Ultrasonic

ISSN 0973-3302
2010
Proceeding of National
Symposium on Accoustic
Ultrasonics
Volume-
Volume-37 Number 1 2010
www.nsa2010.gpgcrishikesh.com
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Journal of Acoustical Society of India
The Refereed Journal of the Acoustical Society of India (JASI)
CHIEF
CHIEFEDITOR
EDITOR Editorial Office:
Mahavir MANAGING EDITOR
MahavirSingh
Singh
Acoustics Section Omkar Sharma
Acoustics
National Section
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Tel +91-11-45609319
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+91-11-45609319
E-mail: mahavir@nplindia.org
Fax +91-11-45609319 Acoustics Section
E-mail: mahavir@nplindia.org National Physical Laboratory
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EDITOR
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Applied Acoustics
Technology Lead
CCL Bangalore
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E-mail:
Trinathtrinathkar@gmail.com
Kar
Technology Lead
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MAHAVIR SINGH
Chief Editor
OMKAR SHARMA
Managing Editor
TRINATH KAR
Associate Scientific Editor
Youdhishter kumar
Anil Kumar Nain
Assistant Editor
Naveen Garg
Assistant Editor
EDITORIAL BOARD
M L Munjal
IIsc Banglore India
S Narayanan
IIT Chennai India
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KSRCT Erode India
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HWU Edinburg. UK
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NRC Ottawa, Canada
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VIT Vellore, India
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NMI Lindfield, Australia
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IISc Banglore, India
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IIT Delhi, India
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NU Chiba Japan
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OU Osaka Japan
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IIT Delhi (Ex) India
AR Mohanty
IIT Kharagpur India
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NPL New Delhi India
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NPL New Delhi ,India
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Sound Transmission through Building Enclosures
The article deals with sound transmission through building enclosures including different forms of
predominantly lightweight wall construction. It gives guidance on how walls comprising a number of
separate element can be assessed. Sound transmission from outside to inside the reader should also see
BS EN 12345-4:2000 if they are concerned with containment of sound within a building.
The performance of a wall or roof has to be considered in terms of the internal spaces. The aim is to
provide a building envelope that gives the required sound pressure levels within a room or other internal
space. The noise level within a room will depend on the amount of sound energy transmitted through the
wall and interreflection of sound inside the room. The room effect is usually determined by the amount of
sound absorbing material in the room. Sound transmission of an assembly of components can be
calculated provided the wall can be analysed as discrete areas for each of which the Sound Reduction
Index is known.
This applies to windows in walls and collections of windows but note that sound transmission through
interface components such a joining mullions between windows may not be known.
Sound transmission through a whole wall Is established by calculating an apparent sound reduction index
(SRI) for the wall. This is used to determined the difference in sound between the outside and inside. The
procedure is to calculate the sound power reduction for each element of the wall. The total sound power
reduction can then be calculated and converted to an apparent reduction index.
When sound of intensity 1W/m2 falls on a wall the sound power (in watts) transmitted by an element is
given by:
Wi =Si 10
Where
Si is the area of an element (m2 )
Ri is the sound reduction Index of that element (dB)
(Mahavir Singh)
4|Page
1 US-1 Velocity and Thermodynamic properties of Binary liquid mixtures of 8-13
Methanol, Ethanol with Ethylacetoactate
P. Paul Divakara, A. Madhusudhanacharyulua & Mrs. K. Samathab
2 US-2 Study of Solvation number and related parameters of Ammonium 14-19
bifluoride in non-aqueous medium
A. Beulah Mary, J.H.Rakini Chandrasekaran, G. Bharathi & K.Ganthimathi
3 US-3 Study of Internal pressure and Equivalent conductance of solutions of 20-22
calcium fluoride in non-aqueous medium
A. Beulah Mary, J.H.Rakini Chandrasekaran, G. Bharathi & K.Ganthimathi
4 US-4 Effect of electronegativity on free volume and vanderwaals constant 23-27
of binary and ternary liquid mixtures
K. VIJAYALAKSHMI, C. Ravidhas
5 US-5 Ultrasonic studies of nn'-methylene bis-acrylamide in water 28-33
T.Mathavan, S.Umapathy, M.A.Jothi Rajan, A. Alfred Nobel Antony,
X.Dolour Selvarajan, J.Hakkim,
V.Stephen Raja & T.S.Vivekanandam
6 US-6 Determination of ultrasonic interaction parameter for Poly (acrylic 34-38
acid) in water
T.Mathavan, S.Umapathy, M.A.Jothi Rajan, B.Valarmathi &
T.S.Vivekanandam
7 US-7 Ultrasonic investigations of n-methylpyrrolidone in 1-propanol 39-44
T.Mathavan, S.Umapathy, M.A.Jothi Rajan, S.Gokila, M.Abirami,
S.K.Dravida Selvi, R.Hemalatha &
T.S.Vivekanandam
8 US-8 A study of solvation effect of some sodium salts in non-aqueous 45-50
medium using ultrasonic velocity
Padmavathy. R, Jasmine Vasantha Rani. E, Seethalakshmi. K &
Rahmathunnisa. R
9 US-9 Thermo - acoustic and spectroscopic study of polymer salt in non- 51-56
aqueous medium using ultrasonic velocity
Jasmine Vasantha Rani.E, Padmavathi.R, Radha.N, Kannagi. & Lavanya.N
10 US-10 Ultrasonic investigations of peg (400) in toluene-clay mixture 57-62
T. Mathavan, S.Umapathy, M.A.Jothi Rajan, M. Megala &
T.S.Vivekanandam
11 US-11 Acoustical Study on Thermo dynamical and Excess parameters of 63-69
binary and ternary mixtures
M.M. Armstrong Arasu & Dr. I.Johnson
12 US-12 Study of Thermo Acoustical Parameters of Some Binary Mixtures from 70-76
volume Expansivity Data
M.M. Armstrong Arasu & Dr. I.Johnson
13 US-13 A comprehensive analysis of solvation number of some organic acid 77-82
salts in non- aqueous medium
Jasmine Vasantha Rani E & Suhashini Ernest
14 US-14 Ultrasonic study on binary mixtures of ethyl benzoate with benzene 83-88
and substituted benzenes at different temperatures
B. Nagarjuna, Y.V. V Apparaoa, G.V Ramaraob, A.V Sarmaa & C.
5|Page
Rambabuc
15 US-15 Study of non linear parameter (b/a) and thermo acoustic parameter of 89-94
binary mixture at different frequencies
G. Nath & R. Paikaray
16 US-16 Thermo-acoustic Studies on Ternary Mixtures of Methyl Iso-butyl 95-100
Ketone, Acetyl acetone and butanols with carbon tetrachloride (CCl4)
T.Karunamoy, S. K Dash, S.K.Nayak & B B Swain
17 US-17 Glueckauff’s model for lowering of dielectric constant of electrolytic 101-110
solutions & Isentropic Compressiblity Studies with aqueous
electrolytic solutions using Ultrasonics –IONS PAIRS (CHLORIDES)
V.Brahmajirao , T. Gunavardhan Naidu , P.Rajendra , T.Srikanth & Shanaz
Batul
18 US-18 Glueckauff’s model for lowering of dielectric constant of electrolytic 111-121
solutions & Isentropic Compressiblity Studies with aqueous
electrolytic solutions using Ultrasonics –IONS PAIRS (SULPHATES)
V.Brahmajirao , T. Gunavardhan Naidu, T.Srikanth , P.Rajendra & Shanaz
Batul
19 US-19 Tempareture variation of velocity in cow milk at different Ultrasonic 122-128
frequencies
Kailash, S. N. Shrivastava & Poonam Yadav
20 US-20 Ultrasonic Study of some Organic Pathological Compounds 129-133
Kailash, S. K. Shrivastava & Jitendra Kumar
21 US-21 High Temperature Study of Anharmonic Properties of TeO 134-138
Kailash, Jitendra Kumar & Virendra kumar
22 US-22 Orientation Dependence of Ultrasonic Attenuation for Calcium Oxide 139-143
in High Temperature Range
Kailash, S. K. Shrivastava & Jitendra Kumar
23 US-23 Molecular radii of Pyridine/quinoline with phenol in benzene using 144-149
acoustical methods at different temperatures
Anjali Awasthi, Bhawana S. Tripathi, Rajiv K. Tripathi & Aashees Awasthi
24 US-24 Ultrasonic and theoretical study of binary mixture of DEHPA(Di-(2- 150-155
ethyl-hexyl) phosphoric acid) with n-hexane at different temperatures
Sujata Mishra & Rita Paikaray
25 US-25 Acoustical Studies of Molecular Interactions in Binary Liquid System 156-163
of Cinnamaldehyde and N-N Dimethylaniline at 303 K
Padmanabhan G, Kumar R, Jayakumar S & Kannappan V
26 US-26 Characterization of Nanofluid of Platinum 164-169
Virendra Kumar, Kailash and Jitendra Kumar
27 US-27 Ultrasonic Behaviour of Mixed Crystals 170-175
Virendra Kumar, Kailash and Bharat Singh
28 US-28 Temperature Dependence of Ultrasonic Attenuation in Strontium 176-181
Oxide Crystal
Kailash, Virendra Kumar, and D.D. Gupta
29 US-29 Ultrasonic Wave Propagation in Refractory Materials 182-188
Devraj Singh , P. K. Yadawa, Ravi S. Singh and S. K. Sahu
30 US-30 Ultrasonic Wave Propagation in II-VI Hexagonal Semiconductor 189-200
6|Page
Compounds
Pramod Kumar Yadawa & Devraj Singh
31 US-31 Sound Velocity And Density Studies To Find The Effect of PEG on 201-208
Aqueous Anionic Surfactant (SDS)
S. CHAUHAN, M.S. CHAUHAN & R.S. THAKUR
7|Page
VELOCITY AND THERMODYNAMIC PROPERTIES OF
BINARY LIQUID MIXTURES OF METHONOL, ETHANOL WITH ETHYLACETOACTATE
AS COMMON SOLVENT
#
P. Paul Divakar *, A.S. Madhusudanacharyulu* and Mrs. K. Samatha
* Research Scholars, Department of Physics, Andhra University, Visakhapatnam – 530 003

#
Professor, Department of Physics, Andhra University, Visakhapatnam – 530 003
email: putla_paul@yahoo.co.in
ABSTRACT: Ultrasonic velocity(U), density(ρ) and viscosity(η) measurements were made in two
binary liquid mixtures for methanol and ethanol with ethylacetoacetate as a common solvent at 303,
308, 313 and 318 K with increasing mole fraction of ethylacetoacetate using single crystal variable
path ultrasonic interferometer at 2 MHz frequency. The experimental data have been used to
calculate adiabatic compressibility, inter molecular free length, free volume, internal pressure,
molar volume and enthalpy. The excess values of the above parameters have been evaluated and
discussed in the light of molecular interactions.
KEYWORDS: Adiabatic compressibility, Inter molecular free length, Free volume, Internal pressure,
Molar volume and Enthalpy.
INTRODUCTION: The ultrasonic velocity measurements are very important and playing vital role not only
in characterizing the behaviour of liquid mixtures but also in the study of molecular interactions. In recent
times ultrasonic velocity has been adequately employed in understanding the nature of molecular
interaction in pure liquids and binary mixtures. Most of the work on binary mixtures is channelized towards
the estimation of thermodynamic parameters like adiabatic compressibility, free length etc., and their
excess values so as to relate them towards explaining the molecular interactions and hydrogen bonding
taking place between the components of the binary liquid mixtures [1-5].
8|Page
The present study involves the binary mixtures of methanol and ethanol with ethylacetoacetate of various
mole fractions at four different temperatures 303, 308, 313, 318 K. The excess values of some acoustical
and thermo dynamical parameters have been calculated from the experimentally measured values i.e.,
ultrasonic velocity, density and viscosity of the mixtures. The excess values are made to use for the
explanation of the intermolecular interactions, intramolecular interactions and also hydrogen bonding.
EXPERIMENTAL DETAILS: The chemicals used in the present work are AR grade of purity 99% from E-
Merck. The densities and viscosities were measured and compared at the working temperature with the
corresponding literature values. Speeds of sound measurement were made with a single crystal variable
path ultrasonic interferometer (Model F-81; Mittal enterprises) at 2 MHz frequency with an accuracy of
±0.01%. The densities were measured using specific gravity bottles by relative measurement method with
accuracy of ±0.01kg/m. The weight of the samples were measured using a single pan balance (electronic,
Keroy). An Oswald viscometer (5ml) was used for the viscosity measurements and efflux time was
determined using a conventional stop-watch. A constant temperature bath has been used to circulate water
through the measuring cell made-up of steel containing the experimental liquid at the desired temperature
with an accuracy of ±0.1K.
THEORY AND CALCULATIONS
Various Physical and thermo dynamical parameters are calculated.
(1) Adiabatic Compressibility βad = 1/(ρU2) cm2 / dyne
(2) Intermolecular free length Lf = k( βad )1/2 A0

–6 –6 –6
where k is a temperature dependent constant. Its values are 627×10 , 631.5×10 , 636×10 and
–6
640.5×10 respectively at 303, 308, 313 and 318K.
(3) Molar volume V = Meff /ρeff cm3 / mole

where Meff is the molecular weight of the mixture in which Meff = ∑ mi xi
where mi and xi are the molecular weight and the mole fraction of the individual constituents
respectively.
(4) Internal Pressure Πi = bRT (Kη/U)1/2 [ (ρ)2/3 / (Meff)7/6] dynes / cm2

where b is the cubic packing which is assumed to be 2 for all liquids and solutions,
η is the viscosity, R is a gas constant and T absolute temperature K is the temperature dependent
constant is equal to 4.28 X109 for all liquids.
9|Page
(5) Free volume Vf = ( Meff U / Kη )3/2 cm3 / mole
(6) Enthalpy H = ΠiV cal / mole
Excess values of the above parameters can be evaluated using AE = Aexp - Aid
Where Aid = ∑ Ai xi where Ai is any acoustical parameter and xi is the mole fraction of the liquid
component.
RESULTS AND DISCUSSIONS

The experimental values of ultrasonic velocity, density and viscosity for the two binary liquid systems at
303, 308, 313 and 318K are given in Table 1. The excess values of acoustical and thermo dynamical
parameters are presented in tables 2-3.
Table 1 : Values of Ultrasonic Velocity(U), Density (ρ ) and viscosity(η )
for mole fraction X of ethylacetoacetate
System I : Methanol +Ethylacetoacetate
X U x 104 cm/sec ρ x 103 gr/cm3 η centi poise
303K 308K 313K 318K 303K 308K 313K 318K 303K 308K 313K 318K
0.0000 1088.5 1070.3 1055.30 1034.20 0.7809 0.7709 0.7656 0.7605 0.4968 0.4747 0.4478 0.4236
0.0381 1097.8 1081.6 1067.85 1048.26 0.8224 0.7976 0.7931 0.7881 0.5548 0.5124 0.4756 0.4548
0.0818 1108.6 1092.4 1080.52 1061.17 0.8650 0.8228 0.8181 0.8127 0.6140 0.5571 0.5110 0.4889
0.1324 1120.9 1105.9 1093.32 1074.63 0.9083 0.8471 0.8418 0.8358 0.6692 0.6073 0.5481 0.5275
0.1919 1135.3 1119.9 1107.53 1089.20 0.9502 0.8704 0.8650 0.8583 0.7239 0.6617 0.5940 0.5709
0.2626 1151.1 1135.6 1123.13 1105.43 0.9900 0.8929 0.8870 0.8795 0.7796 0.7190 0.6411 0.6181
0.3482 1168.2 1152.2 1139.68 1123.34 1.0281 0.9138 0.9075 0.8994 0.8383 0.7726 0.6940 0.6681
0.4539 1188.9 1172.8 1159.75 1143.01 1.0621 0.9340 0.9273 0.9184 0.9019 0.8251 0.7420 0.7200
0.5876 1215.6 1199.7 1186.15 1169.69 1.0914 0.9543 0.9470 0.9373 0.9704 0.8791 0.7928 0.7668
0.7622 1251.6 1235.7 1221.24 1204.98 1.1131 0.9750 0.9670 0.9562 1.0480 0.9416 0.8540 0.8083
1.0000 1303.0 1286.1 1270.00 1253.00 1.1298 0.9960 0.9870 0.9750 1.1391 1.0192 0.9250 0.8443
System II : Ethanol + Ethylacetoactate
X 303K 308K 313K 318K 303K 308K 313K 318K 303K 308K 313K 318K
0.0000 1132.1 1116.2 1098.5 1080.8 0.7806 0.7763 0.7718 0.7676 0.9856 0.8970 0.8299 0.7670
0.0539 1141.9 1142.0 1144.6 1132.0 0.8199 0.8073 0.8037 0.7998 1.0025 0.9090 0.8389 0.7750
0.1135 1152.7 1153.0 1172.0 1160.9 0.8587 0.8370 0.8334 0.8285 1.0189 0.9222 0.8530 0.7839
0.1180 1164.8 1169.0 1194.4 1181.0 0.8978 0.8653 0.8610 0.8567 1.0366 0.9366 0.8643 0.7951
0.2546 1178.1 1184.0 1212.8 1197.4 0.9373 0.8932 0.8871 0.8826 1.0540 0.9531 0.8783 0.8072
0.3387 1193.2 1195.0 1225.0 1209.9 0.9769 0.9192 0.9124 0.9067 1.0692 0.9685 0.8911 0.8208
0.4345 1210.3 1211.0 1236.0 1220.0 1.0157 0.9424 0.9360 0.9297 1.0816 0,9761 0,8964 0.8243
0.5445 1229.4 1235.0 1245.1 1231.0 1.0522 0.9630 0.9577 0.9499 1.0936 0.9843 0.9020 0.8276
0.6720 1250.4 1255.0 1252.0 1238.7 1.0828 0.9785 0.9720 0.9629 1.1076 0.9949 0.9075 0.8313
0.8218 1274.6 1267.0 1260.8 1247.3 1.1082 0.9902 0.9819 0.9719 1.1230 1.0058 0.9156 0.8373
1.0000 1303.0 1286.0 1270.0 1253.0 1.1298 0.9960 0.9870 0.9750 1.1391 1.0192 0.9250 0.8443
10 | P a g e
The ultrasonic velocity values increases with increase in concentration of ethylacetoacetate in both the
systems. An increase in the ultrasonic velocity with increase in concentration appears to be associated with
an overall increase in the cohesion in both the systems.
The viscosity values from observations are regularly increasing without having any maxima with the
increase of mole concentration of ethylacetoacetate at all the temperatures. Moreover it has been
decreasing with increase in temperature for both the binary systems. The linear increase in with mole
fraction concentration of ethylacetoacetate confirmed the increase of cohesive forces because of strong
molecular interactions.
In order to substantiate the presence of interaction it is essential to study the excess parameters such as
internal pressure, free volume and enthalpy apart from excess adiabatic compressibility, excess free length,
and excess molar volume.
Table 2: Excess values of adiabatic compressibility (βad E ) , Free length ( LfE ) and
Molar volume (VE) for mole fraction X of ethylacetoacetate

X βadE cm2/ dyne LfE x10-8 cm VE cm3 / mole
303K 308K 313K 318K 303K 308K 313K 318K 303K 308K 313K 318K
0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
0.0381 -5.048 -3.962 -4.636 -5.271 -0.014 -0.011 -0.013 -0.014 -0.350 -0.568 -0.639 -0.688
0.0818 -9.521 -7.384 -8.531 -9.815 -0.027 -0.020 -0.024 -0.026 -0.746 -1.119 -1.241 -1.326
0.1324 -13.19 -10.08 -11.466 -13.260 -0.038 -0.028 -0.032 -0.035 -1.185 -1.638 -1.785 -1.891
0.1919 -15.83 -11.88 -13.221 -15.121 -0.047 -0.033 -0.037 -0.041 -1.654 -2.107 -2.249 -2.359
0.2626 -17.16 -12.58 -13.605 -14.759 -0.051 -0.036 -0.039 -0.042 -2.120 -2.493 -2.605 -2.701
0.3482 -16.95 -12.09 -12.583 -11.446 -0.052 -0.035 -0.036 -0.038 -2.517 -2.760 -2.821 -2.891
0.4539 -15.15 -10.50 -10.464 -4.610 -0.048 -0.030 -0.030 -0.031 -2.720 -2.849 -2.862 -2.907
0.5876 -12.05 -8.311 -8.104 -4.010 -0.039 -0.024 -0.023 -0.024 -2.511 -2.665 -2.674 -2.718
0.7622 -8.091 -6.038 -6.427 -3.250 -0.025 -0.017 -0.018 -0.019 -1.590 -1.980 -2.063 -2.146
1.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
System II: Ethanol +Ethylacetoacetate
X 303K 308K 313K 318K 303K 308K 313K 318K 303K 308K 313K 318K
0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
0.0539 -3.855 -6.111 -9.998 -11.454 -0.011 -0.018 -0.030 -0.035 -0.330 -0.510 -0.620 -1.710
0.1135 -7.056 -10.418 -16.874 -19.128 -0.020 -0.031 -0.052 -0.059 -0.682 -1.023 -1.184 -1.343
0.1180 -9.516 -12.887 -20.575 -22.992 -0.028 -0.039 -0.062 -0.071 -1.046 -1.528 -1.684 -1.892
0.2546 -11.14 -13.580 -21.212 -23.249 -0.033 -0.042 -0.067 -0.073 -1.406 -1.999 -2.106 -2.343
0.3387 -11.86 -12.750 -19.243 -20.562 -0.036 -0.040 -0.063 -0.066 -1.730 -2.400 -2.430 -2.680
0.4345 -11.63 -10.880 -15.985 -15.985 -0.036 -0.034 -0.052 -0.053 -1.973 -2.675 -2.631 -2.882
0.5445 -10.45 -8.325 -11.463 -11.359 -0.033 -0.028 -0.040 -0.039 -2.056 -2.741 -2.661 -2.909
0.6720 -8.328 -6.929 -8.469 -8.4969 -0.026 -0.023 -0.030 -0.030 -1.873 -2.465 -2.642 -2.662
0.8218 -5.117 -5.404 -6..689 -7.4241 -0.016 -0.017 -0.022 -0.025 -1.260 -1.650 -1.710 -1.900
1.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11 | P a g e
The excess adiabatic compressibilities (βadE) are negative as observed for both the systems. The excess
adiabatic compressibilities are not only negative but also vary non-linearly with increase in temperature,
i.e., it reaches negative maximum till the mole concentration reaches 0.5 (approx) then again begins to
increase as the mole fraction increases. Fort et.al [2] found that the negative values of excess
compressibilities indicates greater interaction between the components of the mixtures. So the βadE is
associated with a structure forming tendency.
In the present case the mutual breaking of hydrogen bonds in alcohols with ester leading to decrease in
free lengths in the mixture contributing to negative deviation in the adiabatic compressibility for both the
systems. It indicates strong molecular interactions in liquid mixtures. Sridevi et.al [6] suggested that the
negative excess values have been due to closely packed molecules which account for strong molecular
interactions
Table 3: Excess values of Internal pressure (ΠiE ), free volume (VfE ) and Enthalpy( HE) for
mole fraction X of ethylacetoacetate
X ΠiE dyne / cm2 VfE cm3 / mole HE cal / mole
303K 308K 313K 318K 303K 308K 313K 318K 303K 308K 313K 318K
0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
0.0381 -181.1 -337.3 -409.5 -357.4 -0.444 -0.283 -0.150 -0.366 -7157 -2712 -784 -1200
0.0818 -393.0 -652.0 -781.8 -738.6 -0.823 -0.636 -0.394 -0.765 -12313 -6128 -2022 -3189
0.1324 -633.9 -932.7 -1101. -997.1 -1.116 -1.048 -0.734 -1.261 -15046 -10205 -3731 -6017
0.1919 -897.2 -1166. -1350 -1252. -1.306 -1.520 -1.162 -1.836 -15011 -14765 -5870 -9643
0.2626 -1163. -1334. -1509 -1437. -1.379 -2.015 -1.638 -2.470 -12126 -19322 -8246 -13791
0.3482 -1392 -1420. -1558 -1529. -1.335 -2.462 -2.074 -3.113 -6940 -22911 -10421 -17789
0.4539 -1508 -1402. -1487 -1498. -1.208 -2.716 -2.287 -3.637 -1275 -23743 -11507 -20200
0.5876 -1378 -1259. -1294 -1311. -1.070 -2.521 -1.980 -3.761 -1131 -19096 -10017 -18506
0.7622 -834.9 -922.3 -946.0 -905.6 -0.941 -1.543 -0.870 -2.905 -36470 -7077 -4546 -9867
1.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
System II: Ethanol +Ethylacetoacetate
X 303K 308K 313K 318K 303K 308K 313K 318K 303K 308K 313K 318K
0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
0.0539 -346.83 -453.4 -520.90 -528.08 -0.2759 -0.1942 -0.0632 -0.0469 -7674 -11165 -16409 -17579
0.1135 -640.81 -813.6 -924.40 -932.67 -0.5510 -0.4459 -0.2115 -0.2134 -14182 -19182 -27899 -29612
0.1180 -874.18 -1073.5 -1202.9 -1206.8 -0.8166 -0.7403 -0.4331 -0.4828 -19365 -24007 -34394 -36064
0.2546 -1037.6 -1277.3 -1351.9 -1347.8 -1.0522 -1.0494 -0.7032 -0.8202 -23031 -25761 -36088 -37230
0.3387 -1122.8 -1275.0 -1375.5 -1360.1 -1.2530 -1.3286 -0.9787 -1.1653 -25010 -24886 -33692 -34024
0.4345 -1122.9 -1204.6 1289.17 -1264.7 -1.3716 -1.5135 -1.1925 -1.4285 -25165 -22211 -28563 -28108
0.5445 -1031.7 -1090.9 -1119.7 -1092.6 -1.3697 -1.5177 -1.1255 -1.4883 -23357 -18919 -22713 -21903
0.6720 -841.10 -887.2 -895.26 -875.7 -1.1884 -1.2495 -1.0648 -1.2186 -19350 -16055 -18179 -17808
0.8218 -526.08 -586.5 -596.20 -593.5 -0.7548 -0.6715 -0.5736 -0.5900 -12394 -12673 -14427 -15102
1.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
12 | P a g e
The excess intermolecular free length (LfE) is negative at all temperatures over the entire composition range
for both the systems. Also the LfE decreases with increase in the mole fraction of ethylacetoacetate. This
ascribes dominant nature of hydrogen bond interaction between unlike molecules. Hence it represents the
existence of greater interactions. Spencer et.al [7] have also reported a similar observation on the basis of
excess values of free length.
The excess values of enthalpy( HE) are negative for both the systems over the entire mole fraction range is
observed. This negative trend of HE indicates that strong interaction between the unlike molecules besides
dipole-dipole interactions are predominant.
In the present study the excess internal pressure (ΠiE )for both the systems shows negative values and
reaches a maximum at middle concentration as mole fraction of ethylacetoacetate goes on increasing .
Moreover the ΠiE values increases with increase in temperature. This trend shows a pre-dominance of
repulsive forces.
The excess free volume (VfE) values are found to be negative for both the systems studied over the entire
mole fraction range and at all the temperatures. Fort et.al 2 noticed that the negative VfE trend is due to
decrease in the strength of the interaction between the unlike molecules. The excess molar volumes also
exhibit a similar trend as that of VfE and are in good agreement with the aforesaid observations, i.e.,
weakening of intermolecular forces between the components.
CONCLUSION
The excess parameters of non-ideal binary mixtures have been satisfactorily used in explaining the extent
of interactions between mixing components [8, 9]. The negative deviation of high magnitude of VfE and
negative values of ΠE and HE indicate the existence of strong interaction such as hydrogen bond formation
between hetero molecules in both the systems. These conclusions are good in agreement with those
parameters derived from ultrasonic measurements.
References:
1. Kinocid, J. Am. Chem.Soc., S1, 2950 (1929)

2. R.J.Forte and W.R.Moore, Trans.Faraday soc, 61, 2102 (1965)
3. S.B.Kasare and B.A.Patadi, Indian J. Pure & Appl. Phys 25, 180 (1987)
4. Mehra.K Sanjami, Indian J. Pure & Appl. Phys 38, 760 (2000)
5. Y Marcus, Introduction to Liquid state Chemistry, Wiley-inter science, NY (1977)
6. U. Sridevi, K. Samatha, A Viswanadha Sarma, J. pure & Appl. Ultras 26, 1 (2004)
7. J N Spencer, E Jeffery & C Robert J. of Phys.chem. 83, 1249 (1979)
8. A.Pal and Anil Kumar J. Chem.Eng. Data 50, 856 (2005)
9. Rita Mehra and Pancholi J. Indian Coun. Chem, 22 ,32 (2005)
13 | P a g e
STUDY OF SOLVATION NUMBER AND RELATED PARAMETERS OF AMMONIUM
BIFLUORIDE IN NON-AQUEOUS MEDIUM
A. Beulah Mary1, G. Bharathi2, K.Ganthimathi2 and J.H. Rakini Chandrasekaran3
1. Department of Physics, Bishop Heber College, Tiruchirappalli.
2. Department of Physics, Holy Cross College, Tiruchirappalli.
3. Department of Physics, Govt. Arts College. Pudukottai.
ABSTRACT
The passage of ultrasonic waves through liquids, disturb the equilibrium between the solute and
solvent molecules. Ultrasonic velocity measurement is used to throw light on various aspects of solvation
chemistry including ion-ion and ion-solvent interactions. In the present study, computation of solvation
number for Ammonium bifluoride in Dimethyl sulfoxide is undertaken for highlighting the existing
interactions. For such study, density and ultrasonic velocity through the non-aqueous solutions of various
concentrations are measured at different temperatures ranging from 35°c to 55°c.From Adiabatic
compressibility, solvation number and its related parameters namely Apparent molal compressibility,
Apparent molal volume, and Apparent solvated volume are calculated. All these parameters are
temperature and concentration sensitive .Hence the variation of all these parameters with respect to
temperature and concentration are analyzed. These parameters provide the sufficient information about the
interaction between the ions and molecules of solvent.
KEY WORDS: Adiabatic compressibility, Apparent molal volume, molar solvation number, apparent molal
compressibility, molar solvated volume.
1. INTRODUCTION
Study of non-aqueous solutions of electrolytes is interesting for the physical understanding of the
ion-solvent interactions. A primary solvation number can be defined as the number of solvent molecules,
which have surrendered their own translational freedom and remain with the ion when it moves relative to
the surrounding solvent. It can also be defined as the number of solvent molecules, which are aligned in the
force field of the ion. The forces will cause some of the solvent molecules to break away from the solvent
network and attach themselves to the ion [1].
14 | P a g e
Solvent has been described as having an open framework structure with many holes in it. When
pressure is applied, the solvent molecules can break out of the solvent network and enter interstitial space
due to the close packing, the volume decreases. In addition to this, on the introduction of ions into the
solvent, solvent molecules are wrenched out of the solvent framework so as to envelop themselves with
solvent sheaths. Because the molecules are oriented in ionic field, the solvent is more packed in primary
solvation sheath as compared to the packing if the ion were not there. The origin of the influence of the ion
is the electric field of the ion. Thus the electric field causes compression of the material upon which they
exert their influence, due to the phenomenon known as electostriction [2].
2. EXPERIMENTAL STUDY
Dimethyl sulfoxide solutions of various concentrations upto saturation of Ammonium bifluoride are
prepared with AnalaR grade substances. The density of the solution is measured with 10 ml specific gravity
bottle. Ultrasonic velocity of the solution is measured with a Mittal type ultrasonic interferometer with an
accuracy of ±2m/s. The temperature is maintained from 35˚C to 55˚C with an accurate thermostat.
3. CALCULATIONS
The simplest but accurate method of determining the adiabatic compressibility is through ultrasonic
study [3]. From the adiabatic compressibility (β), the solvation number (nh) can be found [4]. The adiabatic
compressibility can be computed using standard relation as given below:
β = 1/ (u 2 ρ) ---------------------- (1)
The molar solvation number is calculated using Barnartt’s [5] relation
nh = [ n1 - βN/ βo ] / n2 -----(2)
where βo is the compressibility of solvent, n1 is the number of moles of the solvent present in 1000 cc of
solution of molar concentration n2 and N is the number of moles of the solvent in 1000 cc of the solvent.
The molal solvation number nh' has been computed through Passynsky’s [6] equation
nh '= [1 - β/βo] N' / n2' -------------------- (3)
where n₂ʹ is the total molal concentration of the solution and N´ is the number of moles of solvent in 1000 g
of the solvent.
The apparent molal volume of the solution (φv) is defined as the volume of the solution containing
one mole of the solute minus the volume of the solvent. It is calculated using the relation (4)
φv = V1 [N n'h / n1 - nh] -------- (4)
It is also computed by the traditional method using the equation,
15 | P a g e
φv = [1000 (ρo -ρ ) / n2 ρo] + M2 / ρo ------ (5)
The apparent molal compressibility is the compressibility of an amount of solution containing

one mole of the solute minus the compressibility of the solvent. It has been calculated using the relation (6)
φk = - V1 βo nh -------- (6)
and the traditional equation.
φk = [1000 (ρo β – βo ρ ) / n2 ρo ] + M2 βo / ρo ---------- (7)
The molar solvated volume (φs) is defined as the volume of the solvated part that comprises the solute
and bound solvent. It is calculated from the following equations
φs = φv + nh V1 --------- (8)
φs = V (β – β0) / n2 β0 ------- (9)
4, RESULTS AND DISCUSSION:
The computed values of solvation numbers, apparent molal compressibility, apparent molal volume
and molar solvated volume of Dimethyl sulfoxide solutions of Ammonium bifluoride are given in Tables 1-2.
The values of apparent molal compressibility, apparent molal volume and molar solvated volume
calculated using solvation number and traditional formula are found to be in agreement.
Solvation number is found to decrease with concentration. A gradual decrease of Solvation number
from lower to higher concentrations is observed standing in agreement with the statement ‘the more dilute
the solution the greater the solvation of the ion’ [7].The value of solvation number decreases with
temperature upto 50⁰C and then increases to a higher value at 55⁰C.Positive Solvation number suggests
that compressibility of the solution will be less than that of the solvent.
Table No.1
Molar solvation number and Apparent molal volume of NH₄HF₂+DMSO System
Temparature Molality n₂' nh nh' Фv*10^6 Фv*10^6
⁰c m³/Mole m³/Mole
By By Traditional
Equation(4) method
35 0.1 10.4167 9.6014 -63.731 -63.731

0.2 6.2352 5.6268 -48.239 -48.239
0.3 4.9958 4.4001 -48.032 -48.032
0.4 4.6827 3.9281 -62.202 -62.202
0.5 4.2182 3.5055 -59.716 -59.716
40 0.1 10.1655 9.2993 -67.885 -67.885
16 | P a g e
0.2 5.9032 5.3721 -42.142 -42.142
0.3 4.8899 4.2748 -49.681 -49.681
0.4 4.5949 3.8257 -63.495 -63.495
0.5 4.0664 3.3361 -61.037 -61.037
45 0.1 9.2469 8.4563 -61.759 -61.759
0.2 5.8912 5.4261 -37.079 -37.079
0.3 4.9907 4.3735 -50.171 -50.171
0.4 4.6095 3.8694 -61.423 -61.423
0.5 4.1116 3.3952 -60.253 -60.253
50 0.1 8.7246 7.9941 -56.999 -56.999
0.2 5.1041 4.6692 -34.321 -34.321
0.3 4.4337 3.8497 -46.956 -46.956
0.4 4.1762 3.4451 -59.924 -59.924
0.5 3.7731 3.0571 -59.477 -59.477
55 0.1 10.8186 10.0651 -60.041 -60.041
0.2 6.0015 5.6505 -28.259 -28.259
0.3 5.1033 4.5187 -48.001 -48.001
0.4 4.7441 4.0331 -59.727 -59.727
0.5 4.2455 3.5417 -59.965 -59.965
Apparent molal volume values are found to change with concentration as well as with
temperature. It is found to be maximam at 0.2 molality and at all temperatures. The decrease in the
apparent molal volume suggests that there is strong ion-ion interaction and increase in apparent molal
volume with respect to concentration supports the solute-solvent interactions.
Apparent molal compressibility increases with concentration at all temperatures and it decreases
upto 50⁰C and then decreases at 55⁰C for all concentrations.
Table No.2
Apparent molal compressibility and Molar solvated volume of NH₄HF₂+DMSO System
Temparature Molality n₂' Фk*E7 m³ Фk E7m³ Фs*10^6 Фs*10^6
⁰c m³/Mole m³/Mole
By By Traditional By By Traditional
Equation(6) method Equation(8) method
35 0.1 -3.281 -3.281 689.51 689.51

0.2 -1.964 -1.964 402.63 402.63
0.3 -1.573 -1.573 313.22 313.22
0.4 -1.475 -1.475 276.41 276.41
0.5 -1.329 -1.329 245.31 245.31
40 0.1 -3.278 -3.278 670.92 670.92
0.2 -1.904 -1.904 386.89 386.89
0.3 -1.577 -1.577 305.71 305.71
17 | P a g e
0.4 -1.482 -1.482 270.45 270.45
0.5 -1.311 -1.311 234.51 234.51
45 0.1 -3.066 -3.066 612.82 612.82
0.2 -1.953 -1.953 392.69 392.69
0.3 -1.655 -1.655 313.91 313.91
0.4 -1.528 -1.528 274.85 274.85
0.5 -1.363 -1.363 239.69 239.69
50 0.1 -2.928 -2.928 581.2 581.19
0.2 -1.713 -1.713 339.04 339.04
0.3 -1.488 -1.488 277.36 277.36
0.4 -1.402 -1.402 245.56 245.56
0.5 -1.266 -1.266 216.51 216.51
55 0.1 -3.761 -3.761 734.19 734.19
0.2 -2.087 -2.087 412.33 412.33
0.3 -1.774 -1.774 326.65 326.65
0.4 -1.649 -1.649 288.56 288.56
0.5 -1.476 -1.476 251.72 251.72
Molal Solvation number of Molar Solvation number

numb of
NH HF +DMSO System NH HF +DMSO System
Fig :1 Fig : 2
Apparent Molal Volume of Apparent Molal Compressibility of

NH HF +DMSO System NH HF +DMSO System
NH₄HF₂+DMSO NH₄HF₂+DMSO
0 -10
Apparent Molal Volume
Compressibility M³
35⁰C 35⁰C
Apparent Molal
-20 0 0.5 1 -20

40⁰C 40⁰C
E+6 m³/Mole
-30
-40
45⁰C -40 45⁰C
-60 Fig : 3 50⁰C Fig :40.2 0.4
0 0.6 50⁰C
-80 Molar55⁰C
Solvated Volume of
Molality Molality 55⁰C
NH HF +DMSO System
NH₄HF₂+DMSO
900
Molar Solvated Volume
700 35⁰C
500
E+6 M³/Mole
40⁰C
300
100 45⁰C 18 | P a g e
0 0.2 0.4 0.6 50⁰C
55⁰C
Molality
Fig : 5
The molar solvated volume is found to decrease in concentration as in the case of salvation
number. This shows that solvation number plays an important role in deciding the value of molar solvated
volume.
The above results show that there is strong solvent-solute interaction.
REFERENCES
1. John O. M. Bokris and Amulya K. N. Reddy, Modern Electrochemistry A Plenum/Rosetta Edition
Vol.1, (1977).
2. Suhashini Ernest Ph.D., Thesis submitted to Bharathidasan University 2010.
3. Jacobson B., Acta. Chem. Scand, 6, 1485 (1952).

4. Pia Thomas and Ganthimathi K., Hydration Number and Apparent Molal Compressibility From
Ultrasonic Measurements, J.Acoust.Soc. Ind., Vol. 27 No. 1–4, (1999) pp 331–333.
5. Barnartt S.J., Chem. Phys., 20, 278 (1952).
6. Passynsky A., Acta Physiochem. 8, 385 (1930).
7. Christian Riechardt “Solvent and Solvent effects in organic chemistry”Wiley VCH Third Edition 2003,
19 | P a g e
STUDY OF INTERNAL PRESSURE AND EQUIVALENT CONDUCTANCE OF
SOLUTIONS OF CALCIUM FLUORIDE IN NON-AQUEOUS MEDIUM
A. Beulah Mary1, J.H. Rakini Chandrasekaran2, G. Bharathi3 and K.Ganthimathi3

1. Department of Physics, Bishop Heber College, Tiruchirappalli.
2. Department of Physics, Govt. Arts College. Pudukotta
3.Department of Physics, Holy Cross College, Tiruchirappalli.
ABSTRACT
Thermodynamic and electrochemical properties of electrolytes find extensive application in
characterizing physico-chemical properties. This paper deals with the thermodynamic and electrochemical
behaviour of solutions of calcium fluoride in dimethyl formamide. Measurement of density, viscosity and
ultrasonic velocity leads to the determination of internal pressure which tells about the interaction between
molecules and ions. Specific conductance values are also measured for studying ionic behaviour of the
solutions. All the measurements are carried out for various concentrations of the solutions in the
temperature range from 35˚C to 55˚C. The relation between equivalent conductance and internal pressure
of the solutions are studied.
KEY WORDS: Ultrasonic velocity, Internal Pressure, Equivalent Conductance, Concentration potential.
1. INTRODUCTION
Dimethyl formamide is a protic solvent and it has very high dielectric constant and dipole moment
(=3.86D, ε=36.7&µ=1.4305) compared to other protic solvents. The high values indicate the existence of
appreciable non specific coulombic interactions and specific forces like hydrogen bonding resulting in
dimers [1].
Internal pressure is a measure of cohesive force in a solution and is considered as a rational basis
to understand thermodynamics of electrolytic solutions [2]. Internal pressure is due to coulumbic interaction
between ions with net charges leading to long range interaction. The ionic behaviour of the solutions is
explained by the equivalent conductance of the solutions. Cohesive energy barrier which is the product of
internal pressure and molar volume also depends on the equivalent conductance.
When we examine values of the equivalent conductance Λc with the variation of concentration
potential Cp, in all the electrolyte solutions Λc decreases with increase in concentration potential [3].The
internal pressure is found to decrease with concentration for some electrolytes and to increase for some
other solutions. Based on this theory C.V. Suryanarayana found the relation [4],
πi V=Λc exp (m₁Cp+k₁) -------------- (1)
to hold good in the case of electrolyte solutions at constant temperature where m1 and k1 are constants.
C.V. Suryanarayana formulated a similar equation for the variation of (πiV/Λc) with temperature,
concentration remaining constant. (i.e)
πi V=Λc exp (m₂T+k₂) --------------- (2)
The validity of these equations is checked for dimethyl formamide solutions of calcium fluoride.
2. EXPERIMENTAL PROCEDURE AND COMPUTATIONS
20 | P a g e
Solutions of various concentrations of calcium fluoride in dimethyl formamide are prepared with
AnalaR grade substances. The density of the solution is measured with 10 ml specific gravity bottle.
Ultrasonic velocity of the solution is measured with a Mittal type ultrasonic interferometer with an accuracy
of ±2m/s. Viscosity is measured with the help of Oswald viscometer. Specific conductance values are also
measured using conductivity meter with a cell constant 1.0. The temperature is maintained from 35˚C to
55˚C with an accurate thermostat.
Internal pressure and equivalent conductance values are computed using the following formulae.
1 2
 kη  ρ2 3
Internal Pressure Π i =bRT  7
atmos ----------- (3)
u 6
M eff
k ×1000
Equivalent conductance ∧ c = c ----------- (4)
N
Where, the terms carry the usual meaning.
3. RESULTS AND DISCUSSION
The computed values of internal pressure and equivalent conductance of the electrolyte solutions
are given in table (1&2.). The variation of internal pressure and equivalent conductance with concentration
of the solutions is shown in Figs (1&2).
In this solution the internal pressure values increase with concentration and decrease with
temperature. This shows that calcium fluoride has structure making nature in dimethyl formamide. The
equivalent conductance is found to decrease with concentration and increase with temperature. Variation of
Ln(πiv/Λ) with Cp and Temperature of solutions are shown in Figs (3&4).They are linear. It proves the
validity of the equations (1&2).
Thus, the equivalent conductance depends directly on cohesive energy barrier and inversely on the
exponential function of concentration potential or temperature [5&6].
Table No.1 Internal Pressure of CaF₂+DMF System in Atmos
Cp 35⁰C 40⁰C 45⁰C 50⁰C 55⁰C
0.00 4285.39 4247.75 4227.99 4183.18 4160.36
0.15 4364.37 4393.29 4407.89 4375.46 4284.89
0.30 4526.47 4548.88 4547.09 4539.65 4405.31
0.45 4715.52 4682.75 4669.87 4648.75 4544.94
0.60 4881.94 4884.71 4893.27 4854.91 4776.42
0.75 4988.41 4985.62 5054.13 4977.67 4890.32
0.90 5133.99 5090.54 5140.88 5097.75 5011.47
1.00 5256.91 5169.61 5223.81 5135.45 5104.55
Table No.2 Equivalent Conductance of CaF₂+DMF System in cm²/ohm

Cp 35⁰C 40⁰C 45⁰C 50⁰C 55⁰C
0.15 23.4955 28.8283 33.4849 36.5429 43.6699
0.30 21.4581 25.4338 27.8562 30.9453 32.2826
0.45 16.5792 20.0249 21.4906 23.9589 25.7584
0.60 14.9031 18.0374 19.8382 21.9684 23.7329
0.75 14.2359 16.1376 17.3905 20.1298 21.3225
21 | P a g e
0.90 12.4907 14.6493 16.2358 18.4618 20.0501
1.00 12.6085 13.9104 15.4907 17.3378 18.7657
Internal Pressure of Equivalent Conductance of

CaF +DMF System CaF +DMF System m
CaF₂+DMF CaF₂+DMF
Equivalent Conductance
50
5500
Internal Pressure Atmos
40
cm²/ohm
5000 35⁰C 35⁰C
40⁰C 30 40⁰C
4500
45⁰C 20 45⁰C
4000 Fig :1 Fig 2
50⁰C
Variation
0 of Ln(πiv/Λ)
0.5 Λ)1with Cp 55⁰C 10 Variation iv/Λ) with 50⁰C
of Ln(πiv/Λ
of Temperature of0.5CaF +DMF System55⁰C
Concentration Potential 0 1
Concentration Potential
CaF₂+DMF
10.5 0
.
Fig 3 Fig 4 3
10
Ln(πiv/Λ)
0
.
9.5 6
REFERENCES 0
.
9 9
8.5
30 40
Temperature50
⁰c 60
1. John E. Mc Grady, Michael.P.and Mingos D.J.Chem. Soc. Perkin Trans., 2 (1995), 228.
2. Suryanarayana, CV.J.IndianchemSoc (1982)562
3. Glasstone S. Introduction to Electrochemistry’ Litton educational Publishing Inc.New York,
82, (1942)
4. Suryanarayana, C.V.Aruna,
una, P. and Natarajan, s.: Ind. J. Tech.Vol.29, 327
327-333
333 (1991).
5. Ganthimathi k. ‘Proton Relaxation Rate, Free Volume and Equivalent Conductance as functions of
Internal Pressure in Aqueous Electrolytes’ , Ph.D.Thesis, Bharathidasan University (1992)
6. Dhanalakshmi
kshmi A.Lalitha V.and Ganthimathi K., J. Acoust. Soc. Ind.Voi.XXI, 1993, 219-222
219
22 | P a g e
EFFECT OF ELECTRONEGATIVITY ON FREE VOLUME AND VANDERWAALS
CONSTANT OF BINARY AND TERNARY LIQUID MIXTURES
K. Vijayalakshmi and C.Ravidhas
Department of physics, Bbishop Heber College, Tiruchirappalli, Tamil nadu, India
Abstract
Ultrasonics is an interesting field of study which makes an effective contribution to many areas of
human endeavor. In the recent years many attempts have been made in the field of physical acoustics and
ultrasound on solids, liquids and gases . One of two fundamental types of solute–solvent intermolecular
interactions are the specific interactions, such as hydrogen bonding complexation between solute and
solvent. The free volume is an important quantity that determines the nature and strength of various inter
molecular interaction in binary and ternary liquid mixtures.In the present work,the ultrasonic velocity
measurements of binary and ternary liquid mixtures of Dioxane, Lactic acid and n-alcohols have been
carried out at 250C temperature using Interferometer technique. From the measured values of density,
viscosity and ultrasonic velocity, the thermodynamic and acoustic parameters such as free volume Vf and
Vander waals constant b have been evaluated. These parameters were successfully employed to
understand the nature of molecular interaction between the interacting components in the mixtures. In
Lactic acid – Alcohol systems ,the free volume increases with percentage of alcohol due to mutual
destruction of association between Lactic acid and alcohol molecules. In all the other ternary systems, Vf
decreases throughout the entire concentration and the Vander waals constant curves are non linear It was
observed that the depolymerisation increases the free volume and electrostatic attraction and association
reduces the free volume. Moreover an increase in the value of b due to increase in the hydro carbon chain
shows a reduction in the free volume.
Keywords: Thermodynamic parameters, molecular interaction, Hydrogen bonding.
1 Introduction
Ultrasonics is an interesting field of study which makes an effective contribution to many areas of
human endeavor. In the recent years many attempts have been made in the field of physical acoustics and
ultrasound on solids, liquids and gases .Ultrasonic velocities and derived thermodynamic parameters are of
considerable interest in understanding the nature and strength of various intermolecular interaction,
formation of Hydrogen bonding etc. [1]. In the present case, work undertaken is to study the thermo-
23 | P a g e
acoustical behavior of binary and ternary liquid mixtures of n-alcohols with Lactic acid and Dioxane from the
variation of Vanderwaal’s constant b and Free volume Vf.
2. Materials and Methods
Binary liquid mixtures of n-alcohols (from Methanol to Hexanol) with Dioxane and Lactic acid and
ternary mixtures of Lactic acid, Dioxane and n-alcohols of various proportions are prepared by volume.
Ultrasonic velocity of the mixtures are measured using Mittal type Ultrasonic Interferometer of fixed
frequency 2MHZ [2]. Using Specific Gravity bottle and Kenon-Fenske Viscometer, density and viscosity of
the mixtures are measured. A constant temperature bath with a compressor unit is used for maintaining the
temperature constant at 25°C.
3.Theory
From the measured values of density ρ, viscosity η and ultrasonic velocity u, the Free volume and
Vander waals constant are computed [3].
3
 Mu  2
Free Volume Vf =  Kη 
 
M RT  2 
 1 + Mu − 1
Vander Waals constant b = 1 −
ρ  Mu 2  3RT 
  
where M is the effective molecular weight of the mixtures, k a constant = 4.28 x 109 independent of
temperature and nature of the system, R the universal gas constant and T the absolute temperature.
4. Results and Discussion
Free volume is the free space available for the molecule to move. The free volume is the effective
volume in which the molecules in the liquid can move and obey perfect gas law. The change in the size and
shape of the molecules results in structural rearrangement of the molecules in the mixture. These structural
changes feature in different types of interaction between like and unlike molecules, during the mixing of
liquids [4].
The free volume of Lactic acid is less and Dioxane is more. However the free volume of n-alcohols
decreases as the hydrocarbon chain increases. Due to overall increase in size of the molecules, their
24 | P a g e
Brownian motion may be affected [5]. Since the molecules are large, they occupy more volume and hence
the free space for their movement is reduced. So the free volume available for their movement is
decreased as the chain length increases from Methanol to Hexanol .This is reflected in the values of
Vander waals constant b, since b may be even 4 times greater than the molar volume [6]. So an increase in
the value of b suggests a reduction in the free volume Vf of the alcohols.
Alcohol-Dioxane system shows an exponential increase in the value of free volume (Fig.1). As the
free volume of alcohols is in the order Methanol > Ethenol > Propanol > Butanol > Pentanol > Hexanol, the
Vf curve goes low as we go from Methanol to Hexanol. The variation of Vanderwaals constant b (Fig. 2),
indicates the specific interaction between alcohol and Dioxane molecules. In Lactic acid – Alcohol systems
[Fig. 3], the free volume increases with percentage of alcohol due to mutual destruction of association
between Lactic acid and alcohol molecules [7].The variation of Vanderwaals constant b is non-linear in
Lactic acid - Alcohol Systems [Fig 4].
1. FIG. 1 FREE VOLUME OF Fig. 2 Vander Waal’s Constant of

Alcohol – Dioxane system
140
0.1
120
0.09
Vander Waal’s Constant (b)
0.08 100
M
0.07 :
D
80
E
0.06 :
2. FREE
D
60
0.05
0.04 40
0.03
20
0.02
0
0.01
0 10 20 30 40 50 60 70 80 90 100
0 10 20 30 40 50 60 70 80 90 100
25 | P a g e
11. FIG. 5 FREE VOLUME 9. FIG. 6 VANDER WAAL’S
0.1 90
0.09

85
0.08
0.07
80
L:
10. FREE
0.06 D
0.05 75
0.04
70
0.03
0.02
65
0.01
0 60
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
% of Dioxane by volume % of Dioxane by volume
8. FIG . 7 FREE VOLUME 7. FIG. 8 VANDER WAAL’S

90
0.09
85
0.08 80
0.07 75
L:D:M
0.06 70
6. FREE
L: D:E
0.05 L: D:P 65
L: D:B
60
0.04 L:D:P
e
L: D:H
55
0.03
50
0.02
45
0.01
40
0 0 10 20 30 40 50 60
0 10 20 30 40 50 60
% of Alcohol by volume % of Alcohol by volume
26 | P a g e
The variation of free volume and Vander waals constant in Lactic acid – Dioxane system [Fig 5, 6],
indicates the possible breaking of hydrogen bonds at higher Dioxane contents[8].That is the variation of Vf
and b with % of solvent shows an exponential behavior, indicating the possible breaking of hydrogen bonds
at higher Dioxane contents. In Lactic acid – Dioxane - Alcohol systems the free volume rise initially at 10%
o Methonal and thereafter Vf decreases. In all the other ternary systems, Vf decreases throughout the entire
concentration (Fig 7), and the Vander waals constant curves are non linear (Fig 8).
From the above observation, it is found that the depolymerisation increases the free volume and
electrostatic attraction and association reduces the free volume [9]. Moreover an increase in the value of b
due to increase in the hydro carbon chain shows a reduction in the free volume.
5. References
1. Rahmat Sadeghi, Roushan Khoshnavazi and Hana Parhizkar, Fluid Phase Equilibria, 260 (2007)
335.
2. Beyer R T and Letcher S V, (1969),Physical Ultrasonics, Academic Press,65.
3. Papadakis E P,(1976), Physical Acoustics:Principles and Methods,
Academic Press New York,12,277-374.
4. Manish S. Kelkar, Jake L. Rafferty, Edward J. Maginn, and J. Ilja Siepmann, Fluid Phase Equilibria
260 ( 2007) 218.
5. Neena Jaggi and Jaiswal R M P.,(2001), Ind J Pure and Appl phys, 39, 122-129.
6. Lalitha, V., (1998), J. Acoust. Soc. Ind. Vol. XXVI, No. 324, pp. 133-138.
7. Baral K K and Mandal R K.,(1998), J Pure and Appl Ultrasonics, 20 , 39
8. Thakare J B., Dongre D T and Deogaonkar,(2000), J Acoust Soc Ind, 28, 365
9. Vijayalakshmi K., (2001), J Acoust Soc Ind, 29, 136
27 | P a g e
ULTRASONIC STUDIES OF
NN'-METHYLENE BIS-ACRYLAMIDE IN WATER
T.Mathavan 1*, S.Umapathy 2, M.A.Jothi Rajan 3, A. Alfred Nobel Antony 1,

X.Dolour Selvarajan 1, J.Hakkim 1, V.Stephen Raja 1
1 Department of Physics, NMSSVN College, Nagamalai, Madurai - 625 019, India.

