Experiment No.

1
Measurement of porosity, average pore size and pore size distribution by
using Mercury Porosimeter for porous powder and solid samples
Objective:

To measure the porosity, average pore diameter and pore size distribution of porous solid

samples.

Introduction:
The frication of void space or empty space in a porous solid material is represented by porosity
of that material. The fraction of the volume of voids over the total volume gives the value of
Porosity.

The

term

porosity

including pharmaceutics, ceramics, metallurgy,

is

used

in

multiple

materials, manufacturing, earth

fields

sciences, soil

mechanics and engineering. For any porous solid or powdered sample porosity is considered as
one of the very important property.
Mercury is ideal as an intrusion liquid in the porosimetry method because it does not wet nor
react with most materials. By measuring the amount of mercury intruded into the pores of a
powdered or solid sample, the porosimeter give valuable data from which pore size, volume and
distribution can be determined. Normally in porous solid samples different pores are present e.g.
through pores, cross linked pores, blind pores and closed pores (as shown in the figure below).
Closed pores are not accessible to mercury. Hence, pororsimetry does not account for closed
pores.

Figure 1 Schematic representation of different pores(Giesche et al.).

Theory:
Mercury porosimetry is based on the capillary law governing liquid penetration into small pores.
This law, in the case of a non-wetting liquid like mercury and cylindrical pores, is expressed by
the Washburn equation:

1
D ( )4 cos ..(i)
P
Where,
D is the pore diameter,
P is the applied pressure,
is the surface tension,
and is the contact angle, all in consistent units. The volume of mercury V penetrating the
pores is measured directly as a function of applied pressure. This P-V information serves as a
unique characterization of pore structure.

Pores are rarely cylindrical; hence the above equation constitutes a special model. Such a
model may not best represent pores in actual materials, but its use is generally accepted as the
practical means for treating what, otherwise, would be a most complex problem. The surface
tension of mercury varies with purity; it is usually accepted value and the value recommended
here is 485 dynes/cm. The contact angle between mercury and the solid containing the pores
varies somewhat with solid composition. A value of 130 is recommended in the absence of
specific information to the contrary.

Mercury extruding from pores upon reduction of pressure is in general accord with the above
equation, but indicated pore diameters are always offset toward larger diameters. This results
from equivalent volumes of mercury extruding at pressures lower than those at which the pores
were intruded. It is also commonly observed that actual pores always trap mercury. The first
phenomenon is usually attributed to receding contact angles being less than advancing ones. The
second is likely due to pore irregularities giving rise to enlarged chambers and inkwell

structures. These phenomena give rise to hysteresis phenomena, i.e., distinct intrusion and
extrusion P-V curves.

Figure 2 Penetrometer having sample in it and filled with mercury.

For mercury porosimetry the sample holder is called the penetrometer (as shown in the figure).
After loading the sample in the porosimeter, the stem and penetrameter is filled with mercury.
Further the mercury is pressurized gradually in low pressure and high pressure chamber
respectively. The decrease in mercury volume is measured after each time step. The outer surface
of the stem of the penetrameter is coated with cadmium. The mercury inside the stem works as
anode and the cadmium works as cathode. The machine internally measures the intrusion volume
after each step based on the electrical transport in the stem.

Instruments required:
i.

Hot air oven

ii.

Weighing balance

iii.

Pycnometer

iv.

Porosimeter

Chemicals required:
i.

Mercury

ii.

2-Propanol-for cleaning the sample holder

Results: (for granular activated carbon samples)

1. Pycnometer data:
Skeleton density of GAC= 1.54 g/cc
Skeleton volume of the sample= 4.72 cc
Total volume of the sample= 13.6cc
Considering 60% inter particular gap sample volume will be= 5.44 cc
Porosity of the sample = 13.23%

2. Pycnometer and BET data:

True density of GAC= 1.54 g/cc
True volume of the sample= 0.65 cc/g
Pore volume calculated from BET data= 0.19 cc/g
Porosity of the sample = 22.06%

3. Porosimeter data:
Pore size distribution

Differential intrusion( ml/g/A)

1E-5

1E-6

1000

10000

100000

Pore size(A)

Porosity = 8.4182 %
Average Pore Diameter = 6299 A

Comparison:
Sample
name
GAC

Average Pore
diameter ()
6299

Porosity(%)

Porosity(%)

Porosity(%)

(Pyncometer)

(Pyncometer& BET)

(Porsimeter)

13.23

22.6

8.4

Analysis & Discussions:

Pycnometer measurement gives Skeleton density value of 1.54 g/cc for GAC samples. Based on
the pycnometer and BET data the porosity is around 22.6 %.The porosity of the sample is around
8.4 % measured by porosimeter. The pore diameter varies in between 300-30, 0000 . The
average pore diameter calculated by the machine is found to be 6299 . The differences in
porosity values are different in both the measurements due to following reasons:
Porosimeter considered pore diameter up to 300 . Hence pores size below 300 is not
accounted in the porosity calculation. As a consequence we are getting lesser porosity
values compared to pycnometer data.
As mentioned earlier, dead end pores are not accounted in porosimeter measurement.

References:
Herbert Gieche, 2006, Mercury Porosimetry: a General (Practical) overview, Part. Part. Syst.
Charact. 23, 1-11.

CL 610 (Experimental Methods)

Experiment 2

Karl Fischer volumetric titration

Instructors
Prof. RajdipBandyopadhyaya
Prof. Y S Mayya
T.A. Incharge
Pushkar Ballal

Group: M1
Member 1(133010001)
Member 2 (133010002)

Experiment Date:

Submission Date:

Department of Chemical Engineering

I.I.T. Bombay

Measurement of moisture content using Karl Fischer volumetric

titration in a sample
Aim:
To determine the moisture content of given samples by Karl Fischer volumetric
titrationtechnique.
Introduction and Principle:
Karl Fischer titration is a widely used analytical method for quantifying water content in a
variety of products. The fundamental principle behind it is based on the Bunsen Reaction
between iodine and sulphur dioxide in an aqueous medium.

I2+ SO2+ 2H2O 2HI + H2SO4

Karl Fischer discovered that this reaction could be modified to be used for the determination of
water in a non-aqueous system containing an excess of sulfur dioxide. He used a primary
alcohol (methanol) as the solvent, and a base (pyridine) as the buffering agent. The reagents
most frequently used today are pyridine-free and contain imidazole or primary amines instead.
Apparatus and Instrument:

Glassware Beakers, Titration flask with magnetic stirrer

Karl Fischer Titrator, Weighing balance

Chemicals:

Karl Fischer reagent,

Karl Fischer grade dry methanol

Di-sodium tartrate dihydrate (purified)

Samples (KCl and Glycerol)

Theory:
Volumetric Karl Fischer titration requires the determination of the titer of the Karl Fischer
reagent. It is usually quoted in mg of water per ml (mgH2O/ml of KF reagent) of Karl Fischer
reagent. In volumetric Karl Fischer, iodine is added mechanically (directly as a component of KF
reagent) to a solvent containing the sample by means of a burette during the titration. Water is
quantified on the basis of the volume of Karl Fischer reagent consumed.

Volumetric titration is best suited for determination of water content in the range of 0.1% to
100%.
Volumetric Karl-Fisher titration: The volumetric Karl-Fisher titration takes advantage of the fact
that iodine contained in the Karl-Fisher reagents reacts quantitatively and selectively with
water as shown below,

I2+ SO2 + H2O + 3Base + CH3OH 2Base HI + Base HSO4CH3

The quantification is based on the stoichiometric principle that 1 mole of iodine (254g) reacts
with 1 mole of water (18g). Water and iodine are consumed in 1:1 ratio in the above reaction.
Once all of the water present is consumed, the presence of excess iodine is detected
Volta metrically by the titrator indicator electrode. The titration systems employ controlled
current-voltage detection (constant-current polarization voltage detection). A constant current
of 1-30A is applied to two platinum electrodes. If the titration solution has a relatively high
water content, a polarization voltage of 300-500mV will be produced. As the Karl Fischer
titration continues and the end-point approaches, the voltage suddenly drops to 10-50 mV.
With volumetric analysis, the endpoint is deemed to have been reached after the voltage has
remained at this level for a specific period of time. In commercially available titration systems,
the period is 30-60 seconds.
The amount of water present in the sample is then calculated based on the concentration of
iodine in the Karl Fisher titrating reagent (i.e., titer) and the amount of Karl Fisher Reagent
consumed in the titration.

Procedure:
Step 1: Place approximately 40-50ml of KF-grade dry methanol into the titration flask which
hasbeen well dried in a hot-air oven overnight.

Step 2: Fill the desiccant tubes with appropriate desiccants e.g. silica gel and molecular sieves
and place them at appropriate positions on the titration flask. Also, attach the KF dispenser
onthe flask.

Step 3: Carry out a pre-titration/Neutralization so as to eliminate all the traces of water that
may have been added along with the solvent. It is however, not necessary to read the amount
of KF reagenttitrated at this time.

Step 4: Add a fixed quantity of Di-sodium tartrate dihydrate into the flask (note the amount
taken) and carry out the titration so determine the titer of the KF reagent being used for
theexperiment.

Step 5: Add the sample containing unknown amount of moisture to the flask and run the
titration.Repeat the titrations for each sample thrice. Note the amount of sample taken in each
run.The Karl Fischer reagent, the titer of which (mgH2O/ml) has now been determined,
istitrated until the end-point is reached. The end-point is detected electrically by means of
adetection circuit built into the titration system.

Step 6: Note the readings and calculate the moisture content of the given samples.

Calculation:
Concentration factor= 5.4102 (mg of H2O/ml of KF)
Leak rate = 10 L/min = 10 10-3 ml/min
Weight of Disodium tartrate dihydrate used in standardization = 107.86 mg
Blank volume = 0 ml
The percentage of moisture can also be calculated from the given formulae
%
=

100

)/

where S = Strength of KF reagent(mg/ml)

W = Weight of Sample (mg)
KF = Volume of KF consumed during titration (ml)
B = Blank volume entered(ml)
L = Leak Rate (l/min)
Sample calculation by formulae:
1st reading KCl %

( .

= 1.06402

Similarly find out % moisture for other reading and Glycerol sample also. Calculated data are
shown in Table 1 (KCl) & Table 2 (Glycerol)

Table 1:Potassium chloride(KCl) Data:

Sr.
No

Weight, W
(mg)

Volume of Karl
Fischer Reagent
Dispensed, KF
(ml)

1
2
3

112.87
90.00
95.25

0.222
0.287
0.246

1.064
1.731
1.400

1.064
1.725
1.397

-0.002
0.339
0.202

0.239

% moisture
(from
experiment)

% moisture
(from
calculation)

% error in
calculation

Coefficient
of
Variation

10.720
9.045
10.706

10.720
9.045
10.706

0.004
0.002
0.003

0.095

% moisture
(from
experiment)

% moisture
(from
calculation)

% error in
calculation

Coefficient
of
Variation

Table 2: Glycerol Data:

Sr.
No

Weight, W
(mg)

Volume of Karl
Fischer Reagent
Dispensed, KF
(ml)

1
2
3

221
96
142

4.379
1.605
2.810

Conclusion:
The average % moisture in Sample1 (KCl) : (1.064 + 1.731 + 1.4 )/3 = 1.398
The average % moisture in Sample2 (Glycerol) : (10.720 + 9.045 + 10.706 )/3 = 10.157
The coefficient of variation is little high in case of solid sample but significantly low in liquid
sample. The reason behind this may be due improper mixing of solid sample granular particle in
solution.
Karl Fischer method widely used because of high accuracy and precision. The advantages
include small sample quantities required, easy sample preparation, short analysis duration,
independent of presence of other volatiles and suitability for automation.

Thin film formation by spin coating and thickness measurement by Ellipsometry

Objective
The objective of this experiment is to make a thin- film of polymer by spin coating and measure
thickness of the polymer thin film by ellipsometry.

Introduction
Optical measurement techniques are normally non- invasive. These techniques do not involve any
physical contact with the surface and do not destruct the surface. This is a lucrative property of a
measurement technique on nanoscale. Several optical measurement techniques based on the
reflection or transmissions of light from a surface are interferometry, reflectometry and
ellipsometry. There are three different types of ellipsometry, namely scattering, transmission and
reflection ellipsometry. This experiment deals with the reflection ellipsometry only. One of the
applications is in the semiconductor industry, which deals with a thin layer of SiO 2 on a silicon
wafer. To ensure the thickness of this film, process engineers use ellipsometry to measure the
film thickness of sample wafers. Ellipsometry is known for the high accuracy when measuring
very thin film, with a thickness in the Angstrm scale or below. Other applications of
ellipsometry involve determination of the refractive index, the surface roughness or the
uniformity of a sample and more.
Instruments required
i.

Ultra-Sonicator

ii.

Spin coater with vacuum pump

iii.

Ellipsometer
Che micals required

i.

Polystyrene

ii.

Toluene

iii.

Silicon wafer (as substrate)

Theory

a) Spin coating
Spin coating is one of the standard methods for obtaining uniformly thick dielectric films.
The substrate on which the desired material is to be coated is mounted on the spin coater and
held by vacuum. The polymer dissolved in a suitable volatile solvent or synthesized in solution is
poured on the substrate and it is spun at high speeds of the order of few thousand rpm. Clearly
the film thickness will increase with the increase in concentration in solution and will reduce
with the increase in spin speed. But other factors like viscosity, volatility of the solvent used,
humidity of the environment, etc. also matter.
The mechanism of film formation can be split into 2 stages. The first stage involves the
interplay between the centrifugal and viscous forces followed by evaporation. Meyerhofer (1978)
predicted the final thickness, hf in terms several solution parameters as given by the following
equation:

e
hf x

2(1 x) K

Where e and K are the evaporation and flow constants defined below and x is the effective solid
constant of the solution.

eC
K

2
3

Where is the rotation rate, is the density of the solution, is its viscosity and C is
a proportionality constant that depends on whether airflow above the surface is laminar or
turbulent and on the diffusivity of the solvent molecules in air.
Substituting e and K in the equation for hf we can see that the thickness varies linearly as the
inverse square root of spinning speed, when other parameters remain the same.

hf

cons tan t

This is the relationship which we will verify experimentally.

b) Ellipsometry
Ellipsometry is primarily used to determine film thickness and optical constants. However, it is
also applied to characterize composition, crystallinity, roughness, doping concentration, and
other material properties associated with a change in optical response.
The polarization change is represented as an amplitude ratio, , and the phase difference, . The
measured response depends on optical properties and thickness of individual materials.
Ellipsometry measures the interaction between light and material.
When light enters a different medium the dielectric constant of the medium changes the electrical
field strength. As light is electromagnetic wave, in a different dielectric medium, it changes its
velocity for which it changes its trajectory and wavelength. When a polarized light beam falls at
the interface of two dielectric media, its electric vector can be separated into two orthogonal
components parallel and perpendicular to the plane of incidence (p and s components
respectively). When these components traverse through the medium and undergo reflection and
refraction, there is a change in the polarization of the light which is a function of amplitude ratio
and phase difference of these components. The change in polarization is the ellipsometry
measurement, commonly written as:

tan exp(i)
Where tan

Rp
Rs

Rp
Rs

which again can be derived from Maxwells theory as a function of total

reflectance R, refractive index, incident angle, wavelength of the incident light and thickness of
the film. Out of these parameters except the thickness other parameters are constant for a given
system, thus calculable (or can be found in literature).

