ORGANIC CHEMISTRY LABORATORY

PROCEDURES

Organic Chemistry I and II

CHEM 2123 and 2125
Richard Wheet
Fifth Edition 2014

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ORGANIC CHEMISTRY LABORATORY PROCEDURES

Fifth Edition

RICHARD L. WHEET

Department of Chemical Technology

Texas State Technical College
2016

Copyright 2016

Copyright 2016, by Richard Wheet. All rights reserved. No part of this book may be
reproduced in any form, electronic or mechanical, including photocopy, recording, or any
information storage system, without permission in writing from the author.

REFERENCES

Morrison and Boyd, Organic Chemistry

Hajian, Modern Chemical Technology

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TABLE OF CONTENTS

LABORATORY SAFETY
SIMPLE DISTILLATION OF A SINGLE SOLUTION

DISTILLATION OF A MIXTURE OF TWO LIQUIDS

FRACTIONAL DISTILLATION

MELTING POINT

13

PREPARATION OF ACETYL SALICYLIC ACID

17

EXTRACTION OF A KNOWN MIXTURE

21

EXTRACTION OF AN UNKNOWN MIXTURE

29

RECRYSTALLIZATION OF ACETANILIDE

35

SYNTHESIS OF ACETANILIDE

39

THE SYNTHESIS OF ESTERS

41

THE SYNTHESIS OF SOAP

45

ESSENTIAL OILS OF PLANTS

49

CHEMICAL TECHNOLOGY SAFETY INSTRUCTIONS

Laboratory work in chemistry can be stimulating to students who appreciate the challenge it
offers to their abilities, but it is not without certain hazards. For your safety, and for that of
your classmates, a few simple regulations will have to be enforced. The observance of
these safety regulations is an integral part of good laboratory technique.
1.

Wear safety glasses at all times in the laboratory. This includes clean-up times and
times when you yourself may not be working on an experiment, but someone else
is.

2.

Shoes must be worn in the laboratory. Sandals or bare feet are prohibited.

3.

Shorts or cut-offs shall not be worn when working in the laboratory.

4.

Light burners only when needed. Promptly extinguish any flame not being used. An
open flame may ignite reagents being used by you or others near you.

5.

Do not eat, drink, smoke, dip or chew tobacco in the laboratory.

6.

Never look directly into the mouth of an open flask or test tube if it contains a
reaction mixture.

7.

Never point the open end of a test tube at yourself or at another person.

8.

Avoid measuring volumes of strong acids or alkaline solutions with your graduated
cylinder held at eye level. Support the graduated cylinder on your bench; add the
hazardous liquids from a beaker a little at a time, inspecting after each addition.

9.

Never weigh a chemical directly on a balance pan. Use a pre- weighed container,
e.g. a watch glass, weighing dish or a small square of clean paper turned up on all
sides.

10.

Make sure all electrical equipment is safely grounded and all wires are insulated.

11.

Report all accidents to your instructor.

SAFETY TEST
NAME OF STUDENT _______________________________
ADDRESS
_______________________________
PHONE
_______________________________
IN CASE OF AN ACCIDENT NOTIFY
ADDRESS
_______________________________
PHONE
_______________________________

1.

2.

3.

The best first aid when a chemical gets into the eyes is to
___________

a)

rub the eyes.

___________

b)

wash the eye with clear water.

___________

c)

put on safety glasses.

With proper precautions, any chemical can be handled safely.

___________

a)

true

___________

b)

false

___________

c)

no opinion

The best way to learn hazardous characteristics of a chemical

is

4.

5.

___________

a)

read the label on the bottle.

___________

b)

ask your classmate.

___________

c)

refer to your textbook.

___________

d)

none of the above.

Safety glasses should be worn in the laboratory

___________

a)

only when working with acids.

___________

b)

only when working with bases.

___________

c)

all of the time.

___________

d)

only when heating a substance.

Horse play is permitted in the laboratory

___________

a)

when cooling a chemical.

___________

b)

when heating a chemical.

___________

c)

during an experiment.

___________
6.

7.

8.

9.

10.

11.

d)

never.

Accidents should be promptly reported to

___________

a)

your partner.

___________

b)

your other classmates.

___________

c)

your instructor.

___________

d)

the school nurse.

Burners should be lighted

___________

a)

only when needed

___________

b)

all the time.

___________

c)

when cooling a chemical.

___________

d)

never.

One should use the contents of an unlabeled container.

___________

a)

always

___________

b)

seldom

___________

c)

never

___________

d)

none of the above.

Foods, drinks, and smoking are permitted in a laboratory.

___________

a)

never

___________

b)

always

___________

c)

once in a while

Which of the following are NOT required for a fire:

___________

a)

oxygen

___________

b)

fuel

___________

c)

heat

___________

d)

carbon dioxide

Unauthorized experiments are NOT to be performed.

____________

a)

true

____________

b)

false

____________

c)

no opinion

12.

13.

14.

15.

16.

Which of the following is a hazardous nature of chemicals?

___________

a)

toxic

___________

b)

flammable

___________

c)

irritating

___________

d)

explosive

___________

e)

all of the above.

___________

f)

none of the above.

Glassware which is chipped or cracked should be

___________

a)

used right away.

___________

b)

discarded

___________

c)

given to your partner.

The proper way to dilute acid is to

___________

a)

add acid and water at the same time.

___________

b)

add acid to water.

___________

c)

add water to acid

___________

d)

none of the above.

Standing on a laboratory stool is a safe practice.

When

___________

a)

true

___________

b)

false

___________

c)

no opinion

dangerous

gases

are

given

off

in

reaction,

the

experiment should be carried out

17.

___________

a)

on your laboratory bench.

___________

b)

outdoors.

___________

c)

in a fume hood

___________

d)

in the hallways.

It is a good practice to read the experiment and follow

the instructions carefully.
___________

a)

true

18.

___________

b)

false

___________

c)

no opinion

Excess reagents should be

___________
___________

a)
b)

placed in a waste container.

should be returned to the reagent

bottle.
___________
19.

20.

c)

consumed by the student.

A chemical may enter the human body through the

___________

a)

mouth.

___________

b)

skin.

___________

c)

lungs.

___________

d)

all of the above.

Lids and stoppers should be replaced on the corresponding

reagent.
___________

a)

true

___________

b)

false

___________

c)

no opinion

THIS IS TO CERTIFY THAT ________________________________________

I have received instruction on laboratory safety and have witnessed a safety film. I certify that I
understand the safety instructions and I am aware that safety glasses must be worn at all times in
the laboratory.

SIGNED

_____________________________ DATE _____________________

Student

SIGNED

_____________________________ DATE _____________________

Student Witness

THIS IS TO CERTIFY THAT ________________ has been given safety instructions and has
satisfactorily passed a safety test.

