Experimental

90

2.1 Description of Experimental Set-up for Density Measurements

2.1.1 Review of the techniques of density measurements:
Generally the density of liquid is measured by using pyknometers which
involves the determination of the weight occupied by the known volume of the
liquid defined by the shape and size of the container. After applying the buoyancy
correction the results are accurate to ± 5 units in the second place after decimal
(density in kg m'3) if the balances of

sufficient accuracies and precision

are available. Any attempt to
increase the accuracy using larger
quantities of liquid is accompanied
by a compensating loss in the
balance sensitivity. Moreover, glass
vessels because of variation of
humidity at their surfaces are always
difficult to weigh with at most
accuracy.
On the other hand, the
dilatometer (Figure 2.1) used for the
measurements of densities of
solutions at different temperatures Figure 2.1 Magnetically operated
achieves the accuracy upto ± 1 * 10'2
dilatometer.
kg m*. In this technique, a small
volume, Vi of a relatively concentrated solution is mixed isothermally with large
volume, V2 of pure solvent. The Helper’s apparatus is used for this purpose.303

Though the method is accurate it has some limitations such as weighing of large
flask reducing the sensitivity of the balance, requirement of high degree of
accuracy in maintaining the constant temperature, for each measurement whole
assembly has to be set-up making the procedure laborious and time consuming.
One of the most accurate methods of density measurement of solutions is the
magnetic float method designed by Lamb and Lee304 and then modified
considerably by others305,306 to obtain the results accurate to 0.1 ppm in the density

measurements. In this method, a glass float with a small bar magnet is dipped in a
 91

cell containing the solution whose density is to be measured, with the help of
platinum weights (Figure 2.2). A solenoid is wound around die cell through which
the current can be passed. Any change in the density of the solution alters the
position of the sinker float in the solution. By passing the current through the
solenoid one can bring the float back to
the original position. The changes in
density can be calculated by measuring Solution
container
the current required to bring the float
Magnetic
back to the original position. This — ~~Float

method is highly accurate but the

measurements involve lot of precautions Support and Pull Down
Leveling Solenoid
Platform
such as high degree of accuracy in Main
Solenoid
temperature control, necessity of purely
non-magnetic material for the
construction of constant temperature Figure 2.2. Magnetic float
baths as well as other parts, dependence densitometer
of the position of solenoid relative to the position of magnet in the float and in the
direction of earth’s magnetic field, alteration in movements of float due to
viscosity of solution etc. Due to all
these precautions method becomes
very stringent.
Most of the difficulties in
the above methods are avoided by
the use of differential float balance
(Figure 2.3) developed by Conway
and Verral and also used by
Kaulgud et a/.308 for the
measurements of densities of
Figure 2.3. Differential float balance aqueous solutions. For different
temperature study, this method is also time consuming. The techniques of density
measurements have been nicely described by Bayer and Levin,309 and Batino.310
2.1.2 Measurements of densities in present work
Densities of all the solutions were determined by a high precision ANTON
PAAR (model DMA 602) digital densitometer. This method is the most accurate
 92

and convenient for the density measurements of liquids. In this method the
measurement of natural vibrational frequency of the oscillating tube containing
liquid under investigation is made. The natural vibrational frequency of the tube is
related to the density of the liquid inside it by
d = A + Bx2
where d is the density of the liquid, A and B are the instrumental constants and x is
the oscillation period of the tube.
2.1.3 Densitometer: Instrumentation
Figure 2.4 shows the general block diagram of the ANTON PAAR digital
densitometer describing the oscillator excitation, amplitude control, and time lapse
measuring and data reception circuitry which was described by Leopold in
detail.311 The motion of transducer, attached to vibrating U-tube (figure 2.5),
induces an alternating voltage in the sensor, proportional to its time dependant
velocity. The signal generated is amplified and used in two circuits.