For a transparent film the Cauchy relationship is typically given as:

n ( ) A

Where, the three terms are adjusted to match the refractive index for the material.

So in the model the only unknown variable remains, is thickness for the film, as the total
reflectance is also a function of refractive index and incident angle.

The ellipsometer experimentally measures the amplitude ratio vs. wavelength of light and phase
difference vs. wavelength of light which is the fitted with the theoretically obtained amplitude
ratio vs. wavelength of light and phase difference vs. wavelength of light, having the fitting
parameters A, B, C (Cauchy parameters) and hf. These parameters are fitted to obtain the film
thickness.
A known polarization is reflected or transmitted from the sa mple and the output polarization is
measured. A sample ellipsometry measurement is shown in Figure 1. The incident light is linear
with both p- and s- components. The reflected light has undergone amplitude and phase changes
for both p- and s- polarized light, and ellipsometry measures their changes.

Figure 1 Typical ellipsometry configuration, where linearly polarized light is reflected from the
sample surface and the polarization change is measured to determine the sample response

Experimental Data: (for PS film over silicon wafer)

ROT
SPEED
(rpm)
2000

4000

6000

MSE
VALUE

THICKNESS
(nm)

3.761
3.564
4.32
3.769
3.717
3.76
4.029
4.028
4.027

58.113
58.004
58.081
43.0886
43.055
43.0067
36.128
36.127
36.127

Mean
thickness

58.066

43.0501

36.12733

Deviation
from
mean
0.047
-0.062
0.015
0.0385
0.0049
-0.0434
0.00067
-0.00033
-0.00033

Square of
deviation
0.002209
0.003844
0.000225
0.0014822
0.000024
0.0018835
4.489*10-7
1.089*10-7
1.089*10-7

Standard
deviation

0.056

0.04115
5.773*10-4

Discussion:
1.

Rotational speed of the substrate during film preparation is most vital parameter which
affects the thickness of film. It is observed from the results that film thickness increases
with decease in rotational speed.
2. Viscosity of the liquid also affects the film thickness. With increase in solution
viscosity, viscous resistance to the flow of liquid outwards due to centrifugal force
decreases, which leads to increase in film thickness.

3.
4.

5.

6.

7.

Lager is standard deviation; more is the non uniformity in the film thickness. In our
experimental results, standard deviation is more in case of low rpm film.
Solution surface tension also plays a role. As the surface tension of solvent decreases,
evaporation rate increases leaving behind the concentrated solution which gives higher
thickness.
Room temperature and relative humidity of surrounding air also affect the final
thickness of film. The larger is difference in partial pressure of solvent between the free
surface of the liquid layer and the bulk of the air, solution will be concentrated more to
make the viscosity high which causes the higher thickness. Temperature also acts in the
same way.
Film thickness decreases from centre to the edges on the substrate due to increased shear
rate with radius. Non Newtonian shear thinning behaviour is observed towards the edge
of substrate.
Higher is the initial concentration of solution higher is the viscosity and hence higher
thickness of film.

Souces of error:
1. During the coating different amount of solution may be put on the substrate, which
causes thickness difference
2. Substrate centre may not be kept at the centre of chuck which always cause the
thickness non uniformity
3. Air bubbles, particles in solution and also particles on the substrate can also cause
the non uniformity in film thickness.
4. Temperature and humidity variation during coating can affect the drying rate of
film resulting in thickness variation.
5. Surface roughness of substrates may be different.
6. Thickness may be measured at different positions for different samples which can
give different film thickness
7. Lager spinning time may lead to low thickness.
8. There may be a mistake in setting the speed.

Conclusion:
The thickness widely varies with each experiment, showing significant error in experiment
condition. The main reason for this is the substrate was not smoo th enough (there were residue
left of the previous experiment. As the silicon wafers were cleaned by the solvent, which in this
case is toluene, is volatile and dries off quickly. There are chances of dust particle attachment on
the surface. These particles are hard to remove by air blowing).
Another reason for error can be because of the different position of the film is measured in
different experiment. As the thickness is a function of the radial position of the film. The only

solution of this problem can be achieved by measuring more number of points, which is difficult
to achieve within given time.

Experiment Report
CL 610 EXPERIMENTAL METHODS
Experiment No. 4

Nanoparticle Formation Using Microemulsion Template and Particle Size Estimation

Using UV-Vis Spectrophotometer

Submitted By: Group No.

Submitted To:
Prof. Rajdip Bandyopadhyaya
Prof. Y S Mayya
Date of Experiment:
Date of submission:

Department of Chemical Engineering

Indian Institute of Technology Bombay

Objective:
To prepare cadmium sulfide (CdS) nanoparticles in water in oil (w/o) microemulsions and
estimate their size with the help of UV-Visible spectrophotometer.

Introduction:
Nanoparticles are collections of atoms or molecules that form clusters with diameters less
than 100 nm. The chemical and physical properties of nanometer-sized materials can differ from
the bulk material. Changes in color and chemical reactivity are readily apparent with many
nanomaterials. Nanoparticles tend to combine to form larger, bulk particles, so special methods
are used, like w/o microemulsion drops as template, to limit their growth.
The potential applications of nanoparticles of metal sulphides are in optoelectronic devices,
photocatalysis for solar energy conversion and photo degradation of water pollutants. Since the
electronic properties of semiconductor nanoparticles are size dependent, in order to modulate
their chemical, optical and electrical properties, a fine size control is required. Among the
various method employed to produce size controlled nanoparticles, a promising one is based on
the use of water in oil (w/o) microemulsions.

Principle and theory:

Microemulsions are a thermodynamically stable dispersion of nanometer-sized water drops in a
continuous oil medium. The stability of these drops is attributed to the presence of adsorbed
surfactant molecules at the oil-water interface of the drop. The drops undergo Brownian motion,
thus colliding with each other and occasionally coalescing. Due to coalescence exchange their
contents thus brings the two reactants together inside a single drop for reaction. So, the insoluble
reaction product nucleates to form a nanoparticle inside the drop.
Coagulation of two nanoparticles during coalescence of the two nucleated drops is responsible
for size enlargement of nanoparticles. However, coagulation is constrained by the fact that the
coagulated nanoparticle size cannot exceed the size of an individual drop. This is based on the
fact that, when a growing nanoparticle approaches the diameter of a microemulsion drop, the
head groups of surfactant molecules surrounding the drop can physically adsorb on the
nanoparticle surface. Thus, the nanoparticle can become strongly encapsulated in the drop, in

comparison to when the particle diameter is much less than the drop diameter. Therefore, it is
hypothesized that particles of diameter equal to the drop diameter cannot coagulate further with
any other nanoparticle.
In this experiment, we will use a uv-spectrophotometer to precisely measure which wavelengths
of light are absorbed by the cadmium sulfide nanoparticles.
Chemicals: Sodium dioctylsulfosuccinate(AOT), Cadmium Nitrate, Sodium Sulfide, isoOctane, Millipore water.
Apparatus: UV-Visible spectrophotometer with a pair of quartz cuvettes, sonicator, analytical
balance, micropipettes of 100, 1000 and 5000 l capacity.

Procedure:
1. Prepare the following three stock solutions:
a. Stock solution 1: 100 ml 0.1 M AOT/Iso-octane solution.
b. Stock solution 2: 10 ml of 0.037M Cd(NO3)2 aqueous solution.
c. Stock solution 3: 10 ml of 0.037 M Na2S solution.
2. Prepare microemulsions A and B for R = 5 (where R is mole ratio of water to surfactant
AOT) and record absorbance spectra:
a. Microemulsion A: for R = 5, take 10 ml of stock solution 1, calculate the amount
of water needed and the total volume (volume of AOT/Iso-octane and water).
Now mix stock solutions 1 and 2 such that Cd2+ concentration is 0.0003315 M
with respect to total volume.
b. Microemulsion B: for R = 5, take 10 ml of stock solution 1, calculate the amount
of water needed and the total volume (volume of AOT/Iso-octane and water).
Now mix stock solutions 1 and 3 such that S2- concentration is 0.0003315 M
respect to total volume.
c.

Sonicate the microemulsions A and B for 10 minutes in a sonicator .

d. To measure the absorption spectrum of the microemulsion , 1.5 ml microemulsion

A was added to the cuvette and placed in the UV-Vis spectrophotometer, after

that 1.5 ml of microemulsion B was added to it and after waiting for 1 minute
absorption spectrum was measured.
e. . Repeat steps c and d two more times do make total four readings for same R.
3. Repeat step 2 for R = 10 and 15.

Observations:
1. Plot absorbance data as a function of wavelength.
Graph1:

Graph 2:

2. Note the region in the spectrum where the absorbance increases linearly. Calculate the X
intercept and slope. Find cutoff wavelength of spectrum cutoff by formula cutoff =(slope/intercept).

Graph 3:

nano
Convert the cut-off wavelength into units of Joules using E g = hc/ where h is Plancks
constant and c is velocity of light.

3. Below is the equation for determining band gap of the nanometer-sized CdS particle.

Rearrange that equation to solve for particle radius. Report the size of particles with mean
and standard deviation.
E gnano E gbulk

h2
8r 2

1
1 1 . 8e 2
* *
m

e m h 4 o r

Use the values of physical constants listed below to calculate the radius of particles.

E gnano = band gap of nanoparticle CdS as determined from the samples UV/visible absorbance

spectrum, J
E

bulk
g

= band gap of bulk CdS at room temperature, 3.88 10-19 J (2.42 eV)

h = Plancks constant, 6.626 10-34 J s

r = particle radius, m
m

*
e

= effective mass of a conduction band electron in CdS, 1.73 10-31 kg

m *h = effective mass of a valence band hole in CdS, 7.29 10-31 kg

e = elementary charge of an electron, 1.602 10-19 C

= pi, 3.14159
= relative permittivity of CdS, 5.7
o = permittivity of a vacuum, 8.854 10-12 C2 (J m)-1

Analysis and Discussion:

Table 1:

S.No.

Time

cutoff (nm)

Eg nano in 10-19 J

Dia (nm)

1 min

363.409

5.46491

6.66

4 min

363.9852

5.4562

6.702

7 min

365.48494

5.4338

6.7239

10 min

365.6526

5.43138

6.7258

Graph 4:

The data obtained shows the similar behaviour of variation of CdS nanoparticle formation as per
literature i.e. size of nanoparticle increases with time but after certain period of time variation in
size become negaligible as shown in graph 4.
Precautions:
1. Make sure the cuvettes are clean and scratch free. Use them gently
2. Wipe the cuvettes using a soft tissue.
3. Keep the sample compartment clean and do not spill any samples into the sample
compartment.
References:
Caponetti E, Pedone L, Chillura Martino D, Panto V and Turco Liveri V, Synthesis, size
control, and passivation of CdS nanoparticles in water/AOT/n-heptane microemulsions,
Materials Science and Engineering C, 2003, 23, 531539.

HPTLC
Experiment No. 5
Objective: To measure the unknown concentration of Benzophenone and Benzhydrol in a
mixture.
Apparatus used: TLC Plate, Applicator, Glass developing chamber, TLC UV Scanner, Syringe,
Beakers, Measuring cylinder, Sample bottles.
Chemicals used: Benzophenone, Benzhydrol, Methanol, Hexane, Toluene.
Introduction
Thin Layer Chromatography (TLC) is an extremely useful technique for monitoring reactions,
identify compounds given in a mixture and determine the purity of a substance. TLC uses a
stationary phase, usually alumina or silica and the mobile phase is a solvent whose polarity is
chosen according to the requirements. The reaction mixture in the form of a solution is applied to
the plate and then the experiment is run by allowing a solvent (or combination of solvents) to
move up the plate by capillary action.
High Performance Thin Layer Chromatography (HPTLC) is an enhanced form of thin layer
chromatography (TLC). A number of enhancements can be made to the basic method of thin
layer chromatography to automate different steps, to increase the resolution achieved and to
allow more accurate quantitative measurements. Automation allows overcoming the uncertainty
in droplet size and position when the sample is applied to the TLC plate by hand.

Principle
Depending on the polarity of the components of the mixture, different compounds ill travel
different distances up the plate. More polar compounds will be retained in the polar silica
stationary phase and travel a shorter distance on the plate. Non-polar substances will have a
higher affinity for the mobile phase and thus travel a larger distance on the plate. The measure of
the distance a compound travels is called the Rf value or the Retention factor. The Rf is defined

as the ratio of distance the compound migrated from where it was originally spotted to the
distance covered by the solvent.
Procedure:
1. Two standard solutions of 150 ppm Benzophenone and 2500 ppm Benzhydrol each was
prepared in 5ml of methanol.
2. Mixtures of Benzophenone and Benzhydrol in unknown proportions were also prepared.
3. 30ml of developing solvent containing Hexane-Toluene in a ratio of 30:70 was prepared
and poured in the developing chamber.
4. The HPTLC instrument (applicator) was started and various parameters like Plate width,
Band width, Band pitch and start position were set. Based on these parameters the
number of tracks available on the TLC plate was calculated to be 13.
5. In the first five tracks, bands of pure Benzophenone solution, in the middle five tracks,
bands of pure Benzhydrol solution and in the last three tracks, bands of unknown samples
were loaded by entering different volumes of the samples in each track.
6. After applying the samples, the TLC plate was kept in the developing chamber containing
the solvent. The plate was removed when the solvent had covered 75% of the plate and
was dried with the help of a dryer.
7. The TLC plate was placed under a UV lamp for identification of the bands after they had
migrated.
8. The plate was then analyzed by using the TLC scanner in order to obtain the
chromatograms using the CAMAG software at 254nm wavelength. Each track was
separately analyzed and depending on the number of components present they showed
one or two peaks. By using the integration option the areas under the peaks were
obtained.
Preparation of standard solutions of Benzophenone and Benzhydrol:
5.94 mg of Benzophenone was dissolved in 50 ml of Methanol (density: 0.791 g/cc) to give a
solution of 150 ppm. 98.99 mg of Benzhydrol was dissolved in 50 ml of Methanol (density:
0.791 g/cc) to give a solution on 2500 ppm.