SIGNED ______________________________
Instructor

DATE _____________________

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SIMPLE DISTILLATION OF A SINGLE SOLUTION

Distillation is a process where a liquid is vaporized, recondensed, and collected. Distillation
is used to purify liquids and to separate one liquid from another. The liquids have different
volatilies which is the relative ease with which the molecules of a liquid escape from the
surface. Volatility is normally the opposite of the boiling point of a liquid. The higher the
volatility of a liquid, the lower the boiling point. The lower the volatility of a liquid, the higher
the boiling point. Vapour pressure is a measure of the force a liquid exerts on the surface
for its molecule to escape.

The liquids will give off molecules, until the atmosphere above the liquid has a vapour
pressure equal to the respective temperature. For example, if the vapour pressure of a
liquid was 760 mm Hg at 60 C, molecules would escape from the surface until there was a
pressure of 760 mm Hg in the atmosphere vapour exerting pressure back at the liquid.
When a solvent is enclosed, the liquid will evaporate until the partial pressure of the gas
above the liquid equals the vapour pressure of the liquid. If some of the gaseous vapour is
removed, more liquid will evaporate in order to equalize the vapour pressure and partial
pressure. This is the principle behind distillation.

A liquid is heated in a distilling flask. The temperature of the liquid will increase (specific
heat) until the vapour pressure/temperature of the first liquid is reached. At this point, all
the heat energy (heat of vaporization) is used to evaporate the liquid. The hot vapour
1

travels upward and reaches a condensing column which removes heat from the vapour.
The gas recondenses back to a liquid and is collected in a receiving flask. Since this
reduces the vapour pressure over the liquid in the distilling flask, more liquid is converted to
vapour to equalize, which in turn recondenses. This is the general idea behind distillation.
If there is only one liquid in the receiving flask, it will be separated from any nonvolatile
solid. These solids would remain in the distillation flask. Thus, the liquid is purified.

EQUIPMENT & CHEMICALS

Water (H20)
20% Sodium Chloride (NaCl)
Organic kit

EXPERIMENTAL OBJECTIVES
Describe the distillation process.
Perform a distillation.

PROCEDURE
1.

Add 100 ml of aqueous 20% sodium chloride (NaCl) to a 200 ml distilling flask. In
picking a certain size of distilling flask, the volume of the flask should be about twice
the size of the volume of liquid.

2.

Add 3 or 4 boiling chips to the flask to avoid bumping.

3.

Assemble the distillation apparatus as shown in Fig 1-2. Remember to put a film of
silicon lubricant between the ground glass joints to prevent freezing of the joints.
The thermometer bulb should be slightly below the sidearm opening.

4.

The upper outlet on the condenser should be for exiting cooling water. This will
prevent the accumulation of air in the condenser.

5.

Turn on the cooling water.

6.

Increase the heat to the distilling flask until the rate of distillate (liquid) into the
receiving flask is about 2-3 drops per second.

7.

Record the temperature of

the vapour every 5 ml of
distillate collected.

8.

Continue to distill until only

a small amount of residue
remains in the distilled
flask. Do not distill to
dryness.

9.

What did you notice about

the temperature of the
vapor?

10.

What did you observe

about the appearance of
the distilling flask after
distillation was almost
complete?

11.

What can you say about

the relationship of the
boiling point of water
(theoretical) and your
experimental result?

DISTILLATION OF A MIXTURE OF TWO LIQUIDS

Simple distillation of a mixture of two liquids will not effect a complete separation. If both
liquids will boil, both will vaporize and be collected. The more volatile of the two liquids, will
vaporize more quickly than the less volatile and form a larger proportion of the distillate in
the receiving flask. When there is a large difference between the volatilities of the two
liquids, most of the first portion of the distillate collected will be almost pure. The last
portion will be purer in relation to the second liquid. The distillate collected in the middle
will contain varying amounts of the two (figure 2-1). You can separate the two liquids by
changing the receiving flask several times and numerous redistillations.

The first portion collected near the boiling point temperature of more volatile liquid will be
almost pure (compound A). The last portion collected when the temperature is nearly
equal to the boiling point of the less volatile will be mostly the less volatile liquid (compound
B).

EQUIPMENT & CHEMICALS

Water (H20)
Ethyl ether
Distillation Apparatus

EXPERIMENTAL OBJECTIVES
Describe the distillation process involving two liquids.
Perform a distillation.

PROCEDURE
1.

Add 100 ml of a 25% ethyl ether/water mixture (v/v) to a 250 ml distilling flask. In
picking a certain size of distilling flask, the volume of the flask should be about twice
the size of the volume of liquid.

2.

Add 3 or 4 boiling chips to the flask to avoid bumping.

3.

Assemble the distillation apparatus as shown in fig 2-1. Remember to put a film of
silicon lubricant between the ground glass joints to prevent freezing of the joints.
The thermometer bulk should be slightly below the sidearm opening.

4.

The upper outlet on the condenser should be for exiting cooling water. This will
prevent the accumulation of air in the condenser.

5.

Turn on the cooling water.

6.

Increase the heat to the distilling flask until the rate of distillate (liquid) into the
receiving flask is about 2-3 drops per second.

7.

Record the temperature of the vapour every 5 ml of distillate collected.

8.

Continue to distill until only about 40 ml remains in the distillation flask. Do not distill
to dryness.

9.

What did you notice about

the temperature of the
vapor?

10.

What can you say about

the relationship of the
boiling points of water and
ethanol (theoretical) and
your experimental result?

11.

Draw a graph of volume

versus temperature and
explain the findings.

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FRACTIONAL DISTILLATION
A simple distillation usually gives a crude distillation where the initial distillate has to be
redistilled to reach optimum purity. The separation and purification of two or more liquids
into various fractions by distillation is called fractional distillation. Fractional distillation is
really the systematic redistillation of the distillates within a column with the fractions
increasing in purity as the fractions move up the column. This is similar to repeatedly
collecting and redistilling the various fractions. The column is filled with pieces of glass,
glass beads, chips, metal wire, etc. These beads act as small condensers.

The vapour leaves the surface of the liquid and travels upwards through the packed
column. It condenses on the cooler beads and falls back as a liquid. The initial vapours
transfer heat to the lower beads. The recondensed vapour then vaporizes again but this
time move a little higher in the column and the process repeats. The less volatile vapours
reach the beads which were heated by the more volatile vapour. Since the temperature of
the beads are less than the boiling point of the less volatile vapour, they also recondense
and fall back. But this now heats the lower beads and the process continues. The more
volatile vapours pass through the column condensing and recondensing. But as the higher
boiling vapours heat the lower beads, these beads revaporize the higher volatile vapours
within the column. Thus the liquids do not return to the distillation flask as they move
upward.

Each repeated distillation causes a greater concentration of the more volatile liquid in the
rising vapour. The less volatile liquids also are in turn enriched as they pass upward
through the column.

