Indian Institute of Science

Education and Research Kolkata

Physical Chemistry Lab, CH1202

Laboratory Manual

2018
 CH 1202
Semester II, January 2018 - May 2018

Time: 2:30 p.m. – 5:30 p.m. (Monday. Tuesday, Thursday and Friday)

GENERAL INSTRUCTIONS
1. Attendance is mandatory. In case of illness etc. the student must contact the instructor and fix a
schedule for making up the missed lab. All labs must be completed in order to get a passing grade.
2. All data and results should be recorded directly in the lab notebook. The recording should include,
title of the experiment, date of experiment, working formula, data in tabulated forms, results and
calculations.
3. The instructor should sign the data before the student leaves the lab.
4. Graph papers and computer print-outs may be directly pasted on the lab notebook.

Grading:
The marking scheme in the lab will be as follows:
1. Mid-semester examination ………………………………………………. 30
2. Lab notebook ………………………………………………. 10
3. Attendance ……………………………………………..... 10
4. Continuous assessment by teacher …………………………………………......... 10
5. Final examination ……………………………………………..... 40

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Page | 3
 List of Experiments

Experiment Experiment Page

No. No.
1. Determination of Order for the Persulphate-Iodide Reaction. 5
2. Conductometric Determination of the Critical Micellar Concentration 7
(CMC) of Sodium Dodecyl Sulphate (SDS).
3. Determination of Isoelectric point of an Amino Acid. 10
4. Study of the Distribution of Benzoic Acid Between Toluene & Water: 15
Determination of the Distribution Co-efficient (KD) of Benzoic Acid
Between Toluene & Water and Dimerization Constant (K) of Benzoic
Acid in Toluene Medium.
5. Determination of Molecular Weight of a Polymer by Ostwald 16
Viscometer.
6. Determination of the Rate Constant for the Acid-Catalyzed Hydrolysis of 19
Ethyl Acetate by Titrimetric Method.
7. Determination of the Degree of Hydrolysis and the Hydrolysis Constant 21
by Potentiometry.
8. Determination of the pKIn Value of an Acid-Base Indicator by 23
Spectrophotometric Method.

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 EXPERIMENT 1

Determination of Order for the Persulphate-Iodide Reaction

Aim: To determine the individual orders with respect to iodide and persulphate and the total order of the
reaction of oxidation of iodide ion by persulphate.
Apparatus Required: Burette 50 cm3, pipettes 5, 25, and 50 cm3, stoppered bottles, 250 cm3 conical
flasks, 250 cm3 standard flasks, porcelain trough, porcelain tiles.
Chemicals Required: Potassium iodide solution (0.1 N); Potassium persulphate solution (0.1 N); Acetic
acid (1.0 N); Sodium thiosulphate solution (0.01 N); Starch indicator, ice cold water.
Principle: The overall oxidation of iodide ion by persulphate can be expressed as
2I- + S2O82- 2SO42- + I2
Or more explicitly
S2O82-+I- SO42-+SO4-+I0
SO4-+I- SO42-+I0
I0+I0 I2
The rate of the reaction is followed by estimating the iodide formed at different time intervals, by
titrating with sodium thiosulphate using starch as indicator. The volume of thiosulphate is plotted as a
function of time. The initial slope of this plot gives the initial rate of the reaction. The values of initial
rates obtained can be used to calculate the total order and individual orders with respect to iodide as well
as persulphate ion.

Procedure: Different reaction mixtures using the volumes given in the Table 1 are prepared. For
example, mix 5 cm3 of 0.1 N acetic acid and 100cm3 of 0.1 N potassium iodide in a stoppered bottle.
Thermostat the same. Add the required amount of water (in this case 45 cm3) so that the final volume is
200 cm3. Pipette out 50 cm3 of 0.1 N potassium persulphate solution in the stoppered bottle, starting a
stopwatch when half the volume of persulphate is added to the bottle. Completely stir the reaction
mixture and pipette out 5 cm3 of the reaction mixture into a conical flask containing ice cold water to
quench the reaction and titrate the iodide liberated against thiosulphate solution using starch as an
indicator. Repeat this at every 5 minutes interval for at least 40 minutes. Carry out similar titrations with
the other combination of solution mixtures in the table below. Standardise the thiosulphate solution.

Table 1. Typical reaction mixtures for determining the order of the reaction between iodide and
persulphate ions.
Bottle Volume of acetic Volume of 0.1N Volume of 0.1 N Volume of
no. acid(1.0 N) (cm3) KI solution (cm3) K2S2O8 solution (cm3) water in (cm3)
1 5 100 50 45
2 5 50 25 120
3 5 100 25 70
4 5 50 50 95

Treatment of Data: Record all your observations systematically as follows:

Construct separate tables for each reaction mixture as given in Table 2. Plot the titre value as a function
of time and evaluate the initial slopes (this can be done either numerically, or graphically or by both
procedures). The slopes obtained at the initial periods of the reaction can be taken to be initial rates.

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(Reason out why we are interested in the initial rates and not the values of rates at any given time of the
reaction).

