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COLLEGE PRACTICAL

CHEMISTRY

* H. N. PATEL, M.Sc., D.H.E.


Plinc.tpal and Head, Department of ChemiStry.
Sheth L.U.J. and Sir M.V. College of Arts. Science & Commerce,
Andhert (East). Mumbai - 400 069.

* S. P. TURAKHIA. M.Sc., D.H.E.


Professor of ChemiStry.
K. J. Somaiya College of Science & Commerce.
Vidyavibar (East). Mumbai - 400 077.

* S. S. KELKAR, M.Sc .• D.H.E., Ph.D.


Professor of Chemistry.
Vartak College of Arts, Science and Commerce.
Vasai (West). Dist. Thane.

* N. S. ISRANEY, M.Sc., D.H.E., D.E.M., D.C.P.A. (UK)


Professor of Chemistry.
R. D. National College of Arts, Science & Commerce.
Bandra (West), Mumbai - 400 050.

* S. R. PUNlYANI, M.Sc., M.Phil., Ph.D.


Professor of Chemistry,
K. C. College of Arts. Science & Commerce.
Churchgate. Mumbai -' 400 020.

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( CONTENTS

1. Chemical Kinetics 1-8

2. Partition Coefficient 9-12

3. Viscosity Measurements (6 Units only) 13-16

4. Potentiometry 17-31

5. Colorimetry/Spectrophotometry 32-46

6. Conductometry 47-54

7. pH-Metry 55-64

8. Gravimetric Estimations 65-69

9. Titrimetric Analysis 70-76

10. Inorganic Preparations and Characterisation 77-84

11. Ion Exchange Methods 85-90

12. Chromatographic Experiments 91-93

13. Separation of Organic Mixtures (6 Units only) 94-113

14. Organic Synthesis 114-127

15. Organic Estimations 128-136

Appendices 137-153
"This page is Intentionally Left Blank"
1
Chemical Kinetics

Some important theoretical aspects


In these experiments, the rate or the velocity of a reaction is studied by determining the
concentrations of reactants and/or products at definite intervals of time. The method of determining
concentration varies from reaction to reaction, depending upon the nature of substances involved
in the reaction. Since the velocity is affected by change in temperature, care must be taken to
maintain the temperature constant, during the course of experiment. This purpose is attained by
keeping the reaction mixture in a thermostat or a water bath.
Some of the important terms encountered in the study of kinetics are explained below:
(1) Rate of a Reaction: It is the amount of reactants transformed into products in unit time.
i.e., sec-I, min-I, hrl etc. It is represented as (-dc/dt) where, (-de) is the decrease in concentration
of the reactants in a time interval dt.
(2) Molecularity: It is the total number of reactant molecules taking part in a chemical
reaction. A reaction is said to be unimolecular, when only one molecule takes part in the reaction
e.g.

A bimolecular reaction involves two reactant molecules, e.g.,


CH3COOC2Hs + NaOH ~ CH3COONa + C2HsOH
A reaction which involves three molecules is said to be termolecular, e.g.
2S02 + 02 ~ 2S03
(3) Order of a Reaction: It is the number of molecules of reactants whose concentration
changes during the course of a reaction and this number affects the rate of that chemical reaction.
2 Col/ege Practical Chemistry (I'. Y. B.Sc.)
During the course of reaction, for a first order reaction only one molecule undergoes change
in its concentration. In a second order reaction, two molecules undergo change in their
concentration. In a third order reaction, three molecules undergo change in their concentration.
However, in certain reactions, change in the concentrations of some reactants is negligible
and in such cases, order of reaction differs from the one expected. e.g.,

CH3COOCH3 + H20 H\ CH3COOH + CH30H


In this case, since water is taken in excess, the change in concentration of water is negligible.
Therefore, it is called a pseudo first order reaction. In the same manner, a pseudo second order .
reaction can also be defined.
(4) Specific Reaction Rate: It is the rate of a reaction when the concentration of reactant
is one mole per dm 3• The rate of a reaction is given from the Law of Mass Action, as,

dc . .
- dt <l c (c = concentratIon of the reactant at tIme t)

dc
- dt = k.c.
When, c = 1 molldm3

dc
dt = k = SpecI'ICfreactIon
i ' rate or the rate constant or velocIty
. constant

Thermostat: It is essentially a water bath which is heated electrically and has a provision
for maintaining constant temperature of the water inside.
First Order Reactions
A reaction is said to be of first order, if the rate is affected by the change in concentration
of one reactant. A typical reaction is the hydrolysis of methyl acetate in presence of H+ ions (In
fact, it is a pseudo first order reaction).

CH3COOCH3 + H20 H\ CH3COOH + CH30H


and its Specific reaction rate k is given as:

2.303 a
k = - t - log (a-x)

where t = time, a = initial concentration of methyl acetate and (a -x) = concentration ofunreacted
methyl acetate at time t.
For first order reaction, above equation can be rewritten as:

kt a
2.303 = log (a - x)

kt
or 2.303 = log a - log (a - x)
Chemical Kinetics

let
or log (a - x) = log a - 2.303

Thus, a graph of log (a - x) against time t is a straight line with slope equal to

Experiment No. 1
Aim: To determine the energy of activation of acid catalysed hydrolysis reaction of methyl acetate.
Requirements: 0.5N HCI solution, 0.1 N NaOH solution, methyl acetate, phenolphthalein indicator
etc.
Theory: The hydrolysis of methyl acetate is a very slow reaction. 'It is catalysed by a mineral
acid. The reaction is represented as:

CH3COOCH3 + H20 ..lJ~ CH3COOH + CH30H


In most of the reactions, the reactants have to be supplied a certain minimum amount of energy
for the reaction to occur. This energy is generally supplied in the form of heat. Due to heat
absorption, the effective collisions between the reactant molecules increase, giving rise to an
increase in the energy of the molecules and they form an activated state or activated complex. The
activated state comprises of a transition state or an intermediate state which immediately gets
converted into products.
Reactants must pass through this activated state before the products can be obtained. The
minimum energy required for reactants to reach the activated state is known as the Energy of
activation (Ea ).
Specific reaction rate is related to the energy of activation by Arrhenius equation:
k = A.e.- Ea/RT

. _ Ea
I.e., loglO k - 10gIO A - ----"=----
2.303xRT
Where, k = Specific reaction rate
A = Constant, which is known as Frequency factor
Ea = Energy of activation
R = Gas constant (8.314 JK-I mol-I)
T = Temperature in kelvin
Hydrolysis of methyl acetate is studied kinetically at two different temperatures and k value
at each temperature is determined. Ea can then be calculated using Arrhenius equation.
Procedure:
This experiment is carried out in two Sets:
Set I: Hydrolysis at room temperature
(1) Take 100 cm 3 of 0.5N HCI solution in a clean glass stoppered .bottle. In another similar
bottle take approximately 25 cm 3 of methyl acetate. Place both these bottles in a water bath to attain
room temperature.
4 College Practical Chemistry (T. Y. B.Sc.)

(2) Rinse and fill a burette with O.IN NaOH solution.


(3) At a known time, carefully pipette out and transfer 5 cm3 of methyl acetate to the bottle
containing 100 cm3 of HCl. Note the time of mixing as zero time and gently shake the bottle to
mix the reactants.
(4) Contents of this bottle are referred to as the reaction mixture and it is always kept in a
water bath. From this bottle titrate 5 cm3 of the reaction mixture, at different time intervals, from
the zero time i.e. from time of mixing, as explained below.
(5) At 5th minute from zero time, pipette out 5 cm3 of the reaction mixture and transfer it to
a conical flask containing a few ice pieces and a drop of phenolphthalein indicator.
(6) Titrate it quickly and carefully against 0.1 N NaOH solution from the burette. The end point
will be from colourless to light pink colour. The pink colour should disappear after about 30
seconds. Record the reading in the tabular form. This is the reading at 5th minute (T1).
(7) Similarly, titrate 5 cm 3 of the reaction mixture at intervals of 10, 15,20,25 and 30 minutes
from the start Le., from the zero time respectively. Record these readings.
(8) Ash for Tao reading
Set II: Hydrolysis at ten degrees above room temperature
(1) Take 100 cm3 of 0.5N HCI solution in a clean glass stoppered bottle. In another similar
bottle take approximately 25 cm3 of methyl acetate.
(2) Place both these bottles in a thermostat maintained at a temperature which is about 10-
12 degrees above the room temperature. Ensure that the thermostat acquires a constant temperature.
(3) At a known time, pipette out 5 cm 3 of methyl acetate kept in thermostart and transfer it
to the bottle containing HCI solution. .
(4) Gently shake the bottle to mix the reactants. Contents of this bottle are referred to as the
reaction mixture. The time of mixing is noted as the zero time.
It should always be kept inside the thermostat. From this bottle titrate 5 cm3 of the reaction
mixture, at different time intervals, from the zero time as explained below.
(5) At 5th minute from zero time, pipette out 5 cm3 of the reaction mixture and transfer it
to a conical flask containing a few ice pieces and a drop of phenolphthalein indicator.
(6) Titrate it quickly and carefully against 0.1 N NaOH solution from the burette. The end point
will be from colourless to light pink colour. The pink colour should disappear after about 15-20
seconds.
(7) Similarly, titrate 5 cm3 of the reaction mixture at the intervals of 10, 15,20 and 30 minutes
from the zero time respectively. Record these readings.
(8) Ask for Tao reading
Observations:
Set I: Room temperature, Tl = ___ K (Kelvin)
Tao = _ _ cm3 (Given)
Chemical Kinetics 5

Time t Titratioll rr. - 1,) log (a - ]C).


ill milllltes mMlbtp (1,) cr - (a -]C) cmJ
OS
10
IS
20
25
30

Similarly, prepare the observation Table for Set II (T2 = K)


[Nole: Tal for both the sets is same.]
Calculations and Graph:
2.303 a 2.303
As k = -- log - - = -- [log a ~ log (a - x)]
I a-x I
log (a - x} = log a - (kt/2.303) .
Thus, plot the graph of log (a - x) against time I (Fig. 1.1) for both the Sets and obtain values
of k from the slope as follows:

Slope = (~)
.. Ik = Slope x 2.3031 (.: slope is negative, k becomes positive)

ab
Slope = -
be
k = Slope x 2.303

b "--_ _ _.....::1000..... Intercept = log a

o0 t minutes
Fig. 1.1

Set Temperature in Specific reaction rate


Nos. min- i
"C K (Obtained from graph)
I
II
T.
T.I
=--
=--
k.
kl =
=
-

Calculate E. using the following formula

k2 (1j12)
E. = 2.303 loglo k x R x (T. _ 7:)
6 College Practical Chemistry (T. Y. B.Sc.)

where,
Ea = Energy of activation for the acid catalysed hydrolysis of methyl acetate.
R Gas constant = 8.314 JK-I morl
kI = Specific reaction rate at temperature TI (in kelvin) i.e., k of Set I
k2 = Specific reaction rate at temperature T2 (in kelvin) i.e., k of Set II.
Calculations of A:

log A = log k - 2.303 RT or

A = Antilog E)
(10g k\ - 2.303RT
0

where,
A The frequency factor

(k + k ) .
k = I 2 2 = Mean Rate constant min-I

Eo = Energy of activation in Joules


R Molar gas constant = 8.314 JK-I mole-I

(1; + 12)
T Average Temperature = in kelvin
2
Results:
= Ea = _
(1) Energy of activation J/mole.
(2) The value of A = _.
Experiment No.2 (6 Units only)
Aim: To study the effect of addition of KCl in the reaction between potassium persulphate and
potassium iodide.
Requirements: Solutions of O.OlM (i.e. 0.02N) K2 S208' O.4M KI, freshly prepared 0.002N
N~S203 and O.4M KC1, freshly prepared starch indicator etc.
Theory: K 2S20 8 oxidises KI to liberate 12. The reaction is:
K 2S20 8 + 2KI ~ 2K2S04 + 12 ... (1)
Progress of the reaction is studied by titrating liberated 12 against standard N~S203 solution
using freshly prepared starch solution as indicator, at specific time intervals. The reaction is:
12 + 2N~S203 -~ N~S406 + 2Nal ... (2)
It is basically a second order reaction but in this case, since one of the reactants, viz. KI is
taken in excess, it becomes a psuedo first order reactionis:
Thus, specific reaction rate (K) is determined by using integrated rate equation and also by
plotting the chracteristics graph of the fiirst order reaction.
Chemical Kinetics 7

When KCI is added to the reaction mixture, the ionic strength of solution increases, this in
tum increases the value specific reaction rate.
Procedure:
Set I:
(1) In two separate clean and dry glass stoppered bottles, take the following solutions:
Bottle No. 1 Bottle No.2
25 em 3 of O.OIM ~S20sl 25 em 3 of O.4M KI
+
75 em 3 of distilled water
(2) Keep both the bottles in a water bath to attain room temperature.
(3) Wash, rinse and fill the burette with O.002N Na2S20 3 solution.
(4) Add KI solution from the bottle No.2 to ~S20S solution. Note the time of mixing as
zero time.
(5) Titrate 10 em 3 of the reaction mixture at intervals of5, 10, 15,20,25 and 30 minutes from
the zero time, against 0.002N N~S203 solution from the burette usi!1g a few ice pieces and freshly
prepared starch solution as an indicator. End point is from blue to colourless.
(6) Record the titre readings as x em 3 in the tabular form as shown below.
Set II:
(1) In two separate clean and dry glass stoppered bottles, take the following solutions:
Bl)ttle No. 1 Bottle No.2
\25 em 3 0f O.OIM ~S20sl 25 em 3 of O.4M KI
+
75 em 3 of O.4M KCI
(2) Follow exactly the same procedure as explained in step. Nos. 2, 3, 4 and 5 of Set I.
Calculations of a and b:
For Set I:
(1) N] = Normality of the K2S20 S taken = O.02N (.: O.OIM == O.02N)
(2) VI = Volume of ~S20S taken = 25 em 3 .
(3) V2 = Total volume of the mixture in Set I = 125 em 3

(4) N2 = Normality of ~S20S in the mixture (effective concentration which is to be


calculated)
Initial concentration Effective concentration
of ~S20S of ~S20S in mixture
N2V2
= N2 x 125
0.02 x 25
125
N2 = O.004N = Effective concentration of ~S20S in the mixture
8 College Practical Chemistry (T.Y. B.Sc.)

(5) a = V3 = Volume ofO.002N N~S203 corresponding to ~S208 in 10 em] of the reaction


mixture
~S208 - N~S203
N2V2 = N3 V3 ,~It""~

0.004 x 10 = 0.002 x V3
:. V3 20
i.e. a 20 em 3
Note: Since both Sets I and II have same concentrations and volumes of ~S208' a = 20 em3
Observations and Calculations:
Set I
(1) a = 20 em3
Time t in Titre reading (a -x) Log (a -x)
minutes x cm) cm3
'-
5
10
15
20
25
30

Set II
(1) a = 20 em 3
(2) Table of observations and calculations are similar to that shown in Set I.
In each Set, plot a graph of log (a - x) against t.
Calculate K for each set from graph (Fig. 1.1)
IK = Slope x 2.303 I
Results:
(1) K for Set I = ------------.
(2) K for Set II = -----------.
Conclusions:
As the ionic strength increases, the K value a!so increases. This shows the positive salt effect.

000
2
Partition Coefficient

Some important theoretical aspects .


Partition coefficient deals with the distribution ofa solute between two liquid phases. To study
the distribution of a solute between these phases, they should be immiscible with each other and
the solute should be soluble in both the phases. When two immiscible liquids (e.g., water and
chloroform) one of which contains a solute, (e.g., iodine) are shaken together, the solute distributes
itself between the two liquids depending upon its relative solubility and attains an equilibrium.
For a solute which exists in the same molecular state in both the liquids at equilibrium, the
ratio of the concentration of the solute in the two solvents is independent of the initial amount of
the solute taken. -

~
i.e., C =K
2

where,
C1 generally refers to the aqueous and C2 to organic solution concentration of solute
in the two solutions respectively.
K = Distribution coefficient or Partition coefficient.
In case of a solute which associates or dissociates in one or both the solvents, C/C2 will
not remain constant.
Consider a case where n molecules of a solute associate in a organic solvent and if C2 is

its concentration in that solven~ then. C/c:;] will be constant


where, n = number of the molecules associated and acting as one big moleCUle.
10 College Practical Chemistry (T. Y. B.Sc.)

Consider a case where the molecules of a solute dissociate in a given solvent and if C2 is
its concentration in that solvent, men, will be constant

C2 (1-a)
where a = is the degree of dissociation of the solute in the given solvent.
Experiment No. 1
Aim: To determine the partition coefficient of iodine between water and the given solvent (CCI,J
and ascertain the molecular condition of iodine in the given solvent.
Requirements: A solution of iodine in carbon tetrachloride, pure carbon tetrachloride, 0.05N
N~S203' O.OIN Na2 S20 3, 10% KI solution, freshly prepared starch indicator etc.
Theory: In this experiment, iodine is allowed to distribute between two liquids namely, H20 and
CCI4 • Then, at equilibrium the concentration of iodine in each of these liquid layers is found out
by titration against standard Na2S20 3 solution.
In this case, the ratio of the concentration of iodine in water and carbon tetrachloride is found
to be constant, thus, Nernst Law is valid. Which means, iodine does not dissociate, associate .or
form complexes in carbon tetrachloride and its molecular condition is same as that in water.
Procedure:
(1) Prepare the following three mixtures of iodine in carbon tetrachloride, pure carbon
tetrachloride and water in three clean and dry glass stoppered bottles as shown below:

Volumeo!
Bottle Iodine in Carbon Distilled
No. Carbon tetrachloride tetrachloride water in cm3
in cm 3 in cm 3
1 20 0 100
2 15 5 100
3 10 10 100

(2) Shake each bottle continuously for about 20-25 minutes, (the stopper should be opened
after every 4-5 minutes to release the pressure built up by the vapours of carbon tetrachloride).
Allow the bottles to stand in a water bath for about 15 minutes to attain equilibrium.
(3) Take a 25 em 3 pipette and insert it in such a way that the tip of the pipette just dips in
the aqueous layer. [Note: The two layers can also be conveniently separated using a separating
funnel. Then they can be directly pipetted out as usual.] Pipette out 25 em 3 of aqueous (upper)
layer, and titrate it against O.OIN Na2S20 3 solution form the burette, using fresh starch solution
as indicator. End point will be from blue colour to colourless. Take three readings for each aqueous
layer. Starch indicator should be added after the brown colour turns pale yellow and 1-2 em3 of
the starch indicator is to be used in each case.
(4) Take a clean and dry 5 em 3 pipette. Tilt the bottle and after closing the upper end of
the pipette, immerse it directly into the organic (lower) layer. Bubble out one air bubble form the
pipette. Pipette out 5 em 3 of organic layer in a conical flask, containing one test tube of 10% KI
solution (to extract iodine in water) and titrate it against 0.05N N~S203 solution from the burette,
Partition Coefficient 11

using fresh starch solution as an indicator towards the end point. End point will be from blue colour
to colourless. (At end point, the organic layer should be colourless). Take three readings for each
organic layer.
(5) Calculate the concentration of iodine in aqueous and in organic layer respectively in terms
of normality and gm, mole lirl (dm 3). Determine the ratio C/C2 (Partition coefficient), w~ere, C1
and C2 are the concentrations of iodine in aqueous and in organic layers, in terms of gm. mole.
lirl respectively. Record the readings.
Observation and Calculations:
(1) Normality of N~S203 solution used for aqueous layer = O.OlN
(2) Normality of N~S203 solution used for organic layer = O.05N
(3) Volume of aqueous layer pipetted = 25 cm 3
(4) Volume of organic layer pipetted = 5 cm3

Bottle Volume of Volume of Noq No'S C1 Cz C1


No. O.OIN Na~z03 O.05N Na~z03 (aqueous) (organic) (aqueous) (organic) K=-
C1
for 25 em3 of for 5 em3 of = Naq/2 = Norg/2
aqueous layer organic layer
VOq Vo

1 (I) (I)
---
(2) (2)
---
(3) (3)
---
Mean - em 3 Mean - em)

2 (I) (1) _ _
(2) (2)
---
(3) (3)
---
Mean - em 3 Mean - em3

3 (I) ( I)
---
(2) (2)
---
(3) (3)
---
Mean - em 3 Mean - em 3

Mean K =

Calculations:
Normality of each aqueous/organic solution can be calculated as follows:
(1) N(aq) = NI
N1V 1 = N2V2
12 College Practical Chemistry (T. Y. B.Sc.)
N) x 25 = 0.01 x CBR (CBR = Constant Burette Reading)
.I
".
N
I
~ 0.01 x
25
CBR I
.
(2) N(org) = N2
N2V2 = N3 V3
N2 x 5 = 0.05 x CBR (CBR = Constant Burette Reading)
:. N = 0.05 x CBR
2 5
Calculate C) and C2 (molar ~oncentrations) as follows:
(1) C(aq) =:C)

Ic, ~~' I
(2) C(org) = C2

Ie, ~ ~' I
(Equivalent weight of iodine is half its molecular weight).
i.e. for iodine, 2 equivalents = 1 mole
and Normality = eq. dm-3
:. Conc~ntration in terms of gm.mole dm-3
= Normality/2
Results:
Bottle' No. Partition Coefficient Mean K
C/C2 = K
) (,
2
3

(1) Partition coefficient of iodine between water and CCl4 = (K) = ___
Conclusions:
The ratio of ClC2 remains practically constant. It shows that iodine exists in same state in
water and the organic solvent. (i.e." iodine is neither associated nor dissociated in CCIJ.

000
3
Viscosity Measurements (6 Units only)

When a liquid flows through a narrow tube, the velocity of the its flow depends on the force
that produces the flow. All the layers of the liquid do not move with the same velocity through
the tube. The middle layers move more rapidly than the layers next to the sides of the tube. In
this way, layers move past one another in the direction of the flow with different speeds. This
displacement of different layers relative to one another is opposed by the viscosity or the internal
friction for the liquid. Some liquids flow more readily than others.
The property of:! liquid owing to which it resists the relative
A motion of its layers, is called its viscosity.
Viscosity is measured in CGS units and has the dimensions
of g, em-I sec-I. The unit is represented as poise. Instead of
determining the' absolute viscosities of liquids, it is easier to
B
compare viscocity ofliquid with one of the known viscosity in the
same apparatus and under the same conditions. The viscosities are
usually determined with respect to distilled water.
Ostwald's Viscometer is used to determine the relative
viscosity of a given liquid. It consists of a U tube with~two limbs
having two bulbs of different capacities and a capillary on one side.
There are two marks on the capillary side - mark A - a little
Fig. 3.1 Ostwald's Viscometer above the bulb (C) and mark B - a little below the same bulb. A
piece of rubber tubbing in attached at the top of the left hand limb
which is used to suck the liquid from one bulb (D) to the other (C).
14 College Practical Chemistry (T. Y. B.Sc.)

Experiment No. 1 (6 Units only)


Aim: To determine molecular weight of polyvinyl alcohol from viscosity measurements,
Requirements: Ostwald's Viscometer, 1% polymer solution (polyvinyl alcohol), distilled w~ter
(solvent), stop watch etc.
Theory: Molecular weight of a polymerr is generally determined by using dilute solution of the
polymer in a suitable solvent. Polyvinyl alcohol is water soluble hence, its solution is prepared in
distilled water. For dilute solutions, the relationship between viscosity and molecuiar weight of solute
(polymer) is given as:
llINT= KMa
where,
llINT Intrinsic viscosity of the polymer (also known as the limiting viscosity number).
M Molecular weight of the polymer
K and a = Constants for the given polymer material and the given solvent respectively.
The intrinsic viscosity is related to the specific viscosity as follows:

lim l1sp ]
llINT. = c~o [ Concentration

Thus, llINT can be found out by determining llsp for various concentrations of the polo/mer
solution at low concentration. Then, a graph of l1sp/c against C is plotted. The intercept is equal
to the llINT'
While l1sp is related to the relative viscosity llrel by the equation:
'11
'ISp
= '11• I reI -1
where,
llrel = Relative viscosity determined using a viscometer.
Procedure:
(1) Using supplied 1% polymer solution prepare the following five dilutions in four different
numbered glass stoppered bottles.

Volume of
Bottle 1% solution of Distilled water Percentage ofthe
No. polymer in cm 3 in cm 3 solution formed

1. 16 4 0.8%
2. 12 8 0.6%
3. 10 10 0.5%
4. 8 12 0.4%
5. 4 16 0.2%

(2) Clean the given viscometer first with chromic acid and then wash it three to four times
with distilled water.
(3) Rinse it with ethyl alcohol. Pass hot air through it, to dry it completely.
Viscosity Measurements (6 Units only) 15
\

(4) Attach a clean rubber tubing with a screw clip over the arm having bulb (C) containing
capillary (See Fig. 3.1). Clamp the viscometer in vertical position using a retort stand.
(5) Pipette out 10 em 3 (or 15 em 3 as per capacity of bulb) of the distilled water and transfer
it into the R.H.S. bulb (D).
(6) Using the rubber tubing, suck the liquid so that it reaches above mark A in the bulb (C).
Screw clip the rubber tubing.
(7) Gradually loosen the screw clip so that the water flows through the capillary tube under
its own weight.
(8) When the water reaches mark A, start the stop watch. Continue observing the level of
the solvent. When it reaches mark E, stop the watch immediately and note down the time
in seconds - as Isolvent (lSI)' This is known as EjJlux lime.
(9) Without disturbing the screw clip position repeat the same procedure by following step
Nos. 8, 9 and 10. Find out Isolvent' for distilled water two times more. Note down as (ls2 )
and (ts/ Find the mean ejJlux lime as (Is)'
(10) Remove distilled water completely from the viscometer. Dry it by passing a jet of hot
air through it, or rinse it twice with a small quality of 0.2% solution.
(11) Clamp the dried viscometer once again on the stand.
(12) Now pipette out 10 em 3 of 0.2% solution (Bottle No.4) of the plastic and transfer it to
the R.H.S. bulb (D).
(13) Follow step Nos. 8,9,10, 11 and determine the mean efflux time for the 0.2% solution.
Note it as 10.2%,
(14) Similarly, find the mean efflux time for 0.4%,0.6%,0.8% and 1% solutions. Note these
as 10.4%' 10.6%, to.8'Yt1 and 1/% respectively.
Observations and Calculations:
(1) Room temperature = .......... OK.
(2) K value (given) = 2 x 10-4.
(3) a value (given) = 0.76.

Bottle %
No. Concentration EjJlux time t seconds TlRel Tlsp Tlspe
1 2 3 Mean
1. Distilled water I(s) - - -
2. 0.2 t(.])%
3. 0.4 t(.4)%
4. 0.5 t(.S)%
5. 0.6 1(.6)%
6. 0.8 1(.8)%
16 College Practical Chemistry (T. Y. B.Sc.)

t(solutiOll) density(soIUtiOll)
~-'-- ...... x ----'--~
flrel = t(SOlution) density(solutiOll)
.: Solutions are very dilute :. d(soln.) ~ d(solv.)

Effiux time for the solution inseconds


flrel = Effiuxtimefor the solvent in seconds

1(0.2)"10
e.g. flrel(0.2%) =- I-
(5)

rsp (0.2%) = (flrel- 1) I


Similarly, find flsp for each solution. Also calculate flsp/c for each solution.
Graph:
Plot a graph of fl$ IC against concentration C (i.e. percentage). It is a straight line graph
Extrapolate the graph t~ meet the Y axis (i.e. conc. ~ 0) (Fig. 3.2).

t
lisp
C

1I1NT

c ..... (gdl-1) __
Fig. 3.2
...
The intercept on Y-axis gives the value of flINT' Using this value calculate molecular weigh
M of the polymer as follows:
flINT = J(MO-
(K and a are the· constants and their values will be supplied by examiner)

Now, Af1 = TJINT


K

M = ~lJ;r
Results: "

(1) Intrinsic viscosity, flINT = _____


(2) Molecular weight' of the given polymer (M) =_ __

[J[J[J
4
Potentiometry

Some important theoretical aspects


The technique of both potentiometry and potentiometric titrations involve measurement of
e.mf ofa Galvanic or Voltaic Cell. The cell consists ofa system of two half-cells; one of which
is called the indicator electrode and the other a reference electrode. Measurement of e.mf
by a voltmeter is not advisable as this would introduce large error due to high internal resistance
of the cell and due to the changes occurring in the concentration of ions resulting from appreciable
passage of current. To avoid such errors, a potentiometer is used for measurement of e.mf
Advantage of this method is that, at the moment when the e.mf of the cell is measured, almost
no current is drawn from the cell.
The magnitude of potential developed on an electrode is affected by the activities of the
reOactants and products involved in the electrode reaction. Relations between these two is given
by Nernst equation. For a general half cell, oxidation reaction is written as:
M'+ + ne- ~M
The Nernst equation is written in the following form:

RT aM
E = EO - In - or in general,
nF aM

RT areduced state
E = EO - In
nF aoxidised state

where,
E = Reduction potential of the electrode
EOI = Standard reduction potential of the electrode
18 College Practical Chemistry (T. Y. B.Sc.)

n = Number of Faradays passing or valency of the metal ion


T = Absolute temperature
R = Gas constant.
In = Natural log (loge) .
Substituting the values of R = 8.314 volt-coulombs (or Joule) K-I morl, T(25°C i.e., 298K),
F(96,500 coulombs) and changing from natural logarithms (In) to loglo' the above equation can
be rewritten as:

E = £0 _ 0.0592 log a(red)


n a(ox)
EO corresponds to the value of electrode potential of the electrode when all the substances
involved in the electrode reaction are in their standard states of unit activity. EO is determined by
measuring Ecell after coupling the electrode with a Standard Hydrogen Electrode (S.H.E.)
The e.mf of such a cell will be equal to the standard oxidation potential of the electrode,
since by convention the e.mf of S.H.E. is assumed to be zero.
Standard p'otential for some electrodes on the Hydrogen-Scale at 25°C are given below:
Electrode Electrode process EO volts
(reduction)
Zn I Zn2+ Zn2+ + 2e = Zn - 0.763

I
Pt I Hlg) atm. W (a=l) H+ + e- =- H2 0.000
2
Cu I Cu2+ Cu 2+ + 2e- = CII +0.337
Pt I Fe2+, Fe 3+ Fe3+ + e- = Fc2+ +0.771
Ag I Ag+ Ag+ + e- = Ag +0.799

Oxidation and reduction potential of an electrode are equal in magnitude but opposite in sign.
The reduction potential can readily be obtained by deriving the oxidation potential and reversing
its sign.
Reference electrodes are used in the measurement of
the potential of an electrode. Primary standard electrode,
against which all other electrode potentials are measured, is
standard hydrogen gas electrode (S.H.E.). Its potential is INLET FOR KCI

arbitrarily assumed to be zero and the electrode is represented SLIDING SLEEVE


as:
Pt I Hlg) atm. I H+ (a = 1)
!
Standard hydrogen electrode is not suitable for routine
work. Consequently, several secondary reference electrodes
have been devised. The most popular of these is the calomel Hg
electrode shown in Fig. 4.1. It is represented as: Paste of
Hg + H92CI2
HglHg2CI 2(s) I(KCl aq )
Its electrode potential depends upon the concentration of' SATURATED KCI
KCl used. The KCl solution may be 0.1 N, IN or saturated.
Its respective oxidation potentials against standard hydrogen FINE CAPILLARY
electrode at 25°C are as follows:
Fig. 4.1 Calomel Electrode
POlenliomelry 19

(i) HglHg2CI 2(s/0.1 N KCI = + 0.334 volt


(ii) HglHg2CI2(s/IN KCI = + 0.210 volt
(iii) HglHg 2CI2(s/saturated KCI = + 0.242 volt.
Saturated calomel electrode is extensively used for practical purposes since it is easy'to
prepare and maintain.
Instructions for proper handling of the Potentiometer
Note: Digital instruments require minimum and easy adjustments before any readings are taken
on them. These are explained by the professor concerned in the laboratory.
However, instructions for a typical instrument are explained below:
(I) Standardisation:
(1) Switch the instrument on for about
5-10 minutes before starting the
experiment
(2) Using· the specially supplied
connector cables, connect the
negative and the positive input I POTENTIOMETER', a::J
terminals with the corresponding r.;;-;"s
I SHAFT STD.
negative and positive standard cell l!!2.!.J CELL

terminals. Or (for better accuracy) DISPLAY @ tIfIJ-


connect the negative and the
positive input terminals with the
corresponding negative and posi-
tive terminals ofa good Weston
Fig. 4.2 Digital Potentiometer
standard cell.
(3) Observe the digital display. It should read 1.018 volts, indicating that the instrument is already
standardised, Ifnot, slowly rotate the standardise knob (shaft) so that the display reads 1.018
volts.
Note: Once standardisation is complete, the standardise knob must not be touched.
(II) Measurement of Potential:
(1) To measure the e.mf of a cell, connect the negative and the positive terminals of the
cell to the corresponding input terminals seen on the potentiometer panel.
(2) Observe the digital display. The reading gives potential of the cell connected to the
potentiometer.
This reading must always be positive. Ifit is negative, reverse the connections of the terminals
of the cell.
Experiment No. 1 (6 Units only)
Aim: To determine the standard electrode potential of the given metaVmetal ion electrodes using
saturated calomel electrode as the reference electrode.
Requirements: O.lM solution of the given metal ions, metal wires, saturated calomel electrode, KCI
and KN03 salt bridges.
. Theory: The electrode potential of every metaVmetal ion electrode depends upon two major factors:
(i) The tendency of an active element to pass into solution in the form of ions.
(ii) The activity of dissolved ions of 'the element to deposit on the metal as atoms.
20 College Practical Chemistry (T. Y. B.Sc.)

At a given temperature, the former is a constant for a stable form of an element, but the
latter varies with concentration. The e.mf of cell formed by the combination of an individual
electrode with a standard hydrogen electrode is taken as its electrode potential. The value is usually
determined by using a saturated calomel electrode as the reference electrode.
Procedure:
In the following steps, the determination of standard electrode potential of Ag+/Ag system
is described. (For that of Cu 2+/Cu, AI3+/AI and Zn 2+/Zn refer to the note given at the end of the
experiment).
(1) Prepare following dilutions form the given O.IM AgN0 3 solution (use of calibrated
apparatus is advisable).
Flask Concentration Volume of AgN03 solution to be
No. in molarity (M) diluted to 100 cm 3 with distilled water
1 0.05 50 em 3 ofO.1M
2 0.01 20 cm) of 0.05M
3 0.005 50 em) of 0.01M

(2) Take a clean small beaker. Rinse it with O.OIM AgN0 3 solution and place about 50 em 3
of O.OIM AgN0 3 solution in it. Immerse one clean Ag wire in this solution. This forms the Ag/
Ag+ electrode (Half cell).