Figure 2.4. Block diagram of ANTON PAAR digital density meter (DMA 602/60)

2.1.4 Excitation control, time lapse measurements and experimental

procedure
The amplified signal is voltage limited and feed back to control the voltage
amplitude of excitation sources. In this way, fixed amplitude of about 0.01 mm
 93

forced harmonic oscillator is maintained and phase shifts are made negligible by
setting a large bandwidth (3 - 10000 Hz) for the excitation and amplitude control
loop relative to the resonance frequency of the tube when filled with liquid
covering the density range 0 - 3000 kg m‘3. However, this chosen bandwidth
results in an uncertainty of 10 ps in
detecting the zero voltage crossing
of the velocity proportional
amplified sensor voltage. Thus, the
sensitivity of the electronic
detection circuitry defines the small
time unit for the time-lapse
measurements. The amplified signal
sensor is concurrently impressed on
the Schmidt trigger. A start
command, which may be effected
by manual depression of a push Figure 2.5. Sketch of a vibrating tube
button automatically following a densitometer

measurement or at a specified time

by a remote command from an external pulse generator, sets flip-flop 1, thereby
allowing the square wave output of the trigger to pass through the gate 1.
Therefore, the first positive zero crossing of the amplified sensor signal will set
flip-flop 2, thereby opening gate 2 to 10 ps pulses emanating from a 100 kHz
quartz crystal oscillator. These pulses are summed continuously in the binary
counter and displayed. Following nj Schmidt trigger output pulses, modulo divider
resets the flip-flop 1 which closes the gate 1. This automatically resets the flip-flop
2. The total time lapse for the pulses is now displayed. The value may be
transferred to the printer, programmable calculator or computer, as desired. The
modular divider and multi-digit counter may then be reset either manually or by
remote command.
Figure 2.6 shows the complete setup of Anton PAAR (model DMA 602)
for the most precise differential density measurements. This model is a set of two
units. In one of them, solution is introduced (sample holder unit) and other gives
digital readouts (reading display unit).
 94

Figure 2.6. Complete setup of Anton PAAR (model DMA 602)

 95

Out of these two units the first one contains a ‘U’ tube for holding sample.
The ‘U’ tube is completely enclosed in a glass envelope, which contains high
thermal conductivity gas. A glass jacket through which a Thermostated liquid is
circulated to reduce the temperature equilibration time surrounds the envelope. In
this model forced harmonic oscillator of fixed amplitude is obtained by the use of
an electro-optical sensor circuit. A phototransistor is irradiated by IR light emitted
by light emitting diode. A small vane, coated with magnetic material, is attached to
the apex of the vibrating ‘LF tube. In its motion the vane chops the light beam,
thereby modulating the phototransistor output. This signal, when amplified and
limited, is fed back to control the magnetization of the ferrite material, which in
turn controls the motion of the oscillator.
As soon as the instrument is switched on the sample tube starts to oscillate
and the instrument is ready for use. If at the time of filling of the sample tube
illumination is turned on, the photoelectric part of the oscillating system will not
operate and the density measurement is suspended. After the illumination is turned
off the instrument is ready for measurement.
A syringe holder is used to hold the syringe while it is being deployed for
filling the sample tube. While loading the vibrating tube with liquid sample, the
precaution is taken that the introduction of the liquid must be made slowly enough
to enable the sample liquid to properly wet the walls of the sample tube. The
meniscus of the liquid while filling the sample tube must be concave and not
convex, to avoid the trapping of micro air bubbles so that the period readings
obtained are stable. The sample tube is completely filled when the liquid meniscus
passes the upper enlarged portion of the sample tube. The opening of the upper part
of the sample tube is to be closed off with Teflon stopper and the illumination is to
be turned off. Once the illumination of the sample is turned off, the tube starts
oscillating and the reading x (tau) will be displayed on the display unit after the
interval of selected time period (k).
The temperature equilibrium can be conveniently followed over several
read out cycles until the x value becomes constant (± 1 x 10"6), indicating complete
temperature equilibrium. At this time, value of x is to be recorded.
 96