2 School of Physics, Madurai Kamaraj University, Madurai – 625 021, India.
3 Department of Physics, Arul Anandar College, Karumathur – 625 514, India.
Corresponding author. E-mail address: tjmathavan@yahoo.co.in
ABSTRACT: NN'-Methylene bis-acrylamide (NN'MBA) is dissolved in water and its physical parameters
such as isentropic compressibility(Ks), adiabatic modulus(B), intermolecular free length(Lf), relaxation
time(τ), absorption coefficient(α/f2), attenuation constant(α), molar volume(V), free volume(Vf), internal
pressure(πi), acoustic impedance(Z), Gibbs energy(G), Rao’s number(R) and Wada’s constant(W) were
determined and studied. The acoustic measurements were carried out for four different concentrations at
temperatures 308 K, 313 K, 318 K and 323 K. Ultrasonic parameters provide information about various
intra and intermolecular interactions in solutions.
KEYWORDS: Thermodynamics, ultrasonic velocity and viscosity.
1. 1. INTRODUCTION
The ultrasonic studies are extensively used to estimate the thermodynamic properties and predict
the intermolecular interactions of binary mixtures [1-3]. The sound velocity is one of those physical
properties that help in understanding the nature of liquid state. Hence an attempt is made to study the
interaction of NN'MBA in water.
28 | P a g e
2. EXPERIMENTAL
ANALAR GRADE (AR) SAMPLE OF NN'MBA SUPPLIED BY S.D.FINE-CHEM. LTD., (BOISAR

401501) HAVING MOLECULAR WEIGHT 154.17G/MOLE AND CHEMICAL FORMULA
(CH2:CH.CO.NH)2CH2 WAS USED AS SUCH WITHOUT FURTHER PURIFICATION. WATER,
DOUBLY DISTILLED OVER ALKALINE PERMANGANATE IN ALL GLASS APPARATUS WAS
USED AS THE SOLVENT FOR PREPARING THE SOLUTION. SINGLE FREQUENCY ULTRASONIC
INTERFEROMETER (M/S. MITTAL ENTERPRISES, DELHI, INDIA, MODEL F81, 2 MHZ) AND
CONSTANT TEMPERATURE WATER BATH (M/S. TOSHNIWAL BROTHERS, INDIA) TO AN
ACCURACY OF 0.01C WERE USED FOR ULTRASONIC VELOCITY MEASUREMENTS. THE
REQUIRED CONCENTRATIONS OF THE SOLUTION (0.5, 1.0, 1.5, 2.0ML-1) WERE PREPARED
AND THE MEASUREMENTS WERE TAKEN FOR 308 K, 313 K, 318 K AND 323 K OBTAINED BY
WEIGHING THE SOLUTE BY A DIGITAL BALANCE (ACCURACY 0.001G) AND MIXING WITH
THE ALREADY PURIFIED WATER IN GLASS BEAKERS, WHICH WERE CLEANED AND DRIED
BEFORE USE.
Densities of the solutions were measured by specific gravity bottle of capacity 5ml to an accuracy
of 0.1 kgm-3. Viscosities of the solutions were measured by pyknometer to an accuracy of 0.05%.
3. ACOUSTICAL PARAMETERS
The ultrasonic velocity (U), viscosity( and density( measurements are extensively used to study
the physical, chemical behavior of liquid solutions. In this work the following parameters were determined.
1. Isentropic compressibility Ks = (U2)-1 ----- (1)
2. Adiabatic bulk modulus B = 1/ Ks ----- (2)
3. Intermolecular Free length Lf = k/(  U2) ----- (3)
k is the temperature dependent constant.
4. Relaxation time  = 4 / 3 U2 ----- (4)
5. Absorption co-efficient /f2 = 82/3U3 ----- (5)
6. Attenuation co-efficient  = 82 f2/3U3 ----- (6)
7. Molar volume (V)
V= Meff/  ----- (7)
Meff = X1M1+X2M2
29 | P a g e
where  is the density of the solution, Meff is the effective mass of the binary liquid, X1 is the mole fraction of
the water, X2 is the mole fraction of NN'MBA, M1 is the molecular weight of water, and M2 is the molecular
weight of NN'MBA.
8. Free volume (Vf)
Vf = (Meff U/k)3/2 ----- (8)
Μ 7/6
9. Internal pressure i = bRT(k/U)1/2 2 / 3/ eff ----- (9)
where R is the universal gas constant and b=1.78 (fcc).
10. Specific Acoustic Impedance Z=  U ----- (10)
11. Gibbs free energy G = RT ln (V/hNa) ----- (11)
where h is the Planck’s constant and Na is the Avogadro number.
12. Rao’s number R = Meff U1/3/ ----- (12)
13. Wada’s constant W = Meff K-1/7/  ----- (13)
Ultrasonic velocity (U) in the solution varies according to the molecular interactions in it. Ultrasonic
velocity in water of NN'MBA shows a general increase in temperature (Fig.1), indicating breaking up of
hydrogen bonds as temperature rises. It is observed from the fig. 2 that Ks varies linearly for 308 K and 318
K for all concentrations, whereas Ks varies non-linearly for temperatures 313 K and 323 K for all
concentrations. The non-linear increase and decrease in Ks values with concentration indicates significant
molecular interactions (association) between the component unlike molecules [4, 5]. In the present
investigation as shown in figure 3, it has been observed that intermolecular free-length decreases as
concentration increases for all temperatures (308 K, 318 K) except for the temperatures 313 K and 323 K
where the free length decreases up to 1%, 1.5% concentrations respectively, and then increases as
concentration increases. The minimum observed at 313 K in the concentration 1.5% is shifted to
the concentration 1% when the temperature is increased to 323 K. The difference in free length of 0.01A
between these two temperatures indicates significant interactions between the components unlike
molecules. Therefore Lf decreases with increase in the volume of water in the solution [6, 7]. Relaxation
occurs in liquids and can be either thermal relaxation type as found in gases or of the type due to structural
rearrangement of the molecules which are usually associated with longer chain molecules. Longitudinal
propagation of waves involves the compressional modulus, which is generally considerably larger than the
shear modulus. The classical absorption of ultrasound arises because the propagating wave loses energy
in overcoming the shear viscosity and thermal conductivity of liquids. However the attenuation due to shear
30 | P a g e
viscosity will be a significant contribution. In the present investigation the relaxation time fluctuates in
between 9.4 x 10-5s for 313 K and 8.5 x 10-5s for 323 K, for low and high concentrations respectively as
shown in fig 4.
In the present study the absorption coefficient α/f2 decreases with increase in concentration of the
solution in general. But it is observed for the temperatures 313 K at 1.5% there is a minimum and at 323 k
at 1.0% there is a minimum respectively. There is a shift of 1.5% to 1% with the corresponding shift in
absorption coefficient of 0.01x10-10 Nms-2 as shown in fig. 5. As the ultrasonic waves pass through the
experimental solution, the hydrogen bonds are weakened or broken during compression. The variation of
the attenuation coefficient with respect to the variation of concentration and temperature is as shown in fig.
6. The molar volume almost remains constant with increase in the concentration of the solution as in fig. 7.
Even when the temperature is increased there is a very small increase in the molar volume for various
concentrations.
Free volume of NN'MBA solution shows a general increase in raise of temperature but the free
volume almost remains constant for all the concentration range as shown in fig. 8. When free volume is
minimum it is inferred that close packing of molecules inside the shell which may be brought about by the
formation of associated complexes due to hydrogen bonding [8]. Internal pressure is a single factor, which
appears to vary due to all the internal interactions [9]. Variations of internal pressure of aqueous solutions
of NN’MBA at various concentrations and at different temperatures were shown in fig. 9. Internal pressure
shows a general decrease with increase in temperature. These suggest that cohesive forces decrease with
increase in temperatures [10]. Specific acoustic impedance is similar to the index of refraction in optics. In
the present investigation the specific acoustic impedance increases with increase in concentration almost
linearly as shown in fig. 10. The same trend is observed when the temperature is increased except for
323K where there is a maximum at 1% concentration. The decreasing trend after 1% of concentration may
be due to the change of dielectric constant of the medium (solute-solvent). From the fig. 11 it is observed
that the Gibbs free energy increases slightly with increase in concentration. There is appreciable increase
in the Gibbs free energy with the increase in temperature for a constant concentration of the solution. This
agrees very well with the theory. Rao’s number gives an idea of how the molecular interactions change
(i.e., from weak to strong and vice-versa). An analysis of the experimental data shows that Rao’s constant
is almost constant up to 1.75% of the solution and thereafter decreases abruptly as shown in Fig.12. This
indicates that the strength of the bond is slowly shifting from higher strength to lower strength. Wada’s
31 | P a g e
constant also gives an idea of the changing nature of the molecular interaction i.e., they are weak or strong
interactions (fig. 13).
2. 5. CONCLUSION
For NN'MBA in water for different concentrations the velocities of ultrasonic waves were
determined at a fixed frequency 2MHz, for four different temperatures. The various parameters calculated
in this work are the premises of the study of interactions and complex formation in solutions.
308K
1575 313K
318K
1570
308K
323K
5.0 313k B
1565 318K 0.428 C
323K D
0.426 E
1560
4.8 0.424
-1
1555
Adiabatic compressibilityx10 m N
0.422
2
-1
Velocity,ms
0.420
-10
1550
4.6
0
0.418
Free length, A
1545
0.416
1540 0.414
4.4
0.412
1535
0.410
1530 0.408
4.2
0.406
1525
0.404
1520 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
4.0
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 Mole concentration,M
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
Mole concentration,M Mole concentration,M
Figure 1 Acoustic velocity Vs Mole concentration . Figure 2 Adiabatic compressibility Vs Mole concentration. Figure.3 Free length Vs Mole concentration .
308k 308K
313K 313K 308K
9.9 318k 0.128 318K 313K
9.8 323K 323K
0.126 51 318K
9.7 323K
0.124
-2
9.6 50
ms
9.5
S
0.122
-10
-10
49
Absorption coefficientx10
9.4
Relaxation timex10
0.120
Attenuation constant
9.3
0.118 48
9.2
9.1 0.116
47
9.0 0.114
8.9 46
0.112
8.8
8.7 0.110 45
8.6 0.108
44
8.5
0.106
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 43
Mole concentration,M
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
Figure.4 Relaxation time Vs Mole concentration. Figure.5 Absorption coefficient Vs Mole concentration. Figure.6 Attenuation constant Vs Mole concentration.
308K 308K
313K 313K
0.0185 318K 88 318K 308K
323K 323K 313K
0.0184 86 3.48 318K
323K
0.0183 3.46
84
Free volume x10 ml/mol
Molar volume ml/mol
0.0182 3.44
Internal pressurex10 amu
82
0.0181
7
3.42
-10
80
0.0180
3.40
78
0.0179
3.38
76
0.0178
3.36
74
0.0177
3.34
72
0.0176
3.32
70
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
Figure.7 Molar Volume Vs Mole concentration. Figure.8 Free volume Vs Mole concentration . Figure.9 Internal pressure Vs Mole concentration.
308K 308K
6.72 313K 313K
318K 0.220 318K
6.70
30 8K 323K 0.219 323K
6.68
1 .6 0 31 3K 0.218
31 8K 6.66 0.217
32 3K 6.64 0.216
Gibb's energyX10 RTunits
-2 -1
1 .5 8 6.62 0.215
Accoustical impedancex10 kgm s
-1
Rao's contantx m mol ms
6.60 0.214
-1
0.213
-6
6.58
4
1 .5 6 0.212
3
6.56 0.211
6.54 0.210
1 .5 4 6.52 0.209
6.50 0.208
0.207
6.48
1 .5 2 0.206
6.46
0.205
6.44 0.204
1 .5 0 6.42 0.203
0 .4 0 .6 0 .8 1 .0 1 .2 1 .4 1 .6 1 .8 2 .0 2 .2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
M o le co n ce n tra tio n ,M
32 | P a g e
Figure.10 Acoustical impedance Vs Mole concentration. Figure.11 Gibb’s energy Vs Mole concentration . Figure.12 Rrao’s constant Vs Mole concentration.
308K
313K
0.406 318K
323K
0.404
0.402
-2
Wadd's constantxm mol Nm
0.400
-1
0.398
3
0.396
0.394
0.392
0.390
0.388
0.386
0.384
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
Figure.13 Wadd’s constant Vs Mole concentration.
6. References
1. A V Rao, G K Raman and A V Rajulu, ‘Acoustical parameters of polystyrene in
Binary mixture’, Asian Journal of Chemistry, Vol 5, p 582, 1993.
2. Kch Rao, A V Rajulu and S V Naidy, ‘Acoustical parameters of poly (trinyl pyrrolidone)’,
Acta Polymer, Vol 40, p 743, 1989.
3. S Das, R P Singh and S Math, ‘ultrasonic velocities and Rao formalism in
Solutions of Poly (ester - imides)’, Polymer Bulletin, Vol 2, p 400, 1980.
4. R J Fort and W R Moore, Trans. Faraday Society, 61, p 2102, 1965.
5. B Garcia, R Alcalde, J M Leal and J S Matos, Journal of Chemical
Society, Faraday Trans, 92, p 3347, 1996.
6. Subba Rao and R Gopal Krishnan, Journal of Acoustical Society of India, Vol 7, p 5,
1979.
7. S M Gaour, J S Tomav and R P Varma, Indian Journal of Pure and
Applied Physics, Vol 24, p 602, December 1986.
8. K Ganapathy and D Anbanathan, “Ultrasonics Investigations of Organic Liquid
Mixtures”, Journal of Acoustic Society of India, 15,1:pp 213-220, 1987.
9. E Jasmine Vasnatha Rani and R Padmavathy, “Analysis of Thermodynamical and
Electrochemical Properties of Potassium Bromide in Formamide”, Journal of
Acoustical Society of India, 28, 1-4, pp 329-332, 2000.
10. D Muraliji, S Sekar, A Dhanalakshmi and A R Rankuna, “Internal
Pressure and free Volume in Phenols”, Journal of Acoustical Society of India, 29,
2-4:270-274, 2001.
33 | P a g e
DETERMINATION OF ULTRASONIC INTERACTION PARAMETER FOR POLY
(ACRYLIC ACID) IN WATER
T.Mathavan 1*, S.Umapathy 2, M.A.Jothi Rajan 3, B.Valarmathi 2

* E-mail: tjmathavan@yahoo.co.in
ABSTRACT: Ultrasonic interaction parameter measurements have been made for
poly (acrylic acid) in water solutions at 1MHz, 4MHz and 5MHz. We report the results for weight
concentrations 0.12, 0.36, 0.60 and 0.84 g/100ml at various temperatures 350C, 400C, 450C and 500C. In
this work it has been found that the effect of interchain forces strengthened interaction between polymer-
solvent molecules, which serve to vary the interaction parameter. Neverthless, remarkable similarities exist
between the interaction parameters obtained from viscometric and relaxation time values. The decreasing
interaction parameter values have shown the effects of increasing temperatures.
1. INTRODUCTON
Ultrasonic absorption measurements for Poly (acrylic acid) (PAA) in water can be attributed to shear
viscosity and possibly, to structural relaxation, which relates to the complex molecular formation [1-4]. In
this report, the study of interaction parameter using the change in Gibb’s free energy employing the
viscosity and relaxation- time values is reported [5]. For a high polar polymer, PAA in a high polar solvent,
water, the ultrasonic investigations have shown the interesting result of strengthening in association and
the interaction effects and the influence of a macromolecule on the other molecules. The measurements
have been discussed about the interaction of molecules indirectly [1-4]. We report here the interaction
34 | P a g e
parameter values for PAA in water which exist the structure changes for increasing concentration and also
present the effects of varying the temperature of the system.
1.1 Theory
The properties of polymer solution depend both on the nature and size of the polymer chains and
also on the interaction between polymer and solvent molecules. The interaction parameter χ measures the
extent with which the polymer interacts with the solvent. Flory-Huggins proposed the method of estimation
of the interaction parameter from relative vapour pressure and by osmotic pressure of solution [5]. The
thermodynamic property Gibb’s free energy is used to estimate the interaction parameter, which can be
expressed as
∆G-G1Φ1
χ = ------------------
n1Φ2
where ∆G is the free energy per unit mole of the solution, G1 is the free energy of the solvent, n1 is the
number of solvent molecules, Φ1 and Φ2 are the respective volume fractions of the solvent and the
polymer [6]. The literature values of viscosity and relaxation time and the estimated values of χ were shown
in tables I - IV.
Table I. Calculated interaction parameter values of PAA in water at 35°°C.
χ
Frequency Concentration Viscosity η Relaxation time τ
ΜΗz Weight % * 103 Nsm-2 * 1012sec
From η from τ
1 0.0 0.7194 0.4178 - -
1.2 1.2928 0.74781 0.0492 0.0412
3.6 1.5694 0.90667 0.0157 0.0130
6.0 1.6968 0.97847 0.0093 0.0077
8.4 1.9483 1.1267 0.0064 0.0053
4 0.0 0.7194 0.41638 - -

1.2 1.2928 0.75493 0.0492 0.0409
3.6 1.5694 0.91702 0.0157 0.0129
35 | P a g e
6.0 1.6968 0.99431 0.0093 0.0076
8.4 1.9483 1.1355 0.0064 0.0052
5 0.0 0.7194 0.41290 - -

1.2 1.2928 0.75255 0.0492 0.0404
3.6 1.5694 0.91010 0.0157 0.0128
6.0 1.6968 0.97285 0.0093 0.0075
8.4 1.9483 1.198 0.0064 0.0052
Table II. Calculated interaction parameter values of PAA in water at 40°°C.
χ
From η from τ
1 0.0 0.6529 0.37524 - -
1.2 1.0772 0.61701 0.0455 0.0377
3.6 1.4138 0.80928 0.0142 0.0116
6.0 1.5526 0.88609 0.0083 0.0068
8.4 1.7606 1.0094 0.0058 0.0046
4 0.0 0.6529 0.37711 - -

1.2 1.0772 0.61573 0.0455 0.0380
3.6 1.4138 0.82472 0.0142 0.0116
6.0 1.5526 0.89423 0.0083 0.0068
8.4 1.7606 1.0186 0.0058 0.0047
5 0.0 0.6529 0.37047 - -

1.2 1.0772 0.61460 0.0455 0.0370
3.6 1.4138 0.82147 0.0142 0.0113
6.0 1.5526 0.88655 0.0083 0.0066
8.4 1.7606 1.02730 0.0058 0.0045
Table III. Calculated interaction parameter values of PAA in water at 45°°C.
χ
From η from τ
0.0 0.5960 0.33877 - -
1.2 0.9514 0.54348 0.0416 0.0535
3.6 1.1574 0.65702 0.0132 0.0172
6.0 1.3771 0.78369 0.0075 0.0099
8.4 1.6120 0.92001 0.0051 0.0068
4 0.0 0.5960 0.34181 - -
36 | P a g e
1.2 0.9514 0.54094 0.0416 0.0344
3. 1.1574 0.66599 0.0132 0.0107
6.0 1.3771 0.78635 0.0075 0.0061
8.4 1.6120 0.91666 0.0051 0.0041
5 0.0 0.5960 0.33667 - -

1.2 0.9514 0.54052 0.0416 0.0335
3.6 1.1574 0.66451 0.0132 0.0104
6.0 1.3771 0.77943 0.0075 0.0059
8.4 1.6120 0.92216 0.0051 0.0040
Table IV. Calculated interaction parameter values of PAA in water at 50°°C.
χ
From η from τ
1 0.0 0.5468 0.30825 - -
1.2 0.9263 0.51812 0.0369 0.0295
3.6 1.1003 0.62414 0.0117 0.0092
6.0 1.3209 0.75545 0.0066 0.0051
8.4 1.5217 0.86244 0.0045 0.0035
4 0.0 0.5468 0.31207 - -

1.2 0.9263 0.52527 0.0369 0.0301
3.6 1.1003 0.63429 0.0117 0.0091
6.0 1.3209 0.75880 0.0066 0.0052
8.4 1.5217 0.85489 0.0045 0.0036
5 0.0 0.5468 0.30873 - -

1.2 0.9263 0.52500 0.0369 0.0295
3.6 1.1003 0.62236 0.0117 0.0092
6.0 1.3209 0.74206 0.0066 0.0052
8.4 1.5217 0.86558 0.0045 0.0035
2. DISCUSSION
An important finding in this investigation was giving the result in numerical scale of inter/intra
molecular interactions as a single parameter χ although the other parameters were there. The negative
values of χ reveal explicitly the strong attractive interaction between interchain molecules [6]. As both PAA
and water are strong polar molecules, it might be expected to show decreasing values of χ for increasing
37 | P a g e
concentrations. Similar behaviour is seen with the χ values of increasing temperatures. This interaction χ is
a measure of the polymer-solvent interaction [7]. Here the interaction may be between (monomer) units or
groups of (monomer) units. In more concentrated solutions, direct segment-segment interactions may exist
3. CONCLUSION
The interaction parameter values obtained from thermodynamic property Gibbs free energy for poly
(acrylic acid) in water which exhibits structure changes for increasing concentration. The effects of varying
the temperature of the system are also reported.
4. REFERENCES
1. J.H.So, R.Esquivel-Sirvent, S.S.Yun and F.B.Stumpf, “Ultrasonic velocity and
Absorption Measurements for Poly (acrylic acid) and Water Solutions”,
J Acoust. Soc. Am. 98 (1), 659-660 (1995).
2. S.K.Hassun, Acoustics Letters, 12(9), 161-165(1989).
3. P.Vigoureuse, Ultrasonic, John Wiley & Sons, New York, 32(1951).
4. B.Valarmathi, “Ultrasonic Investigations of Poly (acrylic acid) in water ”, M.Phil
Dissertation, School of Physics, Madurai Kamaraj University, India, (1997).
5. S.Kalyanasudaram and J.Hemalatha, “Ultrasonic studies on PVC in Chlorobenzene,”
J.Plym.Mater.14, 285-289(1997).
6. P.J.Flory, “Thermodynamics of High Polymer Solutions,” J.Chem.Phys.10, 51(1942).
7. R.A.Orwoll and P.A.Arnold, “Phys Prop Poly.Hand Book,” AIP Press, Newyork,
170(1996).
8. A.M.Bell, W.North, R.A.Pethrick and P.B.Jeik, J.Chem.Soc.Faraday Trans
11, 75, 1115(1979).
38 | P a g e
ULTRASONIC INVESTIGATIONS OF
N-METHYLPYRROLIDONE IN 1-PROPANOL
T.Mathavan 1*, S.Umapathy 2, M.A.Jothi Rajan 3, S.Gokila 1, M.Abirami 1, R.Hemalatha 1, S.K.Dravida Selvi 1
1 Department of Physics, N.M.S.S.Vellaichamy Nadar College, Nagamalai, Madurai - 625 019, India.
* Corresponding author. E-mail : tjmathavan@yahoo.co.in
3. Abstract: LOW POWER ULTRASONIC TECHNIQUE IS ONE OF THE MOST POWERFUL

AND USEFUL NONDESTRUCTIVE TESTING TOOLS TO INVESTIGATE PROPERTIES OF
SOLUTIONS. THE LOW POWER ULTRASONIC MEASUREMENTS ARE CARRIED OUT AT
FIVE DIFFERENT CONCENTRATIONS AND AT TWO DIFFERENT TEMPERATURES FOR
N-METHYLPYRROLIDONE IN 1-PROPANOL. THE ACOUSTICAL AND
THERMODYNAMICAL PARAMETERS ARE COMPUTED ON THE BASIS OF
EXPERIMENTALLY DETERMINED VALUES OF ULTRASONIC VELOCITY, DENSITY AND
VISCOSITY. N-METHYLPYRROLIDONE (NMP) IS MIXED WITH 1-PROPANOL AND ITS
PHYSICAL PARAMETERS SUCH AS DENSITY, VISCOSITY AND VELOCITY WERE
MEASURED EXPERIMENTALLY. FROM THESE VALUES THE EXCESS PROPERTIES
SUCH AS ηE, βAE, LFE, VE AND ПIE ARE FOUND OUT AND THESE GIVE INSIGHT ABOUT
THE NATURE OF THE INTERMOLECULAR ASSOCIATION BETWEEN THE NMP AND 1-
PROPANOL.
KEYWORDS: NMP, 1-Propanol, low power ultrasound, Thermodynamical parameters, Excess parameters.
39 | P a g e
4. 1. INTRODUCTION
N-Methylpyrrolidone (NMP) is a dipolar aprotic solvent. Large amounts of NMP are consumed in
the polymer industry as a medium for polymerization and as a solvent for finished polymers. The study of
propagation of ultrasonic waves in liquids and liquid mixtures is well established for examining the nature of
molecular interactions [1-7]. Ultrasonic velocity studies on NMP in 1-propanol may reveal its suitability of
being used as coating agent in aircrafts under high pressure and various atmospheric conditions. In this
work an attempt is made to study the interaction of NMP in 1-propanol for five different concentrations and
two different temperatures by measuring the various thermodynamics parameters.
2. Experimental
2.1. Apparatus
Analar grade sample of NMP supplied by s.d.fine-chem. Ltd., (BOISAR 401501) having molecular
weight 99.13g/mole and chemical formula (CH2: CH.CO.NH)2CH2 is used as such without further
purification. 1-Propanol, doubly distilled over alkaline permanganate was used as the solvent for preparing
the solution. Single frequency (2 MHz) ultrasonic interferometer (M/S. Mittel Enterprises, Delhi, India, Model
F81) was used for ultrasonic velocity measurements and the measured intensity was 5.5W/cm2. This works
on the principle of piezo-electric effect and imparts ultrasonic waves into the solution in a 12 ml
thermostatic cell.
The solutions of different concentrations were prepared by weighing the solute by a digital balance
(accuracy ±0.001g) and mixed with the already purified 1-propanol in cleaned and dried glass beakers. The
required amount of the solution was placed in the cell and maintained at a predetermined temperature
using a constant temperature water bath (M/S. Toshniwal Brothers, India) to an accuracy of ±0.01°C. Thus,
velocity measurements were made for five different concentrations (0.2, 0.4, 0.6, 0.8 and 1.0 ML-1) of the
experimental solution. For each concentration of the solution velocity measurements were made for two
different (constant) temperatures (308 K and 313 K). Densities of the solutions were measured by specific
gravity bottle of capacity 5ml to an accuracy of ±0.1 Kgm-3. Viscosities of the solutions were measured by
Oswald viscometer to an accuracy of ±0.05%.
2.2. Theory
The ultrasonic velocity, viscosity and density measurements are extensively used to study the
physical and chemical behavior of liquid solutions. Studies of excess thermodynamic functions such as
excess viscosity, excess free length, excess adiabatic compressibility, excess molar volume and excess
40 | P a g e
internal pressure are useful in understanding the nature of intermolecular interactions in liquid mixtures [1-
4]. The excess value of the above parameters provides the nature and strength of the interactions [5-7].
The non-zero values confirm the presence of interaction i.e., excess values are the indicators of magnitude
of the relative strength of interaction. In this work the following parameters were determined:
Excess viscosity (ηE)
The excess viscosity is given by
ηE = ηexp – [X1η1 + X2η2] ----- (1)
where ηexp is the viscosity of the solution, X1 is the mole fraction of NMP, X2 is the mole fraction of 1-
propanol, η1 is the viscosity of pure NMP and η2 is the viscosity of pure 1-propanol.
Excess free length (LfE)
The excess free length is given by
LfE = Lfexp – [X1Lf1 + X2Lf2] ----- (2)
where Lfexp is the free volume of the solution, X1 is the mole fraction of NMP, X2 is the mole fraction of 1-
propanol, Lf1 is the free length of pure NMP and Lf2 is the free length of pure 1-propanol.
Excess adiabatic compressibility (βE)
The excess adiabatic compressibility is given by
βE = βexp – [X1β1 + X2β2] ----- (3)
where βexp is the adiabatic compressibility of the solution, X1 is the mole fraction of NMP, X2 is the mole
fraction of 1-propanol, β1 is the adiabatic compressibility of pure NMP and β2 is the adiabatic
compressibility of pure 1-propanol.
Excess Molar volume (VE)
The excess molar volume is given by
VE = Vexp – [X1V1 + X2V2] ----- (4)
where Vexp is the molar volume of the solution, X1 is the mole fraction of NMP, X2 is the mole fraction of 1-
propanol, V1 is the molar volume of pure NMP and V2 is the molar volume of pure 1-propanol.
Excess internal pressure (ПiE)
The excess internal pressure is given by
ПiE = Пiexp – [X1Пi1 + X2Пi2] ----- (5)
where Πiexp is the internal pressure of the solution, X1 is the mole fraction of NMP, X2 is the mole fraction of
1-propanol, Πi1 is the internal pressure of pure NMP and Πi2 is the internal pressure of pure 1-propanol.
3. Results and discussion
41 | P a g e
The excess viscosity ηE calculated shows the reverse trend of βE as shown in the Fig. 1. The
excess free length of NMP with 1-propanol at two different temperatures 308K and 313K are found out. The
variation of ultrasonic velocity in a solution depends upon the increase or decrease of intermolecular free
length after mixing the components. In the present work the positive values of LfE signify decreasing dipole-
dipole interactions due to decreasing proton donating abilities. The positive LfE values decrease with
increase of temperature suggesting a decrease in hetero-association of molecules at elevated
temperatures (Fig. 2) [8, 9].
The excess adiabatic compressibility of NMP with 1-propanol for two different temperatures 308K
and 313K are studied (Fig. 3). The βE decreases as temperature increases. Positive values in excess
properties correspond mainly to the existence of dispersion forces and a positive βE tending towards a
negative one shows that the strength of interaction increases. In this case the tendency of change from
positive values to negative values indicating the strong interaction between the unlike molecules [10].
The partial molar volume as a function of X1 suggests that these values are positive in the NMP+1-
propanol system. In this system there may be a strong interaction between the
1-propanol molecules due to hydrogen bond and the addition of NMP may weaken the interactions. The
observed value of VE can be qualitatively explained by considering the factor, which influences this excess
function, namely the mutual disruption of associates present in the pure liquid (Fig.4). This factor
contributes to positive value of VE, and also suggests that this effect is due to break up of dipolar
association of NMP+1-propanol predominates over that of hydrogen bonding between unlike molecules
making VE values positive (Fig. 4). The positive VE values can also be attributed to the weak dipole-dipole
interaction leading to weak complex formation between unlike molecules [8]. The increase in negative
values of ΠiE suggests the predominance of hydrogen bonded interactions over the interstitial
accommodation of component molecules at higher concentration of 1-propanol (Fig. 5) [11].
4. Conclusion
Acoustic investigations were carried out for five different mole concentrations of NMP+1-propanol
system. When the concentration of the solution is increased, correspondingly its various physical
parameters change considerably. Similar changes in physical parameters are also observed when the
temperature of the solution is varied. Ultrasonic parameters provide information about various intra and
intermolecular interactions in solutions.
42 | P a g e
0.035
308 K 308 K
313 K 313 K
0.000 0.030
-0.005
0.025
-2
v i s c o s i t y, Nsm
-0.010
-0.015 0.020
o
Lf , A
-0.020
0.015
E
-0.025
0.010
-0.030
Excess
-0.035
0.005
-0.040
0.000
-0.045
-0.050 0.2 0.4 0.6 0.8 1.0

0.2 0.4 0.6 0.8 1.0
Mole concentration
Mole concentration
Fig. 1 Mole concentration vs Excess viscosity. Fig. 2 Mole concentration vs Excess freelength.
0.018
0.8 308 K
308 K
0.016 313 K
313 K
0.014
0.6
-1
0.012
β , 10 m N
-1
2
V , 10 M
-10
-4
0.4 0.010
E
E
0.008
0.2
0.006
0.004
0.0
0.002
0.2 0.4 0.6 0.8 1.0
0.2 0.4 0.6 0.8 1.0
Mole concentration
Mole concentration
Fig. 3 Mole concentration vs βE Fig. 4 Mole concentration vs VE
0.010
308 K
0.005 313 K
0.000
π , 10 atm
-0.005
10
Ε
-0.010
-0.015
-0.020
0.2 0.4 0.6 0.8 1.0

Mole concentration, M
43 | P a g e
Fig. 5 Mole concentration vs П E
5. REFERENCES
1. A.V. Rao, G.K. Raman and A.V. Rajulu, ‘Acoustical parameters of polystyrene in Binary
mixture’, Asian Journal of Chemistry, 5, (1993), 582.
2. Kch Rao, A.V. Rajulu and S.V. Naidy, ‘Acoustical parameters of poly (trinyl pyrrolidone)’,
Acta Polymer, 40, (1989), 743.
3. S. Das, R.P. Singh and S. Math, ‘ultrasonic velocities and Rao formalism in Solutions of Poly
(ester – imides)’, Polymer Bulletin, 2, (1980), 400.
4. R.A. Pethrick, ‘Acoustic studies of Polymer solutions’, Journal of Macromolecule Science
Review, Macromolecule, Chemistry, C9, (1973), 91.
5. J. I. Dunbar, A.M. Pethnik and D.B. Steinhauer, ‘Acoustic Absorption of dilute solution of
polystyrene in Toluene and cyclohexane’, Journal of Polymer Science, Physics Edition, 15,
(1977), 263.
6. T. Boubbik, ‘Statistical Thermodynamics of Molecules’, Molecular Physics, 27,
(1974), 1415-1477.
7. S.X. Sheng, J.Y. Huang, J. Li and O.P. Guo, ‘Phase Behavior and Properties of PMMA-
Polyvinyl acetate’, Journal of Applied Polymer Science, 699(4), (1998), 675.
8. Amalendu Pal, B.R., Harsh Kumar, Arbad and A.B. Tekale, Indian J. of Pure and
Applied physics, 41, (2003), 113-120.
9. A.V. Narashimham and A.T. Seshadri, Indian Journal of Physics, 65B (3), (1992), 44-48.
10. A.V. Narashimham, Indian Journal of Physics, 65B (4), (1991), 312-318.
11. Rita Mehra, Rekha Israni, J. Acous. Soc. India, 30, (2002), 72.
44 | P a g e
A STUDY OF SOLVATION EFFECT OF SOME SODIUM SALTS IN NON-AQUEOUS
MEDIUM USING ULTRASONIC VELOCITY
Padmavathy.R1, Jasmine Vasantha Rani. E2, Seethalakshmi.K3, Rahmathunnisa.R4
123Department of Physics, Seethalakshmi Ramasami College, Trichy-2, Tamil Nadu 4Department of

Physics, Govt. Arts College, Pudukkottai, Tamilnadu
5. ABSTRACT
Ultrasonic studies of solutions yield valuable information about the ionic interactions, the
nature and strength of the interactions. Velocity of sound waves in a medium is fundamentally
related to the binding forces between the molecules. The ultrasonic velocity data combined with
density constitute the standard means of determining the compressibility of the system. When an
electrolyte is added to a solvent the volume of the solvent changes and hence there is a change in
compressibility. These changes have been determined quantitatively as solvation number. In the
present case, the effect of temperature and concentration on solvation is analyzed for some sodium
salts in non acqueous medium, thus various interactions taking place between the solute and
solvent are interpreted.
Keywords: solvation number, solute - solvent interaction, structure maker/breaker
1.Introduction
The passage of ultrasonic waves through solutions and liquids disturb the equilibrium between the
solute and solvent molecules. The velocity of such a wave is a thermodynamic quantity and it is related to
the physio-chemical properties of the medium. Ultrasonic velocity measurement is used to throw light on
various aspects of solvation chemistry including ion-ion and ion-solvent interaction. By measuring the
fundamental quantities such as density and ultrasonic velocity of sodium citrate, sodium molybdate, sodium
45 | P a g e
salicylate and sodium calcium edetate in formamide from 5oc to 55oc at different concentration, the
solvation number were computed. From the analysis of solvation, the sodium salts in formamide reveals
the structural interaction taking place in the solutions.
1.1 Experimental technique

Solutions of sodium citrate, sodium molybdate, sodium salicylate and sodium calcium edetate of
various concentrations are prepared in formamide with (AR/BDH) salt. Density of the solutions is
measured using 25ml specific gravity bottle with an accuracy of .001gm/cc. Mittal’s interferometer of
frequency to 2MHz, with an accuracy of ±2m/s is used for the measurement of ultrasonic velocity.
The solvation number was calculated using the formula:
nh = (ns / ni )[1 − ( β / β o )]
1.1(a)Results and Discussions

Solvation is the attraction and the association of the molecules of a solvent with molecules or ions
of the solute. The solvation numbers reflect the dynamic situation of the ion as it moves around in the
solution. The structure of the solvent near an ion will be having three regions. In the primary or structure
enhanced region next to the ion, the solvent molecules are immobilized and oriented by the ionic field.
Then there is a secondary or structure broken region, in which the normal bulk structure of the solvent is
broken down in various degrees. The in-between solvent molecules, however, do not partake of the
translational motion of the ion. The structural changes in the primary and secondary regions are generally
referred to as the solvation.[1]
The general observations made on solvation number of the system studied in relation to
temperature and molality are as shown in figs.(1,2,3,4). The solvation number is positive at a high
temperature, it is negative at low temperature and no abrupt change in solvation number is found at higher
molalities. At lower molalities, the solvation number changes from negative values to the positive values.
Solvation number is decided by relative values of compressibility of solution and solvent. Constant values
of solvation number only indicates that no change occurs in the compressibility value of the solvent when
the solution is formed. This may be due to ion solvent interaction energy equal to intermolecular interaction
energy. Therefore no change in compressibility. Negative values of solvation number at lower molalities,
emphasizes that solutions are more compressible than solvent, hence the negative sign for the solvation
46 | P a g e
number. Positive solvation number of the solution suggests that the compressibility of the solution at high
temperature and at low molalities will be less than that of the solvent. But however a fall in the solvation
number at high temperature or rise in solvation number from negative maximum towards zero at low
temperature may be attributed to decreasing ion-solvent interactions[2].
The solvation approach is used to interpret ion - solvent interaction[3]. The negative solvation
number for various molalities is reported in literature[4,5,6]. The decrease in solvation number with
increasing molality is due to either not enough solvent molecules available for ions or preferentially ion -
pairing occurred[7].
1,1(b)Conclusion:
In the present investigation, the solvation number of the sodium salts reveal very high solvation
number in formamide.
The solvation number of an ion depends on the solvent.
The concept of solvation is a measure of the ionic force field and ion - solvent interaction energy of
the solutions.
Structural elucidation of the solute in the solvent. i.e. sodium citrate& sodium molybdate in
formamide acts as structure makers and sodium salicylate & sodium calcium edetate in the solvent
acts as structure breakers fig(5,6,7,8).
47 | P a g e
2. Figures and Tables
Solvation Number
Table –1 Sodium citrate
Molality(m) 5°C 15°C 25°C 35°C 45°C 55°C
0.001 -137.24 -17.53 -198.70 70.93 318.38 329.58
0.005 -21.16 -4.12 -22.58 33.03 83.37 77.64
0.010 -0.77 1.75 -21.59 11.82 33.87 33.41
0.025 3.40 7.95 -2.27 8.56 18.18 18.47
0.050 5.23 10.40 2.74 6.71 12.97 12.17
Table – 2 Sodium molybdate

Molaity(m) 5°C 15°C 25°C 35°C 45°C 55°C
0.001 -300.10 -26.10 -232.44 -24.22 235.92 266.51
0.005 -43.95 19.09 -31.70 2.07 79.53 73.51
0.010 -6.41 16.16 -4.34 6.30 45.77 44.58
0.050 1.83 3.94 0.85 5.17 10.63 13.71
0.100 3.67 4.67 2.56 5.73 7.92 8.97
0.150 4.19 5.66 3.56 5.25 6.30 7.10
Table – 3 Sodium salicylate

0.001 -592.58 -436.84 -1236.30 -784.00 -146.83 419.33
0.005 112.37 -22.75 -1.17 87.32 174.44 192.54
0.010 20.55 63.63 -5.06 -1.36 9.01 57.80
0.050 -0.75 5.75 -1.42 3.13 9.33 10.78
0.100 -9.22 -4.01 -1.25 5.84 12.48 6.30
0.200 9.53 9.58 5.18 8.45 11.48 6.85
Table – 4 Sodium calcium edetate

0.001 485.01 752.59 745.61 1457.11 1438.94 1355.54
0.005 -4.51 -13.26 -191.44 -65.98 30.30 96.27
0.010 -186.06 -190.16 -189.96 -148.22 -107.64 -65.46
0.020 -9.02 -1.12 0.19 27.86 23.50 33.92
0.030 57.94 59.43 59.82 60.53 85.72 108.72
48 | P a g e
6. SOLVATION NUMBER
Fig – 1 SODIUM CITRATE Fig – 2 SODIUM MOLYBDATE
Molality Vs Solvation number

400 300
300 200
Solva tion num be r

Solvation number
5°C 100 5°C

200
15°C 0 15°C
100
25°C 0 0.01 0.01 0.05 0.1 0.15 25°C
-100
0 35°C
35°C
0.001 0.005 0.01 0.025 0.05 -200
-100 45°C 45°C
-300
-200 55°C
55°C
-400
-300
Molality (m)
Molality(m)
7. IG – 3 SODIUM SALICYLATE FIG –

4 SODIUM CALCIUM EDETATE

600
1600
400
1400
200
1200 5°C
Solvation number
Solvation number
0 5°C 1000 15°C

-200 0 0.01 0.01 0.05 0.1 0.2 15°C 800
-400 25°C
25°C 600
-600 35°C 400 35°C
-800 200 45°C
45°C
-1000 0
55°C 55°C
-1200 -200 0.001 0.005 0.01 0.02 0.03
-1400 -400
Molality(m) Molality(m)
Fig - 5 Fig - 6
49 | P a g e
Fig - 7 Fig - 8
3. References:
1. John O.M. Bockris and Amulya K.N. Reddy, “Modern Electrochemistry”, A Plenum / rosetta Edition,
Vol 1, (1997)
2. Bhullar.k, Bhavneet.K.Bakshi. M.S., Jasbir.S., Sharma S.C. and Joshi I.M.Acoustica. Vol.73(1991)292.
3. Padova J, Isr At. Energy Comm,(1963) IA – 823, (16PP), A-830(23PP)
4. Lit vinenko, Zh.Strukt, Khim.,4(1963) 830
5. Rao M.G.S. and Rao B.R., J.Pure and applied Phys.,1(10) (1963) 362.
6. Rajkotia, et.al.,J.Pure and Appl. Ultrasonics, 21(1999)132-135
7. KuppuswamiJ.,Lakshmanan A.S., Lakshminarayanan R. Rajaram N., and Suryanarayana C.V.Bull.
Chem. Soc. Japan , 38, (1965) 1610.
50 | P a g e
THERMO - ACOUSTIC AND SPECTROSCOPIC STUDY OF POLYMER SALT IN NON -AQUEOUS
MEDIUM USING ULTRASONIC VELOCITY
*JASMINE VASANTHA RANI.E, *PADMAVATHY.R, #RADHA.N,

@KANNAGI.K, &LAVANYA.N
*Department of Physics, #Department of Chemistry

@ Dr. Kalaignar arts and science college, Lalgudi.
Seethlakshmi Ramaswami College, Trichirapalli-2, Tamil Nadu, INDIA
src_padmaram@yahoo.co.in&jasstephen@yahoo.com
ABSTRACT
Polyaniline (PANI) is an organic metal. Its thermo power has been classified as metallic. In
this present investigation acoustic and thermodynamic properties are studied for poly aniline
perchlorate in Formamide from 5°C to 55°C at different molalities using ultrasonic velocity. Various
molecular interactions have been analyzed and these interactions indicate the structural
enhancement of this material in formamide. This results are also confirmed by FTIR and UV
spectra.
Keywords: Thermodynamic properties, ultrasonic velocity, FTIR, UV.
1. Introduction:
Polymers conduct electric current without the addition of inorganic dopants. It has unlimited
worldwide commercial availability. PANI is an organic metal, its specific conductivity are semi-metallic. Its
thermo power has been classified as metallic. Polyaniline salts have been synthesized by chemical
oxidative polymerization of aniline in the presence of phenoxy acetic acid.[1] PANI is one of the most widely
studied materials.[2] A wide range of technological applications have been associated with polyaniline. In
electrostatic dissipation, anticorrosion coatings in various optoelectronic devices and as an antistatic
material, polyaniline salts are used.[3][4] The present work dealt with the acoustic and spectroscopic study
of polyaniline perchlorate in formamide. Density, viscosity and ultrasonic velocity are determined at various
molality from 5°C to55°C. Using the above values, internal pressure , free volume and acoustic parameters
at different concentrations and at different temperatures are evaluated.
1.1.Experimental technique and computation:
51 | P a g e
Formamide is taken as the solvent for preparing polyaniline perchlorate solution. It is
unusual in its properties. It has high dielectric constant 109 with low molecular weight 45.04. The
experiment has been carried out at various temperatures and at different molalities (0.001m, 0.005m,
0.01m, 0.015m, and 0.02m). Significance of thermodynamics such as internal pressure and free volume in
liquids had been emphasized by Richards, Hildebrand and others. Internal pressure (πi) and the free
volume (Vf) and various acoustic parameters, Rao’s (R) Wada’s (W),van der Waal’s (b) constants and
adiabatic compressibility (βad) are computed using the following formulae
πi = bRT(kη/u) 1/2 *(P2/3 / Meff7/6 ) atms
Vf = (Meff * u/kη) 3/2 cc
R = Meff (u) 1/3/ ρ
W = Meff (βad) -1/7/ ρ
b = (Meff/ρ) ((1-RT)/ Meff u2) (1+( Meff u2/3RT-1))1/2
βad = 1/u2ρ dynes/cm2
The values are given in the Tables 1-6
1.2. Results and discussion:

1.2 (a) Thermodynamic study:
Internal pressure is the single factor which varies due to all the internal interactions. Internal
pressure is the measure of cohesive energy. In the present investigation, the internal pressure increases
with concentration. The variations are shown in Figure-1. This increase in internal pressure suggests that
there is a strong solute and solvent interaction.[5] But, at higher temperatures, when the temperature is
increased there is a tendency for the ions to move away from each other, hence there is a reduction in
internal pressure[6]. This result is also confirmed from the study of free volume. It is shown in Figure-2.
The variations of adiabatic compressibility with respect to concentration and temperature are given
in Figure3.The irregular behaviour of Rao’s constant, Wada’s constant and van der Waal’s constant
supports that there is a strong ion-solvent interaction occurring in the solution.[7] These non-linear
variations emphasize that there is an association between molecules of the solution.(Figures 4-6)
52 | P a g e
1.2 (b) Spectroscopic study:
Infrared spectroscopyy is the subset of spectroscopy that deals with the infrared region of the
electromagnetic spectrum. Solution of Polyaniline perchlorate (PAPC) in formamide is prepared using AR
grade salts and IR spectra have been taken at St.Joseph’s college [ACIC center
center],], Tiruchirapalli, Tamil
Nadu. The molecular structures of formamide and polyaniline are given below (I& II).
I. Structure of Formamide IIII-structure of polyaniline
From the IR spectrum of formamide, (figure-7 and Table-7) a strong N-H

H stretching absorption
occurs at 3416.98cm-1.At 2886.82 cm-1, C=O stretching absorption known as amide I band is observed at
1686.35 cm-1. Well defined peaks are observed at 1390.36, 1308.77 cm-1 this confirms the presence
presenc of C-H
group. The low frequency absorption of amide I band is due to the resonance in the amide functional group.
Also these shifts indicate the presence of hydrogen bonding, between the C=O and N=H groups in
formamide and confirm the cage structure[6] ..In the spectrum there is also an N-H
H out of plane bending
absorption at 601.89 cm-1. When PAPC is added to formamide(figure -8) the N-H
H stretching absorption is
shifted to 3417.45 cm -1. (i.e.) towards higher frequency side by 1 cm-1. C=O stretching is shifted
shi to 1688.34
cm -1. (i.e.) towards higher frequency side by 1.99 cm-1. These slight deviations in the absorption peaks are
due to the tightening of hydrogen bonds in the caged structure. No shift is observed in N-H
N out of plane
bending. The deviations inn the peaks support the tightening of hydrogen bonds in the caged structure of
formamide. This confirms that structure making nature of the solutes in the solvent[7] The same results are
reported from the thermodynamic study[8]. It is already confirmed that,
hat, when PANI is dissolved in polar
non-aqueous
aqueous solvent, It promotes a thermodynamically more stable chain[9]. PAPC exhibits peak at
λmax=349.94 nm and another peak at 677.82 nm. These two peaks in PAPC are the characteristics of the
benzenoid and quinoid moieties. The ratio of the intensities of the quininoid to benzenoid peak is 0.5. This
indicates PAPC has more benzenoid forms than that quinoid forms.(figure -9).
In the present study, the structure making nature of the PAPC is confirmed from the spectroscopic
spectr
and thermodynamic studies. It is found to be in good agreement with the result reported in literature.
2. Figures and Tables:
Figure – 1 Figure - 2
53 | P a g e
Figure – 3 Figure – 4
Figure – 5 Figure – 6
ACIC ACIC
St.Joseph's Colleg e ( Autonomo us ) St.Joseph's College ( Autonomous ) ACIC
Trichy-2 T richy-2 St.Jo seph's Colle ge( Auton omo us)
Trich y-2
Date: 1/8 /2010

FTIR S PECTRUM FT IR SPECT RUM
UV sp ectru m
Date: 08-1-2010 Date: 07-1-2010
Spe ctrum Name: PAPC.SP
Spectrum Name: Sam = Formamide.sp Spectrum Name: SRC-P APC.sp
0.800
100.0 100 .0
0.75
2395.44
90 90 0.70
2366.52
2197 .03 25 4.05 ,0.555 16
2191.63 0.65
80 80
0.60
2 691.97
2774.31
70 70 2 57 .0 5,0 .52 33 2
0.55
1052.87
2771.58
60 0.50
60
1 054.13 0.45
50
50 %T 3 49 .94 ,0 .27 98 5
%T 0.40
A
2889.86
40 0.35
40
0.30
30 67 7.82 ,0.220 60
30
0.25
2886.82
20 0.20
20 1390.26 601.82
1390.36 601.89 1311.27

0.15
10
10 1308.77 1605.34
0.10
3417.45 1688.34
34 16.98 1686.35 0 .0
0.0 0.05
4000.0 3000 2000 1500 1000 40 0.0
4000. 0 3000 2000 1500 1000 400.0 cm-1
cm-1 0.000
SRC-PAPC.pk 250.0 300 400 500 600 700 800 900 1000 1100.0
Sam = Formamide.pk nm
SRC-PAPC.s p 3601 4000.00 400.00 6. 44 100.00 4.00 % T 5 1.00 Instrument Model: Lambda 35
SAM_FO~1.S P 3601 4000.00 400 .00 7.94 100.00 4.00 %T 5 0.50
REF 4000 99.61 2000 98.53 600
REF 4000 99.42 2000 98.83 600 3417. 45 7.73 2889.86 47. 94 2774.31 81. 47 2395.44 97.62 2191.63 93.95
3416.98 7.94 2886.82 33.27 2771.58 71.90 2691.97 82.59 2366.52 94 .37 1688. 34 6.44 1605.34 16. 69 1390.26 23. 96 1311.27 23.36 1052.87 72.97
2197.03 92.51 1686.3 5 8.77 1390.36 22.60 1308.77 18.43 1054.13 61 .42 601.82 23.93
601.89 21.04
IR Spectrum UV Spectrum
Figure – 7 Figure – 8 Figure - 9
Table -1 Internal Pressure (atms)
Molality(m) 5°°C 15°°C 25°°C 35°°C 45°°C 55°°C
54 | P a g e
.001 19178 16357 13412 12678 11396 10450
.005 19453 16542 13664 13178 11862 11056
.01 19933 16848 13945 12931 11951 10823
.015 19987 16953 13312 13282 11434 11502
.02 20458 17084 13592 13387 11913 11238
Table- 2 Free Volume (cc)
0.001 0.32 0.59 1.03 1.67 2.07 2.6
0.005 0.22 0.49 0.87 1.42 1.69 2.53
0.01 0.21 0.48 0.82 1.34 1.56 2
0.015 0.21 0.48 0.8 1.28 1.5 1.87
0.02 0.19 0.46 0.74 1.21 1.39 1.78
Table - 3 Adiabatic Compressibility (10^-13)
.001 361 353 344 360 344 334
.005 377 360 347 378 398 379
.01 354 353 362 344 384 334
.015 367 358 281 361 315 401
.02 377 359 293 370 363 378
Table - 4 Rao’s Constant
.001 2116 2143.5 2166 2165 2213 2243
.005 2132 2136.8 2162 2154 2160 2196
.01 2127 2140.8 2149 2185 2171 2237
.015 2134 2139.4 2240 2169 2247 2156
.02 2104 2136.6 2221 2161 2193 2200
Table - 5 Wada’s Constant
.001 1221 1234.5 1245 1245 1269 1283
.005 1229 1231.1 1244 1240 1243 1260
.01 1226 1233.1 1237 1255 1248 1281
.015 1230 1232.4 1282 1247 1285 1241
.02 1215 1231.1 1273 1243 1259 1262
Table-6 van der Waal’s constant
.001 118.9 119.5 119.9 115.1 118.5 119.8
.005 118.0 118 119.1 112 107.7 110.3
.01 120.7 119.3 116.1 118.9 110.2 119.5
.015 119.5 118.5 136.5 115.3 125.6 105
.02 115.9 118.2 132.5 113.5 114.4 110.8
Table-7 Polyaniline perchlorate (PAPC)
Wave number in cm -1 Possible functional groups
55 | P a g e
3417.45 N-H Stretching
2889.86 Intermolecular hydrogen bond O-H Stretching
2774.31 C-H Stretching
2395.44 N+H2 and N+H Stretching
1688.34 C=O Stretching
1390.26 Inplane O-H bending
1311.27 C=O Symmetric Stretching
1052.87 C-O Stretching
601.82 N-H out of plane bending
3. References:
1) Lynne.A; Samuelson Althea Angnostopoulos; K.Shridhara Alva; Jayant Kumar and Sutant; K.
Tripathy. Macromolecules 1998, 31, 4376-4378.
2) Li-MingHuanga; Cheng-Hou Chena and Ten-Chin Wen Electrochimica Acta; 2006,51,(26)5858-
5863.
3) P.C.Ramamurthy; W.R.Harrell; R.V.Gregory, B.Sadananda and A.M.Rao;Polymer Engineering
Science.,44,28,2004
4) Gilbert R.G, Pure and Applied Chemistry, 2002, 74, 857- 867.
5) Ravichandran.G;Srinivasa Rao.A and Nambinarayanan. T.K;Indian Journal of Pure and Applied
Physics., vol. 32, 1994.
6) Jasmine Vasantha Rani, E.Suhashini Ernest., Padmavathy.R, Radha.N ,An investigation of
solvation number, Electrochemical and Thermodynamical properities of Calcium lactate solution
using ultrasonic velocity –(2005).
7) Analysis of internal pressure, Free volume and also some acoustical parameters of sorbiton
monosterate – J.Acoustic Soc. India vol xxx pp23-25 NSA 2002.
8) Jasmine Vasantha Rani , E.Suhashini Ernest,Study of molecular interactions of calcium
pantothenate in non-aqueous medium through ultrasonic speed measurement and spectroscopic
analysis .(2005).
9) Bidhan C.Roy,Maya Dutta Gupta, Leena Bhoumik, Spectroscopic investigation of water-soluble
polyaniline copolymers – Synthetic Metals 130(2002) 27-32.
56 | P a g e
ULTRASONIC INVESTIGATIONS OF PEG (400) IN TOLUENE-CLAY MIXTURE
T.Mathavan 1, S.Umapathy 2, M.A.Jothi Rajan 3, M. Megala 1