Table 2. Volume of thiosulphate consumed for a known aliquot of the reaction mixture at various time
intervals.
Normality of thiosulphate solution taken =...N
Reaction mixture (bottle no.1)
Time in minutes Burette readings Volume of
Initial Final thiosulphate(cm3)
0
5
10
15
20
25
30

Normality in a chemical reaction the rate of the reaction is proportional to the concentration of the
reactants raised to the power m, where m is the order of the reaction with respect to the reactant. For the
reaction between iodide and persulphate ions the rate expression can be written as
Rate  [I-] m [S2O82-]n = k[I-] m [S2O82-]n
The ratio of the initial rate values obtained for bottles 1 and 4 can be written as
rate1/rate4 = k[100]m [50]n/ k[50]m[50]n
(Here the volumes taken are assumed to be proportional to concentration since the total volume of the
reaction mixtures is kept constant.). Therefore,
rate1/rate4 = [2]m ; Or, log {rate1/rate4} = mlog2
So the value of m, the order with respect to iodide can be found out. Similarly the ratio of the rates for
bottles 1 and 3 can be written as
{rate1/rate3}= k[100]m[50]n/k[100]m[25]n
Or log {rate1/rate3} = nlog2
So the value of n, the order with respect to persulphate can be calculated. The overall order of the
reaction = m+n.
Also, the ratio rate1/rate2 = k [100]m[50]n/k[50]m[25]n
Or, log {rate1/rate2} = (m+n) log 2
Hence, the overall order of the reaction (m+n) can be calculated.

Result:
Report the individual orders and overall order of the reaction. Comment how the observed reaction
orders accounts for the mechanism of the reaction.
Note:
1. The reaction is also believed to occur in steps:
slow
I- + S2O82- (S2O8I)3-
(S2O8I) 3- fast 2SO42- + I2
2. Suggest any alternate ways of studying the kinetics of the reaction between iodide and
persulphate ions.

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 EXPERIMENT 2

CONDUCTOMETRIC DETERMINATION OF THE CRITICAL MICELLAR CONCENTRATION (CMC) OF

SODIUM DODECYL SULPHATE (SDS)

THEORY:
Surfactants are amphiphilic molecules that possess both hydrophobic and hydrophilic properties.
A typical surfactant molecule consists of a long hydrocarbon ‘tail’ that dissolves in hydrocarbon and
other non-polar solvents, and a hydrophilic ‘headgroup’ that dissolves in polar solvents (typically
water). One example of a dual character molecule having a head-group and a non-polar tail is sodium
dodecyl sulphate (SDS), NaOSO3C12H25.
When a sufficient amount of SDS is dissolved in water, several bulk solution properties are
significantly changed, particularly the surface tension (which decreases) and the ability of the solution to
solubilise hydrocarbons (which increases). These changes do not occur until a minimum bulk SDS
concentration is reached. This concentration is called the critical micelle concentration (CMC).
Several experiments, including light scattering and NMR, show that below the CMC, the
surfactant exists mainly as solvated monomeric species, whereas above the CMC these monomers
undergo self-assembly to form roughly spherical structures (having an overall diameter of ~5 nm)
known as micelles. Micelles are the simplest of all self-assembly structures.
Technically, a micellar solution is a colloidal dispersion of organised surfactant molecules. Non-
ionic surfactant molecules can cluster together in micelles of 1000 molecules or more, but ionic species
tend to form micelles of between 10 and about 100 molecules because of electrostatic repulsions
between head-groups.
One of the key aspects of micelle structure is that the interior of the micelle consists of an
associated arrangement of hydrocarbon chains (an ‘oil droplet’). The exterior coat is constructed of the
polar, ionic moieties (the SO4- groups in the case of SDS). This ionic surface (which also contains
associated water of hydration) is called the Stern layer. Surrounding this ionic mantle is a region that
contains both counterions and oriented water molecules – the Gouy-Chapman layer. Together the Stern
and Gouy-Chapman layers are known as the electrical double layer.
But it is the oil-like interior of the micelle that gives it its many diverse and interesting
properties. The hydrocarbon core (~3 nm in diameter) has the capacity to accommodate guest molecules.
The most common application of micelles is as detergents but they can also act as micro-reaction vessels
for organic syntheses and drug delivery agents. In this experiment you will determine some fundamental
properties of the SDS micelle: the CMC and the free energy, enthalpy and entropy of micellisation. You
will measure the CMC by measuring the conductivity of the system as a function of SDS concentration.
The thermodynamic properties are obtained by determining the CMC at various temperatures.

Conductivity of Electrolyte Solutions

Because SDS is charged it acts as an electrolyte and so obeys Ohm's Law. This means that when
a voltage (V) is applied across a cell containing the SDS solution the current (I) that flows is
proportional to V. Ohm's Law can be written in two equivalent ways:

V = IR or I =VG ……………………………………………..1

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where R is the resistance and G (=1/R) the conductance of the solution. The conductance of the solution
depends upon the dimensions of the cell and the nature of the solution. The conductance of a solution
contained in a cell of length l and area A is
G = (A / l) κ ………………………………………...………2
where κ is the conductivity of the solution and is independent of the shape of the cell.
Conductivity has the units Ω-1 m-1 or S m-1 where S is the SI unit of conductance – the Siemen.
The glass cell used with this experiment has fixed electrodes, and the ratio l/A is a constant – the cell
constant. An approximate value can be obtained from the geometry of the cell. Equation 2 can be written
as
κ = G × (cell constant) …………………………………….3
The cell constant is usually obtained by calibrating the cell using a 0.01 mol kg-1 KCl solution at 298 K.
For accurate work a correction must be made for the conductance of the solvent (water) so that
κ = [G(solution)−G(water )] × (cell constant) ……………………….…...4
Having determined the cell constant, the conductivity of any electrolyte solution can be determined from
Equation 4. Most conductivity bridges give values of G directly, although it can also be obtained from a
measurement of the resistance R since
G = 1/R ……………………………………………………..5
We now introduce a very useful quantity called the molar conductivity. For a solution of concentration c
mol m-3 the molar conductivity, Λ (with units S m2 mol-1), is given by
Λ = κ c ……………………………………..………...6
Molar conductivity is a very convenient way of quantifying conductivity because it highlights the
properties of the electrolyte. For instance, doubling the concentration of an electrolyte solution would be
expected to double the number of ions and thus to double the conductivity. In this case the molar
conductivity would be unchanged. In most cases, however, the molar conductivity actually decreases
with increasing concentration owing to the influence of concentration on interactions between
electrolyte ions or on an ionic dissociation process.
The molar conductivity of an electrolyte depends upon the extent to which the electrolyte dissociates
into ions. Strong electrolytes (e.g. KCl) are almost completely ionised, whilst weak electrolytes (e.g.
CH3COOH) are ionised to only a small extent. Dilution of an electrolyte solution increases the extent of
dissociation, and at infinite dilution the molar conductivity reaches a maximum value Λo (sometimes
written Λ ).
For strong 1:1 electrolytes, Λo can be obtained from a plot of Λ against c1/2 and extrapolating to c = 0.
Λ = Λo − Ac1/2……………………………………..…..7
where, A is a constant.

Kohlrausch Law of Independent Migration of Ions

At infinite dilution ion-ion interactions are eliminated, the anions and cations travel
independently. Kohlrauch found that the molar conductivity of a salt could be separated into a
component from each, called ionic conductivities ( λo ).
Λ = λo+ + λo−……………………………..……………..8
So for example, the molar conductivity of sodium chloride is the simply the sum of the ionic
conductivities of the sodium and chloride ions. The ionic conductivity as a function of temperature (θ, in
°C) is given by the equation:
λ±o = λ±o (at 25°C) + a(θ − 25) + b(θ − 25)2 + c′(θ − 25)3 ……………………9

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 Below the CMC, the addition of surfactant to
an aqueous solution causes an increase in the number
of charge carriers (Na+ (aq) and -OSO3C12H25 (aq))
and consequently, an increase in the conductivity.
Above the CMC, further addition of surfactant
increases the micelle concentration while the
monomer concentration remains approximately
constant (at the CMC level). Since a micelle is much
larger than a SDS monomer it diffuses more slowly
through solution and so is a less efficient charge
carrier. A plot of conductivity against surfactant
concentration is, thus expected to show a break at the CMC.

PROCEDURE:
1. Turn on the thermostatted bath and conductivity meter.
2. For all measurements use conductivity water.
3. The conductance cell should have been left full with purified water in a 100 mL beaker. Empty it
and rinse it twice with purified water, then fill it with purified water and place it in the thermostatted
bath, allow 5 min for the cell to reach equilibrium, measure the conductance of purified water. Wash
out the cell with purified water, and repeat the measurement until you have three similar readings.
4. Prepare 100 ml of an approximately 0.04 M aqueous stock solution of SDS.
5. Transfer 60 ml of purified water into a 100 mL beaker with a burette and place the conductance cell
into the beaker. Check if the two electrodes of the conductance cell are immersed in water. If the
electrodes are not completely immersed in water, add more water. Remove the conductance cell
from the beaker. Using a burette add 0.5 ml of the SDS stock solution to the water and gently stir the
solution with a glass rod making sure you do not create too many bubbles. Place the conductance
cell into the beaker and read the conductance which should stabilise after 1-2 min; record the value
in your notebook. Add additional 0.5 ml volumes of the SDS stock until 40-45 aliquots have been
added.

Added Electrolyte
6. Prepare 250 ml of an approximately 0.02 M aqueous NaCl solution. Use this as the solvent for
making up 100 ml of an approximately 0.04 M aqueous stock solution of SDS. Pipette 60 mL of salt
solution into the conductance cell and measure the conductance. Add 0.5 ml of the SDS stock and
record the conductance after the reading has stabilised (1-2 min). About 30-40 additions are
appropriate.

Measuring the Cell Constant

7. Prepare by accurate weighing, a 0.01 molal solution of KCl. (N.B. A molal solution contains 1 mole
of solute in 1 kg of solution.) Rinse out the conductance cell with water, and then with some of the
KCl solution. Fill the cell with KCl solution and measure its conductance. Empty the cell, and repeat
until conductance measurements are consistent (three readings). Finally wash out the cell with
conductivity water twice, and leave it filled with water.

DATA ANALYSIS
Plot concentration of SDS in the X- axis and conductivity in the Y-axis and determine CMC.

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 EXPERIMENT 3

DETERMINATION OF ISOELECTRIC POINT OF AN AMINO ACID.

OBJECTIVE: To explore the acid-base behavior of an amino acid.