2.1.5 Calculation of A and B constants and calibration of tbe densitometer

(Anton Paar DMA 602)
The set-up of the densitometer and thermostating unit is shown in Figure
2.6. The temperature of the sample holder assembly was maintained constant by
circulating thermostating liquid (water) through the jacket of the sample holder
from Cryostat Julabo F25 MP. The temperature constancy was about 0.02 °C. The
temperature was monitored with the help of a thermometer (1/10*), which was
calibrated against platinum resistance thermometer and the fluctuations in
temperature were noted by Beckmann thermometer occasionally.
The calibration of the densitometer was carried out with 5k time cycle
period. Air and doubly quartz distilled water was used as standard samples, the
density of air being corrected appropriately taking into consideration of pressure
and humidity effects, x values at 5k of water and air were measured several times
as a part of test of constancy over extended periods (Table 2.1). The x values of air
and water are related to their densities by

dm = A + Bx2

dyivta A + Bx
108.766 x 10'5 = A + B (1.286304)2
0.997047 = A + B (1.683578)2
A = -1.3956007
B = 0.84414357
By using the values in the table 2.1 the values of A and B (instrumental
constants) were calculated at 25° C. These A and B constants are temperature
dependent. These constants were used for the calculations of the densities of the
solutions.
For each density measurement of a solution being studied at a given
temperature, the A and B constants were determined separately by calibrating the
instrument with air and water, i.e., for every measurement of density of solution
the x values for air and water were recorded. As a check of authenticity of the
density measurements, the measurements for known systems were carried out and
compared with the best literature data312 reported. The graphs of -103 (do - d)
 97

against concentration for aqueous alkali halide solutions at 25° C are reproduced in
figure 2.7 along with literature data.312

TABLE 2.1 Values of A and B constants at 25° C and 5k time scale and
calculations of densities.
Sample x at 5k t Mean Density at 25° C
/g cm'3
Air 1.286304
1.286305
1.286304 1.286304 108.7664 x 10'5
1.286304
1.286304
Water 1.683578
1.683578
1.683577 1.683578 0.997047
1.683579
1.683578

45

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35

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(a)
 30
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0.2 0.4 0.6 0.8

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Figure 2.7. Comparison of densities of alkali halides determined in this work with
the literature312 (a - NaCl, b - KC1, c - NaBr, d - KBr, e - CsBr).
 100

2.1.6 Accuracy
Accuracy of the instrument is mostly dependent on the temperature control
since the A and B constants are temperature dependent. The densitometer is
capable of measuring the densities with the accuracy ±1 * 10'3 kg m‘3 provided the
temperature of the sample is maintained to the accuracy about ± 0.001° C or better.
The temperature accuracy of the present work is about ± 0.02° C. The accuracy of
density measurements in the present work was estimated to be of the order of ± 5 x
10'3kgm'3.

2.2 Experimental Set-up for Osmotic Vapor Pressure

Measurements
Vapor pressure is not measured directly due to difficulties in sensitivity, but
is measured indirectly by using thermistors to measure voltage changes caused by
changes in temperature. In the present work we have used the KNAUER K-7000
Vapor Pressure Osmometer (K-7000 VPO) shown in figure 2.8 and the complete
experimental set-up is shown in figure 2.9. In this model, two thermistors are
placed in measuring chamber with their glass enclosed sensitive bead elements
pointed up. The thermistors are covered with pieces of fine platinum screen to
ensure a constant volume of the drop of the analyte, which is present on the bead
for each measurement. The chamber contains the reservoir of solvent and wicks
(the wick provides a large surface area for the solvent and its transfer to the
atmosphere inside the chamber) to provide a saturated solvent atmosphere around
the thermistors. If pure solvent on one thermistor is replaced by a solution,
condensation of solvent into solution from the saturated solvent atmosphere will
proceed. Solvent condensation releases heat so the thermistor will be warmed.
Condensation will continue until the thermistor temperature rises enough to bring
the solvent vapor pressure of solution upto that of pure solvent at the surrounding
chamber temperature.
The measuring cell used in K-7000 Vapor Pressure Osmometer is shown in
figure 2.10 while Figure 2.11 represents the side view of the basic design of K-
7000 VPO. The detector for K-7000 model consists of a Wheatstone bridge, two
thermistors, an oscillator for bridge power, ac amplifier and digital panel meter.
The precision control can control the temperature to a few thousands of a degree.
 101

