80

CHAPTER 2

Experimental techniques

81

Experimental techniques
A brief account of experimental techniques employed by various
researchers for determination of ultrasonic velocity, density and viscosity is given
in sections 2.1, 2.2 and 2.3. Experimental techniques employed in the present
investigation are described in sections 2.4, 2.5 and 2.6.

Review of experimental techniques

2.1 Ultrasonic velocity measurement
Techniques used for the measurement of ultrasonic velocity are, in general,
classified into two categories1-3. They are 1) Continuous wave methods and 2)
Pulse techniques.
2.1.1 Continuous wave methods
Some of the important continuous wave methods namely, Striation method,
Optical diffraction method, Interferometer method and Brillouin scattering involve
the measurement of frequency and wavelength of sound wave in a given medium.
The velocity of ultrasound is the product of frequency and wavelength of the wave.
Optical methods4-9 use basic fact that when a sound beam passes through a
medium it alters the local density

and hence the refractive index of the medium.

Striation or Schlieren method was developed by Toepler10 in 1866 for measuring

wavelength of sound waves. In this method sharp image of a vertical slit is focused
on a vertical wire through a cell containing the liquid. Stationary sound waves are
setup in the cell by a crystal and plane parallel reflector arrangement. A series of
alternate bright and dark fringes can be seen by focusing a telescope on the wire.

82

The distance of separation between these fringes is proportional to the wavelength

of sound. The acoustic wave remains virtually stationary because of slowness of
speed of sound compared with speed of light.
The optical diffraction method was invented almost simultaneously by
Debye Sears11 and Lookas Biquard12,13 in 1932. In this method a parallel beam
of ultrasonic waves in a transparent medium acts as a diffraction grating for light
which moves with of the speed of sound. It is virtually stationary because velocity
of sound is very much less compared to that of light. Since the order of diffraction
and wavelength of light are known, wavelength of sound can be determined by
measuring the angle of diffraction. The velocity of sound can be computed by
multiplying wavelength of sound with its frequency. The outstanding advantage of
optical methods is that they do not require any precision mechanical system and
use small quantities of test liquids. One disadvantage with this method is that
normal acoustic beam is not a plane wave, and several distortions appear in the
resultant light image. The accuracy in velocity measurements with this technique is
0.1%.
The interferometer method is the most widely used technique for the
measuring of sound velocity with high accuracy. It is easy to maintain the
temperature steady for the sample. Subba Rao and Ram Chandra Rao14
developed a simple and accurate interferometer method by modifying the fixed
path type to determine the temperature coefficient of sound velocity. Kor and
Tripathi15 followed the method devised by Fox. Stationary waves are produced in
this method and the effect of varying path length is investigated. A reversible

83

crystal transducer is used in a variable path interferometer to both generate and

detect the sound waves.

The frequency of vibration of transducer crystal is

adjusted such a way that the crystal

vibrates at its natural frequency. As the

crystal attains resonance it vibrates with maximum amplitude. The sound waves
generated by the crystal travel through the liquid medium to a plane reflector that
is maintained accurately parallel to crystal surface. When the distance between
transducer and

reflector is an integral multiple of half wavelength of sound,

standing waves are set up between reflector and the crystal. The reflected sound
wave arriving back to crystal surface after being reflected by reflector is 1800 out of
phase with the motion of the crystal. This results in the drop of current through the
crystal due to decrease of amplitude of vibration.
An accuracy upto few parts per million in velocity measurements is attained
due to recent advances in this technique. The NRL16 measurements are accurate
to 0.0013%. The interferometer method is a versatile technique. Wavelength of
sound can be easily measured by varying the acoustic path length. The frequency
of crystal oscillation is easy to determine when compared to tedious measurement
of transition time in pulse technique. The temperature of the cell can be
maintained steady with ease. Frequency stability of oscillator is high due to high
Q-factor of quartz crystal. Several workers have found interferometer technique
more suitable for the

determination of temperature coefficient of sound velocity.

The superiority of this technique is well documented by Del Grasso17.