Corresponding author. E-mail address: tjmathavan@yahoo.co.in
ABSTRACT: Low power ultrasonic technique is one of the most powerful and useful non-destructive
testing tools to investigate properties of polymer/clay composite solutions. When the concentration of the
solution is increased, correspondingly its various physical parameters change considerably. Similar
changes in physical parameters are also observed when the temperature of the solution is varied.
Poly(ethylene glycol)-400 (PEG-400) in toluene-bentonite clay mixture solution and its physical parameters
such as adiabatic compressibility, intermolecular free length, acoustic impedance, adiabatic bulk modulus,
relaxation time, Rao’s number, absorption coefficient, surface tension and refractive index are determined.
The acoustical and thermodynamic parameters are computed based on experimentally determined values
of ultrasonic velocity, density and viscosity. Ultrasonic parameters provide information about various intra
and intermolecular interactions in solutions.
1. INTRODUCTION
The main aim of this study is to bring out the structural changes, if any in association with the
formation of mixture of a polymer solute and clay-solvent mixture due to molecular interaction between
them. Ultrasonic studies in polymer solutions have drawn the attention of several investigators in the recent
years [1-5]. The present study is undertaken on the ultrasonic study of PEG (400) in Toluene-Bentonite
(Clay) mixture at several concentrations for four different temperatures (300C, 350C, 400C and 450C).
Toluene is chosen because it is a good solvent. It is important to select favorable reaction media for use of
enzymes in organic synthesis. In recent years, aqueous polymer solutions have found widespread
applications, mostly because of their use in two-phase aqueous systems for separation of biomolecule
mixtures. Specially, solutions of polyethylene glycol (PEG) in water have attracted much attention. These
solutions have been used in bio-chemistry and biochemical engineering to separate and purify biological
products, biomaterials, proteins, enzymes from the complex mixtures in which they are produced. Bentonite
is a lightly absorbent clay-like substance that helps to lift impacted waste matter which has accumulated on
the walls of the gastrointestinal tract. In this report ultrasonic method is used to study the physical
parameters and investigate the associative nature, if any between the solute and solvent-clay mixed
molecules.
57 | P a g e
2. EXPERIMENTAL
Analar grade (AR) sample of PEG (400), toluene supplied by Merck, India and clay (Aldrich) were
used as such in the sample preparation. Water, doubly distilled over alkaline permanganate in all glass
apparatus was used as the solvent for preparing the solution. Single frequency ultrasonic interferometer
(M/S. Mittal Enterprises, Delhi, India, Model F81, 2 MHz) and constant temperature water bath (M/S.
Toshniwal Brothers, India) to an accuracy of ±0.01° K were used for ultrasonic velocity measurements. The
required concentrations of the solution (0.5, 1.0, 1.5, 2.0 ML-1) were prepared and the measurements were
taken for 308 K, 313 K, 318 K and 323 K obtained by weighing the solute by a digital balance (accuracy
±0.001g) and mixing with the already purified water in glass beakers, which were cleaned and dried before
use. Densities of the solutions were measured by specific gravity bottle of capacity 5ml to an accuracy of
±0.1 Kgm-3. Viscosities of the solutions were measured by pyknometer to an accuracy of ±0.05%.
3. ACOUSTICAL PARAMETERS
The ultrasonic velocity (C), viscosity ( and density ( measurements are extensively used to study
the physical and chemical behavior of liquid solutions. In this work the following parameters were
determined:
1. Isentropic compressibility βd = (C2)-1 ----- (1)
2. Intermolecular Free length Lf = k/(  C2) ----- (2)
k is the temperature dependent constant.
3. Specific Acoustic Impedance Z=  C ----- (3)
4. Adiabatic bulk modulus K = 1/ βd ----- (4)
5. Relaxation time  = 4 / 3 C2 ----- (5)
6. Rao’s Number (R) is given by R = C1/3 V ----- (6)
Where V is the molar volume which is equal to molecular weight/density of the
solution.
7. Absorption co-efficient /f2 = 82/3C3 ----- (7)
8. Surface tension  (C3/2) X (6.3×10-4) X  ----- (8)
58 | P a g e
The variation of the measured and derived parameters for various concentration(0.1M, 0.2M,
0.3M, 0.4M, 0.5M, 0.6M, 0.7M, 1M) of polyethylene glycol (400) in toluene-bentonite clay mixture at for
different temperatures (300C, 350C, 400C, 450C) were studied and shown graphically in figures 1-10.
Variation of ultrasonic velocity in any solution generally indicates nature of the interaction existing in
between molecules in them [1]. The ultrasonic velocity increases with increasing concentration. This is due
to formation of more hydrophobic character with increase in concentration as result of solute-solvent-clay
interaction. And also it shows non-linear behavior. It indicates that, there is complex formation between the
unlike molecules [2]. The ultrasonic velocity decreases with increasing temperature. It indicates that weak
polymer solvent interactions between PEG in Toluene-clay mixture. In this, non-linear increase in velocity
may be due to the molecule-clay association. The variation of the acoustic velocity is given by graph in
figure 1.
The isentropic compressibility (βd) values of the solutions of different concentrations were
calculated from the density and the ultrasonic velocity. The βd value decreases with increase of
concentration and increases with increase of temperature. The value of isentropic compressibility
decreases in all system which indicates the presence of molecular interaction in these systems (fig. 2) [3].
In this work, it indicates that there is a complex formation between the solute and solvent-clay mixture. One
of the important properties of a liquid is the free length (Lf) between the surfaces of the neighboring
molecules and is the distance covered by the propagating acoustic waves between two neighboring
molecules. It directly gives information about complex formation between solute and solvent (fig. 3) [4].
The experimental solution shows a decrease in intermolecular free length with increase in concentration
and it increases with temperature; and hence an increase in ultrasonic velocity is observed. The velocity
deviation depends upon the increase or decrease in the freelength in the solution after mixing [5]. It
indicates significant interaction between solute and solvent-clay molecules due to which to structural
arrangement [6] in the neighborhood of constituent ions are considerably affected. The experimental
solution shows an increase in acoustical impedance with increasing concentration and also it shows a
decreasing value of acoustical impedance with increasing temperature (fig. 4). This is in agreement with
requirement both ultrasonic velocity and density increase with increase in concentration and also due to
effective solute solvent-clay interaction [7]. The adiabatic compressibility decreases with increasing
concentration and increases with increase in temperature (fig. 5). This is due to strong molecular interaction
of PEG (400) in toluene-clay mixture.
59 | P a g e
Relaxation time gives the orientation of the molecules in a particular direction. For increase in
concentration, the structure of the solution changes by forming association of molecules and clay layers
(fig. 6). This result in high viscous nature and hence the time taken for the flow of ultrasonic wave in the
viscous medium increases [8, 9]. It may be understood that this relaxation is a structural relaxation. The
value of Rao's constant shows decrease with increase in temperature and also increases with increase in
concentration (fig. 7). This variation confirms the changes in molecular interactions. The classical
absorption factor of experimental polymer-toluene-clay mixture shows increase of concentration and
decreases with increase of temperature and it is characteristic of polymer solvent-clay interaction (fig. 8). It
shows the value of classical absorption factor of the experimental solution, increases while increasing the
concentration and decreases while increasing the temperature. Surface tension value increases with
increase of concentration and decreases with increase of temperature. The variation of surface tension is
shown in figure 9. The value of surface tension is plotted against concentration for four different
temperatures (300C, 350C, 400C, 450C). The value of the refractive index decreases with increase of
concentration and increases with increase of temperature. The variation of refractive index with
concentration has been plotted in fig. 10. From the figure, it is clearly evident that the variation is non-linear.
5. CONCLUSION
Acoustic investigations were carried out for different mole concentrations of polymer/clay
mixture in toluene. When the concentration of the solution is increased, correspondingly its various physical
parameters change considerably. Similar changes in physical parameters are also observed when the
temperature of the solution is varied. Poly(ethylene glycol)-400 (PEG-400) in toluene-bentonite clay mixture
solution and its physical parameters such as adiabatic compressibility, intermolecular free length, acoustic
impedance, adiabatic bulk modulus, relaxation time, Rao’s number, absorption coefficient, surface tension
and refractive index were determined. Ultrasonic parameters provide information about various intra and
intermolecular interactions in solutions.
0
30 C
10.0 0
0
30 C 12.5
35 C
0
1380
0
35 C 40 C
0 12.0 0 9.5 0
40 C 30 C 45 C
1360 0 0
45 C 35 C
11.5 0 9.0
40 C
1340
2
0
βdX10 N m
11.0 45 C
-1
8.5
1320
-10
LfX10 m
10.5
-11
1300 8.0
C (m/s)
10.0
1280 9.5 7.5
1260 9.0 7.0
1240 8.5
6.5
1220 8.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 6.0
0.1 0.2 0.3 0.4 0.5 0.6 0.7
Mole concentration
MOLE CONCENTRAT IO N MOLE CONCENTRATION
Fig 1. acoustic velocity Vs Mole concentration. Fig 2. Isotropic compressibility Vs Mole concentration. Fig 3. Free Length Vs Mole concentration.
60 | P a g e
0
30 C
0
35 C 0
0 30 C
0 0.125 40 C 18 0
30 C 0 35 C
0.90 0
35 C 45 C 0
0
0.120 16
40 C
0.88 40 C 0
45 C
τX10 sec
0
0.86 45 C 0.115
-12
14
ZX10 Kg/m s
0.84
2
KX1010Nm-2
0.82
0.110
12
6
0.80
0.105
10
0.78
0.76 0.100
8
0.74
0.095
0.72 6
0.70 0.090
0.68
4
0.66
0.085
2
0.0 0.2 0.4 0.6 0.8 1.0
0.080
MOLE CONCENTRATION 0.0 0.2 0.4 0.6 0.8 1.0
0.0 0.2 0.4 0.6 0.8 1.0
MOLE CONCENTRATION MOLE CONCENTRATION
Fig 4. Acoustic impedance Vs Mole concentration. Fig 5. Adiabatic bulk modulus Vs Mole concentration. Fig 6. Relaxation time Vs Mole concentration.
0
30 C
7.4 0
35 C 0
0 30 C
40 C 0
30 C 10.0 0
7.2 0 35 C
45 C 0
35 C 0
25 40 C
0
40 C 9.5 0
7.0 45 C
0
45 C
9.0
6.8 20
8.5
6.6
3
RX10
15
α/f X10 m/s
-1
8.0
γX10 Nm
-14
6.4
4
7.5
10
2
6.2
7.0
6.0 5 6.5
5.8 6.0
0 0.0 0.2 0.4 0.6 0.8 1.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
MOLE CONCENTRATION MOLE CONCENTRATION MOLE CONCENTRATION
Fig 7. Rao’s Number Vs Mole concentration. Fig 8. Classical Absorption Factor Vs Mole concentration. Fig 9.Surface tension Vs Mole concentration.
1.500 0
30 C
0
35 C
1.495 0
40 C
0
1.490 45 C
1.485
1.480
1.475
n
1.470
1.465
1.460
1.455
0.0 0.2 0.4 0.6 0.8 1.0
Mole concentration
Figure 10. Refractive index Vs mole concentration.
61 | P a g e
6. REFERENCES
1. Vijayalakshmi T.S & Naidu P.R, Indian J Pure and Appl. Phys., 28, 215, (1990).
2. Nomoto O, J. Phys. Soc., Japan, 8, 553, (1953).
3. Velmurugan S, Nambinarayanan T.K, Srinivasa Rao A and Krishnan B, Indian J. Phys., 61B,
105, (1987).
4. Kalyana Sundram S, Manuel Stephen A and Gopalan.A, J Polym. Materials, 12, 177,
(1995).
5. Sosamma S, Nambinarayanan T.K and Srinivasa Rao A, Indian J. Phys., 62B, 31, (1988).
6. Singh R.P, and Srivastava T.N, Proc. Net. Acad sci. India, 57(A), 285-291, (1987).
7. Sheo Prakash S, Srinivastar B and Prakash O.M, Indian J. Pure and Appl. Phys., 13, 191,
(1975).
8. Narashimham A.V, Indian J. Phys, Vol 65 B, No.4, 312-318, August (1991).
9. Narashimham A.V and Seshadri A.T, Indian J. Phys., Vol.65 B, No.3, 44-48, (1992).
62 | P a g e
ACOUSTICAL STUDY ON THERMO DYNAMICAL AND EXCESS PARAMETERS OF
BINARY AND TERNARY MIXTURES
M.M. Armstrong Arasu and Dr. I. Johnson
Centre for Nano Science and Applied Thermodynamics, Dept. of Physics,

St. Joseph’s College, Trichy – 620 002, India.
ABSTRACT: Industry demands reliable and accessible reference data on the physical and chemical
properties of a wide variety of compounds. These data are required in the development of process design
and efficiency and in the evaluation of possible environmental impacts.
1. INTRODUCTION
In this paper density, viscosity and speed of sound is measured for binary mixture of Propanol +
Ethyl acetate for temperatures 308.15K. The density, viscosity and speed of sound for ternary mixture of
Propanol + Ethyl acetate + water were measured at 303.15K. The excess volume, Wada constant,
ultrasonic relaxation time, deviations enthalpy, ultrasonic velocity, adiabatic compressibility viscosity, free
length, internal pressure, acoustic impedance, free volume& Gibb’s free energy were calculated for binary
mixture at the constant temperature of 308.15K, for ternary mixture at the constant temperature of 303.15K.
2. EXPERIMENTAL
The binary and ternary mixtures were prepared by mass, by mixing the calculated volumes of
liquid components in airtight glass bottles. In all the measurements, INSREF thermostat with a constant
digital temperature display accurate to ±0.01K was used. For all the mixtures and pure solvent, triplicate
measurements were performed and the averages of all values were considered in the calculation. The mass
measurements (±0.0001g) were made using an electronic balance. The accuracy of density measurements
was 0.0001g.cm-3. A set of 18 and 11 compositions were prepared for ternary and binary mixtures
respectively and also their physical properties were measured. Viscosity is measured by calibrated
Ostwald’s Viscometer. The speed of sound was determined using a constant frequency (2MHz) ultrasonic
interferometer with an accuracy of ± 2 m.s-1.
3. THEORY
The excess molar volume VE was calculated from the density data by the relationship
VE = VM –Σ xiVi , (1)
i
where Vi represents the molar volume, xi the mole fraction of the ith component and VM is the molar
volume of the mixture, given as
VM = (x1M1+x2M2) /ρm , (2)
where ρm is the density of the liquid mixture.
The adiabatic compressibility βa was obtained from sound velocity and density measurements as
βa= 1/(u2ρ) (3)
The excess adiabatic compressibility was calculated as
 βa = βam –Σφi βai ,
i (4)
where the φi is the volume fraction of the ith liquid,
63 | P a g e
φi = xiVi/ΣxiVi , (5)
i
The excess viscosity is obtained as

 η = ηm – Σxiηi , (6)
i
where ηm and ηi refer to the viscosity of the mixture and pure components respectively .
The Wada’s constant was calculated using the formula
W = (Meffβa -1/7)/ρ (7)
The inter molecular free length was calculated using the formula given by Jacobson et al.
Lf = KJ √ βa , (8)
where KJ is Jacobson’s constant.
KJ is the temperature dependent parameter which varies directly with the square root of the absolute
temperature i.e.,
K J α √T (9)
The excess free length is given as
 Lf = Lf mix – (ΣxiLfi) (10)
i
where xi and Lfi, are the mole fractions and inter-molecular free lengths of the respective components.
Lfmix is the free length of the ternary mixture.
The acoustic impedance is given as
Z = ρu, (11)
where u is the ultrasonic velocity and ρ the density.
The excess acoustic impedance is given as
 Z = Zmix - Σxizi (12)
i
The free volume of a liquid and liquid mixture can be calculated using the formula
Vf = [Mu/Kaη]3/2 , (13)
Where M is the molar mass of the liquids, u is the ultrasonic velocity, Ka is the constant having value of
4.28x109, independent of the temperature and nature of the liquids and η is the viscosity.
On the basis of the dimensional analysis using the free volume concept, Suryanarayana suggested
the expression for the internal pressure as
Pi = bRgT [Kaη/u] 1/2ρ2/3/Meff7/6, (14)
where b is the space packing factor (equal to 2 in the present case) ,Rg ,is the gas constant and T is the
temperature in degree Kelvin .
Equations (13) and (14) are used for mixtures for which parameters such as M, u, ρ and η
corresponds to those mixtures.
The excess free volume of the mixture is given as
3
 Vf = Vfmix - Σ xiVfi (15)
i=1
The excess internal pressure of the mixture is obtained using the relation
3
 Pi = (Pi)mix –Σ xiPi (16)
i=1
The dispersion of the ultrasonic velocity in this system should contain information about the
characteristic time τ of the relaxation process that causes the dispersion. The relaxation time τ is estimated
from the following relation
64 | P a g e
τ = 4η/3ρu2 (17)
From the Eyring’s rate process theory, the Gibb’s free energy of activation for the relaxation process ∆G
was obtained as
1/τ = KT/h) exp (-∆G/kT), (18)
where k is the Boltzmann’s constant and h is the Planck’s constant.
The excess enthalpy of a binary mixture is obtained from the fundamental relation
3
H= Σ (xiPij Vj - (Pi)mixVm. (19)
i=1
The classical absorption or relaxation amplitude is given by

(α/f2)cl= (8∏2η/3ρu2 ) (20)

In reference with table 1and 2 gives experimental results density, viscosity and speed of sound
for 35 C for the system of binary mixtures of Ethyl acetate + Propanol and the excess volume, Wada
0
constant, ultrasonic relaxation time, deviations in enthalpy, ultrasonic velocity, adiabatic compressibility,
viscosity, free length, internal pressure, acoustic impedance, free volume & Gibb’s free energy are
calculated at the constant temperature of 308 K.
For the system of binary mixtures Ethyl acetate + Propanol the excess adiabatic compressibility and
excess volumes values are also positive which indicates that influence of -OH bonding interaction or
chemical forces. V , βa are negative indicate interstitial accommodation of one liquid molecule into
E E
another. LEf are positive which shows that there is increase in free length and compressibility. The excess
internal pressure is negative which shows the presence of cluster formation. The free volume plays an
important role in ultrasonic wave propagation in liquids. It has been found that the free volume of liquid
molecules depends on the particular temperature of the liquid at which it is measured. The trend of
variation of Vf is opposite to the change in the Pi. The Vf values are positive while VEf are negative. The
mathematical relations for specific acoustic impedance, Z = uρ adiabatic compressibility, βa = 1/ (u2ρ)
shows that the behaviour is opposite. Specific acoustic impedance is the complex ratio of the effective
sound pressure at a point to the effect particle velocity at that point. The relaxation amplitude and Gibbs
free energy also positive in most of the mixture. When the mole fraction of any one of the three liquids kept
constant and the mole fraction of the other three liquids have been varied Wada’s constant variation is
linear.
For the system of ternary mixtures (Ethyl acetate+ Propanol + Water) at 303.15.K (Table 3&4), the ηE
values are positive in most of the combinations of the ternary system studied. According to Fort and Moore
ηE values are negative in system of unequal molecular size which is very much evident. ηE are negative
and positive, the negative value suggest that the force between pairs of unlike molecules are less than the
forces between the forces of like molecules while positive value suggest that the force between pairs of
unlike molecules are greater than the forces between pairs of like molecules . LEf are negative and positive.
The negative values suggest that there is a decrease in free length and compressibility. The positive values
suggest that there is a increase in free length and compressibility .The excess internal pressure is negative
which shows that the presence of cluster formation. The free volume plays a important role in ultrasonic
wave propagation in liquids found that the free volume of liquid molecules depends on the particular
temperature of the liquid at which is measured. The relaxation amplitude and Gibbs free energy also
negative in most of the mixture. When the mole fraction of any one of the three liquids kept constant and
the mole fraction of the other three liquids have been varied Wada’s constant variation is nonlinear.
Excess volumes are positive which proves the influence of – OH bond interactions over
dispersion type interactions. The excess adiabatic compressibility values are also positive which confirms
65 | P a g e
the above fact.. The VE and βaE are negative indicate interstitial accommodation of one liquid molecule into
another. The free volume plays an important role in ultrasonic wave propagation in liquids found that the
free volume of liquid molecules depends on the particular temperature of the liquid at which is measured. βa
= 1/ (u2ρ) shows that the behavior is positive .Specific acoustic impedance is the complex ratio of the
effective sound pressure at a point to the effect particle velocity at that point. The relaxation amplitude and
excess Gibbs free energy also positive in most of the mixture. When the mole fraction of any one of the
three liquids kept constant and the mole fraction of the other two liquids have been varied.
Table -1 Ethyl Acetate +Propanol
S. X(i) ρ x10-3 η U W τD x102 ∆G Z x105 Z x105 P i x106

Pi x106
NO kgm-3 N.sm-2 ms-1 pa KJ/mole Kgm-2s-1 Kgm-2s-1 Pa
pa
1 1.0000 0.8244 0.00048 1085 2855 0.0007 - 7.2012 8.9447 0.000 0.1055 0.0000
2 0.9002 0.8209 0.00049 1090 2778 0.0007 -7.1946 8.9478 5.3501 0.1101 -0.0051
3 0.7999 0.8085 0.00054 1096 2726 0.0007 -7.1514 8.8612 1.7534 0.1186 -0.0063
4 0.7001 0.8005 0.00056 1100 2659 0.0008 -7.1348 8.8055 1.2305 0.1247 -0.0099
5 0.6002 0.7991 0.00058 1107 2574 0.0008 -7.1246 8.8460 10.332 0.1317 -0.0126
6 0.5001 0.7866 0.00061 1112 2517 0.0008 -7.1002 8.7470 5.4862 0.1393 -0.0147
7 0.4004 0.7747 0.00063 1118 2458 0.0009 7.0846 8.6611 1.9396 0.1462 -0.0176
8 0.3002 0.7703 0.00067 1123 2376 0.0009 -7.0598 8.6505 5.9352 0.1570 -0.0165
9 0.1980 0.7549 0.00070 1129 2320 0.0010 -7.0371 8.5228 1.665 0.1660 -0.0174
10 0.1003 0.7493 0.00081 1134 2240 0.0011 -6.9756 8.4971 0.6958 0.1863 -0.0066
11 0.0000 0.7403 0.00088 1140 2166 0.0012 -6.9397 8.4394 0.0000 0.2026 0.0000
Table -2 Ethyl Acetate + Propanol
66 | P a g e
S.
X(i) VE βa U H G α/f2 Vf Vf Lf x106 Lf
x106 x10-10 ms-1 KJmol-1 Kg mol-1 x10 -15 x 106 x 10 m3/mol x 106
NO
cm3/mol m2n-1 M-1s-2 m3/mol m3/mol m3/mol
1 1.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.1055 0.0000 64.6100 0.0000
2 0.9002 -0.3853 -0.0578 -0.4890 0.0031 -0.9407 -0.4890 0.1101 -0.0051 64.4506 -0.1875
3 0.7999 0.3108 -0.0216 -0.0055 0.0024 0.0567 -0.0055 0.1186 -0.0063 64.5874 -0.0790
4 0.7001 0.4028 -0.0019 -1.4945 0.0046 -0.5124 -1.4945 0.1247 -0.0099 64.6733 -0.0212
5 0.6002 -0.357 -0.1224 0.0110 0.0062 -1.1328 0.0110 0.1317 -0.0126 64.3206 -0.4020
6 0.5001 0.1794 -0.0618 -0.4945 0.0076 -1.3814 -0.4945 0.1393 -0.0147 64.5382 -0.2127
7 0.4004 0.5836 -0.0247 0.0221 0.0101 -2.1084 0.0221 0.1462 -0.0176 64.6829 -0.0960
8 0.3002 0.0405 -0.0676 -0.4890 0.0094 -2.1129 -0.4890 0.1570 -0.0165 64.5786 -0.2286
9 0.1980 0.6888 0.0207 -0.1100 0.0111 -2.6259 -0.1100 0.1660 -0.0174 64.8873 0.0513
10 0.1003 0.1970 -0.0044 -0.4835 0.0033 -0.4720 -0.4835 0.1863 -0.0066 64.8422 - 0.021
11 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.2026 0.0000 64.8918 0.0000
Table: 3. Ethyl Acetate + Propanol + Water at 303.15 K
βa η Lf Pi Z

S. V x106 H G U x 106 x105
X (i) Y (i) x10-10 Kg x10-3 x103
No m3 Kg mol-1 ms-1 Pa Kgm-2s-1
m 2n- mol-1 m2s-2 A0
1 0.7214 0.1005 -0.849 -7.751 -0.0094 5.0567 0.0000 -19.367 -1.206 -0.1029 -45.0507
2 0.6277 0.1013 -0.843 -7.129 -0.0115 7.4368 0.0000 -28.411 -0.451 -0.1526 -23.8818
3 0.5056 0.0978 -0.056 -3.654 -0.0058 7.9435 0.0000 -65.872 3.0749 -0.2233 -67.1043
4 0.4206 0.0977 0.1923 1.0247 -0.0026 10.540 0.0001 -46.903 4.4056 -0.2642 -130.728
5 0.3195 0.0988 -1.272 0.3595 -0.0048 13.331 0.0001 46.183 -0.188 -0.2905 -54.6449
6 0.2129 0.0963 -0.208 0.9844 -0.0418 22.368 0.0005 -23.433 3.6783 -0.2142 -137.012
7 0.1005 0.0982 -1.954 1.7183 -0.0011 12.979 0.0002 164.332 -3.398 -0.2749 -7.1016
8 0.0992 0.2048 -1.669 0.8048 -0.0154 15.910 0.0003 115.777 -2.201 -0.2456 -26.0531
9 0.1010 0.3084 -1.409 0.8051 -0.0081 13.140 0.0002 92.543 -1.431 -0.2505 -41.4531
10 0.1001 0.4105 -0.375 0.9399 -0.0115 11.996 0.0002 12.969 1.8625 -0.2161 -96.7512
11 0.0988 0.5128 -0.645 1.0809 -0.0037 9.1613 0.0001 38.350 0.4016 -0.1926 -63.2401
12 0.0971 0.6374 -0.359 0.9648 -0.0025 6.6955 0.0001 20.018 0.6575 -0.1391 -52.2058
13 0.0962 0.7296 -0.110 0.8286 -0.0083 6.6639 0.0001 4.2955 0.9078 -0.0855 -42.9605
14 0.0994 0.8116 0.1595 0.9700 -0.0027 3.1532 0.0001 -10.096 1.2242 -0.0484 -35.9857
15 0.1890 0.7254 0.8763 1.0948 0.0021 0.901 -0.0001 -55.817 3.5664 -0.0552 -68.4114
16 0.3051 0.6114 1.1157 1.8614 0.0068 -0.436 -0.0001 -65.827 4.3443 -0.0619 -81.2803
17 0.3998 0.5166 0.5194 1.7196 0.0087 -0.407 -0.0001 -34.074 2.4920 -0.0653 -54.2248
18 0.5156 0.3973 0.4136 1.2972 0.0110 -1.320 -0.0001 -31.199 2.1951 -0.0706 -47.9292
67 | P a g e
Table: 4. Ethyl Acetate + Propanol + Water at 303.15 K
S. U τD Lf
ρ x10-3 η βa x10-10 G Z x105 Pi x 106
N X (i) Y (i) ms-1 W x102 x103
kgm-3 N.sm-2 m 2n Kg mol- Kgm-2s-1 Pa
o ps A0
1 0.7214 0.1005 0.9063 0.00067 1129 0.0483 2200 0.0008 -7.0109 10.2321 0.1599 58.7083
2 0.6277 0.1013 0.9113 0.00071 1131 0.0342 1994 0.0008 -6.9904 10.3068 0.1842 58.4435
3 0.5056 0.0978 0.8831 0.00070 1108 0.0082 1769 0.0009 -6.9660 9.7847 0.2133 60.6017
4 0.4206 0.0977 0.8277 0.00077 1137 -0.0098 1689 0.0010 -6.9206 9.4109 0.2403 61.0004
5 0.3195 0.0988 0.8438 0.00087 1242 -0.0314 1471 0.0009 -6.9515 10.4800 0.2937 55.3080
6 0.2129 0.0963 0.8433 0.00130 1185 -0.0580 1205 0.0015 -6.7438 9.9931 0.4567 57.9856
7 0.1005 0.0982 0.8393 0.00099 1386 -0.0641 999 0.0008 -6.9870 11.6327 0.4842 49.6944
8 0.0992 0.2048 0.8311 0.00110 1336 0.0265 1147 0.0010 -6.9080 11.1035 0.4385 51.8079
9 0.1010 0.3084 0.8093 0.00100 1311 0.0713 1323 0.0010 -6.9210 10.6099 0.3582 53.5022
10 0.1001 0.4105 0.7911 0.00099 1230 0.0935 1472 0.0011 -6.8623 9.7305 0.3205 57.6778
11 0.0988 0.5128 0.7767 0.00093 1254 0.1042 1653 0.0010 -6.8970 9.7398 0.2720 57.0959
12 0.0971 0.6374 0.7661 0.00091 1234 0.1089 1849 0.0010 -6.8868 9.4537 0.2379 58.4213
13 0.0962 0.7296 0.7602 0.00097 1217 0.1094 1991 0.0011 -6.8453 9.2516 0.2264 59.4668
14 0.0994 0.8116 0.7533 0.00090 1201 0.1122 2131 0.0011 -6.8617 9.0471 0.2025 60.5344
15 0.1890 0.7254 0.7613 0.00079 1146 0.1784 2177 0.0011 -6.8815 8.7245 0.1858 63.1054
16 0.3051 0.6114 0.7656 0.00071 1124 0.2238 2271 0.0010 -6.9123 8.6053 0.1679 64.1597
17 0 3998 0.5166 0.7757 0.00068 1146 0.2325 2350 0.0009 -6.9521 8.8895 0.1567 62.5170
18 0.5156 0.3973 0.7898 0.00062 1137 0.2134 2414 0.0008 -6.9917 8.9800 0.1443 62.4468
68 | P a g e
5. REFERENCES
Periodicals
[1] I. Johnson, M.Kalidoss and R.Srinivasamoorthy, 2001, Acoustical investigation of some
binary and ternary liquid mixtures – Proceedings of the 17th international congress on
Acoustics (ROME), ,Vol.I,Physical Acoustics – Part B,(12).
[2] Pandey,J.D. and Ashok kumar, 1994,Ultrasonic velocity in pure liquids, J. Pure and
Applied Ultrasonic, 16(63).
[3] J.P.E.Grolier, and A.Viallard, 1971, J.chem.phy. 68(1442)
[4] J.ortaga, J.A.Pena, M.I. Paz-Andrade, and E. Jimnez, 1985 J. Chem.
Thermodyn.17(1127).
[5] V.D.Gokhale and N.N.Bhagavat, 1989, Evaluation of Ultrasonic Velocities in some Binary
Liquid Mixtures by Rao Specific Sound Velocity. J.Pure and Appl.Ultrasonic., 11(21).
[6] C.V Sorianarayan , 1976 ,J Acoustics Soc. Of India ,4 ( 76).
[7]Senanayake,P.C., Gee,N. and Freeman,R.G.1987Can. J.Chem.Eng.Data,65(2441).
[8] Kalidoss.M and Srinivasamoorthy .R, 1997 J.Pure and Appl.Ultrasonic 19,(9).
[9] Viswanatan ,S, and Anand rao,M, 1999.J.Chem. Eng.Data 45,(764).
[10] Ambinabhavi ,M and Virupakashagouda , 1998,J.Chem.Eng.Data 43,(497)
Books
[1]Riddick,J.A., Bunger,W.B., Sanako,T.K., 1986, Physical properties and methods of

purification , John Willy & Sons ,New York,
[2] Hirschfelder, J.O, Curtio, and Byron bird .R., 1950,Molecular theory of gases and
liquids.John Willy & Sons, New Yark.
Others
[1] R.N.Fort and W.R.Moore – 1965Trans.Faraday Society 61,(2102)

[2] Handbook of Chemistry and Physics, 1984, The Chemical Rubber
Company, USA,
[3] Zorebski,E Zak, A Z.1999 Physikalis che Cheie. 210,(223).
[4] Chauhan , M.S. Sharma, K.C et al .1995 Acoustics letters 18,12,(223)
[5] Mukhrejee,A.Kamila ,S et al ,1999, Acoustics letters 23,1,(17)
[6] Belsae, N.s. Akhare, V.P and Deogaonkar, V.S, 1990, Acoustic letters 14,2,(37)
69 | P a g e
STUDY ON THERMO-ACOUSTICAL PARAMETERS OF SOME BINARY MIXTURES
FROM VOLUME EXPANSIVITY DATA
M.M. Armstrong Arasu and Dr. I. Johnson
Centre for Nano Science and Applied Thermodynamics, Dept. of Physics,

St. Joseph’s College, Trichy – 620 002, India.
ABSTRACT: Researches have previously shown that the contribution of internal pressure and the
temperature coefficient of volume to the sound velocity in the condensed phase is significant and that
volume expansivity is the controlling factor for satisfactory description of the various parameter which
describe the thermo-acoustic properties of polycrystalline solid, metal, alkali halide salt, polyatomic ionic
liquid and organic liquid mixtures. Such a description employs only volume expansivity data. From the
volume expansivity data the isothermal, isobaric and isochoric acoustical parameters, Moelwyn-Hughes
parameter, fractional free volume, Huggin’s parameter, sharma’s parameters and repulsive exponent in
Mie’s potential have been evaluated.
Keywords: volume expansivity , Gruneisen parameter, Moelwyn-Hughes parameter, fractional free
volume, Huggin’s parameter and Sharma’s parameters.
1. INTRODUCTION
The volume expansivity data is highly useful for evaluating Gruneisen parameter which is a
useful quantity in studying the internal structure, molecular order and thermo acoustical properties of liquids
and polymers. The important of volume expansivity in evaluating various thermo acoustical properties has
been amply demonstrated earlier. In this paper an attempt is made to analyze the relationship between
different parameters that are used for system description like Moelwyn-Hughes parameter, fractional free
volume, Huggin’s parameter, Sharma’s parameters and repulsive exponent in Mie’s potential have been
evaluated in the mixtures Ethyl acetate + n-propanol and Methyl acetate + n-propanol at 308.15K. It is
interesting to note that all these thermo acoustical properties are linked to a single experimentally
determinable quantity, volume expansivity.
2. EXPERIMENTAL
The binary mixtures were prepared by mass, by mixing the calculated volumes of liquid
components in airtight glass bottles. In all the measurements, INSREF thermostat with a constant digital
temperature display accurate to ±0.01K was used. For all the mixtures and pure solvent, triplicate
measurements were performed and the average of all values was considered in the calculation. The mass
measurements (±0.0001g) were made using an electronic balance. The accuracy of density measurements
was 0.0001g.cm-3. A set of 11 compositions was prepared for binary mixtures and their physical properties
were measured. Viscosity is measured by calibrated Ostwald’s Viscometer. The speed of sound was
determined using a constant frequency (2MHz) ultrasonic interferometer with an accuracy of ± 2 m.s-1.
3. THEORY
The volume expansivity is given by
1 dV 1  dρ 
α= =   (1)
V dT ρ  dT 
70 | P a g e
Let V,  and  respectively molar volume, Volume expansivity and isothermal compressibility. If * and V* are the
characteristic compressibility and volume (at absolute zero temperature and zero pressure), the their reduced values
are given by,
~ β ~
β = = V C1 (2)
β*
3
~ V  αT 
V = 1+
V *  3(1 + αT ) 
(3)
The Moelwyn-Hughes parameter is

dlnβ 13 4
C 1
=
dlnV
=
3
+ αT( )
−1
+ αT
3
(4)
The Sharma’s parameters are expressed as,

 1 + 2αT 
S0 =  ~ (3 + 4αT ) (5)
 
 V C1 
4
S * = 1 + αT (6)
3
S 0* =
(1 + 2αT ) (7)
 4 
1 + α T 
 3 
Huggin’s parameter F is given in terms of Sharma’s parameters given above as,
F = 2− S *+
(
S 0 S1* - 1) (8)
αT
Eqns. (1)-(8) demonstrate the importance of  in the evaluation of the parameters V, C1, S, S0, S0* and F, since all
the parameters involved therein may be determined from the knowledge of  alone. The volume dependence of
sound speed in liquids at constant pressure and at constant temperature is represented by isobaric and isothermal
acoustical parameters k and k’ respectively, due to Rao, Carnevale and Litovitz. While examining the relationship
between sound velocity u and density  in liquids and determining the difference between k and k’ in liquids, Aziz,
and Sharma have shown that the isochoric acoustical parameter k’’ is given by.
k’ = k = k’’ (9)
In which
 ∂lnu  1  ∂lnu 
k = -  = -   (10)
 ∂ ln V  P α  ∂T  P
 ∂lnu  1  ∂lnu 
k' = -  = -   (11)
 ∂V  T β  ∂P  T
1  ∂ ln u  1  ∂lnu 
k" = k' = k =   −   (12)
α  ∂T  P β  ∂P  T
Alternatively, the isobaric and isochoric acoustical parameters may be expressed in terms of α as
5 1 2αT
k= + + (13)
3 2αT 3
71 | P a g e
− C1
(2αT ) −1
−V +1
k" = - (14)
− C1
V
Using these calculated values of k and k’’, the isothermal acoustical parameter k’ can then be calculated
for the binary liquid mixtures, using eqn(9).
The sound speed can be expressed as u2 =  s, where  = Cp/Cv, Cp and Cv are respectively the isobaric and
isochoric heat capacity of the liquid.
The fractional free volume f which is a measure of disorder due to the increased mobility of molecules in a liquid and
can be expressed as,
f = Va/V = (k’+1)-1 (15)
The repulsive exponent n in the Mie’s potential is given by,
n = 3 (2k’ -3) (16)
The equation (13) can be rearranged to give the dimensionless thermo acoustic parameters A* and B* as,
f
A* = 1+ (17)
k'
f
B* = 1+ (18)
k
The pseudo-Gruneisen parameter used for structural study of liquids is usually expressed as
αV Mu 2α (γ − 1)
Γ= = = (19)
β s Cv Cp αT
The Gruneisen parameter is an important quantity of current interest because of its usefulness in
studying the internal structure, molecular order and other thermo acoustic properties of polymers and liquids. We
have a distinct relationship between the microscopic isothermal Gruneisen parameter ’ (as a measure of
anharmonicity of the normal mode frequency v of the molecular vibrations), and the conventional thermodynamic
Gruneisen parameter ’ (used for the structural study of liquids). There are two distinct modes are of low frequency
and are anharmonic. They are characterized by high values of ’. The low frequencies of these modes are
determined almost entirely by the weak intermolecular forces. The intra molecular optical modes of vibration are of
high frequency and are harmonic. They are characterized by low values of , and arise from the strong intra molecular
forces which are altered little by pulling the molecules apart. The anharmonic (microscopic isothermal) Gruneisen
parameter ’ is determined primarily by the intermolecular vibration, while  is an average over all modes of vibration,
including intermolecular and intra molecular vibrations which employ capacities of the liquid. As relatively little is
known about the influence of the intermolecular vibration, while r is an average over all modes of vibration, including
intermolecular and intra molecular vibrations which employ thermodynamic parameters such as the isochoric Cv and
isobaric Cp heat the intermolecular vibrations on the heat capacity Cp in quasi spherical molecular liquids and
fluorocarbon fluids, the analysis of the theoretical foundations of the relationship between ’ and t is essential for this
class of liquids. The ratio of the Gruneisen parameters (/’) is utilized to measure the intermolecular isobaric heat
capacity and the adiabatic bulk modulus due to the molecular vibrations in these liquids.
Much confusion has existed in literature to recognize the difference between ’ and for liquids. It may
be clearly pointed out that the concept of ’ and  is appropriate to all the solids, molten metals, liquids, liquefied
gases and polymers which show anharmonicity of molecular vibrations. However, K.M. Swamy overlooked the basic
conceptual aspect that  and ’ may not have the same values for different substances. It was shown that ’ and  in
case of organic liquids differ from one another. For organic molecules, experimentally it is observed that ’> which
implies that a certain fraction of the molecules in a molecular liquid has a finite and common fractional frequency
dependence on the volume at a constant temperature and the remaining modes are unaffected by volume changes.
Following Hart-mann, this fact can be explained by noting that not all the normal mode contributions to heat capacity
Cp also contribute to the volume change of the sound speed (molecular rotation, for example). The analogous
situation in the case of polymeric materials has already been noted. In order for  to be as large as ’, only a fraction
Cp’ of the total cp that is taken up by the molecular vibrations which interact with volume, should be used in eqn.(15).
72 | P a g e
Thus
’u α/Cp’ (20)
From eqns (19) and (20) it follows that
X-1 = /’ = Cp’/Cp (21)
Eqn(21) shows that the quantity X = /’ is of some interest since it gives a simple method to measure the ration
C’p / Cp for a complex liquid and hence Cp which refers to that part of the isobaric heat capacity taken up by
molecular vibrations which interact with volume.
The Andeson-Gruneisen parameters has been expressed as
1  ∂inβ s 
∆=   = 2k + 1 (22)
α  ∂T  P
Beyer’s nonlinearity parameter B/A of liquids can be obtained from the distortion of the finite
amplitude waves, and from the variation with pressure and temperature of the sound velocity. The B/A is a particular
combination of the temperature and pressure derivation of the sound of speed is a given by
B  ∂u   2uαT  ∂u 
= 2 ρ u  +    (23)
A  ∂T  T  C P  ∂T  P
which can be rewritten as
B/A = (B/A)’ + (B/A)” (24)
Where (B/A)’ =  (C1-1) (25)
(B/A)” = - ( -1) (-1) (26)
Eqns (23) - (26) lead to a way to determine the Beyer’s nonlinear parameter theoretically.

In the table 1to 4 give the calculated values of , s, C,~ ,S, So, S*, F, k, k”, f, N, A*, B* and k/ k’, for
binary liquid mixture of Propanol + Ethyl acetate and Methyl Acetate + n-proponol using only the
experimental data of density at three different temperatures. It may be absorbed from table 1 and 2 that C
values vary from 6.8 to 9.8 for the liquid mixture studied in agreement with the value of C, in other non-
associated of the liquids. This signifies the non –linear variation of volume expansivity of the liquids with
mole fraction.
The value of reduced compressibility s ranges from 5.2 to 13.1 as compared to the range from
about 5 to 14 for the molen alkali halides and 4 to 6 for polymers. The value of So remains fairly constant
within the experimental error. The estimated values of So are on the average, lie the range 1.2 to 1.49. The
Sharma’s parameter So may be termed a molecular constant which varies its constancy for a wide verity of
binary mixtures for investigating thermo acoustic and an harmonic properties.
The calculated values of S* are around 1.1 to 1.2 for the binary mixture as compared to 1.5 for
polymers .It may be interesting to note that So* is equal to 1.1 to 1.2 similar to that of poly crystalline
solids. The Value of the Huggin’s parameter ranges from about 0.4 to 1.3 which is of the same order as
observed for polymers, crystalline and molten alkali halides, liquid alkali metals and ionic liquids.
The Calculated acoustical parameter k range from 0.2 to 4.4 in the mixtures, the value of the
ratio k/k’ is close to about unity, for liquid. The value of n is found to 13.3 to 18.8 with different mole fraction,
which is the same order as reported by Sockiewies.
The average values of the dimensionless parameters A* and B* for the liquid mixtures examined
have the value 1.03 to 1.07 respectively in the case of fluorocarbon fluids. This means that on the average
the approximate relationship A* = B* = 1.05 for holds for these liquids mixtures as compared to A* =B*
=1.05 for fluorocarbon fluids.
73 | P a g e
Table -1 Nonlinear parameter of Ethyl Acetate + proponol (Temp=30,35and 40 0 C)
Note: x(i) is Mole fraction of Ethyl Acetate
X(i)1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0
1 1.3616 1.3328 1.2335 1.3286 1.2373 1.2145 1.1930 1.2189 1.1219 1.0978 1.0349
VX(i)~ 1.0
1.3256 0.9
1.3203 0.8
1.3014 0.7
1.3195 0.6
1.3022 0.5
1.2978 0.4
1.2936 0.3
1.2986 0.2
1.2795 0.11.2746 0.0 1.2618
 
 1C 7.2760
2.2874 7.3156
2.1791 7.4708
2.0784 7.3216
1.9747 7.4644
1.8565 7.5042
1.7460 7.5435
1.6201 7.4964
1.4903 7.6867
1.3683 7.7404
1.2414 7.8940
1.0991
V~ ~ 7.7766
1.4734 7.6355
1.4579 7.1609
1.4434 7.6149
1.4280 7.1785
1.4098 7.0724
1.3921 6.9730
1.3713 7.0926
1.3488 6.6506
1.3268 6.5438
1.3030 6.2702
1.2749
SC 1.1064
6.6918 1.1075
6.7178 1.1111
6.7486 1.1077
6.7880 1.1110
6.8441 1.1118
6.9093 1.1125
7.0020 1.1116
7.1230 1.1146
7.2671 1.1153
7.4573 1.1168
7.7373
So 1.5594 1.5476 1.5068 1.5459 1.5083 1.4990 1.4901 1.5008 1.4609 1.4510 1.4252
S* 1.1793 1.1769 1.1681 1.1765 1.1685 1.1664 1.1644 1.1668 1.1577 1.1554 1.1491
F 0.9135 0.9294 0.9848 0.9318 0.9827 0.9954 1.0075 0.9930 1.0476 1.0613 1.0972
k 3.1380 3.1578 3.2354 3.1608 3.2322 3.2521 3.2718 3.2482 3.3434 3.3702 3.4470
k” 0.7181 0.7096 0.6766 0.7083 0.6780 0.6697 0 6613 0.6713 0.6321 0.6213 0.5904
k’ 3.8562 3.8674 3.9121 3.8691 3.9102 3.9218 3.9336 3.9195 3.9756 3.9915 14.037
f 0.2059 0.2054 0.2035 0.2053 0.2036 0.2031 0.2020 0.2032 0.2009 0.2003 0.1985
n 14.137 14.204 14.472 14.215 14.461 14.531 14.600 14.517 14.853 14.949 15.225
A* 1.0533 1.0531 1.0520 1.0530 1.0520 1.0518 1.0515 1.0518 1.0505 1.0501 1.0491
B* 1.0652 1.0650 1.0629 1.0649 1.0630 1.0624 1.0619 1.0625 1.0601 1.0594 1.0575
k/k’ 81376 0.8165 0.8270 0.8169 0.8266 0.8292 0.8318 0.8287 0.8409 0.8443 0.8537
Table -2 Nonlinear parameter of Ethyl Acetate + proponol (Temp=30,35and 40 0 C)

Note: x(i) is Mole fraction of Ethyl Acetate
X(i)    (B/A)’ (B/A)” (B/A)

1.0 7.27615 1.692 1.64924 10.61914 -4.34309 6.27603
0.9 7.31574 1.65691 1.59940 10.46456 -4.14892 6.31563
0.8 7.47094 1.62270 1.63815 10.50033 -4.02948 6.47084
0.7 7.32172 1.58901 1.43861 10.04519 -3.72356 6.32162
0.6 7.46449 1.55469 1.45479 10.05019 -3.58580 6.46439
0.5 7.50428 1.51888 1.38637 9.879134 -3.37495 6.50418
0.4 7.54363 1.48480 1.31869 9.715938 -3.17239 6.54354
0.3 7.49654 1.45090 1.20045 9.425764 -2.92932 6.49644
0.2 7.68684 1.41481 1.19984 9.460561 -2.77381 6.68674
0.1 7.74051 1.38008 1.12354 9.302373 -2.56194 6.74042
0.0 7.89416 1.345 1.08175 9.272562 -2.37848 6.89407
Table -3 Nonlinear parameter of Methyl Acetate and n-proponol (Temp=30,35and 40 0 C)

Note: x(i) is Mole fraction of Methyl Acetate
74 | P a g e
~ 13.355 12.588 11.904 11.228 10.493 9.8372 9.1257 8.4303 7.8099 7.1979 6.5499
S 1.0499 1.0583 1.0656 1.0728 1.0806 1.0873 1.0943 1.1007 1.1061 1.1109 1.1152
So 1.9398 1.8953 1.8539 1.8113 1.7627 1.7173 1.6656 1.6123 1.5622 1.5100 1.4516
S* 1.2422 1.2362 1.2303 1.2239 1.2163 1.2088 1.1998 1.1899 1.1799 1.1689 1.1555
F 0.4210 0.4769 0.5292 0.5835 0.6459 0.7043 0.7723 0.8422 0.9095 0.9804 1.0606
k 2.8459 2.8589 2.8745 2.8940 2.9220 2.9546 3.0010 3.0615 3.1339 3.2287 3.3686
k” 0.8720 0.8614 0.8504 0.8377 0.8214 0.8038 0.7806 0.7522 0.7201 0.6794 0.6219
k’ 3.7179 3.7203 3.7247 3.7318 3.7434 3.7585 3.7817 3.8138 3.8537 3.9082 3.9906
f 0.2119 0.2118 0.2116 0.2113 0.2108 0.2101 0.2091 0.2077 0.2060 0.2037 0.2003
n 3.3085 13.322 13.348 13.390 13.460 13.551 13.690 13.882 14.122 14.449 14.943
A* 1.0570 1.0569 1.0568 1.0566 1.0563 1.0559 1.0553 1.0544 1.0534 1.0521 1.0502
B* 1.0744 1.0740 1.0736 1.0730 1.0721 1.0711 1.0696 1.0678 1.0657 1.0631 1.0594
k/k’ 0.7654 0.7684 0.7716 0.7755 0.7805 0.7861 0.7935 0.8027 0.8131 0.8261 0.8441
Table-4 Nonlinear parameter of Methyl Acetate and n-proponol

(Temp=30,35and 40 0 C)
Note: x(i) is Mole fraction of Methyl Acetate
X(i)    (B/A)’ (B/A)” (B/A)

1.0 6.691925 1.692 .9817346 9.630624 -3.938812 5.691812
0.9 6.717931 1.656918 .9782763 9.474034 -3.756214 5.717821
0.8 6.748702 1.622704 .9722448 9.328334 -3.57974 5.748593
0.7 6.788105 1.58901 .9679546 9.197252 -3.409254 5.787998
0.6 6.844169 1.554692 .9695939 9.085779 -3.241714 5.844065
0.5 6.909399 1.518882 .964404 8.975575 -3.066279 5.909297
0.4 7.002077 1.484806 .9710738 8.911823 -2.909846 6.001978
0.3 7.123152 1.450904 .9817998 8.884011 -2.760957 6.123055
0.2 7.267194 1.414816 .9837708 8.866835 -2.599735 6.2671
0.1 7.457465 1.380082 .9935296 8.911737 -2.454365 6.457373
0.0 7.737373 1.345 1.018563 9.061678 -2.324394 6.737284
75 | P a g e
5. REFERENCES:
Periodicals
[1] I. Johnson, M.Kalidoss and R.Srinivasamoorthy, 2001, Acoustical investigation of some binary and
ternary liquid mixtures – Proceedings of the 17th international congress on Acoustics (ROME),
,Vol.I,Physical Acoustics – Part B,(12).
[2] Pandey,J.D. and Ashok kumar, 1994,Ultrasonic velocity in pure liquids, J. Pure and Applied
Ultrasonic, 16(63).
[3] J.P.E.Grolier, and A.Viallard, 1971, J. chem. phys. 68(1442)
[4] J.ortaga, J.A.Pena, M.I. Paz-Andrade, and E.Jimnez, 1985 J. Chem. Thermodyn.17 (1127).
[5] V.D.Gokhale and N.N.Bhagavat, 1989, Evaluation of Ultrasonic Velocities in some Binary Liquid
Mixtures by Rao Specific Sound Velocity. J.Pure and Appl.Ultrasonic., 11(21).
[6] C.V Sorianarayan , 1976 ,J Acoustics Soc. Of India, 4 (76).
[7]Senanayake,P.C., Gee,N. and Freeman, R.G.1987 Can. J. Chem. Eng.Data,65(2441).
[8] Kalidoss.M and Srinivasamoorthy .R, 1997 J.Pure and Appl.Ultrasonic 19,(9).
[9] Viswanatan, S, and Anand rao,M, 1999.J.Chem. Eng.Data 45, (764).
[10] Ambinabhavi, M and Virupakashagouda, 1998, J.Chem.Eng.Data 43,(497)
[11]K.M. Swamy, Acoustic (Germany) 29,197(1973)
Books
[1]Riddick,J.A., Bunger,W.B., Sanako,T.K., 1986, Physical properties and methods of purification ,

John Willy & Sons ,New York,
[2] Hirschfelder, J.O, Curtio, and Byron bird, R., 1950, Molecular theory of gases and liquids.John Willy
& Sons, New Yark.
Others
[1] R.N.Fort and W.R.Moore – 1965Trans.Faraday Society 61,(2102)

[2] Handbook of Chemistry and Physics, 1984, The Chemical Rubber
Company, USA,
[3] Zorebski,E Zak, A Z.1999 Physikalis che Cheie. 210,(223).
[4] Chauhan , M.S. Sharma, K.C et al .1995 Acoustics letters 18,12,(223)
[5] Mukhrejee,A.Kamila ,S et al ,1999, Acoustics letters 23,1,(17)
[6] Belsae, N.s. Akhare, V.P and Deogaonkar, V.S, 1990, Acoustic letters 14,2,(37)
76 | P a g e
A COMPREHENSIVE ANALYSIS OF SOLVATION NUMBER OF SOME ORGANIC
ACID SALTS IN NON- AQUEOUS MEDIUM
Jasmine Vasantha Rani E^ and Suhashini Ernest *

^ Dept. of Physics, Seethalakshmi Ramaswamy College, Trichy-620002, India.
*Dept. of Physics, Urumu Dhanalakshmi College, Trichy-620019, India.
E mail: suha_ernest@yahoo.co.in
jasstephen@yahoo.com
Ultrasonic measurement can be used as a powerful probe to study the structural, physical and
chemical properties of matter. In the present study, measurements of ultrasound velocities, and
densities for various concentrations of non-aqueous formamide solutions of calcium salts of some
organic acids for different temperatures have been made in order to investigate the compressibility
behaviour in the solutions. Calculation of solvation number of the solutions is undertaken to highlight
the interactions existing in the solutions. The result obtained from compressibility method is seen to
agree well with the results from different theoretical and experimental methods.
Keywords: Solvation number, formamide, calcium salts of some organic acids
INTRODUCTION
Ultrasonic measurements have gained momentum in recent years for the study of liquids, liquid
mixtures, aqueous and non-aqueous electrolytes solutions. The ultrasonic velocity data
combined with density constitute the standard means for determining the compressibility of the system
under consideration. The compressibility of the system throws light on the ion- ion and ion-solvent
interactions. The samples chosen are calcium salts of carboxylic acids and its derivatives. The study of
molecular interactions existing in the non-aqueous solutions of calcium salts has been made through
ultrasonic velocity measurements.
EXPERIMENTAL PROCEDURE AND COMPUTAION
Ultrasonic velocity (u) of AR grade Calcium salts in Formamide is measured at the frequency of 2 MHz
with a Mittal Interferometer with an accuracy of ± 2 m/s. The density (ρ) measurements are made with
accuracies of ±0.001gm/cc.
Solvation number (ns) is computed using the following formula

Solvation number ns = (nf /ni) (1-(β / β0))
77 | P a g e
where u the ultrasonic velocity, ρ the density , β , β0 the adiabatic compressibility of the solutions and the
solvent and nf , ni is the number of moles of solvent formamide and number of ions solvated.
8. RESULT AND DISCUSSION
Passynski has taken consideration of the adiabatic compressibility of the solute and solvent for
deriving solvation number[1]. The study of solvation number is used to interpret ion-solvent interactions.
The solvation number is defined as the number of solvent molecules per ion, which remain attached to a
given ion long enough to experience its translational movements. The values of solvation number for
various values of temperatures and molalities are presented in Table 1
The decrease in the solvation number with increasing concentration reveals that either there is not
enough solvent for all the ions or preferably ion pairing has occurred.
The positive solvation number for the solutions suggests that the compressibility of the solution at
high temperatures may be less than that of solvent.
However, the fall in solvation number at high temperatures and the rise in solvation number from
negative maximum towards zero at low temperatures may be attributed to the decreasing ion-solvent
interactions but with further increase in concentration, it remains constant. This may be due to the
dominant effect of intermolecular attraction of solutes over ion- solvent interactions.The general
observations on solvation number of the system studied in relation to temperature and molality may be
summarized as follows.
• The solvation number is positive above room temperature and is negative below room
temperature.
• Gradual increase of solvation number from lower to higher concentrations is observed.
• The solvation number values are approximately found to be zero near higher concentration of 0.1m
and 0.15m mostly at lower temperature.
• The sign of the solvation number indicates the relative values of compressibility of solution and the
solvent.
78 | P a g e
The negative values of solvation number at temperatures emphasize that the solutions are more
compressible than the solvent. This may be attributed to the mobility of the ion being low at the low
temperatures. Therefore solution is more compressible than the solvent and hence the negative sign for the
solvation number.
Positive solvation number suggests that compressibility of the solution at high temperatures at all
molalities will be less than that of the solvent supporting the fact that ions gain high mobility and have more
probability of contacting solvent molecules. Therefore an increase in interaction between ion and solvent
molecules is expected.
Zero value of solvation number indicates that no change occurs in the compressibility value of the
solvent when the solution is formed [2].
The rise in solvation number from negative value towards zero at low temperatures and fall in
solvation number at higher temperature with increasing concentration may be attributed to decreasing
solute-solvent interaction.
The constant values of solvation number at higher concentrations and higher temperatures may be
due to the strong ion-ion attractions between the electrolyte molecules than the ion-solvent interactions[3].
The perusal of Table 2 shows that the number of solvent molecules in the coordination sphere
varies with anions [4]. An inspection of Table.1 stands in agreement with the fact that ‘the more dilute the
solution ,the greater the solvation of a given ion’[5].Table.3 presents the solvation number computed from
different methods, which agree with the values calculated in the present measurements.
CONCLUSION
The solvation number of calcium ion calculated from the compressibility study for sample solutions
agree well with the values reported from other methods.
79 | P a g e
REFERENCES
1. Passynski A, (Acta Physicochem.8, 385.,)1930.
2. Kuppuswami J., Lakshmanan A.S., Lakshminarayanan R., Rajaram N. and Surayanarayana C.V. (Bull.
Chem. Soc. Jap 38, 1610.,)1965.
3. Bhuller S.K., Bhavneet K., Bakshi M.S. Jabir S., Sharma S. C and Joshi I.M., (Acoustica, Vol. 73,
292.,)1991.
4. Kothai S and Kannapan V.,(Proceedings of National Symposium on acoustics,437-441.,) 2007.
5. Christian Riechardt,’Solvent and solvent effects in organic chemistry,(Wiley VCH Third
Edition,35.,)2003.
6. Samoilov O.Ya., ‘Structure of Aqueous Electrolyte solutions and hydration of numbers at 25OC’,
(Consultants Bureau New York, N.Y.,) 1965.
7. Yasutiro Umebayashi, Yutaka Mune, Taiga Tsukamoto Yue Zhang, Shin Chi Ishiguro. ( J. mol. liquids
vol.118, issues 1-3, pp. 45-49.,) 2008.
8. Ulström, Ann-Sofi Warminska, Dorata Person Ingmar.,( vol.158, Number 7, 12,pp 611-612.,) 2005.
9. Anan Tongraar, Kritsana Sagarik, Bernd Michal Rode.,( phys. chem. chem. phys, 4, 628-634.,) 2002.
10. Asada M., Fujimori.T., Kanzaki,K.,Umebayashi, R., Ishiguro,S.,(J. of Raman spectroscopy vol. 38,
no.4.,)2007.
11. Meyes Jünde Grosz Tamas Radnai Tamas Bako Imrl Palinkas Gabor,(J. Phys. Chem. vol.108, No.35,
pp 7261-7271.,) 2004.
12. Gapon, E.N., Z. Anorg.,(Allg. chem., 168, 125.,) 1927.
13. Ulich H,( Trans Faraday Soc 23, 392.,)1927.
14. Passynski .,( A., Acta Physicochim U.R.S.S 8,385.,)1938.
15. Azzam A. M., (Can .J.Chem. Vol 38, 993-1002.,) 1960.
80 | P a g e
Table - 1
SOLVATION NUMBER
Molality (m) 5˚ C 15˚ C 25˚ C 35˚ C 45˚ C 55˚ C

0.001 -168 -94 -244 34 250 377
0.005 -133 -17 -36 28 73 91
PANTOT LACTATE
CALCIUM
0.01 -34 5 -12 -6 24 35

0.05 -9 1 -1 3 3 7
0.1 -3 2 1 3 4 5
0.001 -818 -391 -168 -84 153 366
HENATE
0.005 -138 -51 10 -8 61 123

CALCIUM
0.01 -30 -6 12 22 48 47
0.05 -6 2 1 -4 11 6
0.1 1 4 4 4 8 18
0.001 -449 77 -481 21 254 274
0.005 -110 -38 -25 15 73 70
ASCORBA
9. CALCIUM
0.01 -43 -10 -8 59 10 44

0.05 -5 5 -15 9 2 28
0.1 5 3 7 11 11 5
0.15 4 6 5 6 8 8
0.001 -268 -88 -247 -486 84 -63
ACETATE
0.005 -44 25 -6 -21 53 84

0.01 -4 19 9 11 32 75
CALCIUM
0.05 -8 -1 -2 1 6 10
0.1 -2 1 0 4 5 9
0.15 0 -1 -1 1 2 4
0.001 -640 -396 -298 200 754 817
PROPIONA
0.005 -228 -53 -53 76 165 243

0.01 -64 -42 -5 53 110 110
CALCIUM
0.05 -12 3 -2 10 18 24
TE
0.1 -10 0 -2 4 12 4
0.15 -6 -3 -1 7 9 4
0.001 -534 -417 -457 117 603 1151
LACTOBI
ONATE
0.005 -91 -44 -83 83 74 248

CALCIUM
0.01 -91 -12 -10 9 62 88

0.05 -10 -5 -5 8 23 31
0.1 -4 4 2 7 7 17
0.001 -629 -97 -327 -149 114 381
CITRATE
0.005 -84 -7 -9 8 49 101

CALCIUM
0.0075 -57 -18 -35 -4 30 70

0.01 -33 3 -14 20 28 51
0.0125 -41 -3 -33 0 12 18
0.001 -255 -281 -260 -153 214 230
LEVULINAT
0.005 -18 -32 -37 3 68 -48

0.01 -17 6 -11 18 52 8
CALCIUM
0.05 -4 -1 -3 -1 8 10
E
0.1 -1 6 -1 2 3 1
0.15 0 1 0 2 3 2
81 | P a g e
Table 2
The solvation number for Ca2+ ion in formamide at 35OC and 0.1m for all the samples
Sample Solvation number

