Experiment 5

Acid-Base Titration: Determination of the Molar Mass and pKa of an Unknown Weak Acid

By:
Bryan Zheng

Lab Instructor: Michael Boucher

October 23, 2015

Introduction:

This experiment was divided into two parts: standardization of a stock NaOH solution
and the determination of the molar mass and pKa of the unknown acid. The ultimate goal of this
experiment was to determine the molar mass and the pKa of an unknown monoprotic weak acid,
labelled 974W. The molarity of an NaOH solution was determined using stoichiometry to be .1M
by performing a titration on about .800 grams of potassium acid phthalate (KHP), an acid with a
known molar mass.
Next, a preliminary titration was performed on the unknown acid to determine the
approximate volume of NaOH that was needed to titrate about .500 grams of the unknown acid.
Small amounts of NaOH were added to the unknown acid solution with phenolphthalein. A pH
meter measured the pH values, which were recorded in order to create a titration curve, with the
equivalence point occurring a rapid change in pH. The molar mass could then me determined
using stoichiometry and the pKa could be extracted from the titration curve and equivalence
point.
Procedure:
First, 3 samples of KHP were placed in three 250mL flasks and dissolved in about 50mL
of distilled water. The mass of these samples are recorded in table 1. 5 drops of phenolphthalein
were added to each acid solution. A burette was then filled with NaOH solution and the initial
volume was recorded. The KHP was then titrated to the point when a faint pink color from the
phenolphthalein in the solution remained for over 20 seconds, which indicated that the solution
had reached the endpoint, where the reaction between KHP and NaOH was complete. The final
volume remaining in the burette was recorded. This process was repeated for the remaining 2
solutions.
An extra titration was performed to ensure that successive titrations resulted in NaOH
concentrations that were within 1%. Both the initial and final volume were recorded in table 1.
The percent difference between the 3rd and 4th trials was .1%, within the 1% threshold.
To determine the molar mass and pKa of the unknown acid, .528 grams of the unknown
acid were dissolved in about 50mL of water and phenolphthalein and titrated with the NaOH
stock solution. The initial volume and final volume are shown in table 2. Since the change in
volume of 34.82mL was between the 30-40mL range recommended, it was concluded that using
approximately .500 grams of the acid would be sufficient for the pH titrations. This was the
preliminary titration
Next, a pH meter was calibrated. Three samples of the unknown acid of about .500 grams
were massed and dissolved in distilled water while being stirred with a magnetic stir bar. 5 drops
of phenolphthalein were added. Small volumes of NaOH were added and the volume was
recorded, as well as the pH. When the pH started increasing rapidly, individual drops of NaOH
were added from the burette.
This process was repeated for the other two samples, however it was determined that
phenol red would be a better indicator for the remaining titrations since it changes from yellow to
dark pink in approximately the 6.5-8 pH units range, and the pH of the solution rapidly changed
at around 6-8 pH units.
The mass, volumes, and pHs for each sample are recorded in tables 3, 4, and 5.

Calculations:

Concentration of NaOH
.862 gKHP
1 molKHP
1 molNaOH

=.0972 MNaOH
.04241 L
204.220 gKHP 1 molKHP
.816 gKHP
1 molKHP
1 molNaOH

=.101 MNaOH
.03964 L
204.220 gKHP 1 molKHP
.868 gKHP
1 molKHP
1 molNaOH

=.0991 MNaOH
.04290 L
204.220 gKHP 1molKHP
.827 gKHP
1 molKHP
1 molNaOH

=.0990 MNaOH
.04085 L
204.220 gKHP 1 molKHP
Percent Difference:

.0991 M .0990 M
=.1
.0991 M +.0990 M
2
Average Concentration of NaOH
.101 M +.0991 M +.0990 M
[ NaOH ] =
=.0100 M
3
Molar Mass of Acid:
.511 gA
1 LNaOH
1 molNaOH

=152 gA/mol
.03380 LNaOH .100 molNaOH
1 molA
difference=

.518 gA
1 LNaOH
1 molNaOH

=148 gA /mol
.03489 NaOH .100 molNaOH
1 molA
.520 gA
1 LNaOH
1 molNaOH

=148 gA /mol
.03510 LNaOH .100 molNaOH
1 molA
Average Molar Mass of Acid:
152 gA 148 gA 148 gA
+
+
mol
mol
mol
149 gA
Molar Mass=
=
3
mol
pKa of Acid
3.253.17
pKa1=3.17+
(16.90 mL16.20 mL )=3.20
17.89 mL16.20 mL
3.963.70
pKa2=3.70+
( 17.45 mL26.09 m L )=2.99
29.26 mL26.09 mL
4.293.94
pKa1=3.94 +
( 17.55 mL28.65mL )=2.59
31.53 mL28.65 mL
Average pKa:
3.20+2.99+2.59
average pKa=
=2.93
3

