Introduction

Extraction involves selectively removing one or more compounds from a solid,

liquid, or gaseous mixture into a separate phase. The substance being extracted will
partition between two immiscible phases that are in contact. The distribution of
these two phases is the result of the partitioning phenomena-which involves the
difference in solubilitys of a substance in two immiscible solvents (selective
dissolution). Liquid-liquid extraction is one of the most common methods for
removing an organic compound from the mixture. It distributes a solute, A, between
two immiscible liquids,

S x , the extracting phase, and

S o , the original phase.

The two immiscible liquids are usually water and an organic solvent-such as diethyl
ether or dichloromethane. The amount of A at a given temperature in g/mL in each
phase is expressed in terms of the constant, K (partition coefficient)-Equation 1.1.

K=

[ A ] S x
[ A ] S o
Equation 1.1

Several extractions with smaller volumes are preferred over one extraction with a
large volume of extracting solvent. An example that would quantify this would be
that for a coefficient of K=5, a single extraction with 30 mL of diethyl ether would
obtain FA=1/16, and with the three extractions of 10 mL portions the FA=1/216. This
would mean that 6.3% of A remains in the aqueous phase when one extraction is
performed, and it is 0.5% when three successive extractions of the same total
volume of the solvent are used. To calculate this we would use Equation 1.2 where
FA= the fraction of A still in the original solvent,
final and initial concentration of the solvent,

Vo

Cf

and

and

Ci

which equal the

V x , which equal the

volume-in mL- of the original and extracting solvents, respectively, K=partition

coefficient, and n=number of extractions performed.

Cf
Vo n
FA= =
Ci KV x +V o
Equation 1.2
To isolate and purify the compounds through extraction the selection of the
appropriate extracting solvent is very important; therefore, certain guidelines
should be followed. The extracting solvent must not react in a chemically
irreversible way with the components of the mixture, it must be immiscible-or
nearly so with the original solution, it must selectively remove the desired
component from the solution being extracted, and the extraction solvent should be
readily separable from the solute with either simple distillation, evaporating the
solvent, vacuum distillation, or some other technique of separation of the solvent
from the solute.
To increase the percent recovery the right type of extraction and separation should
be used. pKa values should be taken into consideration, and the amounts of solvent
used should be reasonable. One base extraction is a technique that can be used to
separate carboxylic acids and phenols (Reaction 1.1 and Reaction 1.2) from solution
because they have functional groups that are polar and hydrophilic. Unless they
contain fewer than six carbon atoms, then such compounds are usually slightly
soluble or insoluble in water because the R/Ar (carbon containing) part of the
molecule.

Reaction 1.1

Reaction 1.2
Once the organic solution is extracted with a basic aqueous solution, the organic
acid will be converted into a conjugate base. If the basic extract is neutralized, then
the conjugate base will be protonated to regenerate the organic acid. Since acid in

water is insoluble, it will appear as either a precipitate or a second layer (liquid).

Organic acid can then be obtained by filtration of separation of the layers. The two
water insoluble compounds (acidic and neutral) that are dissolved in organic solvent
can be separated by selectively extracting the acidic compound into a basic
aqueous phase. Once the aqueous and organic phase are separated the acidic
compound can be recovered with neutralization, and the neutral compound can be
recovered by removing the organic solvent. The difference between this type of
extraction, and a one base extraction is that this one is done two times with two
different bases. .
Acid base extraction is a technique that can be used to separate three-component
mixtures. With this extraction a strong acid is used because amines are usually
soluble in aqueous acids where the pH<4. This happens because they are converted
into their respective ammonium salts (Reaction 1.3). When the aqueous phase
(acidic solution) is neutralized with the aqueous base, the ammonium ion is
deprotonated and converted into the original water insoluble organic base. The
organic phase of the first extraction is then extracted with a strong base, and the
aqueous phase of the extraction is neutralized with acid to get the acid. The solvent
is then removed from the organic layer.