Calcium levulinate 2
Calcium lactate 3
Calcium pantothenate 4
Calcium acetate 4
Calcium propionate 4
Calcium lactobionate 7
Calcium ascorbate 11
Table 3
The solvation number of Ca2+ reported from different studies in different solvents.
Study Solvation
number.
From Aqueous solutions at 25OC [6] 4
CaClO4 in DMPA at 298 (from Raman spectroscopy)[7] 6
Calcium ion in DMS (LAXS)[8] 6
Ca2+ in Aq. Ammonium solutions (QM/MM simulation)[9] 7.2
Ca2+ in DMF & DMA (Raman Spectroscopy & DFT calculations)[10] 7
CaCl2 in water and methanol solutions (X-ray Diffraction and ab initio 8 (water)
calculations[11] 6 (Methanol)
Ca2+ in water at 25OC (diffusion methods)[12] 9
Mobility Experiments[13] 7.5-10.5
Compressibility Study[14] 16
Theoretical studies on divalent ions at 25OC[15] 12.3
82 | P a g e
Ultrasonic study on binary mixtures of ethyl benzoate with benzene and substituted
benzenes at different temperatures
B. Nagarjuna, Y.V. V Apparaoa, G.V Ramaraob, A.V Sarmaa, C. Rambabuc
a Department of Physics, Andhra University, Visakhapatnam.
b Department of Physics, DAR college, Nuzvid.
c Department of Chemistry, ANU, Dr.M.R.Appa Row Campus, Nuzvid.
ABSTRACT :
Densities, ultrasonic velocities and viscosities of ethyl benzoate + benzene, + Chloro benzene, +
nitrobenzene have been measured at temperatures 303.15 – 318.15K. The measured data used to
compute adiabatic compressibility (βad), deviation in adiabatic compressibility (∆βad), deviation in viscosity
(∆η), intermolecular free length (Lf) and molar volume (Vm). The excess molar volume (VmE) and excess
free length (LfE) are also evaluated for all the systems. These results were satisfactorily correlated by
Redlich-Kister polynomial. The excess parameters are used to discuss molecular interactions between
unlike molecules.
KEYWORDS: Ultrasonic velocity, excess properties.
1. Introduction
The thermodynamic study of esters has attracted increasing interest because these chemicals
have an extensive variety of applications [1,2,3
Ultrasonic velocity together with density, viscosity data furnish a wealth of information about the
sum total of interactions between ions, dipoles, H- bonding, multi polar and dispersion forces[4-7]. The
extensive uses of polymeric materials in technology have prompted ultrasonic studies to help to understand
the structures of polymers and molecular interactions in solutions and nature of polymers[8,9]
The present paper deals with the study in the binary liquid mixtures of ethyl benzoate (1)
+ benzene (2), + chlorobenzene (2), + nitrobenzene(2) at 303.15K, 308.15K, 313.15K and 318.15K.
Further the data has been obtained at different temperatures with a view to understand the effect of
temperature on these properties.
2. Experimental Details
Ethyl benzoate (EB), benzene, Chlorobenzene and nitrobenzene were purified using fractionating
column[10,11,12].
83 | P a g e
The accuracy in the measurement of density employing the specific gravity bottle method is better
than + 0.01%. Viscosity was determined by Ostwald’s viscometer,. The values are accurate to +0.001c.p.
Velocities were determined using single crystal ultrasonic interferometer (Model M-81, Mittal enterprises,
India) working at 2 MHz.
3. Theoretical considerations
Assuming that ultrasonic absorption is negligible, adiabatic compressibilities can be obtained from the
densities and ultrasonic sound velocities using the relation
βad = (ρu2) -1 ……….. 1
The molar volumes of the binary mixtures were calculated using the equation
V = (X1M1+X2M2 ) / ρ ……….. 2
Intermolecular free length (Lf) was calculated from the measured density and ultrasonic velocity by
using the following relation
Lf = K/ uρ 1/2 ………… 3
where K is the temperature dependent Jacobson constant 13 and T is the absolute temperature.
The excess properties such as ∆βad, VE , ∆η and LfE have been calculated using the equation
YE = Ymix - (X1Y1+X2Y2) ……………. 4
where YE is βad or VE or ∆η or LfE, and X represent mole fraction of the component and subscripts
1 and 2 stand for the components1and 2.
On the basis of a model for sound propagation proposed by Eyring and Kincaid[13], ultrasonic velocity
should decrease if the intermolecular free length increases as a result of mixing of components. This fact is
observed in the present investigation for Ethyl benzoate+ Benzene and Ethyl benzoate + Chlorobenzene
systems. In Ethyl benzoate + Nitrobenzene system, velocity decrease as free length increases with
concentration of ethyl benzoate. The ultrasonic velocity varies non - linearly with concentration without any
maxima or minima at all temperatures [14] as evident from Table 1.
The deviations in adiabatic compressibility are negative for all the three systems of ethyl
benzoate with benzene, chlorobenzene and nitrobenzene as shown in Figs. 1.2, 2.2 and 3.2. The adiabatic
compressibility is proportional to strength of interaction between unlike molecules.
The ∆βad values fall in the order Benzene > Chlorobenzene >Nitrobenzene
84 | P a g e
The sign of deviation in adiabatic compressibility and excess free length plays a vital role in assessing the
compactness due to molecular interactions in liquid mixtures through charge transfer, dipole-dipole
interactions, dipole-induced dipole interactions, interstitial accommodation and orientation ordering leading
to more compact structure [15]
The VE values become more negative at higher temperature( Figs.1.1,2.1,3.1), suggesting an
increase in interaction between component molecules[16,17] Excess molar volumes for ethylbenzoate
+ nitrobenzene system are more negative than that of ethylbenzoate + chlorobenzene system or
ethylbenzoate + benzene system ( Figs.1.1,2.1,3.1)
The general trend in variation of excess molar volume of the mixtures follows the sequence.
Benzene> Chloro benzene>Nitro benzene.
As temperature increases dissociation of associated species takes place releasing more and more
free molecules but because of favorable packing of ethyl benzoate and benzene or substituted benzene
molecules into each other’s structure [18,19] .
The values of ∆η for the whole mole fraction range for all the three systems are positive as evident from
Figs. 1.4, 2.4 and 3.4. For the systems where dispersion and dipolar interactions were operating the values
of viscosity deviations are found to be negative where as specific interactions tend to make deviations
positive[20]. The ∆η values have the following trends for binary mixtures with ethyl benzoate as common
component,
Nitro benzene > Chloro benzene > Benzene
85 | P a g e
Molefraction of Ethyl benzoate
0.0 0.0
Deviation in adiabatic
compressibility(∆βad)
0.0 0.2 0.4 0.6 0.8 1.0 -0.5 0.0 0.2 0.4 0.6 0.8 1.0
Excess molar volume(VE)
-1.0
-0.5
-1.5
-2.0
-1.0 -2.5
303.15K
303.15K -3.0 308.15K
308.15K -3.5 313.15K
313.15K 318.15K
-1.5 -4.0
318.15K
Fig 1.1 - Variation of excess molar volume with molefraction of Fig 1.2- Variationof deviation in adiabatic compressibility with
Ethyl benzoate for Ethyl benzoate + Benzene system molefraction Ethyl benzoate for Ethyl benzoate + Benzene system
Molef raction of Ethyl benzoate 0.20

Excess int.mol.free length(LfE)
303.15K
Deviation in viscosity (∆η)

0.000 308.15K
-0.002 0.0 0.2 0.4 0.6 0.8 1.0 0.15 313.15K
318.15K
-0.004
0.10
-0.006
-0.008 0.05
-0.010 303.15K
308.15K
-0.012 313.15K 0.00
-0.014 318.15K
0.0 0.2 0.4 0.6 0.8 1.0
Fig 1.3 - Variation of excess intermolecular free length with
molefraction of Ethyl benzoate for Ethyl benzoate + Benzene Fig 1.4 - Variation of Deviation in viscosity with molefraction of
system Ethyl benzoate for Ethyl benzoate + Benzene system
Molefraction of Ethyl benzoate Molef raction of Ethyl benzoate

0.0 0.0
Excess molar Volume(VE)
0.0 0.2 0.4 0.6 0.8 1.0 -0.5 0.0 0.2 0.4 0.6 0.8 1.0
Deviation in adiabatic compressibility(∆
-1.0
-0.5
-1.5
-2.0
-1.0 -2.5
303.15K
β ad)
303.15K
308.15K -3.0 308.15K
313.15K
-1.5 -3.5 313.15K
318.15K
318.15K
-4.0
Fig 2.1 - Variation of excess molar volume with molefraction Fig 2.2 -Variation of deviation in adiabatic compressibility with
of Ethyl benzoate for Ethyl benzoate +Chloro benzene molefraction of Ethyl benzoate for Ethyl benzoate +Chloro
system benzene system
303.15K
0.2 308.15K
Deviation viscosity (∆η)
313.15K
Excess int.mol.free length(LfE)
0.000 318.15K
0.0 0.2 0.4 0.6 0.8 1.0

-0.005 0.1
-0.010
303.15K
-0.015 308.15K 0.0
313.15K 0.0 0.2 0.4 0.6 0.8 1.0
-0.020 318.15K Molef raction of Ethyl benzoate
Fig 2.3 -Variation of excess inter molecular free length with
Fig 2.4-Variation of deviation in viscosity with molefraction of Ethyl
molefraction of Ethyl benzoate for Ethyl benzoate +Chloro
benzoate for Ethyl benzoate +Chloro benzene system
benzene system
86 | P a g e
Deviatio n ad iabatic co mp ressibility (∆ βad)

0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Excess m olar Volum e(VE)
-1.0
-0.4
-2.0
-0.8
-3.0
303.15K
-1.2 303.15K
-4.0 308.15K
308.15K 313.15K
313.15K 318.15K
318.15K -5.0
-1.6 Fig 3.2 -Variation of deviation in adiabatic compressibility with
Fig 3.1-Variation of excess molar volume with molefraction of molefraction of Ethyl benzoate for Ethyl benzoate +Nitro benzene
Ethyl benoate for Ethyl benzoate + Nitro benzene system system
Molefraction of Ethyl benzoate 2.00 303.15K

308.15K
0.000 313.15K
Deviation in viscosity(∆η)
1.50 318.15K
0.0 0.2 0.4 0.6 0.8 1.0
Excess int.m ol.free length(L fE)
-0.004
1.00
-0.008
0.50
-0.012
303.15K
-0.016 308.15K 0.00
313.15K 0.0 0.2 0.4 0.6 0.8 1.0
-0.020 318.15K Molefraction of Ethyl benzoate
Fig 3.3 -Variation of excess inter molecular free length with Fig 3.4 -Variation of deviation in viscosity with molefraction of
mole fraction of Ethyl benzoate for Ethyl benzoate + Nitro Ethyl benzoate for Ethyl benzoate + Nitro benzene system
benzene system
87 | P a g e
References
1. Reddy B R & Reddy D L, Indian J Pure & Appl Phys, 37, 13(1999).
2. Perez E, Cardoso M & Mainar A M, Parde J I & Urieta J S, J.Chem Eng Data,
48, 1306(2003).
3. Nayak J N, Aminabhavi T M & Aralaguppi, M I, J Chem Eng Data, 48, 1112(2003).
4. Wankhede D S, Lande M K& Arbad B R, J Chem Eng Data, 50, 455(2005).
5. Pal A, Sharma H K& Singh W, Indian J Chem, 34A, 987(1995).
6. Oswal S L & Patel N B, J Chem Eng Data,40, 845(1995).
7. Aminabhavi T M & Gopala Krishna B, J Chem Eng Data,40, 856(1995).
8. Nikam P S & Kharat S J, J Chem Eng Data, 50, 455(2005).

9. Chen J-T, Shiah I-M & Chu H-P, J Chem Eng Data, 50, 1038(2005).
10. Vogel A I, A text book of practical organic chemistry, 5th Edn (John Willey,
New York)(1989).
11. Riddick, J A, Bunger W B & Sokano T K, Techniques in Chemistry, Vol 2, Organic
solvents, 4th Edn (John Willey, NewYork) (1986).
12. Weissberger A, Proskaner E S, Riddick J A & Toops E E Jr, Organic Solvents, Vol II
2 nd Ed, Weissberger A Ed, Wiley Interscience, New York (1955).
13. Eyring H, Kincaid J F, J Chem Phys, 6, 620(1996).
14. Appa Rao Y V V, Ph.D Thesis, Andhra University, October (2009).
15. Thirumaran S, Earnest Jayakumar, Indian J Pure Appl Phys, 47, 265, (2009).
16. Babu P, Sekhar G C & Rao N P, Indian J Pure Appl Phys, 38, 425(2000).
17. Anil Kumar Nain, Rajni Sharma, Anwar Ali & Swarita Gopal, J Mol Liq,144, 124(2009).
18. Ali A, & Tariq M, J Mol Liq, 137, 64(2008).
19. Nandhibatla V Sastry, Rakesh R, Thakor & Mitesh C Patel, J Mol Liq, 144, 13(2009).
20. Subhash C Bhatia, Rachna Bhatia & Gyan P Dubey, J Mol Liq, 144, 163(2009).
88 | P a g e
STUDY OF NON LINEARITY PARAMETER (B/A) AND THERMO ACOUSTIC
PARAMETER OF BINARY MIXTURE AT DIFFERENT FREQUENCIES
G. Nath1 and R. Paikaray 2

1Dept. of Engg. Physics, Dhaneswar Rath Institute of Engg. and Management Studies (D.R.I.E.M.S.), Tangi,
Cuttack -754022, Odisha, India.
2P.G.Dept. of Physics, Ravenshaw University, Cuttack -753003, Odisha, India.
ABSTRACT:
Experimental data on speed of sound(C) values at 303K for different frequencies like 1MHz, 3MHz
and 5MHz are presented for the binary mixture of di isopropyl ether (DIPE) and xylene (XY). From these
experimental data for sound speed and density (ρ) of the binary mixture the thermo acoustic parameter like
isentropic compressibility (βs), isothermal compressibility (βT), coefficient of thermal expansion (α) are
calculated for different frequencies. The experimental values of sound speed have been fitted Ballou’s and
Hartmann’s equation for non linearity parameter and variation of these parameters with the frequencies has
been discussed in the context of molecular interactions.
KEYWORDS: Ultrasonic speed, binary mixture, isentropic compressibility isothermal compressibility, coefficient of
thermal expansion, heat capacity ratio, non linearity parameter
1. Introduction:
The propagation of acoustic waves of infinitesimal amplitude has been used to deduce most of the
parameters involved in ultrasonic studies. But when a sound wave of high amplitude propagates, non-linear effects
occur such as harmonic distortion and acoustic scattering. It has become of much interest to predict the extent of
various kind of non-linear effects which are due to deviation from nonlinearity in ordinary acoustics [1-4].A number
of information about some physical properties [5-6] of the liquid such as internal pressure, intermolecular spacing,
clustering, acoustic scattering, wave form distortion and structural behaviour etc.can be obtained from the
knowledge of this parameter. Researchers found that the acoustic non linearity parameter (B/A) was not only the
parameter describing the degree of non linearity, but also the parameter which may provides some structure and
state information of media.[7].Now a days the acoustic nonlinearity parameter B/A is of potential possibility to be
treated as a new parameter in tissue characterizing,dignosis and imaging .Obviously the study of acoustic
nonlinearity parameter B/A in liquid binary mixture is very helpful in discovering the mixture law of acoustic
nonlinearity parameter B/A in biological tissue as well as in developing and computing the theory of medical
89 | P a g e
ultrasonic and the theory of nonlinearity acoustics. During recent years [8-10 ] a no. of experimental and theoretical
studies have been performed on the nonlinearity parameter of liquid and liquid mixture but also to the best of our
knowledge, computation of B/A at different frequencies has not been done so far. The present work deals with the
computation of thermodynamic parameters in one binary liquid mixture at different frequencies and at temperature
303K. In addition with this we have taken an attempt to compute acoustic nonlinearity parameter B/A of the binary
mixture using two different method like Ballou’s empirical relation and Hartmann’s relation and the well known heat
capacities ratio (γ ) is calculated at different frequencies which is well agreed the values for all the substances.
2. Theory:
Since sound propagation is an adiabatic process, so the different factors like density ,temperature and frequency of
the sound wave may changes the sound speed [11-12].The experimental measured values of sound speed with
different frequencies are used to compute the various thermo acoustic parameter like isentropic compressibility(βs
),isothermal compressibility(βT), coefficient of thermal expansion ( α) and the heat capacity ratio (γ ) from the well
known thermodynamic relation[13-14 ]
1
Isentropic compressibility (β S )mix =
ρC 2
1.71 × 10 −3
Isothermal compressibility (β T )mixture = 4 4
T 9 C 2 mix ρ 3
mix
75.6 × 10 −3
Coefficient of thermal expansion (α )mix = 1 1 1
T 9C 2
mix ρ 3
mix
(β T )mix
Heat capacity ratio (γ )mix =
(β S )mix
General formulation for the nonlinearity parameter in terms of the acoustical parameters of liquid
has been made using the expression for the sound speed. According to the empirical rule of Ballous
employed by Hartmann [15], there is a linear relation between the nonlinearity parameter of liquid and
reciprocal sound speed as
B
= −0.5 +
(1.2 × 10 4 )
A C
90 | P a g e
Hartmann [15] has shown theoretically the physical basis of Ballous equation assuming the
intermolecular potential energy is the domain factor in determining the sound speed and derivatives in
liquids. The expression for nonlinearity parameter due to Hartmann [15] is given as
B
= 2+
(0.98 × 10 4 )
A C
3. Results and Discussions:
Experimental values of ultrasonic speed and calculated values of density of the mixture has been
used to determine the different parameters with the help of well known thermodynamic relation. Thermal
expansion coefficient and isothermal compressibility are obtained using the relation [13-14 ].The values of
the nonlinearity parameter B/A of the binary liquid mixture have been calculated at different frequencies
ranging from1MHz to 5MHz and at temperature 303K with the help of two different methods like Ballous
empirical relation and Hartmann’s theoretically derived relation .The variation of these thermo acoustic
parameter and nonlinearity parameter with frequency are plotted in figure1-7and discussed in the light of
molecular interactions. The ultrasonic speed decreases with mole fraction of DIPE followed by an increase
at higher mole fraction for all three frequencies. The decrease in ultrasonic speed is attributed to the
depolymerisation of polarity in xylene caused by the addition of non polar DIPE.The ultrasonic speed is also
increases with the increase of frequency for all concentration as shown in fig.1.Considering the effect of
frequency, it is found that in low frequency range like 1MHz the molecules of the two liquid find greater time
of interaction for which the ultrasonic speed is low. But when the frequency increases from 3MHz to 5MHz,
the interaction between the molecules decreases so that they have small relaxation time [16] and move
with high speed as compared to low frequency range.
Fig.1 Variation of ultrasonic ve locity with mole fraction

of DIPE
Ultrasonic velocity
1500
1M Hz
1000
3M Hz
500 5M Hz
0
0
1
29
41
65
87
0.
0.
0.
0.
Mole fraction of DIPE
The variation of ultrasonic speed is supported by that of isentropic compressibility, isothermal

compressibility and also coefficient of thermal expansion.The values of isentropic and isothermal
91 | P a g e
compressibility increases up to ≈ 0.70 mole fraction of DIPE and decreases thereafter for all three
frequencies as shown in fig.2 and fig.3.The positive variation of both the profiles suggest that there is
association of xylene molecules breaks up progressively with the addition of DIPE leading to expansion in
volume and hence isentropic and isothermal compressibility increases. However, in higher mole fraction of
DIPE the dipolar association is observed between the DIPE molecules for which both the compressibility
decreases.
Fig.2 Variation of isentropic compressibility with mole

Fig.3 Variation of isothermal compressibility with mole
fraction of DIPE
fraction of DIPE
3
co m pressibility
1MHz
Isentro pic
compressibility
1M Hz 4
Isothermal
3M Hz 3MHz
1 2
5M Hz 5MHz
0 0
1
29
41
65
87
0
1
29
41
65
87
0.
0.
0.
0.
0.
0.
0.
0.
Mole fraction of DIPE Mole fraction of DIPE
It is observed in low frequency like 1MHz, the interaction between the unlike molecules is very high for
which both the compressibility are low. But when the frequency changes from 3MHz – 5MHz the interaction
between the unlike molecules is weak due to small relaxation time, which leads to in compressibility at
every concentration of DIPE . Considering the variation of coefficient of thermal expansion as shown in fig.4
it is found that the value of α increases with increase of mole fraction of DIPE up to 0.70 mole fraction, then
decreases in DIPE rich region. Such variation can be
Fig.4 Varitaion of coe fficie nt of the rmal e xpansion with Fig.5Variation of he at capacity ratio with mole
mole fraction of DIPE fraction of DIPE
Coefficient of thermal
2
Heat capacity ratio
1.5
expansion
1.55
1 1.5
0.5 1MHz 1.45
1MHz
0 3MHz 1.4
1.35 3MHz
5MHz
0
1
9
5MHz
2
1
29
41
65
87
0.
0.
0.
0.
0.
0.
0.
0.
Mole fraction of DIPE Mole fraction of DIPE
well explained on the basis of the fact that with increase of density, speed of sound decreases which
increases the value of α .This increases in α, increases the volume and hence both type of compressibility
also increases up to certain mole fraction. Again in higher concentration of DIPE as the density of the
mixture decreases, the speed of the sound increases which decreases the value of α. With increase of
92 | P a g e
frequency from 1MHz-5MHz velocity increases as described on fig.1 which decreases the value of α with
increase of frequency. The heat capacity ratio of the binary mixture is found to be increase in a linear trend
with the mole fraction of DIPE as shown in fig.5 for all frequencies .Though it increases linearly with mole
fraction of DIPE but its value varies from 1.42-1.6 which is well agreed with that of the result for other
substances. The authors have also put the interest to calculate the non linearity parameter B/A using
Ballou’s and Hartmann’s relation. Many authors have calculated this parameter with variation of pressure
but in the present investigation the nonlinearity parameter are calculated with different mole fraction for
different frequencies at a constant temperature. With a close perusal of the data shown in fig.6 and fig.7 for
Ballou’s and Hartmann’s, it is observed that the nonlinearity parameter are increases with increase of mole
fraction of DIPE up to 0.65 mole fraction of DIPE and then deceases for higher concentration of DIPE .This
variation of B/A with mole fraction of DIPE in presence of xylene is only due to variation of ultrasonic speed
in the binary mixture which is described earlier.
Fi g.6 Variation of Hartman n's n on l in e arity param e te r Fi g.7 Variation of Ball ou's n on l i ne arity parame te r
with m ole fraction of DIPE with mole fraction of DIPE
Hartmann'snon linear
20
Ballou's non linear
20
parameter
parameter
15 15
10 10
1M Hz 1MHz
5 3M Hz
5
0 3MHz
0 5M Hz
5MHz
29
41
65
87
0
1
29
41
65
87
0
0.
0.
0.
0.
0.
0.
0.
0.
Mole fraction of DIPE Mol e fracti on of DIPE
Again considering the variation of B/A with frequency it is observed that in low frequency the B/A
value has high value in compare to the value obtained in high frequencies like 3MHz and 5MHz.This is due
to fact that at low frequency the speed of the ultrasonic sound is small for which the B/.A value is high as
the value of B/A varies inversely with speed of sound in both the cases.On the basis of the above
discussion it can be concluded that the variation of different thermo acoustic parameter and values of B/A
by Ballos and Hartmann is not only affected by the variation of pressure but also with the frequencies.
References:
1. R T Beyer, J.Acoust.Soc.Am.32, 719 (1960)
2. R T Beyer and S V Letcher, Physical Ultrasonic, Academic Press, New York, 202, 2043, (1961)
3. K P Thakur, Acustica, 39,270 (19780
4. RPJain, JDPandey and K P Thakur, Z Phys. Chem, (Neue Folge), 94, 211, (1975).
5. P S Westrvet, J.Acoust.Soc Am. 32,8 (1960)
93 | P a g e
6. J L S Bellin and R T Beyer, J.Acoust Soc.Am.34, 1051(1962)
7. H Endo, J.Acoust, Soc.Am.83, 2043(1986)
8. P Kuchhal, R Kumar and DNarsingh ,Pramana J.Phys.52,321 (1999)
9. G P Dubey, V Sanguri and R Verma Indian J.Pure and Appl. Phys.36, 678 (1998)
10. J Jugan, R Abraham and M A Abdulkhadar, Pramana J.Phys.45,221 (1995)
11. G Nath and R Paikaray, JUSPS, 21, 1, 99, 2009
12. G Nath and R Paikaray, Indian J Phys.83, 9, 1309 (2009)
13. J D Pandey, G P Dubey,N Tripathi and A KSingh J.Int Acad .Phy Sci.,1, 117,(1997)
14. J D Pandey and R Verma Chem. Phys.270, 429 (2001)

15. B Hartmann, J Acoust. Soc. Am. 65, 1392 (1979)
16. M S Chouhan, K C Sharma S Gupta M Sharma ands Chouan, Acost Lett., 18,233 (1995)
94 | P a g e
THERMO-ACOUSTIC STUDIES ON TERNARY MIXTURES OF METHYL ISO-BUTYL
KETONE, ACETYL ACETONE AND t- BUTANOL WITH CARBON
TETRACHLORIDE(CCl4).
T. Karunamoy1*, S. K. Dash1, S. K. Nayak2 and B. B. Swain3

1DESM, Regional institute Of Education (NCERT), Bhubaneswar-751022
2Department of Chemistry, Revenshaw University, Cuttack-753003
3Plot No. 15, Chintamaniswar Area, Bhubaneswae-751006
ABSTRACT
The ultrasonic velocity, density and viscosity of the ternary mixture of MIBK/HAA+t-butanol+ CCl4
were measured at 301.16 K. The thermo acoustic parameters such as isentropic compressibility,
inter molecular free length, acoustic impedance, free volume, internal pressure, available volume,
relaxation time and relaxation amplitude were computed with the help of measured values of u,
and . In an attempt to explore the nature of molecular interaction between the polar-polar,
polar-non polar species of the ternary mixture the excess properties were derived. The molecular
interactions are dipole-dipole, dipole-induced-dipole and dispersive type in the ternary mixtures
containing HAA. However in MIBK there is an indication of complex formation in its the ternary
mixture containing t-butanol and CCl4
KEY WORDS MIBK, HAA, t-butanol, ternary mixture, thermo-acoustic parameters.
1. Introduction
Methyl-iso-butyl ketone (MIBK) and acetyl acetone (HAA) has been extensively used as extractant in
various polar and apolar modifiers/diluents for extraction of actinides and lanthanides in atomic energy
industry [1]. Some physico-chemical studies on thermo-acoustic properties of ternary mixtures on
MIBK/HAA+t-butanol in the presence of CCl4 have been undertaken. The molecular interaction between the
like as well as unlike molecules in the given ternary systems have been studied in the light of several
thermodynamic and acoustic parameters. The ultrasonic velocity and dielectric constant of the organic
phase changes by blending MIBK/HAA with polar and apolar liquids. To understand the molecular behavior
of associating molecules, involving MIBK/HAA, it is necessary to determine various thermo-acoustic
parameters which are related to inter and intra molecular association with temperature as well as
concentration variation. In an earlier report [2] one of the author (SKD) have been evaluated the Kirkwood-
Fröhlich linear correlation factor, g, excess molar polarization ∆P and excess free energy of mixing ∆F for
binary mixtures of MIBK in three apolar solvent viz. benzene, CCl4 and p-xylene using dielectric studies.
Although several reports are available for studying the molecular interactions in binary liquid mixtures [3, 4]
involving polar-polar and polar-apolar systems it is sparse in ternary liquid mixtures involving the nuclear
extractant MIBK/HAA. Therefore attempt has been made towards investigations on thermo-acoustic
95 | P a g e
behavior in ternary mixtures on MIBK and HAA with t-butanol and CCl4 in the five polar compositional
stochiometry for assessment of molecular interactions between the component molecules.
2.Experimental
All the chemicals used in the investigations were of AR grade, purified by standard procedures [5] and
redistilled before use. The purity of the sample was checked by comparing the measured value of density
and viscosity with those reported in the literature [6]. The ultrasonic velocity was measured by single crystal
variable path interferometer at 2 MHz with an accuracy of ± 0.5 ms -1. Circulating water from thermostatic
regulated bath around the sample holder with double wall maintained the temperature of the system
constant with an accuracy of ± 0.1oC. The density was measured by a digital microbalance with a
pykonometer of 25 ml capacity with an accuracy of ±2x10-5 g cm-3. The viscosity was measured by Ostwald
viscometer immersed in constant temperature water bath with an accuracy of ±10-6 Pas. The binary
mixtures of MIBK/HAA+t-butanol was prepared by weight for five sets of compositional (mole fraction)
stoichiometry viz (0.1+0.9), (0.3+0.7), (0.5+0.5), (0.7+0.3) and (0.9+0.1) separately. For each set of
compositional stoichiometry the ternary mixtures of MIBK/HAA + t-butanol + CCl4 was prepared with the
decreasing mole fraction of CCl4.
Ultrasonic velocity (u), viscosity() and density () of the ternary mixtures of MIBK/HAA+t-butanol +CCl4 in
the polar compositional stoichiometry of (0.1+0.9), (0.3+0.7), (0.5+0.5), (0.7+0.3) and (0.9+0.1) with the
function of mole fraction of CCl4 were measured at 303.16 K. Various thermo acoustic parameters such as
such as isentropic compressibility(βs), inter molecular free length(Lf) acoustic impedance(Z), free
volume(Vf),internal pressure(πi), available volume(Va), relaxation time( τ) and relaxation amplitude (/f2)
were measured by using standard relations [7,8].Some of the relevant data are presented in Table-1 and
displayed graphically in Fig-1. In perusal with Table-1, it is observed that the values of u and Va increases
while that of  and Z decreases non linearly with the increase in mole fraction of polar solute i.e. (MIBK/HAA
+ t-butanol) in all the ternary mixtures containing CCl4. Further, the values of  and α/f2 increases in
(0.1+0.9), (0.3+0.7) while decreases in other compositions of polar solute non linearly with mole fraction of
CCl4 in the ternary mixtures. However, the non linear variation in the values of βs, Lf, πi, and Vf depends
upon the combined effect of the increasing or decreasing trend of u,  and which is observed in the
present study. This shows molecular interactions as well as interstial accommodations among the polar-
polar and polar-non polar components of the MIBK/HAA + t-butanol + CCl4 mixtures. The relaxation time (
τ) which is of the order of 10-12 s probably due to structural relaxation process [9] and in such situation it is
96 | P a g e
expected that molecules get rearranged due to co-operative process.
HAA, MIBK and t- butanol are strongly associated polar liquids having dipole moment 2.91 D, 2.70 D and
1.66 D respectively. The dielectric study involving HAA, MIBK and t-butanol reveals that Kirkwood-Fröhlich
linear correlation factor, g, in all the three protic liquids viz. gHAA= 1.56, gMIBK = 1.3 gt-butanol =2.18 is greater
than one [10, 11]. This indicate that there is re-enforcement of parallel dipolar alignment among the like
polar molecules of MIBK, HAA and t-butanol respectively which may be attributed by the presence of 3-
dimensional network of H-bondings among themselves and stacked together by head-tail arrangement [12].
HAA/MIBK molecules are equilibrium mixtures of two tautomers such as keto and enol forms and the
molecules are arranged in head-tail structure due to C and O  linkage resulting intramolecular association.
In seemingly non-interacting medium like CCl4, the dipolar alignment of MIBK/HAA is influenced by non-
specific interaction due to the solvent effect and dipole-dipole interaction through H-bondings between H
and O is also expected among the MIBK/HAA + t-butanol molecules.
In perusal with Fig-1, it is observed that the values of βs shows negative in the entire range of concentration
in (0.1+0.9) and up to 0.3 mole fraction of CCl4 in (0.3+0.7) compositions. Further, it shows positive in the
entire concentration range of concentration in (0.7+0.3) and (0.9+0.1) with a negligible variation in (0.5+0.5)
compositions in HAA + t-butanol + CCl4 ternary mixtures. However the magnitude of negative values of βs
decreases in the order of composition of (0.1+0.9)> (0.3+0.7)> (0.5+0.5)> (0.7+0.3).The values of LfE are
observed to be negative in the entire range of mole fraction of CCl4 in the composition of (0.1+0.9), while it
shows negative up to 0.75 mole fraction of polar solute thereafter shows positive in (0.3+0.7) of the ternary
mixtures containing HAA. However in other higher composition the values of LfE shows positive with the
mole fraction of CCl4. On the otherhand Fig -1 shows that the values of ZE and VfE are positive for all the
compositions except (0.9+0.1) in the ternary mixtures containing HAA. The magnitude of ZE, VfE and LfE are
maximum in (0.9+0.1) compositions. Further the values of VaE are negative in all the compositions while πiE
are also negative in all compositions except in the compositions of (0.9+0.1) with a decreasing magnitude
(0.1+0.9)> (0.3+0.7) > (0.5+0.5)> (0.7+0.3). This indicates that the degree molecular interaction is relatively
higher in the (0.1+0.9) composition in the ternary mixtures containing HAA. In the presence of t-butanol the
molecular interactions between HAA and alcohol molecules takes place through the intermolecular H-
bondings between O of two carbonyl group of HAA and H of hydroxyl group of alcohol CCl4 molecules
are almost spherical in shape and can be easily trapped inside the interstitial voids of the interacting
moieties containing HAA and probably favours the stronger molecular interaction in (0.1+0.9) composition
in the ternary mixtures of HAA + t-butanol + CCl4. From the close observation of Fig-1, it is observed that
97 | P a g e
the values of βsE and LfE are negative throughout with the mole fraction of polar solute in compositions of
(0.3+0.7) and (0.5+0.5) while it shows partly negative, then positive in other compositions in the ternary
mixtures containing MIBK. Further the values of ZE are positive while πiE and VaE are negative with the
solute mole fraction in all the compositions of this ternary mixture. From the trend of variation VfE with solute
mole fraction it is observed that the values of VfE are positive in all the composition except (0.9+0.1) in the
ternary mixtures. From such observation it is found that the magnitudes of the excess thermodynamic
parameters are not prominent in any of the compositional stochiometry of the ternary mixtures containing
MIBK. Although the molecular interaction of tt-butanol and MIBK is possible between O of MIBK with H of
OH groups of alcohol the interstitial accommodation along with the dispersive forces between C of CCl4
and H of alcohols molecules cannot be overruled. As such it is probable that there may be complex
formation between the components
mponents present in the ternary mixtures of MIBK + tt-butanol
butanol + CCl4 system.
4.Conclusion
The present investigation reveals that the nature of molecular interaction involving MIBK/HAA with t-butanol
t
and CCl4 may be dipole-dipole,
dipole, dipole
dipole-induced
induced dipole and dispersive type. As such HAA may be used as an
effective extractant in the presence oof the modifier t-butanol and diluent CCl4 at compositional stochiometry
(0.1+0.9) in the extraction process.
150000 150000
100000 (0.1+0.9 (0.1+0.9)
100000
(kg m-2s-1
ZE x10-6
(kg m -2 s -1 )
)
(0.3+0.7)
Z E x10 -6
50000 50000
(0.3+0.7
0 (0.5+0.5)
) 0
0.00
2.00 (0.7+0.3)
(0.5+0.5 -50000 0.00 1.00 2.00
X2 ) X2 (0.9+0.1)
5E-11 6E-11
(0.1+0.3) 4E-11 (0.1+0.9)
βsE x1010
βsE x1010
(N-1m2)
(N-1m2)
(0.3+0.7) 2E-11 (0.3+0.7)

0
(0.5+0.5) 0 (0.5+0.5)
0.001.002.00
(0.7+0.3) -2E-11 0.00 0.50 1.00 1.50
(0.7+0.3)
-5E-11
X2 (0.9+0.1) -4E-11 (0.9+0.1)
-6E-11 X2
98 | P a g e
10000000 10000000
πi Ex10-6…
0 (0.1+0.9) (0.+0.9)
0
-1E+08 0.001.002.00 (0.3+0.7) 0.00 1.00 2.00 (0.3+0.7)
πi Ex10-6…
-1E+08
-2E+08 (0.5+0.5) (0.5+0.5)
-3E+08 (0.7+0.3) -2E+08 (0.7+0.3)
-4E+08 (0.9+0.1) -3E+08 (0.9+0.1)
X2
(X2)
0 0
(0.1+0.9) (0.1+0.9)
0.00 2.00 0.00 1.00 2.00
(m3kmol-1)
(m3kmol-1)
-2000 (0.3+0.7) -2000 (0.3+0.7)
VaEX105
(0.5+0.5)
VaEX105
-4000 (0.5+0.5) -4000

(0.7+0.3) (0.7+0.3)
-6000 -6000
(X2) (0.9+0.1) (0.9+0.1)
X2
(a) (b)
Fig-1 Variation of Zβs πiEand Vawith mole fraction(X2) of (a) HAA+t-butanol+ CCl4 (b) MIBK+t-butanol+ CCl4 with
compositions of (0.1+0.9), (0.3+0.7), (0.5+0.5), (0.7+0.3) and (0.9+0.1).
Table-1 Variation of density (),ultrasonic velocity (u), viscosity (), adiabatic compressibility (βs), relaxation
time (),relaxation amplitude (α/f2) free volume (Vf), available volume (Va) internal pressure (πi) and
acoustic impedance (Z) with mole fraction(X2) of polar solute (MIBK/HAA+t-butanols)at(0.1+0.9).
X2  u  βsX1010 (N- x1012 α/f2×1014 VfX107 (m3mol- VaX105 πiX10-6 (pa) Z ×10-6 (kg
( kg m-3) (m/s) Nm-2s) 1m2) (s) (s2 m-1) 1) (m3kmol-1) m2 s-1)
(HAA + t-butanol) + CCl4)
0.00 1588.00 914.33 0.0009 7.53 0.90 1.95 0.815 2.46 853 1.451956
0.10 1479.00 910.00 0.0009 8.16 0.96 2.09 0.766 2.72 859 1.345890
0.19 1408.03 912.40 0.0009 8.53 1.02 2.21 0.700 2.95 886 1.284684
0.30 1328.00 915.00 0.0009 8.99 1.08 2.33 0.642 3.26 911 1.215120
0.39 1273.15 933.20 0.0009 9.02 1.12 2.37 0.577 3.65 954 1.188102
0.49 1185.05 951.20 0.0010 9.33 1.22 2.52 0.502 4.33 993 1.127219
0.60 1108.00 975.00 0.0010 9.49 1.33 2.68 0.420 5.14 1060 1.080300
0.69 1034.74 997.60 0.0011 9.71 1.47 2.91 0.348 6.10 1130 1.032255
0.80 950.00 1037.50 0.0013 9.78 1.67 3.17 0.273 7.82 1220 0.985625
0.90 869.00 1077.00 0.0015 9.92 1.96 3.58 0.204 10.00 1340 0.935913
1.00 801.97 1115.20 0.0017 10.00 2.31 4.08 0.148 12.45 1510 0.894353
(MIBK + t-butanol) + CCl4)
0.00 1588.00 914.33 0.0009 7.53 0.90 1.95 0.815 2.46 853 1.451956
0.10 1455.00 910.00 0.0009 8.30 1.03 2.23 0.713 2.81 872 1.324050
0.18 1382.40 912.80 0.0009 8.68 1.09 2.36 0.655 3.08 891 1.261855
0.25 1330.00 915.00 0.0009 8.98 1.13 2.44 0.618 3.28 910 1.216950
0.37 1238.00 934.00 0.0009 9.26 1.17 2.47 0.572 3.89 933 1.156292
0.47 1164.30 949.00 0.0010 9.54 1.32 2.74 0.465 4.47 1000 1.104921
0.58 1057.00 967.50 0.0011 10.01 1.50 3.05 0.384 5.53 1005 1.022648
0.67 1016.10 984.00 0.0012 10.02 1.66 3.33 0.307 6.09 1016 0.999842
99 | P a g e
0.80 890.00 1037.50 0.0014 10.04 1.99 3.79 0.225 8.83 1026 0.923375
0.90 845.00 1082.50 0.0017 10.01 2.34 4.27 0.156 10.67 1046 0.914712
1.00 782.60 1132.50 0.0021 9.96 2.78 4.84 0.11 13.53 1067 0.886294
References
[1] A.K.Dey,S.M.Khopkar and R.A.Chalmers, Solvent extraction of metals (Van-Nostrand-Reinhold,London, 1970).
[2] J.K.Das, S.K.Dash, V.Chakravortty and B.B.Swain, .Indian .J.Chem.Tech 1 230 (1994).
[3] J.Conosa, A.Rodrigucz and Z.tozo, Fluid phase equilibrium 156 (1999) 57.
[4] M.Dominguez,S.Martin, J.Shantafa, H.Atigas and F.M.Royo, Thermochemica Acta.381(2002) 181.
[5] J.A.Riddick, W.B.Bunger and T.K.Sakano, Organic Solvents,4thEdn.(Wiley- Inter Science, New York)( 1986).
[6] CRC Handbook of chemistry and physics edited by DR.Lide,87th Edn.(CRC Press Boca Raton FL) (2006).
[7] T.Sumathi and J.Uma.Maheswari, Indian J.Pure& Appl.phys.47 (2009) 782.
[8] D.Sravana Kumar and D.K.Rao, Indian J.Pure& Appl.phys. 45 (2007) 210.
[9] M.Selva Kumar and D.K Bhat, Indian J.Pure& Appl.phys. 46 (2008) 712.
[10] J.K.Das, S.K.Dash & B.B.Swain. J.Physical Socity of Japan Vol.64 (1995) 2636.
[11] S.Acharaya, S.K.Dash,J.N.Mohanty & B.B.Swain,J .Mol Liq. Vol.71 (1997) 73.
[12] S.K.Dash,J.K.Das, B.Dalai and B.B.Swain, Indian J. Phys.83(11),1557 (2009).
100 | P a g e
GLUECKAUFF’S MODEL FOR LOWERING OF DIELECTRIC CONSTANT OF ELECTROLYTIC SOLUTIONS &
ISOENTROPICCOMPRESSIBILITY AND ION ASSOCIATION STUDIES WITH AQUEOUS ELECTROLYTIC
SOLUTIONS USING ULTRASONICS ,ION-PAIRS (CHLORIDES)
V.Brahmajirao 1**, T. Gunavardhan Naidu 1, P.Rajendra 3 , T.Srikanth 2 , Shanaz Batul 4
Matrix Institute of technology, Cheekatimamidi (V), Bommalaramaram (M), Jawaharlal Nehru

1
Technological University HYDERABAD, Pin Code – 508116 ; 2 Jawaharlal Nehru Technological University
(Jagtyal Campus) Jagtyal.A.P.; 3 LNBC Institute of Engineering and Technology,Raigaon, Satara,
Maharastra ; 4 Main campus, Jawaharlal Nehru Technological University, HYDERABAD-500072. ; ( 1** E-
mail ID for all correspondence: profvrbr1@hotmail.com )
Abstract
This paper reports the specific evidence of the formation of three types of Ion pairs from the ultrasonic
studies in aqueous solutions of six chlorides from our laboratories in J.N.T.U., and the plots of
thermodynamic parameters , using equations for partial molal compressibility & apparent molal
compressibility, from literature Several correlating arguments cited by, a host of earlier workers , about
the findings of Gucker et.al, are incomplete & naïve, since the parameter of the dependence of dielectric
constant on concentration is missing in them . Margaret Robson Wright & Robinson and Stokes pointed
that the internal field around the central ion of the ionic atmosphere created by the charged solute ions in
the solvent of the electrolytic solution, tend to reduce the value of the dielectric constant of the electrolytic
solution. The author used the relevant equations modified by him .Using these equations, the mechanism
of formation of three types of ion pairs envisaged earlier by Eigen et.al. observed in the plots is explained
on firm grounds. The plots clearly show an excellent agreement with many of the recent cited findings.
Discrete variation in the slopes of the straight line graphs are explained, correlating them with the
prevailing concepts proposed by several scientists, in their respective different types of studies in the very
recent literature.An excellent evidence for all of the concepts of all the cited workers is reported .Several
unsuccessful attempts made so far to deduce a comprehensive model, and to modify the D-H Theory for an
electrolyte solution were cited, and the need to use M.C.Simulations, to incorporate the depression in the
dielectric constant of the dielectric continuum , due to solute-solvent interactions was outlined
KEYWORDS: Glueckauff’s model, Isentropic compressibility, Monte Carlo Simulations , Ion-pairs in

aqueous electrolytes, Debye Huckel theory, Gucker’s equations , Lowering of dielectric constant of
dielectric continuum
Introduction
The departures exhibited in the properties of electrolytic solutions, as the concentration increases, cannot be
satisfactorily explained, by the Debye Huckel model even with its several recent modifications that were
developed during the last half a century, mainly because of so many shortcomings, in the presumptions of the
theory & its later developments, by a host of others. Electrolytic ions entering into the solvent of the dielectric
constant “D” creates an internal field around the central ion of the ionic atmosphere & the average effect of all
±) of the solvent of the electrolytic solution.Glueckauff
such ions is to reduce the effective value of D to ( D − D
[1] & Von Hippel [2] showed that the dielectric constant in the vicinity of the central ion is modified by the
volume fraction of the ions in layer of the solvent around the central ion. Treating the solvent as a continuously
non uniform system having spatial distribution of the ions .For a volume fraction φ to ( φ +d φ ), where φ =
101 | P a g e
8π Nr 3
( ) , dφ = 2 N (4π r 2 dr ) and “r” is the distance of the point of calculation from the centre of the
3
reference ion. The integration of this within suitable limits yield
[dD / d log(1 − φ )] = [3D( Dφ − D) /(2 D + Dφ )] .
This equation is used for the estimation of lowering of the dielectric constant. Further the thermodynamic
variables that can be estimated from ultrasonic data, are related to the modification to the free energy of the
central ion, in the solvent and the details are available in literature
Gucker et.al. [3]& [4] established with standard notation the equation for the partial molal compressibility as:
∂2 ∂
(V2 − V 0 2 ) = ( K 2 − K 0 2 ) . In this K 0 2 , V2 , G 0 2 , are parameters corresponding to
0
2
(G2 − G 0 2 ) =
∂p ∂p
infinite dilution. Treating the dielectric constant as a variable it can be shown that, the partial molal
compressibility
3 5 ∂D 2 1 ∂ 2 D β ∂D 1 ∂V 1
Gets modified to: ( K 2 − K 2 ) = χ [ 2 ( ) + ( 2 ) + ( )] . In this β = [− ( )] = 2 ,
0
2 D ∂P D ∂P D ∂P V ∂P v ρ
is the isentropic compressibility, ρ is the density, and “D”, is the dielectric constant, (which is a variable, as
3 6
per the new revelations ), and, χ = [(π N e )
1
2 ] 2
and N is Avogadro Number .These
(1000 D kT )
equations clearly reveal that (
Cversus K 2 − K 2
0
) plot will not be linear Also the apparent molal
∂φv2 SV β
compressibility is φk = ( )T , and φK2 = φK + S K C , in which S K = (∂SV / ∂P )T + ( ) , leading to
0
∂p 2
χ ∂β 6 β ∂D 15 ∂D 2 6 ∂ 2 D
(∑ν i zi )3 2 [ β 2 + 2(
2
SK = )T − ( )T + 2 ( )T − ( 2 )T ]
6 i ∂P D ∂P D ∂P D ∂P
Hence ( φK vs C ) plot cannot be linear in view of the modifications made, to account the solute solvent
interactions. SK becomes a function of concentration and dielectric constant. The author opines that: the
inherent change of slope of the plot reveals conspicuously the interactions between the ions and the
solvent in a discrete way namely the ion-solvent-ion interactions, as detailed in the discussion of the
results. Also according to Gucker [3] & Gucker et.al, [4]. S K = (6.3 X 10−10 )δ is a constant, where δ is
independent of the ion-solvent-ion interactions as per the deductions arrived by the cited workers above.
This will be invalid, and needs a total review. Harned & Owen [5], Krishnamurthy [6], B.R.Rao & K.S.Rao
[7], Marks [8], Bhimasenachar & Subramanyam [9], Padmini& Rao [10], Mason [11], pointed out the
deviations in the Gucker’s equations qualitatively, without rigorous explanation of the same. These
shortcomings in the Gucker’s equations are to be attributed mainly to the solvation and the ion-ion & the
solvent-ion interactions, consequent of internal field modifications around the central ion inside the ion-
atmosphere, as the electrolytic ions enter the solvent, with the increase in concentration. Borukhov et.al.
[12] Attempted to arrive at a modified Poisson-Boltzmann Equation but for no complete avail, since several
recent findings are not taken care of. The model for viscosity of electrolytic solution by Lencka et.al [13],
Wang & Anderko [16]for water as solvent was later improved into a comprehensive model for calculating
the viscosity of aqueous or mixed-solvent electrolyte systems ranging from dilute solutions to fused salts, is
informative , and several concepts in the approaches are useful to be applied in the M.C.Simulations . The
B coefficients data for a large number of aqueous species used by Wang & Anderko was determined by
analyzing extensive experimental viscosity data by Marcus [14] for a number of ions in pure organic
102 | P a g e
solvents at 250 C. For systems for which the B coefficients are not available in literature sources, their
values have been determined from experimental viscosity data at low electrolyte concentrations (usually
below 0.05 M) in pure solvents using a method described by Lencka et al. The temperature dependence of
the B coefficients can be expressed using the equation of Out and Los [15]. Still these models find little use,
having failed to incorporate the solute solvent interactions, to make the model applicable to ion pair
formation analysis. The Wang & Anderko [16] model incorporates a mixing rule for calculating the viscosity
of solvent mixtures and a method for predicting the effect of finite electrolyte concentrations. The effect of
electrolyte concentration on viscosity is modeled by combining a long-range electrostatic term obtained
from the Onsager-Fuoss theory, a contribution of individual ions, which is quantified by the Jones- Dole B
coefficients, and a contribution of specific interactions between ions or neutral species. Formulations have
been developed for the contributions of individual ions and species-species interactions. The model
reproduces the approach to viscosity of systems such as salts in water, organic or mixed water-organic
solvents and aqueous acids or bases up to the pure solute limit. However it is necessary to develop it
further in the light of recent findings about solute solvent interactions
Experimental and Calculations:
This paper reports the data, of our ultrasonic studies using Ultrasonic pulse echo technique similar to that
of Mc Clements & Fairley [17] in aqueous solutions of sulphates. Density measurements are made using
the bicapillary pyknometer. The
conductance data was obtained using the ‘PHILIPS’ Conductivity Bridge Model P.R.-9500 similar to the one
used by Power et.al & Singh .et.al. [18] And Bikash Kumar Panda et.al & Mishra et .al. [19]. The bridge
used has a cell constant of (1.39). The ionic polarization effecting the Conductivity measurements is
balanced the usage of an inbuilt oscillator generating 1 KHz signal, applied to the bridge network as a
whole The experimental details for dielectric determinations are given else where [20] The ultrasonic,
dielectric and conductance data of the author were used in the calculations, using a programme, in “C-
language” and details of analysis of variations in thermodynamic parameters, are presented as graphs with
0
C as abscissa and φK2 & ( K 2 − K 2 ) , as ordinates separately.
Discussion of the results: All the plots record three conspicuous gradient changes per each electrolyte.
Each gradient change corresponds to the formation of a type of ion pair. These graphs record distinct
changes in slope, at three concentrations, corresponding to, the formation of solvent separated, solvent
shared & contact pairs in tune to the expectations of Eigen [21] and is different from the findings reported
earlier in literature. As pointed out by Eigen& DeMaeyer [22] the internal field around the central ion of the
ionic atmosphere created by the charged solute ions in the solvent of the electrolytic solution, tend to
reduce the value of the dielectric constant of the electrolytic solution. Avery exhaustive review on the Ion
association & complexation studies is available by Covington & Lilley [23]. Solute solvent interactions of
several mixed solvent systems with many electrolytes are studied by Maitra & Bagchi [24]. The Gibbs
energy of solvation, as given by log s, where s is the solubility has been found to depend on various modes
of solute–solvent interaction and also on the Hildebrand solubility parameter representing the cohesive
energy density (solvent–solvent interaction) of solvent. A dimensionless quantity has been defined to
represent the deviation of the observed log s values from the mole fraction average. Results have been
explained in terms of various modes of solvation interaction.
M. J. Blandamer, D.Waddington & J. Burgess et.al. [25] Studied properties of solutions of binary aqueous
mixtures from the standpoint of solute-water and solute-solute interactions, using pair wise interaction
parameters. With an increase in the amount of solute, strong evidence is obtained for clustering of both
aqueous and non-aqueous components. These trends are explained in terms of preferential solvation of
initial and transition states using Kirkwood-Buff integral functions. The analysis is applied to kinetic data
describing the dependence on the ethanol mole fraction of the first order rate constant for the solvolysis of
103 | P a g e
t-butyl chloride in aqueous solution. Kaatze. et.al. (26) discussed the aqueous systems for which
measurements of the complex electric permittivity (103 Hz ≤ ν ≤ 1011 Hz) and of the attenuation coefficient
of acoustic waves (105 Hz ≤ ν ≤ 3·109 Hz) had been recently experimented over a broad range of
frequencies. The liquids include aqueous solutions of multivalent electrolytes, of transition metal chlorides,
of micelles and bilayers, and of small organic molecules. It is shown that, In many cases, the two
spectroscopic methods can be favourably used to yield complementary aspects of structural properties and
interesting molecular dynamics of liquid mixtures .The qualitative explanation of the mechanism of
formation of the three types of ion-pairs, was detailed by Margaret Robson Wright [27] , Robinson and
stokes[28] , J.O”M. Bockris & Amulya K.N. Reddy [29], & J.O”M. Bockris et.al. [30] The outlines of the
same are available at Brahmajirao, [31].From the plots of [ C versus φK2 ] Gucker showed that lim φ K
c →0
represents the reduction in the hydration number. In the reported plots, this intercept is obtained on the φK2
axis .This decreasing intercept clearly signifies the reduction in the number of water molecules around the
(v f − n1 v10 )
central ion. Also we can write lim φ K = β = - nh v10 β 0 in which n1 is the total number of
c →0 n2
molecules of water and n2 is the number of moles of electrolytes and nh is the hydration number which is
the number of water molecules in the primary hydration sheath round the central ion. Fuoss [32],
&Kraus et. al. [33] showed that the solvent with lower dielectric constant favours ion-pair formation to a
more marked degree. They showed that at the critical distance defined by q = [( z1 z2 e 2 ) / 2 DkT ] , the
potential energy of the ion pair is “2kT”. This fulfils the condition that the energy required to separate the ion
pair is comparable to the thermal energy. The decrement in the dielectric constant makes the value of ‘q’
greater than the ionic diameter. An equation for association constant was deduced, applying the method
devised by Boltzmann to the equilibrium between ion pairs and free ions. He obtained for the degree of
association (1 − α ) = K Acα 2 f 2 , where c is concentration, f is Debye-Huckel activity coefficient , α is the
fraction of the (1-1 ) electrolyte present as free ions and K A is the association constant .For 1-1 electrolyte
he deduced K A = [4π Na3eb ]/[3000] , in which a is ionic diameter, b = e 2 / aDkT ,since [ z1=z2 ],D is the
dielectric constant, k is Boltzmann’s constant , and T is the absolute temperature .
4π Na 3e 2
⇒ log K A = [log ] ⇒ A plot between log K A as ordinate and (1/D) as abscissa, had to be a
3000aDkT
straight line with constant slope, if D remains constant But the solvent mixture is treated as a dielectric
continuum, with no modification attempted for accounting the solvent solute interactions, that would lead to
the continuous variation of the dielectric constant as the solute concentration gradually increases .Hence
this theory requires modification in the light of the Glueckauff’s model. Consequently Fuoss’ equations fail
to predict the behavior of the ion pairs to a better extent the graph between log K A versus (1/D) will not
have constant slope and so its analysis reveals valuable information about Ion-pair formation.
104 | P a g e
Several workers [34] in addition to Fuoss and Kraus used mixtures of solvents aqueous as well as non
aqueous and established the ion pair formation in each of them, exactly in the same lines and hence Fuoss
and Kraus theory was applied therein. However the fact that the dielectric constants of the solvent
continuum changes once the solute ions enter it is not implanted into their analysis and observations.
Hence their observations are incompetent to explain the ion-solvent interactions Stillinger [35] using the
dielectric measurements of Hasted, Ritson, and Collie [20] made an attempt to give a mathematical shape
to the logical structure of mechanism of ion pair formation for a symmetrical electrolyte, so that the pairing
process could be generalized to accommodate unsymmetrical electrolytes in such a way as to divide ions
uniquely into uncharged "molecules" with minimal internal distances. KCl was chosen for numerical
analysis. Petrucci et .al [36]. Using studies in infrared, Raman spectra, and conductance measurements,
supported by dielectric and ultrasound relaxation and related thermodynamic evaluations attempted a
systematic analysis of Ionpair mechanism. However their work is to be extended to other sources of data to
ensure generalizations. Ohtaki et.al... [37] in their X-ray diffraction & NMR studies in a series of papers
1990’s studied ionic solvation, Rohman [38] in his Ph.D., thesis “Ultrasonic Velocities and Transport
Properties of Aqueous and Nonaqueous Electrolytes,” published voluminous data with non -aqueous
solvents also. Buchner et.al [39], recently in their dielectric relaxation studies over a wide range of
frequencies and concentration ranges similar to those of the author recorded marked evidences of the
simultaneous existence of double-solvent-separated, solvent-shared, and contact ion pairs at all the ranges
of temperatures studied, with tendency for the formation of contact pairs to be more as the temperature
increases. Exactly in the similar lines in our ultrasonic studies, our plots with GKG parameters reported in
this paper, record more than two or more gradient changes at places of formation of solvent separated as
well as solvent shared ion pairs, with nearly the same stability, since the slopes at these places of formation
corresponding to the value of SK is not much different. Buchner et.al [39], used a dielectric relaxation
technique that restricts the thermodynamic analysis of the individual ion pairs .They concluded that both the
ions influence solvent water molecules beyond the first hydration sphere. They concluded that both the ions
influence solvent water molecules beyond the first hydration sphere. Very recently Honggaing Zhao et.al
[40], & H.Weingartner [41], attempted the development of an equation of state that considers the statistical
conditions to account for association contribution of the solute to the solvent through the reduction of the
dielectric constant. We are attempting to use this model, and intend to report our findings shortly. Results
for sulphates appear separately at Brahmajirao et.al [42].
105 | P a g e
Rahmat Sadeghi et.al, [43], reported apparent molar volumes and transfer of isentropic compressibility’s of
l-alanine from water to aqueous potassium di-hydrogen citrate (KH2Cit) and tri-potassium citrate (K3Cit)
from ultrasonic measurements. It was found that the apparent molar isentropic compressibility and the
apparent molar volume of alanine in both KH2Cit and K3Cit aqueous solutions is negative and increases by
increasing temperatures and salt concentrations. Very recently in the ionic volume measurements Marcus
[44], studied the properties of electrolytes in solutions and observed the interactions of the constituent ions
with solvent and other ions. The interactions with the solvent alone are manifested at infinite dilution. From
the measurement of partial molar volume, & density, additive ionic contributions, for small ions due to the
electrostriction of the solvent were obtained from an iterative shell-by-shell calculation from a continuum
model of the solvent. The solvation number ‘S ‘ defined by the ratio of the solvent shrinkage per mol of ions
to, the molar electrostriction of the solvent is calculated & compared with the experimental values, and
good agreement for many univalent ions in both single solvents and in some binary solvent mixtures, is
reported. He opines that when no appreciable preferential solvation takes place, ion pairing sets in under
certain circumstances of ionic charge and solvent permittivity. In his studies on structural and
thermodynamic aspects of the hydrophobic effect. from analysis of the solvation structure around solutes
and various water models by the RISM integral equation method, Soda [45] concluded that with increasing
solute radius from 0 to 3A, the average orientation of hydrating water varies from an inward to an outward
orientation, this shows that some reorganization of water occurs in response to the change in solute size. It
is predicted from the scaled particle theory that the solvent exclusion effect caused by the introduction of
solute into solvent is an important factor of the hydrophobic effect. Chen. et.al. [46], from a detailed analysis
of a series of lengthy molecular dynamics simulations of alkali-halide solutions carried out over a wide
range of physiologically relevant concentrations find evidence for pronounced non ideal behavior of ions at
all concentrations in the form of ion pairs and clusters which are in rapid equilibrium with dissociated ions.
The phenomenology for ion pairing seen in these simulations is congruent with the multistep scheme
proposed by Eigen and Tamm based on data from ultrasonic absorption. For a given electrolyte, it was
shown that the dependence of cluster populations on concentration can be described through a single set
of equilibrium constants. They confirm the conclusions of Fuoss and co-workers, based on conductometric
experiments. Ion pairs and clusters form on length scales where thesize of individual water molecules is as
important as the hard core radius of ions. Ion pairing results as a balance between the favorable Coulomb
interactions and the unfavorable partial desolvation of ions needed to form a pair.Afanasievet.al. [47] and
Gardas et.al. [48] With their extensive measurements of the speed of ultrasound, density, and isobaric heat
capacity, isentropic compressibility of aqueous solutions, over wide temperature and concentration ranges,
evaluated parameters including hydration numbers and osmotic virial coefficients .Several observed
deviations were attributed to the change in the dielectric permeability of water in direct proximity to ions,
leading to Ionic hydrophobic influence. Gardas et.al compared their results with that of X-ray data analysis
in the solid phase. Their interpretations are yet to be confirmed in detail. Jönsson et.al.[49] Worked out
Monte Carlo simulations of the hydrophobic effect in aqueous electrolyte solutions which reveal several
structural characteristics of the solvent around the central ion during ion pair formation. However the
attempts are yet in the primary stage of development, but have a promising scope to understand the
solvent behaviour. Pitzer et.al.’s [50] formalism, developed in a series of papers has been put to use and a
model was developed by Soto et.al. [51] to correlate the activity coefficient, apparent molar volume and
isentropic compressibility of glycine in aqueous solutions of NaCl, based on detailed experimentation with
ultrasonic techniques. The results show that the model can accurately correlate the interactions in aqueous
solutions of glycine and NaCl.
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107 | P a g e
REFERENCES:
(1) GLUECKAUFF, Trans.Faraday.Soc. 60 1637, 572(1964); “Digest of literature on dielectrics” Nat.Acad.Of Sci., National
research council Washington .D.C.; (2) VONHIPPEL, “Dielectric materials and applications “, The Technology Press, M.I.T.,
Massachusetts, U.S.A.; (1954), (3) GUCKER, J.Amer.Chem.Soc 55 2709 (1933) & Chem. Revs 15 111. (4)
GUCKER&BACHEM Zeits.F.Physik. 101 541(1936), Z.Electrochem. 41 570(1936), (5) HARNED &OWEN,” The Physical
Chemistry of Electrolytic solutions “: Reinhold publishers (1958); (6) KRISHNAMURTY J. Sci. Ind. Res. 9B 215(1951), 10B
149(1952), (7) B.R.RAO& K.S.RAO J.Sci. Ind. Res. 17B 444(1958), (8) MARKS J. Acous.Soc.Amer. 31 936(1960, (9)
BHIMASENACHAR & SUBRAMANYAM J. Acous.Soc.Amer. 32 835 (1960), (10) PADMINI& RAO, Ind. J .Phys. 34
565(1960); (11) W.P.MASON “Physical Acoustics”, Vol-II, Chapter 6, 426.Academic press, New York & London (1965), (12)
BORUKHOV et.al. Phys.Rev.Let.79 (3) pp435-438(1997), (13) LENKA et al., Intl. J. Theomophys., 19 367(1998). (14)MARCUS
et.al , “Ion Properties “. Marcel Dekker Inc. New York 1997. (15)OUT and LOS, J. Solution Chem., 9 (1980) 19. (16)WANG &
ANDERKO” Modeling Viscosity of Aqueous and Mixed-Solvent Electrolyte Solutions” Presented at‘14th International Conference
on the Properties of Water and Steam in Kyoto ‘: Proceedings’ pp116-121 (2004), Ibid (2001), Fluid Phase Equil. 186 103; Ibid
(2003), Ind. Eng. Chem. Res., 42 3495. Ibid (2002), Fluid Phase Equil. 203 141. (17)McCLEMENTS & FAIRLEY Ultrasonics, 29
(1) Pages 58-62. (1991); (18) POWER et.al, ‘Complexes of 8-Amino-2-methylquinoline with cobalt (II)’ Australian Journal of
Chemistry, 25(9), 1863 – 1867 (1972); SINGH et.al. Can. J. Chem., 54, 1563(1976); Ibid, Inorganic.Chem. (1981); 20(8) 2711-
2713; (19) PANDA et.al. ‘European Journal of Inorganic Chemistry’ 2004(1) 178-184; MISHRA et.al. Can. J .Chem. 45 2459-
2462(1967); (20) HASTED, RITSON, and COLLIE, J. Chem. Phys., 16, 1 (1948). (21) EIGEN.M., Z.Phys.Chem.Frankfurt vol. 1
176(1954); Discussions .Faraday.Soc.24 25 ;(22)EIGEN& EMAEYER “Investigation of rates and mechanisms of reactions
in“Techniques of Organic Chemistry “, vol VIII, Part 2, Chapter 18, Interscience, New York(1963), ; (23)COVINGTON & LILLEY,
Electrochemistry, Volume 1, Specialist periodical reports / Chemical Society Edited by G.J.Hills, Pub.By Royal Society of
Chemistry, Article 5 on “: Ion pair and complex formation” (1970) ; (24)MAITRA & BAGCHI. Study of solute-solvent and solvent-
solvent interactions in pure and mixed binary solvents J.Mol. Liquids 137(1-3)10 131-137(2008); (25) M. J. BLANDAMER &
J.BURGESS,”Interaction and Activation in Aqueous mixtures “, Colloids and Surfaces, 48, Pages139-152 Blandamer et.al.
(1973), Advances in Molecular Relaxation Processes, 5(4), pp333-338 Blandamer et.al. (1970), Advances in Molecular
Relaxation Processes, 2(1), pp1-40Blandamer et.al. J.Molecular.Liquids (1992), 52, (1), PP15-39, (26) KAATZE et.al.
J.Molecular. Liquids, 49(2) pages 225-248(2001),; (27)MARGARET ROBSON WRIGHT: “An Introduction to Aqueous Electrolyte
108 | P a g e
Solutions” Art.1.12 Formation of Ion pairs from free ions, page 17, John Wiley & Sons Ltd, The Atrium, Southern Gate, Chi
Chester, West Sussex PO19 8SQ, England(2007) ; (28)ROBINSON AND STOKES “Electrolytic Solutions “,Second revised
edition,Chapter9,page 238:“Theoretical Interpretation of Chemical Potentials &Influence of ion solvent interactions on Ion
atmosphere” and Also” Ion Association”: Chapter11&14, Pages 392 & 429(2002); (29)J.O”M.BOCKRIS & AMULYA K.N.
REDDY: “Modern Electrochemistry”, 1977 edition, Plenum Press Chapter3 on “Ion –Ion “interactions: & Chapter 4.6 on
“Influence of Ionic Atmosphere on Ionic Migration”; (30) J.O”M.BOCKRIS et.al. “Ionic Solvation Numbers from Compressibilities
and Ionic Vibration Potentials Measurements,” J. Phys. Chem., 76, 2140(1972). (31) BRAHMAJIRAO.V, “Cationic motilities of
electrolytic solutions-Ion pairs–EIGENmechanism”Transactions. Of. Saest, 14(2) (1979)53; Ibid (1976),
Ind.J.Pure.Appl...Phys.14 646; Ibid (1980), Ind. J. pure & Appl. Phys. 18 12 (1980) 1021; Ibid (1980), “Influence of variation of
Dielectric constant.Gucker’s equations…” Proceedings of International Conference onUltrasonics, ICEU-July 1980, held at New
Delhi. INDIA; Ibid (1980) “Application of ….. Variation of Dielectric.....GKG and Dagget equations “, Proceedings of
International Conference on Nonaqueous Solutions, ICNAS-7, held at Regensburg, WEST GERMANY. (Aug 1980); Ibid (1981),
Ind. J.Pure & Appl. Phys. 19 (1981) 254; Ibid (1981) “Application of Glueckauff’s model for depression in Dielectric ...Ion pair
formation”, Proceedings’ of ‘Ultrasonics International-81’, held at Brighton U.K. 30th JUNE to 2 nd JULY 1981;Ibid “Analysis of
solute- solvent interactions …in relation to ion pair formation”,Procedings of International Symposium on Electro analytical
Chemistry Held at Chandigarh, INDIA December1982;Ibid “Study of …in chosen electrolyte solutions “ Proceedings’ of Sir
J.C.Ghosh Memorial symposium held at Calcutta, INDIA,Feb1982; Ibid “Electrostatic Potential energies of Ion pairs in
nonaqeous media from” Ultrasonic measurements”, Proceedings of Eighth International Conference on Nonaqueous
Solutions, Nantes (Cedex) FRANCE, 19th to 23 rd July 1982 ;Ibid “Ultrasonic studies in solute solvent
interactions…..Ionpairs”Procedings of ICNAS-IX Held at Pittsburgh, Pennnsylvania,U.S.A. in August 1984; Ibid “Solute –Solvent
interaction and Ion pair formation in the light Of depression in Dielectric constant” Proceedings of VIth International Symposium
on Solute–Solvent–Solute…Interactions, Tokyo, JAPAN, July1982.Ibid “Application of Glueckauff’s model of variation of
dielectric Constant to association constant – Calculations in relation to Ion pair Formation “Proceedings of 2nd International
symposium on Industrial and Oriented Electrochemistry, Held at Karaikudi, INDIA (Dec 1980) (32).FUOSS “Ionic
Association.III.The Equilibrium between Ion Pairs and Free Ions”, J. Am. Chem Soc., 80 (19),5059–
5061(1958),KRAUSet.al.(1963)“Mechanisms underlying the equilibrium reactions between ions and ion pairs In solutions of
electrolytes, II The effect of temperature”, Proc Natl Acad Sci U S A. (1963) 49(2):141-6.;(33) KRAUS et.al. “Mechanisms
underlying the equilibrium reactions between ions and on pairs in Solutions of electrolytes, I Solutions in p-Xylene and Benzene
Interactions between benzene, Toluene, and p-xylene (BTX) during their biodegradation. ... J Phys Chem. B 110(30):14961-70.
(2006) ;( 34) FUOSS and KRAUS J.Amer.Chem.Soc, 551019and21dioxan-ater mixtures (1933)); JONES et.al Ibid 76 3247,
acetic acid (1954); HNIZDAet.al, Ibid 71 1565, liquidammonia (1949); EL-AGGAN et.al, J.Chem.Soc. 2092 ethanol (1958);
GOVER et.al, J.Phys.Chem 60 330, n-propenol1956); HIBBARDet.al, J.Amer.Chem.Soc 77 225, ethylenediamine (1955);
REYNOLDS et.al, Ibid 0 1709 acetone (1948); BURGESS et.al, Ibid 70 706 Pyridine (1948); (35) STILLINGER et.al. (1968) J.
Chem. Phys., 48, 3858, and the paper immediately following it. (36)PETRUCCI et.al. (1994) J. Phys. Chem., 98, 8234-8244; Ibid
J. Phys. Chem., 88, 5100-5107 ;( 37) OHTAKI, RADNAI & YAMAGUCHI (2003) Chem. Soc. Rev (Washington, D.C.) .97 (1997),
pp 26, 41 & 51; Mol. Phys., 87, 103 (1996); Bull Chem. Soc Japan 65: 1445; Chem. Rev. (Washington, D.C.) 93, 1157 (1993).
28; Bull Chem. Soc Japan 56: 443: ...; Chem. Phys. Lett., 1998, vol. 286, p. 46-50.; Ibid on ‘ionic Solvation in Aqueous and
Nonaqueous Solutios,pp1to32, ‘Highlights in solute-solvent interactions’editor: Wolfgang Linert, pub. By Springer wein,
Newyork (2002) ;( 38) ROHMAN, “Ultrasonic Velocities nd Transport Properties of Aqueous and Nonaqueous Electrolytes “,
Ph.D Thesis, the Dibrugarh University, Assam, India (2000). (39) BUCHNER et.al J Phys Chem. B. 110(30): 14961-70.
(2006); (40) HONGGAING ZHAO et.al, J.Chem.Phys.126 244503(2007);
(41) WEINGARTNER, et.al. Pure. Appl.Chem. vol 73 No. 11, page1733 (2001). Ibid 2000), J.Chem.Phys.113 762; Ibid (2001)
Adv.Chem.Phys 116 1; Ibid (1991), Ber.Bunsenges.Phys.Chem. 95 1579; Ibid (1995) J. Stat.Phys.78 169; Ibid (1999) J Phys
Chem. B. 103 738; Ibid (1999), J. Solution.Chem. 28 435; Ibid (1989) Ber.Bunsenges.Phys.Chem .93 1058; (42)
BRAHMAJIRAO et.al, “Glueckauff’s model for lowering of dielectric const. Isentropic ompressibility Studies ….. With aqueous
… using Ultrasonic’s - ‘ION PAIRS ‘- (SULPHATES) “Paperpresented to NSA-2010, Rishikesh, INDIA), Nov 11th to 13th, (2010);
Ibid “On GLUECKAUFF’S model for variation of dielectric constant of electrolyte Solution, and its Influence on thermodynamic
variables, determined by acoustic tools & onfirmation of Eigen Mechanism of ION PAIRS “Paper presented to: I.C.A -2010,
Sydney AUSTRALIA, to be held during AUG23rd TO 27th of (2010);(43) RAHMAT SADEGHI et.al, J. Mol. Liquids, 141, (1-2),
Pages 62-68. (2008) ;( 44) MARCUS Biophys.Chem, 124(3), pages 200-7(2006), MARCUS, “Ion Solvation,” Wiley
Interscience, New York. (1985) ;( 45) SODA, Adv Biophys. 29 1-54(1993). ;( 46) CHEN et.al., J Phys Chem. B. 111(23): 6469-
78 (2007). ;( 47) AFNASIEV et.al. J Phys Chem. B. 13(1): 212-23 (2009), ;( 48) GARDAS et.al. J Phys Chem. B; 112(11):3380-
89(2008). ;( 49) Jönsson et.al., J Phys Chem.B.110(17): 8782-8(2006). (50)PITZER et.al. J.Phys.Chem. 77, 268 (1973); Ibid
J.Am.Chem.Soc, 96, 5701 (1974); Ibid J.Solution Chem., 18, 1007(1989); Ibid (2010) Molecular Structure and statistical
Thermodynamics Selected papers of Kenneth S Pitzer’ World Scientific, Singapore Ion interaction approach: Theory and data
109 | P a g e
correlation.’ In: “Activity Coefficients in Electrolyte Solutions. 2 “– Editor: Pitzer KS, Boca Raton, Florida, USA: CRC Press;
(2010) pp. 75–153; (51) SOTO et. al., Biophys.Chem. 74(3): 165-73 (1998).
110 | P a g e
GLUECKAUFF’S MODEL FOR LOWERING OF DIELECTRIC CONSTANT OF
ELECTROLYTIC SOLUTIONS : ISOENTROPIC COMPRESSIBILITY AND ION-
ASSOCIATION STUDIES WITH AQUEOUS ELEECTROLYTIC SOLUTIONS BY
ULTRASONICS -Ion pairs (SULPHATES)
V.Brahmajirao 1** , T. Gunavardhan Naidu 1, T.Srikanth 2 , P.Rajendra 3 Shanaz Batul 4
Matrix Institute of technology, Cheekatimamidi (V), Bommalaramaram (M), Jawaharlal Nehru