Parameters entered:
Plate width = 200 mm
Space between bands = 10 mm
Band width = 4 mm
Start position = 10 mm
Observations:Table 1:
Calibration data for Benzophenone standard

Track no

Volume (l)

Peak Area

1
2
3
4
5

4
6
8
10
12

5740.7
7178.1
8628.4
9974.9
10908.1

Amount of
Benzophenone (g)
0.47
0.71
0.95
1.19
1.43

Peak Area vs Amount of Benzophenone

12000
y = 5526.8x + 3233.4
R = 0.9938

10000

Area

8000
6000
4000
2000
0
0

0.2

0.4
0.6
0.8
1
1.2
Amount of Benzophenone (g)

1.4

1.6

Table 2: Calibration data for Benzhydrol standard

Track no

Volume (l)

Peak Area

6
7
8
9
10

4
6
8
10
12

2367
3725.3
4419.5
5296.1
6039

Amount of
Benzhydrol (g)
7.92
11.88
15.84
19.80
23.75

Peak Area vs Amount of Benzhydrol

7000
6000

y = 225.14x + 803.46
R = 0.9844

Area

5000
4000
3000
2000
1000
0
0

10

15

20

25

Amount of Benzhydrol (g)

Table 3: Unknown
Track no

Volume (l)

11
12
13

12
14
16

Therefore:
For BP, y = 5526x + 3233

Peak Area
corresponding to BP
7391
8035.2
8810.7

Peak Area
corresponding to BH
3532.8
3903.3
4399.1

For BH, y = 225.18x + 803.4

For concentration in ppm: ((amount in g) / (vol in l x 791)) x 106
For volume ratio: V1/V2 = (ppm of BP x 2500) / (ppm of BH x 150)

Table 4: Amount and concentration of unknown

Track no
11
12
13

Volume of
sample (l)
12
14
16

Amount of
BP (g)
0.75
0.87
1.00

Amount of
BH (g)
12.13
13.77
15.97

ppm of
BP
79.27
78.47
79.75

ppm of
BH
1277.42
1243.56
1262.15

Volume ratio of
original solutions
1.03
1.05
1.05

Results:
For the unknown sample:
Average concentration of Benzophenone = 79.16 ppm
Percentage error = 5.55 % (Actual concentration = 75 ppm)
Average concentration of Benzhydrol = 1261.04 ppm
Percentage error = 0.88 % (Actual concentration = 1250 ppm)
Average volume ratio of standard solutions of Benzophenone to Benzhydrol added to make

Height (AU)

the unknown solution = 1.04

80
70
60
50
40
30
20
10
0

Benzophenone

Benzhydrol

20

40
Distance (mm)

60

A representative chromatogram

80

Conclusions:
1) HPTLC was used to measure the unknown concentrations of Benzophenone and
Benzhydrol in the given mixture.
2) There exists a linear relationship between peak area and amount of component in a
solution.
3) Benzhydrol being more polar experiences more interaction with the stationary phase
(silica) compared to Benzophenone. Benzophenone thus has a higher value of Retention
factor (Rf) which explains Benzophenone travelling a greater distance in the TLC plate.

Comments on errors:

1. If the compound runs as a streak, the sample may have been overloaded or it may contain
many components which appear as a streak. In this case, dilute the sample and run again.

2. While scanning the TLC plate, take care to place the UV light bean exactly on top of the
spot failing which one may get an erroneous intensity value.
3. While preparing the sample try to keep the samples covered as methanol is a volatile
compound and it evaporates even at room temperature thus drastically changing the ppm
concentration of the sample.

EXPERIMENTAL METHODS
CL 610

EXPERIMENT NO. 6
TA ARSHNOOR KHAN

ATOMIC
ABSORBTION SPECTROSCOPY

OBJECTIVE OF THE EXPERIMENT:

To determine the concentration of metal ion using Atomic Absorption
Spectroscopy (AAS) and study its extraction using suitable extractant.

THEORY:
PRINCIPLE OF WORKING:
The technique makes use of absorption spectrometry to assess the concentration of
an analyte in a sample. It requires standards with known analyte content to
establish the relation between the measured absorbance and the analyte
concentration and relies therefore on the Beer-Lambert Law. In short, the electrons
of the atoms in the atomizer can be promoted to higher orbitals (excited state) for a
short period of time (nanoseconds) by absorbing a defined quantity of energy
(radiation of a given wavelength). This amount of energy, i.e., wavelength, is
specific to a particular electron transition in a particular element. In general, each
wavelength corresponds to only one element, and the width of an absorption line is
only of the order of a few picometers (pm), which gives the technique its elemental
selectivity. The radiation flux without a sample and with a sample in the atomizer
is measured using a detector, and the ratio between the two values (the absorbance)
is converted to analyte concentration or mass using the Beer-Lambert Law.
Atomic absorption spectroscopy (AAS) is a spectroanalytical procedure for the
quantitative determination of chemical elements employing the absorption of
optical radiation (light) by free atoms in the gaseous state.

In analytical chemistry the technique is used for determining the concentration of a

particular element (the analyte) in a sample to be analyzed. AAS can be used to
determine over 70 different elements in solution or directly in solid samples
employed in pharmacology, biophysics and toxicology research.
Atomic absorption spectrometry was first used as an analytical technique, and the
underlying principles were established in the second half of the 19th century by
Robert Wilhelm Bunsen and Gustav Robert Kirchhoff, both professors at the
University of Heidelberg, Germany.

APPARATUS AND INSTRUMENTS:

Syringe

Sampling bottles

Glass wares

Atomic Absorption Spectrometer (Model: GBC-902)

CHEMICALS USED:
1000 ppm stock of metal ion
Tetrabutyl phosphate(TBP)
8N HNO3

0.1N HCl

Paraffin oil

Distilled water

EXPERIMENTAL PROCEDURE:
1. First we have to prepare the sample.

2. A stock solution of 1000 ppm is given which is diluted with distilled water to
form samples of different concentrations.
3. An emulsion is prepared

4. Quantity of emulsion prepared: 20 ml

97% v/v of Paraffin=19.4 ml
3% v/v of TBP= 0.6 ml
5. The aques /feed phase is of the sample provided of unknown conc of same metal
ion (50 ml).
6. To this sample emulsion is dispersed

7. This emulsion will be provided.

Step1:
An amount of emulsion and aqueous phase is stirred with the help of stirrer at
some fixed rpm.
Step2:
With the help of syringe, sample is collected from aqueous phase in sampling
bottles, with the help of syringe

Setting up of instrument:
The exhaust and hood is put on.
The corresponding slit width (0.2mm) and wavelength(386 nm) is fixed.
The lamp is selected and fitted corresponding for the given metal ion.
The power is switched on .
The current for the lamp is setted up.

Get the maximum signal in the energy meter of the instrument.

Air cylinder is opened and the flow rate is adjusted .
Similarly acetylene cylinder is opened and the flow rate is adjusted.

EXPERIMENTAL OBSERVATIONS & CALCULATIONS:

Sample preparation:
The given stock solution (1000 ppm) should be diluted with distilled water
to prepare concentration of solutions,
500 ppm,
400 ppm,
300 ppm,
200 ppm .
CALIBRATION TABLE for Cu

Sample Concentration
no.
(ppm)

Absorbance
Observation Observation Observation average Std
1
2
3
deviation

200

0.212

0.211

0.207

0.210

300

0.292

0.294

0.299

0.295

400

0.371

0.374

0.374

500

0.412

0.413

0.414

0.373
0.413

0.00057

0.00294
0.008539
0.001

Plot of absorbance vs. Concentration for Cu:

Cu
y = 0.0008x + 0.082
R = 0.977

0.45
0.4

Absorbence

0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
0

100

200

300

400

500

600

conc in ppm

CALIBRATION TABLE for Fe

Sample Concentration
no.
(ppm)

1
2
3
4

50
80
120
140

Absorbance
Observation Observation Observation average Std
1
2
3
deviation
0.065
0.066
0.067
0.066
0.0030
0.001
0.121
0.121
0.122
0.121
0.000577
0.176
0.179
0.182
0.179
0.000577
0.233
0.234
0.232
0.233

Plot of absorbance vs Concentration for Fe:

Fe
absorbence

0.25
0.2
0.15

y = 0.0018x - 0.0238
R = 0.9884

0.1
0.05
0
0

20

40

60

80

100

120

140

160

conc in ppm

UNKNOWN SAMPLE:
Sample

Absorbance for Absorbence for fe

Cu
1

Concentration Quantity of
extract ant

0.243

Quantity of
aques phase

Conc of
Cu in
ppm
0.130 201

Absorbence
after
extraction

Conc of fe
in ppm
153

Conc in aq
phase

Distribution
coeffecient

1000 ppm of
Cu

2 ml

20 ml

0.203

180 ppm

4.5

Seperation Factor = ( Distribution coefficient of Cu) / ( Distribution coefficient

of Fe)

UNKNOWN SAMPLE:
Sample

time(min)
absorbance
1
2
3

0
1
1.5
2

0.78
0.167
0.127
0.107

Readings
from
caliberation
1000
122.4
63
35.2

ln(CA0/CA)

0
2.1
2.76
3.34

ln CA0/CA

3.5
3
y = 1.7821x
R = 0.9751

2.5
2
1.5
1
0.5
0
0

0.5

1.5

Time (min)

RESULTS:
In caliberation ,concentration v/s absorbance fits the linear data.
ln CA0/CA v/s time also fits a straight line with slope= 1.7821

2.5

Here slope= k,
So rate constant (k) = 1.7821
The unknown sample had 153 ppm of Fe and 201 ppm of Cu
D for Cu is 4.5

DISCUSSIONS:
Last two readings of absorbance were neglected, as they were corresponding
to negative concentration, which is not possible. One reason for this error
may be due to presence of dust particle in environment.
Calibration curves are straight lines with a good fit of trend line.

CL 610
EXPERIMENTAL METHODS IN CHEMICAL
ENGINEERING
Particle size analysis and zeta potential

Submitted by:
Prerna Chandna
Roll No:114020012

Aim:
The aim is to compare the size of aqueous C-Tab micelle with &without decane and also compare size
of silica particle with and without decane solution.
Introduction and Principle:
Interaction of light with the electric field of

When photon collide with particle it induces oscillating dipole

small particle or molecule.

in the electron cloud .As dipole energy

changes ,it is radiated in all directions called Scattered light. Dynamic Light scattering is the
characterization technique to find the size of particles, emulsions or molecules, which is dispersed /
dissolved in a liquid.
Stoke Einstein Theory: Intensity fluctuations yields the velocity of the Brownian motion and hence
the particle size .Brownian motion of particles / molecules in suspension causes light to be scattered at
different intensities.
Mie Theory: It describe how spherical particles of all sizes and optical properties scatter light .When
particles size become larger than 1 /10 of laser wavelength(), then scattering is not isotropic (same in all
direction) but it gives maxima and minima with respect to angle.
The Zetasizer Nano uses Mie theory to convert the intensity size distributions into volume and number
for all sizes of particles.
Chemicals: C-tab, Silica nano-particles with and without decane ,NaOH pellets.
Stock Solutions Required:
C-Tab in NaOH(12mg)-Water(24ml) solution=12mg
C-Tab in NaOH(12mg)-decane(1.2ml)-Water(24ml) solution=12mg
Silica particles in water(10ml)=10mg
Silica particles with decane in water(10ml) =10mg

Apparatus Used:
DLS
Stirrer
Weighing machine
Sonicator

Theory: Dynamic light scattering probes the diffusion of particulate materials either in
solution or in suspension. By determining the rate of diffusion (the diffusion coefficient),
information regarding the size of particles can be obtained. The common property of these
particles that is probed is their movement.
The relative positions of the particles in the scattering volume at any instant determine
the magnitude of constructive or destructive interference of the scattered light. Since the
diffusion rate of particles is determined by their sizes in a given environment, information
about their size is contained in the rate of fluctuation of the scattered light. The scattered
light and its changes in intensity are detected as the following signals:

Intensity vs time signal

Procedure:
1)Sampling bottles are washed and oven-dried to remove any impurities present.
2)Stock solution of C-tab- water solution is prepared and slowly stirred at300rpm for 45minutes.Then
filtration is done with syringe filter.
3)Stock solution of C-tab, water-decane is prepared and slowly stirred it for 300rpmfor 45 minutes. Then
filtration is done with 0.22m syringe filter.
4)Solution of silica particles with water is prepared, then filter it with syringe filter and sonicates it for
20 minutes.
5)Solution of silica-decane particle is prepared ,then filter it with syringe filter and sonicate it for
20minutes,
6)The size distribution is measured for all prepared samples using DLS apparatus, using the known
values of viscosities and refractive indices of the solutions.
Observations:
Micelle of C-tab water solution

Micelle formation of C-tab-water-decane solution:

Silica particles with water:

Silica particles water-decane solution

Results:
Solution
CTAB without decane
CTAB with decane
Silica particles without decane
Silica particles with decane

Number mean diameter (nm)

Run 1
Run 2
Run 3
4.8286
4.9786
4.7711
5.7310
6.2326
6.2996
38.710
70.660
117.39
162.19
160.60
186.20

Mean diameter (nm)

4.8594
6.0877
75.590
169.66

Conclusion:
Size of C-tab decane micelle is greater than C-tab micelle.
Size of Silica nano-particles with decane is greater than Silica nano-particle without decane.