SATURATED
CALOMEL WIRE
ELECTRODE

KN0 3
SALT
BRIDGE

SATURATED KCI AgN03


SOLUTION
SOLUTION

Fig. 4.3 Cell set up


(3) In another similar beaker take about 50 em 3 of saturated KCI solution. Immerse a saturated
calomel electrode in it.
(4) Put a KN0 3 salt bridge connecting the two beakers i.e. half cells, as shown in Fig. 4.3.
(5) Connect other end ofthe Ag wire to the positive terminal and wire from the saturated calomel
electrode to the negative terminal of the potentiometer. (Ensure that all contacts are made
tight).
Potentiometry 21
The cell is represented as:
e Saturated Calomel Electrode (SCE) II AgN03 (O.OIM) I Ag$
(For aluminium and zinc, cell can be represented as 9M!M+ II SCE)$
(6) If necessary, standardise the instrument. Determine the e.mf. of the cell. (Refer to the-
operation of the potentiometer on page No. 19 or follow the procedure as explained by
your professor). Record values of e.mf. in the tabular column.
(7) Repeat the experiment with 0.05M and 0.1 M AgN03 and other solutions, as explained
above, by successively replacing the AgN0 3 solution in the right hand side half cell and
record the e.mf values. .
Observations and Calculations:
Concentration Activity Activity Log aAg E.mf o/cell Electrode Standard
o/AgNOJ Coefficient o/metal Ece// Potential Electrode
solution (y) ion- aAg+ in volts EAgvolts Potential
(M) m xy E"Ag volts
(i.e. mAg+)

0.100 0.733
0.050 0.790
0.025 0.850
0.010 0.892 !

0.005 0.924
Mean E"Ag =

For the cell is represented as:


e Saturated Calomel Electrode II AgN0 3 I Ag ED
(SCE)
E(cell) = E Ag - ESCE
:. E Ag= (Ecell + E SCE )
But, ESCE = + 0.242 volts (given)
Now,
(0.0592) a red
EAg =E Ag
O
- n log aox (n = valency of metal ion)

o (0.0592) aAg
= EAg - n'
log ;-+
Ag
where, aAg= 1 by convension
and a. Ag+ = molal concentration of AgN0 3 solution activity co-efficient for corresponding
.
..
concen,tratlon
=m x r
=my
Since, the solutions are prepared in distilled water and then diluted with it,
1, Molar solution E 1 molal solution.
1M .. 1m
22 College Practical Chemistry (T. Y. B.Sc.)

:. in the following equation, m can be substitute4 by the molarity or'the solution.,

. EAg -- EOAg + 0.0592


.• n
log (rwv)
... ,

For Ag, n = 1.
° 0.0592'1'Og'(rwv)
:. E Ag = EAg - n. ... ,

E~ can also be calculated by direct substitution in the following equation:

E oAg = [(0.242) + (Ecell) ] - 0.0592


- 1- (1 og ~ A)
MY)] (n = 1 lor g

Graph:
Plot a graph of E~g values against concentra-
tion. It is a straight line graph. Extrapolate it to meet
O ... --0.8
the Y-axis. The intercept is equal to the E Ag i.e.,
Standard reduction potential of the electrode.
X-co-ordinate of the origin chosen should be 0, while
for Y-coordinate take suitable voltage.

Results:
0.6
Standard electrode potential
-2.0 -1.0 0.0
£0Ag' (i.e. reduction)
log (a,.>
_ _ _ _ volts (by calculations)
_ _ _ _ volts (by graph)
Fig. 4.4
Note:
The procedure of determination of electrode potential calculation, graph etc. of Cu/Cu2+ is
similar to that of AgiAg+. For the determination standard electrode potential of Aluminium and Zinc,
SCE will be connected to the +ve terminal and metal rod (AI or Zn) in corresponding solution will
be at the -ve teqninal.
In case of AglAg+ experiment, NH4N03 or KN0 3 salt bridge must be used in place of KCI
salt bridge.
Following are the activity coefficient values for the different concentrations.

Concentration Activity coefficient


rn molality of C;uS04 ZnS0 4 Al/SOJ J
m
0.010 0.41:
0.05 0.31
0.10 0.15

EOCu can be calculated from the following equation:


0.0592
g Cu = [(+ 0.242) - (Ecell) - 2 (log MY)]
Potentiometry 23
Experiment No.2
Aim: To detennine standard free energy change (!J.(/) and equilibrium constant for the reaction:
Cu + 2Ag+ ~ Cu2+ + 2Ag
Requirements: O.lM CuS04 and O.lM AgN0 3 solutions, Cu and Ag metal wires, KNOj salt
bridge etc.
Theory: The above mentioned reaction can be studied by setting up the following cell:
9Cu I eu2+ II Ag+ I Ag 6l
The oxidation reaction for the left hand half cell is .represented as:
Cu = Cu2+ + 2e- ... (i)
and the reduction reaction for the right hand half cell is:
2Ag+ + 2e- = 2Ag ... (ii)
Adding (i) and (ii) we get the Net cell reaction as:
Cu + 2Ag+ = Cu2+ + 2Ag
Standard free energy change (!J.GO) for this reaction is related to the e.mf of the cell (E),
by the equation.
!J.GO = - nF EO
and its relationship to the equilibrium constant K is given as:·
!J.Go = - RT In K
The value of EO for the cell can be calculated by measuring e.mf of the cell at different
concentrations, since the activities of the ions in the solution are known. Then from !J.Go, the
equilibrium constant can be calculated.
Procedure:
(1) Prepare 0.05M and 0.01 M CuS04 and AgN0 3 solutions by respectively diluting the given
CuS04 and AgN0 3 solutions. (Method already explained on page No 20).
(2) Take a small clean beaker. Place about 50 em 3 of 0.0 I M CuS04 solution in it. Immerse
a Cu wire in this solution. This fonns the CulCu2+ half cell.
(3) Similarly, place O.OIM AgN03 solution in another beaker. Immerse a Ag wire in this
solution. This fonns the AgiAg+ half cell.
(4) Place a KN03 salt bridge connecting these two half cells.
(5) Connect the other end ofCu-wire to the negative and the Ag-wire to the positive tenninal
of the potentiometer.
(6) The cell is then represented as:
SCu(s) I CuS04(aq) II AgN03(aq) I Ag~)
(7) Standardise the potentiometer and detennine the e.mf of the cell as described on page
No .19. Record this value as EI"
(8) Repeat the experiment using 0.05M CuS04 and 0.05M AgN0 3 solutions respectively in
the two beakers in place of O.OlM solutions. Detennine e.mf of this cell. Record it as
E1 ·
(9) Similarly, carry out step No.8 using O.lM CuS04 and O.1M AgN0 3 solutions respectively
in the two beakers in place of 0.05M solutions. Detennine e.mf of this cell. Record it
as E3•
24 College Practical Chemistry (l'. Y. B.Sc.)

Observations:
(Since solutions are dilute~ M = m)
Obs. CuS04 Mean AgNOJ Mean E.m.J EOorlI
Nos. Conce,,- 1 r.roIWII'Jt~-. COlfCen-' . act~vit)l._ of cell (volts)
tration coefcieint tral!.qn co-ejftc:ient EorlI
(m/) for (mJ for AgN0J (volts)
CuSOlyJ (y,)
1. 0.01 0.40 0.01 0.89 E.=_
2. 0.05 0.216 0.05 0.79 E2 =
r
3. 0.1 0.16 0.1 0.733 E3 =
-
, Mean E"
=-
Calculations:
(i) £0, (Standard e.m.f. of the cell)
Using the' Nemst Equation, we can write:

[eu +][Agr
2
0.0592
2
log I 0
[Ag+ r [Cu]

By convention [Cu] =iAg] = 1 and


[Cu2+] = mlYI and [Ag+] m 2Y2
Substituting these in the above equation, we get:
o 0.0592 mlYI
ECeli =E Cell - X 10g l0 2
2 (m2Y2)

0.0592 1 mlYI
:. £Ocell = Ecell + 2 X oglo ( 2 2)
m2Y2

(ii) A(JO (Free energy change)


A(? =- nFEoceli

i.e., I A(? =- 2 X 96,500 x EOcell(Mean) I


= Joules
(iii) K (Equilibrium constant)
0.0592
EOcell = 2 10g l0 K

E~ell x2
10gIO K = 0.0592

.I.e., _. (E~'ll X2)


Anti log 0.0592
K -
Potentiometry 25
Results:

(1) Mean E~ell volts.


(2) !lO° for the reaction = joules.
(3) Equilibrium constant K for the reaction = _ __
Experiment No.3
Aim: To determine the amount Fe(II) in the given solution by titrating it potentiometrically with
potassium dichromate, and to calculate formal redox potential of Fe3+lFe2+ electrode.
Requirements: O.IN ~Cr207 solution, the given sample containing Fe(II) ions, calomel electrode,
platinum wire etc.
Theory: In this method, a cell is set up which consists of calomel as reference and redox (Fe3+/
Fe2+) as indicator electrode. In this case, the indicator electrode is made up of excess ofFe2+ ions
which get progressively oxidised to Fe3+ ions during the course oftitration. This changes the relative
activities of Fe2+ and Fe3+ ions in the solution, thus changing the potential of Fe3+lFe2+ indicator
electrode. Since the e.mf of the cell depends upon potential for the indicator electrode, the e.mf
measurements can be used to determine the equivalence point of titration of Fe2+ ions against
dichromate solution.
The potential of Fe3+lFe 2+ electrode is represented as follows:

RT a Fe 2+
E = £0 - - In - -
nF a Fe3+
where, £0 is the standard redox potential of Fe3+IFt!+ electrode. If the standard redox potential
is calculated. by taking concentration terms instead of ionic activities, it is called formal redox
potential.
This can be calculated by determining the potential of the Fe3+IFt!+ electrode at half
equivalence point during the titration. At this stage, the concentrations of Fe3+and Ft!+ are
identical.
aFJ+
E = EO, as In
aF,J+
=0
i.e., the electrode potential will be equal to the formal redox potential of Fe2+IFe3+ electrode
at half neutralisation point.
Procedure:
(I) Rinse and fill the burette with O.1N ~Cr207 solution.
(2) Dilute the given solution of ferrous ions to 100 cm 3 with distilled water in a standard
measuring flask and pipette out 10 cm 3 (or any other specified volume) of it in a 100
cm 3 beaker. Add one test tube of 4N H2S04 solution to it.
(3) Immerse a platinum electrode in this beaker and connect it to the positive terminal of
the potentiometer.
(4) Take saturated KCI solution in another beaker after cleaning and rinsing it.
(5) Place a saturated calomel electrode in KCI solution and connect it to the negative terminal
of the potentiometer.
26 College Practical Chemistry (l'. Y. B.Sc.)

(6) Put KCI salt bridge connecting the two beakers as shown in Fig. 4.3 on page No. 20.
This cell is represented as follows:
€>saturated Calomel Electrode II Fe2+, Fe3+ I pte
(7) Standardise the potentiometer and measure the e.mf of the cell as usual.
(8) The titration is carried out by initially adding 0.5 em 3 of ~Cr207 solution at a time. (for
better accuracy 0.2 em 3 towards the end point). (The solution should be stirred thoroughly
after each addition and e.mf measured after waiting for about 20 seconds). Record the
e.mf value after addition of K2Cr20 7.
(9) Add further 0.5 em3 of~Cr207 solution, stir the solution and measure e.l• .~ of the cell..
The titration is carried out by adding 0.5 em3 of ~Cr207 solution at a time. Towards
the end of titration i.e., towards the equivalence point there will be a sudden sharp increase
in the e.mf (0.2 em 3 of~Cr207 solution may be added at a time and titration is continued
till the changes in e.mf i.e. the increase e.mf between two successive readings is very
small and the e.mf values remain nearly constant.)
(10) Plot a graph of (i) e.mf against volume of K2Cr20 7 solution (titrant) added, and
(ii) tlEll1Vagainst volume of titrant (i.e., K2Cr20 7 solution) added, determine the volume
Vx required for complete oxidation ofFe2+ ions from the equivalence point (Fig. 4.5). Thus
calculate the normality and amount ofFe2+ ions in the given solution. Calculate the formal
redox potential of Fe 3+IFe 2+ system, from the graph (Fig. 4.5).
Observations and Calculations:
Volume of Fe(I1) solution pipetted out for titration (VJ) = __ em 3 •
Normality of K2Cr20 7 solution = 0.1 N
Obs. Volume of E.m.f Difference Difference in ~
Nos. K]Cr]07 of Cell E in e.mj M volume I1V I1V
added in cm j in mV in millivolts in cm j mVlcm j
(V)

1 Vo Eo - -
2 VJ EJ EJ - Eo VJ - Vo
3 V] £] E] - E J V]- VJ
4 Vj Ej E j - E] Vj - V]

where,
I1V = Difference in two consecutive volumes of titrant added in em 3 (always positive)
and tlE = Difference in two consecutive readings in millivolts (always positive).
PotenJiomelry 27
Graphs:
(i) E.mf. of cell against volume of ~Cr207 solution added.

(0.0) Volume of Titrant Added (c;rn3) -

Fig. 4.5

!lE
(ii) AV against volume of titrant added in em 3

t
AE
AV
Volume of ~Cr207 Required

(0,0) Volume of Dichromate Added (cm3) -

Fig. 4.6
Calculations:
(1) Normality of Fe(II) solution
Volume ofO.IN ~Cr207 solution required for equivalence point:
(i) From graph of e.mf against volume of titrant added, Vx/ = ..... em 3.
llE
(ii) From graph of AV against volume of titrant added, VX
2
= ..... em 3•
28 College Practical Chemistry rr. Y. B.Sc.)
Vx, +VX2
Mean =< V
x
= 2
=

Fe(II) == ~Cr207
N\V\ = N 2 V2
N 2 V2
N\ = Vi

0.1 x Vx
N=
\ 10
N.
:. Nonnality of diluted Fe(II) solution = _N.
(2) Amount of Fe(II) in the given solution
10 em 3 of Fe(II) solution required Vx em 3 of O.IN ~Cr207 solution
:. 100 em 3 of 10 Vx em 3 _ _ _ _ _ __
3
1000 em of IN K2Cr20 7 = 55.85 g of Fe(II)
3 _ 55.85 x 10Vx x 0.1
. 10 Vx em of O.IN ~Cr207 - 1000

= __ g of Fe(II)
(3) Formal Redox (oxidation) potential of Fe2+/Fe3+ system
V
In graph (i) at half equivalence i.e., at ;' point, the activity of Fe3+ ions = Activity of F~+
ions.
i.e., aFe3+ = aFe2+
Electrode potential Fe2+lFe3+ solution is given by:

RT ap: 2+
E = E o - - l n -e-
nF

if aFel+ = a Fe2+
then, E = EO

i.e., Electrode potential at half] Fonnal redox potential of

equivalence (V)
; point
:: [ Fe3+IFe2+ system

Detennine e.mf (EX> of the cell corresponding to half equivalence point from the graph
(E against V)
Ex = _ volt
Potentiometry 29
By definition,
E.m! of the cell Ex = E'Fe3+/Fe2-Ecal
• • EOFe3+/Fe2+(ox) = E cal + E x
.
i.e. EOFe3+/Fi+ = (0.242) + Ex
volts.
i.e. Formal redox potential of Fe3+/Fe2+ system = _ _ volts.
Conclusions:
(1) Volume of O.1N ~Cr207 required for titration of 10 cm 3 of diluted Fe(II) solution
= Vx = _ cm3.
(2) Normality of diluted Fe(II) solution = _ N.
(3) Amount of Fe(II) in the given solution = _ g.
(4) Formal redox potential of Fe3+lFe2+ system = _ volts.
(Note: This titration can also be carried out with cerric sulphate solution instead of ~Cr207
solution. Experiment details and calculations shall remain similar to those explained above.)
Experiment No.4 (6 Units only)
Aim: To determine the solubility and solubility product of silver chloride potentiomentrically using
a chemical cell.
Requirements: Potentiometer, silve rods, calomel electrode O.IM KCI solution. Saturated KCI
solution, NH4N03 or KN0 3 salt bridge, O.1M AgN03 solution.
Theory: Silver chloride (AgCl) is a sparingly soluble salt. It's solubility product (Ksp) can be
expressed as:
KSpAgCI = [Ag+] [Gil or (aAg) x (a cr)
Where [Ag+] or (a Ag+) and (Cn or (a C\-) represent the activity of the Ag+ and CI- ions in
AgCI solution at 298K.
The aAg+ can be calculated by setting up the following chemical cell.
E>Saturated Calomel Electrode I KCI (aq) + a few drops of AgN0 3 solutionlAg+
Since aCI can be calculated from the concentration of the KCI solution, the solubility product
and solubility of AgCI can be calculated.
Procedure
(I) Prepare 0.05M, 0.02M, O.OIM and 0.005M KCI solutions from the given O.1M KCI
solution, using 100 cm3 standard measuring flask as follows:
Solution Volume Final Resultant
No. of Volume Concentration
O.lM KCI in em3 M

1 50 100 0.050
2 25 100 0.025
3 10 100 0.010
4 05 ' 100 0.005

(2) Set up the potentiometer and standardise it as explained before.


30 College Practical Chemistry (T. Y. B.Sc.)

(3) Take O.lM KCl solution in a 100 cm 3 amber coloured beaker. Add 2-3 drops of O.lM
AgN0 3 solution to it and stir the solution.
(4) Dip a silver rod into this solution and connect the silver electrode so formed to the positive
terminal of the potentiometer.
(5) Connect the saturated calomel electrode (SCE) assembly to the negative terminal of the
potentiometer. Dip the NH 4NO/KN0 3 salt bridge connecting the two beakers to establish
an ionic contact between calomel electrode and silver electrode. Measure potential of
this cell i.e. take three readings.
O.IM +2-3 drops of
GsCE KCl O.IM AgN0 3 Ag$
Solution

(6) Repeatthe measurement of the cell by replacing O.IM KCl solution with 0.05, 0.025, 0.010
and 0.005M KCl solution adding 2-3 drops of O.IM AgN0 3 solution to the respective
solutions each time. Take three constant readings for each solution. (Note: Instead of
adding drops of AgN0 3 solution, a pinch of solid AgCl (AR) can be added to make the
solution saturated with AgCl).
(7) Record all readings into the tabular from and calculate the solubility proauct and solubility
of AgCI as shown under calculations.
Solution Concentration Activity Cell e.mf Activity of aCT Ksp = a Ag+ x acr
No. of Co-ef in Volts Ag+ ions = m.y (AgCI)
KCI (M) ofKCI I 2 3 Const aAg+
(i.e. mcrJ

1 0.005M 0.927
2 O.OIM 0.902
3 0.025M 0.869
4 0.05M .0.816
5 O.IM 0.771

Explanation of Calculations:
Potential of Cell, Ecell can be given by:
EcelJ = E Ag - ESCE - (I)
where, ESCE = potential of saturated calomel electrode
However, using Nernst Equation, e.m.f. of silver electtrode can be given as:

• aAg
EAg = E Ag - 0.0592 log - -
a Ag +

by convention aAg = 1

0.0592
:. EAg = E;g - log


Potentiometry 31

(II)
Using the value of potential of silver electrode, EAg in equation (I), we get,
Ecell= E"Ag + 0.0592 log aAg+ - ESCE
:. Ecell = (E"Ag - Esc~ + 0.0592 log a Ag+
:. 0.0592 log aAg+ = Ecell - (E"Ag - E SCE )
Ece/l - (EO Ag - E SCE )
.. log aAg+ = 0.0592

Since, E"Ag = + 0.799V and ESCE = 0.242V


Ece/l - (0.799) - 0.242
0.0592

Ecell - 0.557)
(
0.0592

. (Ecell -0.557)
= Anti log 0.0592

and
acr = Molality of KCl x activity cell of chloride

I act = mKC1 x YKCI I


Then, Ksp (of AgCl) = (a Ag+) x (a cr)

and

I Solubility of AgCl = ..pc:; =x Imolldm 3

Also, solubility in Kgldm 3 = y = x x 143.5 x 10-3

Results:
(1) The solubility product of AgCl = Ksp = _ __
(2) The solubility of AgCl (s) = mo/ldm 3 •
(3) The solubility of AgCl (y) = Kgldm 3 •

000
5
Colorimetry/Spectrophotometry

Some important theoretical aspects


Chemical analysis through measurement of absorption of light radiation in the visible region
of the electromagnetic spectrum is known as colorimetry. Knowing the amount of light absorbed
and making use of a suitable calibration curve, it is possible to find out concentration of any given
sample solution. Whereas, by observing the region in which the light is being absorbed, nature of
the absorbing substance can be determined.
A solution appears coloured because it absorbs light radiations of a particular wavelength from
the visible region of electromagnetic spectrum. It absorbs maximum radiations in that wavelength
region which is complementary to its own colour, e.g., a blue solution will absorb maximum light
in 575-580 nm region (corresponding to yellow colour which is the complementary of blue colour).
In the following table, some ofthe coloured solutions and their complementary colours, along
with their wavelength region at which they absorb, are given:

Sr. Colour of the Complementary colour Wavelength region


No. solution (the colour absorbed) absorbed
in nm
I. Yellow Blue 465-482
2. Orange Greenish blue 482-487
3. Red Bluish green 493-498
4. Reddish purple Green 498-530
5. Violet Yellowish green 530-570
6. Blue Yellow 575-580

Amount of light absorbed by a solution depends upon the thickness of the absorbing material,
through which the beam of light has to pass and to the concentration of the solute present.
Dependence on these two factors is given by Lambert's law and Beer's law respectively.
C%rilllelrylSpeclropholomelry 33

Lambert's Law: When monochromatic radiation passes through a transparent medium.


the rate of decrease of incident intensity with respect to the thickness of the medium is directly
proportional to incident intensity of the radiation.
Beer's'Law: When monochromatic radiation passes through a medium containing the
light absorbing substance. the rate of decrease of intensity with respect to the concentration
of absorbing species is directly proportional to the incident intensity of the radiation.
These two laws are combined to give Beer Lambert's Law (commonly known as Beer's
Law), which may be expressed in the following form (applicable only at low concentrations):

10
log I, A = &.c.t. (& = epsilon)
where, 10 and It Intensity of the incident and transmitted light respectively.

10
log I, Optical density or absorbance

e Molar extinction co-efficient or molar absorptivity


c = Concentration of the solute in g moleldm3
t = Thickness of the absorbing medium in cm
The terms commonly used for expressing amount of light absorbed are:
(i) Optical Density or Absorbance:
It gives intensity of light absorbed
10
A = log I I

(ii) Percentage Transmittance (or Percentage Transmission):


I,
%T= Io x 100

Instructions for proper handling of the Colorimeter:


Note: Digital instruments require easy and minimum adjustments before any readings are taken
on them. These are explained in details by the professor concerned in the laboratory.
However, instructions for a typical instrument are explained below:

gDD7 DISPLAY
FlL11!R PORT
A
SAMPLE PORT

*.
SEfZERO
T"-O.o.

Fig. 5. J Digital Colorime~r


34 Col/ege Practical Chemistry (T. Y. B.Sc.)

(I) Zero adjustment:


(I) Put the colonimeterlspectrophotometer for at least 5-10 minutes before start on the
experiment.
(2) Insert the required filter from the non-filter end (back) into the filter port.
(3) Fill the ~ample carrier (cuvette) with the blank solution. Wipe it clean from outside. Place
the cuvette into the sample port. Push the off-on switch to on position.
(4) Put the % Transmitance Optical Density (%T - o.D.) switch on the % T position.
(5) Rotate the zero adjustment knob so that the digital display shows zero.
(6) Remove the cuvette containing blank from the sample port and again place it back taking
care that the printed mark on the cuvette comes to the same position. (see Fig. 5.1)
(7) Check the reading on the digital display. It should once again show zero. If it does not
show zero, then repeat step Nos. 3 and 4 until the display reads zero.
Note: Once ~ero is adjusted, the zero adjustment knob must not be touched.
(II) 100% adjustment:
(I) Push the off-on switch to off position.
(2) Remove the filter from the filter port and re-insert it from the filter side. Or if no filter
is kept i'nside, choose the required filter and insert it into the filter port from the filter
side.
(3) Fill the cuvette with the blank solution and wipe it clean from outside. Place this cuvette
into the sample port. Push the off-on switch to on position.
(4) Place the % Transmittance - Optical Density (% T - O.D) knob on the % T position.
Rotate the 100% Coarse knob slowly so that the display shows about 97-98%.
(5) Now rotate the 100% Fine knob slowly, so that the display ~hows exact 100%.
(6) Remove the cuvette containing blank from the sample port and replace it back taking
care to see that the printed mark on the cuvette always comes to the same position.
(7) Check the reading on the display. It should show 100%. If it does not show 100%, then
repeat the step Nos 4, 5 and 6 until the display reads 100%.
Note: Once 100% is adjusted, then 1009/o-coarse and 100% fine knobs must not be
touched.
(III) Measurement of the Absorbance:
(1) Let the off-on switch be kept at on positiop. Check that the filter kept inside the filter
port is the required filter.
(2) Rinse and fill the cuvette with the sample solution whose absorbance is to be determined.
Wipe it clean from outside. Place this cuvette into the sample port.
(3) Check that the % T - o.D knob is kept on (o.D) position and the printed mark on the
cuvette has been kept at the same position.
(4) Read the display and note down the reading. This is the absorbance of the sample
solution.
Some important precautions:
(I) Wipe the curvette clean before putting it inside the sample port.
(2) Always check that the mark on the cuvette is kept at the same position with respect to
the sample port.
Colorimetry/Spectrophotometry 35
(3) Put the instrument On for about 10 minutes before starting the experiment and do not
switch it off unless the experiment is over or the filter needs to be changed. .
(4) After the filter or the sample solution is changed, wait for about 20 - 30 seconds before
noting down the reading from the display.
A Calibration Curve is a plot of optical density (absorbance) against concentration. For
solutions obeying Beer's Law, this is a straight line passing through origin. Using standard
solutions of different known concentrations, a calibration curve for any particular solute is obtained.
It is then used for determining the concentration of the same solute in different samples.
Experiment No.1
Aim: To test the validity of Lambert-Beer's law (using methylene blue) and to determine (i) Amux
(ii) Molar extinction coefficieIJ.t (E).
Requirements: 10 ppm methylene blue solution, ten 100 cm 3 standard measuring flasks,
colorimeter or spectrophotometer etc.
Theory: Methylene blue is a water soluble synthetic dye used extensively in staining of biological
specimens. It gives a beautiful blue colour in water. Different concentrations of this dye are
prepared.
To find the Amux i.e. the wavelength at which maximum absorption of light takes place; a
moderately coloured solution is selected. Using a colorimeter, at different filters/wave lengths its
absorption is measured. The wavelength at which maximum absorption is observed shall correspond
to Amux.
To find the value of E molar extinction coefficient and to verify Lambert-Beer's law i.e.
A = Ebc
where, A = Absorbance of the solution
b = Path length in cm
E = Molar extinction coefficient
c = Concentration of the solution in moles/dm 3•
In this (:ase, absorbances of different solutions are measured at the max. Then, E can be
calculated from the Lambert-Beer's equation or by plotting a graph of absorbance against the
concentration. This shall also verify the law.
Procedure:
(1) Take 10 ppm stock solution of methylene blue in a standard measuring flask. Using this
stock solution prepare the six different dilutions in serially numbered 100 cm 3 standard
measuring flasks as given below:

Flask No. 1 2 3 4 5 6
Volume of 10 ppm solution 10 20 30 40 50 60
(in cm 3)
Concentration in ppm 1 :2 3 4 5 6

Part I : To find A.mux :


(1) Select the 5 ppm (or 10 ppm) methylcne solution and transfer it to the sample cell.
(2) Select the lowest value wavelength/filter available.
36 College Practical Chemistry (T. Y. B.Sc.)

(3) Measure absorbance of this solution using distilled water as the blank.
(4) Select. the next filter/wavelength and repeat step No.3.'
(5) Similarly, repeat step No.3 with all available filters/wavelengths.
(~) Note down absorbance value for each solution.
(7) Plot a graph of wavelength against absorbance readings. The wavelength at which the
absorbance value is the highest corresponds to the Amax'
Note: Amax wavelength for filter must be used for the second part of the experiment.
Part II: Determination of the molar extinction coefficient and verification of Lambert-
Beer's Law:
(1) Select the wavelength/filter that corresponds to Amax as explained in Part 'I of the
experiment.
(2) Detennine the absorbance of the solution No. 1 using distilled water as the blank.
(3) Similarly, measure and note down absorbance of each solution.
Observations:
Part I: Determination of Amax:
Blank solution = Distilled water, Concentration of Methylene blue solution = 5 ppm!
10 ppm
Filter No. Wavelength Observed
in absorbance
nm
I
2
3
4
5
6

:. Wave length corresponding to maximum absorbance = nm,

Part II: Verification of Beer-Lambert's Law:


Blank solution = Distilled water.
Filter used = Amax = ____ nm.
Flask No. Concentration of Concentration in Observed
methylene blue molesldm 3 absorbance
in ppm c A
I I
2 2
3 3
4 4
5 5
6 6
Colorimetry/Spectrophotometry 37
Calculations:
(i) To obtain concentration in molesldm3 :
(ii) To obtain molar extinction coefficient, e:
Consider, where A = Absorbance
A = she e = Concentration in moleldm 3
A
:. £ =: e = Extinction coefficient
be

Concentration in ppm x 10-3


Concentration in moleldm 3 (e) = Molecular Weight of Methylene Blue
(Ask for the path length, b = _ _ em).
Using this equation, calculate s for each solution. It would be nearly constant. Find Qut the
mean value of s.
Graph:
A = ehe is a equation of a straight line.
i.e., a plot of absorbance A against molar concentration e i.e. a straight line graph passing through
origin. It has a slope = eb :. e = slope/b.
Plot of graph of absorbance (O.D) against concentration of methylene blue solution in ppm (c).

A Slope = m = &.b
A
Slope
:.t--
b

(0,0) C (0,0) c
(ppm)_ (ppm)_
Fig. 5.2

Calculations:
Molar extinction coefficient from graph for absorbence against concentration in ppm
s = Slope x 103 x M (Molecular weight of the solute)
Results:
(1) AIIIIU for methylene blue = ____ nm.
(2) smean as calculated _ _ __
(3) £graph obtained from graph _ __
38 College Practical Chemistry (T. Y. B.Se.)

Conclusions:
(1) Lambert Beer's law is verified since the graph of absorbance A against molar
concentration C or concentration in ppm is a straight line passing through the origin.
(2) Constancy in the values of E, as calculated for the various dilutions also verifies Lambert
Beer's law.
Experiment No.2
Aim: To determine the sta15ility constant of Fe3+ - Salicyclic acid system using spectrophotometric
method.
Requirement: O.OOIM Fe(III) ions solution in 0.002M HCI, O.OOIM salicylic acid in 0.002M HCI,
saturated salicylic acid in 0.002M HCI, 0.002M HCI solution, 250 cm 3 and 100 cm 3 standard
measuring flasks, colorimeter with suitable filters, calibrated pipettes, etc.
Theory:
Fe(III) and salicylic acid form a deep red coloured complex with the absorption maximum
(Amux) at about 525 nm. The complexation reaction can be represented as:
Fe3+ + S.A. -+ [Fe (SA)P+ ... (1)
or
Fe3+ + C6H4(OH) COOH -+ Fe[C6HiOH)COOH]3+ ... (2)
The optimum pH range for the stability of iron (III) - Salicylic and complex is 2.6 - 2.8 which
is obtained by using solution made in 0.002M HCI.
The formation of stability constant for the I: 1 complex can be given by:

[Fe (SA)]
~ =
[Fel[SA]
[Concentration of complex]
... (3)
[Concentration of Fe 3+ions] [Concentration of salicylic aCid]

If x moles is the concentration of the complex formed .and a and b are the initial concentrations
of ferric ion and salicylic acid respectively, then stability constant,
K or ~ = (x)/(a - x) (b -x) ... (4)
The concentration x can be obtained by using calibration curve method or by using Beer's
Law.
Procedure:
Perform the experiment as follows:
Part I : Determination of molar absorptivity, e:
(1) Filter (if necessary) the supplied solution of saturated salicylic acid in 0.002M HCI through
cotton.
(2) Pipette out 1.0, 2,0, 3.0,4.0 and 5.0 cm3 of O.OOIM Fe(III) ions solution in five serially
numbered 10 cm 3 standard measuring flasks (or test tubes).
ColorimetrylSpectrophoiometry 39
3
(3) Add 5 cm of saturated salicylic acid solution to each standard measuring flask and make
up the volume 10 cm 3 using adequate amount ofO.002M HCl solution as ghen in T~.'Jle
5.1. Shake each flask thoroughly.
(4) Measure the absorbance of each solution at 525 nm against 0.002N HCl as blank.
(5) Record the readings in Table 5.1 as follows:
Table 5.1 Determination of molar absorption (£):
Path length, b = ___
A. = nm
Obs Volu~e in cm) Resultant O.D.
No. O.OOIM Fe(/lJ) soluti~n Saturated salicylic O.002M Hel concentraion
acid solution ofFe(l/I)
1 1.0 5.0 4.0
2 2.0 5.0 3.0
3 3.0 5.0 2.0
4 4.0 5.0 1.0
S 5.0 5.0 0.0
(6) Plot a graph of absorbance (O.D.)
against the concentration of Fe (III) ions solution
(Fig. 5.3). Considering the complete complex
formation, determine from the slope' molar
absorptivity, E of the complex.
Part II: D.etermination of absorbance at
Slope =E
different concentrations of Fe (III)
and Salicylic acid:
(1) Mix the supplied O.OOlM Fe (III) ions
solution and O.OO! M salicylic acid solution provided
in different proportions (9: 1 to 1:9) in serially
numbered 10 cm3 standard measuring flasks as (0,0) Cone. of Fe (III) in M dm3

shown in Table 5.2 Fig. 5.3: Absorbance against concentration


(Note: If test tubes are used shake each of Fe (1/1) ions
solution carefully).
(2) Measure the absorbance of each solution at the wavelength of 525 nm against 0.002M HCl
as bl,.ruc.
(3) Record the ab&.lrbance (A*) of the various mixtures prepared in Table S.2
Table 5.2 Determination of Absorb~nce·
-. -"-
Obs.
- - Volume in cm) of
No. O.OOIM Fe (/lJ)ions so/utior 0.001 M Salicylic acid solution Absorbance (A·)
1 9 1
2 8 2
3 7 3
4 6 4
I
5 5 5
6 4 6
7 3 7
8
9 i 2
I
8
9
40 College Practical Chemistry (T. Y. B.Sc.)

