EXPERIMENT 4

DETERMINATION OF ASPIRIN BY INDIRECT TITRATION

OBJECTIVES
1. To evaluate the purity of an aspirin sample.
2. To develop the techniques for the proper dilution of a solution to a definite volume and the use
of a volumetric pipet.
3. To learn how to carry out calculations involving back-titration.

INTRODUCTION

Direct titration methods are those in which the substance to be measured (or a constituent
chemically equivalent to it) is directly titrated to an end point by a standard solution. Indirect methods
do not involve measuring the substance itself but a quantity of a reagent is added which is known to
be in excess with respect to a specific reaction, and the unused excess is determined by titration.
Aspirin is a compound derived from two acids, acetic acid and salicylic acid. It can be
hydrolyzed by alkali and the two components neutralized simultaneously.
The weak acid salts of acetic acid and salicylic acid would give a pH at the equivalence point
that lies within the range of phenol red indicator (pH 6.8-8.4), although phenolphthalein may be used.
The procedure given is an indirect one since it degrades the aspirin. More sophisticated methods such
as HPLC or quantitative TLC can readily analyze intact aspirin. It is quite important to distinguish
between intact aspirin and its degraded form in assessing the potency of the drug.

MATERIALS

250mL Erlenmeyer Flask standard 0.1N NaOH solution (from Expt. 3)

250mL Volumetric Flask concentrated HCl solution
100mL Volumetric Flask phenol red and phenolphthalein indicator
20.00mL pipette clean reagent bottle
50.00mL pipette ordinary pan/digital balance
50.00mL acid burette analytical balance
50.00mL base burette hot plate
25.00 or 50.00mL graduated cylinder aspirin sample (tablet or sample from Chem 31.1)

PROCEDURE

A. Preparation and Standardization of 0.1 N HCl Solution

Prepare 250mL 0.1N HCl solution using a volumetric flask. Let instructor check your
calculations before proceeding with the preparation. Store prepared solution in a clean and properly
labeled reagent bottle.
Pipet out 20.00mL of the prepared acid solution into a 250mL Erlenmeyer flask. Dilute with
25mL water and add 2-3 drops phenolphthalein. Titrate with the standard NaOH solution until a
permanent pink color is achieved. Perform 3 trials.

B. Analysis of Aspirin
Weigh out to the nearest tenth of a milligram 0.1g of previously ground aspirin sample into a
250mL Erlenmeyer flask. Add 20.00mL of standard 0.1N NaOH solution. Simmer gently for 10-15
minutes to hydrolyze the aspirin sample.
Cool the reaction mixture and transfer into a 250mL volumetric flask. Wash the flask several
times with 10mL portions of distilled water and pour into the volumetric flask. Dilute the reaction
mixture and washings to the mark with distilled water, then mix well by several inversions of the
stoppered flask.
Titrate 50.00mL aliquot portions of the stock solution of hydrolyzed aspirin with the
standardized HCl solution using 2-3 drops indicator. Make 3 trials.

POST-LAB QUESTIONS
1. What would be the effect of a more dilute solution of NaOH on the titration?
2. What volume of 1.0 N NaOH is used in the hydrolysis of four 250mg tablets of aspirin (90%
pure acetylsalycilic acid) if 10.00mL of 0.05 N HCl is consumed in the back titration?

RECOMMENDED REFERENCES
1. Blaedel, W.J. And V.W. Melonche, Elementary Quantitative Analysis: Theory and Practice. 2nd ed.
Harper and Row, New York, 1993.
2. Christian, G., Analytical Chemistry, 3rd ed. John Wiley and Sons, New York, 1980.
3. Laboratory Manual for Elementary Analytical Chemistry, UP Diliman, 2nd ed., 1994.

PRELABORATORY QUESTIONS
1. Provide the following information for acetylsalycilic acid (ASA):
a. Chemical Formula
b. Chemical Structure
c. Formula Mass
d. Number of acidic protons or H+ per particle
2. Give the balanced chemical equation pertinent to the reaction between ASA and NaOH.
3. Define back titration.
4. Give an example of a back titration problem and the pertinent calculations.