EXPT 13ab Report Perez

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Jan 9, 2024

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Date: 3/01/2023 Name: Keren Perez Section E2 LAB REPORT FOR EXPERIMENT 13 a “The Fischer Esterification: Synth of an Ester” PRE-LAB: Aim/Objective: In this experiment we will be given an unknown alcohol to react with acetic acid in an esterification reaction. The aim is to isolate, purify, and identify the product ester by performing a micro boiling point determination, transesterification, and IR spectroscopy of the product. Material Safety and Physical Constants: Compound MW (g/mol) MP (Celsius) BP (Celsius) Safety Glacial acetic acid 60.052 16.6 118 corrosive to tissues, and concentrated acetic acid solutions (greater than 80% acid) can cause moderate to severe burns Concentrated sulfuric acid 97.97 10.31 337 exposures may cause a build-up of fluid in the lungs (pulmonary edema), a medical emergency 10% sodium carbonate 105.99 851 NA May cause eye irritation. Ingestion: May cause irritation of digestive tract. Inhalation: May cause respiratory tract and mucous membrane irritation. n-propyl acetate 102.131 -93 102 exposure can cause drying and cracking of the skin. Inhaling n-Propyl Acetate can irritate the nose and throat n-butyl acetate 116.16 -78 126 Acute exposure to n-butyl acetate can cause contact irritation, headache, muscle weakness, dizziness, ataxia, confusion, delirium Isopropyl acetate 102.1 -73 89 Repeated exposure can cause dryness and cracking of the skin. Breathing Isopropyl Acetate can irritate the nose, throat and lungs causing coughing, wheezing and/or shortness of breath Isobutyl acetate 116.16 -99 118 Exposure to Isobutyl Acetate can irritate the eyes, nose, and throat Sec-butyl acetate 116.16 -99 112 Contact can irritate the skin and eyes. Breathing sec-Butyl Acetate can irritate the nose and throat causing coughing and difficult breathing
Procedure: 1. Weigh an empty 25 mL round-bottom flask 2. Place approximately 3.0 mL of your unknown alcohol in the flask and reweigh 3. Add 5 mL of glacial acetic acid 4. After placing a few boiling chips in the flask, add 3-4 drops of concentrated sulfuric acid 5. Connect a water-cooled reflux acid to the flask 6. Heat the round-bottom flask using an aluminum block 7. Continue to reflux for 45 minutes 8. Very carefully, raise the reaction vessel off the aluminum block, and clamp the flask in air to allow the glassware and contents to cool 9. While stirring, slowly add 4-5 mL of 10% sodium carbonate 10. Stir until CO2 formation ceases 11. Transfer the reaction mixture to a centrifuge tube or large test tube and let the layers settle 12. Remove the lower aqueous layer with a Pasteur pipet 13. Repeat extraction of the organic solution with carbonate 2 more time 14. Use a pipet to mix the layers by taking up some of the bottom layer into the pipet 15. Add smalls amount of anhydrous sodium sulfate and cap for 10 minutes 16. Transfer the dry ester to a small round-bottom flask and add a few boiling chips 17. Assemble the distillation apparatus using the Hickman still head 18. Place the distillation assembly on an aluminum block heated to 180 degrees Celsius and distill the acetate 19. After distillation, transfer the acetate to a pre-weighed vial and obtain the mass 20. Obtain IR of the ester spectrum and submit sample for NMR analysis 21. Save the rest for experiment 13b Balanced Chemical Reactions: Reaction Mechanism:
Observation: Esters are used in flavoring and perfume industries. They are commonly added to foods and beverages to produce fruity flavors. Nonetheless, the ester we obtained from alcohol #5 did not have a very fruity or pleasant smell. It was rather strong and did not have a very sweet smell. In contrast, the carboxylic acids usually have very unpleasant smells. The reaction mechanism for the formation of ester is shown below. This was very congruent with our reaction because there was a very strong unpleasant odor in the formation of the carboxylic acid. Data and Results: Alcohol #5 was used for synthesis of ester Mass of round flask: 20.473 g Mass of round flask + alcohol: 23.07 g Amber vial weight: 7.788g Amber vial + final product weight: 9.505g Calculations: Mass of alcohol #5: 23.07g 20.473g = 2.597 g Final product (Ester) weight: 1.717 Theoretical yield: 2.597 x (1mol/74.122g secbutanol) (1 mol secbutyl acetate/1 mol secbutanol) (116.16 secbutyl acetate/1 mol) = 4.07g IR Spectrum
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NMR Analysis of Sec Butyl Acetate Discussion: In this experiment we used Fischer esterification to synthesize an ester. In this reaction, it was very important to use an excess of carboxylic acid so that the reaction is driven towards the product. An unknown alcohol was used and reacted with glacial acetic acid. Sources of error in this experiment could be due to excess acetic acid not being added to the reaction, which would cause the reaction to not have yielded as much product, which may have occurred due to the lack of product obtained. For the workup, we designed it strategically to deal with the contaminants. For instance, we used excess of acetic acid to push equilibrium towards product, yet because it is an equilibrium reaction, we still expected to have some of our unknown alcohol leftover. We used 5 mL of 10% Na2CO3 to get rid of the excess acid. We got rid of excess moisture by drying it in Na2SO4. And to further purify the product, we distilled it using the Hickman head via micro-scale distillation technique.
