Esterification

Source: Lara Al Hariri at the University of Massachusetts Amherst, MA, USA

1. EsterificationExpand

   In this lab, you will synthesize an ester from a carboxylic acid and an alcohol in the presence of sulfuric acid. This reaction is called Fischer esterification. The sulfuric acid makes the carboxylic acid more reactive towards the alcohol. Without it, esterification would be slow and unfavorable. Esterification is highly reversible, so you'll use an excess of alcohol to drive the reaction towards the ester.

   You will be assigned one of seven carboxylic acid-alcohol pairs for your reaction. Each of the seven possible product testers has a distinct fruity scent. When you finish the reaction, you will waft your products vapor towards yourself and identify it based on the fruit that it smells like.

   • Before you get started, put on a lab coat, safety glasses, and nitrile gloves. Note: Your instructor will demonstrate wafting before handing out the reagents. Always smell compounds by wafting, rather than direct inhalation.
   • Once you are ready to begin, get your assigned carboxylic acid and alcohol and bring the vials to your fume hood. The vial labeled ‘A’, ‘B’, or ‘C’ is your carboxylic acid. The other vial is the alcohol. Record the letters of your carboxylic acid and alcohol in your lab notebook.

     Table 1: Scent of Carboxylic Acid, Alcohol, and Ester

     	Letter	Scent
     Assigned carboxylic acid
     Assigned alcohol
     Synthesized ester

     Click Here to download Table 1
   • Now, get a piece of filter paper and a Pasteur pipette. In the fume hood, use the Pasteur pipette to apply a drop of your alcohol to the filter paper.
   • Bring the filter paper to the front of the hood and waft the scent of the alcohol towards yourself. Be careful because it might smell unpleasant.
   • Then, put the filter paper back in the hood and write a brief description of the scent of the alcohol in your lab notebook. Do the same for your carboxylic acid if it's a liquid using a new pipette and piece of filter paper. Note: If you were assigned a solid carboxylic acid, write 'solid' in your lab notebook and skip this step.
   • Now, attach an open 3-prong clamp to a lab stand in your fume hood. Place a lab jack at the base of the stand and set a stir plate and a heating mantle on top of it. Move the temperature controller next to the setup.
   • Then, place a small stir bar in a 50-mL round-bottom flask and securely clamp the flask over the heating mantle.
   • Add the carboxylic acid to the flask using a funnel. Rinse the carboxylic acid vial into the flask with 1 or 2 mL of your alcohol, and then add the rest of the alcohol to the flask.
   • Next, bring a 10-mL graduated cylinder to the fume hood reserved for acids, and carefully measure 4 mL of 3 M sulfuric acid. Note: It's highly toxic and corrosive, so be careful with it.
   • Cover your graduated cylinder with plastic paraffin film. Then, bring the acid back to your hood and add it to the flask. It's OK if the liquids form two layers.
   • Now, use one piece of tubing to connect the lower arm of the standard condenser to the water tap in your fume hood. Attach the other piece of tubing to the upper arm and direct it to your drain. Make sure that the connections are secure.
   • Apply vacuum grease to the lower ground glass joint of the condenser. Fit the condenser into the round-bottom flask and ensure that the grease forms a good seal.
   • Secure the condenser in place with a second 3-prong clamp and make sure that the tubing is out of the way. Use a laboratory wipe to remove excess grease, and then secure the connection with a joint clip.
   • Now, slowly open the water tap until water is flowing smoothly through the condenser. Make sure that the water is flowing into the drain and that there are no leaks.
   • Then, raise the lab jack until the round-bottom flask is sitting in the heating mantle. You are now ready to start heating your reaction mixture to reflux.
   • Set the stir motor to medium speed and start heating the mixture on medium heat or with a set point of about 110 °C.
   • The first boiling point of your mixture will be between 65 and 100 °C. So, keep an eye on it as it heats and adjust the temperature setting as needed.
   • Once the mixture reaches an even boil, let it reflux for 50 min.
   • Then, turn off the heat, lower the lab jack, and replace the heating mantle with a round bottom flask holder.
   • Let the mixture cool to room temperature with the condenser still in place, which usually takes about 10 min. During that time, prepare an ice bath in a 600-mL beaker and bring it to your fume hood.
   • Once the mixture has cooled completely, turn off the flow of water to the condenser. Carefully separate the condenser from the flask and move it out of the way. Then, raise the ice bath up to the flask and let it cool for 10 min.
   • After that, bring a clean 10-mL graduated cylinder to the base hood and obtain 5 mL of saturated sodium bicarbonate.
   • Back at your hood, use a lab wipe to remove vacuum grease from the inside of the neck of the round bottom flask.
   • Then, obtain several clean Pasteur pipettes and some pH paper. Use a pipette to slowly add 1 mL of saturated sodium bicarbonate to the flask and stir the mixture with a stir bar or a glass rod.
   • Add the rest of the sodium bicarbonate solution a milliliter at a time, stirring after each addition.
   • Then, use a new pipette to check the pH of the solution. If the pH is < 7, get a few more milliliters of sodium bicarbonate and add it 1 mL at a time, stirring and checking the pH after each addition.
   • Once the solution is at a neutral pH, remove the ice bath and dry the outside of the flask with a paper towel.
   • Let the mixture sit for a few minutes to see whether it settles into two layers.
   • Then, obtain a clean Pasteur pipette and a new piece of filter paper. Carefully draw up a small amount of the product solution and apply one or two drops to the filter paper. If your product mixture separated, test the top layer first.
   • Bring the filter paper to the edge of the fume hood and waft the set towards yourself. The seven possible scents are apple, banana, grape, orange, pear, pineapple, and strawberry.
   • Record the fruit that you think your ester smells like in your lab notebook. If you aren't sure which fruit it is, ask your instructor for the reference scents to help you decide.
   • Once you've identified the smell of your ester, retrieve the stir bar, and dispose of your reaction mixture in the non-halogenated organic waste container. Clean your glassware and stir bar using your usual methods.
   • Next, unclamp the condenser and carefully tilt it to let the water drain through the outlet tubing. Disconnect the inlet tubing from the water tap, keeping the end raised to avoid spills, and let the remaining water flow through the condenser to the drain.
   • Then, disconnect the condenser from the tubing and remove the vacuum grease on the bottom joint with lab wipes. Clean the inner walls of the condenser using your usual methods.
   • Leave the filter papers in the hood until they stop smelling strongly of fruit. Dispose of used Pasteur pipettes in the glass waste and throw out any other trash in the lab trash container.
   • Lastly, put away your equipment and clean your hood before you leave.
2. ResultsExpand

   Here are the seven possible esters that you could have made and their scents: propyl acetate smells like pear, isoamyl acetate smells like banana, octyl acetate smells like orange, butyl butyrate smells like pineapple, ethyl butyrate smells like strawberry, methyl butyrate smells like apple, and methyl anthranilate smells like grape.

   • Compare the scent of your ester to find the corresponding structure. For example, a strong scent of pears means that you made propyl acetate.
   • Determine your starting carboxylic acid and alcohol. Note: Remember that alcohol attacks the carboxylic acid in this reaction. The resulting intermediate rearranges and eliminates a water molecule to form an ester.
   • Studies have shown that the alkoxy oxygen comes from the alcohol, not the carboxylic acid. So, we'll split the ester diagram at the carbon-oxygen single bond and fill in the missing OH and H to get the starting materials. For example, if we split propyl acetate at that bond, add an OH to the carbonyl carbon and add a hydrogen to the alkoxy oxygen, we get acetic acid and 1-propanol as the starting materials.