Thursday, April 25, 2019

Finding pH of tri-protic acid


I am studying for my final and I am given this problem:




A solution of sodium phosphate is made from 10.5 g sodium phosphate in 150 mL of water. What is the pH of this solution



Given: Ka1, Ka2.


The solution says that we can simply calculate this pH with the following eqution: pH=pKa1+pKa22 However this makes absolutely no sense to me, as this is the pH at the equivalence point. What am I missing as towhy this equation can be used?



Answer





A chemical species that behaves both as an acid and as a base is called amphoteric. This property depends upon the medium in which the species is investigated: HX2SOX4 is an acid when studied in water, but becomes amphoteric in superacids.




from the IUPAC goldbook.




For ampholytes like NaHX2POX4 the pH is independent on the concentration (in first approximation). Consider the reactions of that are possible: HX2AX+HX3X+O HX3A+HX2O HX2AX+HX2O HAX2+HX3X+O HAX2+HX2O AX3+HX3X+O 


As the first approximation, we will assume that everything happening in equation (3) is negligible, as is will only very little influence the concentration of HAX2. Therefore we can focus on the acidity constants Ka1 of (1) and Ka2 of (2): Ka1=c(HX3X+O)c(HX2AX)c(HX3A)Ka2=c(HX3X+O)c(HAX2)c(HX2AX) We will just go ahead and multiply these equations, since they are coupled, simultaneously happening processes. Then we will cancel whatever cancels. Ka1Ka2=c(HX3X+O)c(HX2AX)c(HX3A)c(HX3X+O)c(HAX2)c(HX2AX)Ka1Ka2=c2(HX3X+O)c(HAX2)c(HX3A) Now another major assumption is that the reactions (1) and (2) are happening to the same extent and therefore we can approximate c(\ce{HA^{2-}})=c(\ce{H3A})\tag8 and rewrite (7) as \begin{align} c^2(\ce{H3+O}) &= K_{a_1} \cdot K_{a_2}\\ c(\ce{H3+O}) &= \sqrt{K_{a_1} \cdot K_{a_2}}\\ \ce{pH} &= \frac12\left(\mathrm{p}K_{a_1}+\mathrm{p}K_{a_2}\right). \end{align}


However, this equation only works as a first approximation. Usually the coupled equilibria are very complex and in most instances a computer needs to be involved to calculate it accurately. More information on polyprotic acids.


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