EXPERIMENT 1

SEPARATION OF A MIXTURE OF BENZOIC

ACID, 2- NAPHTHOL AND 1,4-DIMETH-
OXYBENZENE BY SOLVENT EXTRACTION
AND IDENTIFICATION OF THEIR
FUNCTIONAL GROUPS

Structure

' 1.1 Introduction

0bjectives

1.2, Solvent extraction

1.3 Principle
1.4 Requirements
1.5 Procedure
Identification of functional groups
1.6 Result

1.1 INTRODUCTION
The mixture mentioned in the experiment title contains two acidic and one neutral
compound.The pK, values of the acidic compounds viz., benzoic acid and 2 naphthol
are 4.17 and 9.51 respectively. Benzoic acid is a stronger acid while 2-naphthol is
weakly acidic.Seperation of this mixture will require the extraction of the acidic
components one by one. You will be using the technique of solvent extraction for
this purpose.Since this technique is new to you we will give a brief account of this in
the next section before describing the experiment.

t i Objectives

After studying and performing this experiment, you should be able to

@ separate a mixture of a neutral and an acidic organic compound by solvent

extraction technique,
@ identify the functional groups of the separated compounds, and
describe the theory behipd the above.

1.2 SOLVENT EXTRACTION

I You are aware that most of the organic reactions normally do not go t o completion.
The reaction mixture contains unreacted reactants and unwanted side products
besides the desired product. In such a situation one of the products (wanted or
unwanted) may need to be separated. One of the methods which can be used to
perform such a separation is called as solvent extraction. This method is based on the
principle of phase distribution . It exploits the differential solubility of a given solute
in two immiscible solvents to separate it from a given mixture. Let us briefly
understand the technique.
Chemistry L a b V Suppose a substance 'X' has difrerent solubilities in two immiscible solvents. If we
take a solution of the substance in any of the solvents and shake with the second
solvent then it distributes itself in two solvents depending on its solubility in
these.For example acetanilide is soluble in ether as well as in water. If we take its
solution in water and shake with ether then part of acetanilide goes to the ether
layer. The two layers can be separated and the ether layer can be evaporated to get
acetanilide. We can repeat the process a number of times whereby more and more of
acetanilide would come to ether and evei!tually all the acetanilide from aqueous
layer would get 'extracted'.

The extracting efficiency of the solvent depends on the distribution' coefficient of

the solute in the two solvents. Distribution coefficient is defined as the ratio of the
concentration of the solute in two solvents.

K.= conentration of the solute in solvent 'A'

concentration of the.solute in solvent 'B'
= solubility of the solute in solvent 'A'
solubilityof the solute.insolvent 'B'

This definition of distribution It is obvious that higher the value of 'K'higher is the extracting efficiency, i.e., in
coefficient holds only in the
solute remains in same molecular event of extraction more amount of the solute would be transferred. Thereby smaller
s~atein both the solvents. lf, volume of extracting solvent would be required. A good extracting solvent should
however, the solute associates or have the following properties.
dissociates in one or both the
solvents the defining equation has
to be modified. You can referto It should be a good solvent for the substance being extracted i.e., solute should have
any standard text on physical
chemistry for these equations.
high solubility in this solvent,

'it should have low boiling point so that the-extracted substance can be recovered
easily,
it should not be expensive,
it should not react with the solute o r the other solvent,'and
of course., it should be immiscible with the other solvent.

In this and the next experiment you will be performing extraction of acidic and basic
compounds respectively from their mixtures with neutral substances.To accomplish
such an extraction the mixture is normally taken in an organic solvent and is shaken
with an aqueous solution of a base or an acid. This process is called as acid base
extraction. Let us take an example of separation of an acidic component from the
rest in a mixture to understand the process of acid base extraction. When we shake
such a mixture with an aqueous solution of a base the acidic compound gets extracted
into aqueous phase as its salt. The extraction process can be visualised as follows.

When we mix the organic solvent (containing acid) with aqueous solution of the
base, the acid distributes itself into organic and aqueous layer depending on its

-
distribution coefficient. The base present in aqueous layer immediately converts the
acid into its salt, Eq. 1.1.
RCOOH + MOH RCOOM + H20 ... (1.1)
The extent of conversion depends on the strength of the base. In any case the
concentration of free acid in aqueous layer becomes very small. As a consequence, to
maintain the distribution coefficient more acid comes into the aqueous phase and
gets converted into the salt. This process continues till the base is able to perform
this conversion completely. The salt formed in this process also distributes itself into
the two solvents. Due to very large solubility of the salt in aqueous phase as
compared to organic phase, most of the salt stays in the aqueous layer. That b,a very
little amount of acid goes back into organic layer as salt.

