Dr.

Khan, 2023

Date: 5/30/23
Unknown Number (if needed): 24
Experiment 4

Extraction – Acid/Base Extraction

I. Objective: The concept of extraction is the removal of one or more materials from a
mixture (usually a solution) by using an immiscible solvent.
A pair of solvents is considered immiscible when they do not form a homogeneous
mixture when combined. A mixture of immiscible solvents will separate into layers when
combined due to the differences in the densities of the solvents. This process can be used to
separate the components of a solid mixture of an unknown organic acid and neutral. The
unknown solid will be dissolved in an organic solvent, and the acid component will react with
the addition of an organic base to the solution. The products of the acid-base reaction, which
include an aqueous salt of the acid (salt dissolved in water) and the unchanged organic neutral
component in the organic solvent, will be distributed between two layers formed by each
immiscible solvent. When the solutions are separated using the separatory funnel, the
components of the unknown solid can be extracted, dried, and identified using melting point
range. Example: extraction of caffeine from tea.
II. Theoretical Description: Extraction of a material is based on the relative solubility
difference of that material in two different ‘media’. In organic chemistry, these ‘media’ are
usually called solvents. If these media are both liquids the process is called a liquid-liquid
extraction. Solvents dissolve materials because of their structural (and therefore chemical)
similarity. For example; sugars are very soluble in water because the sugars have many
very polar -OH (hydroxyl) groups and water H-O-H, is essentially only hydroxyl groups.
Sugars are not soluble in hydrocarbons, like hexane (CH3-CH2-CH2-CH2-CH2-CH3). The
two solvents involved in an extraction must, by necessity, be immiscible!

A) Here are two examples:

1) Neutral solute: compounds of the flavinoid family known as flavonols can be obtained
from certain plant materials by processing in water. To purify and isolate the flavonols
you must extract them from the aqueous mixture using an organic solvent. The mixture
of flavonols in water is shaken with ethyl acetate and then the two solvents (water and
ethyl acetate) are left to separate into two distinct layers with a discernible interface. By
using a separatory funnel, the two different solvents can be physically separated. The
solute (the flavonols) will be distributed between the two different solvents. The partition
coefficient (comparison of the solubility of the solute in the two different solvents) will
help you calculate how much of the solute will be in each solvent. More on this later.
Dr. Khan, 2023

2) Acid or base as solute: para-toluic acid is rather soluble in organic solvents but poorly
soluble in water. But it can be removed from an organic solvent by extracting it with an
aqueous base (NaOH dissolved in water). The distribution will occur exactly like the
extraction described in 1) above, but it will distribute into the aqueous layer from the
organic layer.
So why does aqueous base help facilitate the extraction of para-toluic acid?
This is also known as chemically active extraction.

B) Partition (or Distribution) Coefficient

The best way to think about this is to start with a solute that is not in solution, then add a
mixture (Not a homogeneous mixture! Why?) of water (or aqueous acid or base) and an
organic solvent (such as diethyl ether). Swirl the solute with the solvent mixture until
everything is dissolved. Then let it stand, because two immiscible solvents were used,
you will have two layers. (Question: Which solvent will be on top, which on the
bottom?) So, some of the solute will be in the aqueous layer and some will be in the
organic layer. How much goes into each is decided by the different solubilities of the
solute in each solvent.
Here is the definition of partition coefficient (K):
Dr. Khan, 2023

The greater concentration is placed as the numerator, so K is greater than 1. This is just
how it is conventionally written, no one reports a K as less than 1!

Exercise: It is found experimentally that the insect repellant DEET (N,N-diethyl-m-

toluamide) has a maximum water solubility (at 250C) of 1.200 grams/mL.
DEET has maximum soluble in hexanes (at 250C) at 5.820 grams/mL.

What is the partition coefficient of DEET with water/hexane mixture?