Part III: Determination of Stability constant of Fe (III) salicylc acid complex:


(1) Using the absorbance (A *) values of various mixtures prepared in Part - II and molar
absorptivity, E obtained from graph in Part - I, Calculate the concentrations of Fe (III) and salicyc1ic
acid remained in uncombined from as follows:
(i) Molar absorptiviti of Fe - SA complex, E =- _ _ __
(ii) Concentration of Fe (III) taken initially in molldm3 = a
(iii) Concentration of SA taken initially in molldm3 = b
(iv) Concentration of Fe - SA complex formed x = (A-)/E.
(v) Concentration of uncombined Fe (III) = (a - x).
(vi) Concentration of uncombined SA = (b - x).
Table 5.3 Calculation of stability constant of Fe (III) - Salicyclic acid complex
Flask Cone of Fe(IIJ)ions Cone of (A-) x
No. in molldm3 Salicylic acid x=-- (a-x) (b - x) K=
a in molldm 3 E (a - x) (b - x)
b
1
2
3
4
5
I MeanK=

(2) Using the values of concentration of Fe - SA complex (x), uncombined Fe (III) ion
concentration, (a - x) and uncombined SA concentration (b - x) for suitable solutions,
obtain the value of stability constant of the complex, K _ (Table 5.3)
Results:
(1) Molar absorptivity (E) == _ _ __
(2) Mean stability constant of Fe (III) - Salicylic acid complex K = ____
Experiment No.3
Aim: To calibrate colorimeter/spectrophotometer (in visible range) using KMn04 solution and to
find concentration of Mn present in the given sample.
Requirements: O.IN KMn04, distilled water, spectrophotometer or colorimeter, sample tubes etc.
Theory: Spectrophotometer (or colorimeter) is an optical instrument used to study absorption of
light by the sample solution. With the help of spectrophotometer it is possible to obtain the
information about the wavelength (range) at which sample absorbs light radiations and absorbance
(O.D.) of the sample .solution.
Every coloured solution shows the property to absorb light radiation at certain wavelength.
It is the characteristic property of coloured material to absorb light radiation at a particular wave
length and have definite value of molar extinction coefficient (e), (For example KMn04 shows
maximum absorption at the wavelength of 525 nm).
A spectrometer can be said to be calibrated (working as desired and expected) if it shows
maximum absorption at a particular characteristic wavelength of the sample solution, it shows linear
Colorimetry/Spectrophotometry 41
relationship for concentration ofthe sample solution and absorbance or O.D., and the value of molar
extinction coefficient (e) is same as given in literature.
Hence, spectrophotometer can be calibrated using standard KMn04 solution and verifying
the value at J... max and e obtained with the particular instrument and comprising with the literature
value.
Procedure:
Perform the experiment as follows:
To calibrate colorimeter/spectrophotometer, it is necessary to check:
(a) If the absorption of light radiation taken place in the expected wavelength range.
(b) Whether it obeys Beer's Law in the expected calculation range.
(c) Whether the practical molar extinction coefficient for the standard substance tallies with
the standard literature value.
Part I: Determination of "'max:
(1) Pipette out 5.0 em 3 of O.IN KMn04 solution in 250 em 3 standard measuring flask and
dilute exactly upto the mark with distilled water. Shake the flask thoroughly well. This
will give 0.002N KMn04 solution. (or 4 x I~ M/dm 3 ).
(2) Prepare the following solutions from 4 x 10-4 M/dm 3 KMn04 solution in serially numbered
100 em 3 standard measuring flasks as given in Table 5.4 below:
Table 5.4
Sr. No. Volume ofO.OO2N Volume ofdistilled Concentration ofMn2 +
KMn04 in cm 3 water in cm 3 in Mdm-J
I 10 90 4 x 10-5
2 20 80 8 x 10-5
3 30 70 12 x 10-5
4 40 60 16 x 10-5
5 50 50 20 x 10-5

(3) Take a clean cuvette and wash it with distilled water. Adjust transmittance to 100% or
optical density (0.0) or absorbance (A) to zero.
(4) Rinse the cuvette with the solution No.3 (i.e. containing 30 em 3 solution)
(5) Dry the outer portion of the cuvette with a clean piece of cloth.
(6) Place the cuvette in the colorimeter and determine the optical density (or absorbance)
of the solution using a filter of wavelength 420 nm (minimum wavelength available) as
per the procedure given in colorimetric experiment No.1.
(7) Determine the absorbance or optical density of the solution using filters of wavelength
470 nm, 530 nm, 620 nm, 700 nm, etc. i.e., upto the maximum wave length available.
Record your observations as given in Table 5.5.
(8) Plot a graph of optical density (absorbance) of the solutions against wavelength of
absorption to find wavelength of maximum absorption A.max •
42 College Practical Chemistry (T. Y. B.Sc.)

Part II : Construction of calibration curve:


(1) Take a clean, dry sample tube (cuvette). Rinse it 3-4 times with the KMn04 solution of
minimum concentration (i.e., solution No.1) as prepared in Table 5.4. Fill it upto the mark.
Wipe it from outside first with tissue paper and then with cotton cloth.
(2) Determine the absorbance of the, solution using the filter which showed maximum
absorbance as per the procedure given in colorimetric experiment No.1.
(3) Repeat the procedure for all the remaining KMn04 solutions at different concentrations.
(4) Record absorbance values of the solutions in tabular form as given in Table 5.5.
Observations:
Table 5.5 Determination of i.....tIX
Filter Peak Wavelength Absorbance
No. i.. or O.D.
I 440
2 -
3 -
4 -
- -
:. Wavelength of maximum absorption, I..max = nm _ __
Table 5.6 Construction of Calibration Curve
Detennination of Absorbance at different concentrations
Path length =__ cm (i..max = _ _ nm)

Obs. 'Concentration ofKMnO4 Absorbance


No. solution in M dm- J of solution
I 4.00 x lO-5
2 8.00 x lO-5
3 12.00 x lO-5
4 16.00 x lO-5
5 20.00 x lO-5

Graphs:
flot the graphS\ of: Absorbance against peak wavelength of filter
:. Wavelength of maximum absorption "'",ax = nm

540 580
peak wavelength
Fig. 5.4
Color;metlylSpectrophotometlY 43
Absorbance against concentration of KMn0 4 solution (i.e., calibration curve):

12.0 20.0
Conc. ofKMnO. solution (DrIuJ) (in mOl/dm"3)
Fig. 5.5

Calculations:
Slope of (Straight line) calibration curve = _ __
:. Molar extinction coeffoicient = dm 3lmollcm.
Results:
(1) Observed Amax for KMn04 solution = nm.
(Literature value ,of Amax = 525 nm)
(2) Nature of graph = _ _ __
(As per Beer-Lambert's law it must be a straight line passing through origin).
(3) Slope of graph of optical density against concentration of KMn04 = ___ dm 31M
(4) Molar of Extinction coefficient, e = ___
(Literature value = 2600).
Experiment No. 4
Aim: To determine the amount ofMn in the given solution by period ate method using least square
method.
Requirements: O. IN KMn04 solution, Cone. HN03 (AR), potassium periodate, distilled water
etc.
Theory: The amount of Mn2+ ions present in the solution can be obtained colorimetrically Mn2+
ions present in solution can be oxidised to permanganate using periodate. The reaction of oxidation
can be shown as:
2Mn2+ + 5104- + 3H20 ~ 2Mn04- + 5103- + 6H+
Permanganate ion formed is quite stable and the presence of free acid does not interfere
in the determination of manganese.
To determine the amount of manganese present in the given sample, a calibration curve-(a
plot ofoptical density or absorbance against concentration) is first constructed. For solution obeying
Beer's Law, this should be a straight line passing through zero. The slope of the line obtained in
the calibration curve can be obtained either graphically or using the method of least square.
44 College Practical Chemistry (T. Y. B.&.)

Least square method is a stastical method used to calculate the slope of the best fitting line
from the data showing linear relationship of the form y = mx or y = mx + e. The method is based
on the theory that the best line is the line whieh makes the sum of the squares of the deviation a
minimum. It represents sum of squares of all difeerences i.e., S = L (y - mx)2 = L (n - 2 mxy
+ m 2 x 2)
ds
.. dm L (0 - 2xy + 2mx2) - (2)

ds
Condition for minimum value dm =0

:. m = - (3)

Procedure:
Carryout the experiment as follows:
Part I: Construction of calibration curve:
(1) Pipette out exactly 5.0 em 3 of supplied O.IN KMn04 in 250 em 3 standard measuring flask
and dilute it to the mark with distilled water. Shake the flasks thoroughly well. This forms
0.002N KMn04 solution.
(2) Prepare the following solutions from 0.002N KMn04 solution in serially numbered
100 em 3 standard measuring flasks as follows:

Flask Volume ofO.OO2N Volume ofdistilled Amount of


No. KMn04 solution water Mn2+ ion
in cm] in cm] in ~g

1 10 90 220
2 20 80 440
3 30 70 660
4 40 60 880
5 50 50 1100

(3) Determine the absorbance (or optical density) of each solution using a filter of wavelength
525 nm on the colorimeter following the procedure described in previous colorimetric
experiment.
(4) Using the values of absorbance and corresponding concentration of Mn2+ ion solution (in
J.lg) obtain best fitting line using least square method.
Estimation of Mn2+:
(A) Preparation of sample solution:
(1) Dilute the given solution of MnS04. H20 to 100 em 3 in standard measuring flask with
distilled water accurately. Shake the flask thoroughly well
(2) Weigh accurately 0.5 g of potassium periodate. Prepare two such packets.
Colorimetry/Spectrophotometry 45
(3) Pipette out 10 em 3 of the diluted Mn2+ solution in 150 em 3 ofborosil/corning conical flask.
Add 15 em 3 of A.R. grade conc. HN0 3 and 0.5 g of potassium periodate powder to the
flask Add about 25 em 3 of distilled water to it and place a small funnel over the flask
(with the stem of the funnel inside the flask).
(4) Boil the solution for about 15 to 20 minutes to ensure complete oxidation of Mn2+. This
will be indicated by the appearance of the pink coloured solution. During boiling, add small
quantities of distilled water from time to time to make up for loss due to evaporation.
(5) Cool the solution completely, transfer it to 100 em 3 standard measuring flask and dilute
it up to the mark with distilled water.
(B) Preparation of solution for blank reading:
(1) Take 15 em 3 of A.R. grade conc. HN0 3 in 150 em 3 ofborosil/coming flask and add 0.5
g of potassium periodate and 40 em 3 of distilled water to it.
(2) Place a small funnel (as described above) and heat the solution for about 15 to 20 minutes
taking the same precautions as described in A.
(3) Cool and transfer the solution to 100 em 3 standard measuring flask and dilute it accurately
with distilled water.
(C) Estimation of concentration of Mn 2+:
(1) Determine the absorbance or optical density of the solution prepared in (A) against the
blank (B) on the colorimeter using filter of wavelength 525 nm (given filter 530 nm) and
estimate the total Mn 2+ in the given solution by reference to the standard curve.
Graph:
Plot a graph of absorbance or optical density against concentration of Mn2+ in Jlgs, taking
the origin as (0, 0). Determine the unknown concentration of Mn2+ from the absorbance or optical
density reading of the sample Mn2+ solution on the calibration curve obtained using least square
method.

(0,0) Cone. of Mn2+ in I1gs

Fig. 5.6
Col/ege Practical Chemistry (I'. Y. B.&.)

Calculations:
To obtain the best fitting line from the calibration curve using least square method prepare
following Table.

Concentration ofMn 2 + Absorbance Concentration ofMnl+ (concentration ofMn1 +JZ


in IlK (0 D.) x absorbance
x y x.y. xl
0 0 0 0
220
440
660
880
1100
Unknown I
Exy = ExZ=

:. slope of the best line, m = :Exy&

(Use this value of slope to obtain amount of Mn 2+ in sample)


Let x be the concentration of Mn 2+ in ).lgs corresponding to the observed optical density or
absorbance of the solution.

.. The amount of Mn 2+ in the 10 em 3 of sample solution ~ ).lg.


slope
.. The amount of Mn2+ in the 100 em 3 of sample (lOx) = ____
Results:
(1) Slope of the line (m) obtained using least square method = _ __
(2) Absorbance (or optical density) of the test solution = _ __
(3) Amount of Mn 2+ in the given solution = ).lg.

000
6
Conductometry

Some imponant theoretical aspects


Electrolytes in liquid state (fused or solution), are able to conduct electric current which is
carried by the movement of ions. The ability of any solution to carry an electric current is measured
as its conductivity. Just like metallic conductors, electroytes also obey Ohm's Law.
Mathematicaly, Ohm's law is given as:
E
1= R
where, 1 is the current in amperes flowing between two similar metal plates kept immersed in an
electrolyte. E is the applied electromotive force (A.C. supply) in volts and R is the resistance
in ohms shown by the electrolyte solution.
For a constant applied e.m. f (E), the current (l) is given as:
I
10.-
R

The reciprocal of the resistance i.e. ~ is called the conductance (L) and is expressed in
R
siemens or (mhos).
The observed resistance of a solution depends directly on the distance (I) between the two
metal plates and inversely upon the area (a).
I
Ra a
48 College Practical Chemistry (T. Y. B.Sc.)

I
R=p-
a
where, p (Rho) is called the specific resistance and is defined as the resistance in ohms of a
specimen having unit length and unit area.

~=.!.. a =K.!!.. =L
R p I I
where, K (kappa) is reciprocal of specific resistance (p) and is called specific conductance.
Specific Conductance (K): It is defined as the conductance of a unit cube of electrolyte
solution measured at a specified temperature. The units of specific conductance are' siemens
me-I (or mho em-I).
Equivalent Conductance (A): It is conductance of all the ions produced by one gram
equivalent of an electrolyte at a given concentration or dilution when placed between two
parallel platinum plates kept unit distance apart and large enough to contain between them,
all the solution.
Equivalent conductivity = A = K x V
where, V is the volume in cm 3 , containing 1 g. eq. of electrolyte.

1000 K
V = C thus Equivalent conductivity A = 1000 C
where, C is the concentration in gram equivalents per 1000 cm 3 (i.e. Normality). The units of
equivalent conductance are siemens m2g Eq-I (or mho cm 2 g Eq-I).
Molar Conductance (J.1): It is defined as the conductance of all the ions produced by
one gram molecular weight of an electrolyte at a given concentration or dilution when placed
between two parallel platinum plates kept unit distance apart and large enough to contain the
entire solution between them.
K
Molar conductance, J.1 = 1000 x M

where, M is the concentration in mole per 1000 cm 3 or (Molarity) where concentration M is


expressed in mol dm-3 and K is the specific conductance. The units of molar conductance will
be siemens m2 moZ-1 (or mho cm 2 moZ-l)
Conductivity Water: Distilled water conducts current to an appreciable extent due to the
presence of impurities such as dissolved gases viz., carbon dioxide, ammonia etc. For accurate
measurements of conductance of a salt, its solution must be prepared in exceptionally pure water
called conductivity water. This is prepared by redistilling the distilled water to which small quantities
of KMn04 and KOH have been added. However, conductivity water also has a definite
conductance, but its magnitude is comparatively very low (of the order of 10-6 to 10-7 siemens.)
Therefore, the conductance of a solution prepared in this water will also include the conductance
of conductivity water.
Conductometry 49

TERMINALS Kohlrausch's Law: It states the equivalent conductance of


an univalent electrolyte at infinite dilution (Aoo) is equal to the
sum of the ionic conductances of all the constituent ions (J... 0+
+ A. 0_) present in the solution at infinite dilution. Its mathematical
expression is:

Conductivity Cell: A simple cell consists of two parallel


GLASS
CASING
plates of platinum fixed in position on a Pyrex glass container as
shown in Fig. 6.1. The cell resistance is in the vicinity of 500-
10,0000 for accuracy and sensitivity. For solutions having low
conductivity, the area (a) should be large and the plates placed close
together, but for highly conducting solutions the area should be small
PLATINUM and the plates placed at a large distance (I) from each other. The
PLATES plates are plated with platinum black to reduce the polarising effect.
When not in use, the cell is generally kept immersed in distilled
water.
Fig. 6.1 Conductivity Cell
Degree of Dissociation (a): It is defined as the fraction of the
total amount of an electrolyte which dissociates into ions at equilibrium at a given
temperature. It can be calculated from conductivity measurements as follows:

where, Ay and Ac = Equivalent conductance at a given dilution or concentration.


Ao and Aoo = Equivalent conductance at zero concentration or infinite dilution.
Instructions for proper handling of the Conductivity meter:
Note: Digital instruments require
minimum and easy adjustments before
any readings are taken on them.
These are explained in details by the
professor concerned in the laboratory.
However, instructions for a typi-
cal instrument are explained below:
(I) Standardisation:·
(A) For approximate purposes:
(1) Switch the instrument on
about 10-15 minutes before
starting the experiment
(2) Keep the Range switch on
2 (milli mho) position.
(3) Keep the standard con-
ductance switch at down FIg. 6.2 Digital COl/dllGth'ity meter
position.
50 College Practical Chemistry (T.Y. B.SeJ

(4) Observe the digital display. If the display shows 1.000, then it means the instrument is
standardised. If not, rotate the standardise shaft so that the display reads 1.000.
(B) Accurate method:
(1) Switch the instrument on about 10-15 minutes before starting the equipment
(2) Keep the conductivity cell (cell constant = 1) in distilled water for about 10-15 minutes.
Connect its terminals to the cell terminals seen on the conductivity meter.
(3) Prepare exact O.IN KCI solution. Take it in a 100 cm3 beaker.
(4) Remove the conductivity cell from distilled water. Wipe it clean softly with a filter paper
and immerse it into O.1N KCI solution.
(5) Wait for about one minute, check the standard conductance switch. It should be kept
on up position.
(6) Select the correct range by rotating the range selector knob so as to get maximum
number of significant figures on the digital display.
(7) Observe the display. It should read the (specific conductance x 103) of O.1N KCI (e.g.
at 25°C, it is 0.01288 mhos). Thus, it should read 12.88.
(8) If it does, then the instrument is already standardised, else, rotatate the standardise shaft
till the correct specific conductance is obtained.
(Specific conductances of various KCI solutions at different temperatures can be obtained
from the universal data).
Note: Once standardisation is complete, the standardise shaft must not be touched.
(II) Measurement of conductance
(1) Switch the instrument on about 10-15 minutes before starting the experiment
(2) Keep the conductivity cell dipped in distilled water for about 10-15 minutes. Connect its
terminals to the cell terminals seen on the conductivity meter.
(3) Confirm that the instrument has been properly standardised.
(4) Take the sample solution whose conductance is to be measured, in a 100 cm3 beaker.
(5) Remove the conductivity cell from distilled water. Wipe it clean gently with a filter paper
and dip it into the sample solution.
(6) Wait for about one minute. Check that the standard conductance switch is kept at up
position.
(7) Rotate slowly the range selector knob till the display. shows maximum number of
significant figures.
(8) Note down the reading shown in the display with an exponent of (-3), e.g., if the display
reads (3.142), note it as (3.142 x 10-3) mhos. This is the conductance of the sample
solution.
Experiment No. 1
Aim: To determine the percentage composition (by weight) of strong acid and weak acid in a given
mixture by titrating against strong base, conductometrically.
Requirements: Mixture of acids in 100 cm 3 standard measuring flask, O.1N NaOH solution,
conducting bridge, burette, pipettes etc.
Conductometry 51
Theory: In a mixture of a strong acid a weak acid, strong acid undergoes almost complete ionisation.
However, the ionisation of weak acid is reversible and incomplete. In presence of excess of H+
ions produced by the ionisation of strong acid its ionisation is further suppressed and it remains
practically undissociated i.e., in molecular form) Hence in such mixture the conductance of
solution is due to H+ and anions produced by the dissociation of strong acid only while
weak acid does not contribute to condutance.
When strong base like NaOH is added to solution, OH- ions of the base combine with H+
ions present in the solution to produce practically unionised water, i.e., H+ ionc are replaced by
Na+ ions which can be shown as:
H+ + NaOH ~ H20 + Na+ ... (1)
The conductance ofNa+ being much smaller than H+ (350), the conductance of the solution
decreases. This decrease in conductance continues till all H+ ions present in solution produced by
ionisation of strong acid are neutralised.
When free H+ ions from the solution are consumed NaOH added reacts with unionised acid
to produce salt, whIch being strong electrolyte,undergoes ionisation contributing to the conductance.
The reaction can be represented as:
. HA + NaOH ----+ H20 + Na+ + A- ... (2)
Due to replacement of un ionised acid molecules (non conducting) by anions (conducting) the
conductance of solution gradually increases.
When all the amount of weak acid has reacted completely (stage II), the further amoun~ of
NaOH added remains unreacted. Being strong electrolyte, it undergoes ionisation completely
producing OH- ion as:
NaOH ----+ Na+ + OH- ... (3)
The conducting capacity of OH- ion being high (200) conductance of the solution starts
increasing rapidly showing 2nd break.
Thus by carrying out titration of mixture of strong acid and weak acid against a strong base,
it is possible to find out the amount of the respective acid given in the solution.
Procedure:
(1) Immerse the conductance cell in conductivity water. Keep it immersed for about 10-15
minutes. This step ensures that the cell becomes clean.
(2) Rinse and fill the burette with O.IN NaQH solution.
(3) Dilute the given acid mixture to 100 cm 3 with conductivity water in the standard measuring
flask and pipette out 10 cm 3 of it in a 100 cm 3 beaker.
(4) Now, transfer the conductivity cell into this beaker and add a minimum quantity of
conductivity water to completely immerse the plates in the solution.
(5) Connect the cell to the conductivity meter and determine the conductance of the mixture
in siemens (mhos), as explained on page No. 49 (or as explained by your professor),
(6) Add a small quantity (say 0.5 cm 3) of NaOH solution at a time from the burette, stir
the solution, wait for about 20 seconds and note down the conductance value.
52 College Practical Chemistry (T. Y. B.Sc.)

(7) Repeat step No.6. Intially conducance will decrease rapidly. Continue the addition of 0.5
cm3 of until the conductance values show a slow increase followed by a rapid increase. Take
four to five more readings. (Generally readings are to be taken till about 25 em 3 of the titrant
have been added.)
(8) Plot a graph of conductance measured against volume of NaOH added. Determine the
volume of NaOH required for neutralisation of strong acid corresponding to the first
minima (Vx)' Similarly, find the volume ofNaOH required for weak acid from the second
minima (Vy)' Thus, calculate the percentages of two acids.
Observations and Calculations:
(1) Volume of acid mixture pipetted out for titration (VI) = 10 em 3•
(2) Normality of NaOH used = O.IN.
Obs. Volume of NaOH added Conductance in
No. Vem 3 mhos
1 0
2
3

Graph:
Plot of conductance measured against volume of
NaOH added.
w
r
0
Calculations:
I Ig
Z

Find V, and V from the graph. thus V, =V- V,


:::>
Percentage composition by 0

(1) Weight basis


z
0
0
"
Vx " \ Vy

(a) lem3 of IN NaOH solution = 36.5 mg of HCI V


3
.. Vx em of O.IN NaOH soution VOLUME OF NaOH --+
= 36.5 x 0.1 x Vx
Fig. 6.3
= x mg of HCI
(b) Similarly,
I em 3 of IN NaOH solution 0 60 mg of CH3 COOH
:. Vy em 3 of O.IN NaOH solution = 60 x Vy x 0.1
= Y mg of CH 3 COOH
Therefore, percentage by weight of strong acid in mixture (P) is given as:

P = [ x x 100]
(x+ y)

Percentage of weight of weak acid = [100 - Pl.


Conductometry 53
(2) Volume basis
Out of V cm 30f 0.1 N NaOH solution, Vx cm 3 is required for neutralisation of strong acid (SA):

:. 100 cm 3 requires ~ x 100,= % of strong acid

which is the percentage of strong acid in the mixture (i.e., % of strong acid)
:. Percentage of weak acid = %WA = (100- % of strong acid)
Results:
(1) Volume of O.lN NaOH solution required to neutralise
(i) strong acid (V) = _ cm 3•
(it) weak acid (V) = _ cm 3.
in 10cm 3 of the diluted sample solution.
(2) Percentage of strong acid = ___ % by volume and _ _ % by weight
(3) Percentage of weak acid = % by volume and % by weight.

Experiment No.2
Aim: Determine the velocity constant ofthe hydrolysis of ethyl acetate by sodium hydroxide solution
by conductometric method.
Requirements: Conductivity bridge, freshly prepared 0.2M Ethyl acetate solution, O.OIM Sodium
acetate solution, 0.05M NaOH solution etc.
Theory: Ethyl acetate gets hydrolysed in the presence of base to form alcohol and sodium acetate.
CH3COOC2Hs + NaOH ----+ CH3COONa + C2HsOH
Hence, the rate of reaction depends on the concentration of ester as well as the base. Due
to the formation of salt, CH3COONa which is completely ionised the conductance solution changes.
Hence, it follows the second order reaction which can be tested experimentally.
Procedure:
(1) Take 20 cm 3 of supplied 0.05M NaOH solution and dilute it to 100 cm 3 in a standard
measuring flask with conductivity water. Determine the initial conductance with O.OlM
NaOH solution (Co) and final with O.OIM sodium acetate solution (Coo) at 25°C. (or ask
for reading)
(2) Now, keep two 150 cm 3 beakers, one containing 20 cm 3 of 0.05M NaOH solution and
50 cm 3 of conductivity water and the other containing 5 cm 3 ofO.2M ethyl acetate solution
and 25 cm 3 of conductivity water.
(3) When each solution is at room temperature, introduce a clean and dry conductivity cell
in the bridge.
(4) Mix both the solutions thoroughly in a 250 cm 3 beaker and quickly insert the conductivity
cell in the reaction mixture and record conductance at time intervals of 0, 2, 4, 7, 10,
15, 20, 25 and ..... 30 minutes. (C,)
54 College Practical Chemistry (T. Y. B.Sc.)

Observations:
Time t in minutes Conductance c, in mhos

0 (Col
2 -
4 -
7 -
10 -
15 -
20 -
25 -
30 -
00 (C..,)
Calculations:
The second order rate constnat (K) for a reaction in which, the two reactant concentrations
are equal, (a = b)
I X
K = -
t a(a -X)
Here, a = O.OIM
a-x = CI-C and x = 0
Q()
C-C I

a = Initial concentration
a-x = Concentration at time t
x = Amount of substance reacted.
Substituting these values in the second order rate constant,

1
K= 0.0151 C
(Co -C,)
-Coo
t

Graph:

. (Co -CCoo t )

(~)
A graph of C _ against t should give
t

a straight line. whose slope = If x 10-2. c, - Coo Slope = K x 10-2

The units of K are morl cm 3 S-l.


Results:
The value of rate constant K = ____

Fig. 6.4

000
7
pH-Metry

Some important theoretical aspects


The acidity or alkalinity of a solution can be expressed in tenns ofH+ ion concentration. Easier
way of expressing the hydrogen ion concentration is by using the pH scale.
pH of a solution is calculated by the taking the negative logarithm of its hydrogen ion
activity.

I
pH = -log [H+] = log [H+]

pH of a neutral solution is 7. If the value of pH is less than seven, then the solution is acidic
and if it is greater than seven, then it is alkaline. (basic)
pH-Measurements:
There are two general. methods of detennining pH of a solution:
(i) Visual: In this method, various indicators are used. The colour produced after addition
-of a particular indicator to the solution under study, is matched with that produced by a standard
solution or with a standard colour scale.
(ii) Electro Motive Force (E.m.f.) or Potentiometric method: Here the e.mf of a cell,
consisting of a standard reference electrode reversible to H+ions, is measured. The most commonly
used electrodes which are reversible to H+ ions are quinhydrone and glass electrode. The reference
electrode popularly used is the calomel electrode. Sometimes, a combined glass electrode is also
used which includes the reference electrode within its construction. pH is then calculated from
the observed values of e.m.j of the cell or it may be obtained directly by using a pH meter; which
is a modified potentiometer.
56 College Practical Chemistry (T. Y. B.Sc.)

Glass electrooe consists of a very thin walled glass bulb blown at the end of a glass tube.
The bulb contains an electrode which has a constant potential (e.g., a platinum wire coated with
Ag/Agel and dipped in 0.1 N Hel solution or a platinum wire dipped .in 0.1 N Hel solution saturated
with quinhydrone. When the bulb is immersed in a sample solution, it acquires a potential whose
magnitude depends upon the H+ ion concentration of the sample solution.

Buffer Solutions:
Buffer .f!olutions are an important class of solutions involving the common ion effect. These
solutions resist change in pH upon (i) addition of small amounts of an alkali or an acid (ii) on dilution
and (iii) on preservation.
pH of a buffer solution is measured with the help of a pH-meter. It is essentially a voltage
measuring device so designed that it can be used with cells of high resistance (viz.~ glass electrode
and a standard calomel electrode as the reference electrode or just the combined glass electrode).

Procedure:

(1) Preparation of standard buffer solutions:


(Note: Readymade buffer tablets are also available.)
(a) For Acidic range, having a pH of 4 at 25°C.
Dissolve 1.021 g of potassium hydrogen phthalate (or the standard buffer tablet) in a minimum
quantity of distilled water (the solution may be warmed, if required) and dilute it to 100 cm 3 with
distilled water in a standard measuring flask.
(b) For alkaline range having a pH of 9.2 at 25°C.
Dissolve 0.38lg of borax (or the standard buffer tablet) in a minimum quantity of distilled
water (the solution may be warmed, if required) and dilute it to 100 cm 3 with distilled water in
a standard measuring flask.
Instructions for proper handling of the pH-meter:
Note: Digital instruments are easy to
operate and require minimum adjustments before
any readings are taken on them. These are
explained in details by the professor concerned
in the laboratory with respect to particular model.
However, instructions for a typical instru-
ment are explained below:
(I) Standardisation:
(l) Switch the instrument on for about 10-
15 minutes before starting the experi-
ment. Fig. 7.1 pH-meter.

(2) Using the specially supplied connector


cable, join the electrode terminal and the (PH = 7) terminal, both situated at the back
of the instrument. OR immerse the combined glass electrode in a buffer ofpH=7 prepared
using appropriate buffer tablet. The cable end of the combined glass electrode should be
connected to the electrode terminal. Put the pH-mV Knob on the pH position.
pH-metry 57
(3) Set the temperature control knob at the temperature of the buffer solution.
(4) Adjust the asymetry potential knob so that the display reads 7.00 pH.
(5) Now remove the connector cable from 7.00 pH and connect it to 4.00 pH terminal
(Situated at the back of the instrument) OR
[Remove the combined glass electrode from pH = 7 buffer wash it thoroughly with a
jet of distilled water. Dip it clean in distilled water and softly dry it with filter paper].
Now, immerse the combined electrode in a buffer of pH = 4, prepared using the
appropriate buffer tablet.
(6) Adust the Slope knob so that the display reads pH = 4.00.
(7) Remove the connector cable from 4.00 pH and connect it to 9.2 pH terminal (situated
at the back of the instrument)
OR
[Remove the glass electrode wash and dry it as explained above in step No.5. Immerse
it in a buffer of pH = 9.2 prepared using the appropriate b\!ffer tablet.]
(8) Observe the digital display. It should show pH = 9.2 indicating that the standardisation
is complete.
Repeat the Step Nos. 5, 6 and 7 to get pH 9.2 display.
[Note: Once the instrument has been standardised, the slope and assymetry potential
knobs must not be touched.]
(II) Measurement of pH:
(1) The instrument must be switched on for about 10 minutes and then standardised as
explained above.
(2) The combined glass electrode must be kept in distilled water for about 5 minutes before
starting the experiment.
(3) The combined glass electrode must be once again thoroughly washed with ajet of water
and then dried softly with a filter paper.
(4) Immerse the electrode into the sample solution whose pH is to be determined. Wait for
about 1-2 minutes.
(5) Set the temperature control knob to show the temperature of the sample solution. Put
the pH-m V knob on the pH position.
(6) Now, observe the digital display, read the pH and note it down.
(7) To find pH of another sample repeat step Nos. 3, 4, 5, 6 and 7.

Experiment No. 1
Aim: To titrate sodium carbonate against HCI using pH meter and suggest indicators for two
inflections.
Requirement: Sodium carbonate solution, O.IN HCI, Buffer solutions of pH = 4.00 and 9.I8,pH
meter, .beakers, pipette etc.
Theory: Sodium carbonate is the salt of dibasic acid, carbonic acid (H2C03). The disscialtion
constnate of H2C0 3 being: KaJ = 4.3 x 10-7 and Ka2 = 5.6 x 10-11 • Na2C0 3 hydrolyses in aqueous
58 College Practical Chemistry rr. Y. B.Sc.)
solution prouucing basic solution. It is possible to titrate solution of sodium carbonate with strong
acid lib HCl. The first stage of titration can be represented as:
N~C03 + HCI -+ NaHC0 3 + NaCI ... (1)
The value associated with first inflection point can be determine with an error of about 1%
[Kall Ka 2 < (10s)].

The second stage of titration can be represented as:


NaHC03 + HCI -+ NaCI + H20 + CO2t
The volum~ asso~iated with second stage equivalence point (inflection point) can be
determined with an error of about 0.5%.
Th~ 1st stage equivalence point appears at pH 8.3 with -¥Hlas 3 = 0.63 pH unit. m- cresol
purple (9.0 to 7.4) or phenolphthalein (0.0 to 8.3) may be suitable indicators which give colour
changes near 1st equivalance point. The 2nd equivalence point is obtained at pH 3.92 with -¥HI
cm3 = 1.1pH units. Methyl orange (4.4 to 3.1) would fit almost exactly into this -¥H.
Hence, it is possible to identify the two equivalnece points carrying out the titration of sodium
carbonate with hydrochloric acid pH-metrically and suggest the best possible indicators for the
inflection points.
Procedure: Conduct the experiment as follows:
Part I : Standaroisation of pH meter:
(In this experiment, it is essential to standardise the pH meter in both acidic and basic range).
(1) Switch on the pH-meter
(2) Wash both the electrodes (combined electrode) several times with distilled water.
(3) Using both buffers (phthalate buffer and borax buffer), standardise the pH-meter carefully
for both acidic and basic range as given in the experiment.
(4) Wash the electrode/s with distilled water.
Part II : Titration of sodium carbOnate against Hel:
(1) Dilute the supplied N~C03 solution in 100 cm 3 st;;tndard measuring flask with distilled
water.
(2) Take 10 cm 3 of this diluted sodium carbonate solution in a 100 cm 3 clean beaker with
the help of pipette.
(3) Immerce the electrodels in solution (if necessary, add a small volume of distilled water).
(4) Wash and rinse the burette with O.IN HCI solution.
(5) Record the pH of the solution before the addition of HCl.
(6) Add 0.5 cm 3 0fHC; from the burette. Stir the solution sufficiently till pH remains constant.
Re90rd the pH of the solution.
(7) Repeat the procedure of adding 0.5 cm 3 ofHCI solution and recording pH of the solution
till it reaches to about 2.5 (Le., add about 20 cm3 of HCI solution).
(8) Plot the graph of pH of the solution against volume of HCI (O.IN) solution added.
pH-metry 59

(9) From the graph obtain pH values corresponding to first and second inflection point.
(10) Calculate the normality and amount of supplied Na 2C0 3 solution.
Observations: .
Temperature: _ _K.
Volume 010. IN Hel solution pH 01 solution
added in emJ

0.0
0.5
1.0
1.5
-
-

Graph:
Plot the graph of pH of solution against the volume of HCI added:
12

1st Equivalence Point .


10

6
2nd Equivalence Point
4

Volume of 0.1 N Hel added

Fig. 7.2
Calculations:
From graph, the volume of O.1N HCI at 2nd inflection point (equivalence point) =
Vx = em3
.: 10 em3 of the diluted N~C03' solution = Vx em3 of 0.1 N HCI solution
:. 100 em 3 = 10 x V
x
em3 - - - - -
·:·1000 em 3 of IN HCI = 53g of N~C03
10 Vx x 53 x 0.1
:. 10 Vx em 3 of O.1N HCI = --'----
1000
60 College Practical Chemistry (T. Y. B.Se.)

