Extracti

on as a
Separati
on Tool

Organic compounds fall into

three broad classes:

organic acids
( c a r b o x yl i c a c i d s a n d
phenols)
organic bases (amines)
neut r al ( est er s,
ket ones, al deh yd es, et her s,
et c)

Organic acids, organic bases,

and neutral organic compounds
can be readily separated from
each other on the basis of their
acid-base characteristics.
Organic acids (carboxylic
acids and phenols) readily react
with alkali bases (NaOH, KOH)
to form water soluble organic
acid salts (ionic compounds).

b
e
n
z
o
i
c

p
k
a
=
4
.
1
9

a
c
i
d
,

(
a

Page 1 of 9

c
a
r
b
o
x
y
l
i
c

soluble
organic
solvents,
insoluble
water
sodium
benzoa
te
(a salt
of a
carbox
ylic
acid)

a
c
i
d
)

an ionic
organic
compound
insoluble
organic
solvents,
soluble
water

a
covale
nt
organi
c
compo
und

2-naphthol, pka = 9.51

naphtholate
(a phenol)
a covalent organic compound
organic compound
soluble organic solvents, insoluble
water
soluble water

The organic acid salts can

readily be liberated (converted
back to organic acids) by
treatment with a strong mineral
acid like HCI or H2SO4.

Page 2 of 9

sodiu
m
benzoa
te
(a salt
of a
carbox
ylic
acid)

4
.
1
9
(
a

an ionic
organic
compoun
d
insoluble
organic
solvents,
soluble
water
b
e
n
z
o
i
c

c
a
r
b
o
x
y
l
i
c
a
c
i
d
)
a
covalent
organic
compoun
d
soluble
organic
solvents,
insoluble
water

a
c
i
d
,
p
k
a
=

sodium naphtholate
9.51
(a salt of a phenol)
an ionic organic 'compound
organic compound
insoluble organic solvents, soluble water

Page 3 of 9

Organic bases, on the other

hand, readily react with
mineral acids to form water
soluble organic base salts
(ionic compounds).

aniline (an aromatic amine)

a covalent organic compound

organic compound
soluble organic solvents, insoluble
water
soluble water

The organic base salts can

readily be liberated (converted
back to organic bases) by
treatment with a strong alkali
base like NaOH or KOH.

anilinium hydrochloride

Aniline (a

an ionic organic compound

insoluble organic solvents, soluble water aniline

a covalen
soluble or

Separation of a Carboxylic
Acid, an Amine, and a
Neutral Compound
Consider the following mixture:

Page 4 of 9

The Experiment
In this experiment, we will
separate a mixture of two
organic
acids
using
the
difference in their pka's.
Benzoic acid (pka = 4.19) will
react with the weak base,
sodium bicarbonate, to form
Page 5 of 9

a water soluble sodium salt,

sodium benzoate.

Benzoic acid, pKa = 4.9

(a carboxylic acid)

Sodium benzoa
(a salt of a car

2-Naphthol, a much weaker

acid (pka = 9.51) than benzoic
acid, does not react with the
weak base, sodium
bicarbonate.
OH

2-naphthol, pka = 9.51

(a phenol)

Page 6 of 9

NaHCO3

A mixture of benzoic acid and

2-naphthol can thus be
separated by extraction of an
organic solution of the two
compounds with sodium
bicarbonate solution. The
sodium salt of the benzoic
acid will dissolve in the
bicarbonate layer while the 2naphthol will remain in the
organic layer. Extraction of the
organic layer containing the 2naphthol with a stronger base
such as sodium hydroxide will
convert the 2-naphthol to its
sodium salt which will be
soluble in the sodium
hydroxide layer.

2-naphthol, pka = 9.51

naphtholate
(a phenol)

Acidification of the sodium

bicarbonate layer with HCI will
convert the sodium benzoate to
benzoic
acid
which
will
precipitate and can be isolated
by filtration. Acidification of the
sodium hydroxide layer with
HCI will convert the sodium
naphtholate
to
2-naphthol
which will precipitate and can
be isolated by filtration.

Page 7 of 9

sodium naphtholate
(a salt of a phenol)

2-naphthol, pka = 9.51

(a phenol)

Procedure for Extraction Experiment

Weigh 1.0 g o benzoic acid and 1.0 g of 2-naphthol into a 125 mL

Erlenmeyer flask. Add 50 mL of toluene and swirl the mixture until solution is
complete. Transfer the toluene solution to a 250 mL separatory funnel and add 25
mL of 10% sodium bicarbonate solution. Swirl the funnel until the frothing
(release of 00 2 ) has subsided, then shake the funnel with frequent venting.
Drain the lower aqueous bicarbonate layer into a clean Erlenmeyer flask. Keep
the upper toluene layer in the separatory funnel. Extract the to luene layer with
another 25 mL portion of 10% sodium bicarbonate solution. Combine this lower
aqueous bicarbonate layer with the first bicarbonate extract. Set the combined
bicarbonate extracts aside. Keep the upper toluene layer in the separatory
funnel.
Add 25 mL of 10% sodium hydroxide solution to the toluene layer in the
separatory funnel. Extract and allow the layers to separate. Drain the lower
aqueous sodium hydroxide layer into a clean Erlenmeyer flask. Set the layer
aside. Remove the toluene layer from the separatory funnel and place in an
Erlenmeyer flask until the experiment is completed, then discard in the
appropriate waste container.
To recover the benzoic acid, cool the bicarbonate extract in an ice-water
bath and slowly acidify with hydrochloric acid (3-6 mL). The bicarbonate extract
will froth because of the release of CO, so this acidification must be done
slowly. Check the solution with pH paper to be sure the mixture is acidic.
Briefly cool in the ice bath and then vacuum filter the precipitate. Wash with
cold water and air dry over the week. Weigh, calculate the % recovery, and
obtain a melting point.
To recover the 2-naphthol, thoroughly cool the sodium hydroxide extract in
an ice-water bath and slowly acidify with hydrochloric acid (3-6 mL). Keep cooling
the extract during the acidification because the 2-naphthol tends to oil out (come
out as a liquid rather than a solid) if the mixture is not kept cold. Check the
solution with pH paper to be sure the mixture is acidic. Continue cooling in the
ice bath and then vacuum filter the precipitate. Wash with cold water and air dry
over the week. Weigh, calculate the % recovery, and obtain a melting point.