INTRODUCTION :
HA(aq) + H2O = H3O+(aq) + A-(aq)
The extent of this reaction is indicated quantitatively using the equilibrium constant, Keq. The
equilibrium constant is given as
Keq = Ka = [H3O+(aq)][A-(aq)]/[HA(aq)]
The equilibrium constant for reaction of an acid with water is usually symbolized Ka, to remind
us of the type of reaction being dealt with. The reactant water, since it is present in huge concentration
and is thus essentially a pure liquid, is not included in the Ka expression. The strength of an acid in
aqueous solution is defined in terms of the magnitude of Ka. Strong acids have Ka values larger than 1;
weak acids have Ka values less than 1.
The equilibrium established when a weak acid reacts with water can be explored using a
procedure called titration, involving the following steps:
The pH of the solution must change as the titration proceeds.
1. At the beginning of the process, before base is added, the pH of the solution is fairly low because it
contains acid.
2. As titration proceeds, acid is neutralized by the added base, and pH rises.
3. Addition of base after all of the acid has been neutralized produces a basic solution, with a high pH.
During the titration, then, pH runs the gamut from low to high. We can detect the equivalence point
from the manner in which the pH change occurs.
A pH meter responds to the electrical potential of an electrode immersed in the solution being
titrated. This potential is a function of [H3O+] in the solution. A plot of pH versus the volume of titrant
added to the solution gives the so-called titration curve.
The curve is shaped something like the letter "S". All titration curves have this characteristic
shape.
This provides us with the second method for determining the equivalence point : we successively
add small volumes of base, measure pH after each addition, and plot the titration curve, from which we

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may find Vbase at the inflection point (the equivalence point). Moles of acid in the original aliquot is
calculated as follows:
4. moles acid = Vbase at inflection point x M base
Amino acids are molecules that contain both a base site (an -NH2 group) and an acid site (a -
COOH group). Individual acids differ only in the identity of the group, -R.
When an amino acid is dissolved in water, the proton from the -COOH group transfers to the -NH2 end
of the molecule, because the NH2 group is a stronger base than -COO-. The resulting structure is called a
Zwitterion.
A titration of the Zwitterion with standard NaOH would provide the Ka value for the -NH3+ acid,
which would be expected to be similar to that of NH4+ (pKa = 9.25). However, it would be nice to also
obtain the Ka value for the -COOH acid. It is possible to generate this acid in solution by adding strong
acid to the Zwitterion. The strong acid transfers a proton to the -COO- base of the Zwitterion, resulting
in a cation.
Titration of a solution of this cation with standard NaOH should then yield two equivalence
points, one for each acid. It should thus be possible to measure both desired Ka values.

APPARATUS: pH meter, beaker, burette, pipette, glass rod, spatula.

REAGENT AND MATERIALS: Potassium hydrogen phthalate, glycine, alanine, HCl, NaOH,
phenolphthalein.

EXPERIMENTAL PROCEDURE:
1 Prepare 100 mL 0.1 M KHP (Potassium hydrogen phthalate) solution.
2 Standardize the supplied ~0.1M NaOH solution against KHP solution using phenolphthalein
indicator (three results).
3 Amino acid titration
a) Transfer exactly 10 mL of the supplied protonated amino acid solution to a clean 100 mL beaker.
b) Add 15 mL of distilled water to the beaker so that the total volume of the amino acid solution is 25mL.
c) Place the beaker on the top plate of a magnetic stirrer. Place a 1-inch stir bar in the beaker. Rinse the
pH electrode and submerge it in the solution containing protonated amino acid. Make sure that the
tip of the electrode is clear of the magnetic stir bar in the beaker, then start the stirrer. The rotation
rate should be reasonably fast, but not so vigorous that splashing of the solution occurs.

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d) Record the initial pH of the solution. Initiate the pH titration by adding 0.5 mL of NaOH solution
from burette.
e) Continue adding NaOH 0.5 mL at a time, recording pH and total volume of NaOH added after each
addition, until the total added volume of base is about 80% of the amount required to titrate the -
COOH proton. (IMPORTANT NOTE: Some amino acids have two -COOH groups, the normal
alpha one, and another one in the R group. For these amino acids, twice as much NaOH will be
needed to reach the first equivalence point as for most amino acids.) At this point, add the NaOH in
smaller increments of first 0.20, then 0.10 mL. Continue adding NaOH incrementally until you are
past the -COOH equivalence point. Go back to adding NaOH 1.0 mL at a time until you have added
80% of the amount required to titrate the -NH3+ proton. At this point, add smaller increments as
above until you are at least 2 mL past the second equivalence point. When finished, discard the
solution. Rinse the pH electrode with distilled water till pH meter reading is approximately equal to
that of distilled water. Leave the pH electrode in beaker of distilled water and turn the meter off.

RESULT:
Table 1. Preparation of 100 mL standard 0.1 N KHP solution
Weight taken (g) Weight to be taken (g) Strength of KHP solution

Table 2. Standardization of NaOH solution using standard KHP solution

Sl. Volume of Burette reading (mL) Average Strength of
No. KHP (mL) Initial Final Difference volume (mL) NaOH solution

Table 3. Titration of amino acid solution using standard NaOH solution

Volume of amino acid (mL) =
Sl. No. Volume of NaOH (mL) pH

CALCULATION :

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DISCUSSION :
Titration of Simple Amino Acids:
Amino acids are more complicated than simple weak acids since amino acids have at least 2
ionizing groups. Glycine, for example, has both a carboxylic acid and an amino group that can ionize: If
we dissolve the free base of glycine in pure water (ie neutral pH), it will ionize by protonating itself. The
equilibrium is far to the right so most of the glycine is in the charged form called the zwitterion and
glycine is still neutral because the +ve charge is netualized by the -ve charge. Glycine is always in the
zwitterion form at neutral pH.

