Chemistry 135

Clark College

POTENTIOMETRIC TITRATION OF A WEAK ACID

A Weak Acid/Strong Base Titration

For this experiment:

1. Complete the Prelab and obtain a stamp before you begin the experiment.
2. Write your lab notebook prelab and get it initialed/signed before you begin the experiment.
3. Obtain an unknown organic acid and record the unknown code in your notebook and on the
data report sheet. Look for the unknown assignments taped to the wall near the Instructors
Station in the lab.
4. Titrate a preliminary sample of your unknown roughly with phenolphthalein to determine
approximate equivalence point.
5. Perform two trials of your titration using the LoggerPro interfaces and the same batch of
NaOH that you standardized.
6. Determine the identity of your unknown from the calculated equivalent weight and estimated
pKa.
Turn in your Data Report Sheet, Stamped Prelab, notebook pages and the following (labeled
and organized graphs for each equivalence point in each titration: pH vs VNaOH, 1st derivative
curve, 2nd derivative curve, and a blow-up of the pKa/buffer region.
Introduction
In a potentiometric titration one makes a graph of the volume of titrant delivered from a buret
against the voltage (or some function directly related to the voltage, such as pH) produced by two
electrodes in the solution being titrated. Provided the equilibrium of the analytical reaction is favorable
and one chooses the right combination of electrodes there will be a sharp change in voltage at the
equivalence point. This change in voltage can be used in place of a color indicator to locate the
equivalence point. This is obviously a very useful technique if one is dealing with a colored solution in
which an indicator would be useless or in a system for which a suitable indicator does not exist.
Although the present experiment deals with an acid-base reaction, potentiometric titrations can
also be used with redox reactions, precipitation reactions and complex formation reactions, as well as
titrations in non-aqueous systems. Furthermore, although the present experiment may give the
impression that the technique is slow, it can, in routine work, be made just as rapid as titrations using
visual indicators, and often gives more accurate results.
The choice of electrodes is critical. One electrode, called the reference electrode, must hold a
constant potential throughout the titration, regardless of the concentration of various reagents in the
solution. The other electrode, called the indicator electrode, must have a potential that depends
directly on one of the reactants or products in the analytical reaction. The electrodes used in acidbase titrations are almost always a calomel reference electrode and a glass indicator electrode. The
potential of the glass electrode depends directly on the hydrogen ion activity in solution, whereas the
potential of the calomel electrode is constant because it is isolated from the solution being titrated by
a salt bridge.
A pH meter, or pH amplifier, such as the one used in this experiment, is essentially an electronic
voltmeter. However, through calibration, its output reads directly in pH units instead of volts. The
apparatus is sketched in Figure 1. One performs the titration by adding increments of titrant from the
buret and reading the pH of the solution after each addition.

Potentiometric Titrations

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Chemistry 135

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Figure 1
Treatment of Potentiometric Data
For each trial set of data, plot the entire titration curve as in Figure 2. The equivalence point is the
point of maximum slope. You will notice, however, that the volume scale of such a graph is too
compressed to read the equivalence point to 0.02 mL as required in order to obtain part-perthousand accuracy. One may prepare a second graph in which one plots the region from about 1-2
mL before the equivalence point to 1-2 mL beyond, as illustrated in Figure 3. The operator must
judge the inflection point. The volume scale is now large enough that the volume at the inflection
point can be read to the nearest 0.02 mL. The main sources of error are the failure to draw a
smooth curve through the data points and in judging the location of the inflection point. The latter
error is somewhat analogous to a titration using a color indicator in which the main source of error is
the operator's judgment as to the color at the end point. We will also use other mathematical methods
to help determine the equivalence point.
TABLE 1 Sample Titration Data
Corrected
Volume NaOH
0.00
2.03
4.00
6.00
8.00
10.00
12.00
14.02
16.00
18.00
20.00
22.00

Potentiometric Titrations

pH
3.86
4.02
4.14
4.28
4.40
4.51
4.61
4.71
4.81
4.90
5.01
5.09

Corrected
Volume NaOH
24.00
26.00
28.00
30.00
32.00
34.00
35.00
35.21
35.39
35.60
35.79
36.00

pH
5.20
5.32
5.44
5.60
5.80
6.13
6.43
6.53
6.64
6.79
6.98
7.35

Revised Spring 2005 NF

Corrected
Volume NaOH
36.20
36.40
36.60
37.00
38.00
40.03
42.00
44.00
46.00
48.00
50.01

pH
9.29
9.84
10.17
10.50
10.87
11.23
11.40
11.53
11.63
11.70
11.77

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Weak Acid Titration

12.00

pH

10.00
8.00
6.00
4.00
2.00
0.00

20.00

40.00

60.00

Volume of NaOH

Figure 2
Estimation of pKa at the Half-titration Point
After you have located the equivalence point in the first titration curve, you can calculate the
volume of sodium hydroxide at the equivalence point in the titration and therefore the volume at which
exactly half of the acid will be neutralized. This is called the buffer point, half-titration point or halfequivalence point. This point is particularly significant because it provides an estimate of the acid
dissociation constant of the acid being titrated.
In general, for any weak acid we have the following equilibrium:
H3O+ (aq) + A- (aq)