Results:
(1) pH at 1st equivalence point = _ __
(2) pH at 2nd equivalence point = ___
(3) Volume of O.1N HCI solution at 2nd equivalence point = _--,_ cm 3.
(4) Amount of N~C03 in given solution = g.
Conclusions:
(1) Is~ inflection point is at pH = _ _, hence most suitable indicator for 1st equivalence
point is _ _ __
(2) 2nd inflection point is at pH = _ _, hence most suitable indicator for 2nd equivalence
point is

Note: Colour change for different acid base indicators


Methyl Orange 3.1 to 4.4 Cresol Red - 7.2 to 8.8
Methyl Yellow 2.9 to 4.0 Phenolphthalein - 8.3 to 10.0
Methyl Red 4.2 to 6.3 Thymol Blue - 8.0 to 9.6

Experiment No.2 (6 Units only)


Aim: To titrate the given acid pH-metrically and to identify the acid on the basis of pKa values.
(- Maleic acid/malonic acid) (diabasic acid) and phosphoric acid (tribasic acid).
Requirements: MaleiclMalonic and phosphoric acid solution, 0.1 N NaOH solution, buffer solutions
of pH 4.01 and 9.18, pH-meter, beakers, burette, pipette etc.
Theory: Maleic acid (HOOC - CH = CH - COOH) and Malonic acid (HOOC - CH2 - COOH)
are diabasic acids which dissociate in two stages:
H2A ~ H+ + HA-
HA ~ H+ + A-
Hence, they yield two dissociation constants. It is possible to locate \he two dissocition
constants for the given acid carrying out pH metric titration. In the neutralisation curve obtained
when the given diabasic acid is titrated against strong base like NaOH, the volumes VI and V2
represent the first and the second equivalence points and with the help of these values it is possible
to obtain the values of pKI and pK2• These values can be compared with the literature values
for the two acids to identify the acid given. From the volume ofNaOH required to neutralise the
given amount of acid, it is possible to find the strength of the given acid.
Phosphoric acid (H3PO4) is a tribasic acid. It ionises is three steps as:
(1) H3P04H+~ + H2P04 or H3P04 + H20 ~H30+ + H2P01 4
(2) H 2P01 4 ~ H+ + H2P024 or H3P01 4 + H20 ~H30+ + HP024
(3) HP0 24 ~ H+ + P034 or HP024 + H20 ~H30+ + PO\
The dissociation constants of phosphoric acid being Ka == 7.5 x 10-3, Ka == 6.2 x 10-8 and
Ka == 4.8 a 10-13 • I 2
3
Hence, when phosphoric acid is titrated with NaOH solution it is possible to locate 1st and
2nd equivalence (inflection) points (at pH's about 4.8 and 9.7 respectively) with an error of about
1%.
pH-metry 61

The values of Ka ~ 4.8 x 10-13 precludes the posibility oflocation ofthe third stage equivalence
point accurately. Thii difficulty however can be overcome by the addition of an adequate amount
of CaCl2 to the second stage equivalence point solution. The reaction can be represented as:
2N~HP04 + 3CaCl2 + 2H20 - Ca3(P04) '" + 4Na+ + 2H30+ + 6Cl. The liberated H30+
ions result in the decrease in the pH of solution and can be titrated with NaOH solution in a simulated
third stage titration, where the equivalence point can be located with good accuracy.
Procedure:
Carry out the experiment as follows:
Part I : Standardisation of pH-meter:
(1) Switch on the pH-meter.
(2) Follow the procedure given in previous experiment to standardise the pH-meter.
(3) Wash the electrode/s several times with the distilled water.
Part II : Titration of given diabasic acid:
(1) Dilute the supplied acid solution (maleic acid, malonic or phosphoric acid) in a 100 cm 3
standard measuring flask. Shake it thoroughly.
(2) Pipette out 10 cm3 of the supplied acid solution (maleic or malonic or phosphoric acid)
in a 100 cm3 clean beaker. Add a small quantity of distilled water if necessary.
(3) Immerse the electrode in this solution. Stir the solution and take the reading.
(4) Wash, rinse and fill the burette with O.IN NaOH solution.
(5) Add 0.5 cm 3 of O.1N NaOH solution and stir it thoroughly.
(6) Record pH of the solution.
(7) Repeat the procedure several times by adding 0.5 cm3 ofO.IN NaOH solution every time.
(8) Take five or six more readings after the second neutralisation point.
(Note: Step No.9 to 16 may be avoided if intructed and obtain nature of aid from pKland p~
values)
(9) Add about 1 g of calcium chloroide (dihydrate) to the solution at this stage and stir the
solution well till calcium phosphate precipitates completely.
(10) Note down the new pH of the solution.
(11) Add O.1N NaOH solution further in same manner as described before and find third
neutralisation point.
(12) Take five or six more readings after this neutralisation point.
(13) Obtain values of corrected pH by adding pH difference between pH observed before
addition of CaCl2 and after addition of CaCl 2 (~ pH) in the observed pH.
(14) Plot a graph of (i) pH against volume of titrant, V (O.1N NaOH) added. (ii) L.\pHl~V
against V (mean).
(15) From the graph determine the pKvalues and the dissociation constants Kt/ ofthe supplied
acid.
(16) From the total volume of NaOH solution required for complete neutralisation of given
acid, determine the amount of acid present in the given solution.
(17) From the pK values obtained and literature pK values, identify the acid present in solution.
62 College Practical Chemistry (T. Y. B.Sc.)

Observations:
Record your observations as follows:
Solution in ~eaker - 10 em 3 of supplied acid solution
Solution in burette - 0.1 N NaOH solution.
Observation Table:
Obs. No. Volume of NaOH pH of the Mean Volume llpH/tJ. V
solution added Vem J solution V",em J

1 0.0 (Vo) - - -
2 0.5 (VI) - Vm I = (Vo + V/ )/2
3 1.0 (Vz) - Vm z = (Vz + V/ )/2
4 1.5 (VJ ) - Vm J = (VJ + V2 )/2
5 - (V) -
Graphs:
(i) Graph of pH against volume V em 3 of NaOH solution added.

Vt = Volume of NaOH obtained for


1st neutralisation point
pH, p~ r-----::.--__--"" V2 = Volume of NaOH obtained for
I 2nd neutralisation point
I
I
'vJ +V2
I
I 2 V2

Fig. 7.3

(ii) Graph of <¥H/~V against Vm

ApH
iN

Mean volume of NaOH added


Fig. 7.4
pH-metry 63

From the graph of pH against volume of NaOH solution


pKI = pH at (VI12 )

pK2 = pH at [( V2 ; VI + VI)] i.e. (V2 ; Vj)

Calculations:
(A) For Maleic acid (Molecular weight - 110.1 g. mot-I)
( .,' Equivalent weight = Molecular weightlBasicity :. Equivalent weight = 110.112 = 55.05)
10 em3 of the diluted acid solution required VI em 3 of 0.1 N NaOH solution
.. 100 em 3 10 VI em 3 _ _ _ __

1000 em 3 of IN NaOH = 55.05 g of Maleic acid


55.05 x 10Vj x 0.1
.. 10 VI em 3 of 0.1 NaOH = 1000

= --- g.
(B) For Malonic acoid (Molecular weight = 104.1 g mot-I)
(Equivalent weight = Molecular weightlBasicity = 104.112 :. Equivalent weight = 52.05)
10 em 3 of the diluted acid solution required V] em 3 of 0.1 N NaOH solution
100 em 3___________________ 10V] em 3_______________________

1000 em'3 of IN NaOH = 52.05 g of Malonic acid

52.05 xl 0 VI x 0.1
.. 10 V2 em3 of O.1N NaOH = 1000

---g.
(C) For Phosphoric acid- (Molecular weight = 98)
(Equivalent weight = Molecular weight/Basicity = 98/3 :. Equivalent weight = 32.67)
10 em 3 of the diluted acid solution required V3 em 3 of 0.1 N NaOH solution
.. 100 em 3 10 V3 em 3 __________

1000 em 3 of 1N NaOH 32.67 g Phosphoric acid

32.67 X 10V3 x 0.1


3
". 10 V3 em of 0.1 N NaOH = 1000

= g.
64 College Practico/ Chemistry (T. Y. B.Sc.)

Results:
(1) First dissociation constant, pK1 = ___
(2) Second dissociation constant, pK2 = _ _.
(3) Amount of maleic/malonic/phosphoric acid in the given solution = ____ g.

Conclusions:
The given acid has dissociation constants, pK1 = ___ pK2 = ___ and
Hence, the given acid is _ _ __
[Dissociation constants of acids at 298 K literature values.
Maleic acid: pK1 = 1.83 pK2 = 6.07
Malonic acid: pK1 = 2.83 pK2 = 5.69]
Phosphoric acid pK] = 2.125, pK2 = 7.208

000
8
Gravimetric Estimations

Gravimetric analysis involves the determination of the quantity of a particular substance. It


covers the techniques of precipitation, digestion, filtration, drying, ignition and finally weighing.
From the weight of the product obtained, the weight or the quantity of the substance taken
or under study is calculated. Each one of the above processes needs a technique of its own in
otder to achieve accuracy.
In most of the cases, the process of isolation of the substance is precipitation method in which
the product obtained due to the reaction between the ion under study and the 'ion of the reagent
used, is always sparingly soluble.
The complete precipitation is carried out under the appropriate condition such as pH,
temperature, common ion effect, nature of the reagent etc.
Precipitate gets coagulated when it is digested on a hot water bath. It helps in faster filtration.
Precipitate, i.e., the product obtained may be stable or unstable. The stable product is filtered
through a selected filter paper, which has pores, small enough to retain the particles of the bigger
size. e.g., filter paper No. 41 has pores large enough to allow BaS04 to filter through it but small
enough to retain ZnNH4P04•
Unstable product or precipitate of the substance is filtered through a counterpoised set of
filter papers or through a selected sintered glass crucible.
In case of unstable product, it is dried carefully and then ignited to convert it to stable form.
In case of unstable complex product, it is dried at a controlled temperature and then weighed, on
a sensitive balance.
Experiment No. 1
Estimation Of Zinc
Aim: Estimate the amount of zinc present in the given zinc sulphate solution containing copper
sulphate and free H2S04 ,
66 College Practical Chemistry (T. Y. B.Sc.)

Theory: Zinc forms a complex (ZnNH4P04) salt when treated with (NH4)2HP04 reagent. This
complex salt is formed at a controlled pH of 6.7 to 6.9.
On strong heating, it gets decomposed and gets converted into stable Z~P 207' This conversion
is prevented by heating the precipitate in an electric oven, in a previously weighed sintered glass
crucible, at a controlled temperature. Cu2+ ions interfere in the precipitation, hence are removed
as CuS, with H 2S in acidic medium.
Procedure:
(1) Dilute the given solution to 100 em 3 in a standard measuring flask, with distilled water.
(2) Pipette out 50 em 3 of it in a 250 em 3 beaker and add 2 test tubes of distilled water to
it.
(3) Acidify it with 5 em 3 of conc. HCI, heat and pass H 2S gas to precipitate Cu2+ as CuS.
(4) Heat the solution and filter the precipitate ofCuS through an ordinary filter paper. Wash
the precipitate thrice with hot boiling distilled water. (Reject the precipitate of CuS.)
(5) Collect the filtrate and all the washings together in a 500 em 3 breaker. Heat the solution
to boil off H2S completely.
(6) Concentrate the solution to about 100 em 3.
(7) Add 2 drops of 1% Methyl Red indicator to the (free from H 2S) concentrated solution
(solution turns pink), and then add one test tube each of 2N CH3COONH4 and 10%
(NH4)2HP04 reagents with stirring, to it.
(8) If any precipitate forms, then, add a few drops of conc. HCI to dissolve it. Heat the solution
to boiling.
(9)' Add 1: 1 NH40H solution to the hot solution, dropwise with constant stirring, till solution
turns yellow or colourless. The precipitate ofZn3(P04)2 forms. At this stage, stop adding
more NH40H solution.
(10) Transfer the beaker to a boiling waterbath. Stir the solution vigorously for about 15-20
minutes to obtain the crystalline precipitate of ZnNH4P04.
(11) Add 2-3 drops of NH40H and stir vigorously, till no more precipitate forms and the
crystalline precipitate becomes silky in appearance (solution remains yellow or colourless).
(12) Allow the precipitate to stand for cooling for about 20-30 minutes.
(13) Cool and filter the precipitate through a previously weighed sintered glass crucible.
(03).
(14) Wash the precipitate with 2% NH4N0 3 solution, till the filtrate is free from CI-, SOl-
and PO l- ions.
(15) Dry the precipitate at 110°C in an electric oven and weigh as ZnNH4P04.
Reactions:
(1) CuS04 + H2S ~ CuS t + H 2S04
(2) 2 ZnS04 + 2 (NH4)2HP04 ~ 2 ZnNH4P04 t t- (NH4)2 S04 + H 2S04
Calculations:
Let the weight of residue (ZnNH4P04) be x g.
Now, 50 em 3 of the diluted solution gave x g of ZnNH4P04
:. 100 em 3 2x g
Gravimetric Estimations 67
From the equation,
ZnNH4P04 = Zn = ZnS04 .7H20
Now, 178.38 g ofZnNH4P04 = 65.38 g of Zinc = 287.38 g of ZnS04 .7H20
65.38 x2x .
.. 2x g of ZnNH4P04 = 178.38 g of Zmc

287.38 x 2x
178.38
Results:
(1) 50 em 3 of the diluted solution gave (x) = ___. g of ZnNH4P04•
(2) Amount of Zinc present = g.
(3) Amount of ZnS0 4.7H20 = g.

Experiment No.2
Estimation of Nickel
Aim: Estimate the amount of nickel present in the given nickel chloride solution containing copper
chloride and free HCI.
Theory: Nickel ions are precipitated as a chelate complex by dimethylglyoxime reagent in an
alkaline medium. This method is the most rapid and accurate one for the estimation of nickel ions.
Such a chelate is stable up to 110°C hence, can be dried safely.
During the estimation of nickel, copper ions interfere, hence, they are first of all removed
as CuS from the solution by passing H2S gas in acidic medium. Thereafter, estimation of nickel
becomes simple.
Procedure:
(1) Dilute the given solution to 100 cm 3 in a standard measuring flask, with distilled water.
(2) Pipette out 50 em 3 of it in a 250 em 3 beaker. Acidify it with 5 em 3 of cone. HCI, heat
and then pass H2S gas to precipitate Cu2+ as CuS.
(3) Heat the solution and filter the precipitate ofCuS through an ordinary filter paper. Wash
the precipitate thrice with hot boiling distilled water. (Reject the precipitate of CuS).
(4) Collect the filtrate and all the washings together in a 500 cm 3 beaker. Heat the solution
to boil off H2 S completely.
(5) Concentrate the solution to about 100·cm 3•
(6) To the solution (free from H2S), add 35-40 cm 3 of 1% dimethylglyoxime (d.m.g.) reagent
and stir it well.
(7) Add 6N NH 40H dropwise with constant stirring to precipitate Ni 2+ as Ni d.m.g. Once
the precipitation is complete, smell ofNH3 should be distinct. (This ensures the alkaline
medium.)
(8) Digest the precipitate on a boiling waterbath for 20-30 minutes. Test the supernatant
solution for complete precipitation with 1-2 drops of the d.m.g. reagent as well as 6N
NH40H solution.
(9) Filter the precipitate through a previously weighed sintered glass crucible. (G3).
68 College Practical Chemistry (T. Y. B.Sc.)

(10) Wash the precipitate with distilled water, till the filtrate is free from Cl- and SOl- ions.
Finally, wash it onee with 5-10 em 3 of ethyl alcohol.
(11) Dry the precipitate at 110°C in an electric oven and weigh as Ni d.m.g.
Reactions:
(1) CuC12 + H 2S ~ Cus..i- + 2HCl
. (2) NiC1 2 + (C4H gN 20 2)2 ~ Ni(C 4H 7N 20 2)2..i- + 2HCl
Calculations:
Let the weight of residue (Ni d.m.g.) be x g.
Now, 50 em 3 of the diluted solution gave x g of Ni d.m.g.
:. 100 em 3 2x g
From the equation,
= Ni = NiC12. 6H20
Ni d.m.g.
288.71 g of Ni d.m.g. = 58.71 g of Nickel = 237.71 g of NiC1 2.6H20

58.71 x 2x
" 2x g of Ni d.m.g. 288.71 g of Nickel

237.71 x 2x
288.71 g of NiCI 2·6H20

Results:
(1) 50 em 3 of the diluted solution gave (x) = g of Ni d.m.g.
(2) Amount of Nickel present = g.
(3) Amount of NiC1 2.6H20 present = g.

Experiment No. 3 (6 Units only)


Estimation of Barium
Aim: Estimate the amount of barium present in the given barium chloride solution containing ferric
chloride and free HCl.
Theory: This method is useful in the separation of barium from similar ions like calcium and
strontium. BaCrO4 precipitate dissolves in strong acid medium, hence, a weak acidic medium like
CHFOOH (pH 5 - 6) is preferred. Also, drying of the precipitate at 110° - 120°C prevents the
loss of oxygen which decomposes or reduces the precipitate. Fe3+ ions interfere, hence are removed
as Fe(OHh with the help of 1:1 NH40H solution.
Procedure:
(l) Dilute the given solution to 100 em 3 in standard measuring flask, with distilled water.
(2) Pipette out 50 em 3 of it in 250 em 3 beaker. Add 1-2 test tubes of distilled water to it.
(3) Add 1 em 3 of conc. HN0 3 to it and boil for 5 minutes till colour changes to straw yellow.
(4) Add about 1 g of pure NH4 Cl to it and heat the solution to about 80°C on a wiregauze.
(5) Keep the beaker on an asbestos sheet and add dropwise with constant stirring 1 : 1
NH4 0H solution to it to precipitate Fe3+ as Fe(OH)3' (Stop addition of excess ofNH40H
solution, if the smell of NH3 is distinct.)
Gravimetric Estimations 69
(6) Heat the precipitate of Fe(OH)3' till it just starts boiling, on a wiregauze.
(7) Filter the precipitate through an ordinary filter paper. Wash the precipitate thrice with
hot boiling distilled water. (Reject the precipitate of Fe (OH)3.)
(8) Collect the filtrate and all the washings in a 500 cm3 breaker. (solution rem3ins colourless
or light yellow).
(9) Concentrate the solution to about 100 cm3• (solution remains colourless or light yellow).
(l0) Add 2 drops of 1% Methyl Red indicator to it (solution remains colourless or light yellow).
(11) Acidify the solution with 2N CH3COOH (solution turns pale or light pink).
(12) Heat the solution about 700 - 80°C. Add about 20 cm3 of 10% ~Cr04 solution to it with
constant stirring to precipitate Ba2+ as BaCr04.
(13) Digest the precipitate on a boiling waterbath for about 10-15 minutes and test the
supernatant solution for complete precipitation with a drop of ~crO4 reagent.
(14) Cool and filter the precipitate through a previously weighed sintered glass crucible.
(G4).
(15) Wash the precipitate with cold distilled water, till the filtrate is free from CI-, SOl- and
l-
crO ions and becomes colourless.
(16) Dry the precipitate at 120o-1300C in an electric even and weigh as BaCr04•
Reactions:
(l) FeCl3 + 3NH40H ~ Fe(OH)3 ,!, + 3NH4CI
(2) BaCl2 + ~CrO4 ~ BaCrO4 ,!, + 2KCI
Calculations:
Let the weight of residue (BaCrOJ be x g.
Now, 50 cm l of the diluted solution gave x g of BaCr04
:. 100 cm3 2x g _ _ _ _ _ __
From the equation,
BaCr04 = Ba = BaCI2.2H20
Now, 253.36 g of BaCr04 = 137.36 g of Barium = 244.36 g of BaClr 2H20
137.36 x 2x .
:. 2x g of BaCr04 = 253.36 g of Banum

244.36 x 2x
= 253.36 g of BaCI2.2H20

Results:
(1) 50 cm3 of the diluted solution gave (x) = ___ g of BaCr04 •
(2) Amount of Barium present = . g.
(3) Amount of BaCI2.2H20 present = g.

000
9
Titrimetric Analysis

Volumetric analaysis is used to determine the strength of solutions by comparing the definite
.volumes of different solutions with known concentration.
Complexometric Titrations: Metal ions form a large number of complex or coordination
compounds, involving, 2,4 or 6 coordination bonds, which may result in complex ion, (positive,
negative or neutral in nature) like amine complex and cyanide complexing agent amongst them is
Ethylene diamine tetra acetic acid (EDTA) as di-Sodium salt. EDTA is an excellent complexing
agent producing quite stable complexes with a number of metal ions, due to the presence of
carboxylic acid groups in it.
Moreover, it is quite cheap and easily available. It contains six electron donor atoms for bonding
with metal ions. The number of the donor atom corresponds to the coordination number of most
metals, thereby producing 1:1 complexes readily.
EDTA forms strainless five membered chelate rings (which produce quite stable complexes)
with almost all the cations, (except Na and K ions) under suitable pH conditions. DesiredpH is
maintained carefully with the help of a buffer solution.
EDTA solution can be stored for quite a long time without affecting its strength.
Three types of titrations' can be carried out with EDTA. These are-
(1) Displacement Titrations - in case, where the suitable indicator is not available, then
the metal ion is treated with the known quantity of - Zn or - Mg EDTA. complex, solution. The
quantity of zinc or magnesium ions liberated are equivalent to the quantity of metal ions present
in the given solution, which are titrated against standard EDTA., solution is added to the metal ion.
Excess of unused EDTA is back titrated against standard ZnS0 4 or MgS04 solution, using
Eriochrome Black T indicator.
Titrimetric Analysis 71
(2) Direct Titration - This is the direct reaction between the metal ion and EDTA, where
the metal complex forms very rapidly. Even the use of a suitable dye (Eriochrome Black T) as
an indicator, brings about the end point much faster and accurately.
Preparation of Buffer Solution
Dissolve 17.5 g of pure NH 4Cl (A.R.) in 142 em 3 of liquid NH3 (specific gravity 0.88 to 0.9)
solution and dilute the solution to 250 em 3 with distilled water (resulting buffer solution will have
apH = 10)
Experiment No. 1
Estimation of Zinc
Aim: Estimate the amount of zinc present in the given zinc sulphate solution.
Theory: Zinc ions are titrated against standard (EDTA) complexing agent, using a suitable dye
as an indicator which forms an indicator-metal complex. When EDTA consumes all the metal ions
of this complex, then the next drop of EDTA reacts with the indicator-complex and liberates the
original dye which has a particular colour, which indicates the end point of the reaction. Buffer
solution is used to maintain pH, which is a very important factor in the reaction.
Procedure:
(1) Prepare 100 em30fO.02MEDTA solution (0.745 gofEDTA dissolved in 100em3 of distilled
water.)
(2) Dilute the given solution to 100 em 3 in a standard measuring flask with distilled water.
(3) Pipette out 10 em 3 of it in a conical flask and add about 2 test tubes of distilled water
to it.
(4) Add 3 em 3 of buffer solution and 3-4 drops (or a pinch) of 2% Eriochrome Black T
indicator to it.
(5) Shake well and titrate the solution against 0.02M EDTA solution from the burette. End
point will be from wine red to blue colour.
Reaction:
ZnS04 + N~CIOH140sN2 ~ ZnClOH140sN2 + N~S04
Calculations:
10 em 3 of the diluted solution required x em 3 of 0.02M EDTA solution.
:. 100 em 3 10 x em 3
1000 em 3 of 1M EDTA = 65.38 g of Zinc = 287.38 g of ZnS04.7~O.

3 65.38 x lOx x 0.02 f.


: . . 10x em of 0.02M EDTA = 1000 g 0 Zmc

287.38 x lOx x 0.02


= 1000 g of ZnS04·7H20

Results:
(1) 10 em 3 of the diluted solution required (x) = __ em 3 of 0.02M EDTA solution.
(2) Amount of Zinc present = g.
(3) Amount of ZnS04.7H20 present g.
72 College Practical Chemistry (l'. Y. B.Sc.)
Experiment No. 2
Estimation of Cobalt
Aim: Estimate the amount of cobalt present in the given cobalt surphate solution.
Theory: Cobalt ions are titrated aginst standard EDTA complexing agent, using a suitable dye as
an indicator which forms an indicator metal complex. When EDTA consumes all the metal ions
of this complex, then the next drop of EDTA reacts with the indicator complex and liberate the
original dye which has a particular colour, which indicates the end pOint of the reaction.
Reaction of cobalt ions is carried out at a pH of 6. pH 6 is maintained by adding hexamine
powder to the solution.
Procedure:
(I) Prepare 100 em J 6r 0.02M EDTA solution. (0.745 g of EDTA dissolved in 100 emJ of
distilled water).
(2) Dilute the given solution to 100 em J in a standard measuring flask with distilled water.
(3) Pipette out 10 em J of it in a conical flask and add one test tube of distilled water to it.
(4) Add 3 drops of 0.5% xylenol orange indicator solution followed by very dilute or 2N ~S04
until the colour just changes from red to yellow.
(5) Adjust the pH of;fue solution to about 6 by adding powedered hexamine (red colour is
restored).
(6) Warm the solution to about 40°C and titrate it against 0.02M EDTA ~lution from the
burette with shaking. EDTA solution should be added dropwise towards the end point.
End point will be from red to yellow orange colour.
Reaction:
CoS04 + N~ClOH)40gN2 -+Co.C)OH)40 gN2 + N~S04
Calculations:
10 em J of the diluted solution required x em J of 0.02M EDTA solution.
:. 100 em 3 lOx em J
1000 em J of 1M EDTA = 58.~3 g of Cobalt = 190.93 g of CoS04.2H20

58.93 x lOx x 0.02 fC b I


:. lOx em J of 0.02M EDTA = 1000 go 0 at

190.93 x lOx x 0.02 of COSO .2H


1000 g 4 2
°
Results:
(1) 10 em J of the diluted solution required (x) = _ _ em J of 0.02M EDTA solution.
(~) Amount of Cobalt present g.
(3) Amount of CoS04.2H20 present = g.
Titrimetric Analysis 73
Experiment No. 3
Analysis of Talcum Powder
Aim: To analyse the percentage of magnesium present in the given sample of talcum powder.
Theory: Talcum powder generally contains zinc oxide or magnesium oxide along with boric acid.
The content varies from sample to sample. .
Magnesium content can be estimated by dissolving talcum powder in acid and titrating it against
by EDTA solution.
Procedure:
(1) Prepare 100 cm 3 of 0.02M EDTA solution (0.745 g of EDTA dissolved in 100 cm 3 of
distilled water).
(2) Transfer accurately weighed 2 g or the supplied quantity of talcum powder to a dry 50
cm 3 breaker.
(3) Add 10 cm 3 of conc. HCI, partially cover it with watch glass and heat carefully till the
volume reduces to about 1-2 cm 3. (Evaporate nearly to dryness).
(4) Then add about 50 cm 3 of distilled \\\ater and boil if for sometime. Filter the solution through
filter paper No. 41 in a 100 cm 3 standard measuring flask.
(5) Wash,the beaker and the filter paper with hot distilled water, 3-4 times and collect all
the washings in the same 100 cm 3 measuring flask. Finally dilute the contents of the flask
to 100 cm 3 with distilled water.
(6) Pipette out 10 cm 3 of it in a conical flask. Add about 2 test tubes of distilled water, 3
cm3 of buffer solution (/JH = 10) and 3-4 drops (or a pinch) of 2% Eriochrome Black
T indicator to it.
(7) Shake well and titrate it against 0.02M EDTA solution from the burette. End point will
be from wine red to blue colour.
Reaction:
MgCl2 + N~ClOH140sN2 ~ Mg,ClOHI40sN2 + 2NaCI
Calculations:
10 cm 3 of the diluted solution required x cm 3 of 0.02M EDTA solution
.. 100 cm3 lOx cm3
1000 cm3 of 1M EDTA= 24.32 g of Magnesium
24.32 x lOx x 0.02
.. lOx cm 3 of 0.02M EDTA= 1000 =Ag

A x 100
. Percentage of Magnesium = Weight of talcum powder dissolved
= %
Results:
(1) 10 cm 3 of the diluted solution required (x) = _ _ _ cm 3 of 0.02M EDTA solution.
(2) Percentage of Magnesium in talcum powder = %.
74 College Practical Chemistry (T. Y. B.&.)

Experiment No.4 (6 Units only)


Estimation of Total Hardness
Aim: To determine the total hardness of the given well water sample.
Theory: Hard water contains dissolved salts of calcium and magnesium in the form of bicarbonates,
sulphates and chlorides.
Hardness of water is of two types:
(1) Temporary hardness.
(2) Permanent hardness.
Hardness is the sum of calcium and magnesium ion concentration - both expressed as CaCO)
in parts per million (ppm) or mg/dm 3
Interference by some metal ions leading to fading or indistinct end points is avoided by adding
inhibitors like N~S, NH 20H.HCI, etc.
A direct method of estimating the total hardness involves EDTA titrations using Eriochrome
Black T indicator at pH 10. This value gives total hardness of the water sample in form Ca2+ and
Mg2+ ions.
Procedure:
(1) Prepare 250 em 3 of O.OIM EDTA solution (0.931 g of EDTA dissolved in 250 em 3 of
distilled water).
(2) Pipette out 25 em 3 of the supplied well water sample in a conical flask., Add 5 em 3 of
buffer solution (PH = 10), 3-4 drops (or a pinch) of 2% Eriochrome Black T indicator
to it.
(3) Shake well and titrate it against O.OIM EDTA solution from the burette. End point will
be from wine red to blue colour.
Reactions:
(I) CaR + N~ClOH140sN2 --+ CaClOH140sN2 + N~R
(2) MgR + N~CJOH140sN2 --+ MgCJOH1 40sN2 + N~R
[Where, R = HCO)-, CI- or SOl-].
Calculations:
25 em 3 of the well water required x em 3 of O.OIM EDTA solution.
1000 em 3 of 1M EDTA = 100 g of CaCO)
:. 1 em 3 of 1M EDTA = 100 mg of CaCO)
:. x em 3 of O.OIM EDTA = 100 x x x 0.01
= Z mg of CaCO)
The total hardness of well water sample is obtained as CaCO) mg/dm3 or ppm.
Since 25 em 3 of well water sample = Z mg of CaCO)
Zx 1000
:. 1000 em 3 ___ ppm.
--- 25
Titrimetric Analysis 75
Results:
(1) 25 em 3 of the well water sample required (x) = ___ em 3 of O.OIM EDTA solution.
(2) Total hardness of given well water sample = CaC03 ppm (mg/dm 3).

Experiment No.5 (6 Units only)


Percentage Purity of Boric Acid
Aim: To determine the percentage purity of boric acid.
Theory: Boric acid acts as a weak monobasic acid. Therefore, it can not be titrated accumtely
against standard alkali solution. However, by the addition of certain organic polyhydroxy compounds,
such as mannitol, glucose, glycerol, it act as a much stronger acid and can be titrated to a
phenolphthalein end point.
Procedure:
Part I: Standardisation
(1) Prepare 100 em 3 of O.IN succinic acid solution (0.590 em 3 of succinic acid in 100 em 3
of distilled water).
(2) Pipette out 10 em 3 of succinic acid, add 1-2 drops of phenolphthalein indicator and titrate
it against O.IN (approximate) NaOH solution from the burette. End point will be from
colourless to pink colour.
Part II: Estimation
(3) Dissolve accurately weighed 2 g or the supplied quantity of boric acid sample in 100 em 3
of distilled water.
(4) Pipette out 10 em 3 ofthe diluted boric acid solution in a conical flask. Add 1.5 g of mannitol
to it. Then, add 1-2 drops of 1% phenolphthalein indicator to it.
(5) Shake well and titrate against standardised NaOH solution from the burette. End point
will be from colourless to pink colour.
Reactions:
(1).(CH 2COOHh + 2NaOH --+ 2NaCH2COO + 2H20
(2) H3B03 + 3NaOH ~ Na3B03 + 3H20
Calculations:
Standardisation of NaOH Solution
10 em 3 of O.1N succinic acid required x em 3 of NaOH solution.
. . 10 x 0.1cm 3
:. Normahty of NaOH solution =
x
=AN
10 em 3 of the diluted boric acid solution required y em 3 of A N NaOH solution.
:. 100 em 3 10 y em 3 _ _ _ _ _ _ __
76 College Practical Chemistry (T.!~ B.Sc.)

1000 em 3 of IN NaOH = 61.84 g of H3B03


3 _ 61.84x10yxA
.. 10 Y em of A N NaOH - 1000
=Z g ofH3B03
Let the weight of sample be W g
W g of H3B03 =Z g of H3B03

ZxlOO
W
=
Results:
(1) Nonnality of NaOH solution = (A) = N.
(2) 10 em3 of the diluted boric acid solution required (y) =_ _ em 3 ofAN NaOH solution.
(3) Amount of boric acid present = g.
(4) Percentage purity of the given boric acid sample = _ _ %.

QQQ
10
Inorganic Preparations and
Characterisation

In this chapter, we will study how an inorganic compound is prepared from the metal ions
solution, when it reacts with a complexing agent under certain contro~ed conditions like pH,
temperature etc. '
Generally, preparation of a compound is based on the properties of reactants. The reactions
involved in these preparations are quantitative and precipitation type of reactions taking place in
stoichiometric proportions. Hence, theoretical yields can be calculated and compared with
experimental yields.
Known quantity of precipitate in the terms of complex is decomposed by suitable acid and
the amount of metal ions in a complex compound can be determined by carrying out titration.
Percentage of metal ions in the complex can be calculated and compared with theoretical percentage
of metal ions in the complex.
Experiment No. 1
Preparation and characterisation of Tris (Ethylene diamine) nickel (II) thiosulphate
[Ni (en)3] S203.
Aim: To pr~are Tris (Ethylene diamine) Nickel (II) thiosulphate and to determine the metal content
by complexometric titration after decomposition.
Theory: Nickel ions form mauve (violet) coloured complex compound when it reacts with very
dilute solution of ethylene diamine reagent.
To the vigorously boiling solution of nickel and ethylene diatpine, a hot thiosulphate solution is added,
stirred vigorously and cooled to obtain the precipitate.
78 College Practical Chemistry (T. Y. B.Sc.)

To detennine the nickel ions content, the precipitate is dried and weighed. To detennine the yield
, of the complex fonned, the known quantity ofthe complex is dissolved in acid. By complexometric
titration method, percentage of its metal content can be calculated.
Requirements: NiS0 4·7H20, conc. HN0 3 conc. HCI, ethylene diamine sodium thiosulphate,
O.OlM EDTA solution (0.372 g of EDTA dissolved in 100 em 3 of distilled water), 0.5% murexide
indicator, 1M NH4CI solution, liq. NH3 etc.
Procedure:
Part I: Preparation of Tris Nickel ethylene diamine thiosulphate complex:
(1) Take 20 em 3 of 5% NiS04 7H20 in a 250 em 3 beaker and wann it on a wire gauze.
(2) To the wann solution of Ni 2+ ions, add 1:5 ethylene diamine solution from the burette
slowly and with constant stirring till the colour of solution changes to mauve (violet) colour.
Add 1-2 drops of ethylene diamine solution in excess.
(3) Now, heat the solution vigorously and to the boiling solution, add hot saturated solution
of sodium thiosulphate with constant stirring till precipitate fonns and gets completed.
(4) Boil the solution for 1-2 minutes or digest the precipitate on a boiling water bafh for 15-
20 minutes.
(5) Cool the solution and filter the complex through whatman filter paper No. 41 using a
buchner funnel.
(6) Wash the complex with distilled water 2-3 times and then with 2-3 em 3 of ethyl alcohol.
(7) Transfer the complex on a watch glass and dry it in an electric oven at 110°C.
(8) Weigh the complex to obtain the yield.
Part II: Analysis of Tris Nickel ethylene diamine thiosulphate complex:
(9) Weigh exactly 300 mg of the complex and transfer it quantitatively to a 250 em 3 beaker.
(10) Add 5-7 em 3 of conc. HN03 to it and boil it nearly to dryness, on a sand bath. Complex
gets decomposed (Repeat the process, if necessary).
(11) Treat the residue with 5 em 3 of conc. HCI and boil it (till no more brown fumes) and
evaporate to dryness.
(12) Extract the residue with 20-25 em 3 of distilled water, boil and then cool it.
(13) Transfer the solution to a 100 em 3 standard measuring flask. Wash the beaker and transfer
the washing also.
(14) Dilute the solution to 100 em 3 with distilled water and pipette out 10 em 3 of it in a conical
flask.
(15) Add one test tube of distilled water and a pinch (or 5-6 drops) of freshly prepared 0.5%
murexide indicator to it. Shake the flask well.
(16) Add haIfa test tube of 1M NH4CI solution and liq. NH3 dropwise, till the solution turns
yellow in colour.
(17) Add about 5-7 em 3 of liq. NH3 in excess to it and shake it well.
(18) Titrate it against O.OlM EDTA solution from the burette. End point will be from yellow
to bluish violet colour.
Inorganic Preparations and Characterisation 79

Reactions:
(1) NiS0 4 + 3C 2H 4 (NH 2)2 ~ Ni [C2HiNH2)2h S04
(2) Ni[C2H4 (NH 2)2h S04 + Na2S20 3 ~ Ni[C 2H 4(NH 2)2h S203 + Na2S04
(3) NiCl 2 + Na2CIOHI40gN2 ~ NiCIOHI40gN2 + 2NaCI
Observations and Calculations:
Weight of [Ni(en)3] S203 = x g.
(I) Yield of the Complex:
(A) Observed Yield of /Ni(en)j SZ03 = x g .
. (B) Theoretical Yield of /Ni(en)j SZ03
When 20 em 3 of 5% NiS047H20 solution is used
100 em 3 of NiS047H20 solution contains 5 g of NiS047H20
:. 20 em 3 , 1.0 g of NiS047H2P
Now, 280.71 g of NiS047H20 gives 350.71 g of [Ni (en)3] S203
:. 1.0 g 350.71 g
280.71
= 1.249 g of [Ni(en)3] S203
(II) Nickel content in [Ni(en)3] S203:
(A) Theoretical Percentage
350.71 g of [Ni (en)3] S203 contains 58.71 g of Nickel

58.71 x 100
:. 100 g
350.71
16.74% of Nickel
(B) Observed Percentage
Observations:
10 em 3 of the diluted Ni 2+ solution required y em3 of O.OIM EDTA solution
:. 100 em 3 lOy em 3 _ _ _ __
Calculations:
1000 em 3 of 1M EDTA 58.71 g of Nickel

58.71 x lOy x 0.01


.. 10 Y em 3 of O.OIM EDTA = 1000

=Z g of Nickel
Since 0.3 g of [Ni(en)3] S203 contain Z g of Nickel
ZX 100
:.100 g _ __
0.3
% of Nickel.
80 College Practical Chemistry (T. Y. B.Sc.)

