Determination of Aspirin using Back Titration

This experiment is designed to illustrate techniques used in a typical indirect or back titration. You will
use the NaOH you standardized last week to back titrate an aspirin solution and determine the concentration
of aspirin in a typical analgesic tablet. You will be graded on your accuracy.
Required Reading
D.C. Harris, Quantitative Chemical Analysis (6th ed., W. H. Freeman, NY, 2003) p. 130, 15.
PreLab Quiz Topics

In addition to being able to explain the purpose of your experiment, the general procedure steps, the
use of all chemicals in this experiment and any specific hazards, your prelab quiz may include explanations of
any of the following terms: back titration, percent composition, the transition range of an indicator. You
should be able to discuss the difference between a direct and a back titration, and know all relevant chemical
reactions for this experiment. Describe the chemical and/or physical processes that will occur when you reach
the endpoint of your titration. Explain clearly why we use a back titration for this particular analysis; i.e., why
can’t we just use the endpoint found from the initial NaOH titration?
Many reactions are slow or present unfavorable equilibria for direct titration. Aspirin is a weak acid that
also undergoes slow hydrolysis; i.e., each aspirin molecule reacts with two hydroxide ions. To overcome this
problem, a known excess amount of base is added to the sample solution and an HCl titration is carried out
to determine the amount of unreacted base. This is subtracted from the initial amount of base to find the
amount of base that actually reacted with the aspirin and hence the quantity of aspirin in the analyte.
COOH COO–

+ OH– + H2O
O O
O (fast) O

CH3 CH3

COO– COO–

+ OH– + CH 3COO–
O
O (slow) OH

CH3
Chemicals and their Location

Balance Room In the Hood

Aspirin tablets (Do not bring your own sample) Hydrochloric acid, conc., 37 wt %
Above/on lab bench Your Drawer
Ethanol Sodium hydroxide, standardized soln
Phenolphthalein, indicator soln
CH455/6 Analytical Chemistry Manual Page (5) Fall 2004
Equipment and its Location

Stockroom In the Hood

Two Burettes Water bath
Mortar & Pestle
Above/on lab bench
Weighing bottle
Boiling chips
Safety Issues and Chemical Hazard Information
Physical Hazards Health Hazards
Aspirin none toxic, irritant, sensitizer
Ethanol flammable irritant
Hydrochloric acid water-reactive, corrosive toxic
Phenolphthalein none irritant
Sodium hydroxide water-reactive, corrosive toxic, irritant
Concentrated hydrochloric acid is highly corrosive. Be careful. Ethanol is flammable — keep away from heat,
sparks, and open flames.
Procedure

There are various components to this procedure. If there is a delay at one step (e.g., all the water baths are in
use), perform another section of this procedure while you are waiting. Depending on the size of your lab
section, your TA may suggest that half of the class work straight through the procedure, and the other half
start at Step 4, returning to Steps 1 – 3 while waiting at Step 8, to reduce congestion in the lab.
Preparation of Approximate Acid Solution (~ 0.1M HCl)

1. Put ~100 mL distilled water into your other large bottle. Before performing this experiment (i.e., in
your prelab), calculate the volume of concentrated HCl you will need to prepare 250 mL of 0.1M HCl.
(Concentrated reagent grade HCl has a density of 1.188 g mL–1 and is 37 wt %. Check your answer with
your TA before making this solution.) Measure approximately this volume of concentrated HCl using a
graduated cylinder. Gradually add the acid to the water in your bottle, mixing well (remember, always add
acid to water, not water to acid.). Add more distilled water, mixing thoroughly with each addition, until the
total solution volume is ~ 250 mL. You do not have to measure the quantities accurately because you are going to
standardize this solution in the next steps to determine its actual concentration.

Comparison of HCl to your standardized NaOH

2. Clean, rinse, and fill your burette with your ~0.1 M HCl solution. To each of three clean, labeled
Erlenmeyer flasks, add 50 mL distilled water and three drops of phenolphthalein indicator. Use your HCl
burette to add approximately 35, 40 and 45 mL of acid to flasks #1, #2 and #3, respectively, recording
exactly how much acid is added to each flask within 0.01 mL. Swirl gently to mix.

