Acid Base Chemistry of a Common Buffer

Valentin Uzunov (author), Tom Ronay and Hans Harshfield

PSU ID#: 964100377
CHM 229H, Lab 269


ABSTRACT
The current lab aimed to demonstrate the well know relationship between the dissociation
constants of a weak conjugate acid base pair and the dissociation constant of water (K
w
)
specifically at room temperature. The dissociation constants of H
2
PO
4
-
and HPO
4
2-
were
determine by titrating 0.10 M of corresponding strong acid (HCl) or base (NaOH) into 50 mL of
0.01 M aqueous solutions of potassium hydrogen phosphate and potassium dihydrogen
phosphate solutions. A pH sensor and logging computer software were used to measure and
record the change in pH of the solution as titrant was added. The dissociation constants were
determined through qualitative analysis of the resulting data. The pK
a
for H
2
PO
4
2-
was
determined to be 7.03, a -2.50 % difference from literature value of 7.21. The pK
b
of HPO
4
2-
ion
was determined to be 6.92, a 1.91 % difference from literature expected value of 6.79. The pK
a

and pK
b
values sum to 14.0 which is precisely accurate when measured to 3 significant figures.

EXPERIMENTALT
The acid dissociation constant for an H
2
PO
4
-
ion was determine by titrating 0.1 M NaOH into 50
mL of 0.01 M KH
2
PO
4
aqueous solution [Rxn 1 ]. The base dissociation constant for HPO
4
2-
was
determined from the acid dissociation constant for the titration of 0.10 M of HCl with 50 mL
K
2
HPO
4
[Rxn 2]. The following reactions are described by the corresponding net ionic reaction:
H
2
PO
4
-
(aq) + OH
-
(aq) HPO
4
2-
(aq) + H
2
O (l) [Rnx 1]
HPO
4
2-
(aq) + H
3
0
+
(aq) H
2
PO
4
-
(aq) + H
2
O (l) [Rxn 2]
pH curves for each acid base titration were recorded and plotted using a pH sensor connected to
computer with Logger Pro software package. The pH sensor was manually calibrated using a 2
point calibration procedure. Base values were taken at pH 3.18 and pH 9.64 from pre-prepared
standard solutions. Calibration was then verified using a pH 7 standard solution. The titrant was
added in 0.30 mL increments initially, then reduced to 0.10 mL as the equivalence point was
approached.



RESULTS
Table 1- Titration results and Ka values of H
2
PO
4
-
and HPO
4
2-


Half-
Equiva
lence
point
(mL)
pH at
Half
equival
ence
Equiva
lence
point
(mL)
pK
a

pK
b

pK
w
K
a
K
b
K
w

H
2
PO
4
-
2.65 7.03 4.95 7.03 14.0 9.33 x 10
-8
1.13 x 10
-14

HPO42- 2.48 6.92 4.98 6.9
2
1.20 x 10
-7



Figure 1- The figure shows the recorded titration curve for H
2
PO
4
-
and NaOH. The inflection points on the pH curve indicate the
half equivalence (2.65 mL of NaOH) and the equivalence points is at 4.95mL. The pH at the half equivalence was 7.03. The pH in
terms of NaOH added over the buffer region is modeled by y = 0.36x +6.07

Figure 2 The figure shows the recorded titration curve for HPO
4
2-
and HCl.. The inflection points on the pH curve indicate the half
equivalence point after 2.48 mL and the equivalence points is at 4.95mL of HCl added respectively. The pH at the half
equivalence was 6.92. The pH in terms of HCl added over the buffer region was modeled by the equation y = -0.40x +7.92
The volume and pK
a
of the strong acid added at the half-equivalence point was determined using
the Logger pro analysis functions to evaluate the inflection points in the data collected (figure 1
and 2). The second derivative over the buffer region was set to zero and solved for mL to
determine exact amount of titrant added. Table 1 show the half-equivalence points for the
titrations of H
2
PO
4
-
and HPO
4
2-
were reached at 2.65 mL of 0.10 M NaOH and 2.48 mL of 0.10
M HCl respectively. At the half- equivalence point according to the Henderson-Hasselbalch
equation, the pH is equal to the pK
a
:

) Simplifies to

, when

= 1 [Eqn
1]
The pH and corresponding pK
a
s for each ion were determined by fitting a line of best fit over
pH curve and the second derivative corresponding to the buffer interval on the titration curve.
The second derivative equation was set to zero and solved, determining the inflection point of the
pH curve over the chosen interval, the value determined corresponds to the pH and pKa of the
analyte. The pH and pK
a
for the H
2
PO
4
-
and HPO
4
2-
were determine to be 7.03 and 6.92
respectively.

From the pK
a
value of HPO
4
2-
, the pK
b
was calculated using the relationship:

[Eqn
2]
Where pK
w
is equal to 14.0 at 25.0 C. The pK
a
or pK
b
s are by definition simply the negative
log of the corresponding constant. Thus the above relationship also holds for:

[Eqn 3]

The product of K
a
the acid dissociation constant of H
2
PO
4
-
and K
b
the base dissociation constant
of HPO
4
2-
, should equal K
w
at 25.0 C. The K
w
determined from the current values was 1.10 x
10
-14
, which bears a 10.00 % difference from literature value of 1.00 x 10
-14
. However the pK
w

was an exact matches the precise value of 14.0, when measured to 3 significant figures [1]

DISCUSSION
The scope of the current experiment was to demonstrate the relationship between the product of
the acid and base dissociation constants and the dissociation constant of water for a constant
temperature [Eqn 3]. Titration curves were plotted for 2 acid-base reactions and subsequently the
corresponding Ka and Kb values were determined. The pKa and Ka results are related by the
definition, where the p prefix denoted negative logarithm of the associated variable or constant.
Using a p-scale to express the measured quantities is advantageous as it compresses the large
range of the dissociation constant scale (which depends of concentrations of the hydronium and
hydroxide ion in the solutions) into more manageable quantities. The p-scale in the case of the
dissociation constants is also less susceptible to error due lack of precision. This is suggested the
results. The Kw calculated had a 10.00 % difference to the expected value, while the pK
w
was an
exact match up to 3 significant figures.
The pK
a
determined for H
2
PO
4
-
was 7.03, a -2.50 % difference from literature value of 7.21, and
the pK
b
of HPO
4
2-
ion. Was determined to be 6.92, with a 1.91 % difference from literature value
of 6.79.
The sum of the pK
a
and pK
b
summed exactly to the pK
w
value of 14.0 as expected. Overall the
experimental results shows clear evidence in support of the relationship expressed in [Eqn 3].
The current margin of error in the results could be attributed to random noise, and precision of
measurements. More trials would allow for further results to filter out much of this random error
associated with the collected data and would be expected to yield more accurate to higher
significant figures at all scales.




CITATIONS
[1] 1- Tro, Nivaldo J.Chemistry: A Molecular Approach. Upper Saddle River, NJ: Pearson
Prentice Hall, 2011. Print.