(Do the calculation!)
K= 5.820 g/mL / 1.200 g/mL= 4.850

Do you think that the K of DEET will change if you used dichloromethane as the organic
solvent?
Probably, since the solubility of DEET in dichloromethane may be different than in hexanes.

III. The Experiment

Apparatus/Diagram (Label all parts clearly of a separatory funnel. Briefly describe how it
works.):

A separatory funnel is used to

separate immiscible liquids.
When a mixture of two solvents
is placed in the funnel, the denser
of the two will settle at the
bottom, leaving the solvents in
two layers. The funnel can then
be used to drain out the solvent
in the lower layer, separating it
from the less dense solvent.
 Dr. Khan, 2023

Table of Physical Constants: (This table should be completely filled when the experiment is done.)
Compound Structure Molar Moles Mass/ Physical Chemical
Properties
Name Mass Volume Hazards
(MP, BP,
density/SG)
Organic Acids 122.12 0.0100 1.216 g Toxic, Hazardous
g/mol mol
MP: 122.4°C
Benzoic Acid BP: 249.2°C
SG: 1.2659

156.57 n/a n/a MP: 138.0- Toxic, Hazardous

g/mol 140.0 °C
ortho-
Chlorobenzoic BP: 285 °C
acid
SG: 1.544
 Dr. Khan, 2023

Organic Neutrals 154.21 0.0085 1.310g MP: 68.5- Toxic, Hazardous

g/mol mol 71°C
BP: 255°C
Biphenyl
SG: 0.991

128.16 n/a n/a MP: 79.0-82.0 °C Toxic, Hazardous

g/mol BP: 218 °C
Naphthalene
SG: 0.990

147.00 n/a n/a MP: 53°C Toxic, Hazardous

g/mol
para- BP: 174°C
Dichlorobenzene
SG: 1.458

Reactions and Mechanisms:

Draw any and all reactions that
occur in the extraction procedure
(chemically active extraction).

Experimental Procedure:
Prelab: In this experiment, you will be given a solid, binary mixture containing one of the list
organic acids and one of the organic neutrals. It is your job to use chemically active (acid/base)
extraction to separate these two components. You will then collect each, as a solid, by the
procedures given below. The solids must be dried, free of water and/or organic solvent, and the
Dr. Khan, 2023

MP and mass or each measured individually. Finally, you must report the identity of the two
materials using MP as your data...so, having the solids pure and free of any solvents is important!
Laboratory procedure:
1. Obtain about 3 grams of unknown from the lab instructor. Record the total mass using
every digit shown on the balance! Place all the unknown into a 125 mL Erlenmeyer flask
and dissolve in diethyl ether (50 mL). Transfer this solution to a 125 mL separatory funnel
and add 3M aqueous NaOH solution (50 mL). There should be two liquid layers. Shake
gently but thoroughly for a few minutes. Place the separatory funnel in a ring stand and
allow the layers to separate. Drain the lower layer into a clean 250 mL Erlenmeyer flask.
Is this the diethyl ether layer or the aqueous layer? Label as such.
2. Add a fresh portion of 3M aqueous NaOH (50 mL) to the separatory funnel (it still has the
50 mL ‘upper’ layer in it), and repeat the shaking process. Allow the layers to separate and
drain the bottom layer into the Erlenmeyer that contains the first 50 mL that were drained
from the separatory funnel. Place this Erlenmeyer flask into a shallow ice water bath.
3. Drain the remaining solution from the separatory funnel (the ether layer) into a clean 125
mL Erlenmeyer flask. To this add a couple of spatulas of MgSO4 (magnesium sulfate
anhydrous). This is known as a drying agent. There are several drying agents that are used
in organic chemistry: sodium sulfate, calcium chloride, potassium carbonate and
magnesium sulfate (all anhydrous) are most widely used. Their role is to remove water
from organic solutions. They are very effective in doing this. Occasionally swirl the
drying agent in the organic solution. Allow the drying agent to be in contact with the
organic solution for about 5 minutes. If the drying agent does not swirl freely, add another
spatula full.
4. Using gravity filtration, remove the drying agent from the organic solution. Filter the
liquid into a tared (previously weighed and recorded) 125 mL round bottom flask. The
diethyl ether will be evaporated using a piece of equipment called a rotary evaporator.
Your instructor will show you how this is done. When the organic solvent is completely
evaporated a solid residue will be in the flask. Which class of the 2 components (organic
acid or organic neutral) is this? Think, but your MP data should help you confirm.
Reweigh the flask with the residue and record the mass of the organic solid. Scrap the
solid from the flask and collect it. Pack a MP capillary or two and measure the MP. Place
the solid into a labeled vial.
5. In a clean 25 mL Erlenmeyer flask, cool 10 mL of distilled water in an ice bath.
To the cooled aqueous extract (from step 2) slowly (but not drop by drop!) add 6M aq. HCl
(about 100mL) until the pH is about 2 to 3. White solid should form. Use pH indicator
paper to check the pH by removing liquid from the flask and putting it on the paper. Do
NOT immerse the paper into the flask. Collect the solid by vacuum filtration and wash the
solid with a few milliliters of the ice cold distilled water. Allow the solid to remain in the
vacuum filtration (with the water running) for several minutes. Using paper towels and a
large piece of filter paper, squeeze any remaining water from the solid. Press down hard
under your weigh on a benchtop, the paper should absorb the water. Do this until the solid
is dry.
Dr. Khan, 2023