CL:610-Experimental Methods

Experiment No:9
COMSOL Multiphysics 4.2a
Course Instructor:
Prof. Rajdip Bandyopadhyaya
Prof. Y.S. Mayya

TA:Rakhi Dhuriya
Email-ID: rakhid@iitb.ac.in

Department of Chemical Engineering

Indian Institute of Technology-Bombay
Spring, 2014

Objective:
To get aquainted with Graphic Uer Interface(GUI) of Comsol Multliphysics 4.2.
To solve and analyse problem related to Chemical Engineering using this software.
Introduction and Theory
Comsol Multiphysics 4.2 provides a powerful interactive environment for modeling and solving all kinds of scientific and engineering problems based on partial differential equations
(PDEs). With this software one can easily extend conventional models for one type of
physics into multiphysics models that solve coupled physics phenomena and do so simultaneously. With the built-in physics modes it is possible to build models by defining the relevant physical quantities such as material properties, loads, constraints, sources, and fluxes
rather than by defining the underlying equations. One can always apply these variables, expressions, or numbers directly to solid domains, boundaries, edges, and points independently
of the computational mesh. COMSOL Multiphysics then internally compiles a set of PDEs
representing the entire model.
When solving the models, COMSOL Multiphysics uses the proven finite element method
(FEM). The software runs the finite element analysis together with adaptive meshing and error control using a variety of numerical solvers. PDEs form the basis for the laws of science
and provide the foundation for modeling a wide range of scientific and engineering phenomena. Therefore one can use COMSOL Multiphysics in many application areas.

A priori requirements

Problem Statement : In this section, a problem that involves certain physical phenomenon will be described. Also, material properties, geometric dimensions, temperature conditions and other relevant specifications to be listed here.

Observations:Typically, this section lists certain noticeable facts or assumptions about

the problem statement.Analyzing the results obtained with change in certain parameters of the physics involved.
2

Basic steps of modelling and simulation

1. Select Dimensionality suitable to the problem(2D or 3D).
2. Choose the physics or multiple physics that is or are required to describe the problem
at hand.Also choose the stationary or transient study as per problem requirement.
3. Using geometry build tool build the geometry required for the problem.
4. Choose material or specify necessary properties manually.
5. Specify all the relevant boundary conditions.
6. Choose the complexity of mesh as needed by the problem.
7. Set the solver parameters.

Problem Statement
One end of cylindrical fin is maintained at temperature T0 .Simulate following scenarios in
2D axisymmetric

Uninsulated Fin
Fin with insulated Tip
Fin with insulated cylindrical surface.
Assume that uninsulated surfaces are losing heat to the surroundings by convection. Assuming constant h, k, and T1, compute total heat transfer, Qf, for all the cases. Compare the
results of these cases with each other to make a judgment and comment on what the effect
of insulating an tip & surface on heat transfer rate is. Thermal and geometric parameters for
the model are listed below.

T0 = 100 C, T1 = 20 C
k= 160 W/m/ C
h= 10 W/m2 / C
3

 Length of fin=30cm,Radius of fin=0.5cm

Task:
Using COMSOL, show the axial temperature distribution for all cases (to be plotted
on single axis).

Using COMSOL, show change the heat transfer flux for all cases.
Case 1: Uninsulated Fin

Figure 1: Uninsultated fin

Figure 2: Uninsulated Tip:Axial Temperature profile

Figure 3: Uninsulated :Axial heat flux profile

Case 2: Insulated Tip

Figure 4: Insulated Tip

Figure 5: Insulated Tip:Axial Temperature Profile

Figure 6: Insulated Tip:Axial heat flux profile

Case 3: Insulated Surface

Figure 7: Insulated surface

Figure 8: Insulated Surface: Axial Temperature Profile

Figure 9: Insulated Surface:Axial Heat flux profile

Conclusion and Discussion

The heat flux is less and is constant for Case3:insulation on cylindrical surface, as compared
to other cases.Moreover, from the temperature profiles 2,5 and 8 it is clear that insulating tip
has a large temperature gradient axially but insulating the surface has very small temperature
gradient.The uninsulated and insulated tip show almost similar temperature and heat flux
profile.
The reason for the above observations lies in the fact that the tip surface area is small as compared to the cylindrical surface area of the fin, therefore insulating curved surface decrease
the heat transfer by a huge margin than insulating a tip of fin.
Considering the fact that fin is mostly used for cooling purpose it is better to use insulted tip
than insulated surface.

Thermo Gravimetric-Differential Thermal Analysis

(TG-DTA)
Objective:
To get acquainted with Thermal Analysis(TA) techniques and to analyse given sample using
coupled TGA and DSC for chemical and physical changes like dehydration, decomposition,
melting temperature, phase change, heat absorption, etc..

Introduction:
On heating, material undergo changes in its structural and chemical composition like fusion,
melting, crystallization, oxidation, decomposition, transition, expansion, sintering, etc.. In
addition to that when subjected to a temperature change, various properties such as heat flow,
mass, pressure, electrical properties, magnetic properties, optical properties may change
depending on sample characteristics. Using Thermal Analysis (TGA and DTA are methods of
thermal analysis), such changes can be monitored in at controlled atmosphere.

Principle:
Table 1. shows different TA techniques and their applications.
Technique

Property Measured

Applications

Thermogravimetric Analysis
(TGA)

Mass difference

Sample purity,
decomposition, dehydration,
oxidation

Differential ThermalAnalysis
(DTA)

Temperature difference

Phase change, dehydration,

decomposition, reactions

Thermo Gravimetric Analysis (TGA):

The thermo gravimetric analysis is a technique in which the mass of a substance is measured
as a function of temperature or time while the substance is subjected to a controlled
temperature programme in a specified atmosphere. In case of temperature dependant
measurements:
m = m(T) or m = m(T)- m(T0) ...........................(1)
In case of time dependent measurements:
m = m(t) or m = m(t)- m(t0) ...........................(2)
Where, m is mass of sample at temperature T in case of non-isothermal measurements or time
t in case of isothermal measurements. The m(T 0) or m(t0) is the initial mass.

DTA /(mW/mg)
Temperature /C
exo
[1]
1000
0.6

TG /%
100

[1]
Mass Change: -29.13 %

90

0.4
800
0.2

80

Mass Change: -7.04 %

600

70
-0.2
60

-0.4

Mass Change: -31.52 %

400
-0.6

50

-0.8
40

200

Residual Mass: 29.21 % (97.5 min)

-1.0
[1]

30

-1.2
0

10.0

20.0

30.0

40.0

50.0 60.0
Time /min

70.0

80.0

90.0

Figure1: TG-DTA curve for CuSO4.5H2O

Factors affecting the TGA curve:
The nature, precision and accuracy of the TGA experiment depend on various factors. They
are,
Furnace heating rate
Furnace atmosphere
Particle size of sample
Sample packing
Differential Thermal Analysis (DTA):
In Differential Thermal Analysis technique, the sample and reference material are
simultaneously heated. The temperature of sample and reference material is sensed and
recorded individually. The temperature change while heating is plotted to analyse chemical
and physical transformations like melting, sublimation, crystal transitions and crystallisation.
Apparatus:
It contains the following components
The electrobalance and its controller: Null point weighing mechanism.
The furnace and temperature sensors: MoSi 2 based furnace with alumina
refractories and a thermocouple Pt-30%Rh(+) Vs Pt-6%Rh (-) for operation to 1500 to
1700oC
Purge gas flow controller
Programmer or computer
Data acquisition device

Instrument in lab:
Company: M/s. NETZCSH Gerabau GmbH.
Model: Simultaneous TGA-DSC Apparatus STA 409PC/4/H LUXX is hyphenated TGA and
DSC.
Temperature range: 25 to 1550oC

Experimental Procedure:
Starting Procedure
Switch ON the power supply for furnace unit, power unit, adapter unit, and the computer
(in all 5 switched to be ON)
Switch ON the equipments in following order,
a. Power unit (switch in front)
b. Furnace unit (switch at back)
c. Gas control unit (switch in front)
d. Water circulation unit (kept near cylinders)
Ensure the connected gases (N2/O2/Zero Air) are ON. Pressure of 2kg/cm2 is to be
maintained.
Analysis Procedure:
Analysis works in two steps,
BASELINE CORRECTION, for removing the impurities and standardizing the
apparatus.
TG-DTA ANALYSIS, to analyze the % weight loss with temperature and time for the
sample under consideration.
Baseline Correction
Weigh the cleaned reference and the analysis pan manually and note down the weight
Furnace unit consist of three switches for operation UP/DOWN (front panel) SAFETY
(side panel). To OPEN the unit PUSH UP+SAFETY switch together till the unit is ready
for further usage.
Carefully place the weighed pan on the sensors using small forks. DO NOT insert the pan
forcefully to the sensors. CLOSE the unit using DOWN+SAFETY switch together.
Kindly note the weight (in mg) of both the pans for further usage.
Baseline correction has to be performed on the same program (heating rate, temp range,
holding time etc.) as going to be used for analysis.
Open the software STA409PC from the desktop icon.
Goto - TOOLS - Weighing Option Manual
File - New - gives anew window with multiple tabs.
o Under MEASUREMENT mark CORRECTION
o Enter SAMPLE ID, and CRUSIBLE MASS
o Under REFERENCE enter CRUSIBLE MASS,

o REFERENCE MASS enter ZERO for Baseline correction.

o Under PURGE GAS, Gas 1 N2 flow 40 ml/min
Gas 2 N2 flow 60 ml/min
Press CONTINUE
Select Calibration File from source: NEW-DTA-CAL-N2
Select Sensitivity File from source: SENSCAL-AL2O3-N2.ESV
We will have new window with multiple tabs.
o Under step conditions: SELECT THE CHECK BOX for STC, GAS 1 and GAS 2.
o Under Category specify Initial Temperature Conditions (say 25oC)
o Press ADD TO END tab
o In side bar select DYNAMIC, Under Category enter the End Temperature and the
Heating Rate ( Acquisition rate in points/K and in points/min will be taken auto)
o Re-Press ADD TO END tab
o You will see the details getting added in the above table.
o In side bar select ISOTHERMAL, if you wish to have a hold time for the sample at some
temperature else skip. If added the details then Re-Press ADD TO END tab
o In side bar select FINAL, enter the emergency reset temperature, excess temperature than
the specified one for analysis. Usually the temperature is given 10 oC.
o Continue to enter the final standby temperature.
Specify the path to save the file and the file name. This will be stored default for the
baseline correction.
Continue to get a COM1 WINDOW. It might take a minute to appear so wait and do not
hustle.
o Press on INTIAL COND ON check the gas flow in the rotameter. If not appearing
correct then kindly set it as required (in case 20 ml/min and 60 ml/min)
o Press TARE tab and wait for START tab to be ready.
o Press the START tab. The program will start and the data acquisition will start

Sample Analysis

Report Generation

Shutdown Procedure

Calculations:
Objective:
To obtain TGA and DTA curves for a given sample.
To analyse the graphs obtained and calculate enthalpy of physical and chemical
transformations occurring in the given temperature range.

1. Sample : CaC2O 4 .H2O

Observations:
Initial Sample Mass =21.192 mg
Temperature range = 25-900OC
Heating Rate = 15 K/min

Calculations:
In TGA, three stages are there.

Sample: CaC2 O4 .H2O

Reaction

Theoretical
Mass
Loss

Step

1
2
3

CaC2O4 .H2O
CaC2O4
CaCO3

CaC2O4 +H2O
CaCO3 + CO
CaO + CO2

Measured
Mass
Loss

12.32%
19.17%
30.13%

% Error

12.41%
19.04%
29.93%

0.73%
-0.67%
-0.66%

3.50E+01
3.00E+01
2.50E+01

DTA (mW)

2.00E+01
1.50E+01
1.00E+01
5.00E+00
0.00E+00
0

100

200

300

400

500

600

700

800

900

1000

-5.00E+00
-1.00E+01

Temperature(C)

Sample contains monohydrate. Hence, in first stage dehydration takes place. Decomposition starts
at the temperature of 520o C and continues subsequently in the third stage. Products of
decomposition can be analysed using above data. The area under the exothermic/endothermic peaks
gives the enthalpy of the thermal event.

2. Heat change observed:

Step
1
2
3

H (KJ/mole)
-26.42
-7.6
-31.38

Result:
The number of water molecules associated with the sample crystal structure was found as one.
Decomposition starts at the temperature of 520o C.

2. Sample: CuSO4.5H 2O
Observations:
Initial Sample Mass = 37.732 mg
Temperature range = 25-1000OC
Heating Rate = 10 K/min

DTA /(mW/mg)
Temperature /C
exo
[1]
1000
0.6

TG /%
100

[1]
Mass Change: -29.13 %

90

0.4
800
0.2

80

Mass Change: -7.04 %

600

70
-0.2
60

-0.4

Mass Change: -31.52 %

400
-0.6

50

-0.8
40

Residual Mass: 29.21 % (97.5 min)

-1.0
[1]

30

-1.2
0

10.0

20.0

30.0

40.0

Calculations:
In TGA, three stages are there.
Sample: CuSO4.5H2O
Step 1: CuSO4 .5H2O

CuSO4.H2O + 4H2O

Theoretical Mass Loss : 28.86%

Measured Mass Loss : 29.13%
Step 2: CuSO4 .H2O

CuSO4 + H2O

Theoretical Mass Loss : 10.13%

50.0 60.0
Time /min

70.0

80.0

90.0

200

Measured Mass Loss : 07.04%

Step 3: Decomposition to CuO
CuSO4
CuO + SO3
Theoretical Mass Loss : 31.85%
Residual mass

: 29.21% (Measured)

2. Heat change observed:

step
1
2
3
4
5

H (J)
-16
-1.6
-10
-0.035
-7.3

Result:
The number of water molecules associated with the sample crystal structure was found as five.
Dehydration takes place in two steps.

Conclusions:
The Simultaneous thermal analysis procedure was used to observe the behaviour of CaC2O4 .H2O
crystals and CuSO4 .5H2O crystals on heating in a temperature range of 25-1000OC. As, sample is
heated dehydration takes place. Enthalpy changes in corresponding to dehydration stages were
calculated. When all the water molecules are removed, and temperature is increased beyond that, then
decomposition of crystals takes place. Enthalpy associated with the thermal events can be known by
calculating the area under the curves of DTA vs time plots.

References:
Brown, M. E. (Ed.), 2007, Introduction to Thermal Analysis: techniques and
Applications, 2nd Edition, Springer, New Delhi, 1-90.

Preparation of langmuir films

EXPERIMENT NO. 10
TA- DEEPTI PATIL
Aim: To prepare Langmuir films and plot (-A) isotherms.
Theory
Adsorption is the adhesion of atoms, ions, biomolecules or molecules of gas, liquid or
dissolved solids. It is a random distribution of molecules on the material surface. For eg:
Capturing and using waste heat to provide cold water for air conditioning.
The most common technique for studying Langmuir monolayers of amphiphilic substances has
been to measure the surface pressure as a function of the surface area. An amphiphile is a
molecule that consists of two parts, each of which has an affinity for a different phase.
When a long chain amphiphilic molecule (e.g. fatty acid) is spread with the aid of a volatile
solvent onto water surface, the solvent evaporates until only a monolayer remains. The polar
head attaches itself to the water surface while the nonpolar tail protrudes into the air.If the
surface tension of the water is lowered by the addition of thesolute (e.g. fatty acid like stearic or
oleic acid) the monomolecular layer of the solute onthe surface may be considered to exert a film
pressure () such that
= 0

(1)

where 0 is the surface tension of pure water and is the surface tension of the monolayer
covered water.
The plot of surface pressure as a function of the area of water surface available to the molecules
at constant temperature is known as surface pressure-area isotherm.