1
Technological University HYDERABAD, Pin Code – 508116 ; 2 Jawaharlal Nehru Technological University
(Jagtyal Campus) Jagtyal.A.P.; 3 LNBC Institute of Engineering and Technology,Raigaon, Satara,
Maharastra ; 4 Main campus, Jawaharlal Nehru Technological University, HYDERABAD-500072. ; ( 1** E-
mail ID for all correspondence: profvrbr1@hotmail.com )
..
ABSTRACT
This paper reports the specific evidence of the formation of three types of Ion pairs from the ultrasonic
studies in aqueous solutions of sulphates. The data is presented as plots, using equations for partial molal
compressibility & apparent molal compressibility. Correlating arguments cited by several earlier workers,
are given in support. Also deductions by a host of others in the application of equations of Gucker et.al, [5]
& [6] apparently are incomplete, since the dielectric constant dependence on concentration is to be
installed into their arguments, to account for the ion-solvent interactions missing in the prevailing theories of
electrolytic state. The author modifies the relevant equations and explains on firm grounds ,the mechanism
of formation of Three types of ion pairs i.e., (1) solvent separated, (2) solvent shared and (3)contact
types, The graphs record an excellent agreement with many of the findings of the very recent work in the
field of electrolytic research cited at the appropriate place . Discrete variation in the slopes of the straight
line plots are explained, correlating the concepts arrived at in the very recent literature, by a host of
workers trying to analyze similar interrelated problems in different angles ,using thermodynamics,
molecular dynamics ,and quantum physics . They obtained valuable information with Monte Carlo
Simulations and all of us land at concurrent & conspicuous conclusions.
KEYWORDS: Glueckauff’s model, Isentropic compressibility, Monte Carlo Simulations , Ion-pairs in

aqueous electrolytes, Debye Huckel theory, Gucker’s equations , Lowering of dielectric constant of
dielectric continuum
Introduction
Robinson and stokes [1], point out that Debye- Huckel theory treats the ions of the ionic atmosphere as
hard, non deformable spheres of equal radius, and hence crudely neglects the short range interactions
between ions and solvent molecules, as well as other possible interactions .which are responsible to create
internal field around the central ion of the ionic atmosphere & the average effect of all such ions is to
reduce the value of the dielectric constant of the electrolytic solution.. Hasted et.al.,[2] ,showed that the first
layer of the solvent molecules of type “B” round the central ion of type “A” of the ionic atmosphere cause
short range interaction leading to the reduction in the bulk dielectric constant of the medium around the
central ion.Glueckauff & Von Hippel [3], Buckingham [4], used this very important point for correction. and
111 | P a g e
developed a model to evaluate the depression in the dielectric constant, of an electrolyte solution as the
concentration of the solute increases, starting from Gibbs free energy given by G = ∂G ( ∂nA ) nB
, at constant
temperature and pressure .This model was used earlier by the author to evaluate the dielectric data, that
was confirmed to be reasonably accurate, experimentally. This data was used in the present work. Gucker
[5] established with standard notation the partial molal compressibility as
2
∂ ∂
[ 2 (G2 − G 0 2 )] = [ (V2 − V 0 2 )] = ( K 2 − K 0 2 ) . In this K 0 2 , V2 , G 0 2 , are parameters corresponding to
0
∂p ∂p
infinite dilution. Treating the dielectric constant as a variable it can be shown that
3 5 ∂D 1 ∂ 2 D β ∂D
( K 2 − K 0 2 ) = χ [ 2 ( ) 2 + ( 2 ) + ( )] .
2 D ∂P D ∂P D ∂P
1 ∂V 1
In this β = [− ( )] = 2 , is the iso-entropic compressibility, ρ is the density, and “D”, is the
V ∂P v ρ
dielectric constant, (which is a variable, as per the new expectations ), and,
3 6
χ = [(π N e )
1
2 ] 2 and N is Avogadro Number .These equations clearly reveal That [
(1000 D kT )
Cversus ( K 2 − K 2 ) ] plots that were expected to be linear previously, cannot be so. The variations in
0
the slope correspond to the ion-solvent, & solvent -solvent interactions, and other factors that require
attention.
∂φv
Also the apparent molal compressibility is [ φk = ( 2 )T ,] and [ φK2 = φK + S K C ], in which
0
∂p
S β
S K = [(∂SV / ∂P )T + ( V )] Leading to
2
χ ∂β 6 β ∂D 15 ∂D 2 6 ∂ 2 D
S K = (∑ν i zi )3 2 [ β 2 + 2( )T −
2
( )T + 2 ( )T − ( 2 )T ]
6 i ∂P D ∂P D ∂P D ∂P
Hence Cversus(φK ) plot cannot be linear, against the predictions of Gucker et.al. The variations in its
slope correspond to the ion-solvent, & solvent -solvent interactions, and other factors, leading to the ion
pair formation as detailed in the discussion of the results.
According to Gucker et.al, [6]. S K = (6.3 X 10−10 )δ is a constant, where δ is independent of
the ion-solvent, ion-ion & and other interactions .But the above expression clearly shows that it is not so.
Earlier Harned & Owen [7], Krishnamurthy [8], B.R.Rao & K.S.Rao [9], Marks [10], Bhimasenachar &
Subramanian et.al. [11], Padmini& Rao [12], Mason [13],Giacomini et.al.[14], Prozorov[15],Barnartt[16]
observed that the linearity of the above plots extends into higher concentration regions where the Debye-
Huckel theory is not contemplated to be applied .Also the SK value showed irrational variation with the
valence of the ion, and no rigorous explanation of these findings is available in the literature.Association
constatant is a parameter which gives an insight into the ion-ion and ion-solvent interactions With the
notation used by Graham Kell &Gordon[17] ,we can show that K A the association constant can be
expressed in terms of conductances Λη the value corrected for volume effect on viscosity produced by the
solute , Λ 0 the value at infinite dilution, and Λ the value at the given concentration ,by the equation
Λη = [ Λ 0 + Eci log ci − S ci + Jci − K A ci f 2 Λη ] , and K A is the mass action term,’ E’ is the
112 | P a g e
electrophoretic term, ’S’ is the Onsager term, ‘J’is the relaxation term ,and ‘ f ’.is the activity coefficient . It
is now established that all these terms are discrete functions of dielectric constant. In addition if ion
association comes into existence, the expression for Λη becomes a cubic equation in γ (to be solved by
n1 ]
a method of continued fractions) where γ = [ , in which n1 is the free charged ion number, and ‘c’ is
c
the concentration. From this equation γ can be obtained by a process of iteration, to give finally
Λ 4 1 3 z
γ = ( ) F ( z ) , where F= F ( z ) = ( ) cos 2 [( ) cos −1 (−3 2. )] , in which’s’ is an independent variable
Λ0 3 3 2
Λ
given by z = ( S 3 )(cΛ )1 2 .This leads to ( ) = Λ 0 − [cΛ 2 f 2 K A ] /[Λ 0 F 2 ] ,called the GKG equation.
2
Λ0 2 F
We find that these equations do not incorporate the happenings around the reference central ion,
consequent of the interactions that generate long range and short range fields in the ion -atmosphere in the
continuous dielectric medium of the solvent. Only thermodynamics and statistical tools can help this .Monte
Carlo simulations, are finding good utility at hand, since the variety of influencing parameters and the
equations to be probed with them is complex .As a preliminary attempt the author used conductance,
dielectric constant and activity coefficient data for several aqueous as well as nonaqeous electrolytic
systems partly his own and partly from Lobo [46] with the above equations. Several plots, for each
electrolyte were drawn. Several findings from recent literature are in consonance with the conclusions from
the author’s plots. Paucity of space restricts the discussion about conclusions with this equation by the
author here in this paper. Some of the prominent expectations of the recent trends are discussed below.
These shortcomings of the respective citations detailed above find a systematic explanation by the author
and are to be attributed mainly to the deficiencies in reckoning the electrical interactions, inside the ion-
atmosphere, around the central ion as the concentration increases Details are available at ref. Brahmajirao
et.al. [39]
Experimental and Calculations:
This paper reports the data, of our ultrasonic studies using Ultrasonic pulse echo technique similar to that
of Mc Clements & Fairley [18] in aqueous solutions of sulphates. Density measurements are made using
the bicapillary pyknometer. The conductance data was obtained using the ‘PHILIPS’ Conductivity Bridge
Model P.R.-9500 similar to the one used by Power et.al & Singh .et.al. [19] And Bikash Kumar Panda et.al
& Mishra et .al. [20]. . . The ionic polarisation effecting the Conductivity measurements is balanced the
usage of an inbuilt oscillator generating 1 KHz signal, applied to the bridge network as a whole The
experimental details for dielectric determinations are given else where [47] The ultrasonic, dielectric and
conductance data of the author were used in the calculations, using a programme, in “C-language” and
details of analysis of variations in thermodynamic parameters, are presented as graphs with C as
0
abscissa and φK2 & ( K 2 − K 2 ) , as ordinates separately.
Discussion of the results:
All the plots record conspicuous gradient changes corresponding to ,the formation of solvent separated,
solvent shared & contact pairs as envisaged by Eigen[21]and worked out by Eigen et.al., [22], entirely
different from the cited , previously reported results The qualitative details of the mechanism of formation
of ion pairs , is briefed below :
In the initial (first) stage an ion pair is formed with no disruption of the individual solvation sheaths of the
individual ions, so that in the ion pair these solvation sheaths of the individual ions are in contact and
solvent is present between the ions. In this stage the solvent co spheres are in contact , but the ions are
113 | P a g e
reasonably distant from one another Hence these are SOLVENT SEPARATED ION PAIRS .In this stage
the solvent co spheres are in contact, and the ions are reasonably distant from one another
In the intermediate (second) stage an ion pair is formed with partial disruption of the individual solvation
sheaths of the individual ions and there is still some solvent present between the ions so that the ions of the
ion pair share the solvent sheath between the ions .Hence these are called SOLVENT SHARED ION
PAIRS .Ion pairs formed in the first two stages are called outer-sphere ion pairs .In an outer-sphere ion pair
one, or at most two, solvent molecules lie between the ions, and the ions yet are not in contact .
In the last (third ) stage an ion pair is formed with total disruption of the solvation sheaths of the
individual ions so that in the ion pair the bare ions are in contact and there is no solvent between the ions.
Hence these pairs are called CONTACT PAIRS or inner sphere ion pairs .In an outer-sphere ion pair one,
or at most two, solvent molecules lie between the ions , but for an inner-sphere ion pair bare ions are in
contact and all solvent sheaths have been eliminated from between the ions.. However, both inner and
outer-sphere ion pairs are still solvated as the composite unit. The ion pairs which can be found are thus
not necessarily identical, and there is the possibility that different experimental methods may pick out and
detect only one kind of ion pair. In literature, the ultrasonic studies is probably the only tool to detect the
formation of all the three types
However as pointed by Margaret Robson Wright [23], ion pair formation totally differs from complex
formation when a complex is formed an intimate chemical interaction between the ions & electronic
rearrangement occurs resulting in covalent interactions, in contrast to the physical columbic electrostatic
interactions involved in the formation of an ion pair. Also the Ultrasonic and spectroscopic methods
probably allow a distinction to be made with reasonable certainty between outer and inner-sphere ion pairs,
while conductance work and scattering of light experiments allow micelle formation to be picked up very
easily. These are quite exceptional achievements in the field of ion association. Inferences made from
thermodynamic and kinetic experiments have often been used, but they rely very heavily on being able to
predict a model for the ideal solution, for which a theory is yet to be conceived.
This is being attempted by the author in the lines of. Larsen et al [29] and. Fennell [30] and others.
Gucker showed that from the [ C versus φK2 ] plots, lim φ K represents the reduction in the hydration
c →0
(v f − n1 v10 )
number. Because we can write lim φ K = β = - nh v10 β 0 in which n1 is the total number of
c →0 n2
molecules of water and n2 is the number of moles of electrolytes and nh is the hydration number which is
the number of water molecules in the primary hydration sheath round the central ion . The slope gradually
decreases for each plot, at three places, to reveal the reduction in the number of water molecules in the
primary hydration sheath of the ion pair.
Very recently Krishnan et.al [24].in his admittance studies of aqueous sodium chloride and NMR relaxation
rate of 7Li+ by Mn2+ or Ni2+ in aqueous solution , observed measurable difference for two models which are
consistent with other magnetic relaxation and thermodynamic data for the solutions. They reported
Enthalpy studies in electrolytes in methanol and dimethylformamide leading to similar observations .They
pointed out from their admittance studies marked evidences for the ion pair formation, exactly in tune to the
authors’ findings
Master ton et.al. [25] reported Conductivity data for solutions of [Co (NH3)5NO2] SO4 in water and aqueous
dioxan. Ion-pair association constants calculated. A plot of [logK A] vs. [1/D] is found to have a slope
considerably greater than that for simple 2:2 salts. A major factor contributing to enhanced association
appears to be ion-dipole interaction. However the effect of addition of electrolyte to the solvent is not
considered, therein... Fuoss [26] &Kraus et. al. [27] showed that the solvent with lower dielectric constant
favours ion-pair formation to a more marked degree. They showed that at the critical distance defined by
114 | P a g e
q = [( z1 z2 e 2 ) / 2 DkT ] , the potential energy of the ion pair is “2kT”. This fulfils the condition that the
energy required to separate the ion pair is comparable to the thermal energy. The decrement in the
dielectric constant nt makes the value of ‘q’ greater than the ionic diameter. An equation for association
constant was deduced, applying the method devised by Boltzmann to the equilibrium between ion pairs and
free ions. He obtained for the degree of association (1 − α ) = K Acα 2 f 2 , where c is concentration, f is
Debye-Huckel activity coefficient , α is the fraction of the (1-11 ) electrolyte present as free ions and K A is
the association constant .For 1-11 electrolyte he deduced K A = [4π Na 3eb ]/[3000] , in which a is ionic
diameter , b = e 2 / aDkT ,since [ z1=z2 ],D is the dielectric constant , k is Boltzmann’s constant , and T is
the absolute temperature . But the he solvent mixture is treated as a dielectric continuum, with no modification
attempted for accounting the solvent solute interactions, leading to the continuous variation of the dielectric
constant as the solute concentration gradually increases .Hence tthis his theory requires modification in the
light of the Glueckauff’s model. Consequently Fuoss’ equations fail to predict the behavior of the ion pairs
to a better extent .Several workers [27] in addition to Fuoss and Kraus [28] used mixtures of solvents
aqueousous as well as non aqueous and established the ion pair formation in each of them, exactly in the
same lines and hence Fuoss and Kraus theory was applied therein. However the fact that the dielectric
constants of the solvent continuum changes once the solu solute
te ions enter it is yet to be implanted into their
observations. Hence their observations are incompetent to explain the ion ion-solvent
solvent interactions Berman et.al
[29], in the N.M.R.Relaxation studies observed Contact ion association behaviour of per chlorate ion with
Li + and Mg 2+ in a variety of solvents .For Mg (ClO4 ) 2 in acetonitrile a combination of N.M.R. and
conductance data shows that the addition of a small amount of water causes transformation from fr contact to
Solvent separated ion pairs Larsen et al [30] studied the ion solvent interactions in relation to dependence
of Bjerrum length on several factors from the Restricted Primitive Model (RPM),, and rigorously worked out
MC simulations of Yukawa potential tential for several other models in vogue to establish several lapses in RPM.
A corresponding state between that of Yukawa case and unscreened coulomb case was conceived, from
which equivalent Bjerrum lengths in the coulomb potential, was correlated usin usingg classical molecular
dynamics simulations,
Fennell et.al [31] studied ion-ionion interactions in water. and the Potentials of Mean Force (PMF) for the full
set of alkali halide ion pairs, and in each case, we test different parameter sets are tested for modeling m
both the water and the ions. Several different PMFs were compared. Association equilibrium constants
(KA) were calculated and compared with two types of experiments. Collins "law of matching water
affinities",, about the relative affinity of ions in solution depending on the matching of cation and anion sizes,
was applied. From observations on the relative depths of the free energies of the contact ion pair (CIP) and
the solvent-shared
shared ion pair (SIP), along with related solvent structure analyses, they th found a good
correlation with the proposition that smallsmall-small and large-large
large should associate in water, and small-large
small
should be more dissociated. Work in the lines of Fennell et.al [27],, is in progress with the authors.
Kaatze et.al. [32] reported ultrasonic absorption spectra at frequencies between 300 kHz and 3 GHz
reported for aqueous solutions of MgCl2, CaCl2, SrCl2, NiCl2, and CuCl2 , many multivalent electrolytes, of
transition metals , of micelles and bilayers, and of small organic molecules.
molecules.They discussed such aqueous
systems for which measurements of the complex electric permittivity (103 Hz ≤ ν ≤ 1011 Hz) and of the
attenuation coefficient of acoustic waves (105 Hz ≤ ν ≤ 3·109 Hz) had been recently experimented over a
broad range of frequencies. cies. It is shown that, in many cases, the two spectroscopic methods can be
favorably used to yield complementary aspects of structural properties and of the molecular dynamics of
interesting liquid mixtures.All spectra reveal a Debye Debye-type relaxation term with small amplitude. The
relaxation time values derived from the spectra display a small range only (0.2 ns τ 0.6 ns),
corresponding with the τ values for solutions of Mg(NO3)2 and Ca(NO3)2 in water. The relaxation term is
115 | P a g e
suggested to be due to the second step in the Eigen Eigen–Tamm
Tamm scheme of stepwise association and
dissociation of ions, namely the equilibrium betw between
een the complex of encounter and the outer sphere
complex. The relaxation amplitudes reflect special properties of the ions. Exactly similar observations are
reported in our studies Recent ideas of the mechanism of dielectric relaxation in hydrogen bonded liquids
are discussed. Comparison is made with some aspects resulting from computer simulation studies..
Concurring views as the authors of this paper that in many cases, the two spectroscopic methods (dielectric
and ultrasonic) can be favorably used to yi yield
eld complementary aspects of structural properties and of the
molecular dynamics of interesting liquid mixtures were expressed. Gaiduk [33] suggested simple model of
dielectric response due to the three--dimensional motion of ions inside a spherical ideally reflecting sheath is
suggested. The present model termed the sphere sphere-confined
confined ionic (SCI) model is combined with the so called
hybrid model, previously used to describe dipolar orientational relaxation The wideband (up to 1000 cm−1)
complex permittivity (ω) and absorption α(ω) spectra of NaCl NaCl-water and KCl-water
water diluted solutions are
calculated as the sum of the contributions due to cations and anions and to reorientation of polar H2O
molecules. A modification of this model is al also
so suggested, in which the walls may also vibrate. Honggaing
Zhao et.al, [34] developed an “ Equation of state for electrolyte solutions by combining statistical
associating fluid theory & Mean Spherical Approximation for the non nonprimitive model” .A major
m fraction of
the interactions between different ingredients of the electrolytic solution ,are attempted to be accounted in
this . Specifically the Statistically A
Associating Fluid Theory for Variable Range ange potentials (SAFT-VR) that
describes long –range ( ion-ion ion ),( ion
ion-dipole ), and (dipole-dipole
dipole ) interactions ,is combined with the
nonprimitive MSA model, in performing the MC simulations . The model yet requires modifications, which
are aimed at by the author Wertheim [35], calculated the association on contribution, statistically, by a double
summation over all the possible sites, and species, accommodating for the fraction of the ions that indulges
in pair formation, at a given site .However the presumptions many times lead to unrealistic situations, and
hence demand more in depth pursuance. M. J. Blandamer, D.Waddington & J. Burgess et.al. [36] Very
recently examined the significance of the term ‘activity’ in the context of the properties of aqueous solutions
for aqueous solutions containing neutral solutes, mixtures of neutral solutes and salts, and also binary
aqueous mixtures... Properties
roperties of aqueous solutions binary aqueous mixtures from the standpoint of solute- solute
water and solute-solute
solute interactions, using pair wise interaction parameters are studied . With an increase
in the amount of solute, strong evidence is obtained for clustering of both aqueous and non-aqueous non
components. These trends are explained in terms of preferential solvation of initial and transition states
using Kirkwood-Buff integralal functions. The analysis is applied to kinetic data describing the dependence on
the ethanol mole fraction of the first order rate constant for the solvolysis of t-butyl butyl chloride in aqueous
solution. Work regarding the application of Kirkwood
Kirkwood-Buff integral
al functions, to the data reported in this
paper is in progress at the authors end Pitzer et.al.’s [37] semi empirical Equations, developed for activity
coefficient work.are used by Moggia et.al. [38] in a pseudo lattice approach using Gibbs-Duhem
Gibbs equation.
However a better alternative with a suitable modification , to develop MC Simulations ,using the Pitzer’s
formalism with its versatile extensions for the force field calculations using Molecular dynamics
simulations of ionic solutions is employ
employed by Fyta et.al., [39] ,by optimizing ionic force fields based on
single-ion and ion-pair
pair properties simultaneously for five different salt solutions, namely, CsCl, KCl, NaI,
KF, and CsI, at finite ion concentration. The force fields of these ions are sy systematically
stematically varied. From the
finite-concentration
concentration simulations, the pair potential is extracted and the osmotic coefficient is calculated,
which is compared to experimental data. They suggest that additional parameters are to be introduced
into the modeling,
ing, for better results The author is attempting this model for comparisons with parameters
obtained with ultrasonic data.
Choudhary et.al. [40] and Dougherty et.al. [41] [41]separately Calculated Entropic and enthalpy and excess
free energy contributions too the hydrophobic interaction between hydrophobic solutes and water using
molecular dynamics simulations in the isothermal
isothermal-isobaric
isobaric (NPT) ensemble with free energy perturbation
116 | P a g e
methodology. The stabilizing contribution to the free energy of association (contact pair formation) was
found to be the favorable entropic part, the enthalpy contribution being highly unfavorable. The desolvation
barrier is dominated by the unfavorable enthalpy contribution, despite a fairly large favorable entropic
compensation. The enthalpy term was decomposed into a direct solute-solute term, the solute-solvent
interactions term, and the remainder that contains pressure-volume work as well as contributions due to
solvent reorganization. The enthalpy contribution due to changes in water-water interactions arising from
solvent reorganization around the solute molecules is shown to have major contribution in the solvent
induced enthalpy change. Their observations require in depth application to more data. The data used
Dougherty et.al[41] with their model include: molecular orbital-molecular dynamics applied to electrolyte
water systems; Raman spectra; infrared spectra; magnetic resonance spectra of ions; the apparent density
of water; and the excess free energy of electrolytes in aqueous solutions. Molecular orbital-molecular
dynamics calculations of relatively large water clusters containing a molecule of sodium iodide show that
the solvent separated ion pair exists in a substantial potential well compared to other possible structures.
Raman spectra of univalent electrolyte solutions as a function of concentration can be quantitatively
modeled using only the spectra of pure water and electrolyte solution at the concentration of the solvent
separated ion pair. This information supplements the author’s observations
Buchner et.al [42], recently in his dielectric relaxation studies over a wide range of frequencies and
concentration ranges similar to those of the author recorded marked evidences of the simultaneous
existence of double-solvent-separated, solvent-shared, and contact ion pairs at all the ranges of
temperatures studied, with tendency for the formation of contact pairs to be more as the temperature
increases. Even our plots reported in this paper, with GKG parameters record gradient changes at more
than two or more places of formation of solvent shared ion pairs, and with nearly the same stability, since
the slopes at these formations corresponding to the value of SK is not much different. Buchner et.al, uses a
technique that restricts the thermodynamic analysis of the individual ion pair’s .They conclude that both the
ions influence solvent water molecules beyond the first hydration sphere. Soto et.al.,[43]developed a model
based on the Pitzer et.al’s. [37] formalism developed in a series of papers to correlate the activity
coefficient, apparent molar volume and isentropic compressibility of aqueous solutions of electrolytes ,
based on detailed experimentation wit ultrasonic techniques . The results show that the model can
accurately correlate the interactions in aqueous solutions of glycine and NaCl. A positive transfer volume of
glycine from a NaCl solution to a more concentrated NaCl solution indicates that the size of a glycine
molecule is larger in a solution with higher NaCl concentration. The negative values of apparent isentropic
compressibility imply that the water molecules around the glycine molecules are less compressible than the
water molecules in the bulk solution. These effects are attributed to the doubly charged behavior of glycine
and to the formation of physically bonded ion-pairs between the charged groups of glycine and sodium and
chloride ions. The formation of ion-pairs, whose extents of binding reactions depend on the concentrations
of both NaCl and glycine, alter the hydration number of glycine. This also explains the reason for the
increase in the size of glycine with an increase in the NaCl concentration. Wang et.al. [44] Studied, the
thermodynamic properties, like the mean activity coefficient, osmotic coefficient, and water activity,etc. for
129 complex aqueous electrolyte solutions using the modified three-characteristic-parameter correlation
model., which considers ion association in a betterway, incorporating solute solvent interactions through
thermodynamic parameters . This model is being worked out and the out come will be published soon
elsewhere, because the technique is other than ultrasonic in nature. Wang et.al. also calculated the
adjustable parameters of the Pitzer model and the Bromley model. and established that their modified
model is fairly suitable for predicting the mean activity coefficient, osmotic coefficient, and water activity of
these electrolytes, incorporating several interactions. This new model is much better than the Bromley
model and shows a better result than the Pitzer model. especially for 3–1 and 3–2 electrolytes. Work on
117 | P a g e
chlorides and sulphates and nitrates in aqeous and nonaqeous solvents and observations about
thermodynamic and ion association parameters and other related evaluations by the author is available
else where at [45] reference
REFERENCES:
(1)ROBINSON&STOKES“Electrolytic solutions“(second revised edition), DOVER publications NEWYORK, page231, chapter 9,”
The limiting law ….Huckel “(2002); (2) HASTED et.al. J.Chem.Phys 16 1(1948). (3) GLUECKAUFF Trans.Faraday.Soc. 60
1637, 572(1964); “Digest of literature on dielectrics “....Nat. Acad, Of Sci., National research council Washington .D.C.; VON
HIPPEL “Dielectric materials and applications “, The Technology press, M.I.T., Massachusetts, U.S.A. (1954); (4) BUCKINGHAM
Disc.Faraday.Soc. 24 151(1957) ;( 5) GUCKER J.Amer.Chem.Soc 55 2709(1933) ; Chem .Revs 15 111(1933). ;( 6) GUCKER
& BACHEM (1936) Zeits.F.Physik.101 541, Z.Electrochem. 41 570;(7) HARNED & OWEN “The Physical Chemistry of
Electrolytic solutions “, Reinhold publishers, ;New York (U.S.A.) (1958);(8) KRISHNAMURTY, J. Sci.Ind.Res 9B 215(1951) ;
Ibid10B 149;(9)B.R.RAO& K.S.RAO, J. Sci. Ind. Res. 17B 444(1958);(10) MARKS J. Acous.Soc.Amer. 31 936(1960) ;( 11)
BHIMASENACHAR & SUBRAMANYAM J. Acous.Soc.Amer. 32 835(1960); (12) PADMINI& RAO Ind. J .Phys. 34 565(1960)
;( 13) W.P.MASON “Physical Acoustics”, Vol-II, Chapter 6, page 426; Academic press, New York & London (1965) ;( 14)
GIACOMINI et.al. Ricerca. Sci. 11 606(1940). (15) PROZOROV Zhur.Fiz.Kim. 14, 384. 391(1940); (16) BARNART
J.Chem.Phys.20 278(1952). ; (17) GRAHAM KELL &GORDON J.Amer.Chem.Soc 79 2352(1957) ;( 18) McCLEMENTS &
FAIRLEY Ultrasonics, 29 (1) Pages 58-62. (1991); (19)POWER et.al, ‘Complexes of 8-Amino-2-methylquinoline with cobalt
(II)’ Australian Journal of Chemistry 25(9) 1863 – 1867(1972); SINGH et.al. (1976) Can. J. Chem., 54, 1563; Ibid,
Inorganic.chem. (1981) 20(8) 2711-2713; (20) PANDA et.al. ‘European Journal of Inorganic Chemistry’ 2004 (1) 178 – 184
(2004); MISHRA et.al. Can. J .Chem. 45 2459- 2462(1967); (21) EIGEN Z.Phys.Chem.Frankfurt vol. 1 176; Discussions
.Faraday.Soc.24 25 (1954). ;(22) EIGEN & De MAYER(1963) “Investigation of rates and mechanisms of reactions in
“Techniques of Organic Chemistry “, vol VIII, Part 2, Chapter 18, Interscience, New York, ; (23) MARGARET ROBSON
WRIGHT: “An Introduction to Aqueous Electrolyte Solutions” Art.1.12 Formation of Ion pairs from free ions, page 17, John Wiley
& Sons Ltd, The Atrium, Southern Gate, Chi Chester, West Sussex PO19 8SQ, England (2007) ;(24) KRISHNAN et.al Int
.J.Electrochem. Sci. 2(2007) 958-972; Chemical Physics Letters (1973), 20 (4) Pages 391-393; J. Phys. Chem., (1971) 75
(23), pp 3606–3612; (25) MASTERTON et.al. J. Sol. Chem. 5(10) 721-731 (1976); (26) FUOSS (1958): “Ionic
Association.III.The Equilibrium between Ion Pairs and Free Ions”, J. Am. Chem. Soc., 80 (19), 5059–5061, ;( 27)
KRAUSet.al. “Mechanisms underlying the equilibrium reactions between ions and ion pairs” In ‘Solutions of electrolytes, II The
effect of temperature “Proc Natl Acad Sci U S A. (1963) 49(2):141-6.Kraus et.al. (2006) “Mechanisms underlying the equilibrium
reactions between ions and ion pairs in Solutions of electrolytes, I Solutions in p-Xylene and Benzene Interactions between
benzene, Toluene, and p-xylene (BTX) during their biodegradation. ...” J Phys Chem. B. (2006)110(30):14961-70 ;( 28) FUOSS
and KRAUS J.Amer.Chem.Soc, 551019and21dioxan-water mixtures (1933)); JONES et.al Ibid 76 3247, aceticacid (1954);
HNIZDA et.al, Ibid 71 1565, liquid ammonia (1949); El-AGGAN et.al, J.Chem.Soc. 2092 ethanol (1958); GOVER. et.al,
J.Phys.Chem 60 330, n-propenol (1956); HIBBARDet.al, J.Amer.Chem.Soc. 77 225, ethylenediamine (1955); REYNOLDS et.al;
Ibid 70 1709 acetone (1948); BURGESS et.al, Ibid 70 706 pyridine (1948). ;( 29) BERMAN et.al “Contact ion association of
perchlorate ion. Chlorine-35 nuclear magnetic resonance study. II. Solutions in mixed solvents”, J. Phys. Chem., 79 (23),
2551–2555(1975); (30) LARSEN et al J Chem. Phys. 65 3431(1976); Ibid (1978) J Chem. Phys. 68 4511(1978); Ibid (1974)
Chem.Phys. Letters 27 47 (1974); Ibid (1980) J Chem. Phys. 72 2578(1980); Ibid (1974) J Chem. Phys. 7 530 (1977); (31)
FENNEL et.al J Phys Chem. B.; 113(19) :6782-91 (2009):. ; (32) KAATZE et.al. Chemical Physics Letters, 384(4-6), PP 224-
228(2004) ; KAATZE& POTTEL (1992) J. Mol. Liquids, 52, PP 181-210; Ibid (1991) J. Mol. Liquids, 49 PP225-248;(33)GAIDUK
“Dielectric Relaxation and Dynamics of Polar Molecules “published by World Scientific, Singapore Gaiduk (2000) J. Mol. Liquids,
80(1-3) PP81-10(1999)9 ; (34) HONGGAING ZHAO et.al J.Chem.Phys.126 244503 (2007); Ibid (2006) J.Chem.Phys.125
4504(2006) ; (35) WERTHEIM, J. Stat. Phys. 35 19, 35, (1984); 42, 459, 477 (1986);;(36) BLANDAMER & .BURGESS,”
Interaction and Activation in Aqueous mixtures “ ColloidsandSurfaces, 48, (1990), Pages139-152; BLANDAMER et.al. Advances
in Molecular Relaxation Processes, 5(4), pp333-338(1973), BLANDAMER et.alAdvances in Molecular Relaxation Processes,
2(1), pp1-40 (1970), ; Ibid . J.Molecular.Liquids (1992), 52, (1), PP15-39; BLANDAMER et.al (2005), Chem. Soc Rev. 34(5):
440-58 (2005), ;( 37) PITZER et.al.J. Phys. Chem., 77, 268 (1973); Ibid J. Am.Chem. Soc, 96, 5701 (1974); Ibid J.Solution
Chem., 18, 1007(1989); Ibid (2010) Molecular Structure and statistical Thermodynamics Selected papers of Kenneth S Pitzer’
(2010) World Scientific, Singapore Ion interaction approach: Theory and data correlation.’ In: Activity Coefficients in Electrolyte
Solutions. 2 – Editor: Pitzer KS, Boca Raton, Florida, USA: CRC Press; 1991. pp. 75–153. ;( 38) MOGGIA et.al. J Phys Chem.
B. (2008); 112(4):1212-7; Ibid J Phys Chem. B. 111(12): 3183-91(2007).;(39) FYTA & NETZ et.al. J Chem. Phys. 132(2):
024911(2010). ;( 40) CHOUDHURY et.al. J Phys Chem. B. 110(16) 8459-63 (2006).;(41) DOUGHERTY et.al. Biophys. Chem.
105(2-3) pp: 269-78(2003). (42) BUCHNER et.al J Phys Chem. B. 110(30) (2006): 14961-70.; (43) SOTO et. al.,
Biophys.Chem. 74(3) 165-73(1998); SOTO et. al “Effect of cation …. Of an electrolyte on apparent molar volume, isentropic
118 | P a g e
Compressibility…… in aqueous solutions”, Biophys Chem. (1999) 76(1): 73-82. ;( 44) WANG et.al J. Chem. Eng. Data,
(2004) 49 (5), pp 1300–1302 ;( 45) BRAHMAJIRAO Ind.J.Pure. Appl .Phys. 14 646(1976) ; Ibid (1979), “Cationic motilities of
electrolytic solutions – Ion pairs –EIGEN mechanism” Transactions. Of. Saest, 14 (2) (1979) 53; Ibid (1980), Ind. J. pure &
Appl. Phys. 18 12 (1980) 1021; Ibid (1980), “Influence of variation of Dielectric constant.Gucker’s equations…” Proceedings of
International Conference on Ultrasonics, ICEU-July 1980, Held at New Delhi. INDIA; Ibid (1980) “Application of ….. Variation of
Dielectric.....GKG and Dagget equations “, Proceedings of International Conference on Non Aqueous Solutions, ICNAS-7, held
at REGENSBERG, West Germany. (Aug 1980); Ibid (1981), Ind. J.Pure & Appl. Phys. 19 (1981) 254; Ibid “Application of
Glueckauff’s model for depression in Dielectric …..Ion pair formation”, Proceedings’ of ‘ULTRASONICS INTERNATIONAL-81’,
held at Brighton, U.K 30th JUNE to 2 nd JULY 1981;Ibid “Analysis of solute- solvent interactions …in relation to ion pair
formation”, Proceedings’ of International Symposium on Electro analytical Chemistry Held at Chandigarh, INDIA December1982.
;Ibid “Study of …in chosen electrolyte solutions “, Proceedings’ of Sir J.C.Ghosh memorial Symposium, held at Calcutta, INDIA,
Feb1982; Ibid “Electrostatic Potential energies of Ion pairs in nonaqeous media from Ultrasonic measurements”, Proceedings
of Eigth International Conference on Nonaqueous Solutions, Nantes (Cedex) FRANCE, 19th to 23 rd July 1982;;Ibid “Ultrasonic
studies in solute solvent interactions…..Ionpairs”Procedings of ICNAS-IX, Held at Pittsburgh, Pennsylvania, U.S.A. in August
1984; Ibid “Solute –Solvent interaction and Ion pair formation in the light Of depression in Dielectric Constant” Proceedings of
VIth International Symposium on Solute –Solvent – Solute Interactions, Tokyo, JAPAN, July1982.; Ibid “Application of
Glueckauff’s model of variation of dielectric Constant to association constant - Calculations in relation to Ion pair Formation “,
Proceedings of 2nd International symposium on Industrial and Oriented Electrochemistry, Held at Karaikudi, INDIA (Dec
1980).;(46) V. M. M. Lobo “Handbook of Electrolyte Solutions”, “Elsevier Science Ltd” (1990); (47) Hasted et.al. J.Chem.Phys
16 1. (1948)
COPPER
COBALT
1.32 1.32
Solvent shared pairs Solvent shared pairs

1.315 1.35
1.31 1.31
1.305 1.305
Contact pairs Contact pairs

1.3 1.3
1.295 1.295
1.29 Solvent separated pairs 1.29
1.285 1.285
Solvent separated pairs
1.28 1.28
0.132 0.137 0.142 0.147 0.152 0.157 0.162 0.167 0.172 0.177 0.135 0.14 0.145 0.15 0.155 0.16 0.165 0.17
119 | P a g e
120 | P a g e
1
0.
0.1
0.
0.
0.
0.
0.0
0.
0.
0.
0.
0.0 0. 0. 0. 0. 1. 1.
20. 0. 0. 0. 0. 0. 1 1. 1. 1.
4 5 6 7 8 9 1 2 3
c With ‘C’ in gm moles per
litre
121 | P a g e
TEMPERATURE VARIATION ULTRASONIC VELOCITY IN COW MILK
AT DIFFERENT FREQUENCIES
Kailash, S. N. Shrivastava* and Poonam Yadav

Department of Physics, B N P G College, Rath, Hamirpur, U.P.
* Department of Chemistry, Bipin Bihari Post-Graduate College Jhansi, U.P.
Email: kailashrath@gmail.com
Milk is considered as an essential food constituent for a foremost segment of population. The present day
need is for development of simple reproducible, Sensitive, Cost effective and fast methods for analysis of
milk and milk products so that generated information can be effectively utilized for human health. Quality
Control may be defined as the operational techniques and activities that are used to fulfill requirement for
quality. It revolves around the assessment of specific product and process attributes to confirm standards
and specifications Very tiny work has been done to study the quality of milk using ultrasonic techniques.
This has motivated us to undertake the present study. In this paper, we have made detailed investigations
of ultrasonic wave velocities in pure milk of Cow at different temperatures using multi frequency ultrasonic
interferometer. The ultrasonic velocity decreases as temperature increases.
INTRODUCTION
The major constituents of milk are water, fat, protein, lactose, ash or mineral matter. The colour of milk is
due to the scattering of light by the fat globules, casein molecules, colloidal calcium phosphate and to some
extent by the pigments caroteine and riboflavin (Walstra and Jenness, 1984). Milk ranger in colour from
yellowish creamy white to creamy white to creamy white depending upon type of milk. The intensity of
yellow colour of cow milk depends upon size of the fat globules and fat percent, apart from breed and feed
(Harper and Hall, 1979). To reduce the fat globules, milk is homogenized. After homogenization, milk
creams very slowly, but is alos altered in other aspects. All sterlised milks or, more generally, all long-life
liquid milk products, are homogenized in practice. The purpose of homogenization usually is not to make,
but to keep a product homogeneous (Jenness and Patton, 1959). The main effect is the disruption of fat
globules into smaller ones, which slows down creaming (Burton, 1954). Milk also cantains certain enzymes,
which are of different types, and are inactivated by heat. The caroteines, which are present in the milk,
impart a yellowish tint. Usually, the extent of colour depends on the ability of the cow to convert caroteine
into vitamin A (Paterson, 1950). These colours depend on the amount of caroteine present in the
122 | P a g e
milk. The product examines sensory and nutritional quality of cow's milk and addresses quality
improvement of a range of other milk-based products. The quality of milk reviews the health aspects of milk
and its role in the diet, as well as the essential aspects of milk quality, including microbial spoilage and
chemical deterioration, sensory evaluation and factors affecting milk vitamin and mineral
content. We discusses various application requirements of milk such as milk quality requirements in
yoghurt-maiking, cheese making, infant formulas and applications of milk components in products other
than foods. Consumers demand quality milk with a reasonable shelf-life, a requirement that can be met
more successfully by the milk industry through use of improved processes and technologies. Guaranteeing
the production of safe milk also remains of paramount importance. Improving the safety and quality of milk
provides a comprehensive and timely reference to best practice and research advances in these areas.
The sensory and nutritional quality of cow’s milk and addresses quality improvement of a range of other
milk-based products. The health aspects of milk, its role in the diet and milk-based functional foods. Part
two reviews essential aspects of milk quality, including milk microbial spoilage and chemical deterioration,
sensory evaluation, factors affecting milk vitamin and mineral content and the impact of packaging on
quality. Chapters in Part three look at improving particular products, such as organic milk, goat milk and
sheep milk. The impact of milk on the quality of yoghurt and cheese is also covered. (Griffiths, M. 2010).
Milk is considered as an important food ingredient for a major sector of population. The present day need is
for development of simple reproducible, Sensitive, Cost effective and fast methods for analysis of milk and
milk products so that generated information can be effectively utilized for human health. Traditionally, the
dairy industry has ensured the quality of its products by employing inspection and test methods managed
under the banners of ‘Quality Control’ and ‘Quality Assurance’. In the newer context, the transition in
concept and organizational structure has moved from Inspection to Quality Control to Quality Assurance to
Continuous improvement and finally to Total Quality Management. Quality Control may be defined as the
operational techniques and activities that are used to fulfill requirement for quality. It revolves around the
assessment of specific product and process attributes to confirm standards and specifications have been
met. In its application Quality Control may become synonymous with the inevitability of product failure,
particularly when it is mainly concerned with final product analysis. The technical requirements during dairy
product distribution network must be considered by the organization for safe marketing and be included in
the quality manual as operational guide. The information on packaging, storage/ warehousing,
transportation, retailing, nature of products, marketing conditions etc. must be obtained and recorded for
periodical assessment and inducing further improvement in the system. The white colour of milk is an
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expression of good qualities in which etiquette does not alter and thereby colours do not lose their identity
in the white. It is the milk in which reside the rhythms and poetry, as well as the colours merge in the white.
The molecular assembly in milk which results in whiteness’ ensures not only its purity, but also rejuvenates
the hope of good nutrition. Once quality of milk is assured, it will make people pure and free from disease.
Therapeutic advances for microbial infections raise expectations that science is on the verge of
understanding all manners of pathogenic microbes and their associated illness.
MEASUREMENTS
The multi frequency ultrasonic interferometer consist of the two parts- the high frequency generator and the
measuring cell. The range of multi frequency ultrasonic interferometer is 1-7 MHz. The high frequency
generator is designed to excite the quartz plate fixed at the bottom of the measuring cell at its resonant
frequency to generate ultrasonic waves in the experimental liquid in the “measuring cell”. A micro ammeter
to observe the changes in current and two controls for the purpose of sensitivity regulation and initial
adjustment of micro ammeter is provided on the high frequency generator. The measuring cell is a specially
designed double walled cell for maintaining the temperature of liquid constant during the experiment. A fine
micrometer screw has been provided at the top, which can lower or raise the reflector plate in the cell
through a known distance. It has a quartz plate fixed at its bottom the ultrasonic interferometer may be
used for determination of ultrasonic velocity in electrolytic and non-electrolytic solutions sound absorption in
medium observing liquid, adiabatic compressibility and internal, pressure, a cortical and thermodynamic
properties. Reaction rates and formulation of complexes, excess enthalpies of binary and trinary systems,
excess properties of binary and ternary systems, latent heat of vaporization of liquids ultrasonic behaviour
in liquid crystals molecular relaxation parameters, insolvent interaction, acoustic properties of substances
near the critical and freezing temperature sinter molecular interaction, chemical and structural nature of
liquid, phase, transition study in liquids, viscous-effects, excess volume and free volume. The measuring
cell is connected to the output terminal of the high frequency generator through a shielded cable the cell is
filled with the experimental liquid before switching on the generator the ultrasonic waves moves normal
from the crystal till they are reflected back from the movable plate and the standing waves are formed in the
liquid between the reflector plate and the quartz crystal. The micrometer is slowly moved till the anode
current meter on high frequency generator shows a maximum. A number of maximum readings of anode
current are passed on and their ‘n’ is counted the total distance (d) thus moved by the micrometer gives the
value of wavelength (λ) with the help of the following relation:
124 | P a g e
d = n× λ /2 (1)
Once the wavelength (λ) is known the velocity (v) in the liquid can be calculated with the help of following
relation:
V= λ ×f (2)
Earlier we have introduced the significance of milk quality. A review of literature on ultrasonic studies
reveals that ultrasonic velocity measurement is used to understand the nature of milk velocity. The
Temperature variation of cow milk is effectual its nutrition quality so our aimed is to find at the Temperature
in pure milk. For this purpose we have take the pure milk of different animal. On using the measurement
techniques presented above, the ultrasonic wave velocities at different Temperature variation are given in
Table I using the data of Table 1. The Equation between velocity and temperature are shown in the Table
II. We have made detailed investigations of ultrasonic Wave velocities in cow’s milk at different
temperatures using multi frequency ultrasonic interferometer (1-7 MHz). The graphs have been plotted
between Temperature and velocity shown as in Figs. 1-7. It is clear from Table and Figs. one can state that
the ultrasonic velocity is decreases as Temperature variation one may say that the higher velocity is the
indication of purity of milk. The present day need is for development of simple reproducible, Sensitive, Cost
effective and fast methods for analysis of milk and milk products so that generated information can be
effectively utilized for human health.
REFERENCES
1. Burton, H. 1954. Colour Chenges in Heated and Unheated Milk I, JI. of Dairy
Res. 21:194.
2. Jenness, R. and Patton, S. 1959. ncipal of Dairy Chemictry, Jhon Wiley and
Sons. 340- 357.
3. Harper, W. J. and Carl W, Hall. 1979. Dairy Technology and Engineering,
Westport, AVI Publishing CO. inc
4. Paterson, W.e. 1950. Dairy Science: Its Principles and Practice, 2nd Ed.,
Chicago, J. B. Lippincot Co.: 519-128.
5. Walstra, P. and jenness, R. 1984. Dairy Chemistry and Physics, New York,
Wiley and Sons: 160-167.
125 | P a g e
6. Griffiths, M. 2010. Improving the safety and quality of milk improving
quality in milk Products. Russian Agricultural Sci.2: 528.
7. Ganguli N.C., An odyssey on milk quality, Indian Dairyman, 54 (2002) 47-50.
8. Sharma R., and Rajput Y.S., Chemical quality of milk its relevance in present situation, Indian
Dairyman, 54 (2002) 71.
9. Dhamendra B.V., Kumar C. G., and Kohli R.K., Significance of ultrasonics in food industry-an
overview, Indian Dairyman, 52 (2000) 21.
10. Venkatesh P.V., and Singh A., Efficiency of additive and multiplicative correction factors for milk
yield in karan fries cattle , Indian journal of dairy science,56 (2003) 320.
11. Singh M., Lodhi R. S., and Nair S., Milk production and reproductive performance of muraha
buffaloes hormonally induced in to lactation, Indian journal of dairy science,55 (2002) 30.
12. Ganguli N. C., An odyssey on milk quality, Indian dairyman, 54 (2002) 47.
13. Sharma R., Rajput Y. S., Chemical quality of milk its relevance in present situation, Indian
dairyma, 54 (2002) 71.
14. Murthy G. L. N., and Kanawjia S. K., Designer milk nutritional and technological significance,
Indian dairyman, 54 (2002) 49.
15. Narang I. K., Our scriptures on cow milk, Indian dairyman 54 (2004) 41.
16. Bhattacharya T.K., Improvement of quality of milk constituents by r DNA technology, Indian
dairyman, 54 (2001) 33.
17. Gupta S., Gaudugdh piye sau sal jiye, Kamdhenu Kripa, Lucknow, October (2005) 3.
18. Dube V., Gay ka doodh hi amrat kyon, Kamdhenu Kripa, May (2006) 8.
19. Garg A., Gau vansh poshan avam swasthya, Kamdhenu Kripa, January (2007) 13.
Table I. Temperature variation of Ultrasonic velocity in cow milk
1MHz 2MHz 3MHz 4MHz 5MHz 6MHz 7MHz