Leonard

and

Suguin18

designed

an

acoustic

interferometer

for

simultaneous velocity and attenuation measurements in liquids over a wide range

of frequencies and a temperature range from room temperature to cryogenic

84

temperatures. A modified method was mentioned by Raghupathi Rao and Krishna

Rao19. Leha et. al20 developed an interferometer for measuring ultrasonic velocities
in electrolytes.
McCartney and Drouin21 configured an acoustic interferometer capable of
measuring ultrasonic velocity with an accuracy of 0.03%. Theory and performance
of differential optical interferometer for measuring velocities of both surface
acoustic waves and bulk waves is described by Palmer et al22. Wright and
Campbell23 developed an ultrasonic interferometer for a range of frequencies 0.1
to 1.5 GHz.
These continuous wave methods are not adequate for measuring sound
velocities in the GHz frequency range. Scattering technique developed by Brillouin
is useful in the frequency range of 1 to 10 GHz.
The random thermal motion of the molecules in a liquid can be considered
to result from a large number of longitudinal waves. It is very difficult to generate
hypersonic waves of fixed frequency and amplitude. As such it is quite convenient
to study the sound waves naturally present in the liquid at hypersonic frequencies.
Brillouin24 predicted that scattering of light

beam may occur when a

monochromatic light beam is passed through a medium in which a sound wave is

propagating. This Brillouin scattering is equivalent to a Bragg reflection from the
acoustic diffraction grating. Light scattered by an acoustic grating suffers a
Doppler shift as the acoustic

grating is moving with the velocity of sound. Thus

the scattered light consists of a doublet split symmetrically about the incident
frequency. The frequency difference between scattered and incident light equals

85

the frequency of the sound wave responsible for scattering. The wavelength () of
sound wave is given by the Bragg's relation
n1 = 2 Sin
Where 1 is the wavelength of light and is the angle of scattering between the
incident beam and plane of grating. Piercy and Hanes25 proposed a simple model
for scattering process which yields the same results. This

method is useful at

hypersonic frequencies. Different methods for determination of hypersonic

velocities were reviewed by Sette26
2.1.2 Pulse techniques
Ultrasonic velocity is determined by electronically measuring the time
required for an ultrasonic pulse to traverse a given acoustic path length in pulse
techniques. Pulse methods comprise the pulse echo method, pulse echo overlap
method, pulse superposition method, pulse comparison method and sing around
method. Some of the inherent disadvantages of continuous wave methods such as
streaming and sample heating are virtually eliminated in pulse methods. A distinct
advantage of pulse method is that velocity and absorption can be measured
simultaneously.
In the single transducer pulse technique27, a piezo-electric crystal
transducer generates a short train of periodically repeated sound pulses. These
pulses are propagated through the liquid medium to a plane reflector.

The

reflector is maintained accurately flatland parallel to the transducer's face. The

reflector can be moved normal to the transducer to and fro. The reflected pulses
are received by the transducer, which then serves as the receiver. Each time a

86

pulse returns to the transducer part of energy is converted to an electrical signal

and the rest energy being reflected. Repetition of this process leads to a series of
detected echoes, each of which has made one more round trip through the sample
than its predecessor. The attenuation and sound velocity are determined from the
echo amplitudes

and transit times. The transit time of a given pulse is

electronically measured and sound velocity in the medium is directly evaluated.

Two transducer pulse technique is generally used when 1) the medium is
highly attenuating which requires short acoustic path lengths and 2) keeping
echoes separated from applied signal is difficult. The first

transducer converts

radio-frequency electrical pulses into ultrasonic pulses. The second transducer

receives these pulses and reconverts them into
transducers must possess exactly the same

electrical signals. The two

natural frequency. In case of single

transducer pulse technique electronic circuit is complicated because it is essential

to block receiver input during

the time interval of transmitted signal. But the size

of measuring cell is generally small in single transducer pulse technique. The

received pulse is amplified and displayed on a cathode ray oscilloscope. The time
base of CRO is synchronized to pulse repetition frequency. A change in acoustic
path length causes a change in transit time. This time delay is used for
determination of ultrasound velocity. Short wavelengths and high absorption
coefficients make it difficult to extend the range of frequency beyond 300 MHz.
below 5 MHz this technique is not reliable due to diffraction problems. The
accuracy in velocity measurement by this technique is 0.2%. Parthasarathy and
Pancholy28-30 used pulse technique to determine velocity of liquids at 21 MHz in
the temperature range 100C to 500C.

