Separation of Organic Compounds by

Acid-Base Extraction Techniques

A commonly used method of separating a mixture of organic compounds is known as
liquid-liquid extraction. Most reactions of organic compounds require extraction at some stage of
product purification. In this experiment you will use extraction techniques to separate a mixture of
an organic acid, a base, and a neutral compound.
Organic acids and bases can be separated from each other and from neutral compounds by
extraction using aqueous solutions of different pH values. Most organic carboxylic acids are
insoluble or slightly soluble in water, but these compounds are highly soluble in dilute aqueous
sodium hydroxide because the acid is deprotonated by the base producing the sodium carboxylate
salt.
RCO2H(solv) + OH(aq) RCO2(aq) + H2O(aq)
The carboxylic acid can be selectively isolated by dissolving the mixture in an organic solvent that
is immiscible with water, and then extracting the solution with sodium hydroxide. The basic
aqueous solution containing the carboxylate salt is acidified, causing the sodium carboxylate salt
to convert back to the carboxylic acid, which is not water soluble. The acid will precipitate from
the solution, as shown here.
RCO2(aq) + H+(aq) RCO2H(s)
Organic bases (e.g., amines) that are insoluble in water can be separated by extraction with
hydrochloric acid. Addition of HCl to the amine produces the corresponding ammonium salt,
which is soluble in water but not in organic solvents.
RNH2(solv) + H+(aq) RNH3+(aq)
The amine can be recovered from the aqueous solution by treatment with a base, converting the
ammonium salt back to the amine. The amine is not water-soluble and will precipitate, as shown
here.
RNH3+(aq) + OH(aq) RNH2(s) + H2O(aq)
Using your understanding of these properties, separation of a mixture containing a carboxylic
acid, an amine, and a neutral compound can be carried out via sequential acid and base
extractions. The precipitates will be collected and characterized by melting temperature analysis.

OBJECTIVES
In this experiment, you will

Separate a mixture containing benzoic acid, 3-nitroaniline, and naphthalene.

Calculate the percent recovery of each component in the mixture.
Measure the melting temperature of each isolated compound.

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MATERIALS
Part I Extraction

60 mL separatory funnel
four 50 mL Erlenmeyer flasks
two 100 mL beakers
ring stand with filtering funnel and ring
filter paper
ring stand with utility clamp
Bchner funnel
filtering flask
spatula
disposable Pasteur pipets and bulb
10 mL graduated cylinder
two watch glasses
pH paper

balance
weighing paper
sample mixture
diethyl ether
6.0 M hydrochloric acid solution
1.0 M sodium hydroxide solution
6.0 M sodium hydroxide solution
sodium sulfate, Na2SO4, anhydrous
cold distilled water in a wash bottle
saturated sodium chloride solution
ice
compressed air

Part II Melting Temperature

LabQuest or computer interface

LabQuest App or Logger Pro
Vernier Melt Station
glass capillary tubes, one end closed
tissues (preferably lint-free)

isolated samples from Part I

mortar and pestle
benzoic acid (optional)
3-nitroaniline (optional)
naphthalene (optional)

PROCEDURE
Part I Extraction

1. Obtain and wear goggles. Protect your arms and hands by wearing a long-sleeve lab coat and
gloves. Conduct this reaction in a fume hood.
2. Weigh out approximately 1.0 g of the sample mixture. Record the mass to the nearest 0.01 g.
Transfer the mixture to a 100 mL beaker and dissolve it in 15 mL of diethyl ether.
CAUTION: Diethyl ether is flammable. Be sure that there are no open flames in the room
during the experiment.
3. Clamp the support ring onto a ring stand and place the separatory funnel into the ring. Pour
the solution into the separatory funnel and add 5 mL of 6.0 M hydrochloric acid.
CAUTION: Handle the hydrochloric acid with care. Can cause painful burns if it comes in
contact with the skin.
4. Cap the funnel and gently shake several times, venting frequently to avoid pressure build-up.
When venting the funnel, point the tip away from your face and open the stopcock to release
the pressure. Place the funnel on a support ring with a clamp and allow the solvent and
aqueous layer to separate. Leave the funnel uncapped.
5. Drain the lower aqueous layer into a 50 mL Erlenmeyer flask. Repeat the extraction with
another 5 mL of 6.0 M hydrochloric acid, draining the second aqueous layer into the same
Erlenmeyer flask. Save the solvent layer in the separatory funnel for later use.