HA (aq) + H2O (l)

Ka =

[H+] [A-]
[HA]

Now, at the half-titration point, exactly half of the acid, HA, has been converted into its conjugate
base. That is, the solution can be considered to be one containing equal concentrations of HA and A-.
Thus, it should be clear that at this particular point in the titration [HA] = [A-]. Therefore, Ka = [H+], or
pKa = pH.
Some typical data at the half-equivalence point are presented in Table 2. These data are for the
same titration as the data in Figures 2 and 3. Thus, the equivalence point occurs at 36.11 mL, the
half-equivalence point at 18.05 mL, and the pKa is approximately 4.90, as determined from Figure 4.
Some disagreement in pKa from handbook is typical, and is a result of the use of molar
concentrations in place of activities in the expression for the equilibrium constant. Nevertheless, it is
valuable information when seeking to identify unknown acids.
Table 2

Expansion of Half-

Half-Equivalence Data
pH

12.00

4.61

14.02

4.71

16.00

4.81

18.00

4.90

20.00

5.01

22.00

5.09

24.00

5.20

Potentiometric Titrations

5.20
5.00
4.80
4.60
13.00

pH

Vol NaOH mL

Equivalence pt.

15.00

17.00

19.00

21.00

23.00

25.00

Volume of NaOH

Figure 3

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First Derivative Plot

We noted above that at the equivalence point, the slope of the titration curve is at a maximum. In
other words, the rate of change of pH with addition of titrant is at its highest at the equivalence point.
So, if we could plot the rate of change of pH with change in volume (pH/V) against volume, then a
"spiked" curve should result and the peak of this spike should occur at the equivalence point. This is
conveniently done by adding equal increments of titrant near the equivalence point. Consider the
data collected during a titration, as shown in Table 3. We want to plot pH/V against the volume to
get the first derivative. Such a plot is shown in Figure 4. The volume used is the average of the two
volumes used to calculate pH. So, the volume for pH/V = 0.71 is 35.50 mL, and so on. The
equivalence point is the maximum of this plot, which, when extrapolated, occurs at 36.10 mL. This
extrapolation leads to an uncertainty that can be partially avoided by a second derivative plot (see
below).
Note that we have used equal volume increments here ( 0.20 mL), and so pH could have been
plotted in place of pH/V. These equal increments are not necessary but do shorten the
calculations. Although the average volume may be calculated to 0.001 mL for plotting,
experimentally, we are not justified in reporting the equivalence point to more than 0.01 mL.
Table 3
First Derivative Data
pH
V
Vol. Avg.

Volume NaOH

pH

35.39
35.60
35.79
36.00
36.20
36.40
36.60

6.64
6.79
6.98
7.35
9.29
9.84
10.17

0.15
0.19
0.37
1.94
0.55
0.33

0.21
0.19
0.21
0.20
0.20
0.20

35.50
35.70
35.90
36.10
36.30
36.50

pH/V
0.71
1.00
1.76
9.70
2.75
1.65

First Derivative Plot

10.00
8.00

dpH/dV

6.00
4.00
2.00

36.50

36.30

Avg. Vol. NaOH

36.10

35.90

35.70

35.50

0.00

Figure 4

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Second Derivative Plot

Mathematically, the second derivative of a titration curve should pass through zero at the
equivalence point. The last four columns in Table 3 illustrate how such a plot can be accomplished.
The second derivative is the rate of change of the first derivative with respect to the change in the
average volume. The average of the two successive volumes used for the first derivative plot is also
used for the second derivative plot (Figure 5). Again, there is some extrapolation, but it is less
significant than in the first derivative plot. The equivalence point is taken as 36.11 mL. As before, we
are experimentally justified in reporting it to the nearest 0.01 mL.
In using derivative methods, the volume increment should not be too large or there will not be
sufficient points near the equivalence point.
Caution should be used with derivative methods. Derivatives tend to emphasize noise or scatter in
the data points, being worse for the second derivative. Therefore, if a particular titration is subject to
noise, a direct plot (pH versus Volume) may be preferred.
Table 4
Vol. Avg.

