Aspirin 24 Feb 2009 Section 2307 Chemistry 2107 TA: Khushabu Thakur Peter Bolgert

Purpose The purpose of the experiment was to synthesize aspirin (acetylsalicylic acid) and to analyze the products molar mass, melting point, and purity.

Procedure Synthesis of Aspirin First, 2.171 grams of salicylic acid were weighed out and combined with 4 mL of in a test tube. 5 drops of sulfuric acid were added, and then the mixture was put in a hot water bath and stirred until all of the salicylic acid dissolved. After about 20 minutes, the test tube was removed was the hot water bath and the mixture was dumped into ice water and mixed thoroughly. The sample was stirred vigorously as it cooled to room temperature so that a precipitate would form. When the mixture reached room temperature it was passed through the vacuum filtration apparatus so that the water would be removed. The beaker that held the mixture was rinsed out several times to obtain as much of the product as possible. After drying for a few minutes, the product was removed from the filter.

Standardization of NaOH Solution The NaOH used in this experiment had to be standardized so that the exact molarity would be known. This was done by preparing three samples of KHP solution to titrate with the NaOH. The number of moles in each sample was known, so that the molarity of the NaOH could be calculated. The average molarity was found to be 0.0984 M.

Analysis First the percent yield was determined. This was done by weighing the dried sample of aspirin. The percent salicylic acid in the sample was determined using spectrophotometry. 0.022 g of pure aspirin, 0.022 g of the sample and 0.028 g of salicylic acid were put into separate 100 mL volumetric flasks. Each sample was dissolved in 10 mL of ethanol. Water was added to the mark while mixing thoroughly. 10.00 mL of each solution were pipetted into test tubes. 8.00 mL of 0.100 M FeCl3 and 2.00 mL of 0.100 M phosphoric acid were added to each test tube and mixed again. The absorbance was each mixture was determined using the spectrophotometer, which was set to a wavelength of 513 nm. The molar mass of the sample was determined by titrating it with NaOH. The sample was titrated three times. Three small samples (0.190 g, 0.199 g, and 0.178 g) of the sample were dissolved in

about 40 mL of ethanol and three drops of phenolphthalein were added. Then each sample was titrated until a faint persistent pink color appeared, and the molar mass was calculated. The melting point of the sample was determined by taking a small portion of the sample and putting it in a capillary tube. The tube was placed in the heating machine and heated up until it melted. The melting point was recorded.

Data/Results Standardization of NaOH Data

Starting Volume (L) Ending Volume (L) Total Volume (L) mass of KHP (g) mol of KHP mol of NaOH Molarity of NaOH Average Molarity Titration 1 0.00104 0.04810 0.04706 0.945 0.004627136 0.004627136 0.098324183 0.0984 Titration 2 0.00002 0.05883 0.05881 1.189 0.00582187 0.00582187 0.09899452 Titration 3 0.00005 0.05154 0.05149 1.028 0.005033541 0.005033541 0.097757635

Melting Point Data

Melting Point (deg C) Trial 1 122.0 Trial 2 117.0 Average 119.5

Titration Data
Starting Volume (L) Ending Volume (L) Total Volume (L) Molarity of NaOH mol of NaOH mol of acid mass of sample (g) Molar Mass (g/mol) Average MM (g/mol) Titration 1 Titration 2 Titration 3 0.01418 0.02400 0.03411 0.02400 0.03411 0.04371 0.00982 0.01011 0.00960 0.0984 0.0984 0.0984 0.000966288 0.000994824 0.00094464 0.000966288 0.000994824 0.00094464 0.190 0.199 0.178 196.6287484 200.0353831 188.4315718 195.03

The analysis for the percent aspirin in the sample could not be carried out because the apparent molar mass was not in between 138 g/mol and 180 g/mol. For example, when the numbers from the first titration are used, the number of grams of aspirin is calculated to be 0.243 grams. This is 128% of the original 0.190 gram sample, which is nonsensical. The other two titrations have calculated percentages of 133% and 115%. The average value is 125% and the standard deviation is 0.0929 or 9.29%.

Spectrophotometry Data
Mass (g) Absorbance 0.022 0.041 0.022 0.040 0.028 1.386 Corrected Absorbance (Absorbance divided by mass) 1.863636364 1.818181818 49.5

Pure Aspirin Exp. Sample Sal. Acid

Corrected Absorbance vs. Percent Salicylic Acid

60 50 Absorbance 40 30 20 10 0 0 20 40 60 80 100 % Salicylic Acid y = 0.4764x + 1.8636

Since the experimental sample had an absorbance of less than 1.86, it was determined that the sample contained 0 % salicylic acid.