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Separation of Organic Compounds by Acid-Base Extraction Techniques

6. Cool the flask containing the acidic aqueous extracts into an ice water bath. Slowly add 6.0 M
sodium hydroxide with a pipet until the aqueous layer is basic. Use pH paper to test.
CAUTION: Sodium hydroxide solution is caustic. Avoid spilling it on your skin or clothing.
7. Set up a vacuum filtration.
a. Weigh the filter paper and record the mass to the nearest 0.01 g.
b. Place a Bchner funnel and filter paper on the filtration flask.
c.
Collect the precipitate by vacuum filtration. Wash the filtrate with 2 mL of cold
distilled water.
d.
Place the filter paper containing the solid on a watch glass and gently direct a
stream of air (low flow) to thoroughly dry the solid.
e.
Weigh the recovered solid and record the mass to the nearest 0.01 g.
f.
Save the solid for the melting temperature analysis in Part II.
8. Extract the saved ether layer in the separatory funnel with three 5 mL portions of
1.0 M sodium hydroxide. Drain the aqueous layer into a 50 mL Erlenmeyer flask. Save the
ether layer in the separatory funnel.
9. Cool the flask containing the basic aqueous extract in an ice water bath. Using a pipet, slowly
add 6.0 M hydrochloric acid until the aqueous layer is acidic. Use pH paper to test.
CAUTION: Handle the hydrochloric acid with care. Can cause painful burns if it comes in
contact with the skin.
10. Set up a vacuum filtration.
a. Weigh the filter paper and record the mass to the nearest 0.01 g.
b. Place a clean Bchner funnel and filter paper on the filtration flask.
c. Collect the precipitate by vacuum filtration. Wash the filtrate with 2 mL of cold distilled
water.
d. Place the filter paper containing the solid on a watch glass and gently direct a stream of air
(low flow) to thoroughly dry the solid.
e. Weigh the recovered solid and record the mass to the nearest 0.01 g.
f. Save the solid for a melting temperature analysis.
11. Add 10 mL of saturated aqueous sodium chloride solution to the ether solution remaining
in the separatory funnel and shake gently. Be sure to vent frequently.
12. Allow the layers to separate and discard the lower aqueous sodium chloride layer. Pour
the solvent layer into an Erlenmeyer flask containing approximately 1 g of anhydrous sodium
sulfate and allow it to stand for about 10 minutes, swirling occasionally.
13. Set up a gravity filtration.
a. Place a filtering funnel into a ring on a ring stand.
b. Weigh the filter paper and record the mass to the nearest 0.01 g. Place the filter paper into
the funnel.
c. Filter the contents in the flask, including the sodium sulfate, into a clean 100 mL beaker.
d. Direct a gentle stream of air at the beaker to evaporate the ether. As the ether evaporates,
a solid will begin to crystallize in the beaker. CAUTION: Diethyl ether is flammable. Be
sure that there are no open flames in the room during the experiment. Do not leave
unattended.

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14. Weigh the recovered solid and record the mass to the nearest 0.01 g. Save the solid for the
melting temperature analysis in Part II.
Part II Melting Temperature

