Solve Acid-Base Equilibrium: Calculate Ka of HA

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The discussion revolves around calculating the ionization constant, Ka, of a weak monoprotic organic acid, HA, based on titration data. The initial calculations for moles of acid, molecular weight, and unreacted HA were completed, but there was confusion regarding the equilibrium concentrations used for Ka. The participant initially assumed that the concentrations of H+ and A- were equal, which led to an incorrect value for Ka. It was pointed out that the total volume of the solution changed after adding NaOH, affecting the concentrations. The correct approach requires accounting for the additional A- ions produced during the neutralization process.
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Homework Statement


1) A 0.682-gram sample of an unknown weak monoprotic organic acid, HA, was dissolved in sufficient water to make 50 milliliters of solution and was titrated with a 0.135-molar NaOH solution. After the addition of 10.6 milliliters of base, a pH of 5.65 was recorded. The equivalence point (end point) was reached after the addition of 27.4 milliliters of the 0.135-molar NaOH.

(a) Calculate the number of moles of acid in the original sample.
Done. 3.70 * 10^-3 mol HA
(b) Calculate the molecular weight of the acid HA.
Done. 184.37 g/mol
(c) Calc the number of moles of unreacted HA remaining in solution when the pH was 5.65.
done. 0.0027 mol
(d) Calculate the [H3O+] at pH = 5.65.
done. 2.2 * 10^-6
(e) Calculate the value of the ionization constant, Ka, of the acid HA.
I am using an ICE chart, with the equation HA <-> H+ + A-
The initial concentration for HA I used was 0.0027 mol/ 0.050 L
the initial concentration for H+ was 2.2 * 10 ^-6, which is also equal to the concentration of A-.
However, when I plug in these values into the equilibrium expression, Ka = ([H+][A-])/[HA], I get 1.1 * 10^ -10, and the answer key says that the correct answer is 1.4 * 10 ^-6.

Am I doing something wrong here, or is the answer key wrong?
 
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Show your work on e). What values of [H+], [A-] and [HA] did you use?
 
Ka = \frac{[H+][A-]}{[HA]}

[H+] = 2.2 * 10^-6 (got this from pH 5.65)
[A-] = 2.2 * 10^-6
[HA] = 0.0027 mol/ 0.050 L
 
If you write out all of the equations you have and plug them into each other, you'll see that [H+] is not equal to [A-]. Your assumption that they are equal is throwing you off.

Also don't forget that the volume of the entire solution changed because you added the NaOH solution.
 
thanks.
I forgot about all the [A-] ions that came into the system as a result of the neutralization of the weak acid with NaOH.
 
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