Thursday, 11 August 2016

acid base - What is the formula for theoretical buffer capacity for a diprotic buffer system?


According to Chembuddy, the formula for theoretical buffer capacity for a monoprotic buffer system is as follows:



β = 2.303\left(\frac{K_\mathrm{w}}{[\ce{H+}]} + [\ce{H+}] + \frac{C_\mathrm{buf}K_\mathrm{a}[\ce{H+}]}{(K_\mathrm{a} + [\ce{H+}])^2}\right)




where C_\mathrm{buf} is the total concentration of buffer and K_\mathrm{w} is the water ionization constant.


However, I have conducted a lab in which I mix \ce{C4H6O4} (tartaric acid; diprotic) with its double salt \ce{NaKC4H4O4} to create a 1.0 M potassium sodium tartrate buffer solution where there are two simultaneous buffer systems. Also, \mathrm{p}K_\mathrm{a1} and \mathrm{p}K_\mathrm{a2} of tartaric acid are quite similar (around 1.6 difference), so I believe that this alternative equation that provides the theoretical buffer capacity for a system with multiple buffers:



β = 2.303\left(\frac{K_\mathrm{w}}{[\ce{H+}]} + [\ce{H+}] + \sum\frac{C_\mathrm{buf}K_\mathrm{a}[\ce{H+}]}{(K_\mathrm{a} + [\ce{H+}])^2}\right)



will not be correct in my case.


Is this right? If so, is there a proper way to theoretically calculate the buffer capacity of the composite system?




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