Glycine

Now if we put Glycine at an acid pH where it is fully protonated (ie. it has all the protons bound to it
which it bind), we can titrate it to reveal its 2 pK values for the alpha-carboxylic acid group and the
alpha-amino group.

From the pK values, the pI (called the isoelectric point or the place where Glycine has no net charge)
can be calculated
pI = (2.3 + 9.6)/2  6 ; (pK1 = 2.3, pK2 = 9.6) Glycine is neutral at pH 6; it has no net charge here.
A few amino acids are classified as triprotic. This is because, in addition to the ionizable protons
of the -COOH and -NH3 groups, they also have a dissociable proton in their R group. Although
triprotic amino acids can exist as zwitterions, under physiological conditions these amino acids will be
charged. If the net charge under physiological conditions is negative, the amino acid is classified as an
acidic amino acid because the R group has a proton that dissociates at a pH significantly below pH 7.
The remaining triprotic amino acids are classified as basic amino acids due to a) their having a net
positive charge under physiological conditions and b) an R group dissociable proton with a pKa near or
greater than pH 7. Titration curves for triprotic amino acids generate the same information as those for

Page | 13
the diprotic amino acids. The pI for a triprotic amino acid can be determined graphically, although this is
somewhat more challenging.

Glutamic Acid Lysine

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 EXPERIMENT 4

STUDY OF THE DISTRIBUTION OF BENZOIC ACID BETWEEN TOLUENE & WATER

THEORY:
When benzoic acid (A) is distributed between toluene and water then benzoic acid is almost
completely dimerised in the toluene layer but in the aqueous layer it remains mostly as single
molecules without any significant dissociation. The two equilibria occur as given below:
KD K
A(water) ↔ A (Toluene) and 2A(Toluene) ↔ A2 (Toluene)

So, KD = [A]b / [A]w and K = [A2]b / [A]b2

Let Cb = total molar concentration of benzoic acid in toluene layer.
& Cw = total molar concentration of benzoic acid in water layer.
So, Cb = [A]b + 2[A2]b & Cw = [A]w
Therefore,
Cb / Cw = ([A]b / [A]w) + 2([A2]b / [A]w)
= KD + 2 x ([A2]b / [A]b2) x ([A]b2 / [A]w2) x [A]w
= KD + 2K KD2 Cw ……………………………………………. (1)
So, if we plot (Cb / Cw) vs. Cw, we will have a straight line with positive intercept (≡ KD) and
positive slope (≡ 2KKD2). From slope and intercept we will find the KD & K at experimental
temperature.
PROCEDURE:
1. Record the room temperature before and after the experiment and average it.
2. Prepare four mixtures using following composition table

COMPOSITION TABLE

Bottle No. Toluene (ml) Distilled Water (ml) Benzoic Acid (g)
I ~25 ~200 1.0
II ~25 ~200 1.5
III ~25 ~200 2.0
IV ~25 ~200 2.5
3. Prepare 100 ml ~0.1(N) oxalic acid solution by accurate weighing.
4. Prepare 500 ml 0.05(N) NaOH solution and standardize it with oxalic acid solution.
5. Titrate 5 ml Toluene layer (twice for each bottle) with NaOH solution for four bottles.
6. Titrate 50 ml aq. layer (twice for each bottle) with same NaOH solution for four bottles.
7. Calculate Cb, Cw and (Cb / Cw) for each bottle.
8. Plot (Cb / Cw ) vs. Cw and find KD & K from the straight-line plot.

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 EXPERIMENT 5

DETERMINATION OF MOLECULAR WEIGHT OF A POLYMER BY OSTWALD VISCOMETER

THEORY: The viscosity co-efficient (η) of a liquid can be measured using Ostwald viscometer with the
help of Poiseuille’s equation (applicable for streamline flow of fluid).
𝜋(Δ𝑝)𝑟 4 𝑡 𝜋(ℎ𝜌𝑔 )𝑟 4 𝑡
𝜂= ≡ (symbols have their usual meaning)
8𝑙𝑣 8𝑙𝑣

If we use same viscometer (for same ‘r’ & ‘l’) for same volume of two liquids (for same ‘v’ & ‘h’) at
same place (for same ‘g’) and temperature then
η1 / η2 =ρ1t1/ρ2t2
 η1 = η2 ×(ρ1t1/ρ2t2)
Hence, we can use the above equation (1) to measure the η1 (i.e., viscosity co-efficient of liquid 1) by
using the known value of η2. So it is a relative method.

The viscosity of a polymer solution (η) is higher than that of the pure solvent (η0) at a specified
temperature and the increase in solution viscosity on dissolving the polymer in the solvent is a function
of both molecular weight and concentration of the polymer solute
The ratio of the viscosity of a solution (ηs) to the viscosity of the pure solvent called relative viscosity ηr
is given by
𝜂𝑠 𝑑𝑠 𝑡𝑠
𝜂𝑟 = =
𝜂0 𝑑0 𝑡0
And for solutions of low concentrations, densities of solutions, ds are almost equal to the density of
solvent d0. Therefore,
𝑡𝑠
𝜂𝑟 =
𝑡0
Thus ηr is an easily measurable parameter for solutions of polymers. Increment in viscosity for any
solution would be (ηs – η0).