87

Fairley et al31 described an ultrasonic pulse-echo reflectometer useful

for

measurement of ultrasonic velocity, attenuation and characteristic impedance of

liquid samples. The devise may be used for determining density, particle size and
concentration of dispersed phases.
Pulse superposition method

32,33

is a variant of pulse technique. A single

transducer is generally used in this method. The pulse generated by the

transducer traverses the medium and gets reflected by a plane parallel reflector.
Each time a reflected pulse returns to the transducer, part of energy is converted
to electrical energy and the rest being reflected. Repetition of this process leads to
a series of detected echoes each of which has made a

round trip. A radio

frequency oscillator excites the transducer. The frequency of radio frequency

oscillator is adjusted until its period is equal to the round trip transit time of
ultrasonic pulse in the specimen. Thus r.f. pulse generator triggers the transducer
once per round trip of ultrasonic pulse. In this

method the reflected echo is

superposed by the triggering pulse. It is essential to trigger the transducer from a

definite phase point of the signal. This method is accurate, but not as versatile as
pulse echo overlap method

as buffer rods cannot be employed. In pulse

methods, generally, a pulse of sinusoidal r.f. voltage is applied to the transducer.

Typically, the voltage amplitude is between a few volts to a few hundred volts. The
pulse width varies between 1-10 s and pulse repetition frequency between 100 to
1000 pulses per second.
In the pulse echo overlap method

34-37

there is no superposition of elastic

waves themselves but rather of the received echo signals when they reach the
oscilloscope. Only one signal pulse is present in the sample at a

time. The

88

oscilloscope sweep is triggered by Continuous Wave Audio Oscillator (CWAO).

CWAO frequency is adjusted such that time between sweeps is an integral
multiple of the round trip transit time of acoustic pulse

in the sample. The

repetition rate of the applied signal is controlled by the same oscillator following a
frequency division by 1000. The repetition rate is sufficiently low such that each
pulse is dissipated in the sample before the next pulse is generated. Overlap of
any two successive echoes is achieved by adjusting the CWAO frequency such
that it is equal to round trip transit time. The reciprocal of CWAO frequency gives
the transit time. Absolute accuracy arises in this method from the fact that this
method is capable of measuring accurately from any cycle of one echo to the
corresponding cycle of next echo. This method is highly accurate method yielding
an accuracy of few parts per million in the velocity measurements.
In the phase adjustment method, the frequency of a gated pulse is varied
such that the second pulse and reflected echo of the pulse through the medium
reach the receiving transducer with a phase difference that is an integral multiple
of 2qe. This is achieved by varying the frequency until the

superposed signal

(on CRO screen) reaches a null. This is repeated for several nulls and single pass
travel time can be computed.
Phase comparison technique38-42 is used in the frequency range 10 200
MHz. In this method a fused quartz spacer of known thickness separates two
delay lines precisely fixed distance apart. A pulse of sound waves from the
transducer is reflected at both the liquid interfaces. Comparison of
reflected echoes at the transducer is used to compute the transit time.

phase of the

89

Stewart and Stewart43 used normal incidence reflection technique at high

frequencies up to 10 GHz. In this technique change in amplitude on reflection of
sound wave incident normally at the delay line gives the longitudinal impedance.
Longitudinal impedance data can be used to evaluate sound velocity, if the density
of liquid is known precisely.
In the singaround technique44,45, a pulse of sound waves from a transducer
passes through the liquid to a second transducer. Here acoustic

pulse is

converted to an electrical signal. This signal is amplified, reshaped and fed back
to the transmitting crystal transducer. The repetition frequency

of the complete

cycle is determined to facilitate evaluation of sound velocity. This technique gives

accuracy better than 1 in 104 parts. Singaround technique developed by Garnesey
et. al46 is capable of determining difference between velocities in dilute aqueous
solutions with an accuracy

of 0.003%. Brammer47 improved the technique and

obtained an accuracy of 0.000001% in solids. Satyabala et. al48 developed

singaround technique in

which velocity measurement was performed with an

accuracy of 0.5 m/s. Sanjeeva Chadda49 developed singaround technique with

capability of digitally displaying sound velocity with an accuracy of 0.3%.
Some of the techniques for measurement of sound velocity are described in
detail in Handbook der Physique50 and Physical Acoustics1.