Results:
The molar mass was determined using stoichiometry (see above). The average molar
mass was found to be 149g of acid per mole.
To find the pKa, the titration curves must be analyzed. At half the volume of the
equivalence point, the ratio of conjugate acid to conjugate base was 1. Therefore, according the
the Henderson-Hasselbalch equation,
pH= pka+log ( 1 )
pH= pKa
For the first titration, the equivalence point was the point of inflection of the pH versus
volume graph. This is also the peak of the graph of the first derivative, where the slope of the
first derivative changes sign from positive to negative. At this point, the volume was 33.80mL
and the pH was 6.58. Half this volume was 16.90mL. There was no point for exactly 16.90mL,
but the point was estimate using the line connecting the two know points (16.20mL, 3.17) and
(17.89mL, 3.25). The estimation for pKa for titration 1 was therefore 3.20. The same estimation
was calculated for the other two titrations (see above). The average value of the pKa was 2.93
However, it should be noted that the estimates for titrations 2 and 3 were likely worse
estimations of the pKa than the estimation from the first titration. This is because the first
titration had values surrounding the volume halfway to the equivalence point. Therefore, the
linear approximation does not have a large error. However, for titrations 2 and 3, the line
connecting the lowest two points was extrapolated, which would result in an error since the
graph was a curve. In other words, a linear approximation was used for an extensive part of the
curve that was concave up. Therefore, the approximations were likely two low, which is
consistent with the fact that both 2.99 and 2.59 less than the estimation from titration 1 of 3.20.
It was impossible to determine the acid from molar mass alone since many acids have
molar masses around 149g/mole. However, the standard deviation from this mean was
2.31g/mole, which is 1.55% the value of the mean. It was also impossible to tell if there was a
systematic error without knowing the true value of the molar mass for the unknown acid.
There was another way using an ICE box to calculate pKa that resulted in values that are
significantly less consistent. The reaction relevant to the titration was as follows

H 2 O+ A
HA +O H
Since at the equivalence point, all of the HA was consumed by OH-, the concentrations of both
these species was 0M, and the same number of moles of A- were formed as the initial number of
moles HA. Using the titration with .511g of acid initially,
mole
.511 g
=.003429 moles
149 g
.003429 moles
=.02556 M
The concentration of A- was
.1 L+.0338 L
A-, which is the conjugate base, creates OH- with the following reaction with the corresponding
ice box

+ H 2 O HA +O H
A
initial:
.02556M
0
0
change:
-x
x
x

equilibrium

.02556M-x

Thus,

Kb=

x
.02556 M x

OH
Since the pH at the equivalence point was 6.58,
x=
2

Thus,

Kb=

( 3.8 1 07 )
12
=5.65 10
7
.02556 M ( 3. 8 1 0 )

pKa=14pKb=14+ log ( 5.65 1012) =2.75

Using the same method, the pKa for second titration was 3.07 and the pKa for the third
titration was 1.69. The average of these values was 2.5 but the values using the previous method
were clearly more precise.
The reason for the lack of precision using this method is likely because the volume of the
solution was not just 100mL plus the volume of NaOH added. Distilled water was added when
adding half-drops of NaOH. Since the volume affected the concentration of each species, the
concentrations were likely more diluted than the calculations indicated.
Conclusions:
The average molar mass of the acid was 149g/mole with 2.31g/mole standard deviation.
The average pKa estimation was 2.93, however the best estimation was likely 3.20, the pKa from
titration 1. Using an ICE box, the average pKa estimation was 2.5. It is impossible to tell our
error without knowing the identity of the unknown acid. However, the experiment could have
been improved by ensuring the points near the volume halfway to the equivalence point were
taken. That way, the approximation of pKa would have been more accurate. Also, had distilled
water not been added to the 100mL beaker, the pKa values from the ICE box would likely have
been more precise.
Additional Questions:
I)
1.) see above for molarity of the standardized NaOH
2.) see above for molar mass of unknown acid for each titration
3.) Phenolphthalein was used for the first titration. Phenol red was used for titrations
2 and 3
4.) see above for average molar mass
5.) see above for pKa of the unknown acid
II) See appendix for graphs of pH versus volume of NaOH. The endpoint for titrations 1, 2,
and 3 occur at (33.80mL ,6.58), (34.89mL, 7.74), and (35.10mL, 7.05) respectively.
III) See appendix for graphs of first derivatives. The equivalence point occurs at the peak
point, where the slope of the first derivative changes from positive to negative.
IV) See appendix for theoretical titration curve.
The theoretical curve was created by adding hypothetical values of NaOH every .5mL.
The moles of acid left from the original mass, specifically .511g, and the moles of conjugate base
can then be calculated by subtracting from the original moles of acid. The ratio of conjugate base
to conjugate acid can then be substituted into the Henderson-Hasselbalch equation to obtain pH.

Since the pKa of 3.20 from the first titration was likely the best estimate of the pKa, the equation
for pH is therefore,

pH =3.2+log
After the equivalence point, the pH changes because of an excess of OH- from the NaOH. So the
pOH was determined from excess OH concentration and subtracted from 14 to obtain the pH.
V) See appendix for theoretical titration curve overlaying actual experimentally determined
titration curve. Titration 1 was chosen, where the acid had a mass of .511grams. The main
difference was that rapid pH increase, is steeper for the theoretical, which was nearly vertical,
than for the experimental. This makes sense since practically, the change in pH could not have be
completely vertical, or have an infinite slope.
VI) Phenolphthalein changed color from clear to pink after the solution reached a pH of about
8. This did not fully capture the range of rapid pH increase. Phenol red changed color from
yellow to dark pink at about 6.5 to 8, which adequately encapsulates the desired range of rapid
increase, which occurred at about 6 to 8 pH units. Thus, phenol red was used for titrations 2 and
3.
(See above for discussion of precision and standard deviation)
A possible source of error could be lack of sufficient points around the point halfway to
the equivalence point. This resulted in extrapolations of lines that would not have been necessary
if more pH values were taken around the halfway point, which would have given a better
indication of the pH, and thus the pKa, of the solution at that point. Another source of error could
have been the addition of distilled water to the 100mL beaker during titration, which changed the
concentrations of all species in the solution.
VII) If the acid was diprotic, there would have been two equivalence points in the titration curve,
or two points of rapid pH increase. There would be two parts of the curve where pH changes
rapidly, one for each hydrogen atom. As long as both equivalence points and both pKa values are
considered, the molar mass should still be calculated accurately.