Monday 12 October 2015

Is sulfuric acid or hydrochloric acid stronger?



Of my belief, sulfuric acid might be a little stronger than hydrochloric acid. Because even though they both are strong acids, one mole of sulfuric acid produces two times as much $\ce{H+}$ as one mole of hydrochloric acid.


Am I wrong?



Answer



When using $\mathrm{p}K_\mathrm{a}$, one typically does not consider multiple dissociations for polyprotic acids, as the acidity of the conjugate base ($\ce{HSO4-}$ in the case of sulfuric acid) can and should be measured (or calculated) separately. Using that metric, $\ce{HCl}$ is stronger (at least per Wikipedia's acid strength page). One needs to keep in mind that $\mathrm{p}K_\mathrm{a}$ is solvent-dependent, and that the values typically given are for relatively dilute solutions. Acidity can sometimes vary widely with concentration ($\ce{HF}$ being a notorious example). It should also be noted that experimentally measuring acidity for very strong acids is actually quite difficult for numerous reasons.


On the other hand, if you evaluate acid strength by, say, the $\mathrm{pH}$ of the resulting solution, then you'd need to take subsequent dissociations into account. Using the crude approximation that an aqueous "strong acid" dissociates completely, then any diprotic "strong acid" is going to be stronger than a monoprotic one for equal concentrations (assuming a non-zero $K_\mathrm{a}$ for the second dissociation). Of course, this is not accurate, and a proper calculation would take into account not only $K_\mathrm{a}$ values for all dissociations, but also water's auto-ionization. I suspect that $\ce{HCl}$ would still be stronger, given that the $K_\mathrm{a}$ for the dissociation of $\ce{HSO4-}$ is fairly small, but one would need to actually crunch the numbers to be sure.


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