CHEMICALS AND EQUIPMENT

Ethanol
Water
Distillation Apparatus
Glass beads

EXPERIMENTAL OBJECTIVES
The student should be able to perform a fractional distillation.
The student should be able to describe the process of fractional distillation.

PROCEDURE
1.

Add 50 ml of ethanol and 100 ml of water to a 250 ml flask. Remember boiling

chips.

2.

Fill a condenser with glass beads. If necessary, use a small plug of glass wool to
prevent the beads from falling through the column.

3.

Assemble the fractionating column (Figure 1).

4.

Slowly heat the distillate to a flow rate of 2-3 drops per minute.

5.

Record the temperature versus the volume every 5 ml.

6.

Plot a curve of volume versus temperature.

7.

Explain how the results differ from a simple distillation.

10

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11

MELTING POINT
The melting point of a solid is the temperature at which the substance begins to change
from a solid to a liquid. Pure organic compounds have very defined melting points.
Through the use of these melting points, the purity of the compound can be determined.
Contaminants normally lower the melting point and broaden the melting point range (the
temperature at which melting starts and the temperature at which the substance is melted).
Narrow range melting points are normally indicative of the purity of an organic compound.
Extremely pure compounds have ranges of 0.1 to 0.3 C.

Commercially available

compounds (technical grade) have ranges of 2-3 C. The normal laboratory grade organic
(ACS) compounds have a 1 C range. The larger the melting point range, the less pure the
compound.

The melting point range is the temperature range between where a compound starts to
melt and completely melts (becomes liquid). It is highly recommended that during a
melting point determination, the temperature be slowly increased. This enables one to
observe the change and temperature range.

Sometimes, mixtures of two organic compounds with the same individual melting point
have a much lower melting point. This temperature depression is useful for determining
unknowns. When an unknown is identified as a suspected compound, this compound can
be mixed with a known compound of identical melting point. The melting point depression
can confirm whether the suspected organic compound is indeed the correct assumption.

Not all organic compounds melt. Some substance will decompose, discolor, soften and/or
shrink as they are heated. If possible, a reference compound should be compared. If a
compound decomposes, this temperature is normally a reliable indicator. The temperature
is followed by the letter "d" to indicate decomposition (198 d).

12

CHEMICALS AND EQUIPMENT

Paraffin Oil

Benzamide

Thiele tube

Acetanilide

250 C Thermometer

p-dichlorobenzene

Capillary tube

Urea

Bunsen burner

Naphthalene

INSTRUCTIONAL OBJECTIVES
The student should be able to perform a melting point determination.
The student should be able to determine the compound and relative purity given the
melting point.

PROCEDURE
1.

Assemble the melting point apparatus (Figure 1 or 2) as directed by instructor.

2.

Fill a capillary tube with the compound to a height of approximately 3 - 4 mm. This
can be accomplished by pressing the upper end of the capillary tube into the
compound and then tapping the closed end on the table.

13

3.

Attach the capillary tube to the thermometer using a small piece of rubber tubing or
a rubber band. The bottom of the capillary tube should be even with the
thermometer bulb.

4.

Gradually heat the arm of the thiele tube. The rate of heating should be about 2 C
per minute.

5.

When the solid in the capillary tube starts to melt, observe the melting point
temperature. When the solid completely melts, observe the temperature. The two
temperatures are called the melting point range.

14

6.

Do the melting points of the following organic compounds:

Acetanilide
Benzamide
Naphthalene
p-dichlorobenzene
urea

7.

Compare the experimental melting points with the theoretical melting points (found
in reference books and indicate your references on your report).

15

PREPARATION OF ACETYL SALICYLIC ACID

Salicylic acid (o-hydroxy benzoic acid) will be reacted with acetic anhydride to form acetyl
salicylic acid (aspirin) which is insoluble in water.

C OH

O
+

C OH

H3C C O C CH3

OH

O C CH3

salicylic acid

acetic anhydride

acetyl salicyclic acid

This reaction will also produce a polymer type by-product which needs to be removed. The
aspirin is reacted with sodium bicarbonate to form a soluble salt. The polymer which is
insoluble is then filtered off.

C OH
O

CH3

O
sodium bicarbonate

acetyl salicyclic acid

insoluble in water

NaHCO3

ONa
C

CH3

sodium acetyl salicylate

soluble in water

The pH of the solution is then lowered with HCl. The addition of HCl converts the soluble
salt back into the water insoluble aspirin. The precipitated aspirin is then filtered and
collected.

O
C

O
ONa

C OH

O
O

HCl

CH3

sodium acetyl salicylate

soluble in water

O
hydrochloric acid

16

CH3

acetyl salicylic acid

insoluble in water

EQUIPMENT & CHEMICALS

Salicylic acid
Acetic anhydride
Sodium bicarbonate (saturated)
Hydrochloric acid (conc)
200 ml beaker
125 ml Erlenmeyer flask
filtration apparatus
melting point apparatus

EXPERIMENTAL OBJECTIVES
1.

Crystallization procedures

2.

Vacuum filtration procedures

3.

Acetylation reaction

4.

Determination of percent yield

PROCEDURE
1.

Weigh 2.0 grams of salicylic acid (0.015 moles) and transfer to a clean and dry 125
ml Erlenmeyer flask.

2.

Add 5 ml of acetic anhydride (0.05 moles) to the flask.

3.

Slowly add 5 drops of concentrated sulfuric acid while swirling the flask (or use a
stirring bar and stirrer).

4.

Gently stir until all the salicylic acid dissolves.

5.

Heat the flask in a hot water bath for at least 10 minutes.

6.

Remove the flask from the hot water bath and allow the mixture to cool to room
temperature.

7.

The acetyl salicylic acid (aspirin) that was produced in the reaction should begin to
crystallize out of solution during the cooling. Note: if no precipitation occurs, scratch
the walls of the flask with a glass stirring rod.
17

8.

After the aspirin has all precipitated and the solution is at room temperature, add 50
ml of water and place the flask in an ice bath.

9.

Vacuum filter the precipitate through a Hirsch funnel and rinse the flask with cold
water until all the crystals have been collected.

10.

Rinse the precipitate with several portions of cold water.

11.

Air dry the precipitate in the Hirsch funnel for about 10 minutes.

12.

Transfer the crude aspirin to a 200 ml beaker.

13.

Add 25 ml of a aqueous sodium bicarbonate (saturated).

14.

Stir the mixture until all activity (bubbling) has stopped.

15.

Filter the solution through a Hirsch funnel to remove any polymers.

18

16.

Rinse with about 10 ml of water.

17.

Carefully add 3.5 ml of concentrated HCl to a 200 ml beaker which contains 10 ml of

H2O.

18.

Carefully pour the filtrate (in small portions) into the 200 ml beaker with constant
stirring.

19.