Reaction 1.3
Data and Observations
Compoun

Starting

Final

Molecula

Melting

Percent

d Name

Weight of

Weight of

r Weight

Point of

Recovery From

and

Mixture

Compound

of the

Final

the Mixture

Structure

Product

Material

Benzoic

in g/mol
122 g/mol

118C-

Acid

2.042

1g

0.919
8g

45% (One
Base)
29% (Two
Base)
17%

121C

(One

(One

Base)
2.009

Base)
0.577

Naphthale

8g

2g

(Acid-

(Two

(Two

Base)

Base)
1.550

Base)
0.266

2g

(Acid-

(Acid-

Base)
2.0421 g

Base)
0.7294 g

128 g/mol

ne

76C-

36%

81C

2-

2.0098 g

0.4531 g

Naphthol
4-

1.5500 g

0.366 g

Nitroanilin

144.17

116C-

g/mol

121C

138.12

142C-

g/mol

146C

23%

24%

One Base Extraction:

-pH of aqueous layer2.0 (very strong-very acidic)
-Temperature of distillation: 34C
-15 mL of HCl added to Hydroxide Extract (Benzoic Acid)
-81% of total mixture recovered
Two Base Extraction:
-22 mL of HCl added to Hydroxide Extract (Benzoic Acid)
-Very Acidic pH2
-10 mL of HCl added to Bicarbonate Extract (2-Naphthol)
-Very Acidic pH2
-52% of total mixture recovered (naphthalene was not extracted in this experiment).
Acid Base Extraction:

-There was a black color that appeared when doing the extraction with
dichloromethane.
-15 mL of HCl added Hydroxide Extract (Benzoic Acid)
-pH2 very acidic
-22 mL of NaOH added to HCl Extract (4-Nitroaniline)
-pH7 very basic
-41% of total mixture recovered (naphthalene was not extracted in this experiment)
Discussion
The mechanisms are attached on paper after the conclusion.
pKa of reactants:
Benzoic Acid: 4.2 (Strong Acid)
Naphthalene: No pKa because it is neutral
2-naphthol: 9.5
4-nitroaniline: 1.0
Carbonic Acid: 6.4
Any base whose conjugate acid has a pKa greater than the pKa of the acid will yield
a value of log 10 Keq> 1 . The reaction where the extraction will be close to 100% is
the one with benzoic acid and aqueous hydroxide.
In the case of the two base extraction it is possible to extract two acids separately
because aqueous bicarbonate does not deprotonate 2-Naphthol, but it does
deprotonate benzoic acid. When the first extraction is done, bicarbonate reacts with
benzoic acid while 2-naphthol and naphthalene stay in their organic phase-which is
then extracted with hydroxide ( will react with 2-Naphthol). Naphthalene stays in
organic phase and all 3 compounds are then separated from the solution. Carbonic
Acid is obtained when benzoic acid reacts with bicarbonate (carbonic acid
decomposition).

Neutralization reactions were used to recover the compounds from the aqueous
phase (equations are on the attached paper). Acidification or basification in the
acid-base extraction experiment was done with more concentrated reagents
because amines (4-Nitroaniline) are soluble in aqueous acid at a pH<4. The amines
are converted to their respective ammonium salts (conjugate acid of amines).
The melting point ranges of the compounds were found to be very close to the
melting points of the original compound.
The recovery yield for benzoic acid was higher in the one base extraction. The
reason for this may have been that since only one extraction was needed there
wasnt much of a chance for some of the compounds to be lost. Usually extractions
tend to be more efficient if they are done multiple times. In the case of this
experiment the recovery yields went lower for a two base extraction, and even
lower for the acid base extraction.
Conclusion
In order to extract the solution successfully the right type of extraction must be
performed. One base extraction is used to separate a solution of an acidic and
neutral compound, two base extraction is used to separate a mixture of 3
compounds (one would be neutral and the other two would be acidic with different
levels of acidity). For two base extractions two different bases are used for
extraction because there are 2 acidic compounds in the solution. An acid base
extraction is performed when separating an acidic, a basic, and a neutral
compound.
Works Cited
Experimental Organic Chemistry 5th Edition
http://www.chem.wisc.edu/courses/116/OtherDoc/pKas_of_Organic_Acids_and_Bases
.pdf