CH229 General Chemistry Laboratory Dr.

Deborah Exton

VOLUMETRIC ANALYSIS OF ASPIRIN 1. Purpose In this laboratory experiment, you will assess the purity of a sample of aspirin and become acquainted with the concept of titration analysis. 2. Pre-lab Reading Volumetric Analysis (accompanying handout) 3. Background The aspirin which you previously synthesized is probably not pure, despite your best efforts. The most likely impurities are acids - either salicylic acid (unreacted starting material) or acetic acid. Even commercially prepared aspirin tablets are not 100 percent acetylsalicylic acid. Most aspirin tablets contain a small amount of binder which helps prevent the tablets from crumbling. The binder is chemically inert and was intentionally added by the manufacturer, but its presence means that aspirin tablets do not have 100 percent purity. Moreover, moisture can hydrolyze acetylsalicylic acid. Thus, aspirin which is not kept dry can decompose. Acetic acid is the hydrolysis product formed by the reaction of water with acetylsalicylic acid:

You may have noticed the smell of vinegar (acetic acid) when opening an old bottle of aspirin, or a bottle which has not been properly sealed. In this experiment you will determine the purity of the aspirin which you previously synthesized. (If you missed the Aspirin Synthesis laboratory or failed to synthesize enough aspirin for analysis, you will be given a sample of acetylsalicylic acid.) More specifically, you will determine the percentage of acetylsalicylic acid in your aspirin sample by means of a titrimetric analysis. In this procedure, you will incorporate a process known as a back titration. In a normal titration, an experimenter is able to determine the amount of analyte present in a solution by carefully adding incremental volumes of a standard solution until reaction between analyte and titrant is judged to be complete. (If you have not yet read “Volumetric Analysis: Titration” you should do so now before reading any further.) Occasionally, it is convenient or necessary to add an excess of the titrant and then titrate the excess with another reagent. This process is called back titration. In this technique, a measured amount of the reagent, which would normally be the titrant, is added to the analyte sample so there is a slight excess of reagent present. After this reagent reacts completely with the analyte, the amount of excess (unreacted) reagent is determined by titration with another standard solution.

excess moles back-titrated Once this quantity has been determined. from such a titration.CH229 Volumetric Analysis of Aspirin The amount of reagent which reacted with the analyte can be found by determining the difference between the amount of reagent added and the amount in excess: moles reagent reacted (with analyte) = total moles added . one could calculate the total number of moles of acid present in the sample by measureing the volume of standardized NaOH required to reach the end point. if acid impurities are present. If the stoichiometric ratios between acid and base are 1:1 (as in this experiment). of esters. The excess base that is not consumed in the hydrolysis will be determined by a back-titration with standard HCl. It will react with additional base reasonably rapidly at elevated temperatures : This reaction represents what is termed a base-promoted hydrolysis. From your data. Thus. only the acetylsalicylate ion is an ester. or saponification. the total number of moles of acid may be calculated by: moles acid = moles base = (liters base) x (molarity base) The titration of an impure sample of aspirin will yield the conjugate bases acetate ion.5130-g sample of aspirin prepared by a student required 27.1000 M NaOH was . titration of the aspirin will neutralize not only the acetylsalicylic acid (previous equation) but the acid impurities as well. At room temperature. you will add a known excess amount of base to cause the saponification to occur. salicylate ion. After you have neutralizd all acidic material in the aspirin by titration with base.78 mL of 0. and acetylsalicylate ion. stoichiometric considerations will allow you to find the moles of analyte initially present. acetylsalicylic acid can be neutralized with base: If acetylsalicylic acid were the only acid present in your sample. The following example may help you understand this calculation: Example: A 0. you could determine the purity of the aspirin by a simple titration of your sample with sodium hydroxide. you will be able to calculate the grams of acetylsalicylic acid in your aspirin sample.1000 M NaOH for neutralization. An additional 42.98 mL of 0. Of these. However. The reaction is the reverse of the esterification process which you employed while synthesizing aspirin.

