For the sequential deprotonations of a polyprotic acid, the equilibrium constants will typically decrease with each successive ionization.
For explaining above statement let's take an example of polyprotic acid like phosphoric acid.
In the phospheric acid [tex]H_{3} PO_{4}[/tex], after deprotonation of one hydrogen results as [tex]H_{2} PO_{4}^{-}[/tex] and equilibrium constant as [tex]K_{1}[/tex] . [tex]H_{2} PO_{4}^{-}[/tex] donate one hydrogen results as [tex]H_{} PO_{4}^{-2}[/tex] and equilibrium constant as [tex]K_{2}[/tex] . Similarly, [tex]H_{} PO_{4}^{-2}[/tex] donate one hydrogen results as [tex]PO_{4}^{-3}[/tex] and equilibrium constant as [tex]K_{3}[/tex] . The removing of hygen ion from nuetral molecule is easier than removal of hydrogen ion from ionic species So, the value of [tex]K_{1}[/tex] is greater than [tex]K_{2}[/tex] and value of [tex]K_{2}[/tex] is greater than [tex]K_{3}[/tex].
So, the equilibrium constants of polyprotic acid will typically decrease with each successive ionization.
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