Application of Langmuir monolayers

1. Langmuir monolayers of oils on ponds are known to have a damping effect on surface
turbulance and retardation of evaporation.
2. Langmuir monolayers at the oil-water interface act as emulsifying agents.
3. Langmuir layers can be transferred to a soild substrate. The resulting Langmuir- Blodgett film
have many potential applications such as molecular electronics, piezoelectronic organic films,

waveguides, nonlinear optics etc. is that monolayers can be deposited on almost any kind of solid
substrate.

Interpretation of Surface Pressure

There is an analogy between and A with p and V of an ideal gas for very large areas.
The and A show a simple inverse proportionality such as pressure and volume for an ideal gas.
Identification of area as the two-dimensional equivalent of volume is a straight forward
geometrical concept. As the area is decreased, a more complex relationship is needed to connect
these variables, just as the equation of state becomes more complex for non ideal gases and
condensed phases. It can be shown that a typical value of 10mNm-1corresponds to about
100atm of three-dimensional pressure. In view of this, it is not too surprising that insoluble
monolayers do not usually display a simple inverse proportionality between and A. At
pressures this high, three-dimensional matter is not likely to obey the ideal gas law either.For the
gaseous state, the two-dimensional equivalent of Amagat's law for gases can be employed:
(A-A0)=qRT

(2)

Where A0 has the aspect of an excluded area per mole and q gives a measure of the number of
moles in the system. Rearrangement yields the linear form:
A =A0 +qRT/

(3)

This form is obeyed fairly well around a value of 5-10 mN-m-l. The value of A0depends on the
chain length of amphiphile used and is larger for longer chain surfactants such ssodium dodecyl
sulphate.
Apparatus: Langmuir balance, volumetric flasks, beakers, microsyringe.
Chemicals: Acetone, Millipore water, Acetone, Millipore water, 1mg/ml Stearic acid/hexane
solution

Procedure:
Step 1: First clean the trough using distilled water and then with acetone. Further wash away the
acetone using distilled water.
Step 2. Pour distilled water in the trough and avoid any air bubbles present in the trough.
Step 3. Click on sgserver icon
Go to control panel
A screen will be shown on which manual control unit will be displayed showing surface
pressure, barrier position & barrier speed.
From the manual control unit set the barrier position & balance as zero because of which the
barriers are at extreme position.
Step 4. Heat the Wilhelmy plate to avoid contamination. Hang the plate on its hook using
tweezers
Step 5.Remove the dirt from water-air interface till surface pressure is close to zero mN/m.Close
in the barriers by means of switch. A positive value of surface pressure is displayed.
Step 6. Bring the barriers to extreme position and set balance and barrier position to zero (use
the switch/manual control unit).
Step 7 Using micro syringe the solution is gently placed on thesubphase.
Step 8. Wait 20 minutes for the solvent to evaporate.
Step 9 Press the icon for KSV LB control software and then go to Experiments.

Go File. New Isotherm

Fill up the screen and set values as

Step 10. Fill up the next screen: Constant rate compression which also includes recording
options and target options.

From go to target (target= mN/m).

Rate is 10 mm/min and then click Go

Step 11 Plot the graph between surface pressure vs. mean molecular area.
Step 12 Stop and save the data.
Step 13 Repeat this procedure for three runs.

Experimental Data Input /Observations:

1) Stearic acid concentration = C = 1 mg/ml,
2) volume of stearic acid poured =V = 20 l
3) Temparature = 240 C = 297K
4) pH = 6.9 (water)
5) Wihelmy plate perimeter = 39.240 mm
6) Trough width = 75.0 mm
7) Water surface tension = 72.86 mN/m, Least Count = 0.01
8) Compression Method = Constant rate compression
9) Compression rate = 10 mm/min
10) Target (Surface pressure) = 55 mN/m
11) Stearic acid molecular weight = M =284 gm/mole
Graphs:
a) Plot vs a, and identify the gas, liquid and solid regions, where a is area per molecule in
angstrom square
b) Plot A vs 1/, restricting values in the range 5 10 mN/m. A must be in m2 and in
N/m. Get slope and intercept to calculate excluded area A0 for all the molecules and q,
the measure of number of moles taken
Calculation:
Step 1: After taking three runs, -A isotherm is plotted for stearic acid on pure water which is
shown in fig 1.

Fig 1: Mean Molecular Area (m2) vs Surface Pressure(mN/m)

Step 2 :Plot Avs1/ to find out the values of A0 and q for stearic acid system on water interface.
The significance of find out the value of slope gives the q value & intercept value is used to
measure the gives the measure of an excluded area per mole.

0.025

Area (m2)

0.02
0.015

Run1
run2

0.01

run3
0.005
0
80

130

180

230

1/

Fig 2: 1/Surface Pressure (N/m) vs Area (m2)

Calculations
Run1

y = 2.71E-05x + 1.46E-02
R = 0.976

Slope = 2.71E-05
C = 1.46E-02

Run2

y = 1.04E-05x + 1.27E-02
R = 0.976

Slope = 1.04E-05

y = 8.2E-06x + 1.15E-02
R = 0.976

Slope = 8.2E-06

Run3

C = 1.27E-02

C = 1.15E-02

For Run 1
From the plot, using equation no (i),
we obtain values of A0 and q
=
=

----------------------(i) compare with y = mx+c

8.314 297

2.71 10
8.314 297
q = 3.0975* 10-09mol
=

A0 = 1.46* 10-2
For Run 2
1.04 10
8.314 297
q = 4.21179* 10-09 mol
=

A0 = 1.27*10-2
For Run 3
8.2 10
8.314 297
q = 3.32084* 10-09 mol,
=

A0 = 1.44*10-2

Results table
Run

q (moles)

A0(m2)

3.0975 * 10-09

0.0146

4.21179* 10-09

0.0127

3.32084* 10-09

0.0144

2.64727* 10-09

6.60E-04

Standard Deviation

Overall Observation

Surface pressure is basically a change in surface tension. It is the function of area of

water surface available for each molecule in the solution.

The most common technique for studying Langmuir monolayers of amphiphilic

substances has been to measure the surface pressure as a function of the surface area.

In Langmuir films, the area decreases the surface concentration increases and surface
pressure increases.

The spreading time for the amphiphilic substance should be sufficient for the proper
distribution on the water surface.

The sample which consists of the solvent should be volatile enough to evaporate so as to
find the surface pressure of the fatty acid easily.

Characteristics of Solvent:
Immiscible in water
Non reactive
High vapour pressure
High volatility

Conclusions:
The Langmuir mono layers are formed and the -A isotherm plotted.

In case of Langmuir film formation, as the area decreases the surface concentration increases and
surface pressure increases.
During the monolayer formation, which is the length of time required for a surface to be covered
by an adsorbate, the molecules are almost flat on the water surface. Then after decreasing the
surface area, the molecules come closer similar to a phase change from gas phase to liquid phase
with the hydrophilic chains beginning to interact with each other.
As in normal phase change, volume changes with pressure similarly for Langmuir film, surface
pressure is dependent on surface area.When the barriers come closer, i.e. the surface area
decreases, beyond the close packed region, similarly to a phase change from liquid to solid
phase, the molecules are forced out of the monolayer.The film breaks and collapses resulting in
the decrease of surface pressure.
Reproducibility could not be achieved may be due to the spreading of surfactant-solvent mixture
on the water surface.
Shut Down procedure:
Clean the trough and the barriers with distilled water and Wilhelmy plate with acetone.

CL 610: Experimental Methods

EXPERIMENT NO. 11

Determination of Dynamic Surface Tension of a Surfactant

Using a Bubble Pressure Tensiometer
TA: Shital D. Bachchhav

AIM:
(1) To determine the dynamic surface tension of a given surfactant solution using the maximum
bubble pressure technique
(2) To calculate the rate constant for demicellization of the given surfactant solution
INTRODUTION: Bubble pressure tensiometry is used to study various dynamic surface
phenomena including industrial and biological applications. Many industrial processes, such as
coating, printing and flotation, operate under dynamic conditions and therefore surface tension
determined within short life spans provides often more relevant information than equilibrium
state values.

THEORY: The method is based on the measurement of the maximum pressure in a bubble
growing at the tip of a capillary immersed into the liquid under study. When a bubble grows at
the tip of a capillary, the pressure inside the capillary is measured. Maximum pressure is reached
when the bubble is hemispherical, after which it grows quickly, separates from the capillary and
a new bubble is formed. The surface tension is calculated by the Laplace equation taking the
capillary radius as radius of curvature
2
Pmax
..(1)
r
The maximum internal pressure in a gas bubble forming at an orifice in a test liquid is the sum of
two components, one hydrostatic and the other due to surface tension. Pressure P is indicated by
the transducer output and is recorded as voltage in the drive of the recorder. Linear relationship
has been taken between maximum pressure and voltage
V kPmax

(2)
1

Where, k=constant.
By substituting equation (1) in equation (2)
V k *
Where, k *

.... (3)
2k
= slope
r

Dependency of the surface tension on the concentration: Concentration is one of the

parameter which has a decisive influence on the surface tension. The equilibrium value of the
surface tension decreases as the number of surfactant molecules accumulating at the surface
increases. It achieves its final value when the surface is completely occupied and offers no place
for further molecules. If the concentration is further increased from this point then the surfactant
molecules will accumulate within the solution and form aggregates, the so-called micelles. The
concentration at which this effect occurs is known as the critical micelle formation
concentration (CMC). It is an important characteristic of surfactants. This means that methods
for measuring the dynamic surface tensions should only be used above the CMC. In such a case
the concentration only influences the chronological function of the surface tension and no longer
has any influence on its static value.
Variation of surface tension with the bubble frequency: For pure solvents the dynamic
surface tension does not change with the bubble rate. In case of multi component solution, the
surface tension increase with the increasing bubbling frequency. At higher frequency the
surfactant molecule does not have adequate time to diffuse to and orient them at the gas/liquid
interface. Hence the surface tension increases.
CHEMICALS AND APPARATUS:
Distilled water, Ethyl alcohol, Sodium dodecyl sulphate (SDS), Volumetric flasks, Conical
flasks, Beakers, Pipette

INSTRUMENTS: Bubble pressure tensiometer

EXPERIMENTAL PROCEDURE:
(1) The instrument was calibrated by measuring the DC voltage signal of DI water, pure ethanol
and the mixture of DI water and ethanol.
(2) 5 mM sodium dodecyl sulphate (SDS) solution was taken as test solution in a glass beaker.
(3) The DC voltage signal of the solution was measured with a bubble pressure tensiometer at
bubble frequencies in the range of 0.5-3 bubbles/s.
(4) Steps 2-3 were repeated with 12.0 mM SDS solution
2

RESULTS AND OBSERVATIONS:

Table1: Calibration for pure water and ethanol
Sample
DI water
15% Ethanol+DI water
40% Ethanol+DI water
Ethanol

Temp
o
( C)
24.1
24.1
24.1
24.1

Voltage
(Volts)
4.10
2.10
1.48
1.00

Surface Tension
(mN/m)
72.00
42.72
30.69
22.39

Figure1: Voltage vs. Surface tension calibration curve

Table2: Dynamic surface tension at different bubbling flow rates of 5 mM SDS solution.
S. No

Bubble frequency
(bubbles/s)

1
2
3
4
5

0.156
0.625
0.833
1.667
2.000

Voltage
(volts)
1.7
1.8
2.0
2.3
2.4

Surface tension (mN/m)

27.41
29.03
32.25
37.09
38.70

Table3: Dynamic surface tension at different bubbling flow rates of 12 mM SDS solution.
S. No
1
2
3
4
5

Bubble frequency
(bubbles/s)
0.250
0.714
1.000
1.666
2.500

Voltage
(volts)
1.78
1.79
1.80
1.91
2.0

Surface tension (mN/m)

28.70
28.87
29.03
30.80
32.25

Figure 2: Surface tension change with respect bubble frequency for () 5 mM SDS and () 12
mM SDS solution.
DETERMINATION OF RATE CONSTANT FOR DEMICELLIZATION:
Critical micelle concentration (CMC) of SDS = 8 mM
We take one above CMC (12 mM) and one below CMC (5 mM) to analyse the characteristic.
Ward and Tordai suggested a model equation for determination of surface tension under such
conditions which are given below for two solutions mentioned above.
4

For concentration below CMC and for diffusion controlled adsorption the reduction of (t)
follows square root decay

D tHBF

(t ) t 0 0 2 R T C

(4)

For concentration above CMC and for diffusion controlled adsorption the reduction of (t)
follows square root decay

(t ) t

eq

RT

2
eq

2 c0tLBF

1
Dk

..