just check your final mass from last week’s synthesis procedure. Once the burets have been filled.509 x 10-3 = 2. we must determine the quantity of base required for hydrolysis of the ester.5 g recrystallized aspirin from the aspirin synthesis experiment.98 mL of base was used to neutralize all acidic material present in the sample. The total number of moles of base added for the hydrolysis reaction is moles NaOH = 0. (No open flames in the presence of ethanol!) .CH229 Volumetric Analysis of Aspirin added.) If not. be sure to record the concentrations of the acid and base in your laboratory notebook Verify that you have at least 1. Fill one buret with acid (HCl) and one with base (NaOH). (It is not necessary to weigh anything at this point . Obtain 75 mL ethyl alcohol (EtOH) in a clean and dry 125mL Erlenmeyer flask.01429 L = 1. Prepare a hot water bath by bringing approximately 350 mL water to a boil in a 600 mL beaker placed on a hot plate. Check out two 25-mL burets from the stockroom window and prepare them for use as described in “Volumetric Analysis”. How many grams of acetylsalicylic acid are in the sample? What is the percentage of acetylsalicylic acid (or the purity)? Solution: First recognize that the 27.769 x 10-3 mol The number of grams acetylsalicylic acid is found using the molecular weight of acetylsalicylic acid: grams = 2.278 x 10 -3 mol The number of moles of HCl used in the titration corresponds to the excess NaOH.04278 L x 0. Preparation: Prepare an ice bath.25 % 4.1056 M HCl. After the reaction mixture cooled.769 x 10-3 mol x 180.4989 g/0. the excess base was back-titrated with 14.4989 g acetylsalicylic acid Thus. Since we are only interested in the quantity of acetylsalicylic acid.509 x 10-3 mol The difference between the number of moles of base added for the hydrolyses and those which were not consumed equals the number of moles of base that brought about hydrolysis. % purity = 0. or the number of moles not consumed in the hydrolysis reaction: mol HCl = mol excess NaOH = 0. Cool the EtOH in the ice bath.278 x 10-3 . and the sample was heated to hydrolyze the acetylsalicylic acid. Procedure 1.1056 M x 0.29 mL of 0. obtain a sample of acetylsalicylic acid from the stockroom window.1.2 g/mol = 0.5130 g x 100 = 97. This is exactly equal to the number of moles of acetylsalicylate ion which is equal to the number of moles of acetylsalicylic acid: 4.1000 M = 4.

that is. 3. Record the final volume. 6. Saponification of Aspirin: To saponify (or hydrolyze) the aspirin. Swirl to dissolve.2 M) NaOH. 7/e. 1997. Remember that the buret reading can be estimated to + 0. Prentice-Hall. The volume of base added is the difference between these two readings. keeping careful record of the quanitity used.025 M) HCl solution until the pink color disappears. Calculations Calculate the grams of acetylsalicylic acid in each of your aspirin samples and the percentage purity of the aspirin samples (see example). you will add additional NaOH from the buret.) Place in a clean. 4. Record the initial volume. The quantity of base to be used is about 8. (Record mass to the nearest 0. 5.01 mL. (This indicates the phenolphthalein end point.) The volume of NaOH used for this titration corresponds to that which is requied to neutralize all acids present in your sample. impurities as well as the acetylsalicylic acid. Record the final volume. Backtitrate the excess NaOH in the Erlenmeyer flask with the standard (≈0. towel-dried 250-mL Erlenmeyer flask.CH229 Volumetric Analysis of Aspirin 2. Discussion / Conclusion Report the mean percentage purity in your aspirin sample. . 5. Repeat steps 2 . swirling occasionally. The first 10 mL can be added quickly. being sure to record starting and finishing volumes. Add 25 mL chilled EtOH. Sample preparation: Weigh about 0. Nelson and Kenneth C. Chemistry: The Central Science. (Use this waiting period to prep and titrate trials 2 and 3. Kemp. followed by slow additions of NaOH until a faint pink color persists.0001 g.5 two more times. It will probably be necessary to add more NaOH to your buret. Heat the basic solution in the Erlenmeyer flask in the water bath for 15 min. References John H. Back-titration of excess base: Record the initial volume of HCl in the second buret. Laboratory Experiments.) If the pink color should disappear after this time.00 mL) on the buret. Add 3 drops phenophthalein. add 2 more drops of indicator.5 mL more than the volume of base used in the previous titration. What are the sources of impurity in aspirin? Comment on why and how titrimetric analysis is used and why it was necessary to perform a back titration to determine the percentage purity. After the heating period. What are the major sources of error when performing a titration? 7. cool the solution on an ice bath. add the base to the Erlenmeyer flask. Acid Titration: Rapidly titrate with standard (≈0.5 g recrystallized aspirin. being careful to stop before reaching the lowest graduation mark (25. 6. Calculate the mean percentage purity and the standard deviation.

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