Conclusion: In conclusion, all our findings from experiment 13a support the claims that our team managed to synthesize a pure unknown ester. In Fischer Esterification, a carboxylic acid was exposed to an alcohol and strong acid catalyst, yielding an ester and water. The mass of the alcohol was determined to be 2.597 g which gave a theoretical yield of 4.07 g. Additionally, the mass of the final collected product of ester was 1.717 g. This was sufficient to carry on experiment 13b the next lab. The IR spectrum showed promising results, as there was a signal at 2970 cm^-1 for the C-H bonds, a strong signal at 1739 cm^-1 for the ester functional group, and a strong signal at 1230 cm^-1 for the C-O bond. This suggests that the desired ester was successfully made as the product. POST-LAB 1. Propionic acid has a higher boiling point because it has hydrogen bonding IM interactions. On TLC plates, more polar molecules / molecules that have hydrogen bonding have a lower RF, so propionic acid will have a lower RF and methyl acetate has a higher RF. 2. Acids have a higher boiling point than esters. Propanoic acid has a higher boiling point. They have free OH group which can associate with hydrogen bonding. This means they have higher boiling point. However, ester will have higher Rf in comparison to acids because acids are more polar than esters. To purify esters, we can remove it by removing a more nonpolar solvent. Alcohol would be very polar to remove in this. 3. 4. The temperature must be increased, concentration of ester must be increased + concentration of alcohol/carboxylic acid must be decreased to favor ester hydrolysis 5. 6. We use concentrated sulfuric acid as a catalyst for esterification of alcohol with carbocyclic acid. We remove any unreacted sulfuric acid from product ester. This is because ester hydrolyses back to alcohol and carboxylic acid. We add a week base like Na2CO3 or NAHCO3 to reaction mixture during product extraction. The reactions are
shown below. Anhydrous sodium sulfate is used as an inert drying agent to remove traces of water from organic solutions. 7.
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LAB REPORT FOR EXPERIMENT 13 b Transesterification and Ester Identification PRE-LAB: Aim/Objective: To identify and unknown ester by defining the boiling point, refractive index, nd synthesizing a derivative to find the melting point Material Safety and Physical Constants: Compound MW (g/mol) MP (Celsius) BP (Celsius) Safety Concentrated sulfuric acid 97.97 10.31 337 exposures may cause a build-up of fluid in the lungs (pulmonary edema), a medical emergency 10% sodium carbonate 105.99 851 NA May cause eye irritation. Ingestion: May cause irritation of digestive tract. Inhalation: May cause respiratory tract and mucous membrane irritation. n-propyl acetate 102.131 -93 102 exposure can cause drying and cracking of the skin. Inhaling n-Propyl Acetate can irritate the nose and throat MtBE 88.15 -109 55.2 Highly flammable liquid and vapor, cause skin irritation/eye irritation or burn. Cause dizziness and suffocation. Harmful if swallowed Procedure: 1. Obtain a micro test tube Add about 10 drops of the unknown ester 5 2. Add a glass bell Open end of it should point down and submerged below the liquid’s surface, and air should be trapped in the glass bell. 3. Attach the micro test tube to a thermometer with a rubber band 4. Above the oil bath, and the thermometer bulb should be next to the test tube liquid 5. Clamp the thermometer with the test tube so they are submerged in the oil bath in the Thiele tube 6. Thiele tube’s shape allows for convention currents to form in the heated oil. 7. Raise temperature slowly until a steady number of bubbles is appearing About 1 bubble per ½ seconds 8. Once bubbling occurs at a fast rate, turn off the heat Bubbles difficult to distinguish from each other 9. Allow temperature to drop Record the boiling point, which is when the last bubble exits the glass bell Here, the vapor pressure in the sample is equal to atmospheric pressure 10. Add 0.75 g of 3,5-dinitrobenzoic acid, 1 drop of concentrated H2SO4, and 1 mL of ester to a 10 mL round bottom flask Set up a reflux condenser with the flask 11. Reflux for 60 minutes If benzoic acid dissolves in 15 minutes, do 30 minutes of reflux