2.2 Density measurements

A number of methods can be employed to measure the density of a liquid.
Conventionally specific gravity bottle is used to determine density of liquids. But
pyknometer is generally preferred due to its versatility and high accuracy i.e. 5 in

90

106 parts. Different methods for measurement of density of liquids are reviewed
briefly here.
Hydrostatic pressure of a given weight of liquid is proportional to its density.
Balancing column method51 is based on this general principle. This method gives
accuracy up to 2 in 104 parts. One advantage of this method is that it utilizes very
small quantities of liquid samples.
A rapid method, useful for the study of temperatures variation of density is
Buoyancy method52,53. This method is based on Archimedes principle. This
method gives an accuracy of 2 in 106 parts under optimum conditions. This
method is not generally preferred due to surface tension problems.
A modified form of buoyancy method, called magnetic float method54-56 is
the most accurate method. In this method a pulse of current carried by a solenoid
counter balances the buoyancy of iron ore submerged in the liquid sample. This
method is specifically used for measurement of densities of

very dilute solutions

with very high accuracy i.e 1 in 107 parts. Some worth mentioning developments in
this method are due to Benjamin57, Franks and Smith58, Millero59, Drost-Hansen et
al60 and Master ton and Seiller61.
Dilatometer method described by Neuback62 can be employed for
determining density of liquid in terms of weight of mercury that is expelled (or
added to the dilatometer) when the

temperature

is changed. Double armed

dilatometer described by Writhe and Losourdo63 and Hildebrand and Carter64 can
be used for measurement of excess volumes and their temperature dependence.

91

Pyknometer method (single stem and double stem) is used widely due to its
simplicity in design, ease with which temperature of the sample can be maintained
and high accuracy of 5 in 106 parts. In this method the mass of a given volume of
liquid is accurately determined using a pre-calibrated pyknometer whose volume
at different temperatures and radius of the capillary of stem are accurately known.
A review of different types of pyknometers was given by Bauer and Lewis51.
Johnston and Adamsconstructed65 an improved form of Gay-Lussac
pyknometer bottle that can be used for both solids and liquids. This device can be
used for determination of density with an accuracy of 5 parts in 106. Pyknometer
designed by Wood and Brusic66 could determine density up to forth decimal place.
Pyknometer constructed by Methot and Desmyter67 consists of two parallel
graduated capillary tubes. Accuracy of this device in determination of density is up
to 5th decimal place. U-tube shaped pyknometer with capillary of small bore
suitable for volatile liquids was constructed by Sprengel and Ostwald68.
Robertson69described a bi-capillary pyknometer that can be used for a variety of
organic liquids. Bi-capillary pyknometers for measuring densities at various
temperatures were designed by Parker and Parker70 and Ward and Brooke71. Pip
kin et al72 described a convenient bi-capillary pyknometer of self filling type that is
capable of yielding an accuracy of 2 parts in 104 for volatile liquids. They reported
that loss of vapor is negligible (due to diffusion) if the length of capillary tube is
more than 10 cm.

2.3 Viscosity Measurement

Viscosity is a measure of resistance of fluids to flow. It is due to friction
between adjacent layers of fluid. The property of a liquid by virtue of which it

92

opposes relative motion between its different layers is known as viscosity73.

Though there are a number of methods by which coefficient of viscosity can be
measured. Oswald viscometer method is generally preferred due to its simplicity.
A brief review of some important methods for determining viscosity is prescribed
here.
In the Poiseuille's method a capillary tube of known length and radius are
fixed horizontally near the bottom of a vessel, in which the level of liquid can be
maintained constant by means of an over-flow arrangement.The liquid is allowed
to flow through the capillary tube and collected in a beaker for a known time
period. If the density of liquid is known, the volume of liquid flowing out per second
can be computed from the mass of collected liquid in the beaker. The coefficient
of viscosity can be evaluated using the Poiseuille equation. This method is suitable
for comparatively less viscous liquids like water.
Stokes' method is suitable for highly viscous liquids. When a body falls
through a viscous medium, its motion is opposed by frictional force which
increases with the velocity of the body. This frictional force increases until it
becomes just equal to the motive of driving force. Then the body attains a constant
velocity called terminal velocity. The coefficient of viscosity can be determined by
measuring the terminal velocity.
Rotational viscometer consists of two coaxial cylinders, with the space
between them filled up with a fluid. The inner cylinder is suspended by means of a
long thin wire. When the outer cylinder is rotated with a constant velocity about
their common axis, a torque is communicated to the inner cylinder through the
intervening fluid. This torque tends to rotate the inner cylinder. This motion is