Results:
(1) Yield of Nickel (ethylene diamine)3 S203 complex:
(A) Theoretical yield = 1.249 g.
(B) Observed yield (x) = g.
(2~ Percentage of Nickel in the complex:
(A) Theoretical percentage = 16.74%.
(B) Observed percentage = _ _ %.
Experiment No.2
Preparation and characterisation of Bis-acetylacetanato copper (II) Cu(acac)l
Aim: To prepare Copper acetylacetanato and to determine the metal content by complexometric
titration after decomposition.
Theory: Copper ions form dark blue coloured complex compound when it reacts with acetyl acetone
reagent. Acetyl acetone is a colourless mobile liquid which is sparingly soluble in water. It is
dissolved in very dilute ammonia, taking care that no emulsion folms.
The precipitate of copper acetylacetonate is dried and a known quantity of it is dissolved in acid
for the determination of its metal content by complexometric titration method.
Requirements: CuS04 .5H20, acetyl acetone solution, 1:4 NH40H solution, ethyl alcohol, cone.
HN03, conc. HCl, O.OIM EDTA solution (0.372 gof EDTA dissolved in 100 em 3 of distilled water),
buffer solution (PH = 10), 0.5% fast sulphone black F indicator etc.
Procedure:
Part I: Preparation of Bis Copper acetylacetanato complex:
(1) Take 20 em3 of 5% CuS0 4.5H 20 solution in a 250 em3 beaker.
(2) Prepare the reagent solution by adding 1:4 ammonia solution slowly to 3.5 em 3 of acetyl
acetone in 100 em 3 beaker with constant stirring taking care that no emulsion is formed.
(3) Now, to the CuS04 solution, add slowly with constant stirring the reagent solution till blue
coloured complex precipitates completely.
(4) Digest the complex on a boiling w~ter bath for 15-20 minutes.
(5) Filter the complex through buchner funnel containing whatman filter paper No. 41.
(6) Wash the complex with distilled water 2-3 times and then with 2-3 em3 of ethyl alcohol.
(7) Transfer the complex on a watch glass and dry it in an electric oven at 110°C.
(8) Weigh the complex to obtain the yield.
Part II: Analysis of Bis Copper acetylacetanato complex:
(9) Weigh exactly 300 mg of the complex and transfer it quantitatively to a 250 em 3 beaker.
(10) Add 5-7 em3 of cone. HN03 to it and boil it nearly to dryness on a sand bath. Complex
gets decomposed. (Repeat the process, if necessary).
(11) Treat the residue with 5 em3·of conc. HC} and boil it (till no more brown fumes evolved)
and evaporate it to dryness.
(12) Extract the residue with 20-25 em 3 of distilled water, boil and then cool it.
Inorganic Preparations and Characterisation 81
(13) Transfer the solution to a 100 em 3 standard measuring flask. Wash the beaker and transfer
the washing also.
(14) Dilute the solution to 100 em3 with distilled water and pipette out 10 em 3 of it in a conical
flask.
(15) Add one test tube of distilled water, 5 em3 0fliq. NH3 and 5-6 drops (or a pinch) of 0.5%
fast sulphone black F indicator to it. Shake the flask well.
(16) Titrate it against O.OlM EDTA solution from the burette. End point will be from blue to
dark green colour.
Reactions:
(1) 2CH3COCH2COCH3 + CuS04 ~ Cu(CH3COCH2COCH3)2 + H2S04
(2) CuCl2 + N~CIOHI40sN2 ~ Cu,CIOHI40sN2 + 2NaCI
Observations and Calculations:
Weight of Cu(acac)2 =x g.
(I) Yield of the Complex:
(A) Observed Yield of Cu(acac)2 = x g.
(B) Theoretical Yield of Cu(acac)2
When 20 em3 of 5% CuS04 solution is us~d:
100 em 3 _of CUS04 solution contains 5 g of CuS04.5H20
:. 20 em3 1.0 g of CuS04.5~O
Now, 249.54 g of CuS04.5~O gives 261.54 g of Cu(acac)2
261.54
:. 1.0 g = 249.54
= 1.048 g of Cu(acac)2
(II) Copper content in the Cu(acac):z:
(A) Theoretical Percentage
261.54 g of Cu(acac)2 contains 63.54 g of Copper
63.54 x 100
:. 100 g - - - =
261.54
= 24.29% of Copp~r
(B) Observed Percentage
Observations:
10 em 3 of the diluted Cu2+ solution required y em 3 of O.OlM EDTA. solution.·
:. 100 em 3 lOy em 3 _ _ __
Calculations:
1000 em 3 of 1M EDTA = 63.54 g of Copper
63.54 x lOy x 0.01
.. lOy em3 of O.OlM EDTA =
1000
= Z g of Copper
82 College Practical Chemistry (T. Y. B.Sc.)

Since, 0.3 g of Cu(acac)2 contains Z g of Copper


ZX 100
:. 100 g
0.3
_ _ % of Copper.
Results:
(I) Yield of Copper acetylacetanato complex:
(A) Theoretical yield = 1.048 g.
(B) Observed yield (x) = __ g.
(2) Percentage of Copper in the complex:
(A) Theoretical percentage = 24.29%.
(B) Observed percentage %.
Experiment No.3
Preparation and characterisation of Bis 8-hydroxyquinolato magnesium (II) [Mg (OX)2]
2H 20.
Aim: To prepare Magnesium oxinate and to determine its metal content by complexometric titration
after decomposition.
Theory: Magnesium ions forms magnesium oxinate when treated with oxine reagent in an alkaline
medium (PH range 9.5 - 13.0). Oxine is a colourless crystalline solid. Generally, acetic acid solution
of oxine is used when the precipitation is carried out.
Magnesium ions are precipitated from an alkaline solution only. During the precipitation process,
a slight excess of oxine reagent should be present in the solution, which is indicated by yellow or
orange colour of the solution. Excess of the reagent is to be avoided as it may coprecipitate with
the complex.
Temperature used for coagulation should not exceed 70°C. The precipitate may be dried at 105-
110°C to get hydrated oxirrate. If heated above 110°C and for a longer time, then the complex
may decompose.
Requirements: MgS0 4.7H20, 5% oxine reagent, NH4CI, 6N NH40H, 1:40 NH40H solution,
O.OIM EDTA solution (0.372 g of EDTA dissolved in 100 em3 of distilled water), buffer solution
(PH = 10), 2% eriochrome black T indicator etc.
Procedure:
Part I: Preparation of Bis 8-hydroxyquinolato magnesium (II) complex:
(1) Take 20 em 3 of 5% MgS047H20 solution in a 250 em 3 beaker.
(2) Add 5 g of solid NH 4CI to it and stir to dissolve it. Add 6N NH 40H solution very slowly
with constant stirring (till distinct smell of ammonia is there). Adust the pH of the solution
to about 9.5.
(3) Heat the solution and add dropwise with constant stirring about 20 em 3 of 5% oxine in
2N acetic acid solution to it till the precipitate forms and the supernatant solution turns
orange.
(4) Digest the complex on a boiling water bath for 15-20 m:nutes with frequent stirring till
the precipitate becomes crystalline and the supernatant solution remains orange in colour.
Inorganic Preparations and Characterisation 83
(5) Filter the complex through a buchner funnel containing whatman filter paper No. 41.
(6) Wash the complex with dilute ammonia solution (1 :40) until the filtrate becomes colourless.
Test for removal of CI- ions.
(7) Transfer the complex on a watch glass and dry it in an electric oven at 110°C.
(8) Weigh the complex to obtain the yield.
Part II: Analysis of Bis 8-hydroxy quinolato magnesium (II) complex:
(9) Weigh exactly 300 mg of the complex and transfer it quantitatively to a 250 em3 beaker.
(10) Add 5-7 em 3 of conc. RN0 3 to it and boil it nearly to dryness on a sand bath. Complex
gets decomposed. (Repeat the process, if necessary).
(11) Treat the residue with 5 em 3 of conc. HCI and boil it (till no more brown fumes evolved)
and evaporate to dryness.
(12) Extract the residue with 20-25 em 3 of distilled water, boil and then cool it.
(13) Transfer the solijtion to a 100 em 3 standard measuring flask. Wash the beaker and transfer
the washing also.
(14) Dilute the solution to 100 em 3 with distilled water and pipette out 10 em 3 of it in a conical
flask.
(15) Add one test tube of distilled water, 5 em 3 of buffer solution (PH = 10) and 3-4 drops
or a pinch of 2% eriochrome black T indicator is it. Shake the flask well.
(16) Titrate it against O.OIM EDTA solution from the burette. End point will be from wine
red to blue colour.
Reactions:
(1) MgS04 + 2(C9H70N) ~ Mg(C9H60N)2 + H2S04
(2) MgCl2 + N~CIOHI40sN2 ~ MgCIOH140sN2 + 2NaCI
Observations and Calculations:
Weight of [Mg(ox 2)]2H20] = x g.
(I) Yield of [Mg(ox2)]2H20]
(A) Observed Yield of [Mg(ox}J2H20J = x g.
(B) Theoretical Yield of the. [Mg(ox}J2H20J
When 20 em 3 of 5% MgS04.7H20 solution is used:
100 em 3 of MgS0 4.7H20 solution contains 5 g of MgS0 4.7H 20
:. 20 em 3 1.0 g of MgS04.7H20
Now, 246.32 g of MgS04 .7H20 gives 348.32 g of [Mg(ox2)]2H20]
348.32
:. 1.0 g _ _ _ __
246.32
= 1.414 g of [Mg(ox2)]2H20
84 College Practical Chemistry (l'. Y. B.Sc.)

(II) Magnesium content in [Mg(ox1)]2H10


(A) Theoretical Percentage
348.32 g of the complex contain 24.32 g of Magnesium

24.32 x 100
:. 100 g - - - - - - = 348.32
6.98 % of Magnesium
(B) Observed Percentage
Observations:
10 cm 3 of the diluted Mg2+ solution required y cm 3 of O.OIM EDTA solution
:. 100 cm 3 lOy cm 3 _ _ _..___<_
Calculations:
1000 cm 3 of 1M EDTA = 24.32 g of Magnesium
24.32 x 100 x 0.01
.. 10 Y cm3 of O.OIM EDTA = 1000

=
Z g of Magnesium
Since 0.3 g of Magnesium [Mg(ox2)]2H20 contains Z g of Magnesium
Zxl00
100g _ _ _ __ = 0.3
= __ % of Magnesium.
Results:
(1) Yiel~ of Magnesium oxinate complex:
(A) Theoretical yield = 1.414 g.
(B) Observed yield (x) = g.
(2) Percentage of Magnesium in the complex:
(A) Theoretical percentage = 6.98%.
(B) Observed percentage = __'_ %.

000
11
Ion Exchange Methods

Ion exchange term indicates the exchange of ions of similar charge between a solution and
a solid of highly insoluble nature, in contact with the solution.
For analytical method of separation of ions, the synthetic organic ion exchangers are used
which may exchange either cations or anions at a time.
Ion exchangers are of complex nature or are polymers which contain electric charges that
are neutralised by the charges on the counter ions. These active ions are cations in a cation
exchanger and anions in an anion exchanger. A number of cation and anion exchangers are prepared
or are available which contain either -COOH, -OH and -S03H groups or primary, secondary and
tertiary amino groups respectively.
At low concentrations and at ordinary temperature, the extent of exchange increases with
increasing valency of the exchange ion. Under similar conditions and constant valence, the extent
of exchange increases with decrease in size of hydrated ion. In other words, higher the valency
of an ion, greater is its affinity for the resin. Also, smaller the size of hydrated ion, greater is its
affinity for the resin in the column.
When a cation in solution is being exchanged for ion of different valency, the relative affinity
of the higher valent ion increase in direct proportion to the dilution. Thus, to exchange a higher
valent ion on the exchanger from one of lower valency in solution, the exchange will be favoured
by increasing the concentration, while, if the lower valent ion is in the exchanger and the higher
valent ion is in solution, exchange will be favoured by high dilution.
The adsorption of ions will-depend upon the nature of the functional groups in the resin. It
will also depend upon the degree ot cross linking as this degr~e increases, resins become more
selective towards ion of different sizes (the volume of ion incfuaes the water of hydration), the
ion with the smaller hydrated volume will usually be adsorbed preferentially.
86 College Practical Chemistry (T. Y. B.Sc.)

The separation is based on adsorption of ions of elements on a suitable ion exchange (column)
medium followed by differential displacement or elution of the individual ions with a suitable eluting
agent.
Having different affinity for the resin, the adsorbed ions progress down the exchange column
at different rates under the influence of an eluting agent.
The total ion exchange capacity of a resin is dependent upon the total number of ion active
groups per unit weight of material and greater the number of ions, greater will be its capacity.

loS em
t--t
BURBTI'EOR
GLASS COLUMN -t+-...... BENT TUBE

lem

Fig. 11.1 Ion Exchange Column

(I) Preparation of Anion Excbange Resin Column


(1) Place about 30-40 g of Amberlite IR 400 or Dowex 1 or De Acidite FF or Zeolite
FF resin in a 250 em 3 beaker. Add about 100 em 3 of 2N HCl to it and allow it to stand
for about 5-6 hours.
(2) Decant the acid and wash the activated resin with about 100 em 3 of distilled water in
the same beaker. (Stir it well to remove traces of HCl.)
(3) Decant the solution as soon as the larger particles of the resin have settled down in the
beaker. Wash the resin repeatedly with distilled water (2-3 times) to remove all of acid
and smaller particles or impurities, till the supernatant layer becomes clear.
(4) Fill a burette completely with distilled water, taking care to see that its nozzle is free from
air bubbles. Now, insert a small wad of glasswool from the top of the burette. Push it
gently and carefully with the help of a long glass rod, taking care that no air bubbles are
trapped in the glasswool. Keep on pushing carefully till it rests firnlly at the bottom of
the burette.
(5) Transfer the resin slurry, a small quantity at a time (tapping the burette all the while to
remove air bubbles), to the burette which is filled with distilled water and plugged with
glasswool as prepared in step No.4.
(6) Transferring ofthe resin should be continued till a compact column of about 25 em length
is obtained.
Ion Exchange Methods 87
(7) Ensure that the resin column is vertical, free from air bubbles, continuous and is always
kept submerged under an eluting agent (or distilled water when not in operation) to prevent
in from drying and deactivation.
(II) Preparation of Cation Exchange Resin Column
(1) Place about 30-40 g of Zeo earb 225 or Amberlite IR 120 resin in a 250 em 3 beaker.
Add about 100 em 3 of 2N Hel to it and allow it to stand for about 5-6 hours.
(2) Follow step Nos. 2 to 7 as mentioned above in Part (I) to prepare the cation exchange
resin column.
Experiment No. 1 (6 Units only)
Estimation of Zinc
Aim: Estimate the amount of zinc present in the given solution of magnesium-zinc mixture, using
an anion exchange resin column.
Theory:' Zinc ions form negatively charged stable chloro complex in presence of 2N Hel. Mg2+
ions do not form any negatively charged chloro complex under these conditions.
The maximum adsorption of ions, is obtained in Hel solution. Zinc ions are eluted with the
help of dilute HN03.
Zinc effluent is collected and estimated quantitatively against a standard EDTA solution, using
an appropriate indicator.
Procedure:
(1) Dilute the given solution to 100 em 3 in a standard measuring flask with 2N Hel and shake
well.
(2) Take a resin column containing Amberlite IR 400 resin (see preparation method on page
No. 89). Wash the burette with distilled water the remove excess of acid from the resin
column. Pass distilled water through the washed coiumn and with its help, adjust the
flow rate to 3 em 3 per minute. Once adjusted, this rate should not be disturbed. Drain
it to about 0.5-1 em level above the bed of the resin.
(3) Pipette out 10 em 3 of the diluted solution and transfer it to the column.
(4) Transfer about 60 em 3 of 2N Hel solution through the column and collect the effluent
of magnesium ions at rate 00 em 3 per minute, through the resin column, in a small beaker.
Reject this effluent.
(5) Arrange a 250 em 3 standard measuring flask for collecting the next effluent of zinc ions
through the resin column.
(6) Transfer about 80 em 3 of 0.25N HN03 solution through the same column and collect the
effluent of zinc ions at the same rate of 3 em 3 per minute in the standard measuring flask.
(7) Dilute the effluent to 250 em 3 with distilled water in the standard measuring flask.
(8) Pipette out 25 em 3 of it in a conical flask. Add two drops of 1% methyl orange indicator
to it. Now, add 2NaOH solution dropwise from a burette to neutralise the acidity of the
solution (solution turns yellow). Note the volume of NaOH solution required for
neutralisation (Reject the solution).
(9) Again pipette out 25 em 3 of the diluted solution in a conical flask. Add 3 test tubes of
distilled water. Now, add the noted volume of 2N NaOH solution to it and shake it well.
88 College Practical Chemistry (T. Y. B.Sc.)
(10) Now, add 10 em 3 of buffer solution (PH = 10) and 3-4 drops (or a pinch) of2% eriochrome
black T indicator to it.
(11) Shake well and titrate it slowly against O.OIM EDTA solution from the burette. End point
will be from wine red to blue colour.
Note: Wash the column with distilled water. (Reject the washings). Charge the column by adding a sufficient
quantity of 2N HCI, at the end of the experiment.
Reaction:
Zn(N03)2 + Na2ClOH140sN2 -~ ZnClOH140sN2 + 2NaN03
Calculations:
25 em 3 of the diluted effluent solution required x em 3 of O.OIM EDTA solution
:. 250 em 3 lOx em 3
i.e., 10 em 3 of the diluted mixture solution required lOx em 3 of O.OIM EDTA solution
.. 100 em 3 100x em 3
1000 em 3 of 1M EDTA = 65.38 g of Zinc

65.38 x 100x x 0.01


.. 100x .em3 of O.OIM EDTA = 1000 g of Zinc

Results:
(I) 25 em 3 ofthe diluted effluent solution required (x) =___ em 3 ofO.OIMEDTA solution.
(2) Amount of Zinc present = g.
Experiment No.2 (6 Units only)
Estimation of Magnesium
Aim: Estimate the amount of magnesium present in the give solution of magnesium-zinc mixture,
using an anion exchange-resin column.
Theory: Zinc ions- form negatively charged chioro complex, which are retained on the resin bed
containing anion exchangers. Mg2+ ions do not form stable negatively charged chloro complex, hence
are eluted out, with 2N HCI.
The maximum adsorption of ions, is obtained in acidic medium and magnesium ions are eluted
quantitatively by 2N HCl while zinc ions which are retained by the resin.
Magnesium effluent is collected and estimated quantitatively against a standard EDTA solution,
using an appropriate indicator.
Procedure:
(1) Dilute the given solution to 100 em 3 in a standard measuring flask with 2N HCI.
(2) Take a resin column containing Amberlite IR 400 resin (see preparation method on page
No. 89).
Wash the burette with distilled water to remove excess of acid from the resin column.
Pass distilled water through the washed column and with its help, adjust the flow rate
to 3 em 3 per minute. Once adjusted, this rate should not be disturbed. Drain it to about
0.5-1 em level above the bed of the resin.
Ion Exchange Methods 89

(3) Pipette out 10 em 3 of the diluted solution and transfer it at a rate of 3 em 3 per minute,
through the resin column. Arrange a 250 cm 3 standard measuring flask for collecting the
effluent.
(4) Transfer about 60 cm3 of 2N HCI solution through the column, and collect effluent of
magnesium ions at the same rate of 3 em 3 per minute, in the standard measuring flask.
(5) Dilute the effluent to 250 em 3 with the distilled water in the standard measuring flask.
(6) Pipette out 25 em 3 of the diluted solution a conical flask. Add 3 test tubes of distilled
water.
Add 10 em 3 of buffer solution (PH = 10) and 3-4 drops (or a pinch) of 2% eriochrome
Black T indicator to it.
(7) Shake well and titrate it against O.OIM EDTA solution from the burette. End point will
be from wine red to blue colour.
Note: Wash the column with 0.25N HN03 first to remove zinc ions and with distilled water
(Reject the washings). Charge the column by adding a sufficient quantity of2N HCl,
at the end of the experiment.
Reaction:
MgCl2 + NazCIOH140sN2 ~ MgCIOH140sN2 + 2NaCl
Calculations:
25 em3 of the dilute effluent solution required x cm 3 of O.OIM EDTA solution.
:. 250 em 3 lOx cm 3
i.e., 10 em 3 of the diluted mixture solution required lOx cm 3 of O.OIM EDTA solution.
.. 100 em 3 IOOx em3
1000 em 3 of 1M EDTA = 24.32 g of Magnesium
24.32 x 100 x 0.01
.. IOOx em3 of O.OIM EDTA = g of Magnesium
1000
Results:
(1) 25 cm 3 ofthe diluted effluent solution required (x) =___ cm 3 ofO.OIMEDTA solution.
(2) Amount of Magnesium present = g.
Experiment No.3
Estimation of Sodium
Aim: Estimate the amount of sodium present in the given sodium chloride solution, using a cation
exchange resin column.
Theory: A sodium salt solution, free from all other cations, is passed through a strong cation
exchange resin in hydrogen form.
The number of sodium ions available from the solution, will displace an equivalent number
of hydrogen ions, which are collected and titrated against a standard alkali solution.
RH + Na+ ~RNa + H+
These H+ ions when titrated, give a reading which corresponds to the number of sodium ions
present in the given solution.
90 Col/ege Practical Chemistry (T. Y. B.Sc.)

Procedure:
(1) Dilute the given solution to 100 em 3 in a standard measuring flask with distilled water.
(2) Take a resin column containing Amberlite IR 120 resin. (see preparation method on
page No. 90).
Wash the burette with distilled water to remove excess of acid. Pass distilled water through
the washed column and with its help, adjust the flow rate to 4 em 3 per minute. Once
adjusted, this rate should not be disturbed or altered.
(3) Pipette out 10 em 3 of diluted solution and transfer it to the top of the column, at the rate
of 4 em 3 per minute. Arrange a 250 em 3 standard measuring flask to collect the effluent.
(4) Transfer of about 100 em 3 of distilled wat.;!r at the same rate, through the same column.
(5) Collect the effluent of hydrogen ions at the same rate of 4 em 3 per minute in the standard
measuring flask. (Effluent contains hydrogen ions equivalent to sodium ions).
(6) Dilute the effluent to 250 em 3 in the standard measuring flask with distilled water.
(7) Pipette out 25 em 3 of it in a conical flask. Add 2 drops of phenolphthalein (or methyl
red) indicator and titrate it against 0.05N NaOH solution from the burette. End point will
be from colourless to pink (or from pink to yellow colour).
Note: Charge the column by adding a sufficient quantity of 2N HCI, at the end of the experiment.
Reactions:
(1) NaCI + RH ~ HCI + RNa
(2) HCI + NaOH ~ H20 + NaCI
Calculations:
25 em 3 of the diluted effluent solution required x em 3 of 0.05N NaOH solution.
:. 250 em 3 lOx em 3
i.e.. , 10 em 3 of the diluted solution required lOx em 3 of 0.05N NaOH solution
100 em 3 100x em 3
From the equations,
INaCI = INa+ == 1 H+ == lNaOH
1000 em 3 IN NaOH = 23 g of Sodium = 58.5 g of NaCI
23 x 100x x 0.05
.. 100x em 3 of 0.05N NaOH = 1000 g of Sodium

58.5 x 100x x 0.05


= g of NaCI
1000
Results:
(1) 25 em 3 of the diluted effluent solution required (x) = ___ em 3 of 0.05N NaOH
solution.
(2) Amount of Sodium present = g.
(3) Amount of NaCI present = ____ g.

000
12
Chromatographic Experiments

Chromatography is a modern technique used for rapid analysis, separation and purification
of components of a compound. In chromatography, separation of the mixture is brought about by
the differential migration of different constitutents through a porous medium under the influence
of mobile phase. Porous media is referred to as stationary phase. The stationery phase may
be a porous solid (such as· silica, alumina etc.) packed in a column or a solution supported by a
strip of filter paper. The moving phase may be some solvent or a gas and is referred to as a
developer or an eluent.
Chromatographic methods are classified on the basis of mechanism of separation, types of
stationary and mobile phase as well as on the basis of equipments used. Two methods namely
paper chromatography and ion exchange chromatography are discussed in detail in this chapter.
Paper Chromatography
Paper chromatography is a type of partition
.......
chromatography. It is the simplest of all known
) J - - - ; - - Glass Hook chromatographic techniques. In this technique
separation of the subastances is carried out on
Filter Paper Strip srips or filter paper like whatman filter paper No.
Rising Solvent Front 1. Condensed water vapour supported by a strip
of filter paper is the stationary phase whereas the
Glass Jar
moving solvent is the mobile phase which rises
_f---f--- Original Spot through the paper due to capillary forces.
=-:--::-
----------
- ---
:= -=_-=-:=-:5"_~-
_________ a
Solvent
Substances are partitioned or distributed
between two immiscible phases. This distribution
brings about the separation.
Fig. J2. J Ascending Paper Chromatography
92 College Practical Chemistry (T. Y. B.Sc.)

In a chromatographic separation, usually a drop of the solution of the mixture to be separated


or analysed is placed near one end of the filter paper strip and the supporting solvent is allowed
to evaporate in air. The strip is then held by a support and suspended in a closed cylinder with
the bottom of the strip just dipping in the solvent present in it. \
The capillary actipn causes the solvent to rise up the strip and the components of the mixture
move up the paper at varying rates with the solvent front. (Fig. 12.1).
The rates at which various components move up depend upon their IVvalues (lVimplies retention
factor). The IV value expresses the rel~tive rate of movement of component and the solvent.
Distance moved up by the component in em
i .. e., IV = Distance moved up by the solvent front in em

Both these distances are measured from the original spot (base) line Thus. as shown in Fig. 12.2
IV value of a substance depends upon a nUmber of factors such as the nature of the constituents
of mixture, the nature of the solvent, temperature, the quality of filter paper employed, the pH of the
solution etc. IVhas no unit and IVvalue is always less than 1. When·the solvent is moving upward
on the paper, it is referred to as ascending paper chromotography.

-IOcm ,.
Chromatogram
"'--~"""""""""'""""""'--Solvent Front

.r-~t---Centre of
the spot
)
.,..5
N r-;===t:;;Positions for spotting

j
r-+-- Base Line

Baseline
'----+--Point of
Application of
Original Spot
B
'---_----J
C
F 2 em A = Metal ion.l
B = Metal ion.2
C = Mixture of meta)
ions (I &: 2)

Fig. 12.2 Fig. 12.3

Experiment No. 1
Separation of Metal Ions - Nll+, Col+, Mnl+ and Zn1+
Aim: To separate two metal ions from a given mixture by ascending paper chromatography.
Requirements:
(A) Materials:
Whatman filter paper No.1 strip (about 25 em x 8 em), paper chromoiographic jar having 30
em height and 10 em diameter, capillary tubes etc.
(B) Chemicals:
(i) Salt solution: 1% acidified aqueous solution of chrorides of any two cations.
Chromatographic Experiments 93

(ii) Developing solvent: A mixture of 22 em 3 of acetone, 105 em 3 of water and 2 em 3 of


conc. HC!.
(iii) Spraying reagent: Saturated alcoholic solution of Alizarine containing 0.1 % rubeanic
acid and 1% salicyldoxime.
Procedure:
(1) Fill the jar with a develping solvent so that height of solvent is approximately 2-4 em from
the bottom. Cover it with a lid and allow it to stand for sometime, so that the jar becomes
saturated with the solvent vapours.
(2) Draw a starting line with lead pencil about 2 em away from one edge of the filter paper
strip (base line). Make three cross marks labelled as A, Band C on this line 2 em apart
from each other as from the edge of the paper. (as shown in Fig. 12.3).
(3) Prepare a mixture of metal ions solution (A) and (B) in equal proportions.
(4) Apply by means of a capillary tube, solution of one of the metal ions on cross marked
as A taking care that the drop does not spread more than 1 mm.
(5) Similarly, by means of another capillary tube, apply solution of another metal ion on cross
marked as B taking care as in step No.3.
(6) Now, apply a drop of mixture solution by means of a capillary tube on cross marked as
C taking care as described in step No.3.
(7) Allow the spots to dry and fix the other end of the filter paper strip on a glass rod by
means of U clip.
(8) Carefully dip the filter paper strip into the jar by taking the following precautions:
(a) It should not touch the walls of the jar.
(b) Developing agent should not touch the baseline.
(9) Cover the jar with the lid. After the solvent has travelled a distance of about 15 em, take
out toe filter paper strip which is now called chromatogram and let it dry in air.
(10) Expose the chromatogram to another jar containing liquor ammonia vapours to neutralise
HC!.
(11) Then spray the chromatogram with spraying reagent to develop the coloured spots. They
will be as follows:
C02+ - brown, Ni 2+ - blue
Mn2+ - brown, Zn2+ - purpl~
(12) Measure the distance travelled by developing solvent and by spots and calculate IVvalues
for ion.
(13) The sequence of IV values is as follows:
Zn2+ > C02+ > Mn 2+ > Ni 2+
Expected IV values of metal ions are:
[Zn2+ = 0.9, C02+ = 0.55, Mn2+ = 0.25, Ni 2+ = 0.1]
Results:
Observed IV values of cations in the given mi~ture are:
(1) ion = _ _
(2) _ _ ion = ---
000
13
Separation of Organic Mixtures
(6 Units only)

The separation of organic mixture is based upon the differences in some physical properties
like solubilities, boiling point etc. and diferences in some chemical properties like reactivity with
aqueous solution of sodium bicarbonate, sodium hydroxide, hydrochloric acid etc.
Generally there are three types of organic mixtures:
(1) Solid - solid mixture:
This may be:
(a) Water soluble solid - water insoluble solid
(b) Both water insoluble solids
(2) Solid - liquid mixture:
This may be:
(a) Solid dissolved in organic liquid (homogeneous mixture)
(b) Solid suspended in organic liquid (heteregeneous mixture)
(3) Liquid - liquid mixture:
This may be:
(a) Miscible liquids
(b) Immiscible liquids
Separation o/Organic Mixtures (6 Units only) 95
Methods of Separation of Organic Mixture:
(1) Separation based upon differences in chemical properties:
If one of the compounds of the mixture reacts with some reagent to form a salt and the
compound can easily be reconverted back to the original compound, then, this fact can be used
to separate the compounds from each other. The reactivity of the compounds with aqueous
NaHC03, NaOH, HCI solution etc. can be used to separate the compounds such as acid, phenol,
base and neutral. According to this chemical separation, the type of binary mixtures are:
(i) Acid - Phenol (iv) Phenol - Base
(ii) Acid - Base (v) Phenol - Neutral
(iii) Acid - Neutral (vi) Base - Neutral
(2) Separation based upon differences in the physical properties:
Difference in the physical properties like boiling points, solubilities in water etc. can be used
for the separation of organic mixtures. Fractional distillation, recrystallisation methods are used for
such separations.
SEPARATION AND ANALYSIS OF SOLID-SOLID MIXTURE
The separation of solid-solid mixture involves:
(1) Determination of type of the mixture
(2) Separation of the mixture into components or compounds
(3) Purification of each compound
(4) Physical constants to check the purity of each compound.
(1) Determination of type of the mixture
The solid-solid mixture may be:
(i) water soluble solid and water insoluble solid
(ii) water insolube solid and water insoluble solid.
The chemical type of solid-solid mixture may be anyone of the following:
(i) Acid - Phenol (iv) Phenol - Base
(ii) Acid - Base (v) Phenol - Neutral
(iii) Acid - Neutral (vi) Base - Neutral
(vii) One compound water soluble acid, phenol, base or neutral and second compound water
insoluble acid, phenol, base or neutral.
The type of mixture can be detected by following tests:

Tests Observations Inferences

1. About 0.5 g of mixture + 2 cm 3 Effervescence Carboxylic acid present.


of saturated NaHC03 solution,
shake well and filter

Filtrate + conc. HCl dropwise (i) A solid reappears Carboxylic acid present.

(ii) Effervescence with NaHC03 Water-soluble acid present.


solution but no solid reappears
on addition of HCI to the fil-
trate.
96 College Practical Chemistry (T. Y. B.Sc.)

Tests Observations Inferences


2. If acid present, wash the residue
from test (I) with NaHC03
solution 2-3 times to remove all
traces of acid and then wash
with water.
Residue + 2 cm 3 of dilute NaOH
solution, shake well and filter.

Filtrate + conc- HCI dropwise. A solid reappears Phenol present

3. If phenol present, wash the


residue from test (2) with dilute
NaOH solution 2 times and then
wash with water
Residue + 2 cm 3 of I: I HCl
solution, shake well and filter.
Filtrate + 20% NaOH solution A solid reappears Basic compound present.

4. Residue from test (3) Neutral compound present.

5. If only one compound is detected from the above tests, then the other compound must be water soluble. The nature
of water soluble compound can be detected as follows:

0.5 g of mixture + I cm3 of Crystals are obtained. Water soluble compound present.
water, shake well and filter.
Collect the filtrate in a porcelain
dish and evaporate it to 1I4th of
the original volume and cool.
Crystals obtained are dissolved
in 2 cm 3 of water and test solu-
tion as follows:

(i) I cm 3 of above solution + I Effervescence Water soluble carboxylic acid present.


cm3 of saturated NaHC0 3
solution.

(ii) 2 drops of above solution + Blue to violet colour Water soluble phenol present
I drop of alcoholic FeCI J
solution.

