Polyprotic acids and bases dissociation constants
include('equation.php'); ?>First, and the simplest approach to defining equilibriums constants for polyprotic acid is to treat every step of dissociation separately:
Reaction("pH-calc-img",3,"a","polyprotic acid dissociation step 1"); ?> Reaction("pH-calc-img",3,"b","polyprotic acid dissociation step 2"); ?> Reaction("pH-calc-img",3,"c","polyprotic acid dissociation step 3"); ?>Then we have three stepwise dissociation constants:
Equation("pH-calc-img",3,1,"1st acid dissociation constant"); ?> Equation("pH-calc-img",3,2,"2nd acid dissociation constant"); ?> Equation("pH-calc-img",3,3,"3rd acid dissociation constant"); ?>There are also overall dissociation constants defined, of which first is identical to the stepwise one, while the second and the third take forms:
Reaction("pH-calc-img",3,"d","polyprotic acid overall dissociation step 2"); ?> Reaction("pH-calc-img",3,"e","polyprotic acid overall dissociation step 3"); ?> Equation("pH-calc-img",3,4,"2nd overall dissociation constant"); ?> Equation("pH-calc-img",3,5,"3rd overall dissociation constant"); ?>It is not very difficult to find out relations:
Equation("pH-calc-img",3,6,""); ?> Equation("pH-calc-img",3,7,""); ?>or
Equation("pH-calc-img",3,8,"3rd overall dissociation constant"); ?> Equation("pH-calc-img",3,9,"3rd overall dissociation constant"); ?>For polyprotic acids with greater number of protons analogous constants are used.
Same holds for polyprotic bases.
In case of polyprotic substances the idea of conjugate acids and bases becomes a little bit confusing, as the same substance can play both roles:
and the numeration of dissociation steps is reversed, so that first acid dissociation step described by Ka1:
Reaction("pH-calc-img",3,"h",""); ?>creates conjugate base for the last dissociation step:
Reaction("pH-calc-img",3,"i",""); ?>described by Kb3. So for the substance with three protons relations analogous to 2.5 take forms:
Equation("pH-calc-img",3,10,"3rd overall dissociation constant"); ?> Equation("pH-calc-img",3,11,"3rd overall dissociation constant"); ?> Equation("pH-calc-img",3,12,"3rd overall dissociation constant"); ?>