Figure 2.8. KNAUER K-7000 Vapor Pressure Osmometer (K-7000 VPO)

 102

Figure 2.9. Complete experimental set-up for osmotic vapor pressure

measurement.
 103

Electrical Connector

Syringe Ports

Cell Cover
Teflon Seal
Syringe Guides
Teflon Support
Thermistors

Support Rods

Glass Beaker

Figure 2-10. Elements and design of measuring cell

Head Thermostat
Monitor Window

Cell Cover
Front Panel

Mirror
Thermistors

Class Beaker

Figure 2.11. Side view with basic design of K-7000 vapor pressure osmometer
 104

2.2.1 Operational Procedures

The first step in preparing for a VPO run is to clean the chamber assembly.
The chamber was removed from the oven, revealing the baffles, wicks and
thermistors. The platinum gauze covering of the thermistors were carefully
removed and placed in a solvent, from which the new samples will be prepared,
which causes the wetting of the thermistor probes with the solvent. The uncovered
thermistors were fully rinsed with the solvent and new wicks placed in the
assembly. The chamber was reassembled with the gauze in place and 20 ml of
solvent poured into center cylinder over the thermistors. The injection syringe were
then removed, cleaned with solvent, loaded with appropriate solutions or solvent
and returned to the apparatus. The temperature control was set to the appropriate
number (the cell at 25 and head at 27 °C) and the instrument was allowed to reach
the operating temperature. This was usually started before the cleaning and
allowed to warm and equilibrate for at least one hour.
2.2.2 Calibration of Vapor Pressure Osmometer
Using the material of known molecular weight, one can do the calibration
of the vapor pressure osmometer. Requirements for standards are vapor pressure
no more than 0.1 % of the solvent, high purity, complete solubility. Sucrose,
mannitol and NaCl are excellent standards for aqueous solutions while benzil,
sucrose-octaacetate are good for organic solvents. In the present work, we have
used aqueous NaCl solutions of known osmolality for the calibration and hence
determined the instrumental constant, K, with the help of which the osmolality of
aqueous solutions of various samples were determined and further used for
estimation of practical osmotic coefficient values. The operating temperature for
these measurements was 298.15 ± 0.001 K. The calibration constant K is
represented by the slope of the regression curve (measurement value as a function
of osmolality of aqueous NaCl solutions) passing through origin and is represented
by the equation.

Kcaiib = Measurement value/Known Osmolality

The osmolality of the sample solution can be calculated with

Osmolality = Measurement Value/ Kcaiib

 105

At the time of each measurement, at least 5-6 readings were taken for the fixed
time settings and the averaged value was used for further processing. Since
KNAUER K-7000 vapor pressure osmometer is a commercial instrument and it
works above the ambient temperature, one cannot do the measurements at 25° C or
below this. Thus it was necessary to have a proper cooling assembly so that the
surrounding of the instrument is kept colder than the working temperature. For this
we have designed and fabricated the special refrigerated thermostated house
working between 0 to 40° C and the instrument was kept in it (figure 2.9). The
accuracy in osmotic coefficient (<j>) measurements was found to be better than ± 1 x
10'3. Comparison of the osmotic coefficient NaCl and KC1 in water obtained in this
work with the literature data313 is shown in figure 2.12a and 2.12b, respectively,

which shows the authenticity of the osmotic vapor pressure measurements done in
this work.

