Sunday 31 May 2015

equilibrium - Calculating approximate pH of polyprotic acids


When I took up ionic equilibria and titrations after a long break, I found it hard to solve the questions regarding pH calculations of polyprotic acds. Consider these two questions as examples:-




  1. Find the approximate pH of a solution with $0.4M\text{ }\ce{HCO3-}$ and $0.2M\text{ }\ce{CO3^2-}$$K_{a1}=4\times 10^{-7}$, $K_{a2}=4\times 10^{-11}$

  2. Find the approximate pH of the resulting solution formed after mixing $20ml$ of $0.1M\text{ }\ce{H3PO4}$ and $20ml$ of $0.1M\text{ }\ce{Na3PO4}$. Express in terms of $pK_{a1},pK_{a2},pK_{a3}$.




I have mentioned 2 questions here because I want to know the method to solve such type of questions and not these two questions here in particular. The problem arises when there is a polyprotic acid with hydrolysable salts. For the second case, the ongoing equilibria are the dissociation of the three acids and the hydrolysis of their respective salts. For the first one, there are just two dissociation equilibria(and the dissociation of water). Even by writing down the equilibrium expressions of these reactions, I am unable to reach the final expression with pH or pOH. And, all the solutions have to be approximate (using approximations like the negligible contribution of hydrogen from the dissociation of water, low value of the successive ionization constants) and not at all accurate.


I would appreciate if someone explained how to do such numericals, taking one of the above as an example (I already have the answers for the aforementioned questions. I just want to use them to illustrate the general principle behind these questions).


Let me know if my question looks too homework-like and off-topic.




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