pH/V

35.50
35.70
35.90
36.10
36.30
36.50

0.71
1.00
1.76
9.70
2.75
1.65

Second Derivative Data

(V)
(pH/V)
V avg
0.20
0.20
0.20
0.20
0.20

0.29
0.76
7.94
-6.95
-1.10

(pH/V)/V

35.60
35.80
36.00
36.20
36.40

1.43
3.81
38.72
-34.75
-5.50

Second Derivative Curve

40.00
20.00

d2pH/dV2

0.00
35.40
-20.00

35.60

35.80

36.00

36.20

36.40

-40.00
Vol. NaOH

Figure 5
Assembling the Data
Once you have obtained the equivalence volumes and pKas, you can use that information to
determine the identity of your unknown acid. The molecular weight can be determined from the
equivalence point data. The pKa values can be determined from the half-equivalence points. Your
unknown acid can be either monoprotic or diprotic. Although this is often readily seen in the titration
curve, some diprotic acids appear to have only one equivalence point, if the two pKa values are less
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than 2 pH units apart. However, the resulting calculated molecular weight will be the equivalent
weight, and thus will be one-half the molecular weight. It is a match (or near-match) of both the pKa
and molecular weight data that determines the identity of your unknown acid. Table 5 gives a list of
possible organic acids for this experiment.
Table 5 Selected Physical Data for Organic Acids
Acid

Molar mass(g/mol)

pKa1

pKa2

Benzoic acid

122.1

4.20

2 Chlorobenzoic acid

157.58

2.94

4 Chlorobenzoic acid

157.58

3.99

trans Crotonic acid

86.09

4.69

Maleic acid

116.04

1.92

6.23

Malonic acid

104.06

2.83

5.69

Potassium hydrogen phthalate

204.23

5.41

Succinic acid

118.1

4.19

Sodium hydrogen sulfite

104.06

7.21

d -Tartaric acid

150.09

3.04

5.57
4.37

m Toluic acid
128.85
4.27
Reference Table taken from Langes Handbook of Chemistry, McGraw-Hill Book. Co. 1979.

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NOTES
Note 1: Buret readings must be made to the nearest 0.01 mL and the pH meter should be
read to the nearest 0.01 pH unit.
Note 2: After you have located the equivalence point in the first titration curve, it is a simple matter to
calculate from the sample weights the location of the equivalence point in the second sample.
EXPERIMENTAL PROCEDURE
Equivalent Weight Estimate
Mass approximately 0.5 grams into a 250 mL Erlenmeyer flask (don't use the analytical balance, this
is for a trial run!), add 100 mL of distilled water and cover with a watch glass. Do a phenolphthalein
titration and calculate the approximate equivalent weight of your unknown organic acid.
Determine the mass of unknown acid needed for a 35-40 mL titration.
Potentiometric Titration
You may work with someone else to help obtain data. Each person must obtain their own sample of
an unknown acid. Assume the samples have a 100.0% purity. One person may operate the buret
while the other records the data. Exchange roles with each person's sample.
If you have a diprotic acid, do the calculations and graph for the 2nd equivalence point.
Technique note: To rinse the electrode, use your waste beaker and hold it under the electrode then
rinse the electrode thoroughly with distilled water, collecting the waste.

1. Using the analytical balance, mass two samples of the unknown acid as calculated above into two
250-mL beakers. Record the mass to the nearest 0.0001 g. Dissolve each in about 100 mL of
distilled water and cover each with a watch glass.

2. Prepare the computer for data collection by opening Experiment 24 from the Chemistry with
Computers experiment files of Logger Pro. You should see a blank data table and graph. The
vertical axis has pH scaled from 0 to 14 pH units. The horizontal axis has volume scaled from 0 to
25 mL. Change the maximum volume to 50 mL by clicking once on the 25 and typing in 50.

3. Calibrate your pH electrode using buffers pH 4 and 7. Find the Collect item in the menu bar and
open Calibrate... Follow directions to calibrate your pH probe using the two buffers. You will
have to type in the appropriate pH values when the voltage values stabilize. Re-check your
calibration with one of the buffers and make sure it is stable. Remember to rinse the pH probe
between solutions, and be sure to Save your calibration.

