Compute pH before/after addition of NaOH?
In the titration of 50.0 mL of 0.100 M \beta -hydroxybutyric acid, HC_4H_7O_3 , with 0.100 M NaOH, compute pH before addition of NaOH, and after the addition of 25.00 mL and 50.00 mL of NaOH. pK_a for HC_4H_7O_3 is 4.39.
In the titration of 50.0 mL of 0.100 M
1 Answer
Here's what I got.
Explanation:
!! EXTREMLEY LONG ANSWER !!
For the sake of simplicity, I'll use
Now, the pH of the solution before the addition of strong base can be calculated by using the fact that the weak acid only partially ionizes in a
beta"-HA"_ ((aq)) + "H"_ 2"O"_ ((l)) rightleftharpoons "H"_ 3"O"_ ((aq))^(+) + beta"-A"_ ((aq))^(-)
If you take
[beta"-HA"] = [beta"-HA"]_0 - x
By definition, the acid dissociation constant will be
K_a = ( [beta"-A"^(-)] * ["H"_3"O"^(+)])/([beta"-HA"])
In your case, this will be equal to
10^(-"p"K_a) = (x * x)/(0.100 - x) = x^2/(0.100 - x)
Since
K_a = 10^(-"p"K_a) = 10^(-4.39) = 4.07 * 10^(-5)
is very small compared to the initial concentration of the acid, you can use the approximation
0.100 -x ~~ 0.100
This means that you have
4.07 * 10^(-5) = x^2/0.100
Solve for
x = sqrt(0.100 * 4.07 * 10^(-5)) = 2.02 * 10^(-3)
You can thus say that
["H"_3"O"^(+)] = 2.02 * 10^(-3) "M"
The pH of the initial solution
color(blue)(ul(color(black)("pH" = - log(["H"_3"O"^(+)])))
will be
"pH" = - log(2.02 * 10^(-3)) = color(darkgreen)(ul(color(black)(2.695)))
Now,
beta"-HA"_ ((aq)) + "OH"_ ((aq))^(-) -> beta"-A"_ ((aq))^(-) + "H"_ 2"O"_ ((l))
The initial solution contains
50.0 color(red)(cancel(color(black)("mL"))) * (1color(red)(cancel(color(black)("L"))))/(10^3color(red)(cancel(color(black)("mL")))) * ("0.100 moles" color(white)(.)beta"-HA")/(1color(red)(cancel(color(black)("L")))) = "0.00500 moles" beta"-HA"
The first solution of sodium hydroxide contains
25.00 color(red)(cancel(color(black)("mL"))) * (1color(red)(cancel(color(black)("L"))))/(10^3color(red)(cancel(color(black)("mL")))) * ("0.100 moles OH"^(-))/(1color(red)(cancel(color(black)("L")))) = "0.00250 moles OH"^(-)
So, after the first sample of sodium hydroxide is added to the initial solution, the moles of hydroxide anions will be completely consumed. You will be left with
n_ ("OH"^(-)) = 0 -> completely consumed
n_ (beta"-HA") = "0.00500 moles" - "0.00250 moles" = "0.00250 moles" beta"-HA"
n_ (beta"-A"^(-)) = "0 moles" + "0.00250 moles" = "0.00250 moles" beta"-A"^(-)
The new volume of the solution will be
V_"solution" = "50.0 mL" + "25.00 mL" = "75.0 mL"
Now, notice that the resulting solution contains equal numbers of moles of weak acid and of conjugate base. This means that you're in the buffer region, i.e. the resulting solution contains a buffer.
This means that the pH of the solution will be equal to the
[beta"-HA"] = [beta"-A"^(-)]
This is known as the half-equivalence point. Consequently, you will have
"pH" = "p"K_a + log ( (color(red)(cancel(color(black)([beta"-A"^(-)]))))/(color(red)(cancel(color(Black)([beta"-HA"]))))) -> the Henderson - Hasselbalch equation
and so
color(darkgreen)(ul(color(black)("pH" = 4.39)))
Finally, you're adding an additional
At this point, it should be obvious that all the moles of acid and all the moles of hydroxide anions will be consumed by the reaction
n_ ("OH"^(-)) = 0 -> completely consumed
n_ (beta"-HA") = "0.00250 moles" - "0.00250 moles" = 0 -> completely consumed
n_ (beta"-A"^(-)) = "0.00250 moles" + "0.00250 moles" = "0.00500 moles" beta"-A"^(-)
The new volume of the solution will be
V_"total" = "75.0 mL" + "25.00 mL" = "100.0 mL"
The concentration of the conjugate base will be equal to
[beta"-A"^(-)] = "0.00500 moles"/(100.0 * 10^(-3)"mL") = "0.0500 M"
The conjugate base will only partially ionize to produce
beta"-A"_ ((aq))^(-) + "H"_ 2"O"_ ((l)) rightleftharpoons beta"-HA"_ ((aq)) + "OH" _((aq))^(-)
An aqueous solution at room temperature has
color(blue)(ul(color(black)(K_a * K_b = 10^(-14))))
and so
K_b = 10^(-14)/(4.07 * 10^(-5)) = 2.46 * 10^(-10)
If you take
[beta"-A"^(-)] = 0.0500 - x
By definition, you know that
K_b = ([beta"-HA"] * ["OH"^(-)])/([beta"-A"^(-)])
which, in your case, is
K_b = (x * x)/(0.0500 - x) = x^2/(0.0500 - x)
Once again, use the approximation
0.0500 - x ~~ 0.0500
to get
2.46 * 10^(-10) = x^2/0.0500
Solve for
x = sqrt(0.0500 * 2.46 * 10^(-10)) = 3.51 * 10^(-6)
This means that the resulting solution has
["OH"^(-)] = 3.51 * 10^(-6) "M"
Consequently, you will have
["H"_3"O"^(+)] = 10^(-14)/(3.51 * 10^(-6)) = 2.85 * 10^(-9) "M"
which means that the pH of the solution is
"pH" = - log(2.85 * 10^(-9)) = color(darkgreen)(ul(color(black)(8.545)))
I'll leave the values rounded to three decimal palces, the number of sig figs you have for the concentrations of the two solutions.
Now, does the result make sense?
You are titrating a weak acid with a strong base, so at the equivalence point, the solution will only contain the conjugate base of the acid.
So even without doing any calculations, you should be able to say that at equivalence point,