93

opposed by the torque of suspension and the cylinder comes to equilibrium after
rotating through an angle . The angle is measured by an optical lever
arrangement in which a mirror is attached to the suspension.
The viscosities of two liquids or the same liquid at different temperatures
can be conveniently compared with Ostwald viscometer. This method can not yield
an absolute value of coefficient of viscosity. In this method a given volume of liquid
is allowed to flow through a capillary tube and the flow time is measured. This
procedure is repeated for the test liquids.

The kinematic viscosities are

proportional to the flow times. So the kinematic viscosity of test liquid can be
evaluated, if the kinematic viscosity of reference liquid is known. If the density of
experimental

liquid is known, the dynamic

viscosity can also be evaluated. In

the present investigation this method has been employed. Commercial glass
capillary viscometers are Cannon-Fenske viscometer, Ubbelohde viscometer74,75,
Fitz Simons unit76, etc. A detailed

description of several viscometers is given by

Van Wazer et al77.

Experimental techniques employed in the present investigation

2.4 Ultrasonic velocity measurement Interferometer Technique
In the present investigation a variable path ultrasonic interferometer (Mittal
enterprises, New Delhi Model M-82) is used to measure the ultrasonic velocity in
liquid mixtures and solutions. The working frequency of variable path ultrasonic
interferometer is 2 MHz.

94

2.4.1 Principle
Ultrasonic interferometer employs an x-cut quartz crystal as transducer.
The opposite faces of the crystal are gold plated and connected

to an oscillator.

The oscillator excites the X-cut quartz crystal at its natural frequency. Due to
resonance, crystal vibrates with maximum amplitude. The

vibrating face of the

crystal generates an ultrasonic wave that passes through the liquid medium. The
wave gets reflected by a reflector, which is held accurately parallel to crystal
surface and can be moved at right angles

to crystal surface in the direction of

wave propagation. Stationary waves are formed in the liquid medium, when the
distance between crystal and reflector is an integral multiple of the half wave
length of the sound wave. The motional impedance of quartz crystal increases due
to rigorous vibration of liquid medium. The wave reflected back to crystal arrives at
1800 out of phase with the motion of the crystal. This results in appreciable
decrease in the amplitude of crystal vibration. This is accompanied by the
decrease in

current through the crystal. The current measured through the

crystal/ voltage measured across the crystal, as a function of distance between

crystal and reflector, exhibits series of minima separated by a distance equal to
half the wavelength of sound wave in the liquid. If the frequency of crystal
oscillation is f, then sound velocity u in the liquid medium is given by the formula u
= f, where = wavelength of sound wave.
Generally a tritet crystal controlled oscillator is used to excite the x-cut
quartz transducer. The variation of voltage across the crystal is observed using a
FET Voltmeter. Water from a constant temperature water bath is circulated
through the double walls of the interferometer cell to maintain the temperature of

95

the liquid sample in the cell. The constant temperature water

bath (thermostat)

can maintain the temperature of water at any desired temperature within 0.010C.
The major sources of error in the interferometer technique are
1. Diffraction and wave guide effects
2. Irregularities in the vibrations of the transducer
3. Lack of parallelism between transducer and reflector
Errors due to diffraction are generally minimized by confining the velocity
measurements to Fresnel zone.
2.4.2 Description of the equipment
The interferometer assembly consists of the following major parts
A. High frequency oscillator (generator) assembly
B. Liquid cell
C. Reflector assembly with vernier micrometer
D. Base to hold the cell and a shielded co-axial cable
A. High frequency oscillator assembly
High frequency oscillator/generator is used to excite the transducer at
the required frequency (2 MHz) in the present study. The oscillator assembly is
provided with a micro-ammeter (0-50 A) to observe the changes in current.
B. The double walled interferometer cell
Interferometer cell used is double walled and Nickel coated. It is provided
with an inlet and an outlet to circulate water around the inner wall of cell, so that
temperature can be maintained at any desired temperature. Water from a constant

