EXPERIMENT 10

ESTIMATION OF PHENOLS

Structure
10.1 Introduction
Objectives
10.2 Experiment 10a : Determination of Hydroxyl Group by Acetylation Method
Principle
Requirements
Procedure
0bservations
Calculations
Result
10.3 Experiment lob : Determination of Phenol by Bromination Method
Pr~nciple
Requirements
Procedure
0bserva tions
Calculations
Result

10.1 INTRODUCTION
Similar to amine groups, hydroxyl groups can also be estimated by two methods. One
of which is based on an acetylation method, while other is based on bromination
method. In acetylation method, the excess of free acetic acid left after acetylation of
hydroxyl group is determined by titration with standard sodium hydroxide solution.
In bromination method, the excess of bromine is determined after bromination of
hydroxyl compounds by the addition of potassium iodide solution and titration of
liberated iodine with sodium thiosulphate solution. If the molecular weight of the
compound is known, the number of hydroxyl groups can then b e calculated.

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

determine the amount of phenol in the given sample,

describe acetylation and bromination methods, and
perform acid-base and iodimetric titrations

10.2 EXPERIMENT 10 a: DETERMINATION OF

HYDROXYL GROUP
BY ACETYLATION METHOD
10.2.1 Principle
In Experiment 9a, you have estimated the amino group by acetylation method. This
method can also be used to determine phenol or hydroxyl groups (alcohols). In this
experiment, we will determine the number of hydroxyl groups in a phenol.

phenol acetic acetyl acetic

anhydride deriv. acid
 In this experiment pryridine is used as a solvent because it is inactive towards the Estimation of Phenol
reagents, it removes the acid products by salt formation, and it also serves as a
catalyst.

ROH + (CH3CO), + C6H5N --4ROCOCH, + (C~H,NH)+(CH,C~O)-

HOH + (CH,CO),O + 2C5H5N--+ 2CH3COO+ ~C,H,NH+

10.2.2 Requirements

You can use the same apparatus, chemicals and solution, which you have prepared
for Experiment 9a. Butjn this experiment, in place of aniline you will use phenol.

10.2.3 Procedure

I Similar to Experiment 9a, first prepare acetylating reagent. Then take two conical
flask, A and B, fitted with reflux water condensers. Weigh accurately about 1 g of
phenol and transfer in flask A. Add 10 cm3 of acetylating reagent to the both flasks
A and B. Connect the flasks to the reflux condensers and heat both flasks o n boiling
water-baths for 30 minutes. Then remove both the flasks from water-bath a d pour
20 cm3 of distilled water down each condenser, shaking the contents of each flask
gently to ensure complete hydrolysis of the unreacted acetic anhydride. Finally cool
each flask thoroughly in cold water and allow it to stand for 10 minutes. Then titrate
the contents of each flask with M NaOH solution, using phenolphthalein or an
indicator. A fine emulsion of phenyl acetate will form when the contents of the flask
A are diluted and should therefore be vigorously stirred throughout {he titration to
ensure that all the free acetic acid is extracted by the sodium hydroxide solution.
Repeat both blank and actual titrations to get at least two concordant readings.
Record the observations in Observation Tables I & I1 for blank and original
titrations, respectively.

10.2.4 Observations
Mass of thpe weighing bottle = m1 -..........................g
Mass of the bottle + phenol = m2 I .......................... g
Mass of the bottle
(after transfer~ingthe compound) = m3 - ..........................g
Mass of phenol transferred =m2-m3 =m=
Molar mass of phenol =M, = 94 g mol-'

Observation Table I
Acetylating Reagent vs. Sodium Hydroxide Solution
(Blank titration)

SI. Volume of Burette Volume of NaOH

NO. Acetylating in cm3
reagent in cm3 Initial Final (Final-Initial)
1 10
2 10
3 10

Volume of NaOH used in neutralising 10 cm3 of Acetylating

reagent = Vl =.............cm3
Chemistry Lab-V Observation Table I1
Sample + Acetylating Reagent v s Sodium Hydroxide Solution
(Actual titration)

S I. +
Sample 10 cm3 Burette Volume of NaOH
N o. Acetylating in cm3
reagent in cm3 Initial Final (Final-Initial)

e
Volume of sodium hydroxide used in neutralising the sample + 10 cm3 of acetylating
reagent = V2 = cm3 ....... cm3

10.2.5 Calculations
Mass of the sample =m = ............g
Difference of sodium hydroxide
Solution required for OT-I & OT-I1 =V1-V2 cm3 - ............ cm3
1000 cm3 M2 NaOH=M2 g mol. NaOH=M2 g mol. CH3COOH=M2 g mol. O H
where M 2 =molarity of'sodium hydroxide solution.
M x (Vl -
(V1 - V2) cm3 of Mz N a O H = g mol. of OH
1000

As you know, this is due to m g of sample, therefore, for 100 gms of the
sample you will have (% of the OH2) group

ii) The number of hydroxy group (OH) in the sample (phenol) can be calculated
as follows:
From above
17xM x V
m g of sample = (
1000
- v2) g of OH group