Measure the mass of this collected solid and determine its MP. Place the solid into a
labeled vial.
Flow Diagram:
Dr. Khan, 2023

Calculations:
Mass of watch glass: 153.694g
Mass of watch glass and organic neutral: 155.004g
Mass of organic neutral: 155.004g-153.694g= 1.31000g
Percent yield (organic neutral): (1.31000g/3.00g)*100= 43.7%

Mass of weighing dish: (tared)

Mass of weighing dish (tared) and organic acid: 1.261g
Mass of organic acid: 1.261g
Percent yield (organic acid): (1.261g/3.00g)*100= 42.0%

43.7% + 42.0% = 85.73% (more than 100% indicates one or both compounds were not
completely dry when measured. less than 100% indicates loss of mass from one or both
compounds.)

Table of Experimental Data:

Compound Structure Literature Observed Mass Theoretic Percent
Melting Melting al Yield (%)
(g)
Point (°C) Point (°C)
Yield (g)
Organic 122.4°C 118-122°C 1.261gg n/a 42.0%
acid:
Benzoic
Acid
Dr. Khan, 2023

Organic 68.5-71°C 70-71°C 1.3100g n/a 43.7%

neutral:
Biphenyl

Unknown #24: identified as Benzoic acid and Biphenyl

Conclusion:
Two organic compounds that were unknown were extracted by utilizing liquid-liquid
multiple extraction. A diethyl ether solvent was used to dissolve the solvent and then placed in a
separatory funnel. To form an aqueous base, sodium hydroxide was added to the solution to
cause an acid-base reaction with the organic acid. The aqueous base drained from the separatory
funnel was precipitated using hydrochloric acid solution (hydrolysis of the salt), then vacuum
filtered to isolate the organic acid. The melting point apparatus is used to measure and test the
dried organic acid. The melting point was within the following range: 118-122°C. This melting
point is a lower and broader range than the literature melting point for Benzoic acid, indicating
that this was the compound but there were impurities in the sample.
Anhydrous magnesium sulfate was used as a drying agent and added to the upper layer of
the separatory funnel after it was drained into another flask. In order to isolate the organic neutral
the solution was then filtered by using the gravity filtration process, then heated and dried on top
of a steam bath. The organic neutral that remained was measured and tested with the melting
point apparatus. The melting point was observed to be between 70-71°C, which is within the
literature range of the compound Biphenyl.
The percent yield between the two recovered compounds was below 100%. This meant
that there was a loss of mass from one or both compounds during the procedure (experimental
error).