CH455/6 Analytical Chemistry Manual Page (6) Fall 2004

3. Clean, rinse, and fill your second burette with the ~0.1 M NaOH solution that you standardized last
week. Titrate the three HCl flasks with the NaOH to the phenolphthalein endpoint.
Sample Preparation

4. Accurately record the weight of a group of three aspirin tablets so that you can determine an average
tablet weight. Use a mortar and pestle to crush enough tablets to produce ~ 1 g tablet powder.
5. Using a clean dry weighing bottle, weigh accurately, by difference, triplicate ~0.3 g samples of tablet,
into labeled 250 mL Erlenmeyer flasks. To each flask, add 20 mL of ethanol (measure by graduated
cylinder) and three drops of phenolphthalein indicator. Swirl gently to dissolve. (Aspirin is not very soluble in
water — the ethanol helps the aspirin dissolve. Note that an aspirin tablet contains other compounds in addition to aspirin. Some of
these are not very soluble. Your solution will be cloudy due to insoluble components of the tablet.)

Aspirin Titration with base

6. (If your TA has told you to perform this step before Steps 1 – 3, clean, rinse, and fill a burette with the ~0.1 M NaOH solution that you
standardized last week, before continuing.) Titrate the first aspirin sample with NaOH to the first permanent
cloudy pink colour.
7. The aspirin/NaOH acid-base reaction consumes one mole of hydroxide per mole of aspirin. The slow
aspirin/NaOH hydrolysis reaction also consumes one mole of hydroxide per mole of aspirin, and so for a
complete titration we will need to use a total of twice the amount of NaOH that you have
already used, plus we will add some excess NaOH to ensure that we really have reacted with all
of the aspirin in your sample (adding excess reactant drives the equilibrium towards products — Le Chatelier’s principle).
Calculate how much extra NaOH you will need to add, following this reasoning: The volume of base to
add for the hydrolysis reaction is equal to the volume of base you have already used to titrate to the
acid-base endpoint in Step 6 plus an additional 10 mL of excess base. (For example: if you used 26 mL of base in
the previous step, the volume of base you would add now would be 26 + 10 = 36 mL. Thus, you would have added a total of 26 + 26 +
10 = 62 mL of base.)

Use your burette (not a graduated cylinder) to add the appropriate amount of extra NaOH to each of
your three sample flasks. (Do not to allow the level of base in the burette to fall below the graduated
markings; if necessary, record an intermediate volume and refill the burette to continue with your
additions.) Record the total volume of NaOH added to each flask within 0.02 mL.
Heating the reaction to completion

8. Add two or three boiling chips to each flask and heat in a water bath to speed up the hydrolysis
reaction. Avoid boiling, because the sample may decompose. While heating, swirl the flasks occasionally.
After 15 minutes, remove samples from the water bath and cool for 5 minutes.

CH455/6 Analytical Chemistry Manual Page (7) Fall 2004

9. If the solution is colourless, add a few more drops of phenolphthalein. If it remains colourless, add
10 mL more of the base and reheat. (Don't forget to add this additional volume of base to the
previously recorded total volume.)
Back titration with acid

10. The only base remaining in each flask will be excess base that has not reacted with the aspirin. Using
your burette with your ~0.1 M HCl solution, titrate the excess base in each flask with HCl until the
pink colour just disappears. The endpoint is best described as “cloudy white”.
Preparation for your next experiment

11. CH456 Gravimetry Prep (Required): You need to perform the first section of the Gravimetry
Procedure, to start preparing for that experiment. If you do not finish these steps today, you will need
to come into the lab before your next lab period and finish them. You may come into the lab during any TA office
hours, during any CH455 lab time (see the front of this manual for the timetable) as long as you do not interrupt the introductory TA
lecture, or at another time with the agreement of the Stockroom who will have to let you into the lab. Realize that CH455 TAs will not be
able to help you with this procedure. Make sure you understand what you are doing. In an emergency, call the stockroom, Lab
Director, or Head TA (numbers by the phone).