(iii) 2 drops of above solution + Red litmus turns blue Water soluble base present.
Red litmus paper

(iv) If all three tests are negative - Water soluble neutral present.
Alternate Method
(1) Determination of type of the mixture
0.5 g of the mixture + 2 em3 of saturated NaHC03 solution, shake well and filter.
,
Filtrate Residue
Add conc. HCI drop by drop, precipitate obtained. If acid present, wash the residue with NaHC03 solution
Acid present. and then wash with water. Residue + 4-5 em] of dilute
NaOH solution, shake well and filter,
Separation of Organic Mixtures (6 Units only) 97

Filtrate Residue
Add conc. HCl drop by drop, precipitate obtained. If phenol present, wash the residue with dilute NaOH
Phenol present. solution and then wash with water.
Residue + 2 cm3 of I: I HCl, shake well and filter.
I
I I
Filtrate Residue

Add 20% NaOH solution drop by drop, precipitate No residue left


obtained. Neutral present.
Base present.
Conclusions:
From all the above tests carried out, it is concluded that the two compounds of the mixture
are and Hence, the type of the mixture is and

Separating reagent is and is regenerated by _ _ _ __


(2) Separation of the mixture into components or compounds
(A) Separating reagent:
The method of separation is based on the principle of selective dissolution of one compound
in a suitable reagent and then after filtration, recovery ofthe compound from its solution by addition
of other reagent called precipitating reagent.
The selection of separating reagent depends upon the type of the mixture. Following table
gives a list of separating reagents, used for sele~tive dissolution and subsequent recovery of the
compounds.
Types of mixture Reagent for separation Precipitating reagent/method
1. Acid - Phenol
2. Acid-Base Saturated NaHC0 3 solution Conc. HCI
3. Acid - Neutral
4. Phenol - Base
5. Phenol - Neutral Dilute NaOH solution Conc. HCl
6. Base - Neutral 1:1 HCl 20% NaOH solution
7. Water soluble-acid! Water Crystallisation
phenol/ basel neutral -

(B) Separation method:


(i) For mixture o/type Nos 1, 2 and 3 (when one of the compounds is an acid):
Place 4 g of the mixture in a 100 cm 3 beaker. Add 25-30 cm 3 of saturated NaHC03 solution
to it. Stir for a few minutes and filter.

Filtrate Residue
Collect the filtrate in a beaker. Add conc. HCl drop by Wash the residue first with NaHC03 solution to remove
drop with stirring till the precipitation is complete. Cool all the traces of acid, then with water and dry it. This
it and filter. Wash the precipitate with water and dry it. is compound B (Phenol / BaselNeutral).
This is compound A (Acid).
98 College Practical Chemistry (T. Y. B.Sc.)

(ii) For mixture of type Nos. 4 and S (when one of the compounds is a phenol):
Take 4 g of the mixture in a 100 cm 3 beaker. Add 25-30 cm3 of dilute NaOH solution to
it. Stir for 2-3 minutes and filter.
Filtrate Residue
Collect the filtrate in a beaker. Add conc. HCl drop by Wash the residue first with dilute NaOH to remove all
drop with stirring till the precipitation is complete. Cool traces of phenol, then with water and dry it. This is
it and filter. Wash the precipitate with water and dry it. compound B (Base/Neutral)
This is compound A (Phenol)

(iii) For mixture of type No 6 (when one of the compounds is a base):


Take 4 g of the mixture in a 100 cm 3 beaker. Add 25-30 cm 3 of 1: 1 Hel solution to it. Stir
for 2-3 minutes and filter.
Filtrate Residue
Collect the filtrate in a beaker. Add 20% NaOH solution Wash the residue first with 1: 1 HCI solution and finally
drop by drop by stirring tiJI the precipitation is with water. Dry the compound. This is compound B
complete. Cool it and filter. Wash the precipitate with (Neutral).
water and dry it. This is compound A (Base)

(iv) For mixture of type No. 7 (when one of the compounds is water soluble):
Take 4 g of the mixture in a 100 cm 3 beaker. Add 25 cm 3 of water to it. Stir for 2-3 minutes
and filter.
Filtrate Residue
Collect the filtrate in a porcelain dish. Heat this carefully Wash the residue with water to remove water soluble
on a wire gauze till the volume of filtrate is reduced to compound completely and dry it.
one-fourth of the original volume. Allow it to coot-Filter This is compound B
the crystals obtained and dry it. This is compound A Water insoluble AcidIPhenoVBase/Neutral)
(water soluble).

(3) Purification of each compound


The compounds obtained after separation are to be purified before taking melting point.
The purification of solid compound is carried out by a process of recrystallisation. Purification
involves two steps, 1st step is finding a suitable solvent. This is the one which dissolves solid only
in hot condition and 2nd step is recrystallisation.
(A) Determination of a suitable solvent
(i) Take a pinch of compound in a test tube, add 1 cm 3 of water and heat to boiling. If the
compound dissolves almost completely then water is a suitable solvent.
If a major part of the compound is found to be insoluble, then add more water (about 2 cm 3 )
and heat to boiling. If the compound is still insoluble, then next solvent is tried as described under
test (ii).
(ii) Take a pinch of the compound in a test tube, add 1 cm 3 of ethyl alcohol and shake for
a few seconds. If the compound dissolves, then, ethyl alcohol is not a suitable solvent, and
next solvent is tried as described under test (iii).
If the compound does not dissolve, heat the contents of test tube to boiling on a water bath.
If the compound dissolves almost completely, then, ethyl alcohol is a suitable solvent. Otherwise,
add more of ethyl alcohol (about 1 cm 3) and continue the heating. See the solubility once again.
If the compound gets dissolved in hot ethyl alcohol, then, ethyl alcohol is used as a suitable solvent,
otherwise carry out test (iv)
Separation o/Organic Mixtures (6 Units only) 99
(iii) Take a pinch of the compound, add 1 em 3 of ethyl alcohol and 1 em 3 of water. Heat
carefully to boiling. See if the compound has dissolved. Add more of ethyl alcohol (about lem 3),
if compound has not dissolved then heat to boiling. Repeat the process by adding 1 em 3 of ethyl
alcohol each time, till the compound dissolves completely in hot condition. Note down the proportion
of water and alcohol and use this as a suitable solvent.
(iv) Other recommended solvents for recrystallisation purification are methanol and isopropyl
alcohol.
(8) Recrystalllsation
Transfer the entire separated compound in a hard glass test tube and add only 3 em 3 of the
suitable solvent to dissolve the compound. Heat to boiling carefully. (If solvent is volatile
and inflammable, then, heating is done on a water bath). If an almost clear solution is not
obtained, then, add more of solvent (about 1 cm 3) and heat to boiling. Repeat this process till a
clear solution is just obtained. Filter it hot (i.e., immediately through cotton). On cooling the filtrate,
crystals are obtained. Filter and wash the crystals on filter paper with 1-2 em 3 of cold solvent
to remove the mother liquor. The crystals, i.e., the pure compound is dried as described below.
Drying of compound
For an organic compound, it is necessary to find out its melting behaviour before taking it
for drying. Take 1 em 3 of hot water in a test-tube add 1-2 crystals of organic compound.
(a) If compound melts and forms globule, then it is a low melting compound. It is dried by
passing air through it on the suction bed followed by air drying.
(b) , If compound does not form globule, then it is a high melting compound.
A high melting compound may be dried by using a water bath, an electric oven, an IR lamp
or by reflected heat method.
The compound to be dried is transferred on a dry watch glass (or on a sheet of filter paper
placed on an asbestos sheet). The watch glass is placed near the base of a burner. A wire gauze
or a water bath is placed over the burner, which provides the reflected heat, as shown in Fig.
13.1.
The reflected heat dries the compound. If the compound is suspected to be a low melting
one, then it is placed at a safe distance from the bu,mer.

DRYING BY REFLECTBD HEAT

WATCH GLASS FILTER PAPER


WITH COMPOUND CONTAINING COMPOUND

Fig. 13.1 Drying by reflected heat

(C) Sublimation
If the compound is not soluble in any solvent, then the purification is <Jone by sublimation.
Take the dry compound in a dry porcelain dish, cover it with a filter paper having four to five
holes. Place an inverted dry funnel with a cotton plug in the stem, on the filter paper. Heat the
100 College Practical Chemistry (T. Y. B.&.)

porcelain dish on a wire gauze on a low flame. The pure sublimate collects on the inside walls
of the funnel.
SEPARATION AND ANALYSIS OF SOLID-LIQUID AND LIQUID-LIQUID
MIXTURES
(1) Determination of type of the Solid-Liquid and Liquid-Liquid mixtures
(a) Solid-liquid mixture may be:
(i) VolatilelNon-volatile liquid-solid (soluble)
(ii) VolatileINon-volatile liquid-solid (insoluble)
(b) Liquid-liquid mixture may be:
(i) Volatile liquid - Non-volatile liquid
(ii) Non-volatile liquid - Non-volatile liquid
The type of the mixture can be detected by the following tests:
Tests Observations lnj£rences
J
I. Take 0.1 cm of mixture in a dry Continuous evolution of air bubbles Volatile liquid present
fusion tube. Place a capillary from the open end of the capillary
tube sealed at one end into it in tube.
such a way that the open end is
dipped into the mixture Suspend
the fusion tube in a boiling water
bath and heat.

2. Pour the hot contents of the (i) A solid appears Solid compound present.
above test tube on a dry watch (ii) No solid appears but liquid re- The mixture is of volatile liquid-
glass. mains. non volatile liquid.

Conclusions:
The physical type of the mixture is and _ __
(2) Separation of the mixture (Liquid-Liquid mixtures and Solid-Liquid mixture)
Separation method, i.e. fractional distillation is based on difference in boiling points of liquid
compounds.
(i) For volatile-non volatile liquid mixture: Place the given mixture in a 25 cm 3 distillation
flask. Add porcelain pieces in the flask to prevent bumping. Attach a water condenser to sidearm
of the flask. Place a thermometer through a cork such that bulb of thermometer just lies opposite
to the sidearm as shown in Fig. 13.2. Heat the flask on a boiling water bath. As the temperature
gradually increases, some liquid distills out which is collected in a receiver labelled as A. When
the temperature becomes nearly constant, the receiver is replaced by a dry test tube. Now, collect
the liquid distilling out and continue to collect till temperature begins to fall down (i.e., all the volatile
liquid is separated) and the test tube containing first fraction is replaced by the receiver A. Label
the liquid in the test tube as first fraction and boiling range is noted down on the label.
Now, the flask is heated carefully on a wire gauze (gently at first). The water condenser
is replaced by an efficient air condenser.
As the heating is continued, temperature increases steadily. When a constant temperature
is attained, the original receiver A is replaced by another dry test tube. Again, liquid distilling out
Separation o/Organic Mixtures (6 Units only) 101

POsmON OF THERMOMETER
OPPOSITE TO THE SIDE ARM

~'::-';''":~--DISTILLATION
C:::::;;~==::::;;:::::I FLAsK WATER INLET

Fig. 13.2

over a range of 2-3°C is collected and labelled as second fraction. Note down the boiling range
on the label.
When a little liquid in left in distillation flask, heating is stopped and the apparatus is
disconnected after cooling.
(iI) For volatile liquid-solid (soluble) mixture: The volatile liquid is distilled over and
collected as described in the first part of procedure for volatile-non-volatile liquid mixture.
After the distillation of volatile liquid is over, temperature falls down. At this stage, heating
is discontinued and the hot residual liquid left in the distillation flask is immediately poured on
a dry porcelain dish. After a few minutes. solid compound is obtained which is collected. It is
purified. dried &lid weighed.
(3) Purification of liquid compounds:
The purification is carried out by redistillation of liquid compound as described below:
Take the separated liquid compound in a dry distillation flask, fitted with a water condenser
(or an air condenser - depending upon the nature of the liquid). A test tube is used as a receiver,
say. receiver A. Heat the flask on a boiling water bath (or on a wire gauze in a case of liquids
having higher boiling points.) The liquid distills out which is collected in the receiver A. When a
constant temperature is reached, then receiver A is replaced by another dry test tube. Now, the
liquid distilling out is collected over a range of 2-3°C (i.e .• constant temperature ±2°C).
This is the pure compound, which is used for determination of boiling point (the liquid collected
in the receiver A is not pure but can be used for other tests).
(4) Determination of Physical Constants
Determination of melting point
The melting point of the substance is defined as the temperature at which the solid and
the liquid phase of substance exist together under one atmospheric pressure.
A pure organic compound has usually a sharp and definite melting point which is a
characteristic of that compound. Hence, in the identification of the compound, the accurate
determination of its melting point plays a very important role. Therefore, the compound must be
purified by recrystallisation as the impurities lower the melting point.
102 College Practical Chemistry (T;¥' B.Sc.)

(1) The apparatus used for the determination of


g . - - - - - THERMOMETER melting points is shown in the Fig. 13.3.
(2) A small amount of pure and dry organic
~!OM----- CUT BARK CORK compound, the melting point of which is to
be determined is finely powdered.
fe----- THIELE'S TUBE
(3) A thin capillary of uniform bore and about
1 4 4 - - - - CAPILLARY 5 cm length is sealed at one end.
(4) The finely powdered organic compound is
then introduced into the capillary. The
compound is pushed down by tapping the
bottom of the capillary. The process is
repeated till about 0.5 cm long compact filling
is obtained.
' - - - BURNER (5) The capillary is then tied to the thermometer
in such a way that the end of the capillary
Fig, J3,3 Determination of melting point of an organic tube containing the compound is in contact
solid using Thiele's Tube with the mercury bulb of the thermometer.
(6) The thermometer is then suspended in a Thiele's tube containing paraffin oil in such a
way that the bulb of the thermometer is in the level of the mouth of side arm of the Thiele's
tube.
(7) Heat the side arm of the Thiele's tube with a low oxidising flame.
(8) When the substance in the capillary starts melting remove the burner and when the entire
solid in a capillary becomes liquid and transparent, the temperature in thermometer is
noted. This is th~ melting point of the substance.
Determination of boiling point
The boiling point of a liquid is defined as the temperature at which the vapour pressure
of the liquid becomes equal to the atmospheric pressure.
The boiling point of the pure liquid is also the characteristic of that liquid. Hence in the
identification of the liquid, the boiling point of the pure liquid plays a very important role.
(1) One third of a thin walled ignition tube is filled with the liquid.
(2) It is then tied to a thermometer in such a way that the lower' end of the ignition tube
is near and in the level of th~ mercury bulb of the thermometer.
(3) The capillary about 5 cm long is sealed at one end and inserted into the ignition tube in
such a way that the open end of the capillary is dipped inside the liquid and the sealed
end remains outside.
(4) The thermometer is then suspended in a paraffin oil bath as shown in the Fig. 13.4 and
the paraffin bath is heated with a low oxidising flame and the oil bath is stirred.
(5) The air bubbles start coming out from the lower end of the capillary at the low rate. At
the boiling point of the liquid, a continuous and vigorous stream of bubbles come out of
the capillary tube.
SepartJtion o/Organic Mixtures (6 Units only) 103

1~~------~0MEnm
STAND

. . . - - - - - SEALEDEND
......- - - - CAPILLARY

~nI4.....--+--IGNI11ON TUBE
~-.'tit-- BEAKER
AfII...,- UQUJD

PARAFFIN 00.

___-WIRE GAUZE

.....--BURNER

Fig. 13.4 Determination 0/ boiling point 0/ an organic liquid

After completing the experiment, report the results as follows:


(1) Type of mixture : + _ __
(2) Weight of the mixture: g/cm3.
(3) Weight of recrystallised/redistilled Compound (A) : g/cm3.
(4) MeltinglBoiling point of Compound (A) : °C.
(S) Weight of Compound (B) : g/cm3•
(6) Characterisation of Compound (B) :
(i) SaturatedlUnsaturated
(n) Aliphatic/Aromatic
(fu) AcidlPhenoVBaselNeutral :
(iv) Elements
·(v) Functional Group
(vi) MeltinglBoiling Point
SYSTEMATIC IDENTIFICATION OF AN ORGANIC COMPOUND
A systematic scheme for the identification of the organic compound is outlined below:
(1) Preliminary Tests
(2) SolubilitylMiscibility Tests
104 College Practical Chemistry (T. Y. B.Sc.)

(3) Detection of Elements


(4) Detection of Functional Groups
(5) Determination of Physical Constants and Identification of the Compound
(6) Confinnatory Tests
(1) Preliminary Tests

Tests Observations Inferences

(a) Nature (i) Solid Carbohydrate, acid, phenol, amine,


higher hydrocarbon may be present.
,
(ii) Liquid Alcohol, ketone, aldehyde, ester, phe-
nol, amine may be present.

(b) Colour (i) Yellow-solid m-Dinitrobenzene, p-nitrotoluene,


nitrophenol, nitroaniline.

(ii) Yellow-liquid Nitrobenzene.

(iii) Brown p-Toluidine, resorcinol.

(iv) Blackish a-Naphthol.

(v) Pink I3-Naphthol.

(vi) Buff or reddish brown Aniline, phenol, aromatic amine.

(vii) Colourless Simple acid, alcohol, ester, ketone


aromatic hydrocarbon.

(c) Odour (i) Carbolic Phenol, cresol.

(ii) Fishy Amine.

(iii) Sweet pleasant Ester, alcohol and halogen derivatives.

(iv) Bitter almonds Nitrobenzene, benzaldehyde.

(v) Moth balls Naphthalene.

(vi) No particular smell Aromatic acid, amide, carbohydrate.

(d) Flame Test


Heat a small amount of com- (i) Sooty flame Aromatic compound or aliphatic com-
pound on a porcelain piece. pound containing small proportion elf
hydrogen e.g CHq3' CCI4•

(ii) Non sooty flame Aliphatic compound.

(iii) Substance chars Carbohydrates, sulphanilic acid.


Separation of Organic Mixtures (6 Units only) 105

Tests Observations Inferences


(e) Beilstein Test Greenish blue flame after the disap- Halogen compounds, certain lower
Heat a small piece of copper foil pearance of initial sooty flame. amide like urea, thiourea may be
till it imparts no colour to the present.
flame. Place a small amount of
the compound on it an~heat.

(t) Test for unsaturation (i) Decolourisation of Br2 water Unsaturated compound.
(i) Bromine water test
Compound + 1 cm 3 0fwater, (ii) Decolourisation with formation Easily substitutable compound.
shake well. + 1-2 drops of precipitate
bromins water.
(iii) No decolourisation Saturated compound.

(ii) KMn04 test (i) Decolourisation of KMn04 Unsaturated or easily oxidisable com-
Compound + 2 cm 3 of water, pound.
shake well + 2 drops of
dilute KMn0 4 solution. (ii) No decolourisation Saturated compound.

(2) Solubility/Miscibility Tests


(A) Perform the following tests, only if the compound is soluble/miscible in water.
Tests Observations Inferences

(a) (i) 0.01 g of compound + 1 cm 3 Substance dissolves Lower member of alcohol, ester,
of water shake well. ketone, carbohydrate.
Test the solution with litmus
paper. (i) Blue litmus paper turns red Water soluble acid or phenol present.

(ii) Red litmus paper turns blue Water soluble base present.

(iii) No action on the litmus paper Water soluble neutral present.

(b) 0.01 g of compound + saturated


NaHC0 3 solution. Strong effer-
vescence and compound dis-
solves.
To this clear solution, add cone. No solid appears Water soluble acid present.
HCI.

(e) 0.01 g of compound + water,


compound dissolves.

To this clear solution, add alco- Blue to violet colour Water soluble phenol present.
holic FeCl3 solution
106 College Practical Chemistry (/'. Y. B.Sc.)

(B) Perfonn the following tests only if the compound is insoluble/immiscible in water:
Tests Observations Inferences
(a) 0.01 g of compound + 1 cm 3 0f Strong eifelVescence Carboxylic acid present.
saturated NaHCO J solution,
shake well.
The compound dissolves.
To this clear solution add conc. A solid appears Carboxylic acid confirmed.
HCI drop by drop.

(b) 0.01 g of compound + 1 cm3 of


dilute NaOH solution, shake
well. The compound dissolves.
To this clear solution, add conc.
HCI drop by drop. A solid or an emulsion appears Phenol confirmed.

(c) 0.01 g of compound + 1 cm 3 of


1: 1 HCI solution, shake well.
The compound dissolves.
To this clear solution add 20%
NaOH solution. A solid appears Base confirmed.

(d) If the compound is insoluble in


NaHCO J • NaOH and HCI solu-
tion. - Neutral compound present.

(3) Detection of Elements


Sodium Fusion Test (Lassaigne's Test)
(a) Take a small piece of dry sodium metal in a fusion tube and heat it gently till the metal
melts or fuses.
(b) Add equal quantity of compound to this fused metal (If the compound is a liquid, then
add two drops of it with a capillary).
(c) Heat it gently, then strongly till it becomes red hot.
(d) Plunge the red hot tube in 5 cm3 or 3f41h of a test tube of distilled water taken in a porcelain
dish, covering it immediately with an asbestos sheet. Crush .the fusion tube completely.
(e) Carry out one more fusion in the similar way. Boil the extract for five minutes, reduce
the volume to about 3 cm 3 and filter. Perfonn following tests using this filtrate.

Tests Observations Inferences

Test for Nitrogen

2 drops of filtrate + a few drops of Blue or green colour solution or blue Nitrogen present.
freshly prepared FeS04 solution, boil precipitate
for a few minutes, cool and add lcm 3
dilute H2SO4 ,
SeparattOTro/Organic Mixtures (6 Units only) 107

Tests Observations Inferences


Test for Sulphur

(i) 2 drops of filtrate + 2 drops of 2N A black precipitate Sulphur present.


acetic acid + 2 drops of lead
acetate solution.

(ii) 2 drops of filtrate + 1 drop of A violet or purple coloration. Sulphur present.


sodiwn nitroprusside solution.

(iii) 2 drops of filtrate + 2 drops of aq. A blood red coloration. Nitrogen and sulphur are present.
FeCl3 solution.

Test for Halogen

(i) 0.5 em 3 of filtrate + 0.5 em 3 of A thick white precipitate Halogen present.


dilute HN0 3 (boil weJl ifN and S
are present) + 0.5 em 3 of 5%
AgN0 3 solution.

(ii) Ifhalogen is present carry out the


foJlowing test: (i) Violet colour Iodine present.
0.5 em 3 of filtrate + 0.5 em 3 of
dilute H2S04 + 0.5 em3 0fCHCl 3 (ii) YeJlow or brown colour Bromine present.
and 0.5 em 3 of chlorine water,
shake welJ and observe the colour (iii) Colourless layer Chlorine present.
of chloroform layer.

Classify the given compound on the basis of elements present


On the basis of the elements present in the organic compound, it belongs to one of the four
groups, which may be further divided in subgroups as follows:
Group I - C, H, (0)
(i) Carboxylic acids
(ii) Phenols
(iii) Neutrals
Group II - C, H, (0) and N
(i) Carboxylic acids
(ii) Phenols
(iii) Bases
(iv) Neutrals
Group III - C, H, (0), Nand S
(i) Acids
(ii) Neutrals
Group (IV) - C, H, (0) and Halogen
(i) Neutrals
(4) Detection of Functional groups
Carry out the tests in serial order listed under appropriate Group and subgroup to determine
the functional group present.
J08 College Practical Chemistry (T.Y. B.Sc.)

Group I - C, H (0), Carboxylic acids


Tests Observations Inferences

(a) 0.01 gofcompound + 1 em] of A strong effervescence and com- Carboxylic acid present.
saturated NaHC03 solution. pound dissolves.

(b) 0.01 g of compound + 1 em3 of (i) Buff coloured precipitate Benzoic acid or phthalic acid.
water, shake well + 1-2 drops
of alcoholic FeCI3 solution. (ii) Violet coloured precipitate Salicylic acid.

(iii) Violet coloured precipitate ob- Acetyl salicylic acid.


tained on heating the solution

(iv) Yellow coloured precipitate Cinnamic acid.

(v) Faint reddish coloured precipi- Sllccinic acid.


tate

(vi) Deep yellow coloured solution Citric acid.

(vii) No change in FeCI3 solution Oxalic acid.

Group I - C, H (0), Phenols

Tests Observations Inferences

(a) 0.01 g of compound + 1 em] Compound dissolves completely. Phenol present.


of dilute NaOH solution.

(b) 0.01 g of compound + 1 em] (i) Violet colour Phenol.


of water shake well and add a
drop of alcoholic or neutral (ii) Blue-violet colour Resorcinol.
FeCI 3 solution.
(iii) White precipitate slowly changing a-Naphthol.
to pink, blue or violet.

(iv) Green colour I3-Naphthol.

(c) Phthalein test (i) Pink colour Phenol.


0.01 g of compound + 0.01 g
of phthalic anhydride +2 drops (ii) Green or bluish green a-Naphthol, l3-naphthol.
of conc. H2S04, Heat gently
until the mixture fuses, cool
and pour it in a beaker con- (iii) Yellowish-green fluorescence Resorcinol.
taining 20 em] of very dilute
NaOH solution.

(d) Liebermann test


0.01 g of compound + 1 em] Red, blue or green colouration. Phenol present.
of cone. H2S04 + 2'crystals of
NaN02 Heat it gently.
Dilute it with water, add 20% Red colouration Phenol present.
NaOH solution.
Separation of Organic Mixtures (6 Units only) 109

Group I - C, H (0), Neutrals


Tests Observations Inferences

Test for Carbohydrates


(Perfonn this test only if
compound is colourless and
water soluble).
Dissolve 0.02 g of compound A violet ring at the junction of two Carbohydrate present.
in 2 em 3 of water + 2-3 drops layers. •
of 10% a-naphthol dissolved
in ethyl alcohol. Add care-
fully I em3 of conc. H2SO4
along the side of the test tube.

(a) Test for Aldehydes and


Ketones
(i) 0.05 g or 1-2 drops of com- Yellow or orange red crystalline precipi- Aldehyde or ketone present.
pound + 3 em 3 of 2,4- tate
dinitrophenyl hydrazine
solution, shake well.

(ii) 0.05 g or 1-2 drops of com- Violet colour immediately develops Aliphatic aldehyde present.
pound + 2-3 em 3 of colourless
Schiffs reagent, shake well. Pink colour slowly develops Aromatic aldehyde present.
"

(iii) O.oI g or 2-3 drops of com-


pound + 2-3 em3 of freshly
prepared Tollen's reagent
(Add NaOH solution to
AgN03 solution till a precipi-
tate just fonns. Add NHpH A silver mirror or grey black precipitate Aldehyde present.
solution dropwise till a clear
solution obtained). Heat it on
a boiling water bath.

(iv) 0.01 g or 2-3 drops of com- Wine red colour or onmge red colour Ketone present.
pound + 1 em 3 of sodium
nitroprusside solution + 2
drops of NaOH solution.

(c) Test for Esters


Dissolve 0.0 I g or 0.5 em] of
compound in I em3 of ethyl
alcohol + a drop of phenol-
phthalein + 2 drops of very Pink colour disappears Ester present.
dilute NaOH solution. Heat
on a boiling water bath.

(d) Test for Alcohols


(i) Take a small piece of dry Na Rapid evolution of H2 Alcohol present.
metal in a fusion tube and add
a few drops of compound.
110 College Practical Chemistry (T. Y. B.&.)

Tests Observations Inferences


(ii) 1 em J of acetyl chloride in a Strong effervescence Alcohol present.
dry test tube + 2 drops of the
compound.

(e) Test for Ethers


0.01 emJ of compound + 1 Purple colour of CS 2 layer changes to Ether present.
cmJ ofiodine in carbon disul- brown colour
phide, shake well.

(f) Test for Hydrocarbons If all the above tests rail Hydrocarbon present.
0.01 g of compound + 1-2
cm3 of water, shake well + 1-
2 drops of very very dilute Decolourisation Unsaturated hydrocarbon present.
KMnO.. solution. Shake again.
No decolourisation Saturated hydrocarbon present.

Group II - C, H, (0) and N, Carboxylic acids


Tests Observations Inferences

(a) 0.01 g of compound + 1 em J Strong effervescence and compound dis- Nitrocarboxylic acid or amino car-
ofsatwated NaHC03solution, solves boxylic acid present.
shake.
To this clear solution add Solid appears Nitro carboxylic acid present.
conc. HCI drop by drop.
No solid appears Amino carboxylic acid present.

(b) Ifnitro carboxylic acid present,


prefonn test of nitro group
(-NOl ). 0.001 gofcompound
+ O.S emJof ethyl alcohol +
0.001 g of solid NH..CI +
0.001 gofZincdust. Boil for
five minutes and filter. To
filtrate, add Tollen's reagent. Black or grey precipitate Nitro (-N02) group present.
(See page No. 113)

(c) If amino carboxylic acid


present, perfonn test for
amino group. 0.001 g or 2
drops of compound + 1 cm J
of I: 1 HCI. Shake well, cool
and add a few drops of 2% \

NaN0l solution. Add this Aromatic primary amino (-NHz)


clear solution to a cold ~ Red or orange dye group present.
naphthol in NaOH solution.
Separation of Organic Mixtures (6 Units only) 111
Group II - C, H, (0) and N, Phenols
Tests Observations Inferences

(a) 0.01 g of compound + dilute Compound dissolves producing deep Nitro phenol or aminophenol present.
NaOH solution yellow or orange colour

Add conc. HCI drop by drop. Solid reappears Nitrophenol present.

No solid reappears Aminophenol present.

(b) If nitrophenol present, per- Black or grey precipitate Nitro (-NO z) group present.
form test for -N02 group,
refer to Test (b) Group II
Carboxylic acids

(c) If aminophenol present, per- Orange red dye Aromatic primary amino (-NH z)
form test for -NH z group, group present.
refer to Test (b), Group II.
Bases

Group II - C, H, (0) and N, Bases


Tests Observations Inferences

(a) 0.0 I g of compound + I cm3 Compound dissolves Amines present.


of 1:1 HCI solution, shake
and filter. Filtrate + 20% Solid reappears or emulsion ob- Amines confirmed.
NaOH solution drop by drop. tained

(b) O.oI g or 2 drops of com- Deep yellow, red or green colour. Aromatic tertiary amino group
pound + 2-3 cm) of I: I HCI, (> N -) present.
shake well. Cool and add a
few drops of 2% NaNOz White or yellow emulsion. Aromatic secondary amino group
solution. ( -NH-) present.

A clear solution, when added to a Aromatic primary amino group


cold solution of p-naphthol in (-NH2) present.
NaOH, gives orange red dye.
/

Group II - C, H, (0) ·and N, Neutrals


-
Tests Observations Inferences

(a) Test for Diphenylamine


1-2 crystals of compound + I Deep blue colour Diphenylamme present.
cm3 of conc. HZS04 + conc.
HN03 or one drop of dilute
NaN02 solution (If this test
is positive, perform group
test listed under Test (b),
Group II. Bases to confirm
the functional group.)
112 Col/ege Practical Chemistry. (T. Y, B.Sc.)

Tests Observations Inforences

(b) Test for Amides


0.01 g of compound + 1 em] of
20% NaOH solution. Boil for 1-2 Evolution of NH3 which turns tur- Amide (-CONHz) group present.
minutes. Test the gas evolved merlc paper brown
with a moist turmeric paper.

(c) Test for Anilides


0.01 g of compound + I em] of
conc. HCI Boil for 2 minutes, cool Orange red dye Anilide group present.
and add 5 em] of water + a few
drops of cold NaN02 solution and
mix well. Add this solution to a
cold solution of l3-naphthol in
NaOH.

(d) Test for Nitro Group


(i) Mulliken's test
0.01 g of compound + I em] of Black or grey precipitate. Nitro (-N02) group present.
ethyl alcohol + 0.1 g of solid
NH4CI + 0.1 g ofZn dust. Boil for
5 minutes and filter. Filtrate +
Tollen's reagent,,(see page
No. 113)

(ii) Azo Dye Test


(If primary amino group absent,
perform this test)
0.01 gofcompound + 0.1 gofTin Orange red dye Nitro ( - N01) group' present
metal + 2 em] of conc. HCI Boil
for 3 minutes, cool, filter and
dilute it with about 5 em] of water
+ a few drops ofNaN02• Add this
solution to a cold solution of 13-
naphthol in NaOH.

(iii) Test for Dlnltro compounds


0.01 g of compound + 1 em1 of Dark ,pwple or violet colour Dinitro compound present.
acetone, shake to dissolve the
compound + 1-2 drops of dilute
NaOH solution.
Separation of Organic Mixtures (6 Units only) 113

Group III - C, H, (0), Nand S, Amino acids and Neutrals


This class includes amino sulphonic acid and thiourea.
Tests Observations Inferences
Test for Amino Sulphonic
acids
(a) 0.01 g of compound + 1 cmJ • of Effervescence and compound Amino sulphonic acid present.
saturated NaHC0 3 solution. dissolves.

(b) Perform test for -NH2 group Orange red dye Aromatic primary amino
(Refer to Test (b). Group II. (-NH2) group present.
Bases)

Test for Thiourea


(Thiourea is soluble in water and
netural to litmus)
0.01 g of compound + 1 cm J of Black precipitate Thiourea present.
20% NaOH solution, boil, cool
and add a few drops of lead
acetate solution.

Group IV - C, H, (0) and Halogens, Neutrals


Generally compound is water insoluble netural, and it may be a halogen derivative of
hydrocarbon e.g., CHCI3, CCI4 , C6HsCI and C6HSBr.
Tests Observations Inferences

0.01 g of compound + 2 cmJ of White or yellow precipitate Aliphatic halide like CHCI3,
dilute NaOH solution. Boil for a CCl4 present.
few minutes. cool + dilute HN03
till acidic + 0.5 cm J of AgN03
solution. No precipitate Chlorobenzene or bromoben- ,
zene present.
14
Organic Synthesis
An organic preparation is very important as it leads to manufacture of various chemicals used
as drugs, dyes, polymers etc. The criteria of a good preparation is its yield, purity of the product and
shape of the crystals.

Experiment No. 1
N - Acylation of aromatic primary amine
Aim: To prepare acetanilide from aniline.