Additional Data Mass of Salicylic Acid: 2.171 g Mass of Experimental Sample: 1.047 g

Results Theoretical Yield of Aspirin Sample Actual Yield of Aspirin Sample Percent Yield Molar Mass of Sample Melting Point of Sample % Salicylic Acid measured by Spectrophotometer 2.832 g 1.047 g 37.0 % 195.03 g/mol 119.5 deg C 0%

Demonstrated Calculations Standardization of NaOH calculations:

Starting Volume (L) Ending Volume (L) Total Volume (L) mass of KHP (g) mol of KHP mol of NaOH Molarity of NaOH Average Molarity

Titration 1 =1.04/1000 =48.1/1000 =B3-B2 0.945 =B5/204.23 =B6 =B7/B4 =AVERAGE(B8:D8)

Titration 2 =0.02/1000 =58.83/1000 =C3-C2 1.189 =C5/204.23 =C6 =C7/C4

Titration 3 =0.05/1000 =51.54/1000 =D3-D2 1.028 =D5/204.23 =D6 =D7/D4

Theoretical Yield Calculations Starting Quantities: 2.171 g salicylic acid 4.0 mL acetic anhydride

Since the stoichiometric coefficients for these chemicals are both 1 for the synthesis of aspirin, salicylic acid is the limiting reactant.

Molar Mass of Aspirin Calculations:

Starting Volume (L) Ending Volume (L) Total Volume (L) Molarity of NaOH mol of NaOH mol of acid mass of sample (g) Molar Mass (g/mol)

Titration 1 =14.18/1000 =24/1000 =B3-B2 0.0984 =B5*B4 =B6 0.19 =B8/B7

Titration 2 =24/1000 =34.11/1000 =C3-C2 0.0984 =C5*C4 =C6 0.199 =C8/C7

Titration 3 =34.11/1000 =43.71/1000 =D3-D2 0.0984 =D5*D4 =D6 0.178 =D8/D7

Average MM (g/mol)=AVERAGE(B9:D9)

Discussion DS1: The theoretical yield of acetylsalicylic acid was 2.832 g. The actual yield was 1.047 g. This was a percent yield of 37.0 %. The melting point of the sample was found to be approx. 120 deg C. The molar mass of the sample was found to be 195.03 g/mol. The percent of aspirin in the sample could not be calculated using the apparent molar mass because the molar mass was not in between 138 and 180 g/mol. The percent salicylic acid in the sample was found to be zero percent using the spectrophotometer.

DS2: The percent yield of the experiment was disappointingly low, at 37%. However, there were many instances during the experiment where small amounts of the mixture were lost. This happened most often when the mixture was transferred from one container to another. In these instances, some sample that was stuck to the sides of the container would not get transferred. The melting point of the sample was 119.5 deg C. The melting point was supposed to be in between 135 deg C and 159 deg C, the melting points of pure aspirin and salicylic acid, respectively. The melting point is closer to that of aspirin, meaning the sample is free of salicylic acid. However, since the melting point is so low, it is possible that the sample was contaminated with some other substance with a low melting point. The molar mass of the sample was found to be 195.03 g/mol. The molar mass was supposed to be in between 180 g/mol (pure aspirin) and 138 g/mol (salicylic acid). Once again, the value found for the sample was much closer to pure aspirin. Like the melting point, the molar mass was outside the range of expected values. This means that while there is little salicylic acid in the sample, it is possible that the sample could have been contaminated by some other substance with a high molar mass. The corrected absorbance of the sample was found to be 1.82. This value was expected to be in between the corrected absorbances of pure aspirin (1.86) and salicylic acid (49.5). Since the absorbance of the sample was lower than that of pure aspirin, it means that there is no salicylic acid in the sample. The fact that the absorbance of the sample was lower than that of pure aspirin is probably due to the high uncertainty of the spectrophotometer.

DS4: Uncertainty of the First Molar Mass Calculation DATA: Concentration of NaOH solution: 0.09840.0006 M Mass of Sample: 0.1900.002 g Starting Volume: 0.014180.00001 L

Ending Volume: 0.024000.00001 mL Combined Equations

Maximum Value

Minimum Value

The molar mass should be given as 1974 g/mol. This value is for the first titration only.

Conclusion The percent yield of this experiment was 37.0 %. The sample was found to have a molar mass of approximately 195 grams per mole. The melting point was found to be approx. 120 deg C. Both of these values are not very close to the theoretical values for aspirin. The theoretical values of aspirin are 180 grams per mole for the molar mass and 135 deg C for the melting point. However, they are much farther away from the theoretical values for salicylic acid. This would indicate that, while the sample may not be very pure, it does not contain any salicylic acid. The sample could have possibly been contaminated by another substance (with a high molar mass and a low melting point). One possibility is the contamination of the sample with KHP. This substance has a molar mass of 204 g/mol. Small traces of KHP in the sample could have artificially raised the molar mass. Part of the discrepancy is also due to the uncertainty of the techniques used (especially for the melting point analysis). Spectrophotometric analysis of the sample also showed that there was no salicylic acid present.