17xM2x(V1 - V2)x94
9 4 g (1 g mol) of sample contain =
lO00xm
Since 16.03 g mass is d u e t o the o n e O H group
17xbf2x(Vl - V2)x94
Therefore phenol contain O H group(s)
l00Oxm x 17

10.2.6 Result
% of O H group in the sample of phenol =............. %
The number of O H group in the phenol = .............
 Estimation of Phenols
10.3 EXPERIMENT lob: DETERMINATION OF
PHENOL BY BROMINATION METHOD
10.3.1 Principle
Bromination with brominating reagents (a mixture of potassium bromide, potassium
bromate and conc. HCI) as described in case of Experiment 9 b, can also be employed
for determination of phenol.

The excess of bromine is determined by the addition of potassium iodide solution

I and titration of the liberated iodine with standard thiosulphate solution.

103.2 Requirements
You can use the apparatus, chemicals and solution, which you have prepared for
Experiment 9 b. But in this experiment in place of aniline you will use phenol.

10.3.3 Procedure
1. First prepare brominating solution as described for Experiment 9 b and then
prepare standard solution of phenol by dissolving accurately weighed phenol
(about 0.4 g) in water in 250 volumetric flask.

2. Titration with brominating solution (Blank titration): In this experiment you

are using same brominating solution which you have used for the experiment
9 b. Therefore, there is no need to repeat this step.

3. Titration with standard phenol solution: Pipette out 25 cm3 of standard

phenol solution in a 250 cm3 conical flask and add 25 cm3 of distilled water
and 5 cm3 concentrated HCI. Brominating mixture (taken in burette) is now
added to this solution till it achieves light yellow colour and then add 5 cm3 of
KI solution. Liberated iodine is titrated against sodium thiosulphate solution
using starch as an indicator. Repeat the titration to get at least two concordant
readings. Record the observations in Observation Table-I.

4. Titration with unknown phenol solution: Take out 25 cm3 of unknown phenol
solution in 250 cm3 conical flask. treat it as described in case of standard
phenol solution and then titrate similarly. Repeat the titration to get at least
two Concordant readings. Record the observations in Observation Table 11.

103.4 . Observation
Mass of the weighing bottle = m1 --...............B
Mass of the bottle + phenol = m2 -............... g
Mass of the bottle = m3 -............... g
(after transferring the phenol)
Mass of phenol transferred - m2 - m3 = m3 =............... g
Molar mass (Mm) of phenol = 94 g mol-'.
 Obsenatlon Table l -
Standard Phenol Solution v a Sodium Thidsulphate Solution

SL Volume d Volume of B u n t b reading Volume of NazSzO3

No. phenoi bmminating solution in
solutlon in cm' solution in Initial Find cm' (Final-Idtisl)
cm'
1 25
2 25
3 25

ObsmPtion Table I1
Unknown Phenol Solution vs. Sodium Thiosulphab Solution

SL Volume of Volume of Burette reading Volume ofNazSzO3

No. unknown phenol Brominating solution in
solution hcm' mlution in Initial Finai cm' (Final-lnitlal)
cm3
1 25
2 25
3 25

103.5 Calculation
i) Weight of phenol in standard solution =m =...............g
ii) Volume of Na2%03 solution in blank =V =...............cm3
experiment against brominating solution
-
(from Observation Table I of Experiment 9b)
iii) Volume of sodium thiosulphate used for = Vi -............... a n 3
standard phenol solution
(from Observation Table 1)
iv) Volume of sodium thiosulphate used = V2 -v.............. cm3
for unknown phenol solution
(from Observation Table 11)
vcm3 of sodium thiosulphate solution =25cm3 brominating solution

Hence 1 cm3 of sodium thiosulphate 25 cm3 bmminating solution

-7
25
Therefore, VIcm3 of sodium thimulphate = 7xV1 cm3 brominating solution

Hence, volume of brominating solution used for 25 cm3 of standard phanol

solution

Similarly, volume of brominating solution used for 25 cm3 of unknown solution

using relation

mass of phenol in known solution - -

mass of phenol in standard solution

Volume of brominatingsolution used in unkown phenol solution

Volume of bromintingsolution used in standard phenol solution
 Estimation of Phenols
v
4
Weight of phenol in unknown solution = m x -
v
3

- strengthof standardpheholsolution x V4
Strength of phenol in unknown solution =
v3

10.3.6 Result
The amount of phenol in unknown solution = ................g
The strength of phenol in unknown solution = ................ g dm-3
The percentage purity of phenol can also be calculated by the following formula
(V - V 2 ) x M x M , x 100
% of purity of phenol =
Mxzx2000
where,
V = Volume of sodium thiosulphate used in blank experiment
V2 = Volume of sodium thiosulphate used in sample of phenol -
M = Molarity of sodium thiosulphate
M, = Molar mass of phenol
m = Mass of phenol taken in g
z = number of bromine atoms substituted in phenol