Analytical Chemistry

MALAYAN COLLEGES LAGUNA

Laboratory

CHE130L

EXPERIMENT NO. 4
POTENTIOMETRIC TITRATION

I. OBJECTIVES

Upon completion of the experiment, the student should be able to:

calibrate an electrometric pH meter;

use potentiometric measurements to determine the pH of an unknown;
determine the factors affecting pH of solutions; and
determine the ionization constant of a weak acid by potentiometric titration.

II. A. LABORATORY EQUIPMENT / INSTRUMENTS

Equipment/ Accessories Quantity

250-mL beaker 2
pH meter 1
Magnetic stirrer 2
Iron stand 1
Pipet 1
Rubber aspirator 1
Stirring rod 1
Iron stand 1
Iron clamp 1

B. CHEMICALS AND REAGANTS

Chemical/ Reagent
Standard NaOH solution
Distilled water in wash bottle
Standard buffer solutions (ph 4.0 and pH 7.0)
Unknown acid

III. DISCUSSION OF FUNDAMENTALS

Introduction

In the previous experiment, we are already concerned of the different concepts that underlies
about acid-base titrations. Acid-base titrations, by concept, is also called a neutralization reaction,
since it involves an acid and a base (that is regardless of strength, either one is weak or one is strong
or either weak or both strong and ad infinitum), and regularly have the products of salt and water.

Experiment 4: Potentiometric Titration Page | 1

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHE130L

EXPERIMENT NO. 4
POTENTIOMETRIC TITRATION

The completion of the reaction is reached when the number of moles of the acid is equal to the
moles of the base, or technically the equivalence point is reached. In this point, if the stoichiometric
ratios of the acid and base are equal, we can solve for the concentration of the unknown by using
the dilution equation, that is, M1 V1=M2 V2. For diprotic and triprotic acids and bases that are titrated
with a strong acid/base, however, have many equivalence points, depending on how protic it is(i.e. a
diprotic acid/base has two equivalence points, whereas a triprotic acid/base has three) since the
acid/base has to converted to its less acidic/basic form, or its intermediates. A good example would
be a diprotic acid titrated using a strong base (in this case, sodium hydroxide), or H 2 A. The reaction
would proceed, forming HA-, and ultimately forming the base, A2-. But in this titration, you cannot
determine its actual pH at a certain aliquot of the titrant, since what we are using in this type of
titration is an indicator, an organic compound added to the solution to see the equivalence point by
a change of color. In doing so, a pH meter is used to monitor the measurement of pH of the titration
process at hand. The pH meter measures the [H+] concentration of the solution, so if the titration
goes from base to acid, the pH must be computed as pH=14-pOH, where pOH is the initial reading of
pH. By using a pH meter in an acid-base titration to monitor the pH variations of the titration
process, we call this process a potentiometric titration, wherein it finds the equivalence point not
through an indicator, but through a graph that signifies the relationship between the recorded
amount of titrant used, and the measured pH of the system.

Discussion

Potentiometric titration as has been introduced

in the previous experiment also needs the slow
addition of a titrant to an analyte to determine the
endpoint. Potentiometric titration makes use of a
pH meter to monitor the pH of the resulting
solution upon addition of the titrant. A plot is then
made of the resulting pH against volume of added
titrant. In cases where the change in pH at the
equivalence point are too small to obtain a sharp Figure 1. Sample of titration curve
endpoint, the slope of the titration curve can be
plotted against the volume of added titrant and a sharp peak corresponding to the equivalence
point can be obtained The tip of the sharp peak, known as the inflection point, corresponds to a
value where the slope goes through a maximum (increasing to decreasing values).

Experiment 4: Potentiometric Titration Page | 2

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHE130L

EXPERIMENT NO. 4
POTENTIOMETRIC TITRATION

Aside from determining amounts of analytes,

titration data, especially the titration curve can help in
the determination of identities of unknown acids and
bases. Various portions of the curve show species that
are present during the course of the titration. The
equivalence point also known as the neutralization
point shows all analyte has been used up, and after
which, the titrant is in excess. For the titration of an
unknown weak acid, the pH at the midpoint (half-way
point), also termed as the point of 50% neutralization
point, gives the ionization constant of the acid.
Figure 2. 1st plot derivative of sample titration curve

Applications

The potentiometric titration method has many applications. These applications, however, seek
proper tests to satisfy the conditions for quantitative analysis, i.e. starting a test of a sample with
known concentration, etc. Potentiometry is mainly applied to acid-base, precipitation and redox
reactions. On acid-base reactions, its practical application would be on the field of knowing the pH
levels of the different manufactured food and many others, as well as common household items. For
precipitation reactions, the determination of how chlorinated the water sample is done by finding
the chloride ions in different water samples, and comparing them. The chloride ions are generally
insoluble to water, so by a precipitation reaction, it will do the trick. Lastly, for redox reactions,
potentiometry is used to determine the ferrous (Fe 2+) ions in certain medicinal tablets, as iron goes
on two states, one having a 2+ charge(ferrous) and one with a 3+ charge(ferric). By the redox
reaction and its counterpart potentiometric titration, we can successfully determine if the iron in
the tablet is ferrous or is ferric.