96

temperature water bath is pumped into the cell. The diameter of the cell is 3.9cm
and inner diameter of the cell is 1.4cm. The depth of the cell is 6.8cm. The
approximate volume of the liquid required to fill the cell is 10ml. At the bottom of
the interferometer cell gold plated x-cut quartz crystal transducer is fixed.
C. Reflector assembly
The pitch of the screw employed to move the reflector is 0.5mm and the
head of the screw is divided into 50 equal divisions. The least count of this setup is
0.001 cm. The bottom of the screw is coupled to the reflector rod through a steal
ball which eliminates errors arising due to non-axiality between them, besides
keeping the reflector free to move axially without rotating along with the screw. To
avoid backlash error, the reflector is spring

loaded. The reflector can be firmly

mounted on the top of the interferometer cell. The reflector is tightly coupled to the
interferometer cell with the help of knurled cap.
D. Base to hold the interferometer cell
A heavy cylindrical base is used to hold the cell. The cell is clamped in
the socket of the base with the help of a screw provided on the side of the base. In
addition to acting as a rigid mount for the interferometer

cell, base provides

contacts to the upper and lower surfaces of the crystal transducer, so that exciting
electrical signal is passed from high frequency oscillator assembly. The base is
connected to high frequency oscillator assembly with a high quality co-axial cable
provided with suitable sockets.

97

2.4.3 Experimental procedure

Ultrasonic velocities in aqueous/non-aqueous liquid mixtures at different
temperatures have been measured in the present investigation at a frequency of 2
MHz. The detailed method of measurement of ultrasonic velocity using ultrasonic
interferometer is described below.
The interferometer cell is cleaned with acetone and then dried using an air
blower. The cell is filled with experimental liquid. The reflector assembly is coupled
to the cell tightly by screwing the knurled cap. The cell is inserted into the base
socket and clamped rigidly with the help of side screw provided to the base. The
inlet and outlet of the double walled construction
temperature water bath by means of transparent

are connected to constant

plastic tubes. Ultrasonic

interferometer with constant temperature water bath setup is shown in figure 2.1.
Water is pumped into the double walled cell with the help of an electrical motor
provided with the constant temperature water bath. Water of constant temperature
is circulated at least for 30 minutes so that the temperature in the cell stabilizes.
After the required temperature is attained in the interferometer cell, high frequency
oscillator assembly is connected to the base of the cell using shielded co-axial
cable. The high frequency oscillator assembly is switched on.
The reflector is gently moved towards the crystal with the help of
micrometer screw. Variation of current through the crystal transducer due to the
motion of the reflector is observed with the help of micro-ammeter provided with
high frequency oscillator assembly.

98

Fig. 2.1 Ultrasonic Interferometer with constant temperature water

bath setup

99

Readings of positions of micrometer screw corresponding to ten successive

maxima (or minima) of current in the micro-ammeter are noted. Then counting
maxima (or minima) up to 20, the readings of 21st to 30th consecutive maxima (or
minima) are noted. The difference between 1st and 21st, 2nd and 22nd, 3rd and
23rd, so on are calculated. These differences should be almost equal. Otherwise
another set of fresh readings are to be taken. Since the difference between
successive sharp maxima (or minima) corresponds to half wave length of sound
wave, the average of the ten differences corresponds to ten wavelengths. From
this data, wavelength of ultrasonic wave is determined. The ultrasonic velocity is
determined by multiplying the wavelength of ultrasonic wave with the frequency of
crystal oscillation (2 MHz in this investigation). The measured ultrasonic velocities
have an accuracy of 0.2%.
2.4.4 Effect of diffraction on the velocity measurement
Diffraction of ultrasonic beam introduces considerable error in the
measurement of ultrasonic velocity and absorption78. These errors are
predominant near the radiator and decrease for differential distance farther from it.
The velocities measured near the source are higher than the plane wave
velocities. These errors are systematic in nature and are amenable to theoretical
and empirical studies.
Several workers79-85 made attempts to evaluate diffraction errors. Errors
arising due to diffraction are discussed in detail by Kranushkin86. The excess
velocities (v) are given by
(v/v) = 2/31.5a2,

100

where is the wavelength and a is the radius of the piston source.