The net result of these processes brings most of the acid into aqueous phase. The
amount of acid which comes to the aqueous layer depends on the amount and nature
of the base (weak o r strong). If sufficient quantity of appropriate base is present then
 Separation of a Mixture of
practically all the acid from the organic layer comes into aqueous layer and we get a Benzoic Acid, 2- Naphthol and
good (!) extraction. The equilibria inbolved in these processes are represented 1,4 Dimethoxybenzene by
schematically in Fig. 1.1. Solvent Extraction and
n Identification of their
[HA],: Concentration of acid Functional Croups
HA, in aqueous layer
Organic soluents like chloro-
[HA],: Conceatration of acid form and carbon tetrachs oride.
HA, in organic layer form lower layer with water
while, solvents like either, and
petrol form upper layer with
[ ~ a ~ ] ~ : C o n c e n t r a t i o n o f t h ewaterinsePoratoVfun?el.
salt NaA in aqueous layer

[NaA],: Concentration of the separation of a Mixture of

salt NaA in organic layer Benzoic Acid, 2 - ~ a p h t h oand
~
1,4-Dimethoxy-henzene by
solvent extraction and
Identification of their
Functgional groups.

Fig. 1.1. Schematic representation of the quilibrie involved in the extraction of

an acidic compound Rom organic to aqueous layers

?'he appropriate base refers to the one which can effectively convert the acidic M a , a s you know is an index of the
compound into its salt. As a rule of the thumb a basic solution whose pH is at least 4 st,ngth of an acid. It is definedas
pH units more then the pKa of the acid to be extracted can afford an almost complete -logKawhereKa is dissociation
extraction. For example benzoic acid (pKa 4) can be extracted quite effectively by a 5 constant of the acid. Higher the
% aqueous solution of sodium bicarbonate (pH - 11). The approximate pK,s of pKavaluweaker the acid.
common organic acids or bases and the pH of the common extracting solutions are
given in Table 1.1 and 1.2 respectively. These would be of help to you in devising the
extraction strategy to separate any other mixture.

Table 1.1 :Approximate pK, values of some common

acidiclbasic compounds

Class of compound Approximate pK, Examples

Mineral acid
Aromatic carboxylic acid 4 benzoic acid
Aliphatic carboxylic acid 5 acetic acid,
propanoic acid
Ani lines 5 aniline, toluidine
Pyridines 6 pyridine
Phenols 10 1-naphtho1,phenol
2-naphthol
Aliphatic amines 11 methyl amine,
ethvlamine
Table 1.2 :Approximate pH values of the solutions (5-10 96 by weight)
commonly used for acid-base extraction

Compounds Approximate

pH HCl; H2S04
Acetic acid
NaHCO,
Na2C0,, K2C03
NaOH, KOH
 Chemistry L a b V Needless to say that the other species (which are not acidic) would stay in organic
layer. Only a small portion would come into the aqueous layer depending on its
solubility and distribution coefficient. These are removed in the event of
acidification o r crystallisation. Further, you may be wondering that we wanted to
separate acid and have landed up with a solution containing salt of the acid. Don't i

I
Worry the acid can be recovered quite easily by acidifying the solution with mineral
acid (pH = 1).

Similarly we can understand the extraction of a basic compound say an amine from 1
an organic solvent by using an aqueous solution of an acid. Again as a rule of the ?
1
thumb the pH of the extracting acid solution should be at least 4 pH units away from
the pKa of the conjugate acid of the base.For example an aliphatic primary amine
(pKa of conjugated acid, RNH = 11 can be effectively extracted by a 5-10 % solution I
of acetic acid ( pKa =3) .The acetate salt so obtained can be converted back to the
amine by using aqueous solution of sodium hydroxide.

Having understood the concept of solvent extraction let us now discuss about the
separation of mixture given in the experiment title.