15. Obtain a small amount of the isolated solid from the acid extraction. The solid should be in
a powdered form. If it is not, use a mortar and pestle to carefully grind the solid to a powder.
16. Prepare a sample for melting.
a. Pack a capillary tube 34 mm (~1/8 inch) deep with your sample by inserting the open end
into a small pile of the solid. A small amount of the solid will be pushed up into the tube.
b. Tap the closed end of the capillary tube on the table top to compress the sample into the
closed end.
c. Check the control knob on the Melt Station to confirm that it is in the Off position.
d. Carefully insert the capillary tube of solid into one of the sample holders of the Melt
Station.
17. Connect the Melt Station power supply to a powered electrical outlet.
18. Connect the Melt Station sensor cable to LabQuest or to a computer interface.
19. Start the data-collection program, then choose New from the File menu. You are now set
up to take melting temperature data for up to 20 minutes.
20. In the first trial, you will want to observe the melting process and make a rough estimate
of the melting temperature of your sample. Dont worry if the heating rate is a bit too rapid,
and the sample melts too quickly. To do this:
a. Start data collection.
b. On the Melt Station, turn the control knob to a setting of 180C. The red light will turn on
indicating active heating.
c. Carefully observe your sample. If the solid begins to melt, click Mark to mark the
temperature on your graph (or press the D key on the computer or the OK button on
LabQuest). When the entire solid has completely melted, click Mark again. The two values
marked on your graph describe the estimated melting temperature range of your substance.
d. If the solid does not melt by the time the temperature gets to 150C, turn the control knob
to the 220C setting. Continue observing your sample, and if the sample begins to melt,
mark the temperatures on the graph as previously described.
e. If the sample has not melted by the time the temperature gets to 190C, turn the knob to
the Rapid Heat setting. When the sample finally begins to melt, mark the graph as
previously indicated.
f. When you have determined the approximate melting temperature range for the sample,
stop data collection. Store the run by tapping the File Cabinet icon in LabQuest, or
choosing Store Latest Run from the Experiment menu in Logger Pro. Discard the capillary
tube and sample as directed by your instructor.
g. On the Melt Station, turn the control knob to the Fan/Cooling setting to get ready for the
next trial. The blue light will turn on indicating that the fan is cooling the Melt Station.

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Separation of Organic Compounds by Acid-Base Extraction Techniques

21. Now that you have a rough idea of the melting temperature, a more accurate
determination of the melting temperature can be made. Use a previously prepared sample in a
capillary tube, as described in Steps 1516, to determine the melting temperature of the
sample:
a. Start data collection.
b. On the Melt Station, turn the control knob to the Rapid Heat setting.
c. Carefully observe the temperature vs. time graph. When the temperature is within
approximately 10C of the lowest possible melting temperature of your sample, turn the
control knob to a temperature setting corresponding to your expected melting temperature.
d. Carefully observe your sample. When the solid begins to melt, click Mark to mark the
temperature on your graph. When the entire solid has completely melted, click Mark again.
The two values marked on your graph describe the estimated melting temperature range of
your substance. When you are finished with this step, stop data collection.
e. Store the run.
f. Discard the capillary tube and sample as directed by your instructor.
g. On the Melt Station, turn the control knob to the Fan/Cooling setting to get ready for the
next trial.
22. Repeat Step 21 until you have determined the melting temperature range of the solid.
Record the range in the data table.
23. Repeat Steps 2021 for the isolated solids from the base and neutral extractions.
24. At the end of the experiment, turn the control knob on the Melt Station to Off.

DATA TABLE
Part I Extraction
Mass of mixture (g)
Mass of sample recovered
(g)
Benzoic acid
3-Nitroaniline
Napthalene
Part II Melting Temperature
Measured melting temperature range
(C)
Benzoic acid
3-Nitroaniline
Napthalene

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DATA ANALYSIS
1. Draw the structure of each of the compounds.
2. Outline a flow chart describing the separation of the mixture and the isolation of each
compound.
3. What was your percent recovery for each of the three compounds? Assume equal amounts of
the carboxylic acid, amine, and neutral compound were present in the unknown mixture.