The aspirin should precipitate. If no precipitate occurs, add additional HCl until the
solution is acidic to litmus paper (blue to red) then proceed to the next step.

20.

Cool the solution in an ice bath to precipitate all the aspirin.

21.

Vacuum filter the precipitate through a Hirsch funnel and wash with ice cold water.

22.

Dry the precipitate overnight.

23.

Weigh the purified dried acetyl salicylic acid.

24.

Calculate the percent yield using stoichiometry.

25.

Determine the melting point (135-136 C)

19

EXTRACTION OF A KNOWN MIXTURE

A technique called extraction will be demonstrated in this experiment. Extraction relies on
the solubility of substances into solvents and the insolubility of the solvents into each other.
In this experiment, three organic compounds (aspirin, -naphthol, and naphthalene) will be
separated from each other. The three compounds are all soluble in ethyl ether (an organic
solvent). By selectively reacting each organic compound, we can make it soluble in water
and insoluble in ethyl ether. Since ethyl ether and water are insoluble in each other, they
will form two phases and can be separated from each other using a separatory funnel. The
reacted organic compound which is in the aqueous portion is then converted back into the
insoluble organic compound which precipitates out of the aqueous portion.
Aspirin, -naphthol, and naphthalene are all soluble in ether.

Sodium bicarbonate

(aqueous) will be added to the ether solution. Only the aspirin reacts with the sodium
bicarbonate.

C OH
O

acetyl salicyclic acid

NaHCO3

ONa
O

CH3

O
sodium bicarbonate

+ CO2 + H2O
CH3

sodium acetyl salicylate

soluble in ether

soluble in water

The aqueous layer is separated from the organic layer (extraction). The aqueous layer
contains the aspirin salt. The naphthalene and -naphthol remain in the ether layer.

The aspirin is then precipitated out of the aqueous layer by reacting it with HCl.

20

O
ONa

C OH

O
C

HCl

+
CH3

sodium acetyl salicylate

soluble in water

hydrochloric acid

NaCl

CH3

acetyl salicylic acid

insoluble in water

The -naphthol is then reacted with sodium hydroxide (aqueous) to form an aqueous
soluble salt.

O Na

OH

H2O

NaOH

+
-naphthol
insoluble in water

-naphthol salt
soluble in water

The aqueous layer is then separated from the organic layer. The -naphthol salt is then
converted back to the insoluble -naphthol and precipitated out.

OH

O Na

HCl

+
-naphthol
insoluble in water

-naphthol salt
soluble in water

The remaining ether layer is then evaporated leaving naphthalene behind.

21

NaCl

CHEMICALS & EQUIPMENT

Ethyl ether
6M Hydrochloric acid (HCl)
10% Sodium hydroxide (NaOH)
5% Sodium bicarbonate (NaHCO3)
Calcium Chloride (anhydrous)
3 - 125 ml Erlenmeyer flasks
125 ml separatory funnel
Hirsch filtration apparatus
Hot water bath

EXPERIMENTAL OBJECTIVES
Extraction procedures
Vacuum filtration procedures
Melting point
Determination of percent yield

PROCEDURE
1.

Weigh out approximately 2 grams of the aspirin, 2 grams of -naphthol, and 2

grams of naphthalene.

2.

Transfer to a 125 ml Erlenmeyer flask.

3.

Add 50 ml of diethyl ether (ethoxyethane) and dissolve the sample by gently

swirling.

4.

Pour the solution into a 250 ml separatory funnel. Make sure the stopcock is in the
closed position.

5.

Rinse the flask into the separating funnel with several small portions of ethyl ether.

6.

Add 25 ml of 5% sodium bicarbonate (NaHCO3) to the separatory funnel. This will

react with the aspirin to form a water soluble salt.

22

7.

Stopper the separating funnel. While holding the stopper in place with your fingers,
invert the funnel and shake several times (Figure 1).

8.

Point the spigot upward and away from yourself or neighbors. Slowly open the
stopcock to relieve any pressure in the funnel.

9.

Close the stopcock and repeat the shaking - pressure release procedure until no
further pressure build up is noticed. This will indicate the aspirin/NaHCO 3 reaction
is completed.

Extraction of Aspirin
10.

Place the separatory funnel into the ring stand to hold the funnel upright.

11.

Remove the stopper from the funnel.

12.

Open the stopcock on the separatory funnel and draw off the lower aqueous portion
of the liquid into a 125 ml Erlenmeyer flask.

13.

Since some of the aqueous solution is still dissolved in the ethyl ether, add an
additional 20 ml portion of 5% NaHCO3 and repeat the extraction procedure.
Combine this second aqueous portion with the first.
23

14.

Place the 125 ml flask into a warm water bath (60 C) and gently heat. This will
evaporate any ether still present in the aqueous portion. Do not overheat.

15.

Cool the aqueous solution to room temperature.

16.

Carefully and slowly, with constant stirring, add 6M HCl with stirring until a pH of 1-2
is indicated by pH paper. The HCl will convert the water soluble salt into the
insoluble aspirin. The aspirin will start to precipitate out as the pH is reduced.

17.

Vacuum filter the aspirin using a Hirsch funnel and use ice cold water to rinse.

18.

Allow to air dry. Weigh, determine melting point, and calculate the percent
composition of aspirin in the mixture.

Extraction of -naphthol
19.

Add 25 ml of 10% NaOH to the separatory funnel containing the ethyl ether portion.

20.

Using the extraction technique learned previously, invert, shake, and relieve
pressure until no further pressure build up is noted. The NaOH is forming a sodium
salt with the -naphthol which is soluble in the aqueous phase.

21.

Draw off the lower aqueous portion into a 125 ml Erlenmeyer flask.

22.

Add a second 25 ml portion of 10% NaOH to the funnel and extract.

23.

Combine this second aqueous portion with the first.

24.

Carefully add 6M HCl to a pH of 1-2 (use pH paper). The HCl will convert the naphthol salt back into -naphthol which is insoluble in water at the reduced pH.
The -naphthol will precipitate out.

25.

Vacuum filter the -naphthol using a Hirsch funnel and rinse with ice cold water.

26.

Allow to air dry. Weigh, determine melting point, and calculate the percent
composition of -naphthol in the mixture.

Collection of Naphthalene
27.

Transfer the ether remaining in the funnel to a 125 ml Erlenmeyer flask.

24

28.

Rinse the funnel with an additional 10 ml of ethyl and combine.

29.

Add anhydrous calcium chloride (CaCl2), about 1/10 the volume of the ethyl ether
solution, to the 125 ml flask containing the ether. Since there is about 1.5% water
still dissolved in the ether, the anhydrous CaCl2 will absorb the remaining water.

30.

Allow the ethyl ether solution to stand over the anhydrous CaCl2 for 15-20 minutes
with occasional swirling.

31.