T(0C) V(m/s) T(0C) V(m/s) T(0C) V(m/s) T(0C) V(m/s) T(0C) V(m/s) T(0C) V(m/s) T(0C) V(m/s)
28 1622.8 28 1538.0 28 1479.3 28 1415.6 28 1324.5 30 1250.4 28 1211.0
30 1609.7 30 1510.8 30 1428.0 32 1355.2 30 1299.0 32 1195.8 30 1189.3
126 | P a g e
32 1599.6 32 1490.6 33 1385.7 36 1302.8 34 1218.5 34 1129.2 33 1062.6
34 1589.5 36 1480.4 36 1370.4 40 1262.4 38 1188.0 36 1075.2 37 1041.6
38 1574.4 40 1472.4 40 1337.7 42 1234.4 42 1127.5 40 984.0 42 978.6
42 1562.4 46 1458.2 42 1304.1 46 1194.8 46 1082.0 44 935.4 46 907.9
47 1544.6 48 1436.0 48 1282.8 48 1158.4 48 1036.5 48 886.8 48 830.2
Table II. Equations showing relationship between V (m/s) and T (0C)
S. No. Freq. (MHz) Equation
1. 1 V = 0.0078*T3 + 0.96*T2 - 42*T + 2.2*103

2. 2 V = -0.00036*T5 + 0.049*T4 - 3.7*T3 +1.4*102 T2 - 2.7* 103*T+2.3*104
3. 3 V = 0.001*T5 - 0.18*T4 + 12*T3 - 4*102T2 + 6.6*103 T-4.1*104
4. 4 V = -0.00024*T5 + 0.045*T4 - 3.3*T3 + 1.2*102T2 - 2.2*103 T+1.8*104
5. 5 V = 0.00027*T5 - 0.053*T4 + 4.1*T3 - 1.6*102 T2 + 2.9*103 T2*104
6. 6 V = 0.0077*T4 + 1.2*T3 - 6.8*T2 + 1.7*103T - 1.3*104
7. 7 V = 0.0014*T5 - 0.28*T4 + 2.1*T3 - 8*102T2 + 1.5*104 T - 1.1*105
Figure1: Frequency Variation of Ultrasonic Velocity in cow milk 1MHz Figure2: Frequency Variation of Ultrasonic Velocity in cow milk 2MHz
1630 1540
Velocity Velocity
1620
1520
1610
Ultrasonic Velocity in m/sec
1600 1500
1590
1480
1580
1570 1460
1560
1440
1550
1540 1420
28 30 32 34 36 38 40 42 44 46 48 28 30 32 34 36 38 40 42 44 46 48
Temperature degree centigrate Temperature degree centigrate
127 | P a g e
Figure3: Frequency Variation of Ultrasonic Velocity in cow milk 3MHz Figure4: Frequency Variation of Ultrasonic Velocity in cow milk 4MHz
1480 1450
Velocity Velocity
1460
1400
1440

1420
1350
1400
1380 1300
1360
1250
1340
1320
1200
1300
1280 1150
28 30 32 34 36 38 40 42 44 46 48 28 30 32 34 36 38 40 42 44 46 48
Figure6: Frequency Variation of Ultrasonic Velocity in cow milk 6MHz

Figure5: Frequency Variation of Ultrasonic Velocity in cow milk 5MHz 1300
1350 Velocity
1250
1300
1200
1250 Velocity
1150
1200
1100
1050
1150
1000
1100
950
1050 900
1000 850
28 30 32 34 36 38 40 42 44 46 48 30 32 34 36 38 40 42 44 46 48
Figure7: Frequency Variation of Ultrasonic Velocity in cow milk 7MHz

1250
Velocity
1200
1150
1100
1050
1000
950
900
850
800
28 30 32 34 36 38 40 42 44 46 48
Temperature degree centigrate
128 | P a g e
ULTRASONIC STUDY OF SOME ORGANIC PATHOLOGICAL COMPOUNDS
Kailash1, S. K. Shrivastava2 and Jitendra Kumar3
1. Department of Physics, BN PG College, Rath, Hamirpur, U.P., 210 431, India
2. Department of Physics, Bundelkhand University, Jhansi, U.P, 284 128, India
3. Department of Physics, Govt. Girls P. G. College, Banda, U.P., 210 001, India
Email: kailash.rath@yahoo.co.in, jitendra_sharma50@yahoo.com
ABSTRACT: The use of organic compounds in managing of pathology has increased in recent
years, as adjunct therapy and alternative medicine. Extensive ultrasonic study about some organic
pathological compounds has been reported in the recent past by some investigators to ensure their
characterization and perfect use in medical industry. In this work the measurement of frequency-
dependent ultrasonic wave velocity in these organic pathological compounds have been done from
1-8 MHz. One of the characteristic of these organic pathological compounds, ultrasonic wave
velocity is measured at room temperature using interferometric technique at different ultrasonic
frequencies. Multi frequency ultrasonic interferometer is used for measuring ultrasonic wave
velocity in pure Ethyl Acetate, Aniline, Xylene, Acetaldehyde, and Sucrose. The measured data
(frequency variation of ultrasonic wave velocity) has been tabulated. The graphical representation
of the data has also been given. Interpretation of data shown in graphs is presented through curve
fitting and has been discussed widely.
KEYWORDS: Pathological, Antibiotics, Ultrasonic interferometer, Herbicides Pigments, Ultrasonic
velocity.
1 Introduction:
Ultrasonic velocity has become a valuable tool for the study of various physical and chemical
properties of the matter [1]. The acoustical properties, compressibility, impedance and viscosity evaluated
from ultrasonic velocity and density measurements have been used to elucidate the structure and the
nature of molecular interaction in aqueous and non-aqueous solutions [2]. Elastic constants of isotropic
solid can be determined ultrasonically when both longitudinal and transverse wave velocities are known [3].
Ethyl acetate is used for the concentration and purification of antibiotics. It is also used as an
intermediate in the manufacture of various drugs [4]. Aniline is the simplest and one of the most important
aromatic amines, being used as a precursor to more complex chemicals [5]. In addition to its use is as a
129 | P a g e
precursor to dyestuffs, such as paracetamol. Xylene is used as a solvent and in the printing, rubber and
leather industries and as a cleaning agent for steel and for silicon wafers and chips, a pesticide thinner for
paint and in paints as varnishes [6]. Acetaldehyde is a significant constituent of tobacco smoke. It has been
demonstrated to have a synergistic effect with nicotine, increasing the onset and tenacity of addiction
to cigarette smoking, particularly in adolescents [7]. People who have a genetic deficiency for the
conversion of acetaldehyde into acetic acid may have a greater risk of Alzheimer's disease. It is used in
medicine as a hypnotic. Sucrose is by far the most important disaccharide which is widely distributed in
plants especially in sugar cane sugar beet and sugar maple [8]. The aim of this work is to study the
characterization of these organic pathological compounds using ultrasonic techniques.
2 Measurement Technique:
The ultrasonic interferometer is simple in construction and operation and gives accurate and
reproducible results. From these results, one can readily determine the velocity of sound in a liquid with
high accuracy [9-11]. In our experimental work we use multifrequency interferometer which can generate
ultrasonic waves of several frequencies from 1 - 12 MHz in the medium. The multi frequency ultrasonic
interferometer consists of two parts, the high frequency generator and the measuring cell. The high
frequency generator is designed to excite the quartz plate fixed at the bottom of the measuring cell at its
resonant frequency to generate ultrasonic waves in the experimental liquid in the measuring cell. A micro
ammeter to observe the changes in current is provided on the high frequency generator. A fine micrometer
screw has been provided at the top to lower or raise the reflector plate in the cell through a known distance.
It has a quartz plate fixed at its bottom the ultrasonic interferometer may be used or determination of
ultrasonic velocity. The measuring cell is connected to the output terminal of the high frequency generator
and is filled with experimental liquid. On switching on the generator the ultrasonic waves moves normal
from the crystal till they are reflected back from the movable plate and the standing waves are formed in the
liquid in between the reflector plate and the quartz crystal. The micrometer is slowly moved till the anode
current meter on high frequency generator shows a maximum. A number of maximum readings n are
taken. The total distance d moved by the micrometer gives the value of wavelength λ with the help of the
relation d= n. λ/2. Once the wavelength is known the ultrasonic velocity v of the compound can be
calculated with the help of the relation V= λ.f .
3 Evaluation:
One of the characterizations of organic compound, velocity is measured at room temperature using
interferometric techniques at different ultrasonic frequencies (1-6 MHz and 8-9 MHz). Multi frequency
130 | P a g e
ultrasonic interferometer is used for measuring ultrasonic wave velocity in Ethyl Acetate, Aniline, Xylene,
Acetaldehyde, and Sucrose. The measured data (frequency variation of ultrasonic wave velocity) are
shown in Table 1. The graphical representation of the data is also given in Figs. 1-5. The coefficients of the
best fit polynomials of data shown in these figures are presented in Table 2.
4 Results and discussions:
The variation of ultrasonic wave velocity with frequency for Ethyl Acetate is presented in Fig 1. It is
clear from figure, that with increase in the frequency of ultrasonic wave, the velocity increases. From 3-5
MHz frequency, decrease in velocity is observed and at 6 MHz frequency, there is a highly increase in
velocity of ultrasonic wave and for 8-9 MHz an increase in velocity is observed. The variation of ultrasonic
wave velocity for Aniline is presented in Fig 2. It is clear from the figure that up to 2 MHz velocity increases
with increase in frequency. At 3-4 MHz frequency, there is a slight decrease in velocity. At 5 MHz frequency
it increases slightly and at 6 MHz it decreases slightly. At 8 MHz it again decreases and becomes
1412.8m/s which is less than the ultrasonic velocity of water 1509m/s. The variation of ultrasonic wave
velocity for Xylene is presented in Fig 3. It is clear from the figure that at 1-2 MHz velocity increases with
increase in frequency. At 3-4 MHz frequency, there is a slight decrease in velocity. At 5 MHz frequency
there is a slight increase in velocity and for 6 MHz it again decreases. For 8 MHz frequency there is a
highly increase in velocity. The variation of ultrasonic wave velocity for Acetaldehyde is presented in Fig 4.
It is clear from the figure that for 1-3 MHz velocity increases with increase in frequency. For 4 MHz
frequency there is a highly decrease in velocity. At 5 and 6 MHz frequency there is a slight increase in
velocity. At frequency 8 MHz the velocity decreases highly to 1382.4m/s. The variation of ultrasonic wave
velocity for Sucrose is presented in Fig 5 . It is clear from the figure that at 1-4 MHz velocity slight
increases with increase in frequency. At 5-8 MHz frequency increase velocity increases highly. The table
shows that as well as on incensement frequency velocity increases. For Sucrose the ultrasonics velocity
increases with increasing frequency. The ultrasonic velocity of Sucrose is more than the ultrasonic velocity
of water that is 1509 m/s, this is because of density, because the density of Ethyl Acetate is much more
than density of water.
These studies can also be used to determined the extent of complexation and calculate the stability
constants of these compounds [12]. Experimental findings shows that ultrasonic wave velocity is not
increasing linearly with frequency, the result shows a slightly deviation from the ideal case but over all
these show that with increase in frequency of ultrasonic wave, velocity shows slight variation.
5 References:
131 | P a g e
1. D. G. FRIEND, ‘Speed of sound as a thermodynamic property of fluids’, Exp. Methods Phys. Sc., 39,
237, 2001.
2. K. Y. JHANG, H. H. QUAN et al, ‘Estimation of clamping force in high-tension bolts through
ultrasonic velocity measurement’, Ultras., 44, 1339, 2006.
3. G. VARUGHESE, A. S. KUMAR et al, ‘Elastic study of Potassium Sulphamate crystal using ultrasonic
Pulse Echo Overlap Technique’, Sol. Stat. Comm., 149, 645, 2009.
4. M. MOLERO, I. SEGURA et al, ‘On the measurement of frequency-dependent ultrasonic attenuation in
strongly heterogeneous materials’, Ultras., 50, 824, 2010.
5. V. BHADAURIA, P. MIRAZ et al, ‘Dual trypan-aniline blue fluorescence staining methods for studying
fungus-plant interactions’, Biotech. and Histochem., 85, 99, 2010.
6. R. KANDYALA, S. PHANI et al, ‘Xylene: An overview of its health hazards and preventive measure’, J.
Oral Maxillofacial Path., 14, 1, 2010.
7. K. NAKAMURA, K. IWAHASHI et al, ‘Acetaldehyde adducts in the brain of alcoholics”, Arch. Toxicol.,
2003, 77, 591.
8. Y. HAYASHI and F. T. BIRD, ‘The use of Sucrose gradients in the isolation of cytoplasmic-polyhedrosis
virus particles’, J. Invertebrate Path., 11, 40, 1968.
9. O. O. KURAKEVYCH and V. L. SOLOZHENKO, ‘300-K equation of state of rhombohedral boron
subnitride’, Sol. State Comm., 149, 2169, 2009.
10. Y. L. GODEC, D. M. GARCIA et al, ‘Compression and thermal expansion of rhombohedral boron nitride
at high pressures and temperatures ‘, J. Phys. Chem. Solids, 61, 1935, 2000.
11. H. MAO, B. SUNDMAN et al, ‘Volumetric properties and phase relations of silica-thermodynamic
assessment’, J. Alloys Comp., 327, 253, 2001.
12. V. KANNAPPAN and N. I. GANDHI, ‘Ultrasonic studies on charge transfer complexes of certain
aldehydes with benzylamine and cyclohexylamine as doners in n-hexane at 303K’, Ind. J. Pure. Appl.
Phys., 45, 221, 2007.
Table 1. Frequency Variation of Ultrasonic Velocity for Organic Pathological Compounds

Velocity (m/sec.)
Frequency (MHz)
Ethyl Acetate Aniline Xylene Acetaldehyde Sucrose
1 1093.6 1501.2 1204.2 1564.8 1518.2
2 1355.0 1652.2 1359.0 1644.4 1563.4
3 1158.7 1522.2 1269.3 1866.6 1638.9
4 1016.2 1335.2 1041.6 1605.6 1684.0
5 962.5 1558.5 1255.0 1615.0 1935.0
6 1215.6 1460.4 1170.0 1725.0 2097.4
8 1652.8 1411.8 1599.2 1382.4 2217.6
9 1873.8 - - - -
Table 2. Coefficient of Best Fit Polynomial for Ultrasonic Velocity

Compound A0 A1 A2 A3 A4 A5
Ethyl Acetate -5.20e+02 2.70e+03 -1.34e+03 2.81e+02 -25.93 0.88
Aniline -6.92e+02 4.06e+03 -2.44e+03 6.42e+02 -76.63 3.38
Xylene -7.96e+02 3.66e+03 -2.17e+03 5.67e+02 -67.83 3.03
Acetaldehyde 2.78e+03 -2.69e+03 2.00e+03 -6.22e+02 84.54 -4.14
Sucrose 1.16e+03 6.42e+02 -3.75e+02 0.99e+02 -10.76 0.40
132 | P a g e
1900 1700
1800
1650
1700
Velocity Velocity
1600
Velocity (in m/sec)
Velocity (in m/sec)

1600
1500 1550
1400 1500
1300
1450
1200
1400
1100
1000 1350
900
1 2 3 4 5 6 7 8 9 1300
1 2 3 4 5 6 7 8
Frequency (MHz)
Frequency (MHz)
Fig. 1. Velocity vs. frequency for Ethyl Acetate Fig. 2. Velocity vs. frequency for Aniline
1600
1900
1500 Velocity
Velocity 1800
Velocity (in m/sec)
Velocity (in m/sec)
1400
1700
1300
1600
1200
1500
1100
1400
1000
1 2 3 4 5 6 7 8 1300
1 2 3 4 5 6 7 8
Frequency (MHz)
Frequency (MHz)
Fig. 3. Velocity vs. frequency for Xylene Fig. 4. Velocity vs. frequency for Acetaldehyde
2300
2200
Velocity
2100
Velocity (in m/sec)
2000
1900
1800
1700
1600
1500
1 2 3 4 5 6 7 8
Frequency (MHz)
133 | P a g e
HIGH TEMPERATURE STUDY OF ANHARMONIC PROPERTIES OF TeO
Kailash1, Jitendra Kumar2 and Virendra kumar1
Email: kailash.rath@yahoo.co.in, jitendra_sharma50@yahoo.com, vir.rath@yahoo.com
ABSTRACT: A proper and systematic evaluation of anharmonic properties of isostructural oxides,
and their dependence on temperature provides the fundamental data for determining the
characteristics of cation-oxygen bonding interactions which are pertinent to the understanding and
theoretical modelling of more complicated oxide compounds. When the values of second and third
order elastic constants and density for any material at a particular temperature are known; one may
get ultrasonic velocities for longitudinal and shear waves in different crystallographic directions
which give important information about its anharmonic properties. In this work, an attempt has
been made to evaluate higher order elastic constants for TeO at an elevated temperature from 50K
to 600K. The data of SOECs, TOECs and FOECs are used to evaluate the FOPDs of SOECs and
TOECs, SOPDs of SOECs and partial contractions. While evaluating these properties it is assumed
that the crystal structure does not change during temperature variation. The data of these oxides
obtained through different techniques also give important and valuable information about internal
structure and inherent properties of materials and can be used in future for different industrial
purposes and further investigations of isostructural oxides.
KEYWORDS: Anharmonic properties, Higher order elastic constants, Pressure derivatives, Divalent
crystals, Partial contractions, Grüneisen numbers.
1 Introduction:
Elastic properties of divalent compounds are important because they relate to the various
fundamental solid state phenomena such as inter atomic potentials, equation of state and phonon spectra.
If the values of second order elastic constants and density at a particular temperature are known for any
substance, one may obtain ultrasonic velocities for longitudinal and shear waves which give an important
information about its anharmonic properties. Elastic properties are linked thermodynamically with specific
heat, thermal expansion, and Debye temperature and Grüneisen parameters.
In the last few years studies of anharmonic properties of solids have attracted the attention of the
physicists since they provide much valuable information regarding crystal dynamics [1-5]. A number of
theoretical and experimental measurements have been made on the anharmonic properties [6]. No
134 | P a g e
complete experimental or theoretical efforts have been made so for in obtaining the temperature variation
of anharmonic properties of divalent crystals having various crystal structures. The elastic energy density
for a deformed crystal can be expanded as a power series of strains using Taylor’s series expansion [7].
The coefficients of quadratic, cubic and quartic terms are known as SOECs, TOECs and FOECs
respectively. Several physical properties and crystal anharmonicities such as thermal expansion, specific
heat at higher temperature, temperature variation of acoustic velocity and attenuation, and the FOPDs of
SOECs and Gruneisen numbers are directly related to SOECs and TOECs. While discussing higher order
anharmonicities such as the FOPDs of TOECs, the SOPDs of SOECs, partial contractions and deformation
of crystals under large forces, the FOECs are to be considered extensively. The present paper is mainly
focussed on the study of temperature variation of higher order elastic constants and their pressure
derivatives up to an elevated temperature up to 600 K (near melting point) for Tellurium oxide (TeO)
crystals using Born-Mayer and Coulomb potential starting from the nearest neighbour distance and
hardness parameter.
2 Formulation:
The elastic energy density for a crystal of a cubic symmetry can be expanded up to quartic terms as shown
below [8];
U0 = U2 + U3 + U4
= [1/2!] Cijkl αij αkl + [1/3!] Cijklmn αij αkl αmn + [1/4!] Cijklmnpq αij αkl αmn αpq (1)
Where Cijkl, Cijklmn and Cijklmnpq are the SOECs, TOECs and FOECs in tensorial form; αij are the Lagrangian
strain components; CIJ, CIJK and CIJKL are the SOECs, TOECs and FOECs in Brügger’s definition and Voigt
notations.
0 vib 0 vib 0 vib
C IJ = C IJ + C IJ , CIJK = CIJK + CIJK and CIJKL = CIJKL + CIJKL (2)
3 Evaluation:
The SOECs, TOECs and FOECs for TeO crystal are evaluated from 50-600 K. Selecting a few
data obtained in this study, the values of SOECs, TOECs and FOECs at 300 K are given in Tables 1, 2.
The FOPDs of SOECs and TOECs, the SOPDs of SOECs and partial contractions are evaluated utilizing
data of Tables 1, 2 and the results are shown in Table 3, 4. All these results are discussed widely and
some of them are presented graphically in Figs. 1–6.
4 Results and Discussions:
It may state that all the SOECs are positive in nature. For TeO crystals the value of C11 and C44
increases and the value of C12 decrease as temperature increases and are represented in Fig 1. For
135 | P a g e
Tellurium oxides, the values of C111, C112 and C166 are negative in nature, while C123, C144 and C456 are
positive in nature. The values of C111, C123, C144 and C166 increases, the value of C112, decreases as
temperature increases, C456 remaining constant. The temperature variation of C111, C112 and C123 are given
in Fig 2. The value of C1111, C1112, C1122, C1144,C1155, C1255, C1266, C4444 and C4455 decreases as temperature
increases, and the value of C1123 increases as temperature increases. The value of C1456 remains constant.
The first three are presented in Fig 3. The value of dC11/dp and dC12/dp decreases and the value of dC44/dp
increases as temperature increases. The value of dC111/dp, dC112/dp, dC144/dp, dC166/dp and dC456/dp
increases as temperature increases, and the value of dC123/dp decrease as temperature increases. The
variation of FOPDs of SOECs are given in Fig 4. The value of d2C11/dp2 and d2C44/dp2 decreases and
d2C12/dp2 increases as temperature increases and are presented in Fig 5. The value of all partial
contractions W11, W12 and W44decreases as temperature increases but W11 decreases very sharply, which
is presented in Fig 6. These elastic constants are used to compute ultrasonic parameters such as
ultrasonic velocities, thermal relaxation time etc [9-11]. The variation of elastic constants [12-14] with
respect to pressure can reveal many important features of the short range forces at high pressure. The
ultrasonic studies [15] can provide interesting information on the specificities of ion-solvent interaction
related to the structure of the solute and the reciprocal effects which arises in the solvent and the role of
collinear and noncolinear phonons in anharmonic scattering processes and in ultrasonic attenuation for
different structured solids [16]. The data obtained in present investigation will be helpful to those workers
who are engaged in studying the temperature variation of anharmonic properties [17–21] of solids at higher
temperatures.
4 References:
1. M. ZHAO and Q. JIANG, ‘Crystal liquid interface energy and surface stress of alkali halides’, Mate.
Chem. Phys., 87, 1, 2004.
2. KAILASH, K. S. KUSHWAHA et al, ‘Internal structure, inherent ananharmonic properties of some
mono- and di-valent materials’, J. Pure App. Ultra., 27, 29, 2005.
3. S. E. DOSSO and N. E. COLLISION, ‘Acoustic tracking of a freely drifting sonobuoy field’ J. Acoust.
Soc. Am., 111, 2166, 2002.
4. Z. H. FANG, ‘Temperature dependence of interatomic separation for alkali halides’ Phy. Stat. Sol. (b),
241, 2886, 2004.
5. C. KITTEL, ‘Introduction to solid state physics’, John Wiley, Newyork, 1981.
6. Z. P. CHANG and G. R. BARSCH, ‘Nonlinear pressure dependence of elastic constants and fourth-
order elastic constants of cesium halides’ Phys. Rev. Letters, 19, 1381, 1967.
7. F. BIRCH, ‘Finite elastic strain of cubic crystals’ Phys. Rev., 71, 809, 1947.
8. P. B. GHATE, ‘Third order elastic constants of alkali halide crystals’ Phys. Rev., 139, A1666, 1965.
136 | P a g e
9. O. N. AWASTHI and V. K. PUNDHIR, ‘Ultrasoniv attenuation in liquid mercury, zinc and gallium
metals’ Ind. J. Pure Appl. Phys., 45, 434, 2007.
10. D. SINGH and D. K. PANDEY, ‘Ultrasonic investigation in intermetallics’ Pramana, 32, 389, 2009.
11. D. SINGH, D. K . PANDEY and P. K. YADAWA, ‘Ultrasonic wave propagation in rare earth
monochalcogenides’ Cent. J. Phys., 7, 198, 2009.
12. B. S. ARYA, M. AYNYAS and S. P.SANYAL, ‘High pressure behaviour of alkaline earth tellurides’ Ind.
J. Phys., 83, 153, 2009.
13. A. RUKMANGAD, M. AYNYAS and S. P. SANYAL, ‘Structural and elastic properties of rare earth
nitrides at high pressure’ Ind. J. Pure Appl. Phys., 47, 114, 2009.
14. C. S. RAO and C. E. REDDY, ‘Finite element modeling of nano ndentation to extract load-
displacement characteristics of bulk materials and thin films’ Ind. J. Pure Appl. Phys., 47, 54, 2009.
15. P.F. YUAN and Z. J. DING, ‘Ab inito calculation of elastic properties of rock-salt and zinc-blend MgS
under pressure’ Physica B, 403, 1996, 2008.
16. I. G. KULEYEV et al, ‘Interaction of collinear and noncollinear phonons in anharmonic scattering
processes and their role in ultrasound absorption of fast quasi-transverse modes in cubic crystals’ J.
Phys: Condens. Matter., 22, 095403, 2010.
17. KAILASH, K. M. RAJU et al., ‘Anharmonic properties of rock salt structure solids’ Physica B, 399, 270,
2007.
18. K. UDO, E. FRIECTER and L. KARL, ‘Ultrasonic velocity measurement in liquids with high resolution
techniques, selected applications and perspectives’ Measur. Sc. Tech., 19, 062001, 2008.
19. S. THIRUMARAN AND K. J. SABU, ‘Ultrasonic investigation of amino acids in aqueous sodium
acetate medium’ Ind. J. Pure Appl. Phys., 47, 87, 2009.
20. S. DAHMEN, H. KETATA, M. H. B. GHOZLEN and B. HOSTEN, ‘Elastic constants measurement of
anisotropic Olivier wood plates using air-coupled transducers generated Lamb wave and ultrasonic
bulk wave’ Ultras., 50 , 502, 2010.
21. A. K. UPADHYAY and B. S. SHARMA, ‘Elastic properties of intermetallic compounds under high
pressure and high temperature’ Ind. J. Pure Appl. Phys., 47, 362, 2009.
Table 1. The SOECs in 1010 N/m2 for TeO crystal at 300 K.
M. P. (K) C11 C12 C44 C111 C112 C123 C144 C166 C456
643 20.711 22.109 22.346 -234.110 -102.256 33.826 32.482 -88.531 31.679
Table 2. The FOECs in 1010 N/m2 for TeO crystal at 300 K.

C1111 C1112 C1122 C1123 C1144 C1155 C1255 C1266 C1456 C4444 C4455
2392.0 301.0 434.1 -77.23 -74.48 387.4 -79.45 447.1 -74.01 452.6 -74.41
Table 3. The FOPDs of SOECs and TOECs for TeO crystal at 300 K.
dC11/dp dC12/dpP dC44/dp dC111/dp dC112/dp dC123/dp dC144/dp dC166/dp dC456/dp
-5.725 -3.414 0.967 -33.881 -6.652 3.096 1.256 1.596 3.044
Table 4. The SOPDs of SOECs in 10-9 m2/N and partial contractions in 1012 N/m2 for TeO crystal at 300 K.
d2C11/dp2 d2C12/dp2 d2C44/dp2 W11 W12 W44
137 | P a g e
0.380 0.124 0.110 43.101 10.842 12.728
23 50
22.5
0
TOECs for TeO(in 1e10 N/sq.m.)

SOECs for TeO(in 1e10 N/sq.m.)
22
-50
21.5 C11
-100
C12
21
Fig. 1. SOECs
C44
Vs Temp. For TeO Fig. 2. TOECs Vs Temp. For TeO
C111
-150 C112
20.5 C123
-200
20
-250
19.5 0 100 200 300 400 500 600
0 100 200 300 400 500 600
3000 temperature(K)
Temperature(K)
FOPDs OF SOEC for TeO(dimensionless)

2
2500 1
FOECs for TeO(in 1e10 N/sq.m.)
0
2000
Fig. 3. FOECs Vs Temp. For TeO Fig. 4. FOPDs of SOECs Vs Temp. FordC11/dp
TeO
-1 dC12/dp
C1111 dC44/dp
1500 C1112 -2
C1122 -3
1000
-4
-5
500
-6
0 -7
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Temperature(K) Temperature(K)
Fig. 5. SOPDs of SOECs Vs Temp. For TeO Fig. 6. Partial Contractions Vs Temp. For TeO
0.5
ddC11 50
SOPDs OF SOEC for TeO(in 1e-9 sq.m./N)
Partial Contractions for TeO(in 1e12 N/sq.m.)
0.45
ddC12 45
ddC44
0.4 40
0.35 35
30 W11
0.3
W12
25
0.25 W44
20
0.2
15
0.15
10
0.1 5
0 100 200 300 400 500 600 0 100 200 300 400 500 600
138 | P a g e
ORIENTATION DEPENDENCE OF ULTRASONIC ATTENUATION FOR CALCIUM OXIDE
IN HIGH TEMPERATURE RANGE
Kailash1, S. K. Shrivastava2 and Jitendra Kumar3

2. Department of Physics, Bundelkhand University, Jhansi, U.P, 284 128, India
Email: kailash.rath@yahoo.co.in, jitendra_sharma50@yahoo.com
ABSTRACT: Ultrasonic velocity and attenuation parameters are well connected to the micro
structural and mechanical properties of the materials. The most important causes of ultrasonic
attenuation in solids are electron–phonon, phonon–phonon interaction and that due to thermo
elastic relaxation. The two dominant processes that will give rise to appreciable ultrasonic
attenuation at higher temperature are the phonon–phonon interaction also known as Akhieser loss
and that due to thermo elastic relaxation are observed in calcium oxide crystal. At frequencies of
ultrasonic range and at higher temperatures in solids, phonon–phonon interaction mechanism is
dominating cause for attenuation. In this work ultrasonic attenuation due to phonon–phonon
interaction (α/f2)p-p and thermo elastic relaxation (α/f2)th are studied in CaO crystal from 100K-1500K
along different crystallographic directions. Temperature dependence of ultrasonic absorption in
CaO crystal along different crystallographic direction reveals some typical characteristic features.
KEYWORDS: Attenuation, Thermo elastic relaxation, Phonon-phonon interaction, Akheiser loss and
Gruneisen constants.
1 Introduction:
The ultrasonic attenuation study of the materials has gained new dimensions with the progress in
the material science [1-4]. The most important causes of ultrasonic attenuation in solids are electron–
phonon, phonon–phonon interaction and that due to thermo elastic relaxation. In recent years, the
ultrasonic attenuation techniques [5-7] are widely used as versatile tool in studying the inherent properties
and internal structure of solids. The two dominant processes that will give rise to appreciable ultrasonic
attenuation at higher temperature are the phonon–phonon interaction [8] also known as Akhieser loss [9]
and that due to thermo elastic relaxation and are observed in calcium oxide crystal.
Oxides and silicates make up the bulk of the Earth’s mantle and crust, and thus it is useful to
predict their behaviour. In this work ultrasonic attenuation due to phonon–phonon interaction (α/f2)p-p and
139 | P a g e
thermo elastic relaxation (α/f2)th are studied in calcium oxide at an elevated temperatures (100-1500 K)
along <100>, <110> and <111> crystallographic directions. For the evaluation of the ultrasonic coefficients
the second and third order elastic constants (SOECs and TOECs) are also calculated using Coulomb and
Born Mayer [10] potentials. Several investigators have given different theories; here the one given by
Mason has been used. Mason’s theory relates the Gruneisen constants with SOECs and TOECs. The
behaviour of ultrasonic absorption and other parameters as a function of higher temperature have been
discussed as the characteristic features of calcium oxide.
2 Formulation:
The expressions for ultrasonic attenuation coefficient due to phonon-phonon interaction [11] over
frequency square (α/f2)p-p are as
D  D 
4π 2 E0  l τ l 4π 2 E0  s τ
 s
 3   3  4π 2 < γ ij > 2 KT
(α / f 2 ) Akh.long = , (α / f 2 ) Akh.shear = and (α / f 2 )th = (1)
2 ρVl 3 2 ρVs3 2 ρV 5
where the condition ωτth <<1 has already been assumed. Here E0 is thermal energy density, f is frequency
of ultrasonic waves, d is the density and Vl, Vs are the ultrasonic velocities for longitudinal and shear waves
respectively.
 3C T 
D in eqns. (1) is given as D = 9 < (γ ij ) 2 > − v  < γ ij > 2
 (2)
 E0 
Where γij,s are the Grüneisen parameters.

3 Evaluation:
The SOECs and TOECs for CaO has been evaluated at different temperatures (100 to 1500 K)
following Brugger’s approach [12] and are presented in Table 1 at room temperature. Grüneisen
parameters have been evaluated using Mason’s Grüneisen parameters tables [13] at different
temperatures along different crystallographic directions with the help of SOECs and TOECs. The non-
linearity constants are evaluated using the average square Grüneisen parameters <γij>2 and square
average Grüneisen parameters <γij2>. The values of <γij> and ultrasonic attenuation (α/f2)p-p and (α/f2)th
along with Vl, Vs, τth and D are presented in Table 2 at room temperature along different crystallographic
directions. The temperature variations of all these properties are presented graphically in Figs. 1–6.
4 Results and Discussions:
It is clear from the Fig. 1 that the value of thermal relaxation time τth is very high at low temperature
and decreases as temperature is increased along all crystallographic directions and of the order of 10-12
140 | P a g e
sec, which is also expected. The temperature variation of ultrasonic velocities is presented in Fig. 2 along
<100> direction. It is clear from the figure that the ultrasonic velocity for longitudinal wave increases as
temperature increases, while for shear wave it decreases.
The thermal ultrasonic attenuation along different directions is presented in Fig. 3. It is clear from
the figure that thermal attenuation increases with temperature along all these directions and of the order of
10-18 Nps2/m which is expected for the type of crystal under inspection. Figs. 4 -6 represents the ultrasonic
attenuation due to phonon-phonon interaction along <100>, <110> and <111> crystallographic directions
respectively. Along all these directions the ultrasonic attenuation increases with increase in temperature,
the situation is little different for shear wave along <110> direction (pol. <1 1 0>) for which the ultrasonic
attenuation decreases with temperature. From the above results one can reach to the conclusion that the
thermal relaxation time, ultrasonic wave velocities and attenuation are the properties which depends on the
crystallographic directions or one can say that these properties are orientation dependent which strongly
supports the results given by other investigators [14] for the same type of crystals that all these properties
are strongly dependent on direction of polarization. The results obtained in this study can be used for
further investigations [15, 16] and industrial research and development purposes.
5 References:
1. R. P. SINGH and R. K. SINGH, ‘Theoretical study of temperature dependent lattice anharmonicity in
TlCl and TlBr’, Current Appl. Phys., 10, 1053, 2010.
2. J. D. PANDEY, A. K. SINGH and R. DEY, ‘Effect of isotopy on thermoacoustical properties’, J. Pure
Appl. Ulras., 26, 100, 2004.
3. A. K. UPADHYAY and B. S. SHARMA, ‘Elastic properties of intermetallics compounds under high
pressure and high temperature’, Ind. J. Pure Appl. Phys., 47, 362, 2009.
4. R. K. SINGH, ‘Ultrasonic attenuation in alkaline earth metals’, J. Pure Appl. Ultras., 28, 59, 2006.
5. S. K. SRIVASTAVA, KAILASH and K. M. RAJU, ‘Ultrasonic study of highly conducting metals’, Ind. J.
Phys., 81, 351, 2007.
6. KAILASH, K. M. RAJU and S. K. SRIVASTAVA, ‘Acoustical investigation of magnesium oxide’, Ind. J.
Phys., 44, 230, 2006.
7. T. YANAGISAA, T. GOTO and Y. NEMOTO, ‘Ultrasonic investigation of Quadrupole ordering in
HoB2C2’, Phys. Rev. B, 67, 115129, 2003.
8. S. K. KOR, R. R. YADAV and KAILASH, ‘Ultrasonic attenuation in dielectric crystals’, J. Phys. Soc.
Jpn., 55, 207, 1986.
9. A. AKHEISER, ‘On the absorption of sound in solids’, J. Phys. (USSR), 1, 277, 1939.
10. M. BORN and J. M. MAYER, ‘Zur Gittertheorie der lonenkristalle’, Z Phys. (Germany), 75, 1, 1932.
11. W. P. MASON, ‘Piezoelectric crystals and their applications to ultrasonics’, D. Van Nortrand Co, Inc,
Prinston, New Jersey, 479, 1950.
12. K. BRUGGER, ‘Thermodynamic definition of higher order elastic coefficients’, Phys. Rev., 133, A1611,
1964.
141 | P a g e
13. W. P. MASON, ‘Effect of impurities and phonon-processes on the ultrasonic attenuation in germanium,
crystal quartz and silicon’, Physical Acoustics, Vol. III B, Academic Press, New York, 237, 1965.
14. K. M. RAJU, KAILASH and S. K. SRIVASTAVA, ‘Orientation dependence of ultrasonic attenuation’,
Physics Procedia, International Congress on Ultrasonics, Santiago de Chile, 3, 927, 2010.
15. J. A. SCALES and A. E. MALCOLM, ‘Laser characterization of ultrasonic wave propagation in random
media’, Phys. Rev E, 67, 046618(1), 2003.
16. T. C. UPADHYAY, ‘Temperature dependence of microwave loss in ADP-type crystals’, Ind. J. Pure
Appl. Phys., 47, 66, 2009.
Table 1. The SOECs and TOECs in 1010 N/m2 at roomtemperature.
Melting Point C12 C44 C111 C112 C123 C144 C166 C456
(K)
2843 12.52 12.71 -252.88 -65.10 20.34 19.43 -51.26 4.71
Table 2. Long. and shear wave velocities in 103 m/sec, thermal relaxation time in 10-12 sec, non linearity constants,
thermal attenuation in10-18 Nps2/m and p-p attenuation for long. and shear waves in 10-16 Nps2/m.
Direction of propagation <γij> V τth D (α/f2)th (α/f2)p-p

<100>long. -0.601 7.520 0.836 15.414 0.373 0.218
shear -0.015 6.171 - 2.886 - 0.037
<110>long. -0.673 9.124 0.782 12.248 0.178 0.091
shear(pol.<001>) -0.039 6.171 - 5.777 - 0.069
(pol.<1 1 0>) -0.512 3.375 - 13.838 - 6.253
<111>long. -0.665 9.599 1.379 14.115 0.135 0.158
shear(pol.< 1 10>) -0.203 4.504 - 8.786 - 0.954
-0.082 4.504 - 13.529 - 1.469
(pol.<11 2 >)
10 8
Thermal Relaxation Time (in 1e-12 sec.)
Along <100> direction

Ultrasonic Wave Velocities(in 1e+3 m/sec)
9
8 7.5
Along <111> direction Vl
7 Vs
7 Vd
6
4 6.5
3
6
2
1
5.5
0 0 500 1000 1500
0 500 1000 1500
Temperature(K)
Temperature(K)
Fig. 1. Thermal relaxation time Vs Temp Fig. 2. Ultrasonic velocities Vs Temp. along <100> dir
142 | P a g e
0.7
Thermal Ultrasonic Attenuation(in 1e-18 Nps2/m)

0.5
Along <100> direction Akh.long
Ultrasonic Attenuation(in 1e-16 Nps2/m )

0.45 Along <110> direction 0.6 Akh.Shear
0.4
0.5
0.35
0.4
0.3
0.3
0.25
0.2 0.2
0.15
0.1
0.1
0
0.05 0 500 1000 1500
0 Fig. 3. Thermal ultrasonic
500 attenuation Vs Temp. Fig. 4. Ultrasonic
1000 1500 attenuation Vs Temp. along <100> dirTemperature(K)
Temperature(K)
7 3
Akh.long Akh.long

6 Akh.Shear1 2.5
Akh.Shear1
Akh.Shear2 Akh.Shear2
5
2
4
1.5
3
1
2
0.5
1
0 0
0 500 1000 1500 0 500 1000 1500
Fig. 5. Ultrasonic attenuation Vs Temp. Along <110>dir Fig. 6. Ultrasonic attenuation Vs Temp. along <111> dir
143 | P a g e
MOLECULAR RADII OF PYRIDINE/QUINOLINE WITH PHENOL IN BENZENE USING
ACOUSTICAL METHODS AT DIFFERENT TEMPERATURES
Anjali Awasthia, Bhawana S. Tripathia, Rajiv K. Tripathib and Aashees Awasthia
aMaterialScience Research Laboratory

Department of Physics, University of Lucknow, Lucknow-226 007, India
bDepartment of Physics, D. A. V. P. G. College, Lucknow-226 004, India
ABSTRACT: The molecular radii of liquid mixtures of heterocyclic compounds viz., pyridine and quinoline
with phenol in benzene have been computed at varying physical conditions using various acoustic
methods. The results indicate that molecular radii of liquid mixtures evaluated from Rao’s method are in
close agreement with the Schaaffs method. The applicability of Schaaffs or Rao’s method for the estimation
of the molecular radii in ternary liquid mixtures has been authenticated. A comparative study of the merits
and demerits of various acoustic methods are discussed in the light of molecular structure and
intermolecular interactions.
KEYWORDS: Molecular radii, Molecular interactions, Ternary liquid mixtures
1. Introduction: Acoustic methods are the most powerful tools for the study of structural and physico-
chemical behaviour of liquids and liquid mixtures [1-3]. The molecular radius is an important parameter,
which reflects the structural features of pure liquids and liquid mixtures. The molecular radius plays an
important role in various liquid state theories [4, 5]. Molecular radius has been utilized to compute various
important parameters of liquid mixtures to explain the process of molecular association among their
components.
Bondi [6] provided a qualitative understanding of the nature of Van der Waals radii and proposed
their qualitative values. Ernst and Glinski [7] have studied the effects of various physical parameters on
molecular radius in pure liquids using several empirical relations, based on acoustic methods, suggested by
Schaaffs [4, 8], Rao [9], Eyring [10,11] and Kittel [12]. Besides these acoustic methods, the relation based
upon the assumption that liquid system is made up of closely packed molecules with face centered cubic
structures, has been used [6]. Recently, Pandey et al. [13] has estimated the molecular radii of pure liquids
and binary liquid mixtures using various acoustic methods. The study suggests the superiority of Schaaffs
144 | P a g e
method for theoretical estimation of molecular radius over the remaining methods. Ali et al. [14] have
evaluated the molecular radii of binary liquid mixtures by employing acoustic and refractive index
approaches. Dey et al. [15] has studied the isotopic effects on non-linearity parameter, molecular radius
and intermolecular free length of various liquids and their deuterium-substituted compounds. These
physico-chemical parameters have been used to study their effects on the intermolecular interactions. In
the present study, the various acoustic methods for estimating the molecular radius have been extended to
ternary liquid mixtures of pyridine/quinoline with phenol in benzene. The deviations in variation patterns of
molecular radii with changing temperature and concentration for ternary liquid mixtures have been studied.
Earlier, any worker has made no such attempt as far as our knowledge is concerned.
2. Theory: Various methods can be employed to evaluate the molecular radii of liquid mixtures using
ultrasonic velocity, density and other related parameters. Schaaffs and Rao’s methods are based upon the
Van der Waals equation of state. Eyring’s and Kittel’s methods are based upon the assumption that the
observed velocity of sound results from the propagation of sound waves inside the molecule and in free
space between them. These acoustical methods for the computation of molecular radii of liquid mixtures
are summarized as under:
2.1 Schaaffs Relation:
[ ( )(
r = 3 M ρ N ⋅ 3 3 16π 1 − γRT Mu 2 . 1 + Mu 2 3γRT − 1( ) )] (1)
2.2 Rao’s Relation:
( ) (
r = 3 M ρ N ⋅ 3 3 16π 1 − γRT Mu 2 . 1 + Mu 2 γRT − 1
  
)
(2)
2.3 Eyring’s Relation:
  3 
(
r = 3 M ρ N ⋅ (1 2) ⋅ 3 1 − 1 − (1 u ). γRT M  ⋅ 2 )
   (3)
2.4 Kittel’s Relation:
r = 3 M ρ N ⋅ (1 2 ) ⋅ 3 1 − (1 u ) ⋅ ( 3γRT M ⋅ 2) (4)
For a system comprising of spheres of mass M/N in a close packed face centered cubic structure (CP-
FCC), molecular radius can also be obtained by the relation [7].
145 | P a g e
2.5 CP-FCC Relation:
r = (1 2).3 M 2 ρN (5)
where u, ρ, M, N and γ have their usual meanings.
3. Results and Discussion: The molecular radii of both ternary liquid systems of pyridine/ quinoline with
phenol in benzene have been computed at various concentrations and temperatures using relations (1-5).
Figures 1 (a-f) show the variation of molecular radii for both the ternary liquid systems as a function of mole
fraction of phenol. The various acoustic methods for estimating molecular radii have been analyzed
graphically at different temperatures. Since the superiority of Schaaffs method has been established by the
earlier workers [7, 13, 14], so it is considered as a reference for determining of molecular radii of both the
liquid systems in the present study. Theoretical values of molecular radii have also been evaluated.
It is observed that the molecular radii data obtained from various acoustic methods are not found to
change significantly with concentration at specific temperature for both ternary liquid mixtures. But, a close
perusal of the figure reveals that the molecular radii obtained from Schaaffs, Rao’s and CP-FCC method
are slightly decreasing with increasing concentration at specific temperature while Kittel’s and Eyring’s
relations exhibit a non-linear behaviour for pyridine-phenol system; for quinoline-phenol system molecular
radii increasing with the increasing concentration from all acoustic methods except Eyring’s relation
showing non-linear trend. Since pyridine has greater pKα value than quinoline and resonating structures of
pyridine and quinoline suggests that in pyridine, the availability of the unshared pair of electrons for sharing
with acids is more than quinoline. Due to this reason pyridine show strong interaction with phenol showing
decreasing trend of molecular radii in pyridine-phenol system while weak interaction in quinoline with
phenol provide increasing trend of molecular radii in quinoline-phenol system. It is also seen that at specific
concentration and temperature, higher values of molecular radii are obtained in quinoline-phenol system as
compared to the pyridine-phenol system. It may be due to bulkier structure of quinoline than pyridine.
PYRIDINE QUINOLINE
N N
.. ..
146 | P a g e
A significant inference has been drawn from the molecular radii data, obtained from Eyring’s
relation, showing a non-linear behaviour with concentrations at specific temperature. In both liquid mixtures,
molecular association process is strongly supported by Eyring’s method, which provide minimum molecular
radius at the same concentrations where maximum molecular association was observed [1]. Moreover, for
pyridine-phenol system the molecular radii obtained from Eyring and Kittel’s relation shows an opposite
trend. Pandey et al. [13] and Ali et al. [14] show similar observations in their studies. It is observed from
figure 1 (a-f) that on increasing the temperature values of molecular radii also increases for both the
systems (except Kittel’s relation). This is because of thermal energy, which weakens the molecular forces,
and hence an increase in molecular radii is expected with temperature [13]. It can also be seen that the
values of molecular radii obtained from Rao’s method are in close agreement with Schaaffs method [13,
14]. Both methods are based on the assumptions that liquids behave like real gases. The molecular radii
obtained from Kittel’s and Eyring’s methods have not been found to be in agreement with the Schaaffs
method. Eyring’s and Kittel’s relation resulted in higher values of molecular radii than obtained by Schaaffs
method. These observations show that the assumptions of free space made by these relations have to be
modified in the present cases [13]. Therefore, in order to get comparable results with the Schaaffs method,
a correction term is needed which will take care of three body effects in the evaluation of molecular radii in
these cases. It is seen from the figures that the values of molecular radii obtained from CP-FCC method
are always found to be higher than the values obtained from any other method. This may be due to the fact
that the CP-FCC method is based upon the assumption that there is no free space between the molecules.
The application of this equation for any liquid system should only be limited to compute the maximum
possible values of molecular radii [13]. The values of molecular radii obtained theoretically are in close
agreement with the values obtained from Schaaffs and Rao’s method. Ernst et al. [7] and Pandey et al. [13]
have also emphasized the superiority of Schaaffs and Rao’s method for the estimation of molecular radii
over other methods.
4. Conclusions:
The variation pattern of molecular radii with the change in various physical parameters seems to be
very convincing for both multicomponent liquid mixtures taken under investigation. Eyring’s method may be
successfully employed to explain intermolecular interactions in the ternary liquid mixtures.
Acknowledgements:
147 | P a g e
The authors gratefully acknowledge the University Grants Commission for providing financial assistance as
a Major Research Project (F. No. 33-34/2007 (SR)).
References:
[1] A. Awasthi, M. Rastogi and J. P. Shukla, Fluid Phase Equilib., 215 (2004) 119.
[2] M. Rastogi, A. Awasthi and J. P. Shukla, Phys. Chem. Liqs., 42 (2004) 117.
[3] A. Awasthi and J. P. Shukla, Ultrasonics, 41 (2003) 477.
[4] W. Schaaffs, Z. Phys., 114 (1939) 110.
[5] H. Reiss, H.L. Frisch and J.L. Lebowitz, J. Chem. Phys., 31 (1959) 369.
[6] A. Bondi, J. Phys. Chem., 68 (3) (1964) 441.
[7] E. Ernst and J. Glinski, Acustica, 13 (1981) 109.
[8] W. Schaaffs, Acustica, 33 (1975) 272.
[9] R.V. Gopala Rao and V. Venkataseshaiah, Z. Phys. Chem., 242 (1969) 193.
[10] J.F. Kinkaid and H. Eyring, J. Chem. Phys., 5 (1937) 587.
[11] J.F. Kinkaid and H. Eyring, J. Chem. Phys., 6 (1938) 620.
[12] C. Kittel, J. Chem. Phys., 14 (1946) 614.
[13] J. D. Pandey, R. Dey and B. D. Bhatt, J. Mol. Liq., 111 (2004) 67.
[14] A. Ali, M. Tariq, R. Patel, F. Nabi and Shahjahan, 15th National Symposium on
Ultrasonics (2006).
[15] R.Dey, A.K. Singh, N.K. Soni, B.S. Bisht and J. D. Pandey, Pramana, 67 (2) (2006) 389.
Fig.1 Molecular radii versus mole fraction of phenol:
Pyridine-phenol in benzene (a, b, c) Quinoline-phenol in benzene (d, e, f)
148 | P a g e
3.0 3.0
mol. radius, r (10-10 m)

2.7 2.7
2.4 At 308.15 K At 308.15 K

2.4
2.1 2.1
1.8 1.8
0.00 0.02 0.04 0.06 0.08 0.00 0.02 0.04 0.06 0.08
mole frac. (x 2) mole frac. (x 2)
(a) (d)
3.0 3.0

2.7 2.7
At 318.15 K At 318.15 K
2.4 2.4
2.1 2.1
1.8 1.8
0.00 0.02 0.04 0.06 0.08 0.00 0.02 0.04 0.06 0.08
mole frac. (x 2) mole frac. (x 2)
(b) (e)
3.0
3.0
2.7
2.7
At 328.15 K
At 328.15 K 2.4
2.4
2.1
2.1
1.8
1.8
0.00 0.02 0.04 0.06 0.08
0.00 0.02 0.04 0.06 0.08
mole frac. (x 2)
mole frac. (x 2)
(c) (f)
149 | P a g e
Ultrasonic and theoretical study of binary mixture of DEHPA
(Di-(2- ethyl-hexyl) phosphoric acid) with n-hexane at different temperatures.
*****
Sujata Mishra, Rita Paikaray
Department of Physics
Ravenshaw University, Cuttack
E-mail: sujataananya@yahoo.co.in
r_ paikaray@rediffmail.com
ABSTRACT
Ultrasonic speed and density of binary liquid mixture of di-(2-ethyl hexyl) phosphoric acid ( DEHPA) with
n-hexane has been determined at 303K, 308K, 313K, 318K over entire composition range. The acoustical
parameters such as adiabatic compressibility ( Ks), Intermolecular free length ( Lf), acoustic
impedance ( Z), Relative association (RA), Molar Volume (V), Molecular interaction parameter ( χ) and also
excess parameters such as excess velocity ( CE), excess free length ( LEf), excess compressibility ( KEs),
excess molar volume ( VE) and excess acoustic impedance (ZE) are computed for the binary mixture at
different temperatures. Variation of acoustic parameters with temperatures have been discussed in terms of
nature and strength of intermolecular interaction existing in the binary system. The ultrasonic speeds
calculated according to Nomoto’s relation, impedance dependence relation, Rao’s specific sound velocity
relation and free length theory ( FLT) are compared with those obtained experimentally. The validity of
these theoretical relations have been discussed for the present liquid system.
Key words:- Binary mixture, Free length of interaction, acoustic parameters,
intermolecular interaction.
1. INTRODUCTION
Ultrasonic study of liquids, liquid mixtures and solutions is a useful technique for understanding its
physico-chemical behaviour and molecular interaction which have demanding applications in many
chemical and industrial processes. In order to detect weak and strong molecular interactions in binary
liquid mixtures consisting of polar as well as non-polar components, ultrasonic velocity measurement have
been employed extensively. Acoustic and thermodynamic parameter have been used to understand
different kinds of association, the molecular packing, molecular motion, and various type of intermolecular
interactions and their strengths [1,2].
Theoretical evaluation of ultrasonic velocity in binary liquid mixtures and its comparison with the
experimental values reflects the molecular interactions in liquid mixtures. Ultrasonic velocities calculated
using Nomoto’s relation (NR) [3], impedance dependence relation ( IDR) [4], Rao’s specific sound velocity
Relation (R) [5], free length theory [6] and are compared with experimental values.
2. THEORETICAL CONSIDERATIONS
The experimentally measured ultrasonic speed (C) and density () are used to calculate the derived
parameters like isentropic compressibility ( ), Intermolecular free length (
), molar volume (V) acoustic
150 | P a g e
impedance (Z), Relative association( ), Interaction parameter (χ ) and excess parameters by using the
following expressions.
= 1 ………………......... ( 1)
C2
= k ( )1/2 ………………… (2)
V= (x1 M1 + x2 M2 ) / mix ………..…(3)
RA= (ρ /ρ o) (Co/C) 1/3 ……………... (4)
Z = …………………………… (5)
χ = ( C2exp/C2ideal)-1………………… .(6)
Where C ideal = x1C1 + x2C2 is ideal mixing velocity.

