4K_w}}{2} }. \]

With concentrations expressed in \(\mathrm{mol\,L^{-1}}\), the given concentration product is \(K_w=1\times10^{-14}\ \mathrm{mol^2\,L^{-2}}\). As \(c_{\ce{HCl}}\to0\), this expression correctly approaches \[ [\ce{H+}]\to\sqrt{K_w} =1\times10^{-7}\ \mathrm{mol\,L^{-1}}. \]

Option (a) neglects water’s contribution and is only an approximation when \(c_{\ce{HCl}}\gg\sqrt{K_w}\). Option (c) adds \(K_w\) instead of the hydroxide concentration; option (d) has the wrong sign in the charge balance. The stated exactness is within the problem’s complete-dissociation, concentration-based equilibrium model.

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