Decant the ethyl ether solution off the CaCl2 into a dried 125 ml Erlenmeyer flask.
Use a cotton plug in an ordinary funnel if necessary.

32.

Cover the flask with paraffin wax and poke large holes in the wax. Place the flask in
the hood and allow the ethyl ether to evaporate overnight. Make sure the fume
hood is turned on so as to vent the ethyl ether vapour.

33.

After the ether has evaporated, naphthalene should remain behind.

34.

Weigh, determine melting point, and calculate the percent composition of

naphthalene in the mixture.

25

EXTRACTION OF AN UNKNOWN MIXTURE

A technique called extraction will be demonstrated in this experiment. Extraction relies on
the solubility of substances into solvents and the insolubility of the solvents into each other.
In this experiment, three organic compounds (aspirin, -naphthol, and naphthalene) will be
separated from each other. The three compounds are all soluble in ethyl ether (an organic
solvent). By selectively reacting each organic compound, we can make it soluble in water
and insoluble in ethyl ether. Since ethyl ether and water are insoluble in each other, they
will form two phases and can be separated from each other using a separatory funnel. The
reacted organic compound which is in the aqueous portion is then converted back into the
insoluble organic compound which precipitates out of the aqueous portion.
Aspirin, -naphthol, and naphthalene are all soluble in ether.

Sodium bicarbonate

(aqueous) will be added to the ether solution. Only the aspirin reacts with the sodium
bicarbonate.
O

C OH
O

acetyl salicyclic acid

NaHCO3

ONa
O

CH3

O
sodium bicarbonate

+ CO2 + H2O
CH3

sodium acetyl salicylate

soluble in ether

soluble in water

The aqueous layer is separated from the organic layer (extraction). The aqueous layer
contains the aspirin salt. The naphthalene and -naphthol remain in the ether layer.

The aspirin is then precipitated out of the aqueous layer by reacting it with HCl.

26

O
C

O
ONa

C OH

O
O

HCl

+
CH3

NaCl

CH3

sodium acetyl salicylate

hydrochloric acid
acetyl salicylic acid
insoluble in water
soluble in water
The -naphthol is then reacted with sodium hydroxide (aqueous) to form an aqueous

soluble salt.

O Na

OH
+

NaOH

-naphthol
insoluble in water

H2O

-naphthol salt
soluble in water

The aqueous layer is then separated from the organic layer. The -naphthol salt is then
converted back to the insoluble -naphthol and precipitated out.
+

OH

O Na

HCl

+
-naphthol
insoluble in water

-naphthol salt
soluble in water

The remaining ether layer is then evaporated leaving naphthalene behind.

CHEMICALS & EQUIPMENT

Ethyl ether

125 ml separatory funnel

6M Hydrochloric acid (HCl)

3 - 125 ml Erlenmeyer flasks

10% Sodium hydroxide (NaOH)

Hirsch filtration apparatus

5% Sodium bicarbonate (NaHCO3)

Hot water bath

Calcium Chloride (anhydrous)

27

NaCl

EXPERIMENTAL OBJECTIVES
Extraction procedures
Vacuum filtration procedures
Melting point
Determination of percent yield

PROCEDURE
1.

Obtain a 6 gram sample of an aspirin/-naphthol/naphthalene mixture from your

laboratory instructor. Record the sample number.

2.

Weigh and transfer to a 125 ml Erlenmeyer flask.

3.

Add 50 ml of diethyl ether (ethoxyethane) and dissolve the sample by gently

swirling.

4.

Pour the solution into a 250 ml separatory funnel. Make sure the stopcock is in the
closed position.

5.

Rinse the flask into the separating funnel with several small portions of ethyl ether.

6.

Add 25 ml of 5% sodium bicarbonate (NaHCO3) to the separatory funnel. This will

react with the aspirin to form a water soluble salt.

7.

Stopper the separating funnel. While holding the stopper in place with your fingers,
invert the funnel and shake several times.

8.

Point the spigot upward and away from yourself or neighbors. Slowly open the
stopcock to relieve any pressure in the funnel.

9.

Close the stopcock and repeat the shaking - pressure release procedure until no
further pressure build up is noticed. This will indicate the aspirin/NaHCO 3 reaction
is completed.

Extraction of Aspirin
10.

Place the separatory funnel into the ring stand to hold the funnel upright.

11.

Remove the stopper from the funnel.

28

12.

Open the stopcock on the separatory funnel and draw off the lower aqueous portion
of the liquid into a 125 ml Erlenmeyer flask.

13.

Since some of the aqueous solution is still dissolved in the ethyl ether, add an
additional 20 ml portion of 5% NaHCO3 and repeat the extraction procedure.
Combine this second aqueous portion with the first.

14.

Place the 125 ml flask into a warm water bath (60 C) and gently heat. This will
evaporate any ether still present in the aqueous portion. Do not overheat.

15.

Cool the aqueous solution to room temperature.

16.

Carefully and slowly, with constant stirring, add 6M HCl with stirring until a pH of 1-2
is indicated by pH paper. The HCl will convert the water soluble salt into the
insoluble aspirin. The aspirin will start to precipitate out as the pH is reduced.

17.

Vacuum filter the aspirin using a Hirsch funnel and use ice cold water to rinse.

18.

Allow to air dry. Weigh, determine melting point, and calculate the percent
composition of aspirin in the mixture.

Extraction of -naphthol
19.

Add 25 ml of 10% NaOH to the separatory funnel containing the ethyl ether portion.

20.

Using the extraction technique learned previously, invert, shake, and relieve
pressure until no further pressure build up is noted. The NaOH is forming a sodium
salt with the -naphthol which is soluble in the aqueous phase.

21.

Draw off the lower aqueous portion into a 125 ml Erlenmeyer flask.

22.

Add a second 25 ml portion of 10% NaOH to the funnel and extract.

23.
24.

Combine this second aqueous portion with the first.

Carefully add 6M HCl to a pH of 1-2. The HCl will convert the -naphthol salt back
into -naphthol which is insoluble in water at the reduced pH. The -naphthol will
precipitate out.

25.

Vacuum filter the -naphthol using a Hirsch funnel and rinse with ice cold water.

29

26.

Allow to air dry. Weigh, determine melting point, and calculate the percent
composition of -naphthol in the mixture.

Collection of Naphthalene
27.

Transfer the ether remaining in the funnel to a 125 ml Erlenmeyer flask.

28.

Rinse the funnel with an additional 10 ml of ethyl and combine.

29.

Add anhydrous calcium chloride (CaCl2), about 1/10 the volume of the ethyl ether
solution, to the 125 ml flask containing the ether. Since there is about 1.5% water
still dissolved in the ether, the anhydrous CaCl2 will absorb the remaining water.

30.

Allow the ethyl ether solution to stand over the anhydrous CaCl2 for 15-20 minutes
with occasional swirling.