Experiment 4: Potentiometric Titration Page | 3

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHE130L

EXPERIMENT NO. 4
POTENTIOMETRIC TITRATION

IV. METHODOLOGY

The pH meter was calibrated The pHs of the standard buffers used
according to the instructions given. for calibration were recorded.

Figure 3. Calibration of the pH meter

After calibrating, the pH of the unknown

acid was recorded.

When the results stray far from the

expected, the probe was calibrated using
the two buffers.

The acid was titrated potentiometrically

with 0.50-mL aliquots until there was no
change in its pH.

Volume and pH were recorded with every

addition.

After every pH measurement, the probe

was washed with distilled water.
A graph showing the relationship between
the pH and titrant volume was made.

Figure 4. Potentiometric titration of unknown acid

Experiment 4: Potentiometric Titration Page | 4

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHE130L

EXPERIMENT NO. 4
POTENTIOMETRIC TITRATION

V. DESCRIPTION OF THE APPARATUS / SET UP

Figure 5. Potentiometric titration set-up Figure 6. pH meter device

A pH meter is an instrument that measures the hydrogen ion concentration of the solution it will
be used into. The experiment weve done uses a portable version, one that can run without plugging
in an electric socket since it runs on batteries. Beside the probe is a metal that detects the
temperature, which can be seen on the display screen. The probe, metal and the surrounding parts
are washed with distilled water as to remove the remaining traces of the last measured sample. The
pH meter has two modes, calibrate and measure. Before measuring any sample, it is a good practice
to always calibrate the probe with the green and red buffer solutions of 4.01 and 7.00 pH
measurements. This is to ensure the accuracy and precision of the results of the measuring to be
done.

VI. DATA SHEET

TITRANT VOLUME pH TITRANT VOLUME pH

6 1.94 22 7.52
6.5 1.99 22.5 7.64
7 2.26 23 7.71
7.5 2.34 23.5 7.86
8 2.4 24 7.99
8.5 2.52 24.5 8.13

Experiment 4: Potentiometric Titration Page | 5

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHE130L

EXPERIMENT NO. 4
POTENTIOMETRIC TITRATION

9 2.64 25 8.3
9.5 2.64 25.5 8.6
10 2.55 26 8.82
10.5 2.82 26.5 9.18
11 2.71 27 9.33
11.5 2.85 27.5 9.72
12 2.8 28 9.9
12.5 3.04 28.5 9.97
13 3.28 29 10.07
13.5 3.45 29.5 10.11
14 4.14 30 10.34
14.5 4.48 30.5 10.57
15 4.95 31 10.74
15.5 5.45 31.5 10.82
16 5.78 32 10.85
16.5 6.24 32.5 11.05
17 6.45 33 11.12
17.5 6.89 33.5 11.21
18 6.95 34 11.45
18.5 6.98 34.5 11.53
19 7.02 35 11.6
19.5 7.05 35.5 11.6
20 7.12 36 11.61
20.5 7.2 36.5 11.62
21 7.37 37 11.65
21.5 7.51 37.5 11.65

VII. SAMPLE COMPUTATIONS

( )

| |

( )

Probable identity of acid: Citric acid (7.4 x 10-3) or Phosphoric acid (7.5 x 10-3)

Experiment 4: Potentiometric Titration Page | 6

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHE130L

EXPERIMENT NO. 4
POTENTIOMETRIC TITRATION

VIII. RESULTS AND DISCUSSIONS

Titration is the controlled

neutralization of an acid and a
base. If we consider the titration
of a weak acid by a strong base,
we can analyze the situation
completely and determine all the
concentrations of the aqueous
species at any volume addition of
the titrant. From the figure, one
can notice that the titration of a
weak acid with a strong base is Figure 7. Titration curve of weak acid titrated by a strong base
different from that of a strong base to
a relatively strong acid titration, primarily in the beginning of the titration, or before the equivalence
point is reached. Moreover, the equivalence point itself is shifted upward in pH, making the
equivalence point arrive in the basic pH.

The experiment started with the calibration of the

pH meter. A pH meter is an instrument that measures the
hydrogen ion concentration of the solution it partakes unto,
and if this should be done, one must need to calibrate it first
to ensure accuracy for the proceeding myriad of
measurements to follow. There are various types of pH
meters, and the one in this experiment is the portable
version, one that can run without plugging it in since it runs
on batteries. By having two standardized buffer solutions of
different concentrations (one preferably neutral and the
other acidic/basic), the pH meter is calibrated accordingly by
the following steps:

1. Turn on meter and set MODE to CAL

2. Wash probe with distilled water.
Figure 8. Example of a portable pH meter. 3. Put the probe on one solution. When display
registers READY, press enter. Read until the desired
concentration is registered.
4. Rinse the probe with distilled water and slightly shake to dry.
5. Repeat 3 for the other solution. When finished, put MODE to MEAS (Measure).

