Experiment 1 Hydrolysis of Methyl Salicylate

The experiment consists of four parts:

I. Reaction by Reflux

II. Acidification

III. Recrystallization for Purification

IV. Weight Measurement and Melting-point Range Determination

I. Reaction by reflux

I.1. Transfer 0.80 mL of methyl salicylate in a round-bottom flask. The volume of methyl salicylate is
measured by a pre-adjusted dispenser. Do not adjust the dispenser by yourself and ask your
instructors/TAs for help when necessary. [How many moles of methyl salicylate have you added?
Use the data on your data sheet for calculation. Note that methyl salicylate is a pure liquid, not a
solution.]

I.2. Measure about 20 mL of 2M NaOH solution by a measuring cylinder. The volume of NaOH is not
necessarily 20 mL, it can have an error of up to ±10%. [How many moles of NaOH have you
added? Is methyl salicylate or NaOH in excess? Why an accurate volume of NaOH is not
necessary?]

I.3. Transfer the NaOH solution into the round-bottom flask. [Is there any
change in the round-bottom flask?]

I.4. Add two pieces of boiling chips to the round-bottom flask. [Why are boiling chips important to
reflux reaction? What might happen without boiling chips?]

I.5. Make sure that there is 1/2~2/3 tap water in the hot water bath. Clamp the round bottom flask and
adjust its height and position so that it sits nicely on the ring of the hot water bath (without a gap
in between). Attach the rubber tubings to the condenser and then fit the condenser to the flask.
[Why shouldn’t there be a gap between the flask and the water bath? What is the use of the
condenser? What is the direction of the cooling water flow in the condenser?]

I.6. Turn on the cooling water and make sure it is circulating properly inside the condenser. Turn on
the heating and reflux the reaction mixture until a homogenous solution is obtained. [There
will be several small particles at the bottom of the flask even after long time of reaction, what
are they?]

I.7. Lift up the flask from the heating source. Cool the flask in air for a while. Remove the
condenser and further cool the flask in an ice-water bath. [Can the hot flask be directly cooled
in the cold-water bath? Why/why not?]

II. Acidification

II.1. Transfer the reaction mixture to a conical flask. Rinse the round-bottom flask with about 10 mL of
de-ionized water and combine the rinse solution to the conical flask. [Why is the rinse process
 necessary?]

II.2. Keep the conical flask in an ice-water bath and acidify the solution with 4 mL of concentrated
hydrochloric acid (12 mol/L). [Hydrochloric acid is corrosive. Take care whenever handling
HCl. How many moles of acid have you added? Is it in excess? Is there any change to the
solution?]

II.3. Swirl the conical flask to completely mix the acid and your solution. Dip a glass rod into your
acidified solution, and then touch the glass rod on one piece of Congo Red paper. Congo Red
paper will turn blue in acidic condition. If your solution is not acidic, add a few more mL of
concentrated HCl. [Why must the solution be acidic?]

III. Recrystallization for Purification

The product is purified by recrystallization using water as the single solvent. [What is the
principle of recrystallization?]

III.1. As a preparation, heat half a beaker (about 120-180 mL) of de-ionized water on the hot plate in
advance.

III.2. Add two pieces of boiling chips to the conical flask and heat the solution to gentle boiling. A
few bubbles per second is a rough indication of gentle boiling.

III.3. Using a dropper, add hot boiling de-ionized water until all the solid particles just dissolve (except
the boiling chips). During the process, always keep the temperature of the mixture at gentle
boiling by turn up/down the heating. Use a paper band to swirl the flask frequently to help
dissolving the solid. [What will happen if excess water is added?]

III.4. Remove the conical flask from the hot plate and allow it to cool in air for about 10 minutes.
Minimum disturbance to the solution is the key to high-quality crystals.

III.5. Cool the solution in an ice-water bath for about 10 minutes to allow complete crystallization.
Minimize the disturbance whenever possible. [Clamp the conical flask so that it will not
topple over.]

III.6. Filter the crystals by vacuum filtration. Wash the crystals once by cold de-ionized water
(roughly 10 mL).

III.7. Folder one piece of filter paper to a “paper box”. Carefully transfer the crystals to the paper box.
Dry the product under the infra-red lamp. [Why is the “paper box” better than just a piece of
filter paper?]

III.8. To check whether the crystals are dry, get a bit of crystals from the bottom of the pile. Place the
crystals on a piece of filter paper and crush the crystals by folding the paper. If the crystals are wet,
there will be moisture on the filter paper. [Why not check the crystals from the top of the pile?]

IV. Melting-point Range Determination and Weight Measurement

IV.1. Melting-point range measurement is an important technique for characterization of organic

compounds. An accurate measurement of melting-point range is essential for identification of
unknown compounds in Experiment 2 of CM1501. [Theoretically, melting point of a pure
 compound is just one temperature. However, in real measurement, it is usually a melting-point
range. Why?]

IV.2. To learn the technique of melting-point range measurement, you need to measure the
melting-point range of your DRY product salicylic acid. To obtain the DRY sample, you can
transfer a few pieces of your crystals onto a piece of filter paper. By folding the filter paper,
the crystals will be crushed to fine powders and should be dried within one minute under the
IR lamp. It is NOT necessary to wait until all the crystals are dry for the melting-point range
determination.

IV.3. Measure the melting-point range of your product. To set up the melting point machine, follow the
instruction manual on the machine. The parameters should be set as:

Set Point: 155 oC

Max Point: 170 oC
-1
Gradient: 1.0 or 0.5 oC·min

Measure the accurate melting-point range at least twice. If the results are not parallel, run a
third measurement or more measurements until the results are parallel. The reason for the
small gradient is to minimize the error of the measurement. [What might be the error if a large
gradient is used?]

IV.4. Weigh an empty plastic bag on the analytical balance. Record the weight on your data sheet.
Pay attention to the significant figure of the balance. The last zero (0) cannot be omitted.

IV.5. Transfer your dried crystals into the plastic bag. Seal the plastic bag with the sealing machine.
Wait for 5 seconds before removing the plastic bag from the hot sealing machine so that the
plastic bag will not break.

IV.6. Weigh the plastic bag with your product inside and record the weight.

IV.7. On your data sheet, calculate the weight of your product, theoretical yield (show brief
calculation) and percentage yield.

V. Submission of Data Sheet and Product

V.1. No formal lab report is required for Experiment 1. The data sheet serves as the pro-forma lab
report.

V.2. Staple your sealed product (with your name and fume hood number) to your data sheet.