4. Obtain a clean 50-mL buret and rinse the buret with a few mL of the ~0.1 M NaOH solution you
have standardized in the last experiment. Dispose of the rinse solution into your waste beaker.
Use a buret clamp to attach the buret to the ring stand as shown in Figure 1. Fill the buret above
the 0.00-mL level of the buret with the ~0.1 M NaOH solution. Drain a small amount of NaOH
solution into the waste beaker so it fills the buret tip and leaves the NaOH at the 0.00 mL level of
the buret. Be sure to record the precise concentration of the NaOH solution in your data table.

5. Prepare your experimental set-up as shown in Figure 1. Use a utility clamp to suspend a pH
electrode on a ring stand, and a buret clamp to attach the buret to the ring stand. Place a stir bar
in one of your acid solutions to use a magnetic stirplate. Position the pH electrode in the acid
solution and adjust its position so that it is not struck by the stir bar. Do not place the magnetic
stirrer close to a computer, the magnet interferes with the monitor!

6. Before adding NaOH titrant, click on the Collect button and monitor pH for 5-10 seconds. Once
the pH has stabilized, click on the Keep button. The computer will hold this pH value and wait for
you to type in the buret reading. Enter the current buret reading (should be 0.00 mL). You have
now saved the first data pair for this experiment.
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7. You are now ready to continue the titration. This process goes faster if one person manipulates
and reads the buret while another person operates the computer and enters volumes.

8. Add the next increment of NaOH titrant (enough to raise the pH about 0.30 units). Again click on
the Keep button and enter in the volume.

9. Continue adding NaOH solution in increments that raise the pH by about 0.30 units (constant pH
increments) and enter the buret reading after each increment. Near the equivalence point, when
the curve starts to rise sharply, change to intervals of 0.20 mL units (or less). Note this is a
change to constant volume increments. This eases the treatment of the data later.

10. After the curve flattens again, you may add NaOH solution in larger increments (going back to
changes of 0.30 pH units) until all 50 mL have been added, or the pH becomes relatively constant.

11. Dispose of any waste beaker contents into the appropriate product collection container.
Treatment of Potentiometric Data
Part of your grade will be determined by your manipulation of the data so that the graphs and tables
are appropriate.
1. Save your data on the desktop in the folder labeled 135. You files should be titled with your
initials and whether this is the first or second titration, e.g. NFacid1. Be sure you save with your
initials or other notation so that you (and I) can keep the different trials separate.
NOTE: You may save your data in the Chem 135 folder on the desktop of the computer if you want to
do so, then you may come back and manipulate the data later. In Logger Pro there are
various ways to accomplish each task and to make the graphs look correct. Please be sure to
save your raw data and to practice a little.
2. The titration curve you have obtained should have a shape similar to the one shown in Figure 2.
Print both the data table and the graph window separately.
3. View the first derivative curve by clicking the y-axis title (pH) and selecting the first derivative (d1).
4. Change the scales on the x- and y- axes to give an expanded graph in the window.
5. Record the equivalence point, which is the peak on the graph, by using the Analyze menu to find
the maximum point for your graph. Print the graph with that point indicated by the analysis bar.
6. Follow the same process to view the 2nd derivative curve. The equivalence point is where the
second derivative equals zero. Change the scales on the x- and y- axes to give an expanded
graph in the window and find the point where the line crosses the x-axis using the Analyze menu.
Then print the graph.
7. Now that you have the equivalence pt. volume of NaOH, go back to the original titration curve and
expand the region about the half-equivalence pt. You may use the Analyze menu to find the pH
at the half-equivalence pt. Print this graph as well.
8. Repeat the procedure with the second sample, and be sure to change units, axis titles on the
computer screen as needed.
NOTE: Expand axes as necessary to provide good-looking, useful results. It is sometimes
advantageous to have the pH, 1st, and 2nd derivative graphs expanded about the equivalence
point using the same scale for the x-axes.

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Chemistry 135

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Processing the Data

1. Calculate the equivalent weight of your unknown using your equivalence point.
2. Find the pKa for your unknown acid from the half-equivalence point and identify the acid using the
table attached.
3. Staple together the report forms, data tables, and the required graphs. Print your name and date
on each graph. A portion of your grade will depend upon the presentation of your data and
graphs. Graphs include:

Complete titration curves based on the data for both titrations.

The first derivative graph showing the equivalence point region on an expanded volume scale
(see Figure 3). You should be able to read volumes to 0.01 mL.

The second derivative graph showing the equivalence point region on an expanded volume
scale (see Figure 4). You should be able to read volumes to 0.01 mL.

Expanded half equivalence pt region for each titration.