Experiment 4: Potentiometric Titration Page | 7

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHE130L

EXPERIMENT NO. 4
POTENTIOMETRIC TITRATION

The titration process is started with the usage of the standardized NaOH solution from
Experiment 3(Acid-base titrations). The NaOH solution is used to fill the burette to the 0.00 mL
mark. By having a known volume of the unknown acid, the initial pH is measured by the pH meter.
This initial pH will be used for the computation of the ionization constant of the unknown acid. After
this, the potentiometric titration process will now commence. Potentiometric titration is mainly
used in this because it does not need an indicator to determine the equivalence point, but by
titrating in aliquots, not considering whether it will break through the equivalence point or not. By
using 1.50, 0.50 and 0.20 (from which our group only did the second aliquot) mL aliquots at different
containers, the acid is to be titrated with it, and measuring the pH for every aliquot that is added to
it. In doing this, one can observe that the change in pH is small, but there would be a sharp change
in pH upon the middle of the titration. This sharp change is characterized by the solutions tendency
to reach the equivalence point of the titration process. The titration is stopped when the pH of the
system is constant. This pH is referred to as the pH of the titrant, from which it will be already
constant since all of the unknown acid has been converted to its salt and water form by reacting
with NaOH. To understand what the values basically mean, the values are plotted as the pH on the
y-axis, and the volume of the titrant (cumulative) on the x-axis. This graph is now what we call as the
titration curve. By observation, the graph looks like an intestine shaped like an S. This type of
graph is what we call a sigmoidal curve, a logistic curve (or one that is related to exponential
functions). The end point will be found in this graph, as the location of the sudden change in pH will
be clear. Since this experiment will be under the preference that it assumes the acid is a
hypothetical monoprotic acid HA, and if was made to react to a strong base, then the resulting
graph would only have one equivalence point.

Experiment 4: Potentiometric Titration Page | 8

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHE130L

EXPERIMENT NO. 4
POTENTIOMETRIC TITRATION

14

12

10

8
pH

0
0 5 10 15 20 25 30 35 40
Volume of titrant (mL) Figure 9. pH vs. Volume of titrant

Based on the graph will be the determination of the ionization constant K a of the unknown acid.
This will come in two ways. First would be the calculation of the ionization constant using titration
data. By getting the volume of the titrant at the equivalence point, on the half-equivalence point,
and the pH value of 50% neutralization, we can compute for the pH of the system by using the
equation: and . After this, the other method would be the
calculation of the ionization constant based on initial pH. By having the assumed concentration of
the unknown acid to be equal to the concentration of the titrant and its initial pH, the pH will be
computed by the following equation: . By comparing both values to some known
acids ionization constants, the identity of the unknown acid will be clarified.

Experiment 4: Potentiometric Titration Page | 9

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHE130L

EXPERIMENT NO. 4
POTENTIOMETRIC TITRATION

IX. SUMMARY AND CONCLUSIONS

This experiment concluded the concepts involving potentiometric titration. By specifically using
a calibrated pH meter using buffer solutions of standardized concentrations, the pH of the solution
is constantly measured as to adding an exact amount of the titrant that is measured accordingly to
its equivalent aliquot. This is done until the pH of the system is constant and more or less basic
(since we are handling an analyte that is classified as an unknown acid, which is being titrated by a
strong base). After plotting the values of pH against volume of the titrant, we form a graph that will
determine the equivalence point of the reaction. By using the values of the volume @50%
neutralization, the equivalence point and the initial value of the pH, we can co mpute for the
ionization constant of the unknown acid, as well as identifying the molecular formula of the acid and
identifying the acid itself. Errors should be avoided especially on the consistency of putting an exact
amount of the titrant, as this will in small amounts, will collectively deter the position as to where
the equivalence point should be, therefore getting an incorrect ionization constant in the following
changes, and it further deteriorates the consistency of the experiment itself.

X. POST LAB QUESTIONS

Which of the two methods of calculation can give the more accurate value for the ionization
constant? Explain your reason. Cite possible errors incurred.

Answer: The more accurate method of knowing the ionization constant is the one using the
initial pH, by the equation: . This is more accurate than the other one, since the
50% neutralization volume in our graph is not clearly determined at the first sight of it, therefore
it will leave us to do interpolation, which might not be needed to do for there is a given formula
for getting the ionization constant, and there wouldnt be any need to do that. Moreover, the
initial pH is among the most accurate of all the pH measurements, since it is the first to be
measured by the freshly calibrated pH meter, and in effect, will have the most accurate
computed ionization constant, Ka .

Experiment 4: Potentiometric Titration Page | 10

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHE130L

EXPERIMENT NO. 4
POTENTIOMETRIC TITRATION

XI. REFERENCES

Christian, Gary D. 2004. Analytical chemistry (6th ed.). John Wiley and Sons Inc.

Hage, David S. and James D. Carr. 2011. Analytical chemistry and quantitative analysis. New
Jersey: Pearson Prentice Hall.

Skoog, Douglas et. al. 2004. Fundamentals of Analytical Chemistry (8 th ed.). Singapore:
Thomson Learning.

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