Okay, next time, try typing the question instead of posting a link to the download of a document, okay?
Quote:
The pH of a solution obtained by addition of 8.2 cm^3 of sodium hydroxide to 25.0 cm^3 of the acid is 4.2. Calculate the concentration of hydroxonium ions in this solution and hence find the dissociation constant of the acid. (5 marks)
Moles of acid in 25cm^3 = 5.08 x 10^-4
Concentration of Sodium Hydroxide = 0.0310
Below is the answer given by my tutor:
From the previous calculation, the number of moles of monoprotic, weak acid in 25.0cm^3 of solution is 5.08x10^-4 moles. The number of moles of sodium hydroxide in 8.2 cm^3 of sodium hydroxide can be calculated too.
Moles NaOH = volume x concentration
= (8.2/1000) x 0.0310
= 2.54 x x10^-4 moles
Since each mole of sodium hydroxide reacts with one mole of the monoprotic acid, then 2.54 x 10^-4 moles of the base react with 2.54 x 10^-4 moles of the acid. This forms 2.54 x 10^-4 moles of salt Na^+A^-. The number of moles of acid left is the difference between the original number of acid and the moles which reacted with the base.
The 2.54 x 10^-4 moles of salt NaA are completely dissociated in aqueous solution forming the same number of moles of A^-, while the weak acid HA dissociated. Since the number of moles of HA and A^- is the same, the concentration of these two species is equal too.
The [H^+] can be found from the pH.
pH = - log [H^+]
[H^+] = 10^(-pH)
[H^+] = 10^(-4.2)
[H^+] = 6.31 x 10^-5 mol dm^-3
The equation for the dissociation constant for the acid, Ka, is:  *
Since the number of moles of HA and A^- is the same, the concentrations of these two species cancel out of the equation.
Ka = [H^+]
Substituting the [H^+], then:
Ka = 6.31 x 10^-5 mol dm^-3
*That's where I don't agree. I think that the concentration of A^- should not be taken the same as that of HA because there are 2.54 x 10^-4 moles of A^- coming from the salt but also 6.31 x 10^-5 from the unreacted acid.
Am I Correct in my thinking of what?
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Well, if you had written the equations, you wouldn't have had any doubt.
The acid is monoprotic, as the base is monobasic. The mole ratio is therefore 1:1. Since there is twice the amount of acid, there is 2.54 x 10^-4 moles of acid in excess.
So, the equations for the reactions occuring:
Now, to the equilibrium equations:
There is initially 2.54 x 10^-4 moles of HA, and there is a common ion effect for the A^- ion. The equilibrium constant equation thus become:
x here is the amount of acid which has dissociated. It's the number of moles (2.54x10^-4) added to x to get the total number of moles of A^- and it is the total number of moles of HA (2.54x10^-4) minus the amount of moles x of HA that dissociated.
Since HA is a weak acid, it is understood that x is very very small and for ease of students, we take [A^-] = [HA]
Also, unless you know Ka, you would not be able to find x here, remember that the equation deals with concentration, which is the number of moles, divided by the volume times the total volume
For instance, with a Ka of 6.31x10^-6 mol dm^-3, you will have something of the other of 3.7x10-5 mol from the 2.54x10^-4 mol of HA, which is ten times less than the original content. That margin of error is okay in A-level and does not require you to go into very precise mathematical skills only to get a value slightly different.