31.

Decant the ethyl ether solution off the CaCl2 into a dried 125 ml Erlenmeyer flask.
Use a cotton plug in an ordinary funnel if necessary.

32.

Cover the flask with paraffin wax and poke large holes in the wax. Place the flask in
the hood and allow the ethyl ether to evaporate overnight. Make sure the fume
hood is turned on so as to vent the ethyl ether vapour.

33.

After the ether has evaporated, naphthalene should remain behind.

34.

Weigh, determine melting point, and calculate the percent composition of

naphthalene in the mixture.

30

RECRYSTALLIZATION OF ACETANILIDE
Most organic substances are initially produced in an impure form. The substance is mixed
with unreacted reagents, side products, and impurities. If the substance is a solid, a
process called recrystallization can purify it.

Recrystallization is a process in which the solid of interest is dissolved in a hot solvent that
is then slowly cooled. The crystals of the purified product are slowly and selectively
precipitated. The impurities remain dissolved in the solution or are removed from the hot
solution (before recrystallization occurs) by decolorizing carbon. The crystals are then
separated from the solution by filtration.

The solvent selected is based on the solubility of the product to be recrystallized. The
product should be highly soluble at high temperatures but only slightly soluble at room
temperatures. If the solubility of the product at room temperature is high, the yield of
product will be greatly reduced. The selection of solvent is usually on a trial and error basis
unless a chemical reference can be found which recommends a solvent.

Many times a mixture of solvents is used. The product is dissolved in a small amount of
solvent which it is very soluble in. While still hot, a second solvent that the product is not
very soluble in is slowly added until cloudiness appears (products begin to precipitate out).
The first solvent is then slowly added until the cloudiness just disappears. The mixture is
then slowly cooled and the product recrystallizes.

The boiling point of the solvent should be lower than the melting point of the product.
Otherwise, the product may melt in the solvent rather than dissolve. This is called "oiling
out". The melted product often contains a great deal of impurities and if allowed to cool,
will recrystallize in an impure state.

Decolorizing carbon is used to remove colored impurities from the solution. The carbon
has a large active surface area which attracts and absorbs impurities. The carbon is added
to the hot solution which prevents recrystallization of the product while the carbon is
31

absorbing impurities.. A process called hot filtration removes the carbon. The solution is
kept hot during the filtration of the carbon to prevent recrystallization and loss of product.

Repeated recrystallization may be necessary to obtain the desired purity.

INSTRUCTIONAL OBJECTIVES
The student will be able to perform a recrystallization.

CHEMICALS AND EQUIPMENT

acetanilide

decolorizing carbon

2 - erlenmeyer flask (250 ml)

hot plate

filter paper

small stirring bar

watch glass

Hirsch funnel

vacuum flask

PROCEDURE
Dissolving the solid
1.

Boil approximately 200 ml of DI water.

2.

Slowly add the hot water to 5 grams of acetanilide in a 250 ml Erlenmeyer flask with
constant stirring until the acetanilide is dissolved in the minimum amount of boiling
solvent. If needed, place the flask in a hot water bath to keep the solution hot and
prevent recrystallization. Do not place directly onto the hot plate because this might
cause oiling out.

3.

Using a minimum amount of solvent will return a greater yield of acetanilide upon
cooling. Also remember that the solid may dissolve slowly. Do not add the hot
solvent too rapidly.

32

Recrystallization
4.

Allow the solution to slowly cool to room temperature. Crystals will begin to form as
the solution cools. It is recommended to leave the solution standing overnight. If
the solvent is volatile, cover it with paraffin or a watch glass. In this experiment, we
will just wait until room temperature.

5.

Place the flask into an ice bath and allow cooling.

6.

Filter the cold solution by vacuum filtration using a Hirsch funnel.

7.

Rinse the collected crystals with COLD solvent.

8.

Continue to pull air over the crystals using the filtration device.

9.

Remove the crystals and filter and allow drying in a covered watch glass.

10.

Weigh and calculate % yield.

33

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34

SYNTHESIS OF ACETANILIDE
Acetanilide can be prepared from the acetylation of aniline by the following reaction:

O
H N

NH2
O
+
aniline

C CH3

O
+

H3C C O C CH3
acetic anhydride

acetanilide

H3C C OH
acetic acid

EQUIPMENT & CHEMICALS

aniline (10 grams)
acetic anhydride (10 ml)
zinc dust (pinch)
erlenmeyer flask (500 ml)

graduated cylinder (10 ml)

hot plate
vacuum distillation apparatus

EXPERIMENTAL OBJECTIVES
Synthesize and purify acetanilide.

PROCEDURE
1.

Using a 10 ml graduated cylinder, add 4.0 ml of aniline (0.04 moles) to a 500 ml

Erlenmeyer flask.

2.

Add 30 ml of DI water and a pinch of zinc dust to the flask.

3.

With constant stirring, slowly add 6 ml of acetic anhydride (0.06 moles). This should
be done in several small portions.

4.

Crude acetanilide should slowly begin to precipitate. Continue to stir the solution for
at least 20 minutes.

5.

Dissolve the precipitant with a minimal amount of hot water. Remember that the
zinc dust will not dissolve.
35

6.

Remove the zinc by performing a hot filtration.

7.

Recrystallize the acetanilide.

8.

Calculate the % yield using aniline as the limiting reagent.

9.

Compare the melting point with the literature value. What does this indicate?

36

THE SYNTHESIS OF ESTERS

The flavor of almost any fruit and many foods is due primarily to a class of organic
compounds called esters. Since esters can be easily produced in the laboratory by a
process called esterification, the food and beverage industries are very interested in these
synthetic esters. While naturally obtained esters are preferable, they are not often suitable
for the food and drink industry. Natural esters can produce "off-flavors" when heated or
may have a short shelf life. Since the demand for flavors has increased dramatically over
the years, the availability of natural flavors cannot meet the demand, thus, the widespread
use of synthetic flavorings. In recent years, the use of synthetic flavors is more common
than the use of natural flavoring. In fact, many of the flavors you associate with fruits, have
nothing to do with the natural flavor. These synthetic flavors have been "enhanced" by the
flavoring industry.

Esterification is the reaction of an alcohol and a carboxylic acid. The reaction is

reversible and uses an acid as a catalyst.

O
R OH

alcohol

R C OH

R O C R'

carboxylic acid

ester

H2O
water

To force the reaction to the right (ester half) an excess of either alcohol or carboxylic acid is
added. The crude product is washed with cold water in a separating funnel to remove most
of the acid and some of the unreacted alcohol and carboxylic acid. The product is then
washed with sodium bicarbonate to convert any remaining acid and carboxylic acid to a
water soluble salt. The partially purified ester is then dried using an anhydrous drying
agent and distilled.