Shutdown procedures

IMPORTANT NOTE: Your NaOH solution must be saved upon completion of the experiment; you
will use it again in future experiments. Save your HCl solution in case you find that something is wrong
with your results from today's experiment.
12. Put all waste in the appropriate waste containers. Clean and dry all glassware. Clear up your work area.
Return items to the Stockroom.
13. Make sure you have recorded information on the sample you studied, including the manufacturer and
brand name and the amount of aspirin reportedly in each tablet from the aspirin packet label, which can
be found posted on the Stockroom door.
Waste Disposal
Waste Chemicals Waste Container Location
Excess HCl, dilute or concentrated Acid Waste cabinet
Excess NaOH, dilute or concentrated Base Waste cabinet
Excess ethanol Ethanol Waste cabinet
Aspirin solutions after titration Neutral Waste cabinet
Aspirin solid waste Solid waste Balance room

CH455/6 Analytical Chemistry Manual Page (8) Fall 2004

Data Analysis

1. Using your NaOH molarity from last week, determine the molarity of your HCl solution from the
volumes of NaOH needed to titrate your flasks of HCl, remembering that you designed it to be
~0.1 M.
2. Using the total volume of NaOH added to each, and the molarity of your NaOH standard solution,
calculate the total number of moles of NaOH added to each sample.
3. Using the volume of HCl needed to back-titrate each aspirin flask, calculate the number of moles of
excess NaOH left in each flask after the reaction with aspirin.
4. From the total number of moles of NaOH added to the sample, and the number of moles of excess
NaOH left after the reaction was complete, calculate the number of moles of base that reacted with
aspirin.
5. Hence determine the number of moles of aspirin in each of your samples. (Don’t forget the factor of two.)
6. Calculate the mass of aspirin in each of your samples. Using the mass of tablet you weighed into each
sample, calculate the weight percent of aspirin in the tablets.
7. From the mass of the four tablets you weighed, calculate the average mass of a tablet. Use this value,
and the weight percent of aspirin you have just calculated, to calculate the mass of aspirin in one of the
original tablets.
Discussion Questions

1. Why did you use your burette and not a graduated cylinder to add the excess NaOH?
2. What would be the consequence of competing equilibria, such as from other ingredients in the tablet,
on your results? What if there were several pain relievers in the same tablet? How could the error from
these interferences be minimized?
3. Ethanol was used in the solutions to help dissolve the acetylsalicylic acid. Ethanol is slightly acidic, and
will react with NaOH. Describe a blank correction experiment; i.e., what experiment you might do to
determine how much NaOH reacts with the ethanol in your solution. Once you have determined this,
how would you use the results of a blank correction experiment in the data analysis?
Conclusions

As part of your conclusions for this experiment, compare the aspirin weight per tablet that you
determined to the weight per tablet claimed by the manufacturer on the label.

CH455/6 Analytical Chemistry Manual Page (9) Fall 2004

 Fall 2004 CH455/6 Lab Report Title Page
Student Use

Name: Class TA:

Lab Partners (if any): Makeup TA (if any):

Class TA Use
Prelab Quiz Score (out of 3): Lab finished:

(TA signature required before student leaves lab)

Due 9 / 9:30 am; 2 pm;
Experiment Date: Report Due Date: Time: 5 pm; 7 pm
Report Received

Date: Time: Initials:

Grading

Report Grade (/15): Late penalty (/15): Report inc. penalty (/15):

Regrade (/13.5): Final Grade (/15) (includes penalty & regrade):

Determination of Aspirin using Back titration

Your report should follow the Lab Report format listed earlier in this manual. Show samples of all calculations,
identify any unknowns, report the average with appropriate significant figures, standard deviation, %RSD and
90% confidence interval and answer the discussion questions. Don't forget to include your conclusion section.

90%
Average ± Std Dev %RSD Average ± confidence
interval

Your HCl concentration

± ±

Measured aspirin mass per

tablet ± ±

Manufacturer’s stated aspirin mass per tablet

Identify your aspirin sample

 Determination of Aspirin using Back titration
Report Grading Breakdown
Your Out of a
Score / possible

Pre-lab Quiz / 3
Calculations/Data Analysis / 3
Results/Accuracy / 3
Discussion & Conclusions / 3
Presentation/Impression / 3
Subtractions

TOTAL / 15