1.00
O'
O'
O
OO
ON
r-
(</>)
osmotic coefficient
xo
Gn
o
o
*•
vO
£
-

0.93

0.92

0.91
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
m 1/2 /mol kg'1

Figure 2.12a. Comparison of experimental osmotic coefficient data of NaCl with

literature313 at 25° C.
 106

Osmotic coefficient ( <p)

m 1/2/mol kg1

Figure 2.12b. Comparison of experimental osmotic coefficient data of KC1 with

literature313 at 25° C.
 107

23 Experimental Set-up for Viscosity Measurements

2.3.1 Instrumentation and methodology
Of the numerous methods of measuring viscosity which have been tried
through the years, considerations of accuracy, simplicity, and susceptibility to
mathematical treatment have led to the continued refinement and use of only few.
Another requirement common to all successful methods is that the measurements
be made in a system where flow is predominantly laminar or ‘streamlined’ i.e.
where the individual particles of the fluid move in regular paths relative to the fluid
boundaries. The method to be used to determine the viscosity of a given liquid
depends upon the whether the liquid is Newtonian or non-Newtonian. There are
variety of viscometers used for viscosity measurements314, 315 but capillary
viscometer is the most widely used for measuring viscosities of low-viscosity
liquids because of the ease with which it is operated, the high precision with which
it is obtained, and the simplicity of calibration. Although the capillary viscometer
is, in principle, suitable primarily for Newtonian fluids, it has been adopted in
situations where the viscosity of liquid is shear-dependant at high flow rates. The
most direct procedure would be to operate an Ubbelohde or Ostwald viscometer at
a constant pressure head and make a series of measurements each at different
pressure heads. Generally the Ostwald type viscometers are used for routine
measurements while for the precise work a two limb Ubbelohde type viscometers
are popular amongst the researchers. There are several modifications of these
viscometers, for example one has to take proper care of flow time measurements
for volatile liquids. Tuan and Fuoss316 have devised a viscometer for viscosity
measurements of salts in non-aqueous solvents like acetonitrile, acetone, etc. Many
workers now a day adopts Ubbelohde viscometers for aqueous solutions.
It is essential to construct the viscometers which can yield results of high
accuracy for dilute concentrations. The accuracy heavily depends upon the time of
flow and the capillary characteristics as well as on the mounting and positioning of
the viscometers. In this regards the pioneering work carried out by Kaminsky229 in
this field is outstanding. We have followed his method and approach during our
experimentation. The details are given below.
 108

23.2 Theory of capillary viscometers

The fundamental classical equation describing the flow of liquids having
viscosity coefficient, q through a cylindrical tube of radius ‘r’ is given by
Poiseuille267,317,318 equation

nr\P0-P)t
^ Wl
where (Po -P) is a pressure drop down the tube of length 7’ and ‘ V is the volume
of the liquid flowing through the tube in 7’ seconds. When the flow of liquid of
density ‘tf is vertically downward through the capillary then,
nrAhmdgt
M
where (Po - P) = h^dg, where hm is the average height of the flowing liquid and g
is the acceleration due to gravity. The equation was derived by Poisuelle on the
basis of following important assumptions:
a) The flow is everywhere parallel to the axis of the tube.
b) The flow is steady; the initial disturbances due to the accelerations from
rest have been damped out.
c) There is no slip at the walls of the tube.
d) The fluid is incompressible.
e) The fluid will flow when subjected to the smallest shearing force, the
viscous resistance being proportional to the velocity gradient.
These conditions are fulfilled for the flow of liquids through the capillaries of
small and uniform bore. Capillary viscometers can be broadly grouped278 as
under.
(1) Viscometers for absolute viscosity measurements
(2) Viscometers for relative viscosity measurements
a. Applied pressure viscometers
b. Kinematic viscometers
The instruments in section (1) are normally only used for the establishment
of primary standards and require very accurate control of applied pressure as well
as precise knowledge of the capillary dimensions. Type (2) viscometers are those
in which measurements are made relative to a primary standard liquid (obtained
with type (1)) or to derived secondary standards. Variable pressure instruments
under subsection (2)a typified by the Bingham viscometer use an externally
 109

