Let's assume there are only two reactions in the solution:
H
2O
H
+ + OH
- (K
w)
HF
H
+ + F
- (K
a)
When you add some fluoride F
- it will react with H
+, removing it from the solution, thus it will shift equilibrium of the first reaction. As long as we are observing only the outcome of the reaction (concentrations of reagents), we can't differentiate between the two step reaction described above and reaction
F
- + H
2O
HF + OH
- (K
b)
Write equilibrium constants for all three reactions and check that K
w=K
aK
b. There are only two independent reactions in the system - doesn't matter which two you will select, you can always write the third equation and calculate the third equilibrium constant.