In this lab, you will determine the percent
purity of two commercially available aspiring
tablets using an acid-base titration. In general,
an acid and a base react to produce a salt and
water by transferring a proton
(H+ ): HA (aq) + NaOH (aq) H2O (l) + NaA
(aq) (1)
acid base salt
The active ingredient in aspirin, and the
chemical for which aspirin is the common name,
is acetylsalicylic acid. To determine the amount
of aspirin (acetylsalicylic acid) in a sample, the
precise volume and concentration of the NaOH,
and the overall reaction, must be known. The
NaOH serves as a secondary standard, because
its concentration can change over time. To find
the precise concentration of the NaOH, it must
be titrated against a primary standard, an acid
that dissolves completely in water, has a high
molar mass, that remains pure upon standing,
and is not hygroscopic (tending to attract water
from the air). Because sodium hydroxide is
hygroscopic, it draws water from its
surroundings. This mean one cannot simply
weigh out a sample of sodium hydroxide,
dissolve it in water, and determine the number
of moles of sodium hydroxide present using the
mass recorded, since any sample of sodium
hydroxide is likely to be a mixture of sodium
hydroxide and water. Thus, the most common
way to determine the concentration of any
sodium hydroxide solution is by titration.
Determining the precise concentration of NaOH
using a primary standard is called
standardization. You will first standardize your
NaOH solution, and then use it to analyze
aspirin tablets for their aspirin content and
purity. An aspirin tablet may also include
inactive ingredients that help produce a
consistent product for consumers. Think of the
purpose these ingredients serve when
considering whether your percent purity is
reasonable for a commercial aspirin tablet.
Aspirin, or acetylsalicylic acid (ASA), is
commonly used as a pain reliever for minor
aches and pains and to reduce fever. It is also
an anti-inflammatory drug and can be used as a
blood thinner. People with a high risk of blood
clots, stroke, and heart attack can use aspirin
long-term in low doses. Aspirin contains
salicylate, which derives from willow bark. Its
use was first recorded around 400 BCE, in the
time of Hippocrates, when people chewed
willow bark to relieve inflammation and fever. It
is often given to patients immediately after a
heart attack to prevent further clot formation
and cardiac tissue death.
Aspirin or acetyl salicylic acid is one of the most
extensively-used nonprescription drug in the
world. It possesses analgesic, antipyretic and
antiinflammatory properties. Due to its
antiplatelet effect, aspirin can also be used to
prevent heart attacks, strokes and blood clots.
The amount of acetylsalicylic acid (C9H8O4)
present in a commercial aspirin tablet can be
obtained using a pH meter with a glass
electrode. In a potentiometric titration, the
volume of NaOH solution can be plotted versus
the potential of the cell (Ecell). Alternatively,
Ecell can be replaced with pH since Ecell and pH
is related. At room temperature, Ecell is equal
to 0.05916pH. The equivalence point of the
curve can be determined by locating the
inflection point. In addition, a first derivative
plot can also be constructed by plotting the
average of the adjacent volumes of titrant
against ∆pH/∆V. A second derivative plot can
also be used to aid in the determination of
endpoint. This is accomplished by plotting the
average of the adjacent volumes from the first
derivative table against ∆(∆pH/∆V). Below are
the endpoints of each titration curve.
Many Acid-Base titrations are difficult to
accomplish using a visual indicator for one of
several reasons. Perhaps the analyst is color-
blind to a particular indicator color change;
there may not be a suitable color change
available for a particular type of titration or the
solutions themselves may be colored, opaque
or turbid. It may be desired to automate a
series of replicate determinations. In such
situations, potentiometric titration, using a
glass hydronium ion selective electrode, a
suitable reference electrode and a sensitive
potentiometer (a pH meter) may be
advantageous
Potentiometric titration is a technique similar to
direct titration of a redox reaction. It is a useful
means of characterizing an acid. No indicator is
used; instead the potential is measured across
the analyte, typically an electrolyte solution.
The purpose of the experiment is to introduce
the student to the use of electrochemical
instrumentation in analytical chemistry,
specifically, potentiometric end-point detection
using derivative techniques.
Any acid-base titration may be conducted
potentiometrically. Two electrodes, after
calibration [to relate potential in millivolts (mV)
to a pH value] are immersed in a solution of the
analyte. One is an indicator electrode, selective
for H3O+ and the other a stable reference
electrode. The potential difference, which after
calibration is pH, is measured after the
successive addition of known increments of acid
or base titrant.
When a potentiometric titration is being
performed, interest is focused upon changes in
the emf of an electrolytic cell as a titrant of
known concentration is added to a solution of
unknown. The method can be applied to all
titrimetric reactions provided that the
concentration of at least one of the substances
involved can be followed by means of a suitable
indicator electrode. The critical problem in a
titration is to recognize the point at which the
quantities of reacting species are present in
equivalent amounts. The titration curve can be
followed point by point, plotting as ordinant,
successive values of the cell emf (pH) vs the
corresponding volume of titrant added. A
typical titration curve is presented in Figure 2.
Figure 3 represent another method for
determining the equivalence point from the
titration curve data. Table I, in Appendix I,
presents typical data obtained from a
potentiometric titration.
In this part of the experiment you will use a pH
meter to determine the active ingredient in an
aspirin tablet. The aspirin tablet will be
dissolved directly in an aqueous-ethanol
solution and titrated with previously
standardized NaOH. The change in pH will be
monitored with the pH meter throughout the
titration. (See Appendix I). The equivalence
point volume in the titration will be determined
graphically from the titration curve and by the
first derivative methods (see Appendix II). From
these results the concentration of acetylsalicylic
acid in the tablet will be determined.