For a polymer solution, the specific viscosity, ηsp, is given by

𝜂𝑠 − 𝜂0 𝜂𝑠
𝜂𝑠𝑝 = = − 1
𝜂0 𝜂0
𝑡𝑠
𝜂𝑠𝑝 = 𝜂𝑟 − 1 = − 1
𝑡0
For polymers, we go a step further and divide ηsp by the concentration of the solute in solution in terms
of grams of solute per 100 ml of solution and we call this parameter reduced viscosity ηred for the
solution.
𝜂𝑠𝑝
𝜂𝑟𝑒𝑑 =
𝑐
The values ηr and ηsp change rapidly with change in concentration but the ηred values of solutions
change less and regularly or linearly. Thus a plot of ηred versus concentration (g/100ml) is very nearly a
straight line (Fig. 1). For this linear relationship, we can write

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 𝜂𝑠𝑝
𝜂𝑟𝑒𝑑 = = 𝑚𝑐 + 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑐
As for a straight line graph, m is the slope of the line and the addition constant is the intercept on the
reduced viscosity axis and is called the intrinsic viscosity of the solution and is given by the symbol [η]
𝜂𝑠𝑝
𝜂 = lim
𝑐=0 𝑐
For any value of c, for the solution
𝜂𝑠𝑝
𝜂𝑟𝑒𝑑 = = 𝑚𝑐 + 𝜂
𝑐
For polymers, the intrinsic viscosity values can be obtained from the ηred versus c graphs. This in turn is
related to molar masses (M) of straight chain polymers by a simple equation,
𝜂 = 𝐾 𝑀𝑎 [Mark-Houwink Equation ].
which is more valid when molar masses are above 10,000. Here K and a are constants for a given pair of
polymer and the solvent at a specified temperature. The values of the exponent constant `a’ also called
the shape factor for a randomly coiled flexible linear chain polymer molecules range from 0.5 to 0.8. It
is most often 0.7 but for rigid rod-like polymer molecules its values may rise to 20. The uncertainty in
values of K and a make viscosity average molar masses somewhat imprecise and different from the
number average and weight average molar masses. But the results still remain useful in practice.

Fig. 1 Intrinsic Viscosity

EXPERIMENTAL PROCEDURE:

1. Weigh 4.0g of dry polyvinyl alcohol on a watch glass.

2. Take about 200 mL of hot distilled water in a beaker. Gradually spread the weighted amount of
polymer in small lots on the surface of hot water and stir slowly without forming bubbles of foam.
3. When the whole of the polymer quantity is thus dissolved, cover the solution and allow it to cool to
room temperature.
4. Transfer the cooled solution slowly to a 250 mL volumetric flask along the side wall to minimise
formation of bubbles. Thermostat the solution.
5. Rinse the beaker with small lots of distilled water and transfer these rinsings to the volumetric flask
till the solution volume is made up to the mark. This is the master solution.
6. Prepare six other solutions whose concentrations are 80%, 60%, 40%, 30%, 20% and 10% of the
master solution, in 50 mL volumetric flask and find the time of flow for each solution with a
Ostwald viscometer.

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 Fig. 2. Ostwald Viscometer

USING OSTWALD VISCOMETER:

1. Adjust the thermostat at certain temperature (preferably 35 ºC) and record its temperature.
2. Clean the viscometer with chromic acid and wash thoroughly with distilled water. Clamp the
viscometer vertically in the thermostat. Introduce a definite volume of water into the tube, by a
graduated pipette, so as to fill the bend of the tube and at least half of the bulb of the wider tube.
When the water in the viscometer will attain temperature of the thermostat then draw the water
through the narrow tube above the upper mark (by applying manual suction through the rubber
tube). Then allow the water to flow down through the capillary in the viscometer. Start the
stopwatch just when the meniscus will pass the upper mark (A in Fig.2) and stop when it will
pass the lower mark (B in Fig.2). Repeat it for at least three times and each time note the flow
time (t2) in second and take its mean. Take out the viscometer, wash with acetone, dry. Clamp it
again in the thermostat and introduce same volume of experimental liquid. Repeat same
procedure (as of water) and note the flow time (t1) in seconds.

Observations:
Temperature of Thermostat = °C
Solvent: Solute:
Values of constants: K= a=

S.No. Concentration Average flow ηr ηsp ηred

(g/100mL) time (seconds)

Plot the ηred values versus concentration (g/100 mL). Obtain the intrinsic viscosity value [η].

Calculating molar mass

𝜂 = 𝐾 𝑀𝑎
log 𝜂 = log 𝐾 + 𝑎 log 𝑀
log 𝜂 − log 𝐾
log𝑀 =
𝑎
log 𝜂 − log 𝐾
𝑀 = 𝐴𝑛𝑡𝑖𝑙𝑜𝑔
𝑎

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 EXPERIMENT 6
DETERMINATION OF THE RATE CONSTANT FOR THE ACID-CATALYZED HYDROLYSIS OF
ETHYL ACETATE BY TITRIMETRIC METHOD

AIM: To determine the rate constant for the acid-catalyzed hydrolysis of methyl acetate.

THEORY: Methyl acetate undergoes hydrolysis, in the presence of an acid (HCl, for example), to give
acetic acid and methyl alcohol.

