Post on 03-Aug-2020
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CHAPTER – 1
Introduction and review of literature
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1.1 Introduction
Study of propagation of ultrasonic waves in liquid systems and solids is now well
understood by means of examining certain physical properties of the materials. The data
obtained from ultrasonic propagation parameters in liquid mixtures and solutions viz.,
ultrasonic velocity and their variation with concentration of one of the components, helps to
understand the nature of molecular interactions in the mixtures further, it provides a means
to verify theories that deal with the structure of liquids. The fact that low amplitude signals
have the added advantage of low distortion of waveform studies in solutions leads to studies
in pure liquids. The advantage is the desired property of the solution can be obtained by
simply varying its concentration [1]. Thus studies in solutions offer wide applications in the
processes of industries and technology [2,3,4]. Several empirical and semi-empirical
formulae have been developed correlating ultrasonic velocity with other parameters.
Several researchers so far studied several acoustic and thermodynamic properties of
non aqueous – non electrolyte, non aqueous – electrolyte, aqueous – electrolyte and aqueous
– non electrolyte liquid mixtures/solutions with the following aims:
1. To study the molecular interactions in liquid mixtures/solutions.
2. To explain the propagation of ultra sound in liquids different theories were suggested and
various expressions were derived and experimental work is carried out to verify the theories
suggested.
3. To study and determine the important characteristic parameters of liquids calculated from
experimental results such as isentropic compressibility, intermolecular free length, specific
acoustic impedance, free volume, internal pressure, molar radius and molar volume etc.,
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4. To study the change of phase occurring in liquids, to study the rates of chemical reactions
and biochemical reactions such as fermentation etc.,
5. To determine the important thermodynamic properties for characterizing the
thermodynamic state of liquid systems.
In the present study, for the liquid mixtures/solutions, the following are discussed:
1. Study of molecular interactions in the light of variation of various acoustic and
thermodynamic parameters.
2. Comparing the ultrasonic velocities computed using various theories with experimental
values and to finding out the suitability of these theories to the systems investigated.
3. Comparing the viscosities calculated using various empirical relations with experimental
data.
4. Study of molecular interactions in the light of deviation/excess properties of calculated
parameters.
5. Fitting of various deviation/excess properties to Redlich-Kister type polynomial and
calculate the standard deviation.
1.2 Review of theories of liquids and liquid mixtures
Solids possess long range order in their structure, while gases lack the order in their
structure. Liquids do neither have the rigidity of solids nor the fluidity of gases. Hence,
liquids exhibit properties intermediate to solids and gases. X-ray studies revealed that liquids
possess short range order. The development of the theory of liquids is based upon their
structure, molecular interactions in the liquid mixtures, and the dynamic processes of the
molecular thermal motion. Based on the above, various theories of liquids are proposed to
understand and predict the ultrasonic, thermodynamic and transport properties of liquids.
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Theories of liquids can be classified broadly into two categories:
1. Distribution function theories
2. Model approach
Distribution function theories are based on evaluation of the probability of finding
groups of molecules in a particular configuration. These theories follow the laws of classical
mechanics and the theorems of statistical mechanics. These theories successfully explained
the behaviour of liquids composed of simple spherical molecules. The physical statistical–
mechanical model e.g., SAFT (statistical associated fluid theory) [5] explain the complex
liquid molecules based on Wertheim’s perturbation theory. Perturbation theories are
developed to explain the liquids composed of complex molecules especially forming H-
bonding. The potential function of perturbation theories is a simple and weak perturbation
potential. Radial distribution functions of well known perturbation functions are described
by Temperly [6].
Model approaches were widely used to explain the liquid mixtures containing
molecules of different sizes. This approach was found to be insufficient to describe overall
behaviour of the liquid state.
In the cell model, each molecule spends much of its time confined by its neighbours
in a comparatively restricted region. According to this model any one molecule moves in a
cell formed by its neighbours and these molecules have significantly more freedom than
those of solids. This model fails to account for features that distinguish a liquid from a solid.
Hildebrand and Scott [7,8] discussed shortcomings of this model. Further developments of
this theory are due to Lennard-Jones and Devonshire [9], (to express thermodynamic
functions of pure liquids in terms of intermolecular forces) Kihara [10] and others [11].