A. Standardization of Dilute NaOH

1. Using a clean weighing paper, weigh 0.200 to

0.250 g dried KHP and transfer to a 250-mL
Erlenmeyer flask without spilling. Record the
exact mass of KHP.

2. Add 50 mL deionized water and 2 drops of

phenolphthalein indicator.

3. Rinse the burette twice with deionized water

and twice with 5 mL dilute NaOH solution.
Remove the air bubbles.

4. Titrate the KHP solution with the NaOH

solution (about 0.125 M) until the appearance
of a faint pink color that persists for 30 seconds.
Record the initial and final volume of NaOH and
calculate the exact concentration of NaOH.

5. Do a second trial. If the results of the first

and second trial are not close, do another trial.
B. Potentiometric Titration of Aspirin Tablet
1. Weigh one aspirin tablet and transfer in a
250-mL Erlenmeyer flask.
2. Add 30 mL of 95% ethanol.
3. Stand for 5 minutes and break the tablets
into fine particles using a glass rod.
4. Shake the mixture carefully for 1 minute to
dissolve the carboxylic acid.
15. Add the NaOH in 1 mL increments until pH is
constant for 5 additions. This denotes a titration
curve which has an almost flat line at the top.
Record the pH every 1 mL increment.
16. Plot the volume of NaOH versus pH and
locate the equivalence point.
17. Construct a first and second derivative plot
to facilitate in determining the equivalence
point.

5. Calibrate the pH meter using pH 4.00 and 18. Repeat numbers 1 to 17 only if the shape of
7.00 standard buffer solutions. the curve does not agree with what is expected.

6. Wash the glass electrode of the pH meter
with deionized water and gently wipe the
electrode with a paper towel.
7. Dip the glass electrode in the Erlenmeyer
flask containing the aspirin sample. Tilt the flask
so that a considerable part of the glass
electrode is in contact with the solution.
8. Record the initial volume and pH.
The objectives of this experiment are the
following:
1. To use a pH meter in constructing a normal
titration curve
2. To locate the equivalence point of a titration
curve using the normal plot, first derivative plot,
and second derivative plot
3. To calculate the percentage of acetylsalicylic
acid present in the aspirin tablet

9. Add 1 mL of the NaOH solution. Shake the

flask.

10. Rinse the glass electrode with deionized

water and dry using a paper towel. Record the Trial 1 Trial 2
Mass of KHP (g) 0.2113 0.2117
pH. The pH electrode must be immersed in
clean deionized water when it is not used.
Initial volume 0 9.1
11. Repeat numbers 9 and 10 until pH is equal of NaOH (mL)
to 4. Final Volume of 8.4 17.5
NaOH (mL)
12. Add 0.2 mL of the NaOH solution and shake Volume of 8.3 8.3
the flask. NaOH used
(mL)
13. Rinse the glass electrode again with Concentration 0.1247 0.129
deionized water and dry using a paper towel. of dilute NaOH
(M)
Record the pH.

14. Repeat numbers 12 and 13 until pH is equal

Status
to 13.
Normal Curve OK
First Derivative Curve OK
Second Derivative OK
Curve

Brand name of Aspirin

Tablet
Volume of NaOH
solution to reach
endpoint
Moles of NaOH
Moles of
Acetylsalicylic acid
Mass of Acetylsalicylic
acid
Mass of Aspirin Tablet
% of Acetylsalicylic
acid