In the presence of an acid, this reaction should be of second order, since two molecules are reacting. But,
it is found to be first order. This may be explained in the following way: The rate of the reaction is given
by

where k’ is the rate constant (or specific rate constant).

Since water is present in large excess, its active mass (molar concentration) virtually remains constant
during the course of the reaction. Therefore, its active mass gets included in the constant, and the above
equation reduces to:

Thus, the rate of the reaction is determined by one concentration term only (that is, by a single power of
the concentration term only). Hence, the reaction is first order. Such reactions are also referred to as
pseudo first order reactions. The progress of the reaction (hydrolysis of ester) is followed by removing a
definite volume of the reaction mixture, at definite intervals of time, cooling it in ice, and titrating the
acetic acid formed against alkali, which has already been standardized. The amount of alkali used is
equivalent to the total amount of hydrochloric acid present originally and the amount of acetic acid
formed in the reaction.
The amount of acetic acid formed (x), at definite intervals of time (t), can be obtained. The amount of
acetic acid formed, at the end of the reaction, is equivalent to the initial concentration (a) of the ester.
Suppose the volumes of the sodium hydroxide solution (titre value) required for neutralization of 5 mL
of the reaction mixture are:
(i) at the commencement of the reaction is Vo
(ii) after time (t) is Vt
(iii) at the end of the reaction is V∞
Then: x (amount of acetic acid formed after time) is proportional to (Vt -Vo).
a (initial concentration of ester) is proportional to (V∞ -Vo).
[a – x] (concentration of ester present after time t) is proportional to (V∞ -Vo) - (Vt -Vo) = (V∞ -Vt)
The first order rate expression given by:

;
Hence, the rate constant (k1) could be calculated.

Page | 19
PROCEDURE:
1. Prepare 100 mL 0.1 N oxalic acid, 100 mL 0.1 N NaOH, and 100 mL 0.5 N HCl solutions.
2. Standardize NaOH solution using standard oxalic solution and determine exact strength of NaOH.
3. Take 50 mL of HCl solution in a 250 mL bottle and add 5 mL of methyl acetate using a pipette and
note the time of half-discharge and mix uniformly.
4. Immediately after mixing, withdraw, using a pipette, 2 mL of an aliquot from the reaction mixture
into 10 mL of ice-cold distilled water in a conical flask, titrate the reaction mixture against NaOH
solution, using phenolphthalein as indicator. This titre value corresponds to Vo.
5. Repeat step 4 at time intervals of 5, 10, 15, 20, 30, 45 minutes. Each titre value corresponds to Vt .
6. Place the remaining solution on a hot water-bath and heat at 60 oC for 20 minutes. Cool to room
temperature, follow step 4. This titre value corresponds to V∞.
7. Plot log [(V∞ -Vo)/(V∞ -Vt)] vs. Time (t) and draw the best straight line passing through the origin and
the experimental points and find k1 from the slope.

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 EXPERIMENT 7

Determination of the Degree of Hydrolysis and the Hydrolysis Constant by Potentiometry

Aim: To determine the degree of hydrolysis and the hydrolysis constant of anilinium hydrochloride by
potentiometry.
Apparatus : Potentiometer, Platinum electrode and calomel electrode.
Chemicals : Anilinium hydrochloride, quinhydrone,
Principle: Anilinium hydrochloride, C6H5NH3+Cl- when dissolved in water, ionizes to form C6H5NH3+
and Cl- ions, and the cation establishes the following hydrolytic equilibrium.
C6H5NH3+ + H2O C6H5NH2 + H3O+
The equilibrium constant for this hydrolytic process is called the hydrolysis constant for the salt and is
given by, Kh = (𝑎𝐻 +  𝑎𝐵 )/ 𝑎𝐵𝐻 + , where 𝑎𝐻 + is the activity of the free acid (H3O+); 𝑎𝐵 is the activity
of the free base (C6HsNH2)· and 𝑎𝐵𝐻 + is the activity of the unhydrolysed salt (C6H5NH3+Cl-). However,
for dilute solutions, we may replace activities by concentration terms;
Hence,
Kh = [H+] [B ] / [BH+] (1)
Hydrolysis constant can also be related to the dissociation constant, Kb, of the base through the ionic
product of water, Kw as
Kh = Kw / Kb (2)
If c equivalents of the salt is dissolved in a litre of water, c equivalents each of free base and free acid
will be formed due to hydrolysis ( is the degree of hydrolysis). Thus, the pH of the solution may be
related to the degree of hydrolysis as,
pH = - log [H+] = - log (c)
Hence, by measuring the pH of the solution, c can be calculated from which the degree of
dissociation,  can be obtained at a given concentration.
Also, expressing K, in terms a. using Kh = c2/( 1 – ), the hydrolysis constant can be calculated.
Substituting for Kh in equation (2) and taking Kw = 1.0 x 10-14 at 25°C. the dissociation constant of the
base, Kb can be evaluated.

Procedure:
Prepare an N/10 aniline hydrochloride solution by dissolving appropriate quantity of the substance in
distilled water (100 mL). From this stock solution, dilute appropriately and get M/20, M/50 and M/100
solutions. Then construct the following cell:
Pt|0.1 M Aniline Hydrochloride, Quinydrone // Calomel
Determine the potential of the cell. Repeat the experiment with each of the other solutions.
Treatment of Data:
1. pH is given by pH = (-Eobs + EQH + Ecal) / 0.0591 where EQH = 0.6996 V and Ecal = - 0.242 V
(Oxidation Potential). From this relation, pH of the solution can be calculated.