(5)

Where,
HBF and LBF are higher and lower bubble frequency respectively
t0 - Surface tension of the solution at highest bubble frequency = 38.70 mN/m
0 - Surface tension of pure water in mN/n = 72.29 mN/m
R - Universal gas constant = 8.314 J/K
T - Temperature of the solution = 296 K
C- Bulk surfactant concentration in mM = 5 mM
Substituting these values in eq(4)
D - Diffusion coefficient in m2/s = 1.67*10-11 m2/s

Substituting the value in equation (5) with the below datas the rate constant for demicellization
t HBF - Surface age corresponding to highest bubble frequency in sec = 6.9 s
t - Surface tension of the solution at lowest bubble frequency in mN/m = 28.70 mN/m
eq - Equilibrium surface tension = 33.997 mN/m
C0 - Critical micelle concentration in mM = 8 mM
eq = -1/RT (d eq/dlnc) = equilibrium surface adsorption in mol/m2 = 3.56*10-6 mol/m2
The rate constant for demicellization k = 1.71*10-4 sec-1

Conclusion:
The increase in bubble frequency causes increase in surface tension, as more bubbles are formed
more is the decrease in surfactant concentration in the bulk because surfactant molecules
preferably attaches on new surfaces(i.e. bubbles) this increases the surface tension. With the
increase in concentration again the surface tension decreases. The rate of demicellization is
1.71*10-4 s-1

CL-610 Experimental Methods

EXP NO.-12 STOPPED FLOW REACTOR

Lab Report
By
Shashikant
(10402003)
Teaching Assistant

Department of Chemical Engineering

Indian Institute of Technology Bombay, Mumbai-400 076

TITLE: - STOPPED FLOW REACTOR

AIM:
To study the reaction kinetics of the reduction of 2, 6-dichlorophenolindophenol (DCPIP) by
Ascorbic acid (AA) in absorbance mode and find the dead time (theoretically) using MOS200/M, a stopped-flow module and Bio-Kine 32 V4.51
INTRODUCTION
A stopped flow instrument is a rapid mixing device used to study the chemical kinetics of a
reaction in solution. After two or more solutions containing the reagents are mixed, they are
studied by whatever experimental methods are deemed suitable. Different forms
of spectroscopy and scattering of radiation are common methods used. A stopped flow
instrument coupled to either a circular dichroism spectrometer or a fluorescence spectrometer is
often used in the field of protein folding, to observe rapid unfolding and/or refolding of proteins.
THEORY
The stopped flow technique is a flow injection technique in which reactants are rapidly injected
in a cuvette mixing chamber by forcing the reagents from syringes through jets and flow is
stopped suddenly in detector cell. This method is used for the study of reaction kinetics of very
fast reaction in solution viz. enzymatic reactions.
Dead time:- It is a critical performance parameter in Stopped flow technique, which is
difference in time between the end of mixing point and the start of observation point. In other
words, It is the ratio of volume of cuvette (V) to the volumetric flow rate in the chamber (q).
REACTION
DCPIP L Ascorbic Acid L-Dehydo Ascorbic Acid

APPARATUS

MOS-200/M ( with 150W Xenon mercury lamp)

FC-15 cuvette
SFM-20 equipped with 10 ml syringes
Bio-Kine software
Beakers, Volumetric flask

CHEMICALS

De-ionized (DI) water

100 ml of 10 mM Ascorbic acid (pH=9)
100 ml of 0.5mM DCPIP

APPLICATION
1. SFM finds application in analysis of very small quantities of material of order of less than 0.7
to 500 L and handling of corrosive materials (e.g H2SO4).
2. It is widely used for the study of mechanism of Ozone- Alkene reaction in gas phase for the
purpose of atmospheric modeling.

Fig. 1: Classical Stopped-flow design

PROCEDURE
A. Prepare stock solutions of concentration 0.5 mM of DCPIP and AA of 10 mM from the
respective salts.
B. Switch on the ALX 250 and ensure that power reaches 150 W. Meanwhile, switch on the
PMS 250 and MPS 70/2.

C. Start Bio-Kine interface software ion on desktop which will control SFM.
D. Set wavelength 524 nm and ensure AUTO MODE in spectrometer settings.
E. After the settings are done, purge the cuvette manually by injecting DI water through
syringes to ensure no previous contamination.
F. Water referencing:1. Fill both the syringes with DI water and fix on SFM
2. Click on Mixing sequence in interface, set appropriate values of mixing ratio,
total volume/shot and total flow rate, ensuring a safe mode(green color)of
operation and click on Ready.
3. Click on device form toolbar, select transient recorder kinetics and on the
acquisition setup start giving shots under shot control with periodic view on yauto-scale and observe absorbance-time plot.
4. Ensure absorbance reading of water reference zero or close to zero, otherwise
reset reference voltage or increase number of shots to make base line zero or close
to zero.
G. After water referencing, a calibration for pure DCPIP (0.5mM) and DCPIP-H2O system
for varying mixing ratio (2:1, 1:1, 1:2, 1:3, 1:4, 1:5) is recorded.
H. Replace the syringe containing DI water with AA of 10mM concentration and 0.5 mM
concentration of DCPIP. Repeat the steps (G) for the reaction mixture of DCPIP-AA
(pH=9) for different mixing ratio (4:1, 3:1, 2:1) kinetics of which is to be determined
through SFM 20.
I. Record absorbance value from absorbance time plot on software interface.
J. Rinse the system with DI water and switch off all the devices.

Let A and B are two reactants such that

rA KC ACB
If B in excess, then KCB will be constant and reaction will be pseudo first order. In such case:
-rA=K1CA
Here K1=KCB

RESULTS
Table 1: Calibration for DCPIP-Water System
C1 (mM) C2 (mM)
0.5
0.5
0.5
0.5
0.5
0.5
0.5

0
0
0
0
0
0
0

Mixing ratio
DCPIP : Water
2:1
1:1
1:2
1:3
1:4
1:5
0:1

V (mL/sec)
4
5.5
5.5
4
4
4
5.5

C (mM)
Absorbance (AU)
0.3333
0.394
0.25
0.268
0.1667
0.199
0.125
0.160
0.1
0.132
0.0833
0.112
0
0.0001

C1: Concentration of pure DCPIP in solution (mM)

C2: Concentration of DCPIP in pure water (mM)
V: Total volumetric flow rate (mL/sec)
C: Concentration of DCPIP in mixture (mM)

Calibration Curve (DCPIP + H2O)

Absorbance (AU)

0.5
y = 1.1192x + 0.0115
R = 0.9897

0.4
0.3
0.2
0.1
0
0

0.05

0.1
0.15
0.2
0.25
Conc. of DCPIP (mM)

0.3

Fig.1: Calibration curve for DCPIP + H2O system.

0.35

DCPIP + Ascorbic Acid (4:1)

Conc. Vs Time
0.5
Conc. (mM)

0.4
0.3
0.2
0.1
0
0.00E+00

1.00E+00

2.00E+00
Time (s)

3.00E+00

4.00E+00

Fig.2: DCPIP + Ascorbic acid with mixing ratio:-4:1

ln(C0/C) vs Time
1.2
y = 0.3395x + 0.045
R = 0.999

1
ln(C0/C)

0.8
0.6
0.4
0.2
0
0

0.5

1.5
2
Time (s)

2.5

3.5

Fig.3: Evaluating rate Constant (k) for DCPIP + AA, Flow Rate:-4:1

DCPIP + Ascorbic Acid (3:1)

Conc. (mM)

Conc. Vs Time
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
0.00E+00

1.00E+00

2.00E+00
Time (s)

3.00E+00

4.00E+00

Fig.4: DCPIP + Ascorbic acid with mixing ratio:-3:1

ln(C0/C) vs Time
1.4
y = 0.3796x + 0.0364
R = 0.9983

1.2
1
ln(C0/C)

0.8
0.6
0.4
0.2
0
0

0.5

1.5
2
Time (s)

2.5

3.5

Fig.5: Evaluating rate Constant (k) for DCPIP + AA, Flow Rate:-3:1

DCPIP + Ascorbic Acid (2:1)

Conc. Vs Time
0.35
Conc. (mM)

0.3
0.25
0.2
0.15
0.1
0.05
0
0.00E+00

1.00E+00

2.00E+00
Time (s)

3.00E+00

4.00E+00

Fig.6: DCPIP + Ascorbic acid with mixing ratio:-2:1

ln(C0/C) vs Time
2
y = 0.4795x + 0.1121
R = 0.9935

1.5
ln(C0/C)

1
0.5
0
0

0.5

1.5
2
Time (s)

2.5

3.5

Fig.7: Evaluating rate Constant (k) for DCPIP + AA, Flow Rate:-2:1

Calculating Dead Time:

ln(Cf/C0) = k * td
Cf = Feed Concentration of DCPIP
C0=Concentration of DCPIP at the beginning of observation
Table 2: Rate constant (k) for DCPIP + AA system
Sl.No. Mixing ratio

Molar ratio

DCPIP : AA

DCPIP : AA

4:1
3:1
2:1

1:5
1:667
1:10

1
2
3

Total
flow rate
(mL/s)
4
4
4

Initial
Conc. (C0),
(mM/lt)
0.392
0.375
0.321

Feed Conc.
(Cf),
(mM/lt)
0.4
0.375
0.333

Rate
constant
(k), (1/s)
0.340
0.380
0.480

Dead
Time
(td), (s)
0.060
0.002
0.078

DISCUSSIONS
1. Concentration of ascorbic acid is kept sufficiently high so as to maintain pseudo first
order reaction.
2. It is seen that concentration and absorbance bears a direct relationship i.e. Absorbance is
directly proportional to Concentration.
3. With an increase in the flow rate of ascorbic acid there is a decrease in the absorbance.
4. As we increase the flow rate of Ascorbic acid we see that the R2 value corresponding to
the linear plots of ln(C0/C) vs t constantly decreases indicating that the linear plot is not
perfect; in other words the reaction no more behaves as a first order reaction.
5. Value of dead time is very high so it creates error in calculation of true value of reaction
rate.

Experiment No-13
High Performance Liquid Chromatography (HPLC)

Aim:
To get an insight to the HPLC, an analytical technique.
To determine the concentrations of the components in the liquid mixtures.
Apparatus and Instruments:
Sample bottles, syringe, HPLC instrument, etc
Chemicals: Glycerol, oxalic acid, HPLC grade ACN, HPLC grade water, etc.
Theory:
HPLC is a method used for separation of compounds in a Liquid mixture effectively compared to
that of column chromatography.
Why ?
But as research advanced there was requirement to analyse all the molecules in a given sample
for better detection of problem (in clinic), impurities and also deficiencies in industry and
research.
Normal-phase chromatography is termed when there is a polar stationary phase in conjunction
with a non-polar (dispersive) mobile phase.
Reverse phase is termed when there is a non-polar stationary phase and a polar mobile phase.
The advantage of reverse phase is that it allows us to use relatively cheap and non-hazardous
solvents like methanol, ethanol, acetonitrile, and even water.

Working

Principle:

It involves the separation of compounds which is due to their relative differences in travel
through the column on application of pressure exerted through mobile phase or carrying
liquid.
The compounds of the mixture travel with different rates due to their relative affinities
with the solvent and stationary phase. Compound with higher affinity towards the
stationary phase of the column travels slowly and vice-versa.

The above principle is similar to that of column chromatography but in HPLC, the
separation is more effective due to greater surface area achieved due to very small
particle size of stationary phase in comparison to that used in column chromatography.

This decrease in particle size increases has disadvantage that it proportionately enhances
the flow time and run time due to increased surface area. To minimize this obstacle the
high pressure is applied to the flow of mobile phase through the column by use of pumps.

Application :
HPLC is one of the chromatography systems which is widely used in the fields of clinical
research, biochemical research, industrial quality control etc. Its applications include detection,
analysis, determination, quantification, derivation of molecules from mixtures of biological,
plant and medical importance.

Column specification and operating guideline:

In this experiment we will use a resin based HPX-87H aminex column (300*7.8mm) with guard
column.
1) Support: Sulfonated divinyl benzene-styrene copolymer
2) Resin ionic form: Hydrogen
3) Maximum pressure: 1500 psi
4) Maximum temperature: 650C
5) pH range: 1-3
6) Flow: 0.4-0.6 ml/min
7) Organic Modifier: ACN 40%, EtOH, IPA, 5%
8) Inorganic modifier: Phosphoric acid, Nitric acid (5%)
9) Avoid from : MeOH, salts, bases, metal ions, amines, other organic solvents, H2O, pH-3

Aminex HPLC columns offer many advantages for the analysis of carbohydrates, alcohols and
organic acids using simple isocratic normal phase eluents like water or dilute acid, and
sometimes with organic modifiers such as Acetonitrile (ACN). The resin packing allows a
variety of partition type separations without the disadvantage of the limited lifetime associated
with bonded phase silica materials.
The fundamental partition process responsible for separation is moderated by the ionic group
bound to the resin and by the choice of the counter ion. Termed ion-moderated partitioning, this
unique process enables these resins to separate compounds via multiple modes of interaction,
involving a combination of ion exclusion, ion exchange, ligand exchange, size exclusion,
reversed phase and normal phase partitioning.
Procedure:
Step 1. Prepare the mobile phase 30% ACN in water which is of 8 mMolar concentration of
H2SO4.
3

Step 2. Sonicate and degasses the prepared mobile phase. Refill the solvent reservoirs.
Step 3. Samples for analysis should be dissolved in water, or one of the other mobile phases, and
introduced into the sample vials using a syringe.
Step 4. Turn on the HPLC, detector and computer, Prime the pump following directions from
your TA and allow the prepared mobile phase to pass through the column for at least 60 minutes.
Make sure the baseline is stable before injecting your standards and unknowns. Set wavelength
to 210 nm and flow rate to 0.6 ml/min. Now you are now ready to set up an analysis.
For the sample preparation the ratio for calibration of glycerol is to be done in the ratio of 1:1,
1:2, 1:3, 1:4 and 1:5 in terms of concentration.
Step 5. Introduce at least 20 l (with the help of micro syringe) of the least concentrated standard
through the 20 l rotary injection valve while in the LOAD position.
Step 6. Turn the valve to the INJECT position and simultaneously begin the computer
integration.
Step 7. Calibrate both Glycerol and Oxalic acid & Allow the peak of glycerol/oxalic acid to be
recorded
Step 8. Repeat this procedure for your other standards as well as your unknowns.
Overall Observations:
Selectivity of the column is a function of temperature and elution orders of peaks may change
and even reverse - some chiral and amino acid separations are very sensitive to column
temperature effects.

Peak width, or sharpness, is an indication of column efficiency.

An ideal peak is a Gaussian distribution.

The ratio of standard deviation to retention time is independent of flow rate.

Peaks become smaller or disappear altogether in sequential runs because of improper

purging or Injector is clogged.