applied pressure to force standard and test liquids through their capillaries. The
second class, (2)b, as exemplified by the Ostwald viscometer, utilizes the head of
the liquid itself to furnish the pressure differential across the capillary. The
inherent simplicity of these latter kinematic viscometers accounts for their almost
universal use in electrolyte studies.
23.3 Design of viscometers
Generally the Ostwald, Cannon Fenske,319 Tuan-Fuoss,316 Jones Vezeys
and Ubbelohde320 viscometers are used for the viscosity measurements. These
viscometers are common capillary viscometers called kinematic viscometers.
Study of sources of errors in different kinds of capillary viscometers led to the
conclusion that the Ubbelohde viscometer (Figure 2.13a) is more suitable for
aqueous solutions while the Tuan-Fuoss viscometer (Figure 2.13b) is better for
non-aqueous volatile liquids. The use of viscometers like Ostwald type gives rise
to following systematic errors.
1) The volume of liquid which is filled in the viscometer requires to be known
very accurately to know the exact pressure head.
2) Due the surface tension the liquid in the upper bulb A (figure 2.13a)
experiences a force in the upward direction. The upward pull varies as the
liquid volume changes during its flow. This effect changes the effective
pressure head and unless a suitable correction in its construction is made, it
introduces error in the measurement of flow time.
3) Some liquid stick to the walls of the upper bulb A leading to the reduction
of the effective volume of the liquid.
By considering all these drawbacks in the present work, the Ubbelohde
viscometer has been used, the design of which is shown in figure 2.13. The
precision of the side tube at the lower bulb B in figure 2.13 makes the pressure
head independent of the volume of liquid contained in the viscometer.
23.4 Kinetic energy correction
The effect arises when the applied pressure is not solely dissipated by
viscous forces, some being used to accelerate the liquid in the entrance reservoir
from the rest to the velocity distribution characteristics of the liquid when obeying
Poiseulle’s Law. Except at very low rates of flow, when there may be a
compensating effect at the exit of the capillary, this extra kinetic energy is
dissipated as heat in the exit reservoir. The correction is therefore dependant on the
 110

D1
>
A A
Tw
2$cc J 3.6

------ -
w«ft%

Figure 2.13a Design of Ubbelohde viscometer (all dimensions in centimeters).

 Ill

flow rate and beconanr negligible at very low values. Its calculation is given in
detail by Barr321 and leads to the expression:

mdV2
Peff =(Po~P)-
JlW
where peS is the pressure actually used in overcoming viscous forces, d is the
density, and m is a numerical coefficient (~ 1) introduced to take account of
particular shape of the capillary ends. Therefore in equation {po - p) must be
replaced by peff as given by above equation

7tr4/ . , mdV

If mean vertical height of the pressure head is hm then the pressure (po-p)~ h„dg.
Therefore we have

_ ur*hmdgt mdV
T1_ Wl ~SuIt

where is called as kinetic energy correction term due to Hagenbach. This

Suit
term is neglected when there is large time of flow so equation can be written as
r\ = a'dt-&(d/t)

mdV
where a'= and p'= are the constants for apparatus. These can be
SVl Sul
calculated from the dimensions of the apparatus. For applying kinetic energy
correction for the relative viscosities, we can write
r\ a'dt-$'(d/t)
flo a'^o ~$'(d0/t0)

where do and to are the density and efflux time for solvent respectively, we have,
q c/(a7-p7Q
flo d0{a't0-^'/t0)
To make necessary corrections in relative viscosity for the loss of kinetic energy
Kaminsky has derived the following equation

flo ^0^0
 112

(
I 1 1 1
where K = \ + k +k 4

v'J t2t2
*0*

and K = —------
w Kg
where K is called the kinetic energy correction factor. K varies with the difference
between t and to. When k « t] the correction factor is negligible.