MSDS Archive:
MSDS*: (Computer generated Material Safety data Sheets (MSDS) of each chemical used. You
must use a highlighter to highlight names of compounds and the section numbers. FOR
EXAMPLE:
Sections: 1 (chemical’s name and all synonyms); 2 (Hazard Identification.); 3 (Composition /
information on ingredients); 9 (Physical and chemical properties)
Dr. Khan, 2023

Benzoic acid Biphenyl

Section 1: Section 1:
Name: Benzoic acid Name: Biphenyl
CAS#: 65-85-0 CAS#: 92-52-4
RTECS: DG0875000 RTECS: DU8050000
Synonyms: Benzenemethanoic acid; Synonyms: Diphenyl
Benzenecarboxylic acid; Phenylcarboxylic acid; Chemical Formula: C12H10
Phenylformic acid; Carboxybenzene; Benzeneformic Section 2:
acid; Dracylic acid CAS#: 92-52-4 99%
Chemical Formula: C7H6O2 Section 3:
Section 2: Potential acute health effects: Causes eye irritation.
CAS#: 65-85-0 >99% Causes skin [Link] cause irritation of the
Section 3: digestive tract if swallowed. Causes respiratory tract
Potential acute health effects: Causes severe eye irritation if inhaled.
irritation, redness and pain. Causes skin irritation. Section 9:
May cause sensitization by skin contact. Absorption Physical state/appearance: crystals
through the skin has produced labored breathing in Molecular weight: 154.21 g/mol
humans. Can cause redness and swelling with itching Color: white/pale yellow
(non-immunological contact urticaria or hives) in Boiling Point: 255°C
most people at the site of application. Harmful if Melting Point: 68.5-71°C
swallowed. May cause irritation of the digestive Specific Gravity: 0.991
tract. Vapor pressure: 9.46 mm Hg @ 115 deg C
Causes respiratory tract irritation if inhaled. May Vapor Density: 5.31
cause respiratory sensitization. Solubility: insoluble
Potential chronic health effects: Prolonged or
repeated skin contact may cause dermatitis
Section 9:
Physical state/appearance: Crystalline powder
Molecular weight: 122.12 g/mol
Color: white
Boiling Point: 249.2°C
Melting Point: 122.4°C
Specific Gravity: 1.2659
Vapor pressure: 0.0012 mm Hg @ 25 deg C
Vapor Density: 4.21
Solubility: 3.4 g/l @ 25°C
Dr. Khan, 2023

Magnesium Sulfate anhydrous Diethyl Ether

Section 1:
Section 1:
Name: Diethyl Ether
Name: Magnesium sulfate, anhydrous
CAS#: 60-29-7
CAS#: 7487-88-9
RTECS: KI5775000
RTECS: OM4500000
Synonyms: Ethyl ether, ethyl oxide, ether
Chemical formula: MgO4S
Chemical formula: C4H10O
Section 2:
Section 2:
CAS#: 7487-88-9 97%
CAS#: 60-29-7 99%
Section 3:
Section 3:
Potential acute health effects: May cause eye
Potential acute health effects: May cause
irritation. May cause skin irritation. May be
drowsiness, headache, unconsciousness, or
harmful if absorbed through the skin. May
vomiting if inhaled. Skin contact may cause dry
cause gastrointestinal irritation with nausea,
skin. Eye contact may cause redness and pain.
vomiting and diarrhea. May be harmful if
Ingestion may cause dizziness, drowsiness,
swallowed. May cause respiratory tract
vomiting.
irritation. May be harmful if inhaled.
Potential chronic health effects: Prolonged or
Potential chronic health effects: Laboratory
repeated skin contact may cause defatting and
experiments have resulted in mutagenic
dermatitis. Prolonged or repeated exposure can
effects.
cause psychic abnormalities such as anxiety,
Section 9:
depression and excitability.
Physical state/appearance: solid
Section 9:
Molecular weight: 120.37 g/mol
Physical state/appearance: liquid
Color: white to grey-white
Molecular weight: 74.1 g/mol
Melting Point: 1124 °C (decomposes)
Color: colorless
Specific Gravity: 2.65
Boiling Point: 35 °C
Solubility: soluble
Melting Point: -116 °C
Specific Gravity: 0.7
Vapor pressure: 58.6 mmHg @ 20°C
Vapor density: 1.9
Solubility: 6.9 g/L (20°C)
Dr. Khan, 2023