There was a negative peak observed. Negative peaks are most often caused by differences
in refractive index between the sample solvent, sample and mobile phase. They are also
caused after routine maintenance when the system has not been reconfigured correctly.
One more reason can be because of wrong polarity, reverse leads or change detector
polarity

Observation Table:
Flow rate: 0.6 ml/min
Pressure: 980 psi
Detector: UV (210 nm) and RI detector used in series
Temperature of column oven: 60 0C
Mobile phase: 30% ACN in water which is of 8 mMolar concentration of H2SO4
Table 1: Calibration data for Glycerol

Glycerol
samples
C1
C2
C3
C4
C5

Concentration
(mM)
0.642
0.321
0.214
0.160
0.128

Calibration data for Glycerol

Area under
Curve(RI)(V.sec)
Height(V)
84.96
3.78
46.51
2.10
31.84
1.44
23.83
1.08
19.05
0.88

Retention
Time(min)
14.414
14.418
14.511
14.478
14.307

Calibration curve for glycerol

Area under Curve((V.sec)

100000000
y = 1E+08x
R = 0.9904

90000000
80000000
70000000
60000000
50000000
40000000
30000000
20000000
10000000
0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Concentration(mM)

Figure 1: Calibration curve for glycerol with respect to area under curve and concentration

Calibration curve for glycerol

4500000
y = 6E+06x
R = 0.9862

4000000

Height(V)

3500000
3000000
2500000
2000000
1500000
1000000
500000
0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Concentration(mM)

Figure 2: Calibration curve for glycerol with respect to height and concentration

Table 2: Calibration data for Oxalic Acid

Calibration data for Oxalic Acid

Oxalic Acid
samples
C1
C2
C3
C4
C5

Concentration
(mM)
0.035
0.018
0.012
0.009
0.007

Area under
Curve(UV)(V.sec)
68.70
36.83
23.55
18.87
15.02

Height(V)
4.030
2.600
1.671
1.317
1.032

Retention Time(min)
7.715
7.716
7.709
7.731
7.752

Calibration Curve for Oxalic Acid

Area under Curve((V.sec)

80000000
y = 2E+09x
R = 0.9958

70000000
60000000
50000000
40000000
30000000
20000000
10000000
0
0

0.005

0.01

0.015
0.02
0.025
Concentration(mM)

0.03

0.035

0.04

Figure 3: Calibration curve for oxalic acid with respect to area under curve and concentration

Height(V)

Calibration Curve for Oxalic Acid

5000000
4500000
4000000
3500000
3000000
2500000
2000000
1500000
1000000
500000
0

y = 1E+08x
R = 0.9309

0.005

0.01

0.015
0.02
0.025
Concentration(mM)

0.03

0.035

0.04

Figure 4: Calibration curve for oxalic acid with respect to height and concentration

Table 3: Determination of the concentration of the unknown sample for Oxalic Acid and
glycerol

Glycerol
Area under
curve (V . sec)
47.025
43.920
46.456

Calculated Conc. by
graph (mM)
0.32
0.32
0.34

Actual Conc.
(mM)
0.32
0.32
0.32

Area under
curve(V . sec)
40.151
36.998
36.567

Calculated Conc. by
graph (mM)
0.020
0.018
0.018

Actual Conc.
(mM)
0.018
0.018
0.018

Std.Deviation
0.0120715

Average
0.32449

Coefficient of
Variance
0.0361

Average
0.01907

Coefficient of
Variance
0.052

Oxalic Acid
Std.Deviation
0.00098

Conclusions:

Calibration curves for both Oxalic acid and Glycerol were standardized with respect to
concentration for a particular retention time.
Glycerol is not detected by UV detector and it is detected by RI because a sharper peak was
observed by RI detector.

For Oxalic acid both detectors that is UV and RI detector used in series but sharper peak is

observed by UV detector.
After the data was calibrated for oxalic acid and glycerol there was proper reproducibility in
the data with respect to the retention time (7.76 min & 14.4 min for oxalic acid & Glycerol
respectively)
From the slope of Glycerol and Oxalic acid from the calibrated graphs was used to calculate the
concentration of the unknown sample. The results obtained matched to the actual concentration
which was calculated initially.
The flow was optimized to 0.6 ml/min. the retention time is depends on flow. Retention time
is inversely proportional to flow.
The calibrated graph also shows that the Area under the curve & Height is decreases with
decrease in concentration of sample.
9

CL 610 (Experimental Methods)

Experiment 14
Washburn Capillary Rise Method for measuring
Wettability of Porous Solids
Instructors
Prof. Rajdip Bandyopadhyay
Prof. Y.S. Mayya

T.A. Incharge
Sonali Kulkarni

Department of Chemical Engineering

I.I.T. Bombay

Washburn Capillary Rise Method for measuring Wettability of Porous Solids

Objective: Measuring the wettability of given porous sample at different forms of packing.
Apparatus: Glass cups, cylindrical powder holders, spatula.
Chemicals: n-Hexane, Distilled water, Powder sample (TiO2).
Theory:
Surface wettability, one of the most crucial surface properties of materials, is a key
parameter for understanding the interactions of materials with their surrounding and for their
applications. Surface wettability is generally characterized by contact angle of a liquid on a solid
surface. For a flat solid surface, many common techniques, e.g. sessile drop and Wilhelmy plate,
can be applied for measuring contact angles. For powders/porous materials, capillary rise, i.e.
flowing of a liquid up a capillary by attractive forces between the liquid and the solid surface, is
normally used to characterize their wettability. In particular, the Washburn capillary rise (WCR)
method, which is derived from the rate of capillary rise of liquid penetrating in a packed
cylindrical tube, has been widely employed.
According to the Washburn theory, when a porous solid is brought into contact with a
liquid it will rise into the pores of the solid as shown in the figure.

Fig-1: Washburn method for measuring the contact angle of porous solids

To deduce the contact angle values, either the rate or the height of the capillary rise is measured.
The equation is based on Poiseuilles law as expressed below:
=
= volume of the liquid
= radius of the cylindrical tube
= pressure drop

(1)

= viscosity of the liquid

= height of the liquid risen
= time required by the liquid to reach height

is the pressure difference between the capillary pressure and the hydrostatic pressure given

by,
=2
Let us neglect the hydrostatic pressure

and use

and substitute =

(2)
in

eq.1. Integration of eq.1 from = 0, = 0 to = , = gives,

=

(3)

Eq. (3) is Washburns equation that presents the relation between a squared height of the
penetrating liquid and the penetrating time. In the case of powders or porous materials packed in
a tube, voids between materials could be described as many bundles of capillary tubes.
Therefore, WCR can be applied to obtain contact angles for powders or porous materials and can
also be expressed in term of a squared mass of the penetrating liquid and the penetrating time as:
=

(4)
(5)
(6)

Where,
= effective radius or the equivalent radius of voids in the packed powders
= cross-section of the tube
= the porosity of the packing in the tube
To determine contact angles of liquids on powders or porous materials using WCR, four
conditions have to be satisfied for the process (i.e. Washburns equation is derived based on
these four assumptions):
1. steady state laminar flow
2. no external pressure
3. negligible gravitational force
4. Zero velocity of the liquid at the solid/liquid interface (no slip).

Procedure:
1. Clean the powder holder tube using sonicator and dry it in the oven.
2. Pour n-Hexane in the cleaned glass cup and place it in the space provided in the
Tensiometer
3. Weigh a fixed quantity of given powder and place it in the powder holder tube using
spatula. Tap the bottom of the tube on a plane surface for uniform filling.
4. Hang the tube to the hook of the electronic balance of the tensiometer.
5. Enter the properties of the reference liquid (n-Hexane) and the measurement liquid
(water) in the parameter field provided in the software.
6. Through the software, obtain the graph of mass2 data versus time.
7. Find the solid constant with the help of slope of the graph.
8. Fill another glass cup with distilled water and place it in the appropriate space of
tensiometer.
9. Empty the previous sample from the tube, clean and dry it as per step 1.
10. Fill the tube with the same powder sample with same mass and measure the contact angle
of the powder for water with the help of the software.
Surface modification:
Two samples of powder have been used, one is the TiO2 powder as purchased and the
other is the HNO3 treated TiO2 powder. The powder is immersed in 5M HNO3 and stirred
for 6hrs. Then the powder is filtered and washed 2-3 times with water. It is dried in the
oven and again crushed in the powder form. The acid treatment modifies the surface of
the particles and gives a concave texture to it. The modified sample is expected to show
lower contact angle with water as compared to the untreated sample.
Results:
Properties of the liquids:
Liquid
n-Hexane
Water

Surface tension (mN/m)

18.4
72.8

Density (gm/cc)
0.66
1

Viscosity (mPa.s)
0.3
0.89

Measurement of constant C:
From Washburn equation we have,

(7)

The constant can be obtained as,

=

(8)

For measuring , a completely wetting liquid is chosen for which one can assume
therefore,

= 0 and

= 1. We have used n-Hexane, as a wetting liquid. Putting the values of ,

and

of n-Hexane and the value of the slope, we calculate .

Following plot of

vs

is obtained for Hexane. The two lines indicate two separate run

8x10

7x10

6x10

5x10

4x10

3x10

2x10

1x10

m /t = 758.45 mg /s

mass (mg )

conducted for measuring .

m /t = 642.91 mg /s

200

400

600

800

1000

Time (s)

Fig-2: Measurement of

Measurement of :
For measuring the contact angle of the powder for water, the powder is contacted with water and
following plot is obtained. The lines indicate that two separate runs have been carried out with
fresh powder sample in the clean powder holder.

m2(mg2)

2.0x10

1.8x10

1.6x10

1.4x10

1.2x10

1.0x10

8.0x10

6.0x10

4.0x10

m /t= 170.67 mg /s

m /t= 170.96 mg /s

2.0x10
0.0

100

200

300

400

500

600

700

Time(s)

Fig-3: Measurement of

Using the properties of water, the value of

and value of slope (

) obtained for water in the

following equation gives,

=

(9)

Calculations:
Sr.
Sample
No
1

TiO2
powder

TiO2
powder

HNO3
treatedTiO2

Slope
)

(N.m-1)

Hexane
Water
Hexane

7.58x10-10
1.71x10-10
6.43x10-10

Water
Hexane
Water
Water

Liquid

0.0184
0.0728
0.0184

(kg.m3
)
660
1000
660

0.0003
0.00089
0.0003

2.84x10-17
----2.41x10-17

1
0.074
1

1.71x10-10

0.0728

1000

0.00089

-----

0.087

7.82x10-10
6.98x10-10
5.91x10-10

0.0184
0.0728
0.0728

660
1000
1000

0.0003
0.00089
0.00089

2.92x10-17
-----

1
0.292
0.247

(Pa.s)

(m5)
0
85.75
0
85.01
8
0
73.04
75.70

Conclusions:
1. TiO2 powder is non-wetting for water and there for has the contact angle is 85 i.e. close
to 90 .
2. The surface modified powder shows greater wettability. The contact angle reduced up to
74 showing the effect of acid treatment on the surface.

References:
1. Suchata Kirdponpattara, Applicability of Washburn capillary rise for determining contact
angles of powders/porous materials Journal of Colloid and Interface Science 397 (2013)
169176

2. Young Lim, Surface Characterizations of Variously Treated Titanium Materials,

International journal of Oral & Maxillofacial Implants, 2001, volum-16.

CL 610 (Experimental Methods)

Experiment 15: Image Analysis of Brownian particle

Instructors
Prof. Rajdip Bandyopadhyaya
Prof. Mayya

T.A.
Kumar Rishu (123020001)

Department of Chemical Engineering

I.I.T. Bombay

Aim:
To obtain an estimate of Boltzmanns constant (kB) using Image Analysis of
the Brownian particle.
Introduction:
Brownian motion was first systematically observed by the botanist Robert
Brown in 1827 and refers to the random motion of colloidal particles suspended in
water. In 1905, Einstein argued that this motion is direct evidence for the atomic
nature of matter and that the mean square displacement of colloidal particles is the
primary observable quantity. Because of the then recent invention of the ultra
microscope, Perrin was able to make precise measurements of submicron particles
and confirm almost all of Einsteins predictions for which Perrin was awarded the
Nobel Prize in physics in 1926. Einstein and Perrins efforts helped raise the status of
atoms from useful hypothetical objects to objects whose existence could no longer be
denied.

Fig 1. Brownian Motion of particles

Theory:
Theoretically, all the suspended particles have same kinetic energy since the
temperature is constant. Also thus it can be easily observed that as the mass of the
suspended particle increases the velocity decreases and vice versa. The particles are in
a continuous random motion due to the collisions with the walls of the container and
also the other molecules present in the solution.
Consequently it is observed that the number of collision of the Brownian
particle is very large with the solvent molecules. These random collisions are looked
upon as force or the resultant force, which is experienced by the Brownian particles.

This force is random in both magnitude and direction. As we have the conservation of
energy principle we have this force experienced by the particle equivalent to the
viscous drag experienced by the particle. This viscous friction is related to the
diffusion co-efficient of the particle by the equation,

D=

k BT
6 nr

D = Diffusivity
KB = Boltzmann Constant
T = Absolute temperature
n = Viscosity
r = radius of polystyrene particle

Thus we have,
<x(t) x(0)>2 = 2Dt
<y(t) y(0)>2 = 2Dt
Adding above two:
<R(t) R(0)>2 = 4Dt


Experimental Procedure:
Following are the steps to be followed during the experiment:
1. A dilute solution of polystyrene particles (size 1 m) in water is prepared.
2. A sample of this solution is placed on glass slide. A cover slip is placed on the
sample. Care is taken to avoid forming any bubbles.
3. The slide is placed on the focus of the microscope. Microscope is manipulated to
obtain a good and readable image.
4. IMAGE PRO software is used to record the movement of the particles. This is done
by taking snapshots at a certain time interval.
5. IMAGE J software is used to find the displacements of the particle at different time
intervals.

6. A standard calibration scale is used to convert pixels to m.

7. Room temperature is noted.

Sample Observation:
For 350 ms: X and Y coordinates in microns
Displacement
in X
Displacement Square of X Square of Y
X (microns) Y (microns) (microns)
in Y (microns) displacement displacement
133.085
65.377
133.383
66.369
0.298
0.992 0.088804 0.984064
134.028
67.063
0.645
0.694
0.416025
0.481636
135.615
67.212
1.587
0.149
2.518569
0.022201
134.97
66.964
-0.645
-0.248
0.416025
0.061504
135.218
67.262
0.248
0.298
0.061504
0.088804
136.26
67.163
1.042
-0.099
1.085764
0.009801
136.26
67.758
0
0.595
0
0.354025
136.012
68.155
-0.248
0.397
0.061504
0.157609
136.012
67.46
0
-0.695
0
0.483025
136.359
67.163
0.347
-0.297
0.120409
0.088209
136.954
67.56
0.595
0.397
0.354025
0.157609
137.897
67.659
0.943
0.099
0.889249
0.009801
139.435
68.304
1.538
0.645
2.365444
0.416025
140.179
68.452
0.744
0.148
0.553536
0.021904
140.427
69.147
0.248
0.695
0.061504
0.483025
141.419
69.097
0.992
-0.05
0.984064
0.0025
141.369
69.345
-0.05
0.248
0.0025
0.061504
142.063
69.742
0.694
0.397
0.481636
0.157609
142.907
69.544
0.844
-0.198
0.712336
0.039204




0.5880472 0.2147399 0.8027871
<x square> <y square> <R square>


Time
(in Sec)
<R square>
0.1 0.251036947
0.15 0.286903684
0.2 0.379811579
0.35 0.802787211
0.45 1.083812526
0.55 1.296114158
0.65 1.130325842
0.8 1.615789842
0.95 1.680448789

Calibration of the instrument:

1 micron = 3.36 pixels (for 40 X lens)





y = 1.9698x
R = 0.93361

R square
2
1.8
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Time in Sec

Calculations:
From the slope of the above graph, 2D is 1.9698 exp(-12) m2 sec-1.
According the equation

D=

k BT
6 nr

at 299 K temperature and for 1 micron diameter polystyrene particles, kB turns out to
be 1.3802 exp(-23) JK-1.
Discussion:

The estimate of Boltzmann constant came out to be very near to the known
value.
Possible sources of error could be in determining the central location of the
particles
At much lower (below 100 ms) and very higher (above 1500 ms) exposure
time the estimate is off the limits because of error in accurately measuring the
displacement of the particles.