Page | 21
 2. As pH = - log [H+] = - log (c), pH = - log c - log , the degree of hydrolysis  can be
calculated at every given concentraion.
3. From , calculate the hydrolysis constant using the relation, Kh = c2/(1 - )
4. The Dissociation constant, Kb can be calculated from the relation Kb = Kw/Kh

Tabulation:
C6H5NH3+Cl- Eobs(V) pH  Kh Kb
N/10
N/20
N/50
N/100

Mean Kh = - ... , Mean Kb = ...

Result:
Report the values of hydrolysis constant (Kh) and dissociation constant (Kb).

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 EXPERIMENT 8

DETERMINATION OF THE pKIn VALUE OF AN ACID-BASE INDICATOR BY SPECTROPHOTOMETRIC

METHOD

THEORY: Acid–base indictaors are weak acids or bases having distinctly different colours in acidic and
alkaline solution, and by virtue of change of colour they indicate the end points of acid-base titrations.
The ionization equilibria of a weak acid indicator (HIn) may be represented according to,

HIn ↔ H+ + In- (1)

Acidic form Alkaline form
for which the ionization constant (KIn) in dilute solution may be defined as the concentration quotient (2)
[H + ][In - ]
KIn = (2)
HIn
where, [ ]’s represent the molar concentrations of the respective species. Transforming the equation (2)
in logarithmic form one obtains,
[In - ]
pH = pKIn + log (3)
[HIn]
(where, pKIn = -log10 KIn and pH = -log10 [H+] in dilute solution).
Thus, if a fixed amount of the indicator is placed in the same volume of a series of buffer solutions of
different known pH values, the ratio, [In-]/[HIn], will increase with increase of pH. If the values of the
ratio at different pH are determined by measuring the colour intensity of the indicator solutions then the
pKIn value of the indicator can be found out if the pH of the buffer solutions is known.
If the alkaline form of the indicator (In-) absorbs at a selected wavelength and Beer’s law is obeyed in
the range of concentration of the indicator used, then the absorbance (A) of the indicatoe solution at a
particular pH will be proportional to its concentration, provided the acid form (HIn) does not absorb at
this wavelength.
A =  [In-] l (4)
In a strongly alkaline solution, HIn is practically absent, and the absorbance (A) will correspond to the
total concentration (TIn) of the indicator.
A =  [TIn] l (5)
Where,  = molar extinction coefficient of In and l = optical path length in cm.
-

Mass balance equation of the indicator is,

TIn = [HIn] + [In-] (6)
 [HIn] = TIn - [In ] -
(7)

From (5) – (4) one obtains,

 A - A  = [H ] (8)
In
l
 A  = [In-] (9)
l
Substituting these values of HIn and In- in equation (3) one obtains,

Page | 23
  A 
pH = pKIn + log10   (10)
 A - A 

A and A may be measured colourimetrically. Therefore, by plotting log10 [A/(A - A) ] against pH of the
buffer solutions a straight line of slope =1 will be obtained, of which the intercept on the pH axis will
give pKIn .

PROCEDURE:

1. Prepare 100 mL of exact 0.4 N acetic acid (pKH= 4.74 at 25oC) and 100 mL of exact 0.4 N
NaOH solutions separately by usual procedure.
2. Take 8 hard glass test tubes of uniform dimensions and label them from 1 to 8. Prepare the
following series of solutions by proper mixing (experimental pH values may be obtained from
chart below, or, may be determined using a pH meter).
Test tube Volume of 0.4 N Volume of 0.4 N Volume of Water pH (Expt.
acetic acid (mL) NaOH (mL) (mL)
1 5.0 0.5 4.5 3.72
2 5.0 1.5 3.5 4.27
3 5.0 2.5 2.5 4.63
4 5.0 3.5 1.5 4.99
5 5.0 4.5 0.5 5.57

In test tube numbers 6 to 8, Take 2.5 mL of 0.4 N NaOH and add 7.5 mL of water.
3. Add a few (~ 3-4) drops of bromocresol green indicator to test tube number 6 using a dropper.
4. Set spectrophotometer at 570 nm, adjust the transmittance of water to 100%.
5. Measure the transmittance of the solution in test tube 6. If the transmittance is below 15% (i.e.
Absorbance is above 0.82), take test tube 7 and add fewer number drops of the indicator to it and
measure the transmittance. In this way by adjusting the number of drops of the indicator, adjust
the transmittance of the alkaline form between 25 to 15 % (absorbance is above 0.60 but below
0.82) using test tube numbers 6 to 8 as required.
6. Add the same number of drops of the indicator as adjusted in step 5 to each of test tubes 1 – 5
and measure their transmittance.
7. Calculate the absorbance (A) values of solutions 1 - 5 and the absorbance (A) of the alkaline
solution of the indicator (6, 7 or 8) using the relation:
A = log (100/T %) = 2 – log T
8. Plot log10 [A/(A - A)] against pH and draw the best straight line of unit slope passing through
the experimental points, using the same scale for pH and log10 [A/(A - A)] axis. Find pKIn from
the intercept on the pH axis.

CONCLUSION: pKIn of bromocresol green is .............

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