NOTE: If you have a diprotic acid, you will actually turn in 14 graphs: you will need to treat each
equivalence point and half-equivalence point separately.
APPENDIX
Concentration Units Normality vs. Molarity.
Most titration calculations can be carried out using either concentration units, N or M. Remember that
normality is the number of equivalents per liter of solution, where an equivalent is the number of
active units per mole of compound. Active units can be H+ or OH for acid/base reactions or electrons
for redox reactions.
Example: A 1.5 M H2SO4 solution is 3.0 N, because there are 2 equivalents of H+ in every mole of
H2SO4.

1.5 mol H2SO4

2 eq H+
x
L
mol H2SO4

3.0 eq
= 3.0 N
L

Equivalent Weight: The equivalent weight of a compound is the mass of compound that can supply
one mole of active units (H+, OH, es)
Example: Determine the equivalent weight of barium hydroxide. The formula Ba(OH)2 has a mass of
171.35 g/mol. Since barium hydroxide has 2 equivalents of OH per mole, the equivalent
weight is 1/2 the molecular weight.

171.35g 1 mol Ba(OH)2

x
mol
2 eq OH-

Potentiometric Titrations

Revised Spring 2005 NF

85.675 g
eq

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SAMPLE CALCULATIONS
A. Weak Acid Strong Base Titrations
The equivalence point of the titration occurs when the milliequivalents of base added exactly equals
the milliequivalents of acid in the flask or when millimoles of base units added exactly equals the
millimoles of acid units in the flask.
meq acid = (mL acid)(N acid)

meq base = (mL base)(N base)

The usefulness of normality in volumetric analysis is demonstrated with following: at the equivalence
point
NAcidVAcid = NBaseVBase
To calculate the number of equivalents contained in a known acid sample, one needs the sample
mass, its purity, and its equivalent weight.

equiv acid =

sample wt.(g) x purity factor

equiv. wt. (g/eq.)

or in more familiar form/path: g sample g acid eq. acid

equiv acid = g sample x

g acid
eq acid
x
100 g sample g acid

Calculations in this experiment are the same as those in the Standarization of NaOH
experiment please review them.
Example 1: Determine the equivalents of acid in a 0.4567 g sample of citric acid which is 92.15%
pure. Citric acid is a triprotic organic acid, C6H8O7.

equiv acid = 0.4567 g sample x

92.15 g acid
1 eq acid
x
= 0.0006571 equiv acid
100 g sample 64.05 g acid

Example 2: A 0.8676 gram sample of a pure organic acid required 38.69 mL (corrected) of 0.1042 N
NaOH for to reach the equivalence point. Calculate the equivalent weight of the acid,
and report with a relative error of 1 part per 1000. Assume a purity of 100% or 1.

Equiv Wt = 0.8676g acid x

1 equiv NaOH

1 equiv acid
Equiv Wt = 215.2 g/equiv (ppth precision)

Potentiometric Titrations

1L
0.1042equiv NaOH

Revised Spring 2005 NF

1
0.03869L

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Chemistry 135

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Chem 135

Potentiometric Titration of a Weak Acid

DATA REPORT SHEET

Name ________________________
Unknown Identification ________

Normality of NaOH _________

Approximate Equivalent Weight Data (Indicator Titration)

Sample Mass =

VNaOH =

Equiv. Weight =

Potentiometric Titration Data. Enter your data in to the appropriate spreadsheet in the lab. Show
Sample Calculations on the back of this page.
Trial 1

Trial 2

Average

Sample Mass (g)

VNaOH, 1st Equiv. pt.
VNaOH, 2nd Equiv pt.
Equiv. Wt.
Molar Mass
pKa1
pKa2
Identity of
Unknown acid

Show sample calculations for Equiv. Wt and Molar Mass on the back.

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Chemistry 135

Clark College

Sample calculations for Equiv. Wt. and Molar Mass

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Chemistry 135

Chem 135

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Potentiometric Titration of a Weak Acid

PRELAB

Name ________________________
You may use this experiment handout, your textbook or any other resources you can find to answer
these questions.
1. Distinguish between the terms endpoint and equivalence point.

2. Draw the correct Lewis structures for phosphoric acid and phosphorus acid and thoroughly explain
why one of these is a triprotic acid and the other is diprotic.

3. Write chemical reactions which represent

a. Ka for benzoic acid.

b. Kb for aniline.

- over -

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4. A 0.0450 M solution of benzoic acid has a pH of 2.78. Determine pKa for this acid.

pKa =

5. A 0.535 M solution of an unknown acid HA is 65% dissociated. Determine the pKa.

pKa =

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