Practicals
Practicals
Practicals
CHEMISTRY
Hal
Glfimalaya GpublishingGflouse
MUMBAI • DELHI • NAGPUR • BANGALORE • HYDERABAD
© AUTHORS
No part of this book shall be reproduced, reprinted or translated for any purpose whatsoever without permission of
the author and publisher in writing.
ISBN : 978-93-5024-511-8
4. Potentiometry 17-31
5. Colorimetry/Spectrophotometry 32-46
6. Conductometry 47-54
7. pH-Metry 55-64
Appendices 137-153
"This page is Intentionally Left Blank"
1
Chemical Kinetics
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).
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:
. _ 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.)
Slope = (~)
.. Ik = Slope x 2.3031 (.: slope is negative, k becomes positive)
ab
Slope = -
be
k = Slope x 2.303
o0 t minutes
Fig. 1.1
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:
A = Antilog E)
(10g k\ - 2.303RT
0
where,
A The frequency factor
(k + k ) .
k = I 2 2 = Mean Rate constant min-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
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
~
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
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
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.)
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.)
1(0.2)"10
e.g. flrel(0.2%) =- I-
(5)
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)
M = ~lJ;r
Results: "
[J[J[J
4
Potentiometry
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.)
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
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
0.100 0.733
0.050 0.790
0.025 0.850
0.010 0.892 !
0.005 0.924
Mean E"Ag =
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.)
For Ag, n = 1.
° 0.0592'1'Og'(rwv)
:. E Ag = EAg - n. ... ,
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.
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]
0.0592 1 mlYI
:. £Ocell = Ecell + 2 X oglo ( 2 2)
m2Y2
E~ell x2
10gIO K = 0.0592
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.
Fig. 4.5
!lE
(ii) AV against volume of titrant added in em 3
t
AE
AV
Volume of ~Cr207 Required
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
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
(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
Ecell - 0.557)
(
0.0592
. (Ecell -0.557)
= Anti log 0.0592
and
acr = Molality of KCl x activity cell of chloride
and
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
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
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
gDD7 DISPLAY
FlL11!R PORT
A
SAMPLE PORT
*.
SEfZERO
T"-O.o.
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
(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
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
(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.)
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:
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.
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.
000
6
Conductometry
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
(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
P = [ x x 100]
(x+ y)
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
Fig. 6.4
000
7
pH-Metry
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:
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)].
(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
6
2nd Equivalence Point
4
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
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.
Fig. 7.3
ApH
iN
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 _ _ _ __
= --- 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_______________________
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 __________
= 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
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.
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.
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
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.&.)
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
=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.)
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
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
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.)
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)
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
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:
Filtrate + conc. HCl dropwise (i) A solid reappears Carboxylic acid 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:
(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
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)
(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).
(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~~------~0MEnm
STAND
. . . - - - - - SEALEDEND
......- - - - CAPILLARY
~nI4.....--+--IGNI11ON TUBE
~-.'tit-- BEAKER
AfII...,- UQUJD
PARAFFIN 00.
___-WIRE GAUZE
.....--BURNER
(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.
(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.
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.
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
(iii) 2 drops of filtrate + 2 drops of aq. A blood red coloration. Nitrogen and sulphur are present.
FeCl3 solution.
(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.
(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.
"
(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.
(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.
(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.
(a) 0.01 g of compound + dilute Compound dissolves producing deep Nitro phenol or aminophenol present.
NaOH solution yellow or orange colour
(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
(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.
(b) Perform test for -NH2 group Orange red dye Aromatic primary amino
(Refer to Test (b). Group II. (-NH2) group present.
Bases)
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.
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
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:
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.
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
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:
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
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.
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:
%.
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
(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.)
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
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
= 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.
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
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.)
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
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
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
3. l:noC
6
Cinnamic acid
2. Compound + soda-lime, heat smell of benzene.
Derivative - on-nitro benzoic acid, M.P. 140°C
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.
~
I. On heating with sodalime, give odour of bitter
almonds.
~ NO Derivative - m-aminobenzoic acid; M.P. 174°C.
2
&~
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.
(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
¢
almonds.
2. On reduction with Sn and HCI, gives p-aminoben-
zoic acid.
Derivative - p-amino benzoic acid; M.P 188°C.
N02
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.&.)
0)
~ ~
" Compound + NaOH solution + CCI4 + Cu filing
~.
~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)
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
(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.
&~ NO
2
yellow colour.
2. Compound + water, shake + 1-2 drops of alcoholic
FeCl3 solution -+ violet red colour.
Derivative - benzoyl; 950C
Appendices 145
¢ N02
I
colour.
2. Compound + Bromine in acetic acid, waim -
precipitate foons.
Derivative - benzoyl; 142°C
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.
&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.
-
&~ 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.)
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
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.
crC'O
~I : :.--..
2. Fusion of compound with sodium, produces deep
blue colour.
Derivative- 2,4- dinitrophenlylhydrazone; M.P. 238°C.
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.
"
~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,
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 -+
~--
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.
42. 205°C
6
Benzyl alcohol
Derivative - adipic acid; M.P 151°C
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,
Hydrocarbons
44. 68°C n-Hexane Colllrless liquid with petrol like odour, floats on water.
CH) - (C~)4 - CH3
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
&~
48. 144°C Derivative - phthalic acid; M.P. 195OC.
(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
&NO 2
Derivative - m-nitroanili.nt'; M.P. 114"(;.
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.
54. 132°C
6' Urea
of bitter almonds.
2. Compound + 20% NaOH solution heat --+ smell
of ammonia.
Derivative - benzoic acid; M.P. 121°C.
Liquids
55. 2100C Nitrobenzene Yellow liquid with bitter almonds smell, immiscible
with water.
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.
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. '