Sodium Hydroxide solution Hydrochloric Acid solution

Section 1:
Section 1:
Name: Hydrochloric acid, 6M
Name: Sodium Hydroxide, 3M
CAS#: 7647-01-0 (HCl), 7732-18-5 (water)
CAS#: 1310-73-2 (NaOH), 7732-18-5 (water)
RTECS: MW4025000 (HCl), ZC0110000
RTECS: WB4900000 (NaOH), ZC0110000
(water)
(water)
Synonyms: Muriatic acid; Chlorohydric acid;
Chemical formula: NaOH (Water, H2O)
Hydrogen chloride solution.
Section 2:
Chemical formula: HCl (water, H2O)
CAS#: 1310-73-2 12%
Section 2:
Section 3:
CAS#: 7647-01-0, 22%
Potential acute health effects: Causes eye
Section 3:
burns. May cause lacrimation (tearing),
Potential acute health effects: May cause
blurred vision, and photophobia. May cause
irreversible eye injury. Vapor or mist may
chemical conjunctivitis and corneal damage.
cause irritation and severe burns. Contact with
Causes eye burns. May cause lacrimation
liquid is corrosive to the eyes and causes
(tearing), blurred vision, and photophobia.
severe burns. May cause painful sensitization
May cause chemical conjunctivitis and corneal
to light. May be absorbed through the skin in
damage. May cause severe and permanent
harmful amounts. Contact with liquid is
damage to the digestive tract. Causes
corrosive and causes severe burns and
gastrointestinal tract burns. May cause
ulceration. May cause circulatory system
perforation of the digestive tract. Causes
failure. Causes severe digestive tract burns
severe pain, nausea, vomiting, diarrhea, and
with abdominal pain, vomiting, and possible
shock. Irritation may lead to chemical
death. May cause corrosion and permanent
pneumonitis and pulmonary edema. Causes
tissue destruction of the esophagus and
severe irritation of upper respiratory tract with
digestive tract.
coughing, burns, breathing difficulty, and
May cause severe irritation of the respiratory
possible coma. May cause systemic effects.
tract with sore throat, coughing, shortness of
Potential chronic health effects: Prolonged or
breath and delayed lung edema. Causes
repeated skin contact may cause dermatitis.
chemical burns to the respiratory tract.
Effects may be delayed.
Exposure to the mist and vapor may erode
Section 9:
exposed teeth. Causes corrosive action on the
Physical state/appearance: liquid
mucous membranes.
Molecular weight: 39.997 g/mol
Potential chronic health effects: Prolonged or
Color: colorless
repeated skin contact may cause dermatitis.
Boiling Point: 100 °C
Repeated exposure may cause erosion of teeth.
Melting Point: 0 °C
May cause fetal effects. Laboratory
Specific Gravity: approximately 1
experiments have resulted in mutagenic
Vapor pressure: 14 mmHg @ 20°C
effects. Prolonged exposure may cause
Vapor density: >1
conjunctivitis, photosensitization, and possible
Solubility: soluble in water.
blindness.
Section 9:
Physical state/appearance: liquid
Molecular weight: 36.46 g/mol
Color: colorless to slight yellow
Boiling Point: 81.5-110 °C
Melting Point: -74 °C
Specific Gravity: 1.0-1.2
Vapor pressure: 5.7 mmHg @ 0°C
Vapor density: 1.26
Solubility: miscible