(1) & (2) is right. (3) looks dodgy.
HA, H+, A- are reflected in terms of number of moles, not concentration, in the tables below:
assuming citric acid is monobasic,
in 250ml solution at equilibrium,
| HA | | H+ | | A- |
eqbm | (0.025 - X) | | X | | X |
Ka = X
2/[0.250*(0.025-X)]
in 300ml solution at equilibrium (upon addition of 50ml),
| HA | | H+ | | A- |
eqbm | (0.025 - X - Y) | | X + Y | | X + Y |
Ka = (X + Y)
2/[0.300*(0.025-X-Y)]
let X be amount of citric acid dissociated in 250ml solution
let Y be amount of citric acid dissociated upon addition of 50ml
given eqbm pH in 300ml solution is 4.6,
(X+Y)/(300x10
-3) = 10
-4.6equation(1): X + Y = 3x10
-5.6assuming both 250ml & 300ml solution are at same temperature, then both solutions share the same Ka value, hence:
equation(2): X
2/[0.250*(0.025-X)] = (X + Y)
2/[0.300*(0.025-X-Y)]
the value of the RHS of equation (2) can be determined by substituting (1) into it. The numerical value corresponds to the required Ka
Ka = 7.54 x 10
-9