The theoretical expression of free field diffraction error due to Bass and
Williams as cited by McSkimin87,88 is given by
(v/v) = 2/22az1/2,
where is the wavelength, a is the diameter of the beam and z is the distance of
the source from reflector at which measurement is made. McSkimin confirmed the
above relation by measuring velocities in solids. The diffraction effects in liquids
were studied by Ilgunas et al89. But they have not correlated their results with
theory.
Subramanyam et al90 found that diffraction errors are 3.2 times the value
predicted by Bass and Williams theory. Thus
(v/v) =3.2( 2/22az1/2 )
The above relation is used to evaluate diffraction errors in the present
investigation. The experimental velocities are corrected accordingly.

2.5 Measurement of density Pyknometer method

In the present investigation double-stem pyknometer is used for
determination of density of solutions at different temperatures.
2.5.1 Basic principle
In the pyknometer method weight of the liquid occupying a known volume
defined by the geometry of a given vessel is determined. Since it

is

not

practicable to determine this volume accurately from the geometry of the vessel,
it is calibrated using a reference liquid of known density such as water.

101

2.5.2 Description of pyknometer

Bauer and Lewis51 discussed many types of pyknometers and their details.
A double stem pyknometer used in the present investigation for the determination
of densities is shown in figure 2.2. This pyknometer is similar to that of Parker and
Parker70 type with minor modifications.
The double stem pyknometer is made of pyrex glass with two stems of
capillary tubing of uniform bore. The two capillary tubes are bent outwards at the
top, making an obtuse angle at the bent. Pyknometer consists of a bulb attached
to one of the stems having a capacity of about 5 ml. Two reference marks are
made on the two stems at about the same heights in order to read the difference
between the liquid levels and reading of the marks of the two capillary stems
conveniently. The upper end of the stems is closed by means of teflon caps to
avoid loss of liquid by means of

evaporation. By this arrangement atmospheric

pressure is maintained in the capillary tube.

2.5.3 Calibration of the pyknometer
The volume corresponding to unit length of each pyknometer stem was
evaluated by measuring the length and weight of various threads of pure mercury
at room temperature. The same values were used for calculation of density at all
other temperatures. The error introduced by using this

procedure in density

measurements is negligible when compared to overall accuracy of pyknometer

method.

102

Fig. 2.2 Pyknometer

103

The volume of the pyknometer between the two reference marks, at different
temperatures, was determined using the triple distilled de-ionized water as
reference liquid.
2.5.4 Experimental procedure
Double-stem pyknometer is cleaned well and dried using an air blower. The
weight of the pyknometer is determined accurately with reference to a dummy.
The weighing is carried using METTLER TOLEDO (Switzerland make) ABB5S/FACT digital balance with an accuracy of 0.01 mg is shown in figure 2.3. The
experimental sample (liquid whose density is to be determined) is injected slowly
into the pyknometer by means of Pyrex syringe until the liquid levels in the two
stems are around the marks. The pyknometer is immersed vertically up to bent
stem portions in water of a constant temperature water bath in which temperature
can be maintained at any desired value. The

pyknometer is kept immersed as

such for about half an hour, so that unfilled portions of stems are to be drained
completely and to allow the establishment of liquid-vapor equilibrium. The amount
of liquid at the initial filling will get adjusted to allow for free expansion (or
compression) due to difference of temperature between the bath and
surroundings. The difference in heights of liquid between the mark and lowest
point of the meniscus in both the stems are measured using a traveling
microscope which can read up to 0.001cm. In obtaining the difference between the
mark and lowest point of the meniscus, correction is employed for the liquid in the
meniscus above the lowest point. Since the meniscus in case of aqueous solutions
is hemi-spherical in shape, one third of the radius of the capillary tube was added
to the observed height. The pyknometer was then removed from the water bath,

104

Fig 2.3 Digital balance (Mettler Toledo)

105

wiped with a clean dry cloth and allowed to cool to the room temperature for about
15 minutes. The weight of the pyknometer along with the previous dummy is
determined using digital balance.
If Vt is the volume of pyknometer between the reference marks, density of
the enclosed liquid can be evaluated using the formula
= M/ (Vt V)
where M is the mass of the liquid in the pyknometer and V is the volume of the
liquid above or below the reference marks. The reproducibility in the measured
density is 3 in 105 parts when the experimental liquid is maintained to 0.010C by
the thermostat.