AE = Aexp – ( x1A1 + x2 A2)……..(7)
Where x1 and x2 are mole fractions of DEHPA and n- hexane, 0 = density of DEHPA Co = Ultrasonic
velocity in pure DEHPA at particular temperature, mix = density of mixture. M1 and M2 are molecular
weight of DEHPA and n-hexane. k (Jacobson’s constant) [ value, 93.875 + 0.375T ) x 10-8 , T is absolute
temperature, AE stands for excess property of parameters ( CE, KEs, LEf, VE, ZE ). The theoretical values of
sound speeds are evaluated using the following relationship .
Sound Speed by Jacobson’s free length theory is calculated using the following formula [ 6].
CFLT = k________

(mix) , ρ EXP1/2 ….(8)
The empirical formula for sound speed in binary liquid mixtures given by Nomoto [3] can be written as
CNOM = x1R1 +x2R2 3 …..(9)
_________
x1V1 + x2 V2 Where X, R = V C 1/3 and V represents mole fraction, molar sound speed
and molar volume respectively. The sound speed in mixture is given by Impedance Dependence relation [4]
CIDR = Σ xi Zi ………… (10)
xiρi
Where xi Zi and ρi are the mole fraction, acoustic impedance and density of the ith component respectively.
Rao’s specific sound velocity relation is given by
CR = Σ ( xi ri ρ)3 ………(11)
Where ri = Ci1/3/ρi is the Rao’s specific sound velocity of the ith component of the mixture.
151 | P a g e
3. EXPERIMENTAL
The ultrasonic speeds in pure liquids and liquid mixtures have been measured using an ultrasonic
interferometer (model Mx-83) supplied by Mittal Enterprises , New Delhi, working at 3 MHz frequency with
an accuracy of + 0.1msec-1. Binary mixtures are prepared by mixing appropriate volumes of the liquid
components in the standard flasks with airtight caps and the mass measurements are performed on high
precision digital balance with an accuracy of +1mg. Density was determined by using a single capacity
Pyknometer of bulb capacity 25 cm3 at different temperatures. The temperature of the sample was
maintained stable by circulating thermo stated water around the interferometer cell that contains the liquid,
with a circulating pump to an accuracy of + 0.10C .
4.RESULT AND DISCUSSIONS
Measured values of density ( ρ) and ultrasonic speed (C) were used to calculate various
thermodynamic parameters and their excess values using equation 1-7 at different temperatures.
Representative graphs of ultrasonic velocity (C), excess velocity (CE), excess isentropic compressibility
(KES), excess free length (LEf), excess molar volume (VE), excess acoustic impedance (ZE) as a
function of concentration and temperature represented in fig.1-6. Table-1 compares experimental and
theoretical values of sound speed and deviations of these theories from experimental sound speeds at
temperature 303k.
molefraction- velocity
molefraction ~excess velocity
1500
30
1400 303K
Velocity
1300 303K 20 308K

excess velocity
1200 308K 313K

1100 10 318K
313K
1000 318K
900 0
0 0.5 1
0 0.5 1 1.5 -10 molefraction of DEHPA
molefraction of DEHPA Fig-2

Fig-1
DEHPA is an acidic extractant which is polar and its molecules exist as dimmers especially in pure
form or in organic diluents due to intermolecular hydrogen bonding.[8] The effect of adding non-polar
second component is primarily to disrupt the associated structure of DEHPA and strength of interaction
decreases. But breaking up of associated structure of DEHPA releases several dipoles, which induce
dipole moments in n-hexane molecules and there exist a dipole- induced dipole interaction between the
component molecules, which is supported by slow increase of relative association (RA) values and increase
of ultrasonic velocity (fig-1). Further ultrasonic velocity decreases with increase in temperature due to
152 | P a g e
thermal agitation of molecules. Similar observation made by Syal etal [9] and Subramaniyam Naidu
and Ravindra Prasad [10]. The free length ( Lf) and compressibility ( Ks) decreases with increase in
concentration of DEHPA and increases with temperature, which shows that dipole-induced dipole
interaction becomes stronger and the system is less compressible . Variation of other parameters like
acoustic impedance ( Z) and interaction parameter (χ) shows the presence of molecular interaction
between component molecules of the system.
molefraction~excess compressibility
0 molefraction ~excess freelength
0
excess isentropic
excess free length

compressibility
0 0.5 1 303K 0 0.5 1

308K 303K
313K 308K
-2 318K -0.5 313K
318K
-4
molefraction of DEHPA -1 molefraction of DEHPA
Fig-3 Fig-4
Excess Thermodynamic parameters give a better insight, into the study of molecular interactions in
a liquid mixture than derived parameters. The variation of excess velocity (CE) [Fig.2] shows negative
deviation is low concentration region and positive deviation in high concentration region of DEHPA. The
negative deviation is due to breaking up of self association of DEHPA in high concentration of non-polar n-
hexane. As the concentration of DEHPA increases, interstitial accommodation of n-hexane molecules
increases which results positive excess velocity which increases with increase in temperature. The
variation of excess isentropic compressibility ( KES) with mole fraction of DEHPA at all temperatures are
shown in [Fig-3]. Deviation in isentropic compressibility is negative with maxima at about ~ 0.37 mole
fraction of DEHPA from 303 to 318K. Mixing of n-hexane with DEHPA will induce breaking up the
associated structures which leads to expansion in volume and hence increase in KES and dipole- induced
dipole interaction is responsible for contraction in volume and hence a decrease in KES. The variation of
excess free length ( LEf) [Fig-4] is similar to that of KES, with negative deviation over entire range of
composition at all four temperatures . The less negative magnitude of LEf itself suggests that the interaction
between component molecules is not so strong i.e a weak dipole- induced dipole interaction present in the
system which dominates over the breaking up of associated structure of DEHPA. Considering the effect of
temperature, it is clear that both KES and LEf become more and more negative with increase in temperature
of the system. Increase in temperature promotes the breaking of associates present in pure liquids,
releasing more and more dipoles which interact with each other. Hence, strength of interaction increases
with rise of temperature [8,9]
153 | P a g e
molefraction~excess molarvolume molefraction~excess acoustic impedance
excess acoustic
30 0
impedance
excess molarvolume
303K
-0.01 0 0.5 1 308K
303
20 K -0.02 313K
308 318K
K -0.03
10
-0.04
-0.05
0 molefraction of DEHPA
0 0.5 1
molefraction of DEHPA
Fig-5 Fig-6
Fig-5 shows variation of excess molar volume ( VE) with mole fraction of DEHPA from 303 to 318
K. The excess molar volumes are positive for the whole range of composition [7] and at all temperatures
with a peak at about ~ .42 mole fraction. The positive values increase with increase in temperature. The
curves at all temperatures show that the self association of DEHPA molecules first breaks which results
increase of VE and then the interaction between unlike components take place due to increase in mole
fraction of DEHPA, which results decrease in VE. It also shows presence of unfavourable interactions
between different groups such as –CH3 , -CH2-, -OH of monomeric DEHPA Similar type of result shown by
other Researchers [2,7].
The variation of excess acoustic impedance (ZE) is shown in fig-6 at all four temperatures. The
negative ZE values indicate dissociation of self association of DEHPA and more than one type of interaction
may be present in the system. The less magnitude of negative (ZE) values suggest that dipole - induced
dipole interaction dominates over dispersion forces which is in close agreement with the variation of LEf
and KES with increasing concentration of DEHPA.
Table-1: Application of various theoretical approaches and percentage of deviation for DEHPA
+n-hexane system at 303K. ∆C/C %
Mole fraction of CEXP CNOM CIDR CR CFLT
DEHPA (X1) ms-1 ms-1 ms-1 ms-1 ms-1 CNOM CIDR CR CFLT
0.000 975.0 975.0 975.0 975.0 975.0 0.000 0.000 0.000 0.000
0.1574 1058.0 1109.3 1081.8 1097.8 1058.6 4.840 2.249 3.761 0.056
0.1717 1065.6 1119.3 1090.7 1108.0 1065.6 5.039 2.235 3.978 0.000
0.2036 1074.0 1141.4 1109.9 1135.9 1074.0 6.275 3.342 5.763 0.000
0.3179 1131.8 1211.0 1174.4 1215.7 1142.6 6.997 3.763 7.412 0.954
0.4026 1170.5 1254.4 1217.8 1285.4 1170.9 7.160 4.041 9.816 0.003
0.5785 1253.3 1328.8 1298.5 1359.8 1253.7 6.024 3.606 8.497 0.003
0.7349 1328.0 1381.3 1360.8 1415.4 1328.4 4.013 2.469 6.581 0.003
0.8312 1380.2 1409.0 1395.5 1436.7 1380.5 2.086 1.072 4.093 0.002
1.0000 1468.5 1468.5 1468.5 1468.5 1468.5 0.000 0.000 0.000 0.000
The theoretical values of ultrasonic speeds were calculated using theoretical and empirical relations [8-11].
Table-1 shows that minimum deviations are observed in case of free length theory ( FLT), followed by
impedance dependance relation ( IDR) and Nomoto Relation (NR). Rao’s specific sound velocity relation
154 | P a g e
shows maximum deviation. The order of applicability of the theories for the present system is as follows:-
CFLT > CIDR > CNOM > CR.
CONCLUSION:
The variation of derived parameters and ultrasonic velocity with concentration of DEHPA and
temperatures indicate the presence of molecular interaction between component molecules excess values
reveal that the interaction mainly of dipole-induced dipole interaction which is weak. The temperature
variation indicates that the strength of intermolecular interaction increases with rise of temperature. Among
four theoretical models, free length theory ( FLT) shows close agreement with experimental ultrasonic
velocity values than IDR, NR and RSSVR, n-hexane acts as a structure breaker for DEHPA.
References:-
(1) Ali A, Yasmin A & Nain AK, Indian J Pure Appl Phys 40 ( 2002)315
(2) Kannappan V & Jaya Santhi R. Indian J Pure Appl Phys 43 (2005) 750
(3) Nomoto O, J Phys Soc Japan, 13 ( 1958) 1528
(4) Shipra Baluja & parsania PH, Asian J Chem 7 ( 1995) 417
(5) D Sravana Kumar & D Krishna Rao, India J Pure Appl Physics Vol.45 ; PP(210-220)2007
(6) Jacobson B, J Chem Phys, 20 ( 1952) 957
(7) V. Ulagendran, R. Kumar, S. Jayakumar & V. Kannappan proceeding of National Sympossium on
Accoustics, 2007 PP. 419-423.
(8) S. Mishra & R. Paikaray, J Accoustic Soc India,Vol-37, No-1, PP- (20 -) 2010
(9) Syal VK, Chauhan S & Uma Kumari, Indian J Pure Apply Phys, 43 ( 2005) 844
(10) Subramaniyan Naidu P & Ravindra Prasad K J Pure Appl. Ultrasonics, 27 ( 2005) 15.
155 | P a g e
ACOUSTICAL STUDIES OF MOLECULAR INTERACTIONS IN BINARY LIQUID SYSTEM
OF CINNAMALDEHYDE AND N-N-DIMETHYLANILINE AT 303 K
Padmanabhan G1, Kumar R2, Jayakumar S3* & Kannappan V4
1. Department of Physics, Sri Sankara Arts & Science College, Kanchipuram.

2. Department of Physics, The New College, Chennai – 600 014.
3. Department of Physics RKM Vivekananda College,Chennai-600 004.
4. Department of Chemistry, Loyola College, Chennai – 600 035.
E-mail: * jayakumar_5454@yahoo.com
Abstract
Ultrasonic velocity (u), density (ρ) and Viscosity (η) were measured for binary liquid system of
cinnamaldehyde (CA) and aromatic tertiary amine N, N – dimethylaniline (DMA) for the entire composition range, at
303K. From these values, adiabatic compressibility(κ), molecular free length (Lf), internal pressure (πi), free volume
(Vf), Lennard – Jones potential (LJP), cohesive energy interaction parameter (χi) and excess thermodynamic
parameters such as excess velocity (uE), excess adiabatic compressibility (κE), excess internal pressure (πiE),
excess molar volume (VmE), excess impedance (ZE) were computed using standard relations. The results are
interpreted in terms of molecular interactions between the component molecules. It is observed that strong molecular
interactions of dipole – dipole and complex formation types exist that depend on the concentration and also the
structural aspects of the components in the mixture.
1. INTRODUCTION
The acoustical investigation of liquids mixtures reveals the significance of molecular interactions
that finds applications in several industrial, technological and biological fields [1 – 3]. The study of
molecular interactions in terms of acoustical and excess thermodynamic parameters identifies the specific
type of molecular interaction and the structural features of molecules in the solution. These structural
dependent molecular interactions are also concentration dependent and this is well reflected by the
behavior of the excess parameters [4, 5]. Cinnamaldehyde (CA) is an industrially important compound. It is
156 | P a g e
used as flavouring agent in chewing – gum, ice – cream candy and beverages and also as fungicide,
insecticide and corrosion inhibitor in steel industries. The interaction between polar groups such as
carbonyl group of aldehyde and amino group is significant in practical applications. Carbonyl group is part
of several biologically important molecules such as protein, lipids and hormones. It has electron deficient
carbon, which can function as electrophile. Amines behave as Lewis bases since they contain nitrogen as
the basic centre with a lone pair of electrons. Thus, the formation of donor – acceptor complexes can be
expected between amino group of N, N – dimethylaniline (DMA) and carbonyl group of CA.
2. EXPERIMENTAL METHODS
AnalaR grade samples are used in the present work. Chemicals are weighed using electronic single pan
balance Shimadzu make and the materials are mixed stoichiometrically. The whole range of compositions was
studied between components of the binary system. The ultrasonic velocity (u) was measured using Mittal ultrasonic
interferometer of fixed frequency of 2 MHz with an accuracy of ± 0.2 m/s, density (ρ) measurements were made
using a 10ml specific gravity bottle and viscosity (η) measurements by rate of flow of solutions through Ostwald
viscometer and digital stop watch with an accuracy of ± 0.01s. The temperature of solutions was maintained constant
by thermostat with an accuracy of ± 0.1K.
3.1 Acoustical Parameters:
The measured values of ultrasonic velocity (u), density (ρ), viscosity (η) and the computed values of
acoustical parameters are tabulated in Table 1. The variation of ultrasonic velocity and adiabatic compressibility with
mole fraction of DMA is shown in Figures 1 & 2. The behavior of ultrasonic velocity is non – linear with the mole
fraction of DMA as evident from Figure 1. It was reported that the non – linear variation of ‘u’ is an indication of solute
– solvent type of interaction which may be of dipole – dipole nature through complex formation between components
in the mixture [6, 7]. The values of adiabatic compressibility and free length show similar variation that increase with
157 | P a g e
increasing concentration of DMA. The increasing trend in both these parameters may be due to the increase in the
void created by the aromatic amine. Though the interaction between the components is stronger, the void makes the
system more compressible. Since the effective molecular area of the components decrease with concentration the
viscous nature decreases and in turn that decreases the internal pressure of the system [8, 9]. The observed values
of cohesive energy are also in the reported range of dipole – dipole and hydrogen bonded types of interactions [10].
(Figure 5)
3.2 Excess Thermodynamic Parameters
The computed values of excess thermodynamic parameters are summarized in Table 2. The variation of excess
velocity and excess compressibility versus mole fraction of DMA are shown in Figures 3 & 4. The larger negative
deviations in uE and ZE from linear dependence on the mole fraction of DMA suggest the presence of complex
formation between component molecules [11]. The observed viscosity deviations ηE are negative over the entire
concentration range investigated. Negative ηE from the rectilinear dependence on mole fraction may occur for the
systems having components of different molecular size [12]. The excess molar volume VmE is found to change sign
from positive to negative. This again supports our earlier view on the molecular interactions between component
molecules and may also due to the difference in the molecular sizes. As CA are much smaller than those of DMA,
which might allow the fitting of CA molecules into the voids created by DMA molecules [13, 14]. A perusal of table 2
reveals that the behavior of excess compressibility with concentration is also well reflected with the behavior of
excess free length. Both these parameters show almost positive deviations which may be due to the expansion in
volume of the system by i) breaking of associated structure of dipolar molecules and ii) increasing concentration of
aromatic component that creates void in the liquid mixture. The weakening of unlike molecular interaction than that of
strong like molecular association may also the reason for the positive values of these two parameters [11].
CONCLUSIONS
The behavior of acoustic parameters shows the existence of strong interaction among the component molecules
of dipole-dipole nature through complex formation. The existing strong interaction is weakened by the addition of
DMA with CA this is due to the bulky size of the aromatic amine that makes the system more compressible. It is also
158 | P a g e
found that there is a possibility of interstitial penetration of the CA into DMA. These conclusion can be drawn by the
suggested variation of excess thermodynamic parameters.
ACKNOWLEDGEMENT
The authors thank the Management of R. K. M. Vivekananda College, Mylapore, Chennai and the
Management of Sri Sankara Arts and Science College, Enathoor, Kanchipuram, for their keen interest and support
shown towards this work.
REFERENCES
1. R. Kumar, S. Jayakumar and V. Kannappan, Ind J Pure & Appl. Phys., 46 (2008) 169.
2. Jayakumar .S Karunanidhi .N and Kannappan V, Ind. J Pure & Appl. Phys., 34 (1996) 761.
3. G. V. Rama Rao, A. V. Sarma and C. Rambabu, Ind. J Pure Appl. Phys., 42 (2004) 820.
4. R. Kumar, P.E. Akilandeswari, M.G. Mohamed Kamil, V. Kannappan and S. Jayakumar, J Mol. Liq., 154
(2010) 69-75.
5. Sivaparasad V, Rajagopal E and Manoharamurthy N, J Mol. Liq., 124 (2006) 1.
6. Subramanyam Naidu P and Ravindra Prasad K, Ind. J Chem., 40 (2002) 264.
7. Isht Vibhu, Avneesh K Singh, Manisha Gupta and Shukla J P, J Mol. Liq., 115 (2004) 1.
8. Nain A K, Chand D, Chandra P and Pandey J D, Phys. Chem. Liq., 47 (2009) 195.
9. Arul G and Palaniappan L, Ind. J Pure Appl. Phys. 43 (2005) 755.
10. Thiyagarajan R, Jaafar M. S and Palaniappan L, J Phys. Sci., 18(2) (2007) 81.
11. Making sense of boiling points and melting points, S. Prahalada Rao et al, Resonance, June
(2007) 48 – 57.
12. Ali A,Yasmin A and Nain.A.K, Ind. J Pure Appl. Phys, 40 (2002) 315.
13. Ali A, Hyder S and Nain A. K, Ind. J Phys., 74B (2000) 63.
14. A. Ali and A. K. Nain, Phys. Chem. Liq., 37 (1999) 161.Ali A, Tiwari K, Nain A. K and Chakravorty
V, Ind. J Phys.74B (5) (2000) 351.
159 | P a g e
Table 1 – Ultrasonic velocity, density, viscosity and other acoustical parameters for cinnamaldehyde + N, N –
dimethylaniline system at 303.15K
η
u ρ κ Lf Z πi Vf CE
x2 10-3 α
m/s kg / m3 10-10 N-1m2 A0 106 Rayl 105 atm 10-8 m3 KJ/mol
Nsm-1
0 1537.6 1058.9 3.43 3.994 0.3997 1.628 4.924 5.145 67.695
0.0999 1528.8 1043.5 3.24 4.100 0.4050 1.595 -0.0112 4.798 5.155 65.726
0.1998 1546 1032.5 2.96 4.052 0.4026 1.596 0.0115 4.557 6.035 62.124
0.2996 1528.8 1026.6 2.71 4.168 0.4083 1.569 -0.0106 4.388 6.733 59.425
0.3995 1509 1018.3 2.43 4.313 0.4153 1.537 -0.0359 4.182 7.772 56.308
0.4997 1479.4 1019.3 2.33 4.483 0.4234 1.508 -0.0731 4.132 7.941 55.140
0.5996 1512.6 1008.3 2.03 4.335 0.4164 1.525 -0.0307 3.814 10.13 50.634
0.6996 1555.6 1000.2 1.87 4.132 0.4065 1.556 0.0254 3.613 11.90 47.676
0.7995 1510.4 991 1.69 4.423 0.4206 1.497 -0.0331 3.485 13.28 45.716
0.9 1491.2 979.8 1.51 4.590 0.4285 1.461 -0.0572 3.318 15.43 43.305
1 1535.6 969.5 1.50 4.374 0.4183 1.489 3.254 15.65 42.243
Table 2 – The values of excess thermodynamic parameters for cinnamaldehyde + N, N –

dimethylaniline system at 303.15K
ηE κE L fE VmE ZE πE
x2 uE m/s
10-4Nsm-1 10-11N-1m2 10-13 m 10 m-3
-10 104 Rayl 104 atm
0.0999 -8.6 0.003 0.678 3.402 7.723 -1.894 0.133
0.1998 8.8 -0.904 -0.181 -0.831 10.30 -0.407 -0.801
0.2996 -8.2 -1.433 0.595 3.014 6.680 -1.693 -0.776
0.3995 -27.8 -2.300 1.665 8.198 5.953 -3.586 -1.197
0.4997 -57.2 -1.401 2.984 14.44 -6.254 -5.055 0.346
0.5996 -23.8 -2.468 1.126 5.544 -3.761 -1.943 -1.326
0.6996 19.4 -2.093 -1.285 -6.187 -4.838 2.527 -1.629
0.7995 -25.6 -1.970 1.252 6.063 -4.535 -1.991 -1.176
0.9 -44.6 -1.795 2.536 12.04 -1.753 -4.163 -1.141
160 | P a g e
FIGURE 1.
1560
1540
1520
U
1500
1480
0.0 0.2 0.4 0.6 0.8 1.0

X2
FIGURE 2.
4.6
4.5
4.4
4.3
K
4.2
4.1
4.0
3.9
0.0 0.2 0.4 0.6 0.8 1.0
X2
161 | P a g e
FIGURE 3.
20
0
EXCESS U
-20
-40
-60
0.0 0.2 0.4 0.6 0.8 1.0

X2
FIGURE 4.
2
EXCESS K
-1
-2
0.0 0.2 0.4 0.6 0.8 1.0
X2
.
162 | P a g e
FIGURE 5.
K
70
65
60
CE(kJ/MOL)
55
50
45
40
0.0 0.2 0.4 0.6 0.8 1.0
X2
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CHARACTERIZATION OF NANOFLUID OF PLATINUM
Virendra Kumar, Kailash and Jitendra Kumar1
Department of Physics, BN PG College, Rath, Hamirpur, U.P., 210 431, Bharat

1. Department of Physics, Govt. Girls P. G. College, Banda, U.P., 210 001, Bharat
Email: vir.rath@yahoo.com, kailashrath@gmail.com
Abstract: Nanofluids are attracting a great deal of interest with their enormous potential to provide enhanced
performance properties, particularly with respect to heat transfer. Nanofluids are stable suspensions of nanoparticles
in a liquid. In order to avoid coagulation of the particles, the particles must be coated with a second distance holder
phase which in most cases, consist of surfactants that are stable in the liquid. An important application of nanofluid
containing nanoparticles is as a coolant, since the addition of only a few volume percent of nanoparticles to a liquid
coolant and significantly improves its thermal conductivity. Platinum nanoparticles with narrow size distribution
dispersed onto smooth, non-catalytic surfaces are of interest as model systems for the investigation of particle shape
and size dependence of the catalytic activity of platinum towards reactions of interest in fuel cell systems. Ultrasonic
velocity is the speed in which sound propagates in a certain material. It depends on material density and elasticity. It
is related in a simple way to the various coefficients of compressibility, isentropic, isenthalpic and isothermal, hence
the importance of its measurement and modeling in temperature and pressure ranges are widely used. Measurement
of ultrasonic velocity gives the valuable information about the physicochemical behaviour of the liquid and liquid
mixtures. In this work we have measured the ultrasonic velocity at different temperature and frequencies of nanofluid
of platinum using Interferometer technique.
Key Words: Nanofluids, Ultrasonic velocity, Nanotechnology and Interferometer Technique.
1. Introduction
Platinum is used in jewelry, laboratory, equipment, electrical contacts and electrodes; platinum
resistance. Platinum occurs naturally in the alluvial sands of various rivers, though there is little evidence of
its use by ancient people. The most important application of platinum is in automobiles as a catalytic
converter, which allows the complete combustion of low concentrations of unburned hydrocarbon from the
exhaust into carbon dioxide and water vapor. Platinum is also used in the petroleum industry as a catalyst.
In the laboratory, platinum wire is used for electrodes; platinum pans are used in thermo gravimetric
analysis. Nanotechnology is a most important and growing area in science. Nano-science, the science
under pinning nanotechnology, is a multidisciplinary subject covering atomic, molecular and solid state
physics, as well as much of chemistry. Nanostructures are known to exhibit novel and improved material
properties. Nanotechnology is design, fabrication and application of nanostructures or nanomaterials, and
fundamental understanding of the relationships between physical properties and material dimensions.
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Application of nanostructures and nano-materials are based on the peculiar physical properties of
nanosized materials, the huge surface are the small size that offers extra possibilities for manipulation and
room for accommodating multiple functionalities. In future, amazing nanotech-based products are
expected, including extraordinarily tiny computers that are very powerful, building materials that withstand
earthquakes, advanced systems for drug delivery and custom-tailored pharmaceuticals as well as the
elimination of invasive surgery, because repairs can be made from within the body. Future developments
and implemention of nanotechnology could certainly change the nature of almost every human made object
and activity. Its ultimate societal impact is expected to be as dramatic as first industrial revolution and
greater than the combined influences that aerospace, nuclear energy, transistors, computers and polymers
have in this century. Nanotechnology development is the need to understand the techniques for atomic and
molecular based study of matter in nanoscale [1-3].
Nanofluids are dilute liquid suspensions of nanoparticles with at least one of their principal
dimensions smaller than 100nm. There is a growth in the use of colloids which are nanofluids in the
biomedical industry for sensing and imaging purposes. This is directly related to the ability to design novel
materials at the nanoscale level alongside recent innovations in analytical and imaging technologies for
measuring and manipulating nanomaterials. This has led to the fast development of commercial
applications which use a wide variety of manufactured nanoparticles. Nanofluids have higher thermal
conductivity and single-phase heat transfer coefficients than their base fluids [4]. Nanofluids could be
applied to almost any disease treatment technique by reengineering the nanoparticles properties. Several
significant gaps in knowledge are evident at this time, including, demonstration of the nanofluid thermal-
hydraulic performance at prototypical reactor conditions and the compatibility of the nanofluid chemistry
with the reactor materials [5].
Ultrasonic velocity has become a valuable tool for the study of various physical and chemical
properties of the matter. Ultrasonic velocity measurement offers a rapid and destructive tool for the
characteristics of materials. Various elastic parameters and estimation of grain size has been going on far
the past several years. Elastic constants of isotropic solid can be determined ultrasonically when both
longitudinal and transverse wave velocities are known [6, 7]. The aim of present work was to study the
characterization of copper nanofluid using ultrasonic techniques.
2. Experimental Details
Interferometry is the technique of diagnosing the properties of two or more waves by studying the
pattern of interference created by their superposition. It is an important investigative technique in the fields
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of astronomy, fiber optics, engineering metrology, optical metrology, oceanography, seismology, quantum
mechanics, plasma physics and remote sensing. An ultrasonic interferometric sensor has been introduced
for the measurement of suitable changes in the physical properties of fluids such as density, viscosity and
bulk modulus [8].
The ultrasonic interferometer is simple in construction and operation and gives accurate and
reproducible results. From these results, one can readily determine the velocity of sound in a liquid with
high accuracy. Formerly, the absorption of sound in the liquid and the coefficient of reflection at the reflector
surface have been obtained through a complicated analysis of the electrical and equivalent electrical
circuits of the quartz crystal and the associated fluid column. In our experimental work we use
multifrequency interferometer. This multifrequency generator can generate ultrasonic waves of several
frequencies form 1 MHz to 12 MHz in the medium. The multifrequency ultrasonic interferometer consists of
the two parts- the high frequency generator and the measuring cell. The high frequency generator is
designed to excite the quartz plate fixed at the bottom of the measuring cell at its resonant frequency to
generate ultrasonic waves in the experimental liquid in the measuring cell. A micro ammeter to observe the
changes in current and two controls for the purpose of sensitivity regulation and initial adjustment of micro
ammeter is provided on the high frequency generator. A fine micrometer screw has been provided at the
top, which can lower or raise the reflector plate in the cell through a known distance. It has a quartz plate
fixed at its bottom the ultrasonic interferometer may be used for determination of ultrasonic velocity. The
measuring cell is connected to the output terminal of the high frequency generator through a shielded cable
the cell is filled with the experimental liquid before switching on the generator the ultrasonic waves moves
normal from the crystal till they are reflected back from the movable plate and the standing waves are
formed in the liquid in between the reflector plate and the quartz crystal. The micrometer is slowly moved till
the anode current meter on high frequency generator shows a maximum. A number of maximum readings
of anode current are passed on and their n is counted the total distance x thus moved by the micrometer
gives the value of wavelength λ with the help of the following relation;
x = n× λ /2 (1)
Once the wavelength is known the ultrasonic velocity V of copper nanofluid can be calculated with the help
of following relation;
V= λ ×f (2)
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3. Evaluation
Ultrasonic velocity measurements have been successfully employed to detect and assess weak
and strong molecular interactions present in nanofluids. These studies can also be used to determine the
extent of complexation and calculate the stability constants of such complexes [9]. Nanofluids are
suspensions of nanoparticles in fluids that show significant enhancement of their properties at modest
nanoparticle concentrations. Nanofluids are considered to offer important advantages over conventional
heat transfer fluids. Nanofluids contain suspended metallic nanoparticles, which increases the thermal
conductivity of the base fluid by a substantial amount [10, 11]. Measurement of ultrasonic velocity gives the
valuable information about the physicochemical behaviour of the liquid and liquid mixtures. Several
relations, semi-empirical formula and theories are available for the theoretical computation of ultrasonic
velocity in liquid and liquid mixtures. Temperature variation of ultrasonic velocity for nanofluid of platinum is
given in Table 1 and frequency variation of ultrasonic velocity for this fluid is shown in Table 2.
4. Results and Discussions
Ultrasonic velocity measurements are helpful to study the ion-solvent interactions in aqueous and
non-aqueous solutions in recent years. Ultrasound has been extensively used to determine the ion solvent
interactions in aqueous containing electrolytes.
The measured data of ultrasonic velocity for nanofluid of platinum at different temperature and frequencies
are given in Table 1 - 2. Graphical representation of data is given in Figures 1 - 2. From Figure 1(i), at
1Frquency(F) in MHz; it is observed that at increasing temperature from 311K to 317K, the ultrasonic wave
velocity is increase and when temperature again increase up to 320K, there is a slightly decreases, when
temperature is reached slightly at 323K, velocity is increase but at 326K velocity again decrease.
Temperature variation of ultrasonic velocity at 2 MHz frequency is shown in Figure 1(ii), one can say from
this figure velocity is increase from temperature 312K to 315K but when we increase temperature at 318K,
velocity decreases. Again increasing temperature till 327K, ultrasonic velocity is increase. This shows
proportionality relation between temperature and velocity. It is clear from Figure 1(iii), on increasing
temperature from 312K up to 318K, the velocity of ultrasonic wave is increase and up to 321K the velocity
is slightly decrease and at 324K the velocity of ultrasonic wave is slightly increase and again at 327K the
ultrasonic wave velocity is slightly decrease. This shows linear and inverse relation separately between
temperature and velocity.
Ultrasonic wave velocity for nanofluid of platinum is measured at different frequencies ranging form 1 - 5
MHz, at room temperature, the result is given in table 2. Frequency variation of ultrasonic velocity for this
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fluid is shown in Figure 2. It is observed that with increase in frequency from 1 MHz to 3 MHz, velocity is
increase; velocity is decreases on increasing frequency to 5MHz.
5. Acknowledgement
The authors are thankful to the University Grants Commission, New Delhi for financial support.
6. References
[1] G. Cao, ‘Nanostructures and nanomaterials’, Imperial College Press, London, 391-412, 2007.
[2] G.A. Mansoori, ‘Principles of nanotechnology’, World Scientific Publishing Co., Singapore, 1-28, 2006.
[3] C.W. Shong, S.C. Haur and A.T. Wee, ‘Science at the nanoscale’, Pan Stanford Publishing, Singapore, 1-
17, 2010
[4] J. Buongiorno, ‘Convective Transport in Nanofluids’, J. Heat Transfer, 128, 240-250, 2006.
[5] K.V. Wong and O.D. Leon, ‘Applications of Nanofluids: Current and Future’, Advances in Mechanical
Engineering, 2010, 519659-519669, 2010.
[6] V. Kannappan and S.C. Vinayagam, ‘Ultrasonic investigation of ion-solvent interactions in aqueous and non-
aqueous solutions of transition and inner transition metal ions’, Ind. J. of pure and Appl. Phys., 45, 143-150,
2007.
[7] A. Kumar and Y. Kumar, ‘Ultrasonic velocity measurement in cylindrical rod material’ J. Pure Appl. Ultras.,
20, 15-19, 1998.
[8] K. Balasubramaniama and S. Sethuraman, ‘Ultrasonic Interferometer Technique’ Centre for NDE and
Department of Mechanical Engineering, IIT Madras, 2006.
[9] V. Kannappan and N.I. Gandhi, ‘Ultrasonic studies on charge transfer complexes of certain aldehydes with
benzylamine and cyclohexylamine as doners in n-hexane ay 303K’, Ind. J. of pure and Appl. Phys., 45, 221-
225, 2007.
[10] S. Kakaç and A. Pramuanjaroenkij, ‘Review of convective heat transfer enhancement with Nanofluids’, Inter.
J. of Heat and Mass Tran., 52, 3187-3196, 2009.
[11] D.P. Kulkarni, D.K. Das and R.S. Vajjha, ‘Application of nanofluids in heating buildings and reducing
pollution’, Applied Energy, 86, 2566-2573, 2009.
Table 1 - Temperature Variation of Ultrasonic Velocity in Nanofluid of Platinum

Temperature (K) 311 312 314 315 317 318 320 321 323 324 326 327
Frequency (F)
1 MHz 1343 1330 1363 1380 1398 1400 1390 1390 1394 1400 1364 1300
2 MHz 1530 1534 1540 1541 1530 1531 1530 1533 1550 1567 1590 1589
3 MHz 1520 1534 1510 1548 1590 1586 1530 1507 1520 1552 1600 1542
4 MHz 1510 1531 1520 1512 1500 1506 1540 1556 1580 1571 1460 1330
Table 2- Frequency Variation of Ultrasonic Velocity in Nanofluid of Platinum

Frequency [MHz] 1 2 3 4 5
Velocity [m/sec] 1329 1513 1570 1430 1414
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Figure 1(i). Temperature Variation of Ultrasonic Figure 1(ii). Temperature Variation of Ultrasonic
Velocity in Nanofluid of Platinum Velocity in Nanofluid of Platinum
Figure 1(iii). Temperature Variation of Ultrasonic Figure 2. Temperature Variation of Ultrasonic

Velocity in Nanofluid of Platinum Velocity in Nanofluid of Platinum
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ULTRASONIC BEHAVIOUR OF MIXED CRYSTALS
Virendra Kumar, Kailash and Bharat Singh

Department of physics, B.N.P.G. College, Rath, Hamirpur, U.P., 210 431, Bharat
Email- vir.rath@yahoo.com, kailashrath@gmail.com
Abstract: In the mixed crystal systems, the anions are substituted by other anions of nearly equal
size without breaking the crystal symmetry and so any ratio of two components yields the mixed
crystal. A mixed crystal has physical properties analogous to those of the pure crystals. The mixed
crystals of alkali halides are found to be harder than the crystals of end members and so they
become more useful. The mixed alkali halides find their applications in optical, optoelectronic, and
electronic devices. In addition, mixed crystals with multiple phases have been found to be more
interesting. Further, it is interesting to prepare multiphase mixed crystals with new composition
from miscible alkali halides. The behaviour of the ultrasonic properties plays an important role in
providing valuable information about the mechanical and dynamical properties, such as inter
atomic potentials, equation of state, and phonon spectra. Elastic properties are also
thermodynamically related to the specific heat, thermal expansion, Debye temperature, melting
point and Grüneisen parameter. The aim of this work is to give a detailed description of the
behaviour of non-linear properties such as second, third and fourth order elastic constants of
mixed potassium and rubidium fluoride and mixed lead selenide and telluride crystals at different
temperature by using Coulomb and Börn - Mayer potentials. The evaluation of other ultrasonic
properties such FOPDs of second and third order elastic constants, SOPDs of SOECs and partial
contractions are computed using higher order elastic constants using this theory.
Key Words: Ultrasonic Properties, Elastic Constants, Coulomb and Börn-Mayer Potentials,
Mixed Crystals and Partial Contractions.
1. Introduction
In recent years considerable interest has been paid to the study of mixed crystal properties as they
are useful in many technological applications such as mixed crystals of alkali halides are used for laser
windows. Lead selenide nano-crystals embedded into various materials can be used as quantum dots.
Lead Telluride is used in a number of industrial applications including infrared detection and imaging. PbTe
single crystals doped with VII A Periodic system group elements will continue to attract a widespread
attention both for their fundamental electronic properties and for the applications in infrared optoelectronic
[1-3]. Studies on mixed crystals are quite useful as they are of considerable technological
importance in the field of storage cells. Ultrasonic characterization of materials is a versatile tool for the
inspection of their micro-structure and their mechanical properties. This is possible because of the close
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association of the ultrasound wave with the elastic and the inelastic properties of the materials; also this
technique offers the possibility of using different frequency ranges and many modes of vibration of the
ultrasound waves to probe into structural level [4].
To study the ultrasonic behaviour of a deformed crystal, the elastic energy density is expanded by
Taylor’s series expansions. One gets a series with higher order coefficients. These coefficients are known
as higher order elastic constants. In this expansion, the second, third and fourth order elastic constants are
the coefficients of second, third and fourth order terms. In last and present decade considerable interest
has been taken in investigation of ultrasonic properties of materials [5-8]. Elastic and dielectric properties of
mixed ionic solids have been carried out by number of workers using different phenomenological models. In
present investigation, some efforts have been made for obtaining SOECs, TOECs and FOECs at an
elevated temperature, the FOPDs of SOECs and TOECs, the SOPDs of SOECs and partial contractions of
mixed (KF)X - (RbF)1-X and mixed (PbSe)X - (PbTe)1-X crystals. In this paper we represent mixed (KF)X -
(RbF)1-X as A and (KF)100 - (RbF)0, (KF)80 - (RbF)20, (KF)60 - (RbF)40, (KF)40 - (RbF)60, (KF)20 - (RbF)80, and
(KF)0 - (RbF)100 as A1----A6. Similarly B for mixed (PbSe)X - (PbTe)1-X and B1----B6 for its fractions.
2. Formulation
As we presented earlier the elastic energy density for a crystal of a cubic symmetry can be
expanded up to quartic terms as shown below [9];
U0 =U2 + U3 + U4
= [1 2!]C ijk l X ij X kl + [1 3!]C ijklmn X ij X kl X mn + [1 4!]C ijklmnpq X ij X kl X mn X pq (1)
These elastic constants have two parts as given below.

CIJ = CIJ0 + C IJvib , CIJK = CIJK
0 vib
+ CIJK , CIJKL = CIJKL
0 vib
+ CIJKL (2)
3. Evaluation
With the help of nearest-neighbour distance and hardness parameter; the second, third and fourth
order elastic constants for A and B crystals are evaluated at different temperature. The values of SOECs at
room temperature for A and B are given in Table 1 and third and fourth order elastic constants at 300K are
given in Tables 2(i)-3(ii) for these crystals. The FOPDs of SOECs and TOECs, the SOPDs of SOECs and
partial contractions for mixed crystals are evaluated utilizing room temperature data, and the results are
shown in Tables 4 – 5.
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4. Results and Discussions
The temperature dependence of elastic constants has been a subject of study in a number of
investigations. The temperature variation of various ultrasonic are represented graphically for A and B.
There are three SOECs for face centered cubic crystals. The values of C11 and C44 are increasing and the
value of C12 is decreasing as temperature increases for A and B. From Figure 1, the value of C11and C44
increases and the value of C12 decreases as temperature increases for A1. For all crystals the values of
C111, C112 and C166 are negative in nature while C123, C144 and C456 are positive in nature shown in Table
2(i)-(ii). Figure 2(i)-(ii) shows that the values of C 111, C123, C 144 and C 166 are increasing; the value of
C 112 is decreasing as temperature increases and C456 remains constant for A 2 . There are three
FOPDs of SOECs for mixed crystals. Figure 3 present the temperature variation of FOPDs of SOECs for
B3. From this figure, it is clear that the value of dC11/dp and dC12/dp decreases and the value of dC44/dp first
increases than decrease as temperature increases. It may be stated that all the second order pressure
derivatives of second order elastic constants are positive. Figure 4 present the value of d2C11/dp, and
d2C44/dp decreases as temperature increases and d2C12/dp decreases first and increases last for B4. From
Figure 5, one can say that the value of Ψ11 , Ψ12 decreases as temperature increases and Ψ44 somewhere
increases or decreases as temperature increases for B5 crystals.
5. Acknowledgement
Table 1. SOECs in 1011 dyne/cm2 at room temperature for A and B

Fraction A1 A2 A3 A4 A5 A6 B1 B2 B3 B4 B5 B6
C11 9.97 8.97 9.20 9.45 9.70 5.29 14.57 14.66 15.02 15.38 15.76 13.04
C12 1.67 1.39 1.47 1.52 1.59 1.54 5.418 4.109 4.375 4.664 4.976 3.938
C44 1.88 1.59 1.66 1.73 1.80 1.67 5.545 4.233 4.502 4.794 5.109 4.052
Table 2(i) TOECs in 1011 dyne/cm2 at room temperature for A

Fraction A1 A2 A3 A4 A5 A6
C111 -106.902 -96.147 -100.034 -101.340 -105.861 -4.933
C112 -26.916 -24.256 -24.831 -25.463 -26.148 -15.302
C123 3.806 3.215 3.352 3.496 3.647 3.455
C144 3.535 3.022 3.141 3.266 3.397 2.952
C166 -7.343 -6.183 -6.450 -6.733 -7.028 -6.591
C456 3.141 2.679 2.786 2.899 3.016 2.578
Table 2(ii) TOECs in 1011 dyne/cm2 at room temperature for B
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Fraction B1 B2 B3 B4 B5 B6
C111 -220.85 -206.11 -209.79 -213.49 -217.18 -202.42
C112 -31.76 -26.53 -27.68 -28.93 -30.29 -25.47
C123 9.42 7.45 7.90 8.37 8.88 7.04
C144 9.04 7.20 7.61 8.50 8.53 6.81
C166 -22.08 -17.08 18.19 -19.39 -20.68 -16.05
C456 8.72 6.93 7.33 7.76 8.22 6.56
Table 3(i) FOECs in 1011 dyne/cm2 at room temperature for A

Fraction A1 A2 A3 A4 A5 A6
C1111 286.74 183.52 207.91 233.31 260.07 169.01
C1112 -206.88 -203.77 -204.60 -205.39 -206.39 -69.936
C1122 -84.00 -89.07 -87.95 -86.72 -85.43 -2.68
C1123 -5.76 -4.60 -4.86 -5.14 -5.43 -6.15
C1144 -7.72 -6.60 -6.86 -7.13 -7.42 -6.31
C1155 27.73 22.97 24.06 25.22 26.43 2.51
C1255 -10.63 -9.16 -9.50 -9.86 -10.23 -8.81
C1266 37.09 31.10 32.48 33.94 35.47 32.56
C1456 -7.33 -6.26 -6.51 -6.77 -7.04 -6.02
C4444 40.80 34.40 35.88 37.44 39..07 35.58
C4455 -7.41 -6.32 -6.57 -6.84 -7.12 -6.41
Table 3(ii) FOECs in 1011 dyne/cm2 at room temperature for B

Fraction B1 B2 B3 B4 B5 B6
C1111 2457.17 2304.64 2343.89 2382.56 2420.38 2264.77
C1112 -10.12 -38.22 -31.75 -24.98 -17.78 -44.16
C1122 71.12 37.80 45.39 53.47 62.03 30.59
C1123 -20.02 -15.53 -16.53 -17.61 -18.77 -14.59
C1144 -20.67 -16.44 -17.39 -18.40 -19.49 -15.56
C1155 101.05 78.11 83.22 88.73 94.66 73.34
C1255 -22.90 -18.33 -19.36 -20.46 -21.64 -17.37
C1266 119.03 92.63 98.52 104.87 111.69 87.13
C1456 -20.38 -16.20 -17.14 -18.14 -19.22 -15.33
C4444 121.83 95.03 101.02 107.47 114.39 89.44
C4455 -20.47 -16.27 -17.20 -18.22 -19.30 -15.39
Table 4. First Order Pressure Derivatives of the SOECs and TOECs for A and B
dC11 / dp -14.40 -14.98 -14.83 -14.68 -14.54 -10.72 -9.86 -10.69 -10.48 -10.28 -10.07 -10.89
dC12 / dp -6.12 -6.34 -6.29 -6.23 -6.17 -5.18 -3.02 -3.03 -3.02 -3.02 -3.02 -3.04
dC 44 / dp -0.05 -0.08 -0.07 -0.07 -0.06 -0.34 0.20 0.09 0.11 0.14 0.17 0.06
dC111 / dp 48.74 63.35 59.58 55.87 52.28 21.49 -68.85 -73.96 -72.78 -71.53 -70.22 -75.07
dC112 / dp 37.56 42.60 41.31 40.03 38.79 18.49 1.20 3.56 2.95 2.34 1.76 4.20
dC123 / dp 1.60 1.49 1.51 1.54 1.57 2.27 2.29 2.16 2.19 2.22 2.25 2.13
dC144 / dp 1.233 1.232 1.233 1.234 1.234 1.789 0.69 0.61 0.63 0.65 0.67 0.59
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dC166 / dp 2.59 2.63 2.62 2.61 2.60 2.93 1.45 1.47 1.46 1.46 1.45 1.48
dC 456 / dp 2.28 2.26 2.271 2.276 2.282 2.623 2.42 2.33 2.35 2.37 2.39 2.31
Table 5. SOPDs of SOECs in 10-10 (dyne/cm2)-1 and Partial Contraction ( Ψ in 1013dyne/cm2) for A and B
2
d C11 / dp 2 3.48 3.99 3.85 3.72 3.59 3.68 1.57 2.01 1.89 1.78 1.67 2.13
d 2 C12 / dp 2 0.90 1.04 1.00 0.96 0.93 1.07 0.22 0.25 0.25 0.24 0.23 0.26
d 2 C 44 / dp 2 0.28 3.04 2.97 2.91 2.85 5.38 0.18 0.19 0.19 0.19 0.18 0.19
Ψ11 -7.20 -8.12 -7.96 -7.72 -7.47 -1.26 25.19 21.97 22.75 23.54 24.36 21.20
Ψ12 -6.10 -6.08 -6.09 -6.10 -6.11 -1.75 0.22 -0.74 -0.55 -0.31 -0.05 -1.00
Ψ44 0.75 0.61 0.65 0.68 0.72 0.71 3.25 2.49 2.66 2.85 3.04 2.34
6. References
[1] S. Prabahar, K. Rajasekar and S. Srikanth, ‘Lead selenide thin films from vacuum evaporation Method-
structural and optical properties’, Chalcogenides Letters, 6, 203–211, 2009.
[2] F. Ren, E. D. Case, J. E. Ni, E. J. Timm, E.L. Curzio, R. M. Trejo, C. H. Lin and M.G. Kanatzidis,
‘Temperature-dependent elastic moduli of lead telluride-based thermoelectric materials’, Philosophical
Magazine, 89, 143–167, 2009.
[3] Y. Zhang, X. Ke, C. Chen, J. Yang, and P. R. C. Kent, ‘Thermodynamic properties of PbTe, PbSe, and PbS:
First-principles study’, Phys. Rev. B, 80, 024304–024316, 2009.
[4] M.S. Gaafar, H.A. Afifi, M.M. Mekawy, ‘Structural studies of some phospho-borate glasses using ultrasonic
pulse echo technique DSC and IR spectroscopy’, Physica B, 404, 1668–1673, 2009.
[5] P. F. Yuan and Z. J. Ding, ‘Ab inito calculation of elastic properties of rock-salt and zinc-blend MgS under
pressure’, Physica B, 403, 1996, 2008.
[6] K. M. Raju, R. K. Srivastava and Kailash, ‘Temperature Variation of Higher Order Elastic Constants of MgO’,
Pramana, 69, 445-450, 2007.
[7] D. Varsney, N. Kaurav, U. Sharma and R.K. Singh, ‘Phase transformation and elastic behaviour of MgX ( X=
S, Se Te ) alkaline earth chalcogenides’, J. Phys. and Chem. of Solids 69, 60, 2008.
[8] J. Sinova, A.S. Nunez, J. Schliamann and A.H. Mcdonald, ‘Electron- Phonon Interaction in
Polyacene Organic Transistors’, Phys. Stat. Sol. (b), 230, 309-312, 2002.
[9] Kailash, K.M. Raju, S.K. Srivastava and K.S. Kushwaha, ‘Anharmonic properties of rock-salt structure
solids’, Physica B, 390, 270, 2007.
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Figure 1 Temperature Variation of SOECs for A1 Figure 2(i) Temperature Variation of TOECs for A2
Figure 2(ii) Temperature Variation of TOECs for A2 Figure 3 Temperature Variation of FOPDs for B3
Figure 4 Temperature Variation of SOPDs for B4 Figure 5 Temperature Variation of Partial Contractions for B5
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TEMPERATURE DEPENDENDE OF ULTRASONIC
ATTENUATION IN STRONTIUM OXIDE CRYSTAL
Kailash, Virendra Kumar and D.D. Gupta1
Department of Physics, BN PG College, Rath, Hamirpur, U.P., 210 431, Bharat

1. Department of Physics, Bipin Bihari College, Jhansi, U.P., 284128, Bharat
Email: kailash.rath@yahoo.co.in, vir.rath@yahoo.com
Abstract: The ultrasonic attenuation is a measure of the relative amplitudes of a wave at two
locations in space. Attenuation, itself, is not relative, however. Attenuation is a definite quantity for
a particular mode of wave motion at a certain frequency in a given material under specific
conditions. Ultrasonic absorption coefficients can be used for non-destructive techniques to
characterize the materials. The temperature dependent part of ultrasonic attenuation has been
explained in terms of model where the acoustic phonon interacts with a number of thermal
phonons in the lattice. In sewage treatment facilities, ultrasonic attenuation is used as a sensing
mechanism to control pumps and maintain sludge levels in setting basins. The strontium oxide
crystal possesses face centred cubic crystal structure. In this work ultrasonic attenuation due to
phonon–phonon interaction (α/f2)p-p and thermo elastic relaxation (α/f2)th are studied in strontium
oxide at an elevated temperatures along <100> direction. For the evaluation of the ultrasonic
coefficients the second and third order coefficients are also calculated using Coulomb and Born
Mayer potentials utilizing nearest neighbour distance and hardness parameter data.
Key Words: Attenuation, Thermo elastic relaxation, Phonon-phonon interaction, Akeiser loss and
Gruneisen Numbers.
1. Introduction
Attenuation is the term used to account for loss of wave amplitude or signal due to all mechanism,
including absorption, scattering and mode conversion. The ultrasonic attenuation gained very wide
acceptance in scientific experiment. The most important causes of ultrasonic attenuation in solids are
electron–phonon, phonon–phonon interaction and that due to thermo elastic relaxation. At room
temperature, electron mean free path is not comparable to phonon mean path and no coupling will take
place. Thus the attenuation due to electron–phonon interaction will be absent. The two dominant processes
that will give rise to appreciable ultrasonic attenuation at higher temperature are the phonon–phonon
interaction also known as Akeiser loss and that due to thermo elastic relaxation [1, 2]. Both these type of
attenuation are observed in calcium oxide crystal. It has been established that at frequencies of ultrasonic
176 | P a g e
range and at higher temperatures in solids, phonon–phonon interaction mechanism is dominating cause for
attenuation. The ultrasonic attenuation study of the materials has gained new dimensions with the progress
in the material science [3-10].
The temperature dependent part of ultrasonic attenuation has been explained in terms of model where the
acoustic phonon interacts with a number of thermal phonons in the lattice. In present work ultrasonic
attenuation due to phonon–phonon interaction (α/f2)p-p and thermo elastic relaxation (α/f2)th are studied in
strontium oxide at an elevated temperatures along <100> direction. For the evaluation of the ultrasonic
coefficients the second and third order coefficients are also calculated using Coulomb and Born Mayer [11]
potentials.
2. Formulation
Here we use phonon-phonon interaction [12] for evaluating ultrasonic attenuation coefficient over
frequency square (α/f2)p-p, the expressions are given as:
(α/f2)l = 4π2 E0( Dl/3) τl / 2dVl3 (1)
and (α/f )s = 4π E0( Ds/3) τs / 2dVs
2 2 3 (2)
where the condition ωτth <<1has already been assumed. Here E0 is thermal energy density, ω is the
angular frequency (=2πf), f is frequency of ultrasonic waves, d is the density and Vl, Vs are the ultrasonic
velocities for longitudinal and shear waves respectively.
The Vl, Vs and VD are given as
3
Vl = (C11/d)1/2, Vs = (C44/d)1/2 and 3/ VD = 1/ Vl 3 +2/ Vs3 (3)
Two relaxation times are related as
2
(1/2)τl = τs = τth = 3K/Cv V D (4)
Where τth is the thermal relaxation time for the exchange of acoustic and thermal energy, K is the thermal
conductivity, Cv is specific heat and VD is the Debye average velocity. The acoustic coupling constant D
in eqns. (1) and (2) is obtained from the values of the SOEC and TOEC data using theoretical formulae for
<(γij)2> and <γij>2 and given as
D = 9 <(γij)2> – (3Cv T/ E0) <γij>2 (5)
Where γi are the Grüneisen parameters corresponding to particular direction of propagation and
j
polarization. The thermoelastic attenuation is obtained as

(α/f2)th = 4π2 <γij>2 KT/2dV5 (6)
We have calculated the SOEC and TOEC for the evaluations of acoustic coupling constants D, thermal
relaxation time τth and ultrasonic absorption coefficients over frequency square of the ultrasonic wave.
3. Evaluation
177 | P a g e
The temperature dependence of second and third order elastic constants for Strontium Oxide has
been evaluated at different temperatures following Brügger’s approach [13] and the method given by Mori
and are presented in Table 1 along with melting point. The theoretical [14] values of SOECs and TOECs in
1011dyne/cm2 at room temperature are also given in this Table for comparison. Using the formulation, the
room temperature data of longitudinal and shear wave velocities, debye average velocity, thermal
relaxation time and non-linearity constants for Strontium Oxide along <100> direction are presented in
Table 2. Grüneisen parameters have been evaluated using Mason’s Grüneisen [15] parameters tables at
different temperatures along <100> direction with the help of second and third order elastic constants. The
non-linearity constants D are evaluated using the average Grüneisen parameters <γij> and average square
Grüneisen parameters <γij2> and are presented in Table 3 along with attenuation (α/f2)l, (α/f2)s and (α/f2)th.
The elastic constants of an isotropic solid specimen can be accurately determined by measuring
the velocities of transverse and longitudinal ultrasonic waves in the specimen. The variation of the wave
velocities with pressure can be used to determine the pressure derivatives of the elastic constants. In the
present study all the SOECs are positive, while among TOECs three are positive and three are negative in
nature. The magnitude of second and third order elastic constants and their temperature variation plays a
crucial role in the investigation of ultrasonic attenuation in Strontium Oxide; their temperature variation is
presented in Figure 1, 2. It is clear from the Figure 3 that the value of thermal relaxation time τth is very low
at low temperature and increases as temperature is increased. The temperature variation of ultrasonic
velocities is presented in Figure 4. It is clear from this Fig. that the ultrasonic velocity for longitudinal wave
and shear wave increases as temperature increases along <100> direction. From Figure 5 one can see
that non-linearity constants decrease as increase temperature. It is clear from Figure 6 that the value of
(α/f2)l and (α/f2)s increases with temperature, the values of (α/f2)l are found greater than those of (α/f2)s
along <100> direction, similar behavior has been observed by other researchers in solids.
5. Acknowledgement
6. References
[1] S. K. Kor, R. R. Yadav and Kailash, ‘Ultrasonic attenuatio in dielectric crystals’, J. Phys. Soc. Jpn.,
55, 207, 1986.
[2] A. Alkeizer, ‘On the absorption of sound in solids’, J. Phys. (USSR), 1, 277, 1939.
[3] D. Singh, D. K.Pandey, P. K. Yadawa and A. K. Yadav, ‘Attenuation of ultrasonic waves in V, Nb and Ta at
low temperatures’, Cryogenics, 49, 12, 2009.
[4] E. S. R. Gopal and B. J. Thangaraju, ‘Physical ultrasonics: current scenario and future prospects’, Pure
Appl. Ultrasonics, 22, 29, 2000.
178 | P a g e
[5] S. K. Kor, R. R. Yadav and D. Singh, ‘Ultrasonic studies of CTAB in glycol’, Mol.Cryst. Liq. Cryst., 392,
75, 2003.
[6] A. K. Upadhyay and B. S. Sharma, ‘Elastic properties of intermetallics compounds under high pressure and
high temperature’, Ind. J. Pure Appl. Phys., 47, 362, 2009.
[7] O. N. Awasthi and V. K. Pundhir, ‘Ultrasonic attenuation in liquid mecury, zinc and gallium metals’,
Ind. J. Pure Appl. Phys., 45, 434, 2007.
[8] R. K. Singh, ‘Ultrasonic attenuation in alkaline earth metals’, J. Pure Appl. Ulrason., 28, 59, 2006.
[9] J. D. Pandey, A. K. Singh and R. Dey, ‘Effect of isotopy on thermoacoustical properties’, J. Pure Appl.
Ulrason., 26, 100, 2004.
[10] K. Foster, R.G. Leisure, J. B. Shaklee, J. Y. Kim and K. F. Kelto, ‘Ultrasonic study of hydrogen
motion in a Ti-Zr-Niicosahedral quasicrystal and a 1/1 bcc crystal approximant’, Phys. Rev. B, 61, 241, 2000.
[11] M. Born and J. M. Mayer, Zur Gittertheorie der lonenkristalle, Z Phys. (Germany), 75, 1, 1932.
[12] W. P. Mason, ‘Piezoelectric crystals and their applications to ultrasonics’, D. Van Nortrand Co, Inc, Prinston,
New Jersey, 479, 1950.
[13] K. Brugger, ‘Thermodynamic definition of higher order elastic coefficients’, Phys. Rev., 133, A1612, 1964.
[14] J. Shanker and J. P. Singh, third and fourth order elastic constants for silver halides, alkaline earth oxides,
and chalcogenides of Pb and Sn, phys. stat. sol. (a) 70, 677, 1982.
[15] W. P. Mason, ‘Effect of impurities and phonon-processes on the ultrasonic attenuation in germanium,
crystal quartz and silicon’, Physical Acoustics, Vol. III B, Academic Press New York, 237, 1965.
Table 1. Room Temperature data of Second and Third Order Elastic Constants in 1011 dyne/cm2 for SrO
Mel. Point C11 C12 C44 C111 C112 C123 C144 C166 C456 Reference
24300C 18.18 10.327 10.495 -249.62 -54.85 16.94 16.18 -41.99 15.66 This Work
17.35 -2.72 1.46 [14]
4.175 5.587 -22.50 -2.21 1.310 1.410
Table 2. Room Temperature data of Longitudinal and Shear Wave