37

EQUIPMENT & CHEMICALS

One of the carboxylic acid and alcohols in list
Sulfuric acid (conc)
Sodium bicarbonate
Sodium sulfate (anhydrous)
Separating funnel
Blue litmus paper
Distillation apparatus

EXPERIMENTAL OBJECTIVES
Describe the esterification reaction.
Perform a reflux.

PROCEDURE
1.

Using Table 1, choose a flavor. The flavor is matched with the carboxylic acid and
alcohol.

Favor

Alcohol

Carboxylic Acid

Banana

Isoamyl alcohol (0.25 moles)

Acetic acid (0.60 moles)

Peach

Benzyl alcohol (0.20 moles)

Acetic acid (0.60 moles)

Pear

Propanol (0.35 moles)

Acetic acid (1.0 moles)

Pineapple

Ethanol (0.35 moles)

Butyric acid (0.70 moles)

Raspberry

Isobutanol (0.30 moles)

Formic acid (0.60 moles)

Methanol (1.5 moles)

Salicylic acid (0.1 moles)

Wintergreen

38

2.

Fill in the following table:

Favor

Ester

Alcohol

Carboxylic acid

Name
Molecular weight
Boiling point
Density
moles needed
grams needed
ml needed
3.

In a 250 ml ground glass flask mix the alcohol and carboxylic acid in the amounts
indicated. Remember: grams = moles x mol wt and ml = grams/density.

4.

Many of the carboxylic acids have disagreeable odors and should be recapped
immediately and spills prevented. Butyric acid smells like rancid butter and should be
done in a hood.

5.

Slowly add 5 ml of concentrated sulfuric acid (H2SO4) and swirl.

6.

Add a couple of boiling chips

and reflux for 2 hours (Figure 1).

7.

The reflux will allow the mixture

to heat without loss of
components
through
evaporation.
The
vertical
condenser
returns
the
evaporated liquids to the boiling
flask.

8.

Cool the mixture to room

temperature and pour into a
separating funnel.

39

9.

Rinse the flask with several portions water and carefully add to the separatory funnel.
Caution is needed because the separating funnel contains concentrated acid from the
reaction.

10. Carefully add ice cold water to the funnel until the aqueous layer is about twice the
volume of the organic layer. This will remove excess acid.
11. Extract and separate the organic layer from the aqueous layer. Make sure you know
which layer is which. If the ester and water layer do not separate because of similar
densities, add about 30 ml of methylene chloride. The lower layer will be the ester
and methylene chloride. The methylene chloride can later be removed in the final
distillation by slowly heating with a warm water bath.
12. Extract the organic layer with an equal volume of cold 10% sodium bicarbonate
(NaHCO3) solution. This will neutralize excess acid and convert any remaining
carboxylic acid to a soluble salt. Remember to frequently release the pressure in the
separatory funnel.
13. Test the organic layer with blue litmus and repeat the extractions with fresh sodium
bicarbonate until all the acid is removed.
14. Transfer the organic layer to a 125 ml erlenmeyer flask and add enough anhydrous
sodium sulfate to cover the bottom of the flask.
15. Allow the crude ester to stand until the liquid clears. Add additional sodium sulfate
(Na2SO4) if necessary.
16. Decant the dried ester into a 250 ml flask and distill.
17. Collect the boiling fraction in the boiling point range listed for your particular flavor.
18. Using stoichiometry, determine the percent yield of your product and the boiling point.

40

SYNTHESIS OF SOAP
The production of soap is one of the oldest chemical procedures known to mankind. The
production of soap is through the alkaline hydrolysis (saponification) of a fat or oil to yield
soap and glycerol. Fats consist of a mixture of triglycerides, which are long chain fatty acid
esters usually from chains of 12 to 18 carbons.

R C O Na

R C O CH2

HO CH2

O
R C O CH

3 NaOH

R C O Na

HO CH

R C O Na

R C O CH2
triglyceride or fat

HO CH2

soap

sodium hydroxide

glycerol

Soap can clean by using its particular chemical structures.

O
C ONa
polar
hydrophilic

nonpolar
lipophilic

The soap molecule has a polar head which is soluble in water and a non-polar head which
is oil soluble. The water soluble head will dissolve in the water (hydrophilic)while the oil
soluble head will dissolve in the oil (lipophilic). Each droplet of oil becomes surrounded by
soap molecules. Repulsion by the positive water soluble head keeps the oil droplets
isolated from each other. When the water portion is removed, the oil portion is removed
with it. (Figure 1)

41

Since oil is what normally holds the dirt in place, removing the oil frees the dirt.

The type of water in which the soap dissolves is very important. Hard water (high mineral
content) which contains dissolved Mg and Na salts, will cause soap to precipitate out of
solution. The Mg and Ca ions replace the Na on the polar (hydrophilic) end. These salts
are insoluble in water (hydrophobic) and the soap precipitates as soap scum.

O
2

R C ONa
soap

O
+2

Ca

R C O Ca O C R

calcium ion

2 Na+1

scum

Sodium carbonate is often added to soaps to act as a water softener. The Na 2CO3
precipitates out the Ca and Mg ions before they can react with the soap

Na2CO3

+2

Ca

CaCO3

42

+
+ 2 Na

EQUIPMENT & CHEMICALS

5% MgCl2

(ethanol)

5% Na2CO3

NaOH pellets

Fat or oil

250 ml round bottom flask

Reflux apparatus

Vacuum filtration apparatus

PROCEDURE
1.

Add 20 ml of water, 20 ml of 95% ethanol and 6 grams of NaOH to a 200 ml round

bottomed flask.

2.

Add 6 grams of a fat or oil (lard, crisco, corn oil, etc.) to the flask.

3.

Reflux for 30 minutes.

4.

Pour the soap solution into 200 ml of a 10% NaCl solution.

5.

Cool to room temperature using an ice bath.

6.

Collect the precipitant by vacuum filtration.

7.

Dry and record the percent yield based on the grams of fat and grams of soap.

8.

Dissolve 1.0 grams of your soap in 50 ml of water.

9.

Place 10 ml into a test tube and shake. Observe the foam.

10. Add 10 drops of a 5% MgCl2 solution, shake and observe. What forms? Base this on
theoretical knowledge.
11. Repeat step 10, but add 10 drops of 5% Na 2CO3 first. State your observation and
explain.

43

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44

ESSENTIAL OILS OF PLANTS

Many plants have compounds within them that produce familiar odours or flavors. These
aromas are the result of volatile essential oils. These essential oils are often isolated from
the respective plant to produce concentrated natural flavorings. These essential oils may
be a combination of organic compounds.
Spices are well known for their flavor and odour. By using a process of steam distillation,
one can separate the essential oil from the organic bulk. One requirement of steam
distillation is that the compound to be removed is insoluble in water. This results in both
compounds distilling at a lower boiling point than the single pure compound.
Each immiscible liquid will exert its own vapour pressure over the liquid, independent of the
other liquid. The total pressure is the sum of the individual vapour pressures (Dalton's Law
of Partial Pressures). The total pressure must be equal to the atmospheric pressure.
Thus, the two compounds will distill at a lower temperature than their normal boiling points.
The oil is then separated from the condensed water using solvent extraction.