12. Put in a centrifuge tube Add 8 mL MtBE Wash 2 times with 4 mL of 5% Na2CO3 13. Let layers be separate before extracting the Na2CO3 (on bottom) 14. Wash 1 time with 4 mL DI water Dry with anhydrous sodium sulfate 15. Evaporate the ether in the fume hood 16. Dissolve the ether that is left (dried) with 2.5 mL boiling ethanol, using a 10 mL Erlenmeyer flask 17. Add boiling DI water very slowly (1 drop at a time) Cloudiness will show 18. Cool the mixture Perform vacuum filtration with a Hirsch funnel 19. Dry 20. Obtain a melting point 21. Obtain the refraction index for the ester used Balanced Chemical Reactions: Reaction Mechanism:
Observation: Some observations were noted about experiment 13b “Transesterification and ester identification”. When the bubbles started to appear during the reaction, it was about 1 bubble per half a second. Additionally, once the bubbles began to occur at a faster rate, they were more and more difficult to distinguish from one another. Our benzoic acid did not reflux in 15 minutes, as a result we had to an hour for the reflux. Lastly, when we added the DI water at a very slow rate (1 drop at a time), cloudiness began to form in our product indicating that crystals were present. Data and results: 0.753 g of dinitro benzoic acid were added Boiling point: 109 Refractive index: 1.387 Melting point: 73 degrees Celsius Predicted ester: sec-butyl acetate Discussion: The unknown alcohol was determined to be sec-butanol, due to the results of the microscale boiling point and refractive index. The microscale boiling point found was around 73 degrees Celsius, and the refractive index found was 1.387. The boiling point was a bit lower than the literature boiling point likely because there were still impurities present in the sample. Additionally, when we did vacuum filtration, we did not leave it for a long enough time. This likely cause some moisture to still be present, lowering the boiling point. The boiling point was also a bit lower, likely due to the same reasons mentioned before. Nonetheless, it is close enough to identify sec-butanol as our alcohol. The refractive index, nonetheless, was very representative of sec-butanol. Ultimately, a source of error was the vacuum filtration. Due to a problem with time, we had to rush as the end of the lab. It can be avoided in the future by carefully following the procedures and understanding the procedures before lab to be more efficient with time. For the workup, we use MtBE to transfer reaction mixture to centrifuge tube and we wash twice with Na2CO3 to react with any leftover acids. And one time with DI H2O and get rid of the aqueous solution to get rid of contaminants. We will get a derivative that will help us identify what the ester is.
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Conclusion: Ultimately, our unknown alcohol was sec-butanol for unknown #5. The objective of the experiment was to determine the identity of an unknown alcohol using its micro boiling point and refractive index, as well as its melting point, which was unfortunately unattainable. The literature values for the identified ester were similar but not identical, indicating a significant margin of error. The experimental evidence suggests that the unknown alcohol in question is most likely sec butanol, with a boiling point of 109 degrees Celsius, a melting point of 73 degrees Celsius, and a refractive index of 1.387. As compared to the literature values of 111 degrees Celsius for boiling point, 76 for melting point, and 1.389 for refractive index, respectively. Possible sources of error in the experiment include the possibility of insufficient addition of acetic acid, resulting in a lower yield of product, and potential parallax errors if the refractive index was not accurately measured, which could lead to incorrect identification of the ester. Additionally, contaminants were still present resulting in a lower melting and boiling point. POST-LAB 1. Excess amounts of 3,5-dinitrobenzoic acid would have to be washed using sodium bicarbonate solution, which dissolves excess acid left in the reaction 2. 1 atm or 760 mmHg 3. a. boiling point was not reached + turning off heat stopped the process, causing liquid to enter bell b. Vapor pressure begins to reach atmospheric pressure making the liquid come out of the bell c. Boiling point is indicated by steady stream of bubbles d. Temperature fell below the boiling point and liquid floods the bell (condensation point) because the vapor pressure is no longer keeping it from entering 3. A. N20 = 1.4250 + 0.0004(23-30) = 1.4262 a. N20 = 1.3780 + 0.0004(23-20) = 1.3748 5. An alcohol peak at 2200-3600 cm^-1 will be present in the ester, not in the derivative.