Posted by Kat on Monday, March 2, 2009 at 10:11pm.
Well, you are correct. The pH SHOULD become more acid but it doesn't because I've led you astray. Check my thinking on this.
The 12 mmoles HCl added uses ALL of the HCOONa and leaves 3 mmoles HCl in excess.
The 9 mmoles HCOONa has changed to HCOOH and there is now 16 + 9 = 25 mmoles HCOOH (and no HCOONa). So the pH is that of 25 mmoles HCOOH in 81 mL + 3 mmoles HCl in 81 mL. I would use the excess HCl as a common ion to determine the (H^+) contributed by HCOOH to the solution in the presence of HCl, then add it to the (H^+) from the excess HCl. The H^+ contributed by HCOOH may be small enough to neglect but I didn't work it out. In other words, I don't think you have a buffer after the HCl is added.
This is how I did it:
HCOOH + H2O <---> HCOO- + H3O+
I 16.00 9.00
I 12.00
C +9.00 -9.00 -9.00
E 25.00 0 3.00
HCOOH + H2O <---> HCOO- + H3O+
I 25.00 0 0
I 3.00
C -x +x +x
E 25 -x x 3+x
(3+x)x
Ka = ------- = 1.8*10^-4
25-x
Assume x is very small, then x = 0.0015
So, [H30+] = (3+x)mmol / 81ml
= (3 + 0.0015)mmol / 81 ml
= 3.0015mol / 81 ml
= 0.03706 M
And pH = -log[H30+]
= 1.43
I know the technicalities are pretty badly used here, but does my answer make sense?
yes, it makes sense.
My answer was similar but slightly different.
3 mmol H^+ from HCl.
Ka = 1.77 x 10^-4 (note slightly differnt Ka) = (H^+)(formate)/(HFormate)
Substitute 3/81 for (H^+) and (25/81 for (Hformate; i.e., formic acid) and solve for formate ion. I get 0.00147 M which is essentially your answer if we used the same Ka value I think.
Then I converted to moles.
moles H^+ from formic acid = 0.00147 x 81 mL = 0.119 mmoles.
moles from HCl = 3 mmoles.
Add to get 3.119 mmoles
Then 3.119 mmoles/81 mL = 0.0385 M
pH = 1.41 which is very close to your answer. Both of us neglected the quadratic if we had solved the Ka with formic acid exactly. The numerator would have been 0.00147 + 0.03704 (we just used 0.03704) and the denominator would have been (0.003086-0.00147)(I used 0.03086 and that could make a difference. A better solution would be to solve that quadratic. In any case, watch the significant figures in the final result.
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