Theory: Replacement of active hydrogen of -NIl, by an acyl group ( - - ~ J


is called .
N-acylation of primary amine. Acetylation can be carrried out by using acetic anhydride or acetyl
chloride.
Reaction:

Aniline
+ Acetylation. 6 ~

Acetanilide
+ C~COOH

Procedure:
(1) Place 2 g of aniline in a dry 100 cm 3 round bottom flask fitted with a reflux condenser.
(2) Add 4 cm 3 of acetic anhydride and 2 cm 3 of glacial acetic acid or one drop of cone. ~SO4
to it.
(3) Reflux the reaction mixture for about 15 minutes on a boiling water bath.
(4) Pour the hot contents of the flask slowly with constant stirring in 50 cm30f eold distilled
water in a 250 cm3 beaker. -
(5) Filter the solid and wash it with distilled water.
Organic Syntltesis llS
(6) Recrystallise the product from hot distilled water.
(7) Dry, weigh and determine the melting point of the purified product.
Calculations:

o
NHCO~

93g
)
6 13Sg
(1) Theoretical yield:
93 g of aniline = 135 g of acetanilide
135x2
:. 2 g of aniline = 93

= 2.9 g
(2) Percentage yield:
Weight of the product x 100
Theoretical yield
= ----%
Results:
(1) Melting point of the product = ____ °C (Expected 114 OC).
(2) Yield of the product = ____ g.
(3) Theoretical yield = 2.9 g.
(4) Percentage yield = %.
Note: (1) N-acetylation of 4-methyliniline and 4-nitroaniline carried out by the same procedure as mentioned
above by taking 2 gof4-methylaniline or4-nitroaniline as starting material and 4 cmJ ofacetic anhydride.
(2) 107 g of4-methylaniline = 149 g of 4-methylacetanilide
149 x 2
:.2g = 107
= 2.78g
(3) 138 g of4-nitroaniline = 181 g ofp-nitroacetanilide
181 x 2
:.2g = -138-
2.62 g ofp-nitroacetanilide
(4) Expected melting point of - -
(a) 4-methylacetanilide =148°C.
(b) 4-nitroacetanilide = 216°C.
(5) N-propylation of aniline and p-Toluidine can be carried out by the same procedure by taking
propanoic anhydride instead of acetic anhydride and glacial acetic acid. Recrystallise the product
from SOOA. alcohol.
116 College Practical Chemistry (1'. Y. B.Sc.)
Experiment No. 2
Condensation of benzaldehyde with acetophenone
Aim: To prepare chalcone (Benzylidene acetophenone)
Theory: The condensation reaction of an aromatic aldehyde containing no a-hydrogen with
aliphatic or mixed alkyl aryl ketone having at least two a-hydrogen atoms in the presence of aqueous
alkali to form a, p-unsaturated ketone is known as claisen schmidt reaction.
Condensation of benzaldehyde with acetophenone to form benzylideneacetophenone is claisen
- schmidt reaction.
Reaction:

o H H 0

+ HF-~-o NaOH > o-~=t-~-o + ~o

Benzaldehyde Acetophenone Benzylideneacetophenone


Procedure:
(1) Dissolve 2.5 g of sodium hydroxide in 20 cm3 of water and mix it with 12.5 cm 3 of rectified
spirit in a 250 cm3 round bottom flask filtted with a mechanical sitrrer.
(2) Immerse the flask in a crushed ice bath and add 5.2 g of freshly distilled acetophenone
and stir it again.
(3) Add 4.4 cm 3 (4.6 g) of pure benzaldehyde to the reaction mixture and maintain the
temperature between 15° and 25°C.
(4) Stir vigorously until the mixture becomes so thick that the stirring is no longer effective
(2-3 hours).
(5) Remove the stirrer and keep the reaction mixture in an ice bath or in a refrigerator
overnight.
(6) Filter the crude product and wash with cold distilled water until the washings are neutral
to litmus paper. Finally wash it with ice cold alcohol.
(7) Recrystallise the product from aqueous alcohol.
(8) Dry, weigh and determine the metling point of the purified product.
Calculations:
(1) Theoretical yield:
106 g of benzaldehyde = 208 g of chalcone

4.6g _ _ _ __ 208 x 4.6


106
9.0 g
(2) Percentage yield:

Weight of the product x 100


Theoretical yield
= %.
Organic Synthesis 117

Results:
(1) Melting point of the product = _____ °C (Expected 56°-57°).
(2) Weight of the product = g.
(3) Theoretical yield = 9.0 g.
(4) Percentage yield = %.
Note: The product should be handled carefully as it is a skin irritant.
Experiment No.3
Condensation of an aromatic aldehyde with a primary am1ne
Aim: To prepare benzylideneaniline from benzaldehyde.
Theory: Primary aromatic amines condense with benzaldehyde to form benzylidene derivatives
known as Schiff's bases, which are often crystalline compounds.
Reaction:
H
l:l ) o-~=N-{) + ~O
Benzaldehyde Aniline Benzylideneaniline

Procedure:
(1) Mix 2 g (4 cm3) of purified benzaldehyde and 2 g (4 cm 3) of redistilled aniline in a small
porcelain dish.
(2) Heat it on a water bath for 20 minutes while stirring mixture frequently with a glass rod.
(3) Cool the reaction mixture and stir well when the product crystallises out.
(4) FilteI the solid and wash with distilled water.
(5) Recrystallise the product from alcohol.
(6) Dry, weigh and determine the melting point of the purified product.
Calculations:
(1) Theoretical. yield:
106 g of benzaldehyde = 181 g of benzylideneaniline

181 x2
:. 2 g
106
= 3.42 g
(2) Percentage yield:
= Weight of the product x 100
Theoretical yield
%
118 College Practical Chemistry (T. Y. B.Sc.)
Results:
(1) Melting point of the product= _ _ °C (Expected 54 °C).
(2) Weight of the product = _ _ g.
(3) Theoretical yield = 3.42 g.
(4) Percentage yield = %.

Experiment No. 4
O-methylation of phenol
Aim: To prepare anisole from phenol.
Theory: Replacement of active hydrogen of -OH group of phenol by a methyl group is known
as methylation of phenol. It is carried out by treating phenol with dimethyl sulphate in the presence
of an alkali.
Reaction:

Phenol Anisole

Procedure:
(1) Dissolve 4 g of phenol in 10 em J of 10% NaOH solution in a 250 em J round bottom flask,
fitted with a reflux condenser. Cool the solution in an ice-bath.
(2) Add 4 emJof dimethyl sulphate slowly and dropwise with constant stining (in about 1 hour
, time).
(3) Reflux the reaction mixture for about 2 hours with stirring.
(4) Cool the solution and add 30 em J of distilled water and transfer the solution to a separating
funnel.
(5) Separate the lower layer, wash it twice with dilute H 2S04 and then with distilled water.
(6) Dry over anhydrous calcium chloride and distill anisole.
(7) Weigh and determine the boiling point of the purified product.
Calculations:
(1) Theoretical yield:
94 g of phenol 108 g of anisole

108 x 4
:. 4 g of phenol
94
4.6 g
(2) Percentage yield:

Weight of the product x 100


Theoretical yield
%
Organic Synthesis 119

Results:
(1) Boiling point of the product = _ _ °C (Expected 154 0C).
(2) Weight of the product ---g.
(3) Theoretical yield = 4.6 g.
(4) Percentage yield = %.
Note:
(1) O-methylation of o-cresol can be carried out by the similar procedure by taking o-cresol instead of phenol.

2Q;,H + 2NaOH + (CH,l,SO. --> 2{ t,OCH,+No,SO.+2H,O

o-Cresol
108 g of o-cresol 122 g of o-methyoxytoluene

122 x 4
:.4g _ _ __
108
= 4.51 g.
(2) Expected boiling point of the product = 171°C.
Experiment No.5

O-methylation of a phenol using dimethyl sulphate


Aim: To prepare methyl 2-naphthyl ether (Nerolin).
Theory: The replacement of active hydrogen of compound containing - OH, -NH2 and
> N-H group by an alkyl group (methyl group) is known as alkylation. Methylation (introduction
of methyl grou;) can readily be done using dimethyl sulphate in the presence of an alkali.
Reaction:

2-naphthol Nerolin

Procedure:
(1) Dissolve 2 g of 2-naphthol in a 15 em J of NaOH solution in a 250 emJ conical flask.
(2) Cool the reaction mixture to 10 °C by immersng the flask in an ice bath.
(3) Add dropwise 1.5 emJ of dimethyl sulphate with vigorous stirring.
(4) Cork the flask and shake vigorously.
(5) After 30 minutes, filter the product, wash with 10% NaOH solution and then with distilled
water.
(6) Recrystallise the product from hot alcohol.
(7) Dry, weigh and determine the melting point of the purified product.
120 College Practical Chemistry (T. Y. B.Sc.)

Calculations:
(1) Theoretical yield:
144 g of 2-naphthol = 158 g of methyl 2-naphthyl ether
158 x 2
:. 2 g =
144
2.19 g.
(2) Percentage yield:

Weight of the product x 100


Theoretical yield
= %.
Results:
(1) Melting point of the product _ _ °C (Expected 72°C).
(2) Weight of the product = --g.
(3) Theoretical yield 2.19 g.
(4) Percentage yiled = %.

Experiment No.6
Oxidation of an aldehyde
Aim: To prepare benzoic acid from benzaldehyde.
o
Theory: Aldehyde /!1OOP~ ~ - ~is an easily oxidisabIe _ and is cotM:ltod inIo ~ acid
~i
Reaction:
ol heating with alkaline KMnO. solulion.

(1) alkaline

KMnO.
(2) HCI
Benzaldehyde Benzoic acid

Procedure:
(1) Take 2 g of benzaldehyde, 60 em3 of saturated KMnO4 solution and 2 g of N~C03 in
a 250 em 3 conical flask.
(2) Heat it on a wire gauze for 15-20 minutes on low flame.
(3) Allow it to cool and filter.
(4) Add concentrated HCI dropwise to the filtrate with constant shaking till the solution is
acidic.
Organic Synthesis 121

(5) Filter the product, wash it with cold distilled water and recrystallise from hot distilled water.
(6) Dry, weigh and determine the melting point of the purified product.
Calculations:
(1) Theoretical yield:
106 g of benzaldehyde = 122 g of benzoic acid
122 x 2
:. 2g _ _ __ = 106
= 2.30 g.
(2) Percentage yield:
Weight of the product x 100
Theoretical yield
= %.
Results:
(1) Melting point of the product = _ _ °C (Expected 122°C).
(2) Weight of the product = g.
(3) Theoretical yield = 2.30 g.
(4) Percentage yield = %.
NotG:
(1) Oxidation of 4-nitrobenzaldehyele can be done by the above procedure by taking 2 g of 4-nitro-benzaldehyde
instead of benzaldehyde.
(I) alkaline KMn04
02N -Q-' CHO + [0] Solution
(2) Hel
)0 0 N
r'~
~COOH

151 g of 4-nitro benzaldehyde = 1()7 g of 4-nitrobenzoic acid

167 x 2
:.2g
151
= 2.21 g.
(2) Expected melting point of the product = 238°C.

Experiment No. 7
Reduction of benzophenone to benzhydrol
AIm: To prepare benzbydrol from benzophenone by reduction.

Theory: ~e Won reduction


group
secondary alcohol.
in the presence of zinc in an alkaline medium gives
122 College Practical Chemistry (T. Y. B.Sc.)
o OH
II I
-c- Zn,OH
-c-
I
H
Reaction:

o-g-o o
Zn,OH
)
OH

o-f-Q
H
Benzophenone BenzhydroJ
Procedure:
(l) Take 2.5 g of benzophenone, 2.5 g of sodium hydroxide, 2.5 g of zinc powder and 25
cm 3 of ethyl alcohol in a 250 cm 3 round bottom flask fitted with a reflux condenser.
(2) Stir the mixture and reflux it on a water bath for 90 minutes.
(3) Filter and wash the residue twice with 15 cm 3 of hot alcohol. Do not allow the residual
zinc powder to become dry as it is flammable.
(4) Pour the filtrate into 100 cm 3 of ice-cold distilled water containing 5 cm3 of cone. HCl
when benzhydrol separates out as a white crystalline mass.
(5) Filter and recrystallise from hot alcohol.
(6) Dry, w~igh and determine the melting point of the purified product.
Calculations:
(1) Theoretical yield:
182 g of benzophenone 184 g of benazhydrol

184 x 2.5
.. 2.5 g
182
2.52 g.
(2) Percentage yield:

Weight of the product x 100


The~retical yield

%.
Results:
(1) Melting point of the product _ _ _ °C (Expected 68°C).
(2) Weight of the product g.
(3) Theoretical yield 2.52 g.
(4) Percentage yield %.
123

Experiment No. 8
Azo coupling reaction
Aim: To prepare I (4' - nitrobenzeneazo) - 2 naphthol.
Theory:
Aromatic primary amine reacts with nitrous acid at O°C to give a diazonium salt. This
process is called diazotisation. The diazonium ion is a weak electrophile, hence, it normally couples
with active substance like phenols. J3-naphthol couples at more active position 1 and a-naphthol
at position 4.
Reaction: -0- OH

8
NaN02 + 2HCI
0J'l ~~ O'C O:zN-o-N=N-CI +
-Nact, -2H20
P-Nitroanilinc

NaOH 2-Naphthol

Procedure:
(I) Dissolve 2.5 g of p-nitroaniline in a warm mixture of 7 cm3 of conc. HCl and 7 cm3 of
distilled water contained in a 250 cm 3 beaker.
(2) Place the beaker in an ice-salt bath and cool to 0-5°C whilst stirring vigorously.
p-Nitroaniline hydrochloride will separate out in the crystalline form.
(3) Add a cold solution of 2.0 g of NaN0 2 in 5 cm 3 of distilled water slowly with stirring
to an end point with Kl-starch paper. Maintain the temperature below 8°C.
(4) Dissolve 3.5 g of NaOH in 15 cm 3 of distilled water and add 2.6 g of J3-naphthol to it
with constant stirring to get a clear solution. Cool it in ice and add the diaotised solution
slowly with stirring.
(5) Add cone. HCI slowly with constant stirring to the cold mixture until it is strongly acidic
to congo red paper.
(6) Filter with gentle suction, wash with distilled water till free from acid. Dry upon filter
paper in the air.
(7) Weigh and determine the melting point of the dried product.
Calculations:
(1) Theoretical yield:
138 g of p-nitroaniline = 307 g of 1 - (4'-nitrobenzeneazo) - 2 naphthol
307 x 2.5
:.2.5 g _ __ = 138
= 5.56 g.
(1) Percentage yield:
Weight of the product x 100
Theoretical yield
= %.
124 College Practical Chemistry (T. Y. B.Sc.)

Results:
(1) Melting point of the product ___ 0c. (Expected°C).
(2) Weight of the product g.
(3) Theoretical yield 5.56 g.
(4) Percentage yield %.
Note: Doazonium salt can be coupled with salicylic acid by following the above procedure by replacing
~-naphthol with salicylic acid.
Experiment No.9
Halogenation
Aim: To prepare 4-bromoacetanilide from acetanilide.
Theory: Acetanilide on treatment with bromine in glacial acetic acid at room temperature permits
monosubstition reaction and gives mainly p-bromoacetaniIide product. This process, is called
bromination.
Reaction:

,loci" """'.
acid
~
Y +

Br
Acetanilide 4-Bromoacetanilide

Procedure:
(1) Dissolve 2 g of finely powdered acetanilide in 10 cm 3 of glacial acetic acid in a dry
250 cm 3 conical flask.
(2) Add the bromine in glacial acetic acid solution slowly with constant shaking to the
acetanilide solution till solution becomes orange coloured.
(3) Allow it to stand at room temperature for 15 minutes with occasional shaking..
(4) Pour the reaction mixture into 50 cm 3 of cold distilled water with constant stirring in a
250 cm 3 beaker. -,
(5) Filter the solid and wash it with cold distilled water.
(6) Recrystallise the product from aqueous alcohol.
(7) Dry, weigh and determine the melting point of the purified product.
Calculations:
(1) Theoretical yield:
135 g of acetanilide = 214 g of 4-Bromoacetanilide
214 x 2
:. 2 g
135
= 3.17 g
(2) Percentage yield:
Weight of the product x 100
Theoretical yield
%
Organic Synthesis 125

Results:
(1) Melting point of the product = _____ °C (Expected 160°C).
(2) Weight of the product = g.
(3) Theoretical yield = 3.17 g.
(4) Percentage yield = _____ %.
Experiment No. 10
Nitration of nitrobenzene
Aim: To prepare 1,3-dinitrobenzene from nitrobenzene.
Theory: The replacement of the hydrogen atom by a nitro group (-N0 2) by treating the compound
with conc. nitric acid in the presence of conc. H 2S04 is called nitration.
Nitration of nitrobenezene is carried out with sodium nitrate and conc H2S04 by heating at 90°C.
Reaction:
N02

we QNO 11,0 2
+
Nitrobenzene m-dinitrobenzene
Procedure:
(1) Take 10 em J of conc. H2S04 and 6 g of NaN0 3 in a dry 250 emJ conical flask.
(2) To this, add 2 em J of nitrobenzene slowly with constant shaking of the flask.
(3) After the addition is complete, heat the reaction mixture in a boiling water bath till no
more brown fumes are evolved.
- (4) Allow the reaction mixture to cool and pour it slowly with constant stirring in 50 em J of
cold distilled water in a 250 em J beaker.
(5) Filter the product and wash it with cold distilled water.
(6) Recrystallise the product from alcohol.
(7) Dry, weigh and detennine the melting point of the purified product.
Calculations:
(1) Theoretical yield:
123 g of nitrobenezene 168 g of 1,3 dinitrobenzene
168 x 1.204 x 2
2 x 1.204 g =
123
3.29 g.
(2) Percentage yield:
Weight of the product x 100
Theoretical yield
= %.
126 College Practical Chemistry (T. 1. B.Sc.)

Result:
(1) Melting point of the product = _ _ _ _ °C (Expected 90°C).
(2) Weight of the product = g.
(3) Theoretical yield = 3.29 g.
(4) Percentage yield = %.
Experiment No. 11
Nitration of salicylic acid
Aim: To prepare 5-nitrosalicylic acid from salicylic acicl.
Theory: Salicylic acid is a phenolic acid and it undergoes nitration readily due to the presence
of phenolic (-OH) group. This group directs the - N02 group in the para position.
Reaction:

A )
O-Ji'(J(OOOH
I + ~O
Qf
Salicylic acid. S-nitrosalicylic acid
Procedure:
(1) Take 2 g of salicylic acid in a 250 em) conical flask and add 10 em) of hot distilled water
to it.
(2) Add slowly 4 em) of conc. HNOJ with constant shaking of the flask.
(3) Heat the flask on a boiling water bath till no more brown fumes come out.
(4) Cool and pour the contents of the flask into a 250 em) beaker containing 50 em) of cold
distilled water with constant stirring.
(5) Filter the product and wash it with cold distilled water.
(6) Recrystallise the product from hot distilled water.
(7) Dry, -weigh and detennine the melting point of the purified product.
Calculations:
(1) Theoretical yield:
138 g of salicylic acid 183 g of 5-nitrosalicylic acid
183x 2
2g =
138
= 2.65 g.
(2) Percentage yield:
Weight of the product x 100
Theoretical yield
= --- %.
Results:
(1) Melting point of the product= _ _ _ °C (Expected 230°C).
(2) Weight' of the product = g.
(3) Theoretical yield 2.65 g.
(4) Percentage yield %.
Organic Synthes", 127

Experiment No. 12
Oxlmatlon of cyclohexanone
AIm: To prepare cyclohexanone oxime from cyclohexanone.
Theory: Cyclohexanone reacts with hydroxyl amine and fonns oxime. It is a condensation reaction
between a carbonyl group and ammonia derivative i.e., hydroxyl amine.
Reaction:
o

6 +~N-OH

Cyclohexanone oxime
Procedure:
(1) Take 2 g of cyclohexanone in a 100 cm3 beaker and add a solution of2.5 g of hydroxylamine
hydrochloride in 5 cm3 of distilled water.
(2) Cool the mixture in cold water and add 8 crrf of freshly prepared 30010 sodium,carbonate
solution slowly to the reaction mixture with constant stirring and maintain the temperature
to 20o-2SoC.
(3) Allow the reaction mixture to stand for 10 minutes.
(4) Filter the product and wash it with a little of distilled water.
(S) Recrystallise the product from aqueous alcohol.
(6) Dry, weigh and detennine the melting point of the purified product.
Calculations:
(1) Theoretical yield:
98 g of cyclohexanone = 113 g of cyclohexanone oxime
113x 2
2g = 98
= 2.31 g.
(2) Percentage yield:
= Weight of the product x 100
Theoretical yield
= --- %.
Results:
(1) Melting point of the product = ~___ °C (Expected 91°C)
(2) Weight of the product = _ _ _ _ g.
(3) Theoretical yield = 2.31 g.
(4) Percentage Yield = %.

QQQ
15
Organic EstimatiQns

The quantitative aspect of organic estimation is determination of a functional group present


in the compound which is quite different from that of inorganic quantitative estimation, where a
particular element is precipitated as a salt and determined.
Organic reactions are quite slow and time-consuming, not like inorganic reactions which are
instant and fast. Hence, for organic estimations known excess of a reagent is added to the solution
and after some time when reaction is over, the unreacted or the unused quantity of the added reagent
is back titrated against a standard solution using an appropriate indicator. As a result, the actual
quantity of a reagent, that is consumed for the reaction by a particular functional group is determined.
From this, the amount of the compound taken is determined or estimated.
Experiment No. 1 (6 Units only)
Estimation of Ester by Hydrolysis
Aim: To estimate the amount of ester present in the given solution.
Theory: Ester is quantitatively hydrolysed when treated with an alkali solution.
Ar.COOC2Hs + KOH ~ Ar.COOK + C2HsOH
Ester is heated with an excess of alkali solution. When hydrolysis is over, the unreacted alkali
is titrated against a standard acid solution.
Procedure:
Part I: Standardisation
(1) Take 10 cm 3 of supplied (IN approximate) alcoholic KOH solution in a standard
measuring flask and dilute it to 100 cm 3 with distilled water.
Organic Estimations 129

(2)!>Ipette out 10 cm 3 of it in a conical flask and titrate it against 0.1 N HCl solution from
the burette using phenolphthalein indicator. End point will be from pink to colourless.
(x cm 3).
Part II: Estimation
(1) Add 10 cm 3 of standardised alcoholic KOH solution to the given ester solution, in a round
bottom flask. Fix a water condenser to the round bottom flask.
(2) Reflux the flask on a water bath for nearly 90 minutes till hydroysis is over (no more
smell of ester, but smell of alcohol only).
(3) Cool the flask and dilute the contents of the flask to 100 cm 3 in a standard measuring
flask, with distilled water.
(4) Pipette out 10 cm 3 of it in a conical flask and titrate it against 0.1 N HCl solution from
the burette using phenolphthalein indicator. End point will be from pink to colourless.
(.I' cm 3).

Reactions:
(1) Ar.COOC2Hs + KOH ~ Ar.COOK + C2HsOH
(2) KOH (unused) + HCl ~ KCl + H20
Calculations:
(1) 10 cm 3 of the diluted KOH solution required x cm 3 of 0.1 HCl solution

x x 0.1
Normality of diluted KOH solution = 10 =A N
Normality of given KOH solution = lOx A
N
(2) Amount of KOH added in terms of O.1N HCl solution = x cm 3
(3) Amount of KOH unused in terms of O.1N HCl solution = y cm 3
(4) Amount of KOH used up by 10 cm 3 of the diluted ester solution = (x - y)
= C cm3
:. 100 cm 3 = 10 C cm 3
(5) Since, 1 KOH = 1 HCl = 1 ester (Ethyl benzoate)
1000 cm 3 of 1N HCl 150 g of Ethyl benzoate
150 x 10Cx 0.1
:. 10 C cm 3 of O.IN HCl
1000
_ _ _ g of Ethyl benzoate
Results:
(1) Normality of given the KOH so~ution = N.
(2) 10 cm3
of the diluted ester solution consumed (C) = ___ cm3 of KOH in terms of
0.1 N HCl solution.
(3) Amount of ester present given solution = g.
130 College Practical Chemistry (T. Y. B.Sc.)

Experiment No.2 (6 Units only)


Estimation of Amide by Hydrolysis
Aim: To estimate the amount of amide present in the given solution.
Theory: Amide is hydrolysed quantitatively with a known volume of standard alkali solution. When
hydrolysis is over, the unreacted alkali is titrated against a standard acid solution.
R.CONH2 + KOH ~ R.COOK + NH3 t
Procedure:
Part I: Standardisation
(1) Take 10 em 3 of supplied (1.5N approximate) KOH solution in a standard measuring flask
and dilute it to 100 em 3 with distilled water.
(2) Pipette out 10 em 3 of it in a conical flask and titrate it against O.1N HCI solution from
the burette using phenolphthalein indicator. End point will be pink to colourless. (x em 3).
Part II: Estimation
(1) Add 10 em 3 of standardised KOH solution to the given amide solution in a round bottom
flask. Fix a water condenser to the round bottom flask.
(2) Reflux the flask on a boiling water bath for about 90 minutes till hydrolysis is over.
(3) Cool the flask and dilute the contents of the flask to 100 el1/ in a standard measuring
flask , with distilled water.
(4) Pipette out 10 em 3 of it in a conical flask and titrate it against O.1N HCI solution from
the burette using phenolphthalein indicator. End point will be from pink to colourless. (y
em 3 ).
Reactions:
(1) R.CONH 2 + KOH ~ R.COOK + NH3 t
(2) KOH (unused) + HCI ~ KCI + H20
Calculations:
(1) 10 em 3 of the diluted KOH solution required x em 3 of O.IN HCI solution

Normality of diluted KOH solution = xxO.l=AN


10
Normality of given KOH solution 10 x A
= N.
(2) Amount of KOH added in terms of 0.1 N HCI solution = x em 3
(3) Amount of KOH unused after hydrolysis in terms of 0.1 HCI solution = y em 3
(4) Amount of KOH used up by 10 em 3 of the diluted amide solution= (x - y)
= C em3
:. 100 em 3 = 10 C em 3
Since,
1 KOH = 1 HCI = 1 Amide
Organic 'Estimations 131

1000 em 3 of IN HCI = 59 g of Acetamide (or 121 g of Benzamide)

59 x 10C x 0.1
.. 10C em 3 of O.1N HCI = g of Acetamide
1000
Results:
(1) Nonnality of given KOH solution = ............ N.
(2) 10 em 3 of the diluted solution consumed (C) = ............ em 3 of KOH solution in tenns
of O.IN HCI solution.
(3) Amount of amide present in the given solution = ............ g.
Estimation No.3 (6 Units only)
Estimation of Nitro. Group by Reduction
Aim: To estimate the amount of nitro group and meta nitroaniline present in the given solution.
Theory: Nitro group is qualitatively reduced to amino group by SnCl 2 solution in presence ofHCI.
This reaction fonns the basis of estimation.

A known excess of SnCl2 solution is added to a given nitro compound and the solution is
refluxed. After the reduction is over, the unreacted SnCl 2 is back titrated against standard iodine
solution.
Procedure:
Part I: Standardisation
(1) Take 10 em3 of supplied (2N approximate) SnCl2 solution and dilute it to 100 em 3 with
distilled water in a standard measuring flask.
(2) Pipette out 10 em 3 of it in a conical flask and titrate it against 0.1 N 12 solution from
the burette using freshly prepared starch as the indicator. End point will be from colourless
to blue. (x em 3 ).
Part II: Estimation
(I) Add 10 em 3 of standardised SnCl] solution to the nitro compound solution, given in a
round bottom flask.
(2) Add 3 em 3 of cone HCl and a small pinch of NaHC0 3 to it.
(3) Fit an air condenser and reflux it on a water bath for nearly 90 minutes, till the reduction
is over, (the solution turns colourless).
(4) Cool the flask and dilute the contents of the flask to 100 em 3 in a standard measuring
flask, with distilled water.
(5) Pipette out 10 em 3 of it in a conical flask and titrate it against 0.1 N 12 solution from the
burette, using freshly prepared starch indicator. End point will be from colourless to blue.
(y em 3 ).
132 College Practical Chemistry (T. Y. B.Sc.)

Reactions:
(1) C 6H4N0 2NH 2 + 3SnCl2 + 6HCI -~ C6HiNH2)2 + 3SnCl4 + 2~O
(2) 2SnCl 2+ 212 -~ SnCl4 + Snl4
Calculations:
(1) 10 em 3 of the diluted SnCl2 solution required x em3 of 0.1 N 12 solution

xxO.l=AN
Normality of diluted SnCl2 solution
10
Normality of given SnCl2 solution 10 x A
= N.
(2) Amount of SnCl2 added in terms of O.1N 12 solution = x em 3
(3) Amount of SnC~ unused after reduction in terms of O.1N 12 solution = y em3
(4) Amount of SnCl2 used up by 10 em 3 of the diluted nitro compound solution =(x - y)
, = C em3
:. 100 em 3 = 10 C em3
Since, 3SnCl2 = 312 = 1N02 group = 1 m-Nitroaniline.
i.e. 6000 em 3 of IN 12 = 46 g of - N0 2 group = l38 g of m-Nitroaniline
46 x 10Cx 0.1
:. 10C em 3 of O.1N 12 = 6000 g of -N02 group

138 x 10C x 0.1


6000 g of m-Nitroaniline

Results:
(1) 10 em 3 of the diluted solution consumed (C) = _ _ _ _ _ em 3 of SnCl2 solution in
terms of 0.1 N 12 solution.
(2) Amount of N0 2 group present = g.
(3) Amount of meta-nitroaniline present = g.

Experiment No.4
Estimation of Saponification Value of an Oil
Aim: To determine the saponification value of an oil in the given solution.
Theory: Saponification value of an oil is milligrams of KOH required to saponify 1 g of oil.
It is called as KoettstorJer number.
Oil being tri-ester of glycerol, when heated with a saturated solution of alcoholic KOH, gets
hydrolysed or saponified into free glycerol and potassium salt of fatty acid.
Organic Estimations 133
CH200C.R
I . Hydrolysis
CHOOC.R CHOH + 3R.COOK
I alcoholic KOH (soap)
CH200C.R CH20H
(glycerine)
The oil solution is heated under reflux with an excess of alkali solution. When hydrolysis is
over, the unreacted alkali is back titrated against a standard acid solution.
Procedure:
Part I: Standardisation
(1) Take 10 em3 of supplied (IN approximate) alcoholic KOH solution in a standard
measuring flask and dilute it to 100 em 3 with distilled water.
(2) Pipette out 10 em3 of it in a conical flask and titrate against O.IN HCI solution from the
burette using phenolphthalein indicator. End point will be from pink to colourless. (x em 3 ).
Part D: Estimation
(1) Add 10 em3 of standardised alcoholic KOH solution to the given oil solution in a round
bottom flask. Fix a water condenser to the round bottom flask ..
(2) Reflux the flask OJt--a water bath for nearly 90 minutes, till the saponification is over.
(3) Cool the flask and dilute the contents of the flask to 100 em 3 in standard measuring flask,
with distilled water. .
3
(4) Pipette out 10 em of it in a conical flask and titrate against O.IN HCl solution from the
burette, using phenolphthalein indicator. End point will be from pink to colourless. (yem3).
Reactions:
(1) C3Hs(COOR)3 (Oil) + 3KOH ~ C3Hs03 + 3R.COOK
(2) KOH (unused) +'HCl~ KCl + H20
Calculations:
(1) 10 em3 of the diluted KOH solution required x em 3 of 0.1 N HCl solution

xxO.l=AN
Normality of the diluted KOH solution = 10

Normality of given KOH solution 10 x A


N.
(2) Amount of KOH added in terms of O.1N HCl solution = x em 3
(3) Amount of KOH unused after hydrolysis in terms of O.1N HCl solution = y em 3
(4) Amount of KOH used up by 10 em 3 of the diluted oil solution = (x - y)
= C em3
:. 100 em3 = 10 C em 3
Since,. 1 KOH = 1 HCI
134 College Practical Chemistry (T. Y. B.Sc.)

1000 cm 3 of IN HCI = 56 g of KOH


56x 10Cx 0.1
.. 10 C cm 3 of O.lN HCI = 1000 g of KOH

= 56
x 10 C x O.l mg of KOH
W g of the oil = 56 x 10 C x O.l mg of KOH
where, W is the weight of the oil.
Now the sponijication value is amount of KOH required in milligrams for saponifying
Ig of the oil.
56 x 10Cx 0.1
W mg ofKOH

Results:
(1) Nonnality of KOH solution = N.
(2) 10 cm of the diluted solution consumed (C)= _ _ _cm 3 of KOH in terms of
3
O.lN HCI solution.
(3) Saponification value of the oil = _ _ _ mg.

Experiment No.5 (6 Units only)


Estimation of Glycine by non-aqueous titration using perchloric acid
Aim: To estimate the amount of glycine in the given solution by non-aqueous titrations.
Theory: Glyine contains amino group (-NH 2) and can directly be titrated against standard
perchloric acid in glacial acetic acid.
Procedure:
Part I : Standardisation
(1) Pipette out 10 cm 3 ofO.IN potassium hydrogen phthalate solution in glacial acetic acid
in a dry 100 cm 3 conical flask.
(2) Titrate it against supplied (O.IN approximate) HCI04 solution from the burette, using
0.5% crystal violet indicator. End point will be from violet to emerald green colour. (x
cm 3 ).
Part II : Estimation:
(1) Dilute the given solution to 100 cm3 in a dry standard measuring flask with glacial acetic
acid.
(2) Pipette out 10 cm 3 of it in a dry conical flask and titrate it against standardiSed HCI04
solution from the burette using 0.5% crystal violet indicator. End point will be from violet
to emerald green colour (y cm 3).
Reaction:
+ -
<;H2 - NH2 + HCI04 - - . . . CH2 - NH3·CI04
I
COOH
Perchloric
~OOH
Glycine
acid
Organic Estimations 135

Calculations:
(1) 10 em 3 of 0.1 N potassium hydrogen phthalate solution required x em 3 of HCI04 solution.
10 x 0.1
Normality of HCI04 solution
x
AN
(2) 10 em3 of thediluted glycine solution required y em 3 of A N HCI04 solution
:. 100 em 3 of = 10 Y em 3 of A N HCI04 solution
3
1000 em of IN HCI04 solution = 75 g of Glycine.
75x lOy x A
.. lOy em 3 of A N HCI04 solution = 1000

= _ _ g of Glycine.
Results:
(1) Normality of HCI0 4 solution = A N.
(2) 10 em J of the diluted glycine solution required (y) = _ _ em 3 of AN HCI04 soluti~n.
(3) Amount of glycine present in the given solution = __ g.
Note:
(1) Preparation of 0.1 N Perchloric acid solution: Mix 8.5 em3 0fHCIO4 with 500 emJ ofglacial
acetic acid and 25 em 3 of acetic anhydride, cool and dilute it to 1000 em 3 with glacial acetic
acid.
(2) Use dry glasswares for non-aqueous titration.
Experiment No. 6 (6 !Jnits only)
Estimation of Vitamin C using ceric amonium sulphate
Aim: To estimate the amount of Vitamin C present in the given solution
Theory: Ceric amonium sulphate acts as an oxidising agent. It reacts with vitamin C and forms
dehydro vitamin C.

CH20H
CHpH
I I
H-C
Yrr-°"1==.o
HI'
Ceric ammonium sulphate
• H-:~o
OH OH OHOH

VitaminC Dehydroascorbic acid


(L - Ascoribic acid)
136 College Practical Chemistry (T. Y. B.Sc.)
Procedure:
Part I : Standardisation:
(1) Pipette out 10 em 3 of 0.05 N ferrous ammonium sulphate solution in a 100 em3 conical
flask.
(2) Add 15 em 3 of dilute H2S04 and titrate it against supplied. (0.05 N approximate) eerie
ammonium sulphate solution from the burette using ferroin indicator. End point will be
from wine red to green colour.
Part II: Estimattion
(1) Dilute the given solution of vitamin C to 100 em 3 with distilled water in a standard
measuring flask.
(2) Pipette out 10 em 3 of it in a conical flask Add 15 em 3 of dilute H 2S04 and titrate it against
standardised eerie ammonium sulphate solution from the burette using ferroin indicator.
End point will be from wine red to pale blue or green colour.
Reaction:
)H 20H )H20H

H-C~Q~O
H/ 'F(-
eeric anunonium
sulphate
) HJ\{=o
OHOH o 0
VitaminC
Dehydroascorbic acid
(L - Ascoribic acid)
Calculations:
(1) 10 em 3 of 0.05N Ferrous ammonium sulphate solution required x em 3 of eerie ammonium
sulphate solution
10 x 0.05
:. Normality of eerie ammonium sulphate =
x
=A'N
(2) 10 em 3 of the diluted Vitamin C solution required y em 3 of A N eerie ammonium sulphate
solution _ _ _ _ _ _ _ _ __
:. 100 em 3 10 y em 3
Since, 1 eerie ammonium sulphate 1 Vitamin C
1000 em 3 of 1N eerie ammonium sulphate 176 g of Vitamin C

3
176x 10yx A
.. 10 Y em of A N - - - - - - - - = 1000
Results:
, (1) Normality of eerie ammonium sulphate (A) = __ N.
(2) 10 em 3 of diluted Vitamin C solution required (y) = __ em3 of A N Ceric ammoniuJD
sulphafe solution.
(3) Amount of Vitamin C present in the given solution g.