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Barker's Tunnel theory [12] is essentially one dimensional disordered cell theory. According
to this model liquid consists of subsystems of lines of molecules moving almost one
dimensionally in a tunnel whose walls are formed by neighbouring lines. The volume and
energy calculated for liquids in this theory were found to be close with the experimental
values. But this theory fails to predict the entropy values. Prigogine and Garikian [13] used
this approach and obtained a complicated expression for the potential function. Prigogine et
al. [14,15] used smoothed potential model by substituting square well potential for Lennard-
Jones and Devonshire potential. When the difference in size of component molecules is
small, this theory predicts positive excess free energy and large excess volume for mixtures.
Theory of significant structures [16] was modified form of Hole theory. It assumes
dynamic vacancies (holes) of molecular size are likely to occur in liquid state. This theory
explains some of the physical properties of simple liquids near the melting transition.
Revelation of short range order in liquids, prompted by many workers to build theories
based on lattice model. The lattice models, founded on Guggenheim–Barker theory [17], and
its further modifications, e.g., LFHB (lattice fluid hydrogen bond) [18], are the well known
models for explaining liquid structures. Though this theory could explain some properties of
polymer solutions, it could not succeed in predicting thermodynamic parameters
quantitatively. Lattice theories [19] and recent significant liquid structure theories [20] could
not explain the behaviour of certain complex structures and radial distribution function
theories are of limited use in case of liquid mixtures.
Theories based on theorem of corresponding states were developed to get rid of
difficulties encountered with cell theories. In these theories the properties of mixture were
expressed in terms of a reference liquid whose thermodynamic behaviour is known apriori.
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Longuet-Higgins [21] proposed the theory of corresponding states and in its modern form by
Pitzer [22]. Longuet-Higgins showed that the properties of mixtures can be accounted
without assuming any specific model. The essence of this theory was that all excess
properties are proportional to one another. But this theory failed to explain the results of the
system carbon tetrachloride and tetra methyl carbon (2,2-dimethyl propane). This short fall
may be due to neglecting second order terms in Taylor series for excess properties. Using
average potential model Prigogine et al [23] evaluated these terms. Estimation of the
interaction is fundamentally a many body problem but it can be reduced to a one body
problem by considering a molecule moving in the average field of its neighbours. This can
be combined with theorem of corresponding states to write expressions for excess functions.
This theory suffered from many limitations due to it’s over simplification. This theory
successfully predicted sign and magnitude of excess properties of simple mixtures/solutions
but failed in case of mixtures/solutions containing molecules of widely different sizes.
Based on the ideas of Prigogine, Balescu [24] and Barker [25] extended their work to
solutions of molecules of different sizes and shapes and different central interaction and non
spherical molecules respectively. Both the theories are not successful in predicting excess
properties. Brown [26] and Salsburg et al [27,28] formulated theory of random mixtures.
The main drawback of this approach is the assumption of random mixing which is contrary
to reality.
Molecular models are used to specify both the nature of the process and to derive
equations for physicochemical properties. Quasichemical models provide the language for
studying both equilibrium and kinetic properties of liquids [29-33]. Quasichemical models of
association processes have been applied in several instances to thermodynamic and
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spectroscopic properties of liquid systems [29-36]. Recently, along with the elaboration of
association models and the thermodynamics of associated solutions, this approach has been
also extended to dielectric, optic, and kinetic properties of mixtures. In this model
thermodynamic property, Gibbs free energy G, enthalpy H, entropy S, and the corresponding
excess properties are considered for liquid mixtures/solutions.
1.3 Review of theories of water structure
The following models were used describing the structure of water:
1. Uniformist models based on the assumption, all water molecules have a single unique
structure.
2. Mixture models based on the assumption, liquid water consists of two or more species.
Mixture models propose existence of clusters having different densities of water
molecules. Nemathy and Sheraga [37], Vandand and Senior [38], Jhon et al [39,40] and
Angell [41] described advanced models depending on the concept of cluster formation. In
these models, it is proposed that liquid water consists of two or more solid like clusters in
equilibrium with monomer water molecular species. These models successfully explained
thermodynamic, dielectric, surface and transport properties of water. Modified cell theory of
Rice [42] and Gel model of Gibbs [43] are other important models that