2.6 Measurement of viscosity Ostwald viscometer method

In the present investigation Ostwald viscometer method

57-60

is used for

determination of viscosities of aqueous solutions at different temperatures.

2.6.1 Basic principle
Viscosities of two liquids or the same liquid at two different temperatures
can be conveniently compared using commercially available Ostwald viscometers,
without tedious measurements of exact dimensions of viscometer91-94. In this
method the time taken by a given volume of liquid to flow through suitable capillary
tube is measured. Similarly the flow time of a reference liquid of known viscosity is
also measured. The ratio of flow times is equal to the ratio of kinematic viscosities.
If the densities of reference and experimental liquids are also known, then
dynamic viscosity or coefficient of

viscosity of experimental liquid can be

determined. This method cannot yield absolute value coefficient of viscosity.

106

2.6.2 Description of Viscometer

A commercial Ostwald viscometer used in the present investigation is
illustrated in the figure 2.4. The viscometer consists of a U shaped tube, with two
bulbs A and B and a capillary portion below the bulb B. Two reference marks M
and N are made above and below the bulb B as shown in figure. A side tube S,
fitted with a tap T is connected to viscometer as shown in figure 2.4.
2.6.3 Experimental procedure
Sufficient quantity of the liquid to be investigated is introduced into the bulb
A through the open end of the viscometer. The whole apparatus is immersed in
the water bath of thermostat. The temperature of the water in the bath of
thermostat can be maintained to 0.010C. Some air is abstracted from the
viscometer by connecting a suitable pump to the side tube (or by directly sucking
the air) so that the liquid column rises above the reference mark M. Then the tap is
closed duly. The viscometer is immersed as such in the water bath for a period for
30 minutes so that the liquid inside the viscometer attains the temperature of the
bath. The tap is now opened. Due to increased pressure on liquid column, the
liquid starts flowing through the capillary. Using a stop clock the time taken by the
liquid meniscus to pass from mark M to mark N is noted. The rate of flow of the
liquid is determined by the capillary portion of the tube. This procedure is repeated
for three times and the average flow time t, is noted. The flow time is measured
using a digital electronic stop clock that can read up to 10-2s.
The experimental liquid is removed from the tube and the tube cleaned with
acetone and dried. Then reference liquid of known density is introduced into the

107

Fig. 2.4 Viscometer

108

viscometer. The flow time t1 of the reference liquid is determined. If K1 is the

kinematic viscosity of the reference liquid then kinematic viscosity of experimental
liquid K is given by
K = (t/t1) K1
The coefficient of viscosity (dynamic viscosity) of the experimental liquid
is given by the relation
= (t/1t1) 1
where 1= coefficient of viscosity of reference liquid
= density of experimental liquid
1 = density of reference liquid
In

the

present

investigation

different

suitable

viscometers

and

correspondingly different reference liquids such as triple distilled water,1,1, 2,2tetrachloro ethane, morph line, 2-chloroaniline etc., have been employed for
different ranges of viscosity, so that viscosity measurements made are reliable.
The reproducibility in the measured viscosity is 0.2%.

2.7 Purification of chemicals

The following chemicals are used in the present work.
Alcohols
1. Methanol
2. Ethanol
3. 1-propanol
4. 1-butanol
5. isopropyl alcohol
6. isobutyl alcohol

109

7. isoamyl alcohol
8. Ethylene glycol
Acrylic esters
1. Methyl acrylate
2. Ethyl acrylate
3. Butyl acrylate
4. 2-ethylhexyl acryalte
Amides
1. Acrylamide (white crystalline solid)
2. Formamide
3. N,N-dimethyl acetamide
Anilines
1. 2-chloroaniline
2. N,N-dimethyl aniline
3. N,N-diethyl aniline
The above said chemicals are purified by standard procedures95,96 like
distillation, fractional distillation under reduced pressure and only middle fractions
were collected. Before use, the chemicals were stored over 0.4 nm molecular
sieves approximately for 72h to remove water content and degassed. The purity of
the chemicals and products obtained are given in the chapters where they are
used. The pure values like ultrasonic velocity, density and viscosity of the
chemicals are compared with the corresponding literature values and they are
reported in the relevant chapters.

110

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