Velocities, Debye Average Velocity in 105 cm/sec2, Thermal Relaxation
Time in 10-12 sec and non linearity constants for SrO along <100>
direction
Vl VS VD τ th Dl DS
6.218 4.693 5.038 7.174 14.195 2.149
Table 3. Room Temperature data of Grüneisen Parameter, Square

Average Grüneisen Parameter, p-p Attenuation for Longitudinal and
Shear Waves in Nps2/cm and Thermal Attenuation in 10-20 Nps2/cm for
SrO along <100> direction
< γ ij > <( γ i j )2> (α/f2)L (α/f2)S (α/f2)th
-0.561 1.764 1.083 0.190 1.399
179 | P a g e
Figure 1. Temperature Variation of SOECs Figure 2. Temperature Variation of TOECs
180 | P a g e
Figure 3. Temperature Variation of Thermal Relaxation Time Figure 4. Temperature Variation of Ultrasonic Velocities
Figure 5. Temperature Variation of non-linearity constants Figure 6. Temperature Variation of Ultrasonic attenuation
181 | P a g e
ULTRASONIC WAVE PROPAGATION IN REFRACTORY MATERIALS
Devraj Singh1*, P. K. Yadawa1, Ravi S. Singh2 and S. K. Sahu2
1 Department of Applied Physics, Amity School of Engineering and Technology

Bijwasan, New Delhi- 110 061, India
2 Department of Physics, D. D. U. Gorakhpur University, Gorakhpur- 207 009(U.P.)
*dsingh1@aset.amity.edu
ABSTRACT: The ultrasonic attenuation of TiC and TiN are investigated at room temperature along
<100>, <110> and <111> orientations using Mason’s theory. For these materials, Second and Third
Order Elastic Constants (SOEC and TOEC), bulk modulus, elastic anisotropy, acoustic impedance,
adiabatic compressibility, molar volume, intermolecular free path length, Rao’s constant, Wada’s
constant, van der Waals constant, ultrasonic velocities, thermal relaxation time, acoustic coupling
constants are computed. Ultrasonic attenuation due to phonon-phonon interaction mechanism is
predominant over thermoelastic relaxation mechanism. All calculated results have been discussed
and comparision with available experimental results are drawn.
KEYWORDS: Ultrasonic attenuation, elastic constants, thermal conductivity
INTRODUCTION: The ultrasonic properties can be used as nondestructive techniques for the detection
and characterization of materials properties not only after the production but during processing as well [1-
3]. The refractory titanium compounds like TiC and TiN is known for its extreme hardness (> 2500 VDH),
high melting temperature and chemical inertness. The usual and interesting properties have attracted a
large number of experimental, theoretical and industrial investigations [4-6], and make it attractive as a
structural material or as a coating for cutting tools.
In present paper some characteristic microstructural thermophysical parameters those make
considerable contribution to orientation and temperature dependence of ultrasonic attenuation in TiC and
182 | P a g e
TiN along <100>, <110> and <111> orientations are discussed. For this analysis, we have also evaluated
second and third order elastic constants, acoustic impedance, adiabatic compressibility, molar volume,
intermolecular free path length, Rao’s constant, Wada’s constant, van der Waals constant, ultrasonic
velocities, thermal relaxation time, acoustic coupling constants.
THEORY
For the evaluation of ultrasonic attenuation, second and third order elastic constant play a vital role.
We calculated SOEC and TOEC following Brugger’s definition of elastic constants at absolute zero (C IJo
and C IJK
o
) [7,8]. The SOEC (C11, C12 and C44) and TOEC (C111, C112, C123, C144, C166 and C456) at room
temperature (300K) are achieved by method developed by Leibfried, Ludwig, Mori, Ghate and Yadav [9-13]
for NaCl-type crystal. Since the crystalline form of stoichiometric titanium carbide and titanium nitride adopt
the simple rocksalt structure.
These titanium compounds have ionic metallic bonding. Here it is assumed that Φµv(r) is the
interaction potential equal to the sum of the electrostatic potential ( Coulomb potential) and the Born-Mayer
short range repulsive potential, i.e.
Φµv(r) = ± (e2/r) + A exp (-r/b)
Where, e is the electronic charge, r the nearest neighbor distance, the ± sign apply like and unlike
charge, A is the strength parameter and b is the hardness parameter. We further assume A and b are the
same for interaction between like (positive and negative) and unlike ions [11-13]. All the formulations used
in the computation of SOEC and TOEC of TiC and TiN are the same as those for previous paper [13].
With the help of second and third order elastic constant (SOEC and TOEC) , the other physical parameters
like zero pressure bulk modulus, elastic anisotropy, acoustic impedance, adiabatic compressibility, molar
volume, intermolecular free path length, Rao’s constant, Wada’s constant and van der Waal constant [14].
The main causes of ultrasonic attenuation for perfect antiferroelectric and antiferromagnetic
crystals are due to phonon-viscosity, the thermal relaxation time and electron-phonon interaction. However
at room temperature these remain only two types of losses, which are due to phonon-viscosity and
thermoelastic relaxation mechanism. The loss due to electron-phonon interaction is only appreciable below
80K and hence it could be ignored safely at room temperature. Akhieser [15] has assumed that the
equilibrium distribution phonons in a crystal can be distributed by the propagation of an acoustic phonon
and the reestablishment of the equilibrium is the relaxation phenomenon. Theory to evaluate ultrasonic
attenuation has been discussed in our previous paper [12-13].
183 | P a g e
RESULTS AND DISCUSSION
Evaluated Second order elastic constants (C11, C12, and C44) are presented in Table 1 with
available comparative experimental and theoretical values. The third order elastic constants are presented
in Table 2. Other physical parameter like bulk modulus, elastic anisotropy, acoustic impedance, adiabatic
compressibility, molar volume, intermolecular free path length, Rao’s constant, Wada’s constant, van der
Waal’s constant were also evaluated by means of second order elastic constants and are presented in
Table 3.
Results of various investigators are different because of they used different theoretical approach.
For example Tan et al. [4] used tight binding model, Nguyen Manh used ab-initio calculation method [4] and
Weber used phenomenological model theory. Our results for C11 is very similar as Tan et al. [4], while
approximately half as ab-initio calculation [4] and experimental [16]. The value of C12 is approximately 10
times less while value of C44 is approximately 5 times less than those obtained by others [4, 16-20]. The
obtained values of C11, C12 and C44 are less because we have taken approximation upto second nearest
neighbor.
The order of achieved SOEC is same as obtained by other investigators [16-20]. From Table 1, it is
known that agreement between theoretical/experimental data of TiC and TiN for C11, C12 and C44 are good.
Table 1 depicts that the higher value of C11 for TiN, shows that the TiN has better mechanical strength than
TiC.
The obtained values of wave velocities are in good agreement with other refractory materials and
are comparable with literature [12-13]. The thermal relaxation time is of the order of the picosecond as
expected for other NaCl-type materials []. The physical constants like bulk modulus, elastic anisotropy,
acoustic impedance, adiabatic compressibility, molar volume, intermolecular free path length, Rao’s
constant, Wada’s constant, van der Waal’s constant are of the same order as obtained for solids.
The ultrasonic attenuation due to phonon-phonon interaction is predominant over total attenuation.
The obtained results are summary of various parameters involved during computing approaches. Ultrasonic
attenuation values of TiN are less than those of TiC. Hence TiN is more ductile than TiC. TiN is more
appropriate for general purpose.
CONCLUSION
On the basis of above discussion, we conclude the following points:
184 | P a g e
1. Although several potentials are available to evaluate elastic constants like Pseudo potential,
Morse-potential and Lenard-Jones potential, but Coulomb and Born-Mayer potential is more
appropriate to find out elastic constant of NaCl-type, TiC and TiN as we found satisfactory
results of SOEC and TOEC in present investigation.
2. The natures of ultrasonic velocities are found satisfactory. The order of thermal relaxation time is
found the order of the picoseconds.
3. On the basis of ultrasonic attenuation values of these materials, we can say TiN is more ductile,
appropriate and useful for its characterization and industrial applications.
Obtained results of present investigation correlated with other physical parameters are applicable for
further investigation.
REFERENCES
1. R. R. Yadav, A. K. Tiwari and D. Singh, “Effect of pressure on ultrasonic attenuation in Ce
monopnictides at low temperature”, J. Mat. Sc. 40(2005) 5319-5321.
2. D. Singh and P. K. Yadawa, “Effect of platinum addition in coinage metals on its ultrasonic
properties”, Platinum Metals Rev. 54 (2010) 169–176.
3. A. Keith, “A numerical method to predict the effects of frequency-dependent attenuation and
dispersion on speed of sound estimates in cancellous bone”, J. Acoust. Soc. Am. 109(3) (2001)
1213.
4. K. E. Tan, A. M. Bretkovsky, R. M. Harris, A. P. Horsfield, D. Nguyen Manh, D. G. Pettifort and A.
P. Sutton, “Carbon vacancies in titanium carbide”, Modelling Simul. Mat. Sc. Eng. 5(1997) 187-
198.
5. V. A. Gubanov, A. L. Ivanovsky and V. P. Zhukov, “Electronic Structure of Refractory Carbides and
Nitrides”, Cambridge University Press, Cambridge, 1994.
6. L. Pintschovius, W Reichardt and B. Scheerer, “Lattice dynamics of TiC”, J. Phys. C: Solid State
Physics., 11(1978) 1557-1562.
7. M. Born and J. E. Mayer, “Zur Gittertheorie der Ionen Kristalle”, Z-Phys. 75 (1931) 1.
8. K. Brugger, “Thermodynamic definition of higher order elastic coefficients”, Phys. Rev. 133 (1964)
41611.
9. G. Leibfried and H. Haln, “Zur temperaturabhangigkeit der elastischen konstantaaen von
alhalihalogenidkristallen”, Z. Phys. 150 (1958) 497.
185 | P a g e
10. G. Leibfried and W. Ludwig, “Theory of Anharmonic effect in cryatal”, Solid State Physics, 12
(1964) 275.
11. S. Mori and Y. Hiki, “Calculation of the third and fourth order elastic constant of alkali-halides”, J.
Phys. Soc. Jpn., 45 (1978) 1449-1456.
12. D. Singh, “Behaviour of acoustic attenuation in rare earth chalcogenides”, Mat. Chem. Phys. 115
(2009) 65-68.
13. D. Singh and D. K. Pandey, “An investigation of ultrasonic properties of NpX (X: S,Se and Te)”,
Braz. J. Phys. (Communicated).
14. S. K. Sahu, M. Phil Thesis submitted to Bundelkhand University, Jhansi, 2009.
15. A.Akhieser, On the absorption of ultrasound, J.Phys.(Moscow)1 (1939) 277-287.
16. R. Chang, L. J. Grahm, J. Appl. Phys. 37 (1996) 3778.
17. W. Weber, Phys. Rev. B, 8(11) (1973) 5082-92.
18. D. Chen, J. Chen, Y. Zhao, B. Yu, C. Wang and D. Shi, “Theoretical study of the elastic properties
of titanium nitride”, Acta. Metall. Sci (Engl. Lett.) 22(2) (2009).
19. Z. Ming, Z. Maosheng and H. E. Jiawen, Chin. J. Mat. Res. 15(5) (2001) 577-582.
20. W. Kress, P. Roedhammer, H. Bilz, W. Tenchent and A. N. Christensen, “Phonon anomalies in
transition- metal nitrides: TiN”, Phys. Rev. B 17 (1978) 111.
TABLE 1. Compared results of Second order elastic constants (SOEC) of TiC and TiN,
Elastic Constants Present work ab initio [4] Experiment [4] [19]

[16]
TiC C11 (x 1011 N m-2) 3.144 6.14 5.15 3.13 5.1
TiC C12 (x 1011 N m-2) 0.26 0.77 1.06 2.07 1.0
TiC C44 (x 1011 N m-2) 0.383 1.83 1.79 1.19 1.8
Elastic Constants Present work [18] [19] [20]
TiN C11 (x 1011 N m-2) 6.044 5.594 4.978 4.978

TiN C12 (x 1011 N m-2) 0.1 1.125 1.056 1.287
186 | P a g e
TiN C44 (x 1011 N m-2) 0.392 1.572 1.681 1.681
TABLE 2. Third order elastic constants (TOEC) are given below,
Material C111 C112 C123 C144 C166 C456

TiC (x 1010 Nm-2) -614.23 -7.74 -3.53 7.19 -14.5 7.12
TiN (x 1010 Nm-2) -152.99 9.279 -30.46 7.62 -13.83 7.6
TABLE 3. Calculated ultrasonic parameters at room temperature
Parameters TiC TiN

Bulk modulus (x 1010 Nm-2) 12.213 20.813
Elastic anisotropy 0.266 0.132
Acoustic impedance (x 107 Kg m-2 s-1) 1.544 2.206
Adiabatic compressibility (x 10-11 m Kg-1 s2) 2.069 1.496
Molar volume (x10-5 m3 mol-1) 1.214 0.849
Intermolecular free path length (x 10-14 m) 2.876 2.834
Rao’s constant (x 102) 8.474 7.65
Wada’s constant (x 102) 5.676 5.349
Van der Waal constant (x 10-6 m3 mol-1) 11.741 11.007
TABLE 4. Longitudinal and Shear velocities (Vl and Vs), Debye average velocity (V) and thermal
relaxation time (τth) of TiC and TiN at room temperature.
Material TiC TiN
<100> Vl (x 105 cm/sec) 7.99 10.54
Vs (x 105 cm/sec) 2.79 2.67
V (x 105 cm/sec) 3.131 3.028
τth(x 10-12 cm) 5.440 4.760
<110> Vl (x 105 cm/sec) 6.51 7.99
187 | P a g e
Vs1 (x 105 cm/sec) 2.79 2.67
Vs2 (x 105 cm/sec) 7.65 10.46
<111> Vl (x 105 cm/sec) 5.93 6.92
Vs (x 105 cm/sec) 4.7 6.24
TABLE 5: Ultrasonic attenuation {(α/f2)long., (α/f2)shear and (α/f2)th} of TiC and TiN at room
temperature.
Material TiC TiN
<100> (α/f2)l (10-17Nps2/cm) 0.2809 0.2179
♣ (α/f2)s1 (10-17Nps2/cm) 0.1376 0.1441
(α/f2)th (10-17Nps2/cm) 0.0134 0.0113
Total 0.9319 0.3733
<110> (α/f2)l (10-17Nps2/cm) 0.5918 0.5830
# (α/f2)s2 (10-17Nps2/cm) 0.0716 0.0520
$ (α/f2)s3 (10-17Nps2/cm) 0.2839 0.2252
(α/f2)th (10-17Nps2/cm) 0.0516 0.0632
Total 0.9989 0.9234
<111> (α/f2)l (10-17Nps2/cm) 0.4706 0.4743
* (α/f2)s4 (10-17Nps2/cm) 0.8250 0.6941
(α/f2)th (10-17Nps2/cm) 0.0779 0.0406
Total 1.3735 1.2090
♣=shear wave polarized along <100>, # = shear wave polarized along <001>, $=
shear wave polarized along 110 and *= shear wave polarized along 110
188 | P a g e
Ultrasonic wave propagation in II-VI hexagonal semiconductor compounds
Pramod Kumar Yadawa* and Devraj Singh

Department of Applied Physics, AMITY School of Engineering and Technology,
Bijwasan, New Delhi-110 061, India
*Tel: +91-11-2806-2106/1487, Fax: +91-11-28061821
*E-mail: pkyadawa@aset.amity.edu
ABSTRACT
The paper presents a comprehensive computation of second- and third- order elastic constants
and then velocities and attenuation of ultrasonic waves along unique direction in hexagonal II-VI group
semiconducting materials like ZnS, ZnSe, ZnTe and CdTe at room temperature. We have developed a
computer program to compute the elastic constants, ultrasonic velocities and ultrasonic attenuation in C++
language. The comparison of our computed results has been made with available theoretical and
experiment results. The value of ultrasonic attenuation of ZnS is smallest in comparison to other chosen
materials. So ZnS is more ductile and more pure than the others. Obtained results, together with other well
known physical properties, may expand future prospects for the applications and study of these materials.
Keywords: Semiconductors, Elastic properties, Thermal conductivity, Ultrasonic properties.
1. Introduction
It is well known that II-VI semiconductor compounds have a large optical gap, but the feasibility of
green-blue opto-electronic devices based on these materials has been demonstrated by Hasse et al. [1].
Due to their wide direct band gap, the electronic properties of II-VI semiconductors, such as ZnS, ZnSe,
ZnTe and CdTe, appear to be rather promising for applications in optical devices. Technological and
theoretical interest in II-VI compound and their alloys is due to its appealing properties in electro-optical and
electron acoustic devices [2-4]. Actually, their technological potential is very great. In addition to their use in
optical devices operating in the short- wavelength radiation range from red to ultra-violet [5], in recent
years, these materials have been used as catalysts when studying photochemical reactions [6]. Due to the
possibility of intense photoexcitation, especially between the top of the valence band and the bottom of the
conduction band at the Γ point, they are used in solar cells [7]. Ultrasonic attenuation is very important
physical parameter to characterize the material, which is well related to several physical quantities like
thermal conductivity, specific heat, thermal energy density and higher order elastic constants [8]. The
189 | P a g e
elastic constants provide valuable information about the bonding characteristic between adjacent atomic
planes and the anisotropic character of the bonding and structural stability [9, 10].
Therefore, in this work we predict the ultrasonic properties of hexagonal structured semiconductor
compounds at room temperature. The ultrasonic attenuation coefficient, acoustic coupling constants, higher
order elastic constants, thermal relaxation time and ultrasonic wave velocities for these semiconductors for
unique direction of propagation of wave are calculated at 300K. The calculated ultrasonic parameters are
discussed with related thermophysical properties for the characterization of the chosen semiconductors.
The obtained results are analyzed in comparison to other hexagonal structured materials.
10. 2. THEORY
In the present investigation, the theory is divided into two parts:

2.1 Second-and third order Elastic constants
The second (CIJ) and third (CIJK) order elastic constants of material are defined by following
expressions.
∂ 2U
C IJ = ; I or J = 1,......6 (1)
∂e I ∂e J
∂ 3U
C IJK = ; I or J or K = 1,......6 (2)
∂e I ∂e J ∂e K
where, U is elastic energy density , eI=eij (i or j = x, y, z, I=1, …6) is component of strain tensor. Eqs (1) and
(2) leads six second and ten third order elastic constants (SOEC and TOEC) for the hexagonal close
packed structure materials [8, 11].
C11 = 24.1 p 4 C ′ C12 = 5.918 p 4 C ′ 

C13 = 1.925 p 6 C ′ C 33 = 3.464 p 8 C ′ (3a)

C 44 = 2.309 p 4 C ′ C66 = 9.851 p 4 C ′ 
C111 = 126.9 p 2 B + 8.853 p 4 C ′ C112 = 19.168 p 2 B − 1.61 p 4 C ′ 


C113 = 1.924 p 4 B + 1.155 p 6 C ′ C123 = 1.617 p 4 B − 1.155 p 6 C ′

C133 = 3.695 p 6 B C155 = 1.539 p 4 B  (3b)
4 6 
C144 = 2.309 p B C 344 = 3.464 p B 
C 222 = 101.039 p 2 B + 9.007 p 4 C ′ C 333 = 5.196 p 8 B 

190 | P a g e
where p = c/a: axial ratio; C ′ = χ a / p 5 ; B = ψ a 3 / p3 ; χ = (1 / 8)[{nb 0 (n − m)}/{ a n + 4 }]
ψ = − χ /{6 a 2 ( m + n + 6)} ; m, n=integer quantity; b0=Lennard Jones parameter.

2.2 Ultrasonic attenuation and allied Parameters
The predominant causes for the ultrasonic attenuation in a solid at room temperature are phonon-
phonon interaction (Akhieser loss) and thermoelastic relaxation mechanisms. The ultrasonic attenuation
coefficient (A)Akh due to phonon-phonon interaction and thermoelastic relaxation mechanisms is given by
the following expression [11, 12].
( )
(A /f2)Akh = 4π 2 3E 0 < (γ ij ) 2 > − < γ ij > 2 C V T τ / 2 ρ V 3 (4) (A /f2)Th
= 4 π 2 < γ ij > 2 kT / 2ρVL5 (5)

where, f: frequency of the ultrasonic wave; V: ultrasonic velocity for longitudinal and shear wave; VL:
longitudinal ultrasonic velocity; E0: thermal energy density; γ i j : Grüneisen number (i, j are the mode and
direction of propagation).
The Grüneisen number for hexagonal structured crystal along <001> orientation or θ=00 is direct
(
consequence of second and third order elastic constants. D = 3 3E 0 < (γ ij ) 2 > − < γ ij > 2 C V T / E 0 is )
known as acoustic coupling constant, which is the measure of acoustic energy converted to thermal
energy. When the ultrasonic wave propagates through crystalline material, the equilibrium of phonon
distribution is disturbed. The time for re-establishment of equilibrium of the thermal phonon distribution is
called thermal relaxation time (τ) and is given by following expression:
τ = τ S = τ L / 2 = 3 k / C V VD2 (6)
Here τL and τS are the thermal relaxation time for longitudinal and shear wave. k and CV are the
thermal conductivity and specific heat per unit volume of the material respectively. The Debye average
velocity (VD) is well related to longitudinal (VL) and shear wave (VS1, VS2) velocities. The expressions for
ultrasonic velocities are given in our previous papers [11, 12]:
where ρ and θ are the density of the material and angle with the unique axis of the crystal
respectively. The ultrasonic velocities have been used for the calculation of ultrasonic attenuation and allied
parameters in the chosen materials.
3. Results and discussion
3.1 Higher order elastic constants
191 | P a g e
The unit cell parameters ‘a’ (basal plane parameter) and ‘p’ (axial ratio) for ZnS, ZnSe, ZnTe and
CdTe are 3.83Å, 4.02Å, 4.28Å, 4.58Å and 1.639, 1.631, 1.637, 1.635 [13] respectively. The value of m and
n for chosen materials are 6 and 7. The values of b0 for these materials are 7.2x10-64 erg cm7, 9.2x10-64 erg
cm7, 14.0x10-64 erg cm7 and 20.0x10-64 erg cm7 respectively. The SOEC and TOEC have been calculated
for these materials using Eq. (3) and are presented in Table 1.
Table1. Second and third order elastic constants (SOEC and TOEC) & bulk modulus (B) in the unit of
1010Nm-2 of materials at room temperature.
C11 C12 C13 C33 C44 C66 B
ZnS 13.643 3.351 2.927 14.151 3.511 5.350 6.650
ZnSe 10.830 2.659 2.301 11.015 2.760 4.247 5.244
ZnTe 8.731 2.144 1.869 9.013 2.242 3.424 4.249
CdTe 6.396 1.571 1.366 6.570 1.638 2.508 3.107
ZnS[12] 13.59 3.33 2.91 14.00 3.49 5.13
ZnSe[14] 10.72 4.46 3.53 11.65 2.50 3.13
ZnTe[15] 8.56 3.70 3.00 9.26 2.02 2.43
CdTe[15] 6.22 3.59 2.91 6.89 1.16 1.31
C111 C112 C113 C123 C133 C344 C144 C155 C222 C333
ZnS -222.47 -35.27 -7.509 -9.54 -47.78 -44.81 -11.12 -7.41 -176.03 -180.56
ZnSe -176.60 -27.99 -5.90 -7.50 -37.21 -34.88 -8.74 -5.83 -139.73 -139.18
ZnTe -142.37 -22.57 -4.79 -6.09 -30.44 -28.54 -7.10 -4.73 -112.65 -114.71
CdTe -104.30 -16.54 -3.50 -4.45 -22.19 -20.80 -5.19 -3.46 -82.53 -83.42
The elastic constants of the material are important, since they are related to hardness and
therefore of interest in applications where mechanical strength and durability are important. Also, the
second order elastic constants are used for the determination of the ultrasonic attenuation and related
parameters. It is obvious from Table 1 that, there is good agreement between the present and reported
theoretical and experimental second order elastic constants of these semiconducting materials [12, 14, 15].
Also, the comparison can be made with the value of Debye temperature of ZnSe and ZnTe. The present
value of Debye temperature for ZnSe and ZnTe are 269.9 0K and 218.4 0K respectively, calculated using
second order elastic constants. The Debye temperature experimentally determined by Lee [14] are 278.5
0K and 225.3 0K respectively. Thus our theoretical approach for the calculation of second order elastic
192 | P a g e
constants for hexagonal structured materials at room temperature is well justified. However, third order
elastic constants are not compared due to lack of data in the literature but the negative third order elastic
constants are found our previous papers for hcp structure materials [8, 11, 12, 16-18]. Hence applied
theory for the evaluation of higher order elastic constants at room temperature is justified. The bulk
modulus (B) for these alloys can be calculated with the formula B= 2(C11+ C12+ 2C13 + C33/2)/9. The
evaluated B for these alloys is presented in Table 1.
3.2. Ultrasonic velocity and allied parameters
The density and thermal conductivity at room temperature have been taken from the literature. The
value of CV and E0 are evaluated using tables of physical constants and Debye temperature. The thermal
conductivity k and calculated acoustic coupling constants (DL & DS) are presented in Table 2.
Table 2: Density (ρ: in 103 kg m-3), specific heat per unit volume (CV: in 106Jm-3K-1), thermal energy density
(E0: in 108Jm-3), thermal conductivity (k: in Wm-1K-1) and acoustic coupling constant (DL, DS) of hcp
semiconductor materials.
ρ CV E0 k DL DS
ZnS 4.09 0.977 1.91 27.0 53.76 1.27
ZnSe 5.262 0.876 1.92 19.0 54.72 1.17
ZnTe 5.636 0.710 1.65 11.0 54.31 1.24
CdTe 5.849 0.600 1.46 6.0 54.58 1.21
The computed orientation dependent ultrasonic wave velocities and Debye average velocities at
300 K are shown in Figs 1–4. Figs 1–3 show that the velocities VL and VS1 have minima and maxima
respectively at 45° with the unique axis of the crystal while VS2 increases with the angle from the unique
axis. The combined effect of SOEC and density is reason for abnormal behaviour of angle dependent
velocities.
The nature of the angle dependent velocity curves in the present work is found similar as that for
heavy rare-earth metals, laves-phase compounds and other hexagonal wurtzite structured materials [8, 11,
12, 16-18]. The chosen semiconductors have shown similar properties with their crystal structure. The
comparative study of ultrasonic velocities is presented in Table. 3.
Table 3: Comparative velocities (in 103 m/s) of hcp semiconductor materials.
193 | P a g e
Velocity Present work Carl et al.[19] Kim et al.[20] Bijalwan et al.[21]
theoretical experimental experimental theoretical
ZnS long. 5.88 5.51 5.45 6.49
shear 2.93 2.65 2.92 3.78
ZnSe long. 4.57 4.25
shear 2.29 2.83
ZnTe long. 3.99 3.58
shear 2.00 2.74
CdTe long. 3.35 3.47
shear 1.67 2.93
Hence values of velocities are in good agreement with experimental/theoretical values. Thus the
angle dependencies of the velocities in these materials are justified.
VD of these materials are increasing with the angle and have maxima at 55° at 300 K (Fig. 4).
Since VD is calculated using VL, VS1 and VS2 [8, 12], therefore the angle variation of VD is influenced by the
constituent ultrasonic velocities. The maximum VD at 55° is due to a significant increase in longitudinal and
pure shear (VS2) wave velocities and a decrease in quasi-shear (VS1) wave velocity. Thus it can be
concluded that when a sound wave travels at 55° with the unique axis of these crystals then the average
sound wave velocity is maximum.
The calculated thermal relaxation time is visualised in Fig. 5. The angle dependent thermal
relaxation time curves follow the reciprocal nature of VD as τ ∝ 3K / C V VD2 . This implies that τ for chosen
materials are mainly affected by the thermal conductivity. The τ for hexagonal structured materials is the
order of pico second [18]. Hence the calculated τ justifies the hcp structure of chosen materials at room
temperature. The minimum τ for wave propagation along θ = 550 implies that the re-establishment time for
the equilibrium distribution of thermal phonons will be minimum for propagation of wave along this direction.
Thus the present average sound velocity directly correlates with the Debye temperature, specific
heat and thermal energy density of theses materials.
3.3. Ultrasonic attenuation due to phonon-phonon interaction and thermal relaxation phenomena
In the evaluation of ultrasonic attenuation, it is supposed that wave is propagating along the unique
axis [<001> direction] of these materials. The attenuation coefficient over frequency square (A/f2)Akh for
longitudinal (A/f2)L and shear wave (A/f2)S are calculated using Eq. (4) under the condition ωτ<<1 at room
194 | P a g e
temperature. The thermoelastic loss over frequency square (A/f2)Th is calculated with the Eq. (5). The
values of (A/f2)L, (A/f2)S, (A/f2)Th and total attenuation (A/f2)Total are presented in Table 4.
Table 4: Ultrasonic attenuation coefficient (in 10-17 Np s2 m-1) of hcp semiconductor materials.
Alloys ZnS ZnSe ZnTe CdTe
(A/f2)Th 0.266 0.513 0.543 0.691
(A/f2)L 254.138 554.962 621.738 832.617
(A/f2)s 24.259 42.223 57.180 74.288
(A/f2)Total 278.663 597.698 678.918 907.596
Table 4 indicates that the thermoelastic loss is very small in comparison to Akhieser loss and
ultrasonic attenuation for longitudinal wave (A/f2)L is greater than that of shear wave (A/f2)S. This reveals
that ultrasonic attenuation due to phonon-phonon interaction along longitudinal wave is governing factor for
total attenuation ((A/f2)Total =(A/f2)Th+(A/f2)L+(A/f2)S). The total attenuation is mainly affected by thermal
energy density and thermal conductivity. Thus it may predict that at 300K the ZnS behaves as its purest
form and is more ductile as evinced by minimum attenuation while CdTe is least ductile. Therefore impurity
will be least in the ZnS at room temperature.
Since A ∝ V −3 and velocity is the largest for ZnS among CdTe thus the attenuation A should be
smallest and material should be most ductile. The minimum ultrasonic attenuation for ZnS justifies its quite
stable hcp structure state. The total attenuation of these compounds are much larger than third group
nitrides (AlN: 4.441x10-17 Nps2m-1; GaN: 14.930x10-17 Nps2m-1 and InN: 20.539x10-17 Nps2m-1) due to their
large thermal conductivity and acoustic coupling constants [18, 22]. This implies that the interaction
between acoustical phonon and quanta of lattice vibration for these alloys is large in comparison to third
group nitrides.
4. Conclusions
On the basis of above discussion, we conclude following points:
195 | P a g e
• Our theory of higher order elastic constants is justified for the hexagonal structured materials.
• The order of thermal relaxation time for these materials is found in picoseconds, which justifies
their hcp structure at 300K. The re-establishment time for the equilibrium distribution of thermal
phonons will be minimum for the wave propagation along θ = 550 due to being smallest value of τ
along this direction.
• The acoustic coupling constant of these materials for longitudinal wave are found five times larger
than third group nitrides. Hence the conversion of acoustic energy into thermal energy will be large
for these materials. This shows general suitability of chosen materials.
• The ultrasonic attenuation due to phonon-phonon interaction mechanism is predominant over total
attenuation as a governing factor thermal conductivity.
• The mechanical properties of ZnS are better than those of CdTe, because CdTe has low elastic
constants and ultrasonic velocities.
Thus obtained results in the present work can be used for further investigations, general and industrial
applications. Our theoretical approach is valid for ultrasonic characterization of these alloys at room
temperature. The ultrasonic behavior in these semiconductor materials as discussed above shows
important microstructural characteristic feature, which are well connected to thermoelectric properties of the
materials. These results, together with other well-known physical properties, may expand future prospects
for the application and study of these materials.
References
[1] M. A. Hasse, J. Qiu, J. M. DePuydt, H. Cheng, Appl. Phys. Lett. 59 (1991) 1272.
[2] M. Matsuoka, K. Ono, J. Vac. Sci. Technol. A 7 (1989) 2975.
[3] M. A. Haase, H. Cheng, D. K. Misemer, T. A. Strand, J. M. DePuydt, Appl. Phys. Lett. 59 (1991) 3228
[4] M. J. Weber (Ed), Handbook of Laser Science and Technology, Vol.III, CRC Press, Cleveland, 1986.
[5] D. M. Bagnall, Y. F. Chen, T. Yao, Appl. Phys. Lett. 70 (1997) 2230.
[6] L. Chen, W. Gu, X. Zhu, J. Photochem. Photobiol. A 74 (1993) 85.
[7] H. W. Shock, Sol. Energy Mater. Soc. Cells 34 (1994) 19.
[8] P. K. Yadawa, D. Singh, D. K. Pandey, R. R. Yadav, The Open Acoustic Journal 2 (2009) 80.
[9] P. Ravindran, L. Fast, P.A. Korzhavyi, B. Johansson, J. M. Wills, O. Eriksson, J. Appl. Phys. 84 (1998)
4891.
[10] L. Louail, D. Maouche, A. Roumili, F. Ali Sahraoui, Mater. Lett. 58 (2004) 2975.
196 | P a g e
[11] A. K. Yadav, R. R. Yadav, D. K. Pandey, D. Singh, Mat. Lett. 62 (2008) 3258.
[12] D. K. Pandey, P. K. Yadawa, R. R. Yadav, Mat. Lett. 61 (2007) 5194.
[13] T. V. Gorkavenko, S. M. Zubkova, V. A. Makara, L. N. Rusina, Semiconductors, 41 (2007) 886.
[14] B. H. Lee, J. Appl. Phys. 41 (1970) 2984.
[15] R. M. Martin, Phys. Rev. B 6 (1972) 4546.
[16] D. K. Pandey, P. K. Yadawa, R. R. Yadav, Mat. Lett. 61 (2007) 4747.
[17] D. K. Pandey, D. Singh, P. K. Yadawa, P.K., Plat. Met. Rev. 53 (2009) 91.
[18] D. K. Pandey, D. Singh, R. R. Yadav, Appl. Acoust. 68 (2007) 766.
[19] F. C. Carl, L. D. Harold, W. H. Glenn, J. Appl. Phys. 38 (4) (1967) 1944.
[20] E. K. Kim, S. I. Kwun, S. M. Lee, H. Seo, J. G. Yoon, Phys. Rev. B 61 (9) (2000) 6036.
[21] R. D. Bijalwan, P. N. Ram, M. D. Tiwari, J. Phys. C: Solid State Phys., 16 (1983) 2537.
[22] Landolt-Bornstein, Numerical Data and Function Relationship in Science and Technology, Group III
Vol. 11, Bellin Springer 1979.
Figure Captions:
Fig.1: VL vs angle with unique axis of crystal

Fig.2: VS1 vs angle with unique axis of crystal
Fig.3: VS2 vs angle with unique axis of crystal
Fig.4: VD vs angle with unique axis of crystal
Fig.5: Relaxation time vs angle with unique axis of crystal
197 | P a g e
6
5.5
ZnS ZnSe
5
V L(103 m/sec)
ZnTe CdTe
4.5
3.5
3
0 10 20 30 40 50 60 70 80 90
angle
Fig.1.
3
V S1(103 m/sec)
ZnS ZnSe
ZnTe CdTe
1
0 10 20 30 40 50 60 70 80 90
angle
Fig.2.
198 | P a g e
ZnS ZnSe
3.5 ZnTe CdTe
V S2(103 m/sec)
2.5
1.5
0 10 20 30 40 50 60 70 80 90
angle
Fig.3.
3.5
3
V D(103 m/sec)
2.5
2
ZnS ZnSe
ZnTe CdTe
1.5
0 10 20 30 40 50 60 70 80 90
angle
Fig.4.
199 | P a g e
11
10 ZnS ZnSe
ZnTe CdTe
9
Relax time (10-12s)

8
5
0 10 20 30 40 50 60 70 80 90
angle
Fig.5.
200 | P a g e
SOUND VELOCITY AND DENSITY STUDIES TO FIND THE EFFECT OF PEG ON
AQUEOUS ANIONIC SURFACTANT (SDS)
S. CHAUHAN, R.S. THAKUR and DEEPIKA KAUSHAL

Department of Chemistry, Himachal Pradesh University, Shimla-171005.
And
V.K.SYAL, KIIT College of Engineering, Maruti Kunj, Gurgaon-122018
ABSTRACT
Polymer- surfactant formulations are used extensively in industrial, pharmaceutical and cosmetic
applications. The versatility in such systems is achieved owing to the reason that polymer–
surfactant interactions influence the behaviour of solution significantly and also these interactions
can be modified to get the enhanced desired benefits, e.g. polymers are often added to control the
rheology of the solution whereas surfactants can cause alterations in wettability, emulsification or
solublization properties of the system under investigation. In the present work, therefore, the effect
of Polyethylene glycol (PEG-6000), a synthetic polymer, on anionic surfactant i.e. sodiumdodecyl
sulfate (SDS) in aqueous solutions has been investigated with the help of density and sound
velocity measurements at different temperatures (15, 20, 25, 30 and 35oC).
From the measured values of density and sound velocity, the acoustical parameters namely,
Specific acoustic impedance (Z), Intermolecular free length (Lf), Molar sound velocity (Rm) and
Relative association (R.A.) have been calculated and their variations with different concentrations
of PEG and SDS have been discussed. Interactions of surfactant with polymer have been found to
indicate the binding of surfactant with the polymer molecule at lower concentration followed by the
usual micellization at higher concentration of surfactant.
KEYWORDS: PEG, SDS, Interaction, Sound Velocity and Density.
INTRODUCTION
Ultrasonic velocity offers a rapid and nondestructive method for characterisation of materials and serves as
a powerful, effective and reliable tool to investigate properties of polymer solutions.In continuation with our
201 | P a g e
previous work on polymers [1-3], in this paper,we report various acoustical parameters for PEG-SDS
system in order to explore polymer- surfactant interactions.
EXPERIMENTAL
Sodium dodecyl sulfate (Biochemical grade from BDH) was further purified as suggested in literature [4].
Polyethylene Glycol (PEG) molecular weight 6000 (L.R grade) from s.d. fine- Chem private limited was
used for this study.
Densities and sound velocities were measured from Density and Sound Velocity Analyzer (DSA-5000)
supplied by Anton Paar Gmbh, Graz, Austria which measures the speed and density of the solution
simultaneously with a resolution of 1×10−1 ms−1 and 1×10−6 gcm−3 respectively and was thermostated with
in ±0.002°C with Peltier heating device. However, doubly distilled water of conductivity in the range <1-2
X10-7 Scm-1 was used in all sample preparation.

Density (d) and sound velocity (v) for surfactant SDS in the concentration range (1-15 mmol dm-3) have
been measured in aqueous solutions of 1, 5, 10 % w/v PEG over wide range (15-35oC) at interval of 5oC.
The Density (d) and sound velocity (v) data has been reported in Table 1-2.
The variation of Rm is non-linear at all concentrations of PEG, however, the marked difference in the of
plots reflect that the PEG concentration is also playing important role. At 1% PEG, there is decrease in Rm
values up to 5mmol [SDS] and then occurs a significant hump in 6-10 mmol [SDS], after which the Rm
value remains almost constant. At 5% PEG solution with [SDS], the Rm value increases initially up to
4mmol [SDS] after which no effect of [SDS] is observed, however, at 10% PEG, the nature of graph shows
no regular trend.The variation of Rm plots remains same at different temperatures studied.This difference
in behaviour of Rm clearly shows that at lower concentration of PEG, PEG- surfactant interactions
dominate and at higher concentration of PEG, polymer-polymer interactions prevail. The variation of R.A
with SDS concentration as well as temperature is shown in [Fig 3]. The values of R.A. remain close to unity
and show slight increase with the increase of [SDS] content in mixtures. This increase is again due to the
fact that the polymer-SDS interactions dominate over polymer- polymer interactions. In case of
carbohydrates (fructose and maltose) also,in binary mixtures of DMSO-H2O system at 25oC, the R.A.
values show a regular increase indicating considerable solute-solvent interactions [5].
202 | P a g e
However,on comparing the behaviour of R.A. at different PEG concentrations, a marked non-linear
behaviour seems to be quite significant at 6-10mmol [SDS] at 1% PEG. This may be taken as a region of
maximum structural changes which may involve micellization to greatest extent.
In fact, PEG offers hydrophobic carbon moiety on which micellization of SDS seems to be facilitated and it
seems true also as maximum such structural changes are significant in [SDS] range of 6-10 mmol as
reflected by Rm and R.A. values at 1% PEG. At higher PEG concentration polymer-polymer interactions
dominate.
The variation of Lf with SDS concentration as well as temperature is shown in [Fig2]. From these plots, it is
observed that Lf decreases regularly with concentration of surfactant but varies in magnitude with
temperature. This kind of trend is similar to the behaviour of polymers PEG in AN- H2O mixtures [1] and
polyvinylpyrrolidone in DMSO-H2O system at 25oC [2].
The variation of Z with SDS concentration as well as temperature is shown in [Fig4]. In the plots of Specific
acoustic impedance (Z) w.r.t SDS concentration, it is observed that Z is also almost independent of
concentration of surfactant but its magnitude increases with increase in temperature and also with
concentration of PEG solution. All these parameters collectively show extent of solute- solvent interaction.
REFERENCES
1. V.K. SYAL, A. CHAUHAN and S. CHAUHAN ‘Ultrasonic velocity and density studies of poly
(ethyleneglycols)(PEG-8,000, PEG-20,000) in acetonitrile (AN) and water (H2O) mixtures at 25oC.’
J. Pure Appl. Ultrason. 27, 2-3 (2005).
2. V.K. SYAL, A. CHAUHAN and S. CHAUHAN ‘A study on solutions of poly (vinylpyrrolidone) in
binary mixtures of DMSO+H2O at different temperatures by ultrasonic velocity measurements.’
Indian J. Phys. 80 (4), 379-385 (2006).
3. V.K. SYAL, A. CHAUHAN, POONAM SHARMA and S. CHAUHAN ‘Ultrasonic velocity and density
studies on solutions of Poly(vinylalcohol) (PVA) in binary mixtures of dimethylesulphoxide (DMSO)
+ water (H2O) mixtures at 25oC.’ J. Polym. Mater. 22 363-368 (2005).
4. S. CHAUHAN, M.S. CHAUHAN, J.JYOTI and RAJNI ‘Acoustic and viscosity studies of sodium
dodecyl sulfate in aqueous solutions of gelatin’ Journal of molecular liquids 148, 24-28 (2009).
5. V.K. SYAL, S. CHAUHAN and R.GAUTAM ‘Ultrasonic velocity measurements of carbohydrates in
binary mixtures of DMSO + H2O) mixtures at 25oC’Ultrasonics 36, 619-623(1998).
203 | P a g e
Table 1 Density d (g cm-3) for SDS in various aqueous PEG solutions at different temperatures.
(ToC)
[SDS] -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
(mmol dm-3) 15 20 25 30 35 15 20 25 30 35 15 20 25 30 35
1% (w/v) PEG 5% (w/v) PEG 10% (w/v) PEG
----------------------------------------------------------------------- ----------------------------------------------------------------------- ----------------------------------------------------------------------------
1 1.00089 0.99994 0.99874 0.99730 0.99564 1.00746 1.00636 1.00502 1.00345 1.00168 1.015006 1.013726 1.012219 1.010503 1.008597
2 1.00094 0.99999 0.99879 0.99734 0.99569 1.00750 1.00640 1.00506 1.00349 1.00172 1.015105 1.013828 1.012317 1.010595 1.008685
3 1.00100 1.00005 0.99884 0.99740 0.99574 1.00754 1.00644 1.00510 1.00353 1.00176 1.015171 1.013884 1.012372 1.010652 1.008733
4 1.00105 1.00010 0.99889 0.99744 0.99579 1.00750 1.00640 1.00506 1.00349 1.00172 1.015172 1.013883 1.012369 1.010648 1.008735
5 1.00110 1.00015 0.99894 0.99749 0.99583 1.00762 1.00651 1.00516 1.00360 1.00182 1.015280 1.013989 1.012472 1.010749 1.008832
6 1.00117 1.00021 0.99899 0.99755 0.99589 1.00767 1.00656 1.00521 1.00364 1.00187 1.015230 1.013941 1.012424 1.010702 1.008788
7 1.00116 1.00019 0.99898 0.99753 0.99587 1.00771 1.00661 1.00525 1.00368 1.00191 1.015319 1.014028 1.012511 1.010786 1.008870
8 1.00120 1.00024 0.99902 0.99757 0.99590 1.00780 1.00669 1.00533 1.00376 1.00198 1.015348 1.014055 1.012536 1.010811 1.008895
9 1.00126 1.00030 0.99908 0.99763 0.99596 1.00781 1.00669 1.00534 1.00377 1.00199 1.015457 1.014162 1.012640 1.010913 1.008993
10 1.00139 1.00043 0.99921 0.99776 0.99610 1.00781 1.00670 1.00535 1.00378 1.00200 1.015453 1.014152 1.012637 1.010908 1.008990
11 1.00144 1.00048 0.99925 0.99780 0.99614 1.00787 1.00675 1.00540 1.00382 1.00204 1.015503 1.014205 1.012684 1.010905 1.009034
12 1.00149 1.00052 0.99930 0.99785 0.99618 1.00790 1.00679 1.00543 1.00385 1.00207 1.015438 1.014140 1.012620 1.010892 1.008973
13 1.00154 1.00057 0.99935 0.99789 0.99623 1.00793 1.00682 1.00546 1.00388 1.00210 1.015522 1.014222 1.012698 1.010969 1.009049
14 1.00158 1.00061 0.99938 0.99793 0.99626 1.00802 1.00690 1.00554 1.00397 1.00218 1.015594 1.014295 1.012769 1.011038 1.009116
15 1.00162 1.00066 0.99943 0.99797 0.99630 1.00802 1.00690 1.00554 1.00396 1.00215 1.015613 1.014313 1.012788 1.011056 1.009133
Table 2 Sound velocity v (ms-1) for SDS in various aqueous solutions of PEG at different temperatures.
1 1472.85 1488.45 1502.22 1514.21 1524.48 1497.21 1510.97 1523.00 1533.33 1542.04 1526.33 1537.80 1547.69 1555.98 1562.82
2 1473.06 1488.70 1502.48 1514.40 1524.66 1497.23 1511.03 1523.06 1533.36 1542.07 1526.70 1538.03 1547.87 1556.14 1562.95
3 1473.30 1488.66 1502.48 1514.40 1524.66 1497.44 1511.10 1523.10 1533.37 1542.07 1526.74 1538.15 1547.97 1556.22 1563.00
4 1473.38 1488.91 1502.63 1514.52 1524.71 1497.23 1511.03 1523.06 1533.36 1542.07 1526.69 1538.08 1547.89 1556.13 1562.90
5 1473.44 1488.95 1502.65 1514.52 1524.72 1497.51 1511.22 1523.20 1533.45 1542.14 1526.97 1538.34 1548.15 1556.36 1563.13
6 1473.54 1489.06 1502.74 1514.64 1524.82 1497.52 1511.23 1523.19 1533.47 1542.13 1526.76 1538.11 1547.88 1556.09 1562.84
7 1473.72 1489.16 1502.79 1514.59 1524.76 1497.53 1511.25 1523.20 1533.47 1542.13 1526.87 1538.23 1548.00 1556.21 1562.96
8 1473.73 1489.15 1502.76 1514.57 1524.70 1497.76 1511.33 1523.28 1533.55 1542.20 1526.78 1538.11 1547.88 1556.08 1562.83
9 1473.66 1489.07 1502.64 1514.42 1524.55 1497.55 1511.20 1523.11 1533.33 1541.97 1526.93 1538.28 1548.06 1556.25 1562.97
10 1473.79 1489.28 1502.94 1514.78 1524.95 1497.55 1511.19 1523.10 1533.31 1541.96 1526.81 1538.04 1547.78 1555.98 1562.70
11 1473.73 1489.24 1502.90 1514.74 1524.88 1497.58 1511.22 1523.15 1533.35 1542.00 1526.86 1538.17 1547.90 1555.86 1562.78
12 1473.82 1489.21 1502.85 1514.70 1524.84 1497.48 1511.14 1523.06 1533.27 1541.90 1526.55 1537.86 1547.61 1555.79 1562.49
13 1473.78 1489.26 1502.89 1514.70 1524.85 1497.46 1511.06 1522.96 1533.15 1541.77 1526.59 1537.90 1547.63 1555.78 1562.51
14 1473.76 1489.22 1502.86 1514.66 1524.78 1497.52 1511.05 1522.95 1533.18 1541.77 1526.61 1537.91 1547.64 1555.80 1562.51
15 1473.71 1489.18 1502.81 1514.62 1524.51 1497.38 1511.01 1522.90 1533.09 1541.69 1526.61 1537.91 1547.64 1555.79 1562.49
204 | P a g e
-0.20 5 % w/v PEG
-0.4
-0.25 -0.6
1% w/v PEG
-0.30 -0.8
o
15 C -1.0
o
-0.35 20 C
o
25 C -1.2 o
15 C
o
-0.40 30 C -1.4 o
20 C
Rm (m s )
-1
o
35 C o
25 C
Rm (m s )
-1.6
-1
-0.45 o
30 C
-1.8 o
35 C
-0.50
-2.0
-0.55 -2.2
-0.60 -2.4
-2.6
-0.65
-2.8
-0.70 -3.0
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
-3 -3
[SDS] (mol dm ) [SDS] (mol dm )
-0.4 10 % w/v PEG
-0.5
-0.6
-0.7
Rm (m s )
-1
o
15 C
o
-0.8 20 C
o
25 C
o
30 C
-0.9 o
35 C
-1.0
-1.1
0 2 4 6 8 10 12 14 16
-3
[SDS] (mol dm )
Fig 1. Molar sound velocity (Rm) (m s-1) for SDS in various aqueous PEG solutions at different
temperatures.
205 | P a g e
1.0008
1% w/v PEG
1.0007 1.0007
5 % w/v PEG
1.0006 1.0006
1.0005 1.0005
1.0004 1.0004
RA
o
15 C
RA
o
1.0003 20 C
1.0003
o o
25 C 15 C
o o
1.0002 30 C 20 C
o
35 C 1.0002 o
25 C
o
30 C
1.0001 o
35 C
1.0001
1.0000
1.0000
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
-3
[SDS] (mol dm ) -3
[SDS] (mol dm )
1.0007
10 % w/v PEG
1.0006
1.0005
1.0004
RA
1.0003 o
15 C
o
20 C
o
1.0002 25 C
o
30 C
o
35 C
1.0001
1.0000
0 2 4 6 8 10 12 14 16
-3
[SDS] (mol dm )
Fig 2. Relative association (R.A.) for SDS in various aqueous PEG solutions at different
temperatures.
206 | P a g e
1% w/v PEG
152000 154400
154000
151000
153600 5 % w/v PEG
153200
150000
Z (kg m-2 s-1)

152800
Z (kg m-2 s-1)
o
152400
15 C
149000 o
o
15 C
20 C
o
152000 o
20 C
25 C
o
o
30 C 25 C
o 151600 o
30 C
35 C
148000 o
35 C
151200
150800
147000
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
-3 -3
[SDS] (mol dm ) [SDS] (mol dm )
157600
157200
10 % w/v PEG
156800
Z (kg m s )
-1
156400
-2
o
15 C
o
156000 20 C
o
25 C
o
30 C
155600 o
35 C
155200
154800
0 2 4 6 8 10 12 14 16
-3
[SDS] (mol dm )
Fig 3. Specific acoustic impedance (Z) (kg m-2 s-1) for SDS in various aqueous PEG solutions at
different temperatures
207 | P a g e
4.29E-011
4.36E-011
o
15 C
o
4.35E-011 20 C
4.28E-011 5 %w/v PEG
o
25 C
1 % w/v PEG o
o 30 C
15 C o
4.35E-011 o 35 C
20 C
o
25 C 4.27E-011
Lf (m)
o
30 C
4.34E-011 o
35 C
Lf (m)
4.26E-011
4.34E-011
4.33E-011
4.25E-011
4.32E-011
0 2 4 6 8 10 12 14 16
0 2 4 6 8 10 12 14 16
-3
[SDS] (mol dm )
-3 [SDS] (mol dm )
4.22E-011
4.21E-011
10 % w/v PEG
4.20E-011 15 C
o
o
20 C
o
4.19E-011 25 C
o
30 C
o
35 C
Lf (m)
4.18E-011
4.17E-011
4.16E-011
4.15E-011
0 2 4 6 8 10 12 14 16
-3
[SDS] (mol dm )
Fig 4. Intermolecular free length (Lf) (m) for SDS in various aqueous PEG solutions at different
temperatures.
208 | P a g e

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ISSN 0973-3302

Copyright @2007, Acoustical Society of India

* Research Scholars, Department of Physics, Andhra University, Visakhapatnam – 530 003

THEORY AND CALCULATIONS

Various Physical and thermo dynamical parameters are calculated.

(1) Adiabatic Compressibility βad = 1/(ρU2) cm2 / dyne

(2) Intermolecular free length Lf = k( βad )1/2 A0

(3) Molar volume V = Meff /ρeff cm3 / mole

(4) Internal Pressure Πi = bRT (Kη/U)1/2 [ (ρ)2/3 / (Meff)7/6] dynes / cm2

(6) Enthalpy H = ΠiV cal / mole

RESULTS AND DISCUSSIONS

System I : Methanol +Ethylacetoacetate

1. Kinocid, J. Am. Chem.Soc., S1, 2950 (1929)

The apparent molal compressibility is the compressibility of an amount of solution containing

35 0.1 10.4167 9.6014 -63.731 -63.731

35 0.1 -3.281 -3.281 689.51 689.51

Molal Solvation number of Molar Solvation number

Apparent Molal Volume of Apparent Molal Compressibility of

-20 0 0.5 1 -20

2. Suhashini Ernest Ph.D., Thesis submitted to Bharathidasan University 2010.

3. Jacobson B., Acta. Chem. Scand, 6, 1485 (1952).

A. Beulah Mary1, J.H. Rakini Chandrasekaran2, G. Bharathi3 and K.Ganthimathi3

2. EXPERIMENTAL PROCEDURE AND COMPUTATIONS

3. RESULTS AND DISCUSSION

Table No.2 Equivalent Conductance of CaF₂+DMF System in cm²/ohm

Internal Pressure of Equivalent Conductance of

K. Vijayalakshmi and C.Ravidhas

Department of physics, Bbishop Heber College, Tiruchirappalli, Tamil nadu, India

Keywords: Thermodynamic parameters, molecular interaction, Hydrogen bonding.

4. Results and Discussion

1. FIG. 1 FREE VOLUME OF Fig. 2 Vander Waal’s Constant of

Vander Waal’s Constant (b)

% of Dioxane by volume % of Dioxane by volume

8. FIG . 7 FREE VOLUME 7. FIG. 8 VANDER WAAL’S

% of Alcohol by volume % of Alcohol by volume

9. Vijayalakshmi K., (2001), J Acoust Soc Ind, 29, 136

T.Mathavan 1*, S.Umapathy 2, M.A.Jothi Rajan 3, A. Alfred Nobel Antony 1,

1 Department of Physics, NMSSVN College, Nagamalai, Madurai - 625 019, India.

ANALAR GRADE (AR) SAMPLE OF NN'MBA SUPPLIED BY S.D.FINE-CHEM. LTD., (BOISAR

Figure.13 Wadd’s constant Vs Mole concentration.

T.Mathavan 1*, S.Umapathy 2, M.A.Jothi Rajan 3, B.Valarmathi 2

1 Department of Physics, NMSSVN College, Nagamalai, Madurai - 625 019, India.

ABSTRACT: Ultrasonic interaction parameter measurements have been made for

interaction parameter values have shown the effects of increasing temperatures.

present the effects of varying the temperature of the system.

Table I. Calculated interaction parameter values of PAA in water at 35°°C.

4 0.0 0.7194 0.41638 - -

5 0.0 0.7194 0.41290 - -

Table II. Calculated interaction parameter values of PAA in water at 40°°C.

4 0.0 0.6529 0.37711 - -

5 0.0 0.6529 0.37047 - -

4 0.0 0.5960 0.34181 - -

5 0.0 0.5960 0.33667 - -

Table IV. Calculated interaction parameter values of PAA in water at 50°°C.

4 0.0 0.5468 0.31207 - -

5 0.0 0.5468 0.30873 - -

the temperature of the system are also reported.

1. J.H.So, R.Esquivel-Sirvent, S.S.Yun and F.B.Stumpf, “Ultrasonic velocity and

Absorption Measurements for Poly (acrylic acid) and Water Solutions”,

J Acoust. Soc. Am. 98 (1), 659-660 (1995).

2. S.K.Hassun, Acoustics Letters, 12(9), 161-165(1989).

3. P.Vigoureuse, Ultrasonic, John Wiley & Sons, New York, 32(1951).

4. B.Valarmathi, “Ultrasonic Investigations of Poly (acrylic acid) in water ”, M.Phil

JASMINE VASANTHA RANI.E, PADMAVATHY.R, #RADHA.N,