000
Appendices

APPENDIX A
Standard Acids, Alkalies, Solvents and Indicators
Acids
1. Conc. HCI 11.3 N
2. Conc. RN0 3 16 N
3. Conc. H2S04 36 N
4. Conc. H 3P04 41.1 N
5. Glacial CH3COOH 17.3 N
6. 4N HCI (360 em3 conc. HClIdm 3)
7. 4N RN0 3 (256 em 3 conc. RNO/dm 3)
8. 4N H2S04 (112 em 3 conc. H2S0idm3)
9. 4N CH3 COOH (240 em3 gla. CH3 COOHldm3)
10. 0.25 M RN03 (16 em 3 cone. RNO/dm3)
Alkalies
1. Liquor NH3 14.3 N (Sp. gr. 0.9)
2. 6N NH40H (430 em 3 liq. NH/dm 3)
3. 4N NaOH (160 g NaOHldm 3)
4. IN KOH (56 g K,oHldm3)
5. IN N~C03 (53 g N~CO/dm3)
Indicators
Liquids
1. 0.5% Bromo Pyrogallol Red (0.5 g/iOO em 3 of 50% ethyl alcohol)
2. 2% Eriochrome Black T (2 gl80 em 3 of triethanolamine + 20 em3 of ethyl alcohol)
138 College Practical Chemistry (T. Y. B.Sc.)

3. 0.5% Fast Sulphone Black F (0.5 g/lOO em 3 of distilled water)


4. 1% Methyl Red (I gllOO em 3 of ethyl alcohol)
5. 1% Phenolphthalein (I giiOO em 3 of distilled water)
6. 0.1 % Pyrocatechol Violet (O.l gilOO em 3 of distilled water)
7. 1% starch solution (to be prepared fresh)
8. 1% Diphenylamine [1 gll90 em 3 of,conc. H 2S04 (A.R.)]
9. 1% Methyl Orange (I gllOO em 3 of ethyl alcohol)
10. 0.5% Xylenol Orange (0.5 giiOO em 3 of distilled water)
II. 0.5% Murexide (to be prepared fresh)
12. 0.5% Crystal Violet (0.5 gllOO em 3 of distilled water)
Solids
1. Mi'S. and grind 0.5 g of Bromo Pyrogallol Red with 50 g of NaCIIKCl (A.R)
2. Mix and grind 0.2 g of Eriochrome Black T with 50 g of KClINaCI (A.R.)
3. Mix and grind 0.1 g of Fast Sulphone Black F with 10 g of NaCIIKCl (A.R.)
4. Mix and grind 0.2 g of Pyrocatechol Violet with 50 g of NaCIIKCl (A.R)
5. Mix and grind 0.5 g' of Xylenol Orange with 50 g of NaCI (A.R.)
6. Mix and grind 0.5 g of Murexide with 50 g of KClINaCI (A.R.)

APPENDIX B
Reagent Papers
1. Starch iodide paper - Mix I g of soluble starch and 0.005 g of KI with a little quantity
of water to form a paste. Then add 500 em 3 of boiling water over the paste to obtain a
solution. Dip the strips of filter paper in it for about 30 minutes and then dry the strips.
Dry paper is used as starch iodide paper.
2. Litmus paper blue - Dissolve I g of blue litmus powder in about 500 em 3 of boiling
water. Dip the strips of filter paper in it for about 30 minutes and then dry the strips after
washing with distilled water. Dry paper is used as blue litmus paper.
3. Litmus paper red - Dip the strips of blue litmus paper in very dilute HCl for about 10-
15 minutes and then dry the strips after washing with distilled water. Dry paper is used
as red litmus paper.
4. Turmeric paper - Dissolve about 2 g of turmeric powder in 500 em3 of ethyl alcohol.
Dip the strip of filter paper in it for about 30 minutes and then dry the strips. Dry paper
is used as turmeric paper. .
5. Congo red paper - Dissolve about 2 g of congo red in about 500 em 3 of ethyl alcohol.
Dip the strip of filter paper in it for about 30-40 minutes and then dry the strips. Dry paper
is used as congo red paper.
6. Potassium·dichromate paper - Prepare a saturated ~Cr207 solution in distilleo water
in a test ·tube. Dip a strip of filter paper in it and use it directly as dichromate paper.
Appendices 139

1. Fehling's Solution A (blue)


Dissolve 70 g of copper sulphate in distilled water and dilute it to one dm 3•
2. Fehling's Solution B (colourless)
Dissolve 350 g of sodium potassium tartarate (i.e. Rochelles salt) and 100 g of sodium
hydroxide in distilled water and dilute it to one dm 3•
Note: Mix equal volumes of solutions A and B immediately before use.
3. Buffer Solution (pH 10)
Dissolve 70 g of pure NH4CI (A.R.) in 568 em 3 of liquor NH3 (specific gravity 0.88 to 0.9)
solution and dilute the solution to one dm 3 with distilled water.
4. Schiff's Reagent
Dissolve 0.4 g of magenta powder in one dm 3 of distilled water. Pass S02 gas in it till the
pink colour is destroyed completely and solution becomes colourless. Store it in a air tight glass
stoppered bottle.
5. Oxine Reagent
Dissolve 2 g of 8 hydroxy quinoline in 20% CH3COOH with constant stirring. Add liquor
NH3 dropwise to it, till it becomes slight turbid. Acidify it with a little of glacial CH3COOH, to
obtain a clear solution. Dilute it to 100 em 3 with distilled water. Store it in an amber coloured bottle.
6. O.lN Perchloric acid solution
Mix 8.5 em 3 ofperchloric acid (60%) with 500 em 3 of glacial acetic acid and 21 em 3 of acetic
anhydride. Cool and add glacial acetic acid to make one dm 3.
7. O.lM P nitro benzaldehyde and o-dinitrobenzene solution
O.IM solutions of each of these compounds are prepared in reagent grade methylcellosolve
(2 methoxy ethanol).
140 College Practical Chemistry (T.Y. B.Sc.)

APPENDIX C
Equivalent Weights of Some Important Substances
Substances Molecular Weights Equivalent Weights
1. KMn04 158 31.6
2. ~Cr207 294 49
3. Na2S20 3·5H2O 248 248
4. 12 254 127
5. SnCI2"2H2O 225 225
6. AgN03 170 170
7. EDTA (Di Sodium salt) 372.24 372.24
8. N~C03 (anhydrous) 106 53
9. FeS04 (NH4)2 S04· 6Hp 392 392
10. Fe2(SOJ3 (NHJ2S04·24H20 963 963
11. (CH2COOH)2 (Succinic acid) 118 59
12. ~S203 270 270
13. KBr0 3 167 167
14. KI 166 166
15. CuS04.5H2O 249.54 249.54
16. ~SO4.AI2(SOJ3.24Hp 948 948
17. ZnS04·7H2O 208.38 208.38
18. FeC13·6H2O 270.35 270:35
19. NaN0 2 69 69
20. KCNS 97 97
21. C6H sCOOH (Benzoic acid) 138 138
Appendices 141
APPENDIX D
Values of Some Important Physical Constants at 25°C
1. Specific conductance of O.IN KCI solution
= 0.01288 mho. em-!
2. Equivalent conductance at infinite dilution (Aoo) for
(i) CH3COOH = 392.0 mho. em2
(ii) KCl = 155.0 mho. em2
(iii) HCl = 441.0 mho. em2
3. Equilibrium constant of the reaction KI + 12 = KI3 == 700
4. Solubility product of some sparingly soluble salts (Ksp)
AgI = 8.3 x 10-17
AgBr = 5.3 x 10 12
AgCl = 1.78 x 10- 10
5. Partition coefficient of Iodine between CC14 and water
= 0.012
Saponificationvalues of oils
Oils Saponification values
(1) Castor oil 175-185
(2) Linseed oil 190-195
(3) Sunflower oil 185-195
(4) Coconutoil 245-270

Physical Constants of Different Liquids at Room Temperature


Liquids Density Viscosity Refractive Surface
Indices Tension
Benzene 0.879 0.564 1.49 27.49
Toluene 0.867 0.525 1.49 27.32
Xylene 0.880 0.809 .1.51 29.54
Ethyl alcohol 0.789 1.002 1.35 21.43
Methyl alcohol 0.796 0.510 1.33 21.91
Isopropanol 0.804 1.765 1.38 20.77
Distilled water 1.000 1.000 1.33 71.18
Carbon tetrachloride 1.589 0.843 1.45 25.33
Acetone 0.788 0.295 1.35 23.33
Chlorofonn 1.484 0.514 1.45 27.10
Acetic acid 1.053 1.314 1.36 27.42
142 Colltge Pr(lctical CheMistry (T.!: B.Sc.)

APPENDIX E
List of tampounds with their structural formulae,
physical constants and characteristic tests
C~ H, (0), Acids (Solids)
Sr. M.P'/B.P Name and Structure of General Description and Special Tests ~
No Compound

1. IOO"C Oxalic acid White crystalline water soluble solid.


COOH 1. Neutral solution of compound very readily gives
i white precipitate with Cael 2 solution, insoluble in
COOH CHFOOH; but soluble in dilute HeL
2. Compound + hot acidified KMnO4 solution, heat
~ violet colour disappears
Derivative - urea oxalate; M.P. 171°C.

2'1 121°C-122°C Benzoic acid White water-insoluble solid.


COOH L Neutral solution of compound gives with a drop
of aqueous FeC1 3, buff precipitate.

3. l:noC
6
Cinnamic acid
2. Compound + soda-lime, heat smell of benzene.
Derivative - on-nitro benzoic acid, M.P. 140°C

Slightly yellowish water insoluble solid.


CH = CH.CooH ! . Wht:n heated with acidified KMnO4 S,):ution, pink
colour disappears and smell cf bitter almonds is

CD given out.
2. Neutral solution of compound gives yellow col-
oured precipitate with a drop of aqueous FeCI3
solution.
Derivative - dibromo cinnamic acid; M.P. 195°C.

4. 135"C Aspirin (01') White, water insoluble solid.


Acet}1 salicylic acid I. Compound + water + alcoholic PeCl) solution, on
heating gives violet colour.
O=OCOCH) Derivative - salicylic acid; M.P. 15SoC.
~ CooH

5. 15SoC Salicylic acid White water insoluble solid.


1. Neutral or aqueous solution of c{)mpound +
aqueous FeCI) solution ~ violet colour or precipi-
O=0H
~ I
CooH tate.
2. Compound + 1 cm3 of CH 30H + drop of cone.
H2S04~ heat on a water bath and then pour it in
cold water ~ smell of oil of winter green.
Derivative - 5-nitro salicylic acid; M.P. 226°C

6. lSSoC Succinic acid. White crystals soluble in cold water.


CH 2COOH 1. Neutral solution of compound + 2 drops of
I aqueous FeCI) ~ reddish brown precipitate.
CH2COOH 2. Fluorescein test: Compound + Resorcinol + 2
drops of conc. H2S04 , heat till mass fuses, cool
and pour in dilute NaOH solution ~ yellowish
-red fluorescence.
Derivative - succinic anhydride; M.P. 120°C.
Appendices 143

7. 195°C Phthalic acid White water' insoluble solid.


I. Fluorescein test: Compound + Resorcinol + 2 drops
of conc. H2SO4' h~t till mass fuses, cool al,ld pour
()cCOOH
in dilute NaOH solution -+ yellowish green
~ COOH
fluorescence.
2. Phthalein test: compound + 2 drops of Phenol + 2
drops.of conc. H2S04, heat till mass fuses, cool
and pour in dilute NaOH solution -+ pink col-
our.
Derivative - phthalic anhydride; M.P. I 28OC.

C, H, (0) and N, Acids (Solids)

8. 141°C m-Nitrobenzoic acid


COOH White crystalline solid insouble in water.

~
I. On heating with sodalime, give odour of bitter
almonds.
~ NO Derivative - m-aminobenzoic acid; M.P. 174°C.
2

9. 14SoC, Anthranilic acid Pale brownish coloured solid soluble in water.


COOH I. Mix a small amount of compound with an equal

&~
amount of CaCl2 and heat. Dissolve the product
in 2 cmJ of ethyl alcohol. Solution becomes red
~I which develops violet fluorescence on standing.
2. Fuse the compound by heating with ZnClr Add
alcohol -+ a yellow colour is produced.
Derivative - dibromo; M.P. 227°C.

10. 147°C o-Nitrobenzoic acid White crystalline solid insoluble in water.

(rNO,
COOH 1. On reduction with Sn and HCI, gives· anthranilic
acid.
2. When heated with sodalime, gives odour of bitter
VI almonds.
:::-....
Derivative - anthranilic acid; M.P. 145°C

11. 239DC p-Nitrobenzoic acid White crystailine solid insoluble in water.


COOH 1. On heating with sodalime, gives odour of bitter

¢
almonds.
2. On reduction with Sn and HCI, gives p-aminoben-
zoic acid.
Derivative - p-amino benzoic acid; M.P 188°C.
N02

C, H, (0), Nand S, Acids (Solids)

12. 288°C Sulphanilic acid White crystalline solid, sparingly soluble in water.

QH
1. On heating, it does not melt but chars.
2. Gives azo dye test.
3. On heating with sodalime, gives smell of aniline.
Derivative - sym-tribromoaniline; M.P. 119DC.
H2
144 College Practical Chemistry (T. Y. B.&.)

C, H, (0) Phenols (Solids)

13. 94°C a-Naphthol Blackish violet solid.


OH I. Compound + alcoh6lic FeCI3 -+ white ·precipi-
tate slowly changes to violet or pink.

0)
~ ~
" Compound + NaOH solution + CCI4 + Cu filing
~.

- warm -+ blue colour.


3. 10 cmJ of mixture of~ and NaOH + 1-2 crystals
of compound, 12 colour reappears and darkens
rapidly.
Derivative - (i) picrate; M.P. 189"(;
(ii) benzoyl (benzoate); M.P. 56OC.
-

14. 118°C Resorcinol Pale-brownish solid, soluble in cold water.


OH I. Compound + alcoholic FeCl3 solution -+ violet

~OH
colour.
2. Compound + NaOH + CHCI 3-+ warm -+ red
colour.
3. Flourescein test: Gives yellowish green flores-
cence (perform a test With this substance as a given
under, phthalein test under phenol)

15. 122°C ~-Naphthol Light pink solid.


1. Compound + alcoholic FeCI) -+ green coloured
OH

W
~I .&
opalescent,
2. Compound + NaOH solution + CHCI 3 warm -+
blue colour.
3. Aniline + dilute HCI + NaN0 2 solution, cool. Add
the above solution to a test tube containing
compound dissolved in NaOH -+ red dye.
Derivative - (i) acetyl; M.P. 700C
(ii) benzoyl; M.P. 1070C
(iii) picrate; M.P. 1560C

C, H, (0) and N Phenols (Solids)

16. 45°C o-Nitrophenol Bright yellow solid insoluble water.

(rNO,
OH 1. Compound + dilute NaOH solution -+ orange
red colour.
2. Compound + NaOH solution,+ NaHS03 solution,
~I boil and cool -+ colourless crystals of
o-aminophenol are obtained.
Derivative - benzoyl; 55OC.

17. 97°C m-Nitrophenol Pale yellow crystalline solid insoluble in water.


1. Compound + dilute .NaOH solution -+ orange

&~ NO
2
yellow colour.
2. Compound + water, shake + 1-2 drops of alcoholic
FeCl3 solution -+ violet red colour.
Derivative - benzoyl; 950C
Appendices 145

18. 1140C p-Nitrophenol Almost colourless solid insoluble in water.


IOH I. Compound + NaOH solution -+ bright yellow

¢ N02
I
colour.
2. Compound + Bromine in acetic acid, waim -
precipitate foons.
Derivative - benzoyl; 142°C

C, H, (0) and N, Bases (Solids)

19. 4SoC p-Toluidine Pale reddish brown (due to exposure) gives peculiar
fishy smell.

9
1. Gives azo dye test.
2. Compound + 2 drops of conc. HCI + 2 cm J of water
+2 drops of FeCI3 solution, heat gently -+ red
orange colour.
3. Compound + SO% H2S04 + I cmJ of ~Cr207
NIl, solution -+ yellow colour.
Derivative - (i) acetyl; M.P. 148°C.
(ii) benzoyl; M.P. IS8°C.

20. S4°C Diphenylamine Slightly greyish cloloured solid.


1. Compound + 1-2 cm J of conc. H2S04 + a drop of

~NH.-o conc. HN03 -+ intense blue colour (on dilution


with water becomes violet).
Derivative - (i) acetyl; M.P. 101°C.

21. 71°C o-Nitroaniline Orange coloured solid.

&00,
~I
N~ I. Compound + NaN0 2 solution + dilute HCI, shake
well, add_to l3-naphthol in NaOH solution -+
red dye.
Derivative - (i) acetyl; M.P. 92°C.
(ii) benzoyl; M.P. 94°C.
-

22. 114°C m-Nitroaniline Yellow orange solid.


I. Take 0.1 g of the compound + 0.1 g of Zn dust +

&~ N01
S cmJ of dilute HCI in a test tube. Shake well and
allow to stand for a few minutes and filter. I cm f
of filtrate + I cm J of dilute NaN02 solution
-+ a red brown precipitate is obtained.
Derivative - (i) acetyl; M.P. ISSoC.
(ii) benzoyl; M.P. ISSoC.
146 College Practical Chemistry (T. Y. B.Sc.)

23. 147"C p-Nitroanilin" Yellow coloured solid.


I. Take 0.1 g of the compound + 0.1 g of Zn dust
.
¢ N02
-. + 5 cmJ of dilute HCI in a test tube. Shake well
and allow to stand for afew minutes and filter. 2
drops of filtrate + 5 cmJ of water + 2 cmJ of dilute
NaOH, mix well + I drop of phenol, shake and add
I cm J of strong chlorine water. After shaking well,
allow to stand for a minute, -+ deep blue colour
develops.
Derivative - (i) acetyl; M.P. 212OC,
(ii) benzoyl; M.P. 199"C.
C, H, N, Bases (Liquids)
24. 184°C Aniline Colourless liquid when pure, reddish brown on expo-
sure, fishy smell.

6
1. Gives azo dye test.
2. A drop of compound + 5 cmJ of water + bleaching
powder (or NaOCI solution, i.e., NaOH + C12)
a purple solution.
3. Compound + KzCr20, + cone. H2S04 , mix -+ blue
colour or black colour.
Derivative- (i) acetyl; M.P. 114°C.
(ii) benzoyl; M.P. 163°C.
(iii) sym. tri~romo aniline; M.P. 119°C.

25. 193°C Dimethylaniline Yellow liquid when pure, on exposure turns brown.
1. It gives a +ve test for aromatic tertiary amines, i.e.
/CH 3

oCH,
N

'7\
~
it gives brown colour/precipitate with dilute HCl
and NaN02 solution. Allow this solution to stand
for at least 5 minutes, add excess of dilute NaOH
solution ~,yellowish green precipitate is ob-
tained.
2. Compound + benzaldehyde + ZnCI2 (anhydrous)
heat and cool -+ deep green colour, on acidifica-
tion.
3. Dissolve about 0.5 g of oxalic acid in 5 cmJ of
ethyl alcohol by careful heating. To this, add a few
drops of compound and shake -+ Immediate white
precipitate of oxalate is obtained. (wash the
precipitate with alcohol, dry and use as deriva-
tive).
Derivative - oxalate; M.P. 139"C

26. 193°C N-Methylaniline Colourless liquid, immiscible with water.


I. Compound + dilute HCI, shake well + NaN02

6~ solution -+ yellow emulsion.


Derivative - picrate; M.P. 145OC.
Appendices 147

a
27. lC)90C 0-Toluidine Colourless liquid when pure, otherwise brown in colour,
eH3 having a fishy smell. Immiscible with water.
I. Gives brown to green colour, with 50% H2 S04
NH
and ~Cr207 solution (details of test are given
~I , under Aniline on page No. 151).
2. With Br2 water, the cOITIp<'und forms white
precipitate of bromo compound.
Derivative - (i) acetyl; M.P. 110°C.
(ii) benzoyl; M.P. 143°C.

C, H, (0), Neutrals (Solids)

28. 49°C Benzophenone


0 White crystalline solid insoluble in water.
\I 1. Compound + Conc. H2S04 -+ yellow solution.

crC'O
~I : :.--..
2. Fusion of compound with sodium, produces deep
blue colour.
Derivative- 2,4- dinitrophenlylhydrazone; M.P. 238°C.

29. 80°C Naphthalene


.
White solid insoluble in water, having smell of naphtha
balls.
I. Compound + 2 drops of freshly prepared FeCI3

CO
~ ~
solution + 3 drops of conc. H2S0 4 -+ reddish
colour changing to violet.
2. Compound + 1 cm J of benzene, shake + I cmJ of
saturated solution of picric acid in benzene, shake
and pour on a watch glass -+ yellow picrate.
Derivative - picrate; M.P. 150°C.

c, ~, (0), Neutrals (Liquids)


Ketones

30. 56°C Acetone Colourless liquid, miscible with water.


0 I. Compound + NaOH solution + sodium
II nitropruside solution -+ red colour.
H3C - C- CH3 2. Iodoform Test: Compound + NaOH solution +
excess of 12 solution -+ yellow crystals of iodo-
form.
3. Compound + m-dinitrobenzene + NaOH solution
-+ violet colour.
Derivative - iodoform; M.P. 1190C

31. 80°C Ethyl methyl Colourless liquid, miscible with water.


Ketone I. Gives iodoform test.
2. Compound + NaOH solution + sodium
0
nitropruside solution -+ red colour.
1/ Derivative - 2, 4 -dinitrophenyl hydroazone;
H3C - C- CH2 - CH 3 M.P. 115°C
148 College Hraet;eal Chemistry (T. Y. B.Sc.)

'32. 200°C Acetophenone Colourless liquid, immiscible with water.


() I. Gives iodofonn test.
2. Compound + conc~ H2S04 -+ orange GOI~ur.

"
~CH,
3. Compound + alkaline KMnO4' heat for 5 minutes,
Cool, filter. Filtrate + conc. HCI -+ white solid.
Derivative - (i) phenyl hydrazone. M.P. 1050C
(ii) benzoic acid; M.P. 121°C.

Aldehydes

33. 179°C Benzaldehyde Colourless liquid with odour of bitter almonds, immis-
cible with water.
CHO 1. Compound + 2 em] of alkaline KMn04 solution,

6 heat for 5 minutes and filter. Filtrate + Conc. HCI


-+ white precipitate of benzoic acid.
2. Compound + Tollen's reagent; heat on a boiling
water bath -+ grey precipitate.
Derivative - benzoic acid; M.P. 1210C

Esters
34. 57°C _ Methyl acetate Colourless liquid, miscible with water.
0 1. Compound + 2 em] _of water + a drop of
II phenolphthalein + 2 drops of dilute NaOH solu-
CH)-C - 0 - CH) tion, heat -+ pink colour disappears.
2. Compound + dilute NaOH solution boil. Add
some more dilute NaOH solution and an excess of
12 solution -+ No yellow precipitate of iodofonn.

35. 77°C Ethyl acetate Colourless liquid, miscible only on shaking with large
0 excess of w~r.
II 1. Gives ester test.
-- -£H) - C- OC2HS 2. Compound + dilute NaOH solution, boil -+
~--

acetic acid and ethyl alcohol are fonned + NaOH


solution + excess of 12 solution -+ yellow
precipitate of iodofOlm.

36. 213°C Ethyl benzoate Colourless liquid, immiscible with water.


COOC2H, I. Gives ester test.
2. Compound + 5 em] of 20% NaOH solution, heat

6 for about 10 minutes and cool + Conc. HCI -+


white precipitate of benzoic acid.
Derivative - benzoic acid; M.P. 1210C
Appendices 149

Alcohols

37. 650C Methyl alcohol Colourless liquid, easily miscible with water.
I. Compound + saliGYlic acid + I drop of conc.
CHpH H2S04, heat on a boiling water bath --¥ smell of
oil of winter green (Iodex smell).
2. Compound + borax + I drop of conc. ~SO4' heat
gently and ignite the vapours -+ green flame.
Derivative - p-nitrobenzoate; M.P. 96OC.

38. 78°C Ethyl alcohol Colourless liquid, easily miscible with water.
CH)CH2OH I. Compound + NaOH solution + Excess of 12
solution -+ yellow crystals of iodoform.
·2. Compound + dry sodium metal -+ rapid effer-
vescence.
Derivative - p-nitrobenzoate; M.P. 57°C

39. 820C 2-Propanol Colourless liquid with alcoholic odour, miscible with
(Isopropyl alcohol) water.
H I. Gives iodoform test.
I 2.. Oxidation of compound with ~ Crp7 and conc.
CH3 -C-CH H2S04 yields a product having sweet smell of
I 3 acetone.
OH Derivative - p-nitrobenzoate; M.P. 110°C.

40. 118°C I-Butanol


(n-Bulyl alcohol)
~ - Colourless liquid miscible with about 10 volumes of
water.
CH)CH2 CH2CH 2OH 1. Compound + dry sodium metal -+ brisk efferves-
cence.
2. Does not give iodoform test.
Derivative - 3, 5 dinitrobenzoate; M.P. 64°C.

41. 161°C Cyclohexanol Colourless liquid soluble in 28 volumes of water.


'OH On oxidation with conc. HNO), yields adipic acid.

42. 205°C
6
Benzyl alcohol
Derivative - adipic acid; M.P 151°C

Colourless liquid miscible with water.


0H I. Compound"" 2 em J of dilute HNO), heat on a

r5 boiling water bath for about 2 minutes -+ pale


yellow emulsion with strong bitter almond smell.
2. Compound + 1 emJ of conc. HCI, heat on a boiling
water bath -+ clear solution initially turns white
emulsion.
Derivative - p nitrobenzoate; M.P. 86OC.

Ethers
43. 154°C Anisole Pleasant smelling liquid, immiscible willi water.
OCHa 1. Compound + conc. H2S04 -+ soluble.
2. Compound + 1 emJ of iodine in carbon disulphide,

6 shake well -+ purple colour changes to brown.


Derivative - picrate; M.P. 81°C
ISO Co/lege,PrtJ..:tica! Chemistry (1'.y. B.Sc.)

Hydrocarbons
44. 68°C n-Hexane Colllrless liquid with petrol like odour, floats on water.
CH) - (C~)4 - CH3

45. 135°C Ethyl benzene Colourless liquid, immiscihle with water.


(1) C.,mpoWld + "N~C03 soluticn + saturated KMn04

6-~
solution, heat for 30 miflutt"-s. Cool &Ild mter.
Filtratl!: ~ cenc. Hel ~ wl>ite precipitate of
benzoi.-: acid.
1 Derivative _.- ber.zoic acid; M.P. 121"C.
I

46. 1380C p-Xylene Colourless liquid with characteristic odour and immis-
cible with water.

¢' CH 3
(1) Alkaline KMn04 oxidation gives terphthalic acid.
Derivative - 2,3, 5-trinitro phthalic acid; M.P. 1370C

47. 139°C m-Xylene Colourless liquid with characteristic odour and immis-
cible with water.

& :::...
o-Xylene
CH,
(1) Alkaline KMn04 oxidation gives isophthalic acid;
Derivative - 2,4,6-trinitro phthalic acid;.M.P. 1820C

Colourless liquid immiscible with water.


(1) Alkaline KMn04 oxidation gives phthalic acid;

&~
48. 144°C Derivative - phthalic acid; M.P. 195OC.

C, H, (0) and N, Neutrals (Solids)

49. 54°C Diphenylamine


Refer to compound No. 20 in Basic compound, on Page
H No. 150).
I

(YN'O
50. 540C p-Nitrotoluene
Pale yellow solid with odour ~f bitter almonds.

~
1. Gives test for nitro group.
2. Compound + KMn04 solution, heat ~ precipitate
of p-Nitrobenzoic acid.
Derivative - p-nitrobenzoic acid; M.P. 238OC.
'N02
Appendices JJJ
i

51. 900(; m-Dinitrobenzene Pale yellow' solid insoluble in water.


I. Compound + acetone";" NaOH solution --+ violet
colour.

&NO 2
Derivative - m-nitroanili.nt'; M.P. 114"(;.

52. 114°C Acetanilide White solid, insoluble in water.


I. Compound + glacial aceti~ acid -) shake + Br2 i

6~
solution in acetic acid --+ decolourisation ¥lith
formation of precipitate.
2. Compound + conc. H2S04, shake + 2 crystals of
K.zCr20 7, shake vigorously --+ green colour.
Derivative - p-bromoacetanilide; M.P. I 69"C.

53. 129"C Benzamide White solid, insoluble in water.


I. Compound + sodalime, heat strongly --+ smell

54. 132°C
6' Urea
of bitter almonds.
2. Compound + 20% NaOH solution heat --+ smell
of ammonia.
Derivative - benzoic acid; M.P. 121°C.

White crystalline solid soluble in water.


I. Compound + 20% NaOH solution heat --+ smell

II of ammonia.
H2N-C-~ 2. Biuret Test: Heat compound till it melts, cool +
NaOH solution + CuS04 solution dropwise --+
red-violet colour changes to deep blue colour.
"- 3. Compound + Hp + conc. RNO) --+ white
precipitate of urea nitrate.
Derivative - Urea nitrate; M.P. 163°C

Liquids

55. 2100C Nitrobenzene Yellow liquid with bitter almonds smell, immiscible
with water.

c5 1. 1-2 drops of compound + I cm3 of conc. HCI +


0.1 g ofZn dust, boil, cool + dilute NaOH solution
+ freshly prepared Cl2 --+ purple colour.
2. Gives test for nitro group.
Derivative - m-dinitrobenzene; M.P. 900C

C, H, (0), Nand S, Neutrals (Solids)


W\lite solid soluble in water.
56. 180°C Thiourea
I. Heat the compound till it melts + FeCI) solution
S --+ blood red colour.
II
H2N-C-~
2. Compound + K4Fe(CN)6 solution + 2N CH)COOH
--+ green colour changes to blue.
Derivative - thiourea hydrochloride; M.P. 1360(;
152 College fractical Chemistry (T. Y. B.Sc.)
C, H (0) and Halogens, Neutral (Liquids)
57. 61°C Chlorofonn Heavy liquid with sweet odour.
CHCIl I. 3 drops of compoWld + 3 em] of dilu~ NaOH
solution +0.3 gofresorcinol, heat-+ redcolouration.
2. Compound + Fehling's solution A and B, heat-+
red precipitate.

58. 76°C Carbon tetrachloride Heavy liquid, with pleasant smell.


CCl4 I. CompoWld + a-naphthol in NaOH solution + Cu
filing, heat -+ blue colouration.
2. CompoWld + Fehling's solution A and B, heat-+
no red precipitate.

59. 132°C Chlorobenzene Pleasant aromatic odour, chlorine is not replaced by


Cl boiling alkali, as it is present in nucleus.

6
1. Gives Beilstein's Test.
2. CompoWld + Conc. HNOl + Cone. ~S04' heat-+
p-nitro chlorobenzene fonns.
Derivative - p-nitro chlorobenzene; M.P. 83OC.
-
60. 156°C Bromobenzene Clear liquid, with aromatic smell, bromine is not replaced
Br by boiling alkali.

6- 1. Gives green flames when compoWld is heated over


oxidised copper foil.
2. CompoWld + Conc. HNOl + Conc. H2S04 -+
p-nitro bromobenzene forms.
Derivative - p-nitrobromobenzene; M.P. 126OC.
Appendices 153
APPENDIX F
Atomic Weights of Elements

Name Symbol Atomic Atomic Name Symbol Atomic Atomic


number weight number . weight

Actinium Ac 89 (227) Mercury Hg 80 200.6


Aluminium AI 13 27.0 Molybdenum Mo 42 95.9
Americium Am 95 (243) Neodymium Nd 60 144.2
Antimony Sb 51 121.8 Neon Ne 10 20.2
Argon Ar r8 39.9 Neptunium Np 93 (237)
Arsenic As 33 74.9 Nickel Ni 28 58.71
Astatine At 85 (210) Niobium Nb 41 92.9
Barium Ba 56 137.36 Nitrogen N 7 14.01
Berkelium Bk 97 (245) Osmium Os 76 190.2
Beryllium Be 4 9.01 Oxygen 0 8 16.00
Bismuth Bi 83 209.0 Palladium Pd 46 106.4
Boron B 5 10.8 Phosphorus P 15 31.0
Bromine Br 35 79.9 Platinum Pt 87 195.1
Cadmium Cd 48 112.4 Plutonium Pu 94 (242)
Calcium Ca 20 40.08 Polonium Po 84 210
Californium Cf 98 (251) Potassium K 19 39.1
Carbon C 6 12.01 Praseodymium Pr 59 140.9
Cerium Ce 58 140.1 Promethium Pm 61 (147)
Cesium Cs 55 132.9 Protactinium Pa 91 (241)
Chlorine CI 17 35.5 Radium Ra 88 (226)
Chromium Cr 24 52.0 Radon Rn 86 (222)
Cobalt Co. 27 58.94 Rhodium Rh 45 102.9
Copper Cu 29 63.54 Rhenwm Re 75 186.2
Curium Cm 96 (247) Rubidium Rb 37 85.5
Dysprosium Dy 66 162.5 Ruthenium Ru 44 101.1
Einsteinium Es 99 (254) Samarium Sm 62 150.4
Erbium Er 68 167.3 Scandium Sc 21 45.0
Europium Eu 63 152.0 Seleninm Se 34 79.0
Fermium Fm 100 (253) Silicon Si 14 28.1
Fluorine F 9 19.0 Silver Ag 47 107.9
Francium Fr 87 (223) Sodium Na 11 23.0
Gadolinium Gd 64 157.3 Strontium Sr 38 87.6
Gallium Ga 31 69.7 Sulphur S 16 32.1
Germanium Ge 32 72.6 Tantalum Ta 73 180.9
Gold Au 79 197.0 Technetium Tc 43 (99)
Hafnium Hf 72 178.5 Tellurium Te 52 127.6
Helium He 2 4.00 Terbium Tb 65 158.9
Holmium Ho 67 164.9 Thallium TI 82 204.4
Hydrogen H I 1.008 Thorium Th 90 232.0
Indium In 49 114.8 Thulium Tm 69 168.9
Iodine I 53 126.9 Tin Sn 50 118.7
Iridium Ir 77 192.2 Titanium Ti 22 47.9
Iron Fe 26 55.85 Tungsten W 74 183.9
Krypton Kr 36 83.8 Uranium U 92 238.0
Lanthanum La 57 138.9 Vanadium V 23 50.9
Lead Pb 82 207.2 Xenon Xe 54 131.3
Lithium Li 3 207.2 Yetterbium Vb 70 173.0
Lutetium Lu il 175.0 yttrium Y 39 88.9
Magnesium Mg 12 24.32 Zinc Zn 30 65.38
Manganese Mn 25 54.94 Zirconium Zr 40 91.21
Mendelevium Md 101 (256)

Parenthetical names refer to radioactive elements; the mass number (not the atomic weight) of the isotope with largest half-
life is usually given.
• Lastest values recommended by the International Union of Pure and Applied Chemistry. 1961. '

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