CL610

5. Rheometry
16
Objective
Study the behaviour of the samples viscosity by varying the solid (silica) volume fraction in the
given liquid sample and verify Einstein equation.

Introduction
Rheology is the science of deformation and flow of matter under controlled testing conditions.
Flow and deformation are interdependent to each other. Rheology studies the relationships
between deformations and stresses in a material, which in general is moving or flowing.
Viscosity, the tendency of a fluid to resist the applied stress, is one of the important properties of
fluid in the field of fluid mechanics. It is used in designing of pumps and piping, mixing and
agitation of dispersions and solutions, coatings, adhesives and other chemical processes. The
viscosity of fluid varies with introduction of dispersed phase, such as emulsions and slurries, and
also depends on physical (size and concentration) and chemical properties of dispersed phase.
Based on the response of the viscosity to the shear rate, fluids can be classified as Newtonian and NonNewtonian and their flow behaviour has been given in fig 1. In this experiment, we are going to study

the effect of the volume fraction of the Fe3O4 particles on viscosity of aqueous solution using
rotational rheometer (concentric cylinders).

Figure 1: Flow behaviour of fluids

CL610

Theory
Various models exist to represent the viscosity of a suspended fluid as a function of volume
fraction of solid particles, i.e., the size and concentration of the solid particles, and viscosity of
pure fluid. Two of them are
Einstein Model (Linear):
It may be used for extremely low concentrations of fine particles (Fe3O4) and particles are
considered as spherical and there is no interaction among them.
=1+

(1)

Guth and Simha Model (Quadratic):

It is developed by considering interaction among the solid particles at higher concentrations of
particles in liquid.
=1+ +
Where

and

(2)

= Viscosity of particle suspended fluid and pure fluid (Water) respectively [Pa.s]

= Volume fraction of suspended solid particles in the fluid

,

= Constants

There are different ordered

terms involved equations also exist.

Rheometer Operating Principle

Common characteristic of all rheometers is the measure of two physical quantities: one is a
dynamic quantity (i.e. a force, torque) and the other is a kinematic quantity (i.e. a velocity, shear
rate, flow rate, time). One of the two quantities is directly controlled (or set) by the instrument.
There are different geometries available as, plate-plate, cone-plate and concentric cylinders,
shown in fig 2.

CL610

Figure 2: Geometries of rheometer

The sample fluid is sheared in an annulus gap between concentric cylinders. The viscosity is
measured as the ratio of the shear stress and the shear rate by rotation mode operation. The
stress is dependent on the torque applied on the inner cylinder and the shear rate is dependent
on the angular velocity. During operation, one of these variables is selected and the other is
measured in controlled stress or controlled strain mode of operations. The following sequence of
calculation happens in rheometer:
1. Shear rate is controlled by angular velocity of inner cylinder

2. Torque applied to shear fluid on inner cylinder is calculated is from power supplied and
angular velocity.
Torque = (power / angular velocity)
3. Shear stress on the inner cylinder

4.

Viscosity = (Shear stress / shear rate)

The proof of the above equations was given in reference 2.

3

CL610

Sample Fluid Suspended solid Silica particles in Silicone oil or Water (solid suspension in
liquid)

Apparatus Rheometer (Anton paar Physica MCR 301), Concentric cylinders (Inner cylinder rotates
and outer cylinder is stationary) and Plate and cone geometry.

Experimental Procedure
1. Prepare the various particle volumes fractioned Silica aqueous or Oil solution samples.
2. Find the viscosity of the pure water (

).

3. Find the viscosity of the other samples (

).

Observations and Results

Table 1: Shear rate vs Shear stress data from rheometer for Silicone oil + Silica
Silicone oil + Silica
Pure silicone oil,

SR (1/s)
1
1.78
3.16
5.62
10
17.8
31.6
56.2
100

= .

=
SS(Pa)
1.09
1.91
3.42
6.07
10.8
19.2
34.1
60.5
107

SR(1/s)
1
1.78
3.16
5.62
10
17.8
31.6
56.2
100

SS(Pa)
1.11
1.97
3.57
6.32
11.2
20
35.4
62.8
111

= .
SR(1/s)
1
1.78
3.16
5.62
10
17.8
31.6
56.2
100

SS(Pa)
1.16
2.02
3.6
6.41
11.4
20.2
35.8
63.4
112

= .
SR(1/s)
1
1.78
3.16
5.62
10
17.8
31.6
56.2
100

SS(Pa)
1.36
2.41
4.06
7.02
12.1
21.1
36.9
64.5
113

** SR-Shear rate [1/s], SS-Shear Stress [Pa]

Results and Discussion

The viscosities have been found by curve fitting of data (i.e., Shear rate vs Shear stress) obtained
from rheometer to a straight line (i.e., Shear stress = Viscosity * Shear rate). The slope of the line
gives viscosity of the sample.

CL610

Figure 3: Newtonian curve fit to find viscosity of Silicone oil + Silica system
From the above figure 3, the viscosity increases with volume fraction of particles in the silicone oil.
The viscosity increase is 3.8%, 0.9% and 1.4% from lower to higher solid fractioned sample. The
viscosity increase should not always be true for all systems. It has also been observed reverse
trend for Glycerol+Silica system. It depends on the pure fluid behaviour i.e., shear thinning or
shear thickening.
Table 2: Error calculation for relative viscosity

Volume
fraction of
particles,

Viscosity
of
suspende
d phase,
[Pa.s]

lower
bound
From
straight
line fit

1.072
1.113
1.123
1.139

1.069
1.109
1.119
1.125

upper
bound
From
straight
line fit

Relative
viscosity,

Lower
error bar

upper
error bar

Oil + Silica
0
0.005
0.01
0.03

1.075
1.116
1.127
1.152

1.00
1.04
1.05
1.06

3.96E-03
4.73E-03
4.75E-03
1.34E-02

3.96E-03
4.03E-03
4.75E-03
1.25E-02

* value is

CL610

Figure 4: Validity of Einstein with the experimental measurements for Silicone oil + Silica
From the figure 4, at lower volume fractions rate of rise of relative viscosity was large compared
to the higher solid fractions and also observed less error in the measurements of the equipment,
Einstein model does not fit for these experimental measurements.

Analysis and Discussions

The viscosity increase is 3.8%, 0.9% and 1.4% from lower to higher solid fractioned sample as solid
fraction increase of 0.5%, 100% and 200%. In order to check the validation of these models it is
better to perform experiments at higher volume fractions (< 0.05) of particles and need more
measurements.

Literature
1. Lauffer, M.A., Motion in viscous liquids. Simplified derivations of the Stokes and Einstein
equations, J. Chem. Educ. 58, 1981, 250-256.
2. http://zeus.plmsc.psu.edu/~manias/MatSE447/13_Rheometry.pdf

TA Report

Experiment:
Vapour Pressure Osmometry
EXPERIMENT NO. 17
Instructors
Prof. Rajdip Bandyopadhyaya
Prof. Y S Mayya
TA
Satyanjay Sahoo

Department of Chemical Engineering

I.I.T. Bombay

Vapour Pressure Osmometry

Objective
Determination of molecular weight of polymer.

Introduction
Determination of the molar mass of polymers is of considerable importance because the chain
length is a controlling factor in the evolution of solubility, elasticity, fiber formation, and
mechanical strength properties. Methods used to determine the molar mass are either relative
or absolute. Relative methods require calibration with samples of known molecular weight
and absolute methods require no such calibration. This report will focus on the use of vapor
pressure osmometry to determine the number average molecular weight. These techniques are
useful in different molecular weight ranges and depend on the change in osmotic pressure and
the lowering of vapor pressure (respectively) by polymers in solution.

THEORY
Determination of number average molecular weight depends on basic equations of dilute
solution chemistry and physical chemistry. In a dilute solution, the vapour pressure of a
solvent is given by basic Raoults Law:
P1=P10 *X1
P1 = partial pressure of solvent in solution
P10 = vapor pressure of pure solvent
X1 = mole fraction of solvent
So, vapour pressure of any solution is lower than vapour pressure of its pure solvent.
Replacing a drop of pure solvent with one drop of solution leads to difference in the vapour
pressure. The vapour of pure solvent condenses on drop of solution until the vapour pressures
are balanced. The increase in vapour pressure of solution leads to an increase in temperature,
which in turn changes resistance and hence, generates a potential difference. This potential
difference is recorded until equilibrium is reached.
The basic relation for molecular mass determination equals:

n = Number of sample molecules

m = Mass of sample and solvent respectively
M = Molecular mass of the sample

For a molecular mass less than 500 g/mol the measurement value is proportional to the
number of moles. This is very similar to the osmolality determination. A sample is measured
where concentration and molecular mass are known (c in mol/kg). The slope of the graph of
measurement value v/s concentration is
with kg/mol.
K

MV
c

Unknown molecular mass of the sample can be determined by a known concentration. The
slope of the curve of measured value gives Kmeasurement
The molecular weight of unknown sample is determined with:
=

Methodology
Vapour pressure osmometer K-7000 is designed to exactly measure the number average
molecular weight of polymers. This measurement is based on the principle that chemical
potential of a solvent is altered in presence of a non-volatile substance. In dilute solution this
phenomenon depends only on the number of particles dissolved. Therefore change in
chemical potential is measured in terms of change of osmotic pressure and number average
molecular weight is determined. Figure 1 gives the internal view of the instrument.

Apparatus
Vapour pressure osmometer, volumetric flasks, pipette

Chemicals
NaCl (AR Grade), Millipore water, Sucrose

PROCEDURE
1. Prepare samples of different concentration for which molecular weight is to be
determined
2. Check whether thermistors are working or not
Press TEST, if it displays OK then carry on, otherwise stop.
3. Fill 25% of beaker with pure solvent along with the wick.

4. Insert the thermistor assembly inside the beaker and place it in an equipment chamber
and tighten to avoid leakage which will disturb the stabilization.
5. Place all the syringes inside the syringe ports. Fill two syringes with pure solvent and
place them back to the syringe holders to attain the temperature of head.
6. Set the temperature according to your requirement but within a limit given in an
equipment manual for different solvents. Selectable cell temperature 20 OC -130OC.
7. After temperature setting, place GAIN value to maximum (256).Then let it stabilize.
Selectable gain settings are 1,2,4,8,16,32,64,128,256
8. Before starting the experiment adjust the Wheatstone bridge signal value to zero with the
help of AUTOZERO function. After that add a drop of one of the solution prepared on
one thermistor. If the signal value is showing OVERLOAD then adjust the gain
accordingly to get signal value. In this way note down the signal and gain value for every
solution.
RESULTS
Table1: Calibration data of NaCl
Concentration of NaCl
(mole/kg)
0.2
0.4
0.6

Signal (mv)

0.8

Gain

Signal (mv)

Signal/Gain

16
8
8
4
8
4
4
2

606
303
652
327
962
481
655
327

37.88
37.88
81.50
81.75
120.25
120.25
163.75
163.50

180.000
Fig.1: Calibration graph for NaCl
160.000
140.000
120.000
100.000
y = 202.4x
80.000
R = 0.998
60.000
40.000
20.000
0.000
0
0.2
0.4
0.6
0.8
1
Concentration (mol/kg)
Fig. 1: Concentration vs Signal (NaCl)

Average Signal
(mv)
37.875
81.625
120.250
163.625

Table2: Osmolality data of NaCl (From Manual)

Conentration (Na+, Cl-)
(mmol/kg)

Conentration (mol/kg)

Osmomolality
(mOsmol/kg)

Osmomolality
(Osmol/kg)

105.6
213.3
323.1
433.8
545
655.7
767.5
823.9
1325.1
1983.2

0.0528
0.10665
0.16155
0.2169
0.2725
0.32785
0.38375
0.41195
0.66255
0.9916

100
200
300
400
500
600
700
750
1200
1800

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.75
1.2
1.8

Osmolality (Osmol/kg)

1.8
1.6
1.4
y = 1.8187x
R = 0.9999

1.2
1
0.8
0.6
0.4
0.2
0
0

0.2

0.4

0.6
0.8
Concentration (mol/kg)

1.2

Fig.2: Concentration vs Osmolality (NaCl)

FromFigure 1
signal 202.4 conc
FromFigure 2

(1)

Osmol 1.818 conc

Dividing equation(1) by equation (2)

(2)

signal 112.3 Osmol

(3)

K cal 112.3

Table3: Data for Sucrose

Concentration Polymer
(gm/kg)

2
4
6
8

Gain

Signal (mv)

Signal/Gain

256
128
64
32
256
128
256
128

220
110
106
53
540
269
600
300

0.859
0.859
1.656
1.656
2.109
2.102
2.344
2.344

Average Signal
(mv)

0.859
1.656
2.105469
2.344

3.000

Signal (mv)

2.500
2.000
1.500

y = 0.302x
R = 0.8789

1.000
0.500
0.000
0

4
6
Concentration (g/kg)

10

Fig.3: Measurement graph of sucrose

From Figure 3
Kmeasurement = 0.302 mv.Kg/gm of sucrose
Molecular weight of sucrose = Kcalibration/ Kmeasurement = 371.85 gm/Osmomol

Conclusion
Molecular weight of Sucrose obtained is 371.85 gm/mol. The actual molecular weight is
342.296 gm/mol. The deviation may be due to moisture content in sample.

Discussion
The actual molecular weight of sucrose is 342.296 gm/mol. The variation with the experimental
determination may be due to:

Moisture content in sucrose

Varying droplet size of solution on the thermistors

Unstable temperature which is noted manually