The kinetic energy correction can be reduced most easily by decreasing the
rate of flow and having a small efflux volume. The time of flow for a given
viscometer can be increased by decreasing the radius of the capillary bore but there
is a practical limit to this course because the presence of dust and fibbers can cause
non-reproducibility in very fine bores. The compromise usually adopted in
measurement to employ capillary radii in the range 0.03 to 0.08 cm.
2.3.5 Surface tension correction
An error due to surface tension may arise from the adhesion of liquid to the
walls of the bulbs immediately above the capillary and in the exit reservoirs. This
has the effect of altering the hydrostatic pressure head of the liquid. In relative
measurements its magnitude will be dependent on the difference in surface
tensions of the calibrating and test liquids. The surface tensions of aqueous
solutions of electrolytes and of low viscous liquids change very little with
concentration, for example the value of 2M sodium chloride solution at 25° C is
only 5% higher than that of pure water. However, if non-aqueous solutions are
being calibrated against water, it must be taken into account; for example the
surface tension of ethyl alcohol is less than a third of that of water.278
The Ubbelohde viscometer is reputed to eliminate the surface tension effect
by the provision of the suspended level at the top of the bulb B which is so
designed as to compensate for the forces operating in the bulb A.
The Tuan-Fuoss viscometer is shown in figure 2.13b. The instrument is
designed so that a series of dilutions can be made on a sample of solute without
opening the viscometer between check runs at a given concentration. In this way,
evaporation errors are eliminated, and contamination of the viscometer contents by
dust or moisture are minimized. The viscometers fit into racks in the thermostat
(298.00 ± 0.005 K) which position them accurately vertical, and which permit
rapid removal and remounting. The working volume is refilled by taking the
 113

viscometer out of the thermostat for

about 10 sec. in order to tip it and run
liquid through the side tube C from the
dilution chamber A to the top chamber
B. The viscometer is then placed back
in the thermostat at about 30° from
vertical on the side of tube C while the
bulb D fills through the tube E. For
carbon tetrachloride (CCU), this
operation takes about 2 min. Then the
viscometer is taken out of the bath for
a few seconds and tipped to run most
of the excess liquid in B back into A
through C; it is then immediately
clamped in its vertical position. It will
be noted that tube E projects 6-8 mm.
above the floor of B; the liquid hold-up
in E above the mark P gives the
operator sample time to position the
viscometer and see the meniscus (P)
passes it, when the stop-watch is started.

23.6 Control and measurement of temperature

The thermostatic bath having 60 L capacity was constructed by fixing two
glass plates at two sides opposite to each other (Figure 2.14). Glass plates were
fixed using rubber strips with the help of water insoluble substance called araldite.
To avoid the heat exchange with surrounding, thermostatic bath was insulated with
thick thermocole sheets at all sides except upper one. This upper side is also
covered with bakelite sheet having holes drilled for 1/10° thermometer, Beckman
thermometer, heater and stirrer as shown in figure 2.9. The bath has been filled
with distilled water as a thermostatic liquid. The temperature of the bath could be
regulated constant. This has been done as follows: The experimental thermostatic
bath in which viscometers were immersed was provided with a copper-tubing coil
(1 cm i.d.). The thermostated liquid was continuously circulated through die
 114

CONTACT THERMOMETER

’ THERMOMETER! t/1**)
stirrer
■ECKMAN THERMOMETER

~* TO DRIVING
HEATER
InigH^MT IT
IlMRtMPUnP IAI

.cormtuRiHC

INSULATION

CLABSAqi'ARRJM

VISCOMETER.1

VISCOMETER}

Figure 2.14. Experimental set-up for viscosity measurements.

copper-tubing fixed inside the experimental bath using another German made U-10
ultra-thermostat or cryostat. The temperature of the bath was measured by means
of standard thermometer (1/10° C). The small fluctuations were noted by Beckman
thermometer. The temperature of the bath was controlled to be better than ± 0.005°
C. Further the movable stand for the thermostat has been also fabricated to avoid
the space problem in the laboratory. The photograph of actual working assembly
for the viscosity measurements is shown in figure 2.15.
 115