EQUIPMENT & CHEMICALS

125 ml dropping funnel
500 ml 3-neck flask
250 separating funnel
heating mantel
ground spice
methylene chloride
anhydrous sodium sulfate

EXPERIMENTAL OBJECTIVES
1. steam distillation
2. solvent extraction

PROCEDURE
1.

Add 15 grams of a ground spice to a 500 ml 3-neck round bottom flask.

2.

Add 150 ml of DI water to the flask.

45

(Figure 1)

3.

Add 125 ml DI to a dropping funnel and assemble the apparatus (Figure 1).

4.

Distill the mixture and add sufficient water from the dropping funnel to maintain the
original water level in the 3-neck flask.

5.

Continue the distillation until no further droplets of oil can be seen distilling over into
the condenser. This is normally after 100-150 ml of water has been collected.

6.

Extract the distillate in a 250 ml separating funnel twice using 15 ml of methylene

chloride each time. Combine the two methylene chloride extractions into a 50 ml
flask.

7.

Dry the methylene chloride over a small portion of anhydrous sodium sulfate.

8.

Decant of the methylene chloride into a pre-weighed dry 50 ml flask.

9.

Remove the methylene chloride by evaporating over a hot water bath. Do this in the
fume hood.

10.

Weigh the dried flask and determine the % yield compared to the original sample of
spice.

46

SYNTHESIS OF ACETYL SALICYLIC ACID FROM OIL

OF WINTERGREEN
Methyl Salicylate (oil of wintergreen) will be reacted with sodium hydroxide to form sodium
salicylate.
OH

ONa
COOCH3

COONa

2 NaOH

methyl salicylate

+ CH3OH +

H2O

sodium salicylate

Sodium methyl salicylate is reacted with sulfuric acid to remove the sodium salts and
produce salicylic acid.
ONa

OH
COONa

COOH

H2SO4

sodium methyl salicylate

Na2SO4

salicylic acid

Salicylic acid (o-hydroxy benzoic acid) will be reacted with acetic anhydride to form acetyl
salicylic acid (aspirin) that is insoluble in water.
O

C OH

O
+

H3C C O C CH3

OH
salicylic acid

C OH
O
O C CH3

acetic anhydride

acetyl salicyclic acid

This reaction will also produce a polymer type by-product that needs to be removed. The
aspirin is reacted with sodium bicarbonate to form a soluble salt. The polymer that is
insoluble is then filtered off.

47

C ONa

C OH

O
O

HCl

CH3

sodium acetyl salicylate

soluble in water

O
hydrochloric acid

CH3

acetyl salicylic acid

insoluble in water

The pH of the solution is then lowered with HCl. The addition of HCl converts the soluble
salt back into the water insoluble aspirin. The precipitated aspirin is then filtered and
collected.

O
C

O
ONa

C OH

O
O

HCl

CH3

sodium acetyl salicylate

soluble in water

O
hydrochloric acid

CH3

acetyl salicylic acid

insoluble in water

EQUIPMENT & CHEMICALS

Methyl salicylate
Acetic anhydride
Sodium bicarbonate (saturated)
Hydrochloric acid (conc)
Sulfuric acid (conc)
Sulfuric acid (3M)
Sodium hydroxide (6M)
200 ml beaker
125 ml Erlenmeyer flask
Vacuum filtration apparatus
200 ml reflux apparatus
PROCEDURE
Synthesis of Salicylic Acid from Oil of Wintergreen
1.

Add 3 ml of methyl salicylate (density = 1.184) to a 200 ml round bottom flask.

2.

Add 50 ml of 6M NaOH to the round bottom flask.

3.

Add a couple of boiling chips.

48

4.

Reflux for 45 minutes from the point the mixture starts to boil.

5.

If the after 45 minutes the reaction mixture still has oil or is cloudy, continue to
reflux.

6.

Once the mixture is clear and homogeneous, check to make sure that it no
longer smells of oil of wintergreen. If the smell still exists, continue to reflux.

7.

Remove the boiling chips and transfer to a 250 ml beaker.

8.

Slowing add 6M H2SO4 until the pH is 2.0.

9.

Cool the mixture in an ice water bath for 10 minutes.

10.

Vacuum filter and rinse with ice cold water.

11.

Dry and weigh.

12.

Using stoichiometry, calculate the percent yield.

Synthesis of Aspirin from Salicylic Acid

1.

Using the salicylic acid produced above, transfer to a clean and dry 125 ml
Erlenmeyer flask.

2.

Add a 3X molar excess of acetic anhydride to the flask.

3.

Slowly add 5 drops of concentrated sulfuric acid while swirling the flask (or use a
stirring bar and stirrer).

4.

Gently stir until all the salicylic acid dissolves.

5.

Heat the flask in a hot water bath for at least 15 minutes.

6.

Remove the flask from the hot water bath and allow the mixture to cool to room
temperature.

7.

The acetyl salicylic acid (aspirin) that was produced in the reaction should begin
to crystallize out of solution during the cooling. Note: if no precipitation occurs,
scratch the walls of the flask with a glass-stirring rod.

8.

After the aspirin has all precipitated and the solution is at room temperature, add
50 ml of water and place the flask in an ice bath.

9.

Vacuum filter the precipitate and rinse the flask with cold water until all the
crystals have been collected.

10.

Rinse the precipitate with several portions of cold water.

49

11.

Air-dry the precipitate in the Hirsch funnel for about 10 minutes.

12.

Transfer the crude aspirin to a 200 ml beaker.

13.

Add 25 ml of an aqueous sodium bicarbonate (saturated).

14.

Stir the mixture until all activity (bubbling) has stopped.

15.

Filter the solution through a Hirsch funnel to remove any polymers.

16.

Rinse with about 10 ml of water.

17.

Carefully add 3.5 ml of concentrated HCl to a 200 ml beaker that contains 10 ml

of H2O.

18.

Carefully pour the filtrate (in small portions) into the 200 ml beaker with constant
stirring.

19.

The aspirin should precipitate. If no precipitate occurs, add additional HCl until
the solution is acidic to litmus paper (blue to red) then proceed to the next step.

20.

Cool the solution in an ice bath to precipitate all the aspirin.

21.

Vacuum filter the precipitate and wash with ice cold water.

22.

Dry the precipitate overnight.

23.

Weigh the purified dried acetyl salicylic acid.

24.

Calculate the percent yield of aspirin from salicylic acid using stoichiometry.

25.

Calculate the overall percent yield based on the original methyl salicylate.

50