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Separation of Organic Compounds by Acid-Base Extraction Techniques

INSTRUCTOR INFORMATION
1. The sample mixture can be prepared with 1:1:1 benzoic acid, 3-nitroaniline, and naphthalene
by mass.
2. The melting temperature ranges of benzoic acid, 3-nitroaniline, and naphthalene are
121123C, 111114C, and 8082C, respectively. Note: If you want to shorten the amount
of time students spend determining these melting temperatures, you could let them know these
three expected melting temperatures ahead of time.
3. Prepare the 6.0 M hydrochloric acid solution by adding 493 mL of concentrated HCl to
distilled water for 1 L of solution. Note: Add acid to water, never water to acid.
4. Prepare the 1.0 M sodium hydroxide solution by adding 40 g of solid NaOH to enough
distilled water for 1 L of solution.
5. Prepare the 6.0 M sodium hydroxide solution by adding 240 g of solid NaOH to enough
distilled water for 1 L of solution. CAUTION: Heat is released. The reaction is exothermic.
6. Prepare a saturated aqueous sodium chloride solution by adding NaCl in distilled water until it
no longer dissolves and a shallow layer of NaCl is visible at the bottom of the bottle.
7. The filter paper can either be fluted or folded in quarters for gravity filtration.
8. Dry each sample thoroughly before taking a melting temperature.
9. The level of peroxide formation in diethyl ether can vary depending on the length of
exposure to air, light, and the container type. Periodically test for peroxides and do not store
for a long period of time.
10. Dispose of hazardous waste properly.

HAZARD ALERTS
Hydrochloric acid: Highly toxic by ingestion or inhalation; severely corrosive to skin and eyes;
wear gloves and eye protection when using this substance. HMIS Classification: Health hazard3,
Flammability0 Physical hazard0.
Sodium Hydroxide: Corrosive solid; skin burns are possible; much heat evolves when added to
water; very dangerous to eyes; wear gloves and eye protection when using this substance. HMIS
Classification: Health hazard3, Flammability0, Physical hazard2.
Benzoic acid: Slightly toxic by ingestion; body tissue irritant; combustible. HMIS Classification:
Health hazard2, Flammability1, Physical hazard0.
Diethyl ether: Serious fire hazard (flash point 40.0C). Irritating to body tissues. Moderately
toxic by ingestion. Vapor causes weakness, fatigue, nausea and headache. Skin and eye irritant.
HMIS Classification: Health hazard2, Flammability4, Physical hazard2.
3-Nitroaniline: May cause respiratory tract irritation. Skin and eye irritant. Moderately toxic by
ingestion. HMIS Classification: Health hazard2, Flammability1, Physical hazard0.

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Naphthalene: Toxic by inhalation and ingestion. Skin and eye irritant. May be harmful if absorbed
through the skin. HMIS Classification: Health hazard3, Flammability0, Physical hazard2.
Sodium sulfate: May cause respiratory tract irritation. Skin and eye irritant. Moderately toxic by
ingestion. HMIS Classification: Health hazard0, Flammability0, Physical hazard0.
Sodium chloride: May cause respiratory tract irritation. May cause skin and eye irritation. HMIS
Classification: Health hazard1, Flammability0, Physical hazard0.
Thehazardinformationreferenceis:
SigmaAldrichCo.,18003253010,www.sigmaaldrich.com/safetycenter/msdssearch.html

COMPOUND INFORMATION

Compound

Chemical formula

Melting temperature
range (C)

Molar mass
(g/mol)

benzoic acid

C7H6O2

121125

122.1

3-nitroaniline

C6H6N2O2

111114

138.1

naphthalene

C10H8

8082

128.1

sodium sulfate

Na2SO4

884

142.0

sodium hydroxide

NaOH

318

40.0

sodium chloride

NaCl

801

58.4

Compound

Chemical formula

Molar mass (g/mol)

Density (g/mL) at 25C

diethyl ether

C4H10O

74.1

0.706

Compound

Chemical formula

Concentration (%)

Density (g/mL) at 25C

hydrochloric acid

HCl

37

1.12

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Separation of Organic Compounds by Acid-Base Extraction Techniques

SAMPLE RESULTS

Melting temperature graph of benzoic acid.

Melting temperature graph of 3-nitroaniline.

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Melting temperature graph of naphthalene.

10

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