EXPERIMENTAL SET-UP FOR

VISCOSITY MEASUREMENTS

Figure 2.15. Photograph showing the actual working assembly for

viscosity measurements.
 116

2.3.7 Loading, cleaning, drying, mounting, positioning and maintenance of

viscometers
The viscometers were cleaned with chromic acid. Then they were washed
with glass distilled water several times and the precaution was taken that no trace
of chromic acid is left behind in the viscometer. It was further rinsed with
conductivity water 3-4 times. Finally it was rinsed with acetone or methanol and
dried by passing a slow current of warm, dry and dust free air from hot air blower.
Then the viscometers were kept in oven at about 70° C for 20 minutes after which
they were allowed to cool slowly by annealing process. Thus the viscometers were
ready for use after the complete cooling to room temperature. The cleaned
viscometer is fixed on a stand and it is inserted in a thermostat. The solution was
sucked by using syringe of large volume.
When the viscometers were not in use, they were kept filled with
conductivity water.
According to Cannon and Fenske319 the change in angle 0 to 0 + d0 in the
vertical alignment of the capillary axis produces a change in liquid pressure head
of 1 - (cos (0 + d0)/cos 0). If the viscometer deviate 2° to 5° from exact vertical
alignment an error of 0.1% is introduced in the measured relative viscosity. Korson
and Drost-Hansen322 through extrapolatory experiments have found that a
deflection of 5° from vertical position of the viscometer produces a difference of
0.7% in flow times. Precaution was taken to fix the viscometers rigidly in vertical
position during measurements. For this purpose special clamping device was
constructed as shown in figure 2.16. It consists of two bakelite plates each
containing three semicircular holes on the same side of the plate. The three limbs
of the viscometer were placed between these plates which were then screwed
together such that the limbs of the viscometer got fixed between semicircular
holes. This grip was made more firms by providing O-rings of rubber between the
grips. The arrangement of three adjustable screwing knobs was also provided for
the leveling of the viscometers exactly in vertical position. Since it is important
that effective pressure head be highly reproducible, a leveling bottle was used to
check the vertical alignment of viscometers. The final vertical alignment was
achieved by using the plumb-line arrangement.
 117

Figure 2.16. Leveling device for fixing and positioning of the viscometers.

2.3.8 Calibration of the viscometers

For the calibration of the viscometers the doubly quartz distilled water was
used as standard sample for measurements. The flow times of water for the
Ubbelohde and Tuan-Fuoss viscometers are (1093.1 ±0.1) s and (1020.1 ± 0.1) s,
respectively, at 298.15 K, the time being monitored using a stopwatch with 0.1 s as
the smallest increment. These values were used for the calculations of relative
 118

viscosity (%) of all samples at 25° C. At other temperatures the time of flow of
water for the corresponding temperature was used to calculate the relative viscosity
of the samples at that temperature. It was essential to use a Tuan-Fuoss viscometer
for CCI4 solutions (the flow time for pure CCI4 is 659.1 s at 298.15 K), as CCI4
evaporates, causing variation in the time of flow when an Ubbelohde viscometer is
used. 18 Since the Tuan-Fuoss type viscometer was constructed using stoppered
standard joints, the evaporation of CCI4 could be prevented and a constant time of
flow value could be determined. All the flow time measurements reported in this
work are averaged over three separate measurements of the same solutions. The
calibration of a Ubbelohde viscometer has been described earlier. 14 The
uncertainty in viscosity measurements with reference to water is estimated using
the guide to the expression of uncertainty in measurements (International

Organization for Standardization, Geneva) to be of the order of ±0.000 15 mPa s.

For the check of authenticity of the data produced in this work, we have
carried-out the time flow measurements for dilute aqueous NaCl solutions at
298.15 K. and using the density data relative viscosities were calculated. These
data were used to determine the viscosity A- and 5-coefficients with the help of the
plot shown in figure 2.17. The experimental values obtained for A- and B-
coefficients are 0.0061 (dm3 mole'1)172 and 0.078 dm3 mol'1, respectively, which
well with the literature275,278 values of0.0062 (dm3 mole*1)172 and 0.0793 cWmol'1.

Also, the viscosity of 20% sucrose solution was determined at 298.15 K and the
value 1.6953 mPa s is obtained which agrees well with the literature278 value of

1.695 mPa s. These reproducibility tests of the literature data determine the
accuracy and precision of the experimental work we have carried-out.
 119

- iy jc ,(mo\ dm'3)
(v\r

Vc /(mol dm'3)172

Figure 2.17. Variation of relative viscosity of NaCl in aqueous solutions as

a function of square root of concentration of NaCl at 298.15 K.