1.3 PRINCIPLE
You would recall from above that we need a basic solution to extract an acid into
aqueous medium whose pH is at least 4 pH units away from the pKa of the acid.We
can see that to extract benzoic acid (pKa 4.17) we need a solution whose pH is atleast
8.2 while for extracting 2-naphthol (pKa 9.51) the solution should have a pH of 13.5
or above. If we use 1 M sodium hydroxide(pH 13) as the extracting solution both the
compounds will be extiacted whereas if we use NaHC03 then only benzoic acid
Benzoic acid
pK, 4.17 would be converted to its salt while 2-naphthol would stay as such. Therefore, to
separate the mixture we perform two extractions. First we extract the mixture with
NaHC03 (to separate benzoic acid)and then we use sodium hydroxide to separate
naphthol from 1'4- dimethoxybenzene. This strategy may be represented in the form
of a flow chart as given below.

Benzoic acid1 2-Naphthol1 1,4-Dimethoxy benzene (in ether )

Extraction with 5% aqueous

OCH, NaHC03 solution
I

I
Aqueous layer
I
Ether layer .
containing sodium benzoate
OCH, (salt of benzoic acid)
p-l)imcthoxyl)cnzcnc
I extraction with

I +H+
'
(Hydroquinone dimethyl ether) aqueous NaOH solution
- (acidification)
~ e n i o i cacid

c
I
Aqueous layer
+H+
I
Ether layer

(acidification) evaporation

2-Naphthol 1,4-Dimethoxy
benzene
 Separation d a M h r e of
1.4 REQUIREMENTS Benzoic Acid, 2- Naphthol and

Solvent Ex~Mc~~QIU and

Apparatus Chemicals Itlentification oftheir
Separatory funnel (100 cm3) 1 Solvent ether 40 cm3 Functional G r o u p
1 Beakers (100 an3) 2 Sodium sulphate
I Conical flask (50cm3 3 Sodium bicarbonate
t Ring clamp 1 Sodium hydroxide
Funnel 1 Acetic acid
Filter paper Sodium chloride

Solutions Provided

1. 10 % aqueous solution of sodium bicarbonate: It can be prepar-ed by

dissolving log NaHC03 in 100 cm3 water.
2. 10 % aqueous solution.of sodium hydroxide: This solution is prepared by
dissolving log NaOH in 100 cm3 of water.
3. Saturated solution of NaCl : It can be preparkd by disiorving excess of NaOH
in water.

1.5 PROCEDURE
The procedural instructions have been given below in sequential order.You are
expected to go through the instructions carefully, and prepare a broad mental outline
: of the same.

i Clean the separatory funnel first with soap water and then with plenty of
water. Grease the stopcock to ensure its smooth movement. Teflon stopcocks need not be
greased
2 Close the stopcock and mount the separatory funnel in the ring support on
an iron stand as shown in the margin. If the ring support is not available you
may use a tripod stand for the purpose.

3. Weigh 3 g of the mixture on a rough weighing balance and dissolve it in

about 30 cm3 of solvent ether in a concial flask

4. Transfer the solution to the separatory funnel after ensuring that the
stopcock is closed.Wash the conical flask with a little (5 ~ m of~ether
) and If you don't release the Pressure
pour this also into the separatory funnel. This ensures complete transfer of ~ ~ ~ ~ ' ~ ~ ' , ~ ' e ~
the mixture. solution

5 Add about 20 cm3 of 10 % aqueous solution of sodium bicarbonate (the

cxtracting solution) to the funnel.Wet the stopper and place it on the
funnel.This is done so as to avoid the spilling of organic solvent from the
sides of the stopper.

6. Gently swirl the contents of the funnel to mix them. Release the pressure
built up inside the flask. This pressure is due to the evaporation of highly
volatile ether. Besides this, 'the neu tralisation of the carboxylic acid group
with sodium bicarbonate evolves C 0 2 gas. To release the pressure, carefully
turn the funnel upside down holding the stopper in place as shown in the
margin and cautiously opening the stopcock.You would hear the sound of
escaping vapours. Close the stopcock again and mix the contents well with
repeated release of pressure. --

7. Allow the mixture to stand in the funnel (on the ring support) until1 the two Venting posltlon, showlngcormt
immiscible layers separate out. way of holding funnel for sheking
and venting.
Chemistry Lab-V 8. Remo"e the stopper at the top and draw off the lower layer into a 50cm3
conical flask labelled 'A'.

9. Add 10 cm3 of 5 % aqueous solution of sodium hydroxide to the separatory

funnel, shake the mixture thoroughly and allow the layers t o separate after
releasing any pressure built up.

10. Remove the stopper and draw off the lower layer in a concial flask labelled
'BY.

11. Put additional 5 cm3 of H 2 0 in the funne1,shake the contents, allow the
layers to separate and draw off the lower layer again in flask 'By.
Commercial samples of anhydrous
sodium sulphate might have 12. Pour about 15 cm3 of saturated aqueous solution of sodium chloride to the
absorbed some moisture. You may separatory funnel. Shake vigorously for about a minute and allow the layers
spread about 10 to 15g of the
crystals of Na2S04 in a petry dish
to separate. Draw out the lower layer and discard it.
or china dish and keep it in as oven
maintained at 110°C for 45 hours. 13. Pour the ether layer into a concial flask labelled as 'C' containing anhydrous
Allow it to come to room sodium sulphate. This treatment removes the water which gets dissolved in
temperature and store in a ether and helps in its drying.
dessicator.
RECOVERY OF THE SEPARATED COMPOUNDS

By following the above procedure you will obtain three flasks containing three
separate compounds.

Flask A : Benzoic acid as sodium benzoate in water.

Flask B : 2-naphthol as sodium salt in water.
Flask C : 1,4-Dimethoxybenzene in ether.
The desired compounds can be obtained as follows.

B e careful ! d o not add acid in Recovery of benzoic acid :You would recall from the introduction that pure benzoic
large amounts as it may lead to acid can be recovered by acidification of its sodium salt. To accomplish this take flask
spilling of the solution. 'A' containing the solution of sodium benzoate and to this carefully add dilute
hydrochloric acid to that, dropwise with constant shaking of the flask. Continue
addition till the solution becomes acidic; (check with the help of a pH paper). You
will observe brisk effervescence, due to the neutralisation of excess bicarbonate.

When the pH of the solution reaches close t o 4, you will see the separation of .
benzoic acid as a white solid. If you don't get it add a few drops more of hydrochloric
acid and leave the solution for a few minutes. If you still don't get the crystals scratch
the sides of the flask with the help of a glass rod and keep the solution in ice\icecold
water. Filter the solid over buchner funnel o r by ordinary gravity filteration. Dry the
crystals in the folds of filter paper and weigh them.Report the amount of benzoic
.acid obtained. Save the sample for functional group determination.

Recovery of 2-Naphthol : Znaphthol, is also recovered in the same way as benzoic

acid, i.e., by acidifying with dilute hydrochloric acid solution. Here you would not be
observing any effervescence as in this case the neutralisation involves reaction of
sodium hydroxide and hydrochloric acid. After acidification ( checked by pH paper )
the solid is separated by filteration ,dried in the folds of filtered paper and weighed.
Report the amount of 2inaphthol obtained. Save the sample for functional group
determination.

Recovery of 1,4-Dimethoxybenzene: Decant the etheral solution from flask 'C' into
another flask. Put about 5 cm3.0f ether into flask 'C' and thoroughly rinse the flask
along with the drying agent. Wait for a minute or two and mix this ether with the
previous lot by carefully decanting it. Take care not to transfer the drying agent.
Evaporate the ether on water bath or preferably distill it.

Caution :This step should be performed in a fuming cupboard. Do not inhale the
vapours of ether. Remove all the flames in the lab before evaporating
 Separation of a Mixture of
You may add a few pieces of pumis stone o r simply a glass tube to facilitate Benzoic Acid, 2- Naphthol and
evaporation. Scratch the solid with a neat spatula and weight it. 1,4 Dimetho~benzeneby
Solvent ~xtractionand
31 Report the amount of 1,4 dimethoxy benzene obtained and save the sample for Identification of their

',I functional p o u p determination. Functional Groups

( 1.5.1 Identification of Functional Groups

As the separated compounds are known, we are providing the characteristic tests for If the etheral solution is not dried
the functional groups of the known compounds. For a generalised scheme for the properly you get the
Instead you would lend up with an
identification of the functional groups in unknown compounds, you can consult oily mass.
Block 2 of CHE-08(L) course o r the books listed in the bibliography.

Test for carboxylic acid group (-COOH ) :Take about 0.1 g of benzoic acid
(recovered above) in a test tube and add about 1 cm3 of 5 % aqueous solution of
. NaHC03 along the sides of the test tube. Observe carefully the point where this

-
solution meets the solid compound. An effervescence along with evolution of a gas
indicates the presence of a -COOH group.

I RCOOH + NaHC03 RCOONa + H 2 0 + C02.

You may repeat the same by taking larger amounts (0.4 g ) of the compound and pass
the evolved gas through a freshly prepared solution of lime with the help of a
delivery tube. Milky colouration confirms the presence of a -COOH group.

Test for phenolic hydroxy group :The second acidic compound in this mixture, viz.,
2-napthol bears a hydroxy group. The presence of such phenolic groups can be
established by a number of tests. We are gidng a few of them here. Generally more
than one test must be made before concluding the presence of phenols. It is so
because the nature and position of the substituents on a phenolic compound strongly
influences the reaction shown by them.

1. Ferric chloride test : Phenolic compounds react with ferric chloride to produce
coloured complexes. T h e ~ e s is,performed
t as follows:
%

Dissolve 10-15 mg of the suspected compound (you will use 2- naphthol separated
above) in about 1 cm3 of water (or aqueous alcohol) and add 1-2 drops of aqueous
ferric chloride solution. Development of an intense colouration (red, blue, purple o r '

-
green) o r formation of coloured precipitate indicates the presence of a phenolic .
r group.

. Phenolic compound + Fe%13 Coloured complex

- The colour may deepen after some time.

Incidentally 2-naphthol does not give colouration in aqueous solution but in

aqueous alcoholic solution the test is positive.

2. Azo dye test :Phenols are common coupling agents in the preparation of azo dyes.
(You will learn about preparation of an azo dye in expedriment 18). This may be
used as a test for phenolic group. The test can be performed as follows.

Take 2-3 drops of aniline in about 3 cm3 of dil. HCI and shake to get a clear solution.
Cool the solution in ice bath o r you may add a clean, small piece of ice to the test
tube. In the meantiine dissolve about 200 mg of the phenol in 3-4 cm3 of 10% NaOH
solution. Mix the two solutions. Formation of orange, scarlet o r red coloured
solution or precipitate indicates the presence of phenolic group.
Chemistry Lab-V 2-naphthol gives scarlet coloured dye

0-~a"
ArNH2 -
NaNo& A~-N: CI-
HCI NaOH

Aniline Azo dye

3. Indicator formation or phthaleln test : Most phenols condense with phthaleic

anhydride to form indicators having blue, red, green or purple colours in alkaline *
solution. The test may be performed as follows.

Take about 200 mg each of the phenol and phthaleic anhydride in a dry test tube and
add 2 drops of concentrated HzSO,;pntly heat the mixture to fuse it and then let
the tube cool down. Add about 1 cm of 10% NaOH solution and stir the mixture.
You may need to use a glass rod to break the fused mass. Add more NaOH s~lution
till the solution is alkaline and observe the colour. Red, blue, purple or green
colouration indicates the presence of a phenol.
0

II
0
phenolphthalein
(wlourlejis)
2-naphthol gives faint green colouration

4. Liebermann reaction : . Phenols with free para position show this test. Phenols are
made to react with nitrous acid to form p-nitroso derivatives. These derivatives react
with excess of the phenol to form the indophenols which are acid-base indicators.
The reaction for phenol can be represented as follows:

p-nitrosophenol Monoxine of
quinone

Blue
The test is performed as per the following procedure.

Take about 100 mg of the compound in a dry test tube and add 1-2 cm3 of
concentrated HZSO, and a few crystals of sodium nitrite (NaN02) to it. Shake the
test tube and warm a little. Green, blue or purple colour action indicates the
 presence of phenolicgroup. Dilute the contents with about 5-10 cm3 of water. The Separation of a Mixture of
Benzoic Acid, 2- Naphthol and
colour changes to red (or blue-red). Add concentrated NaOH solution till the 1,4 Dimethoxybenzene by
solution becomes alkaline. Its colour changes t o blue (or green). Solvent Extraction and
Identificetion of their
Functional Groups
Test for Ether group

The third compound of the mixture viz., 1,4-dimethoxybenzene, is a neutral

compound and has ether functiodal group. In general, ethers are quite inert and their
identification iS quite difficult. Normally they are identified by elimination rather
than by direct test i.e., if all the classes/funclional groups are absent then the
compound may be an ether.

1.6 RESULT
The given mixture has been separated into its constituent i.e., benzene acid,
1 2-naphthol and 1-4 dimethoxybenzene.

I The separated compound have been tested for their functional groups; a carboxylic
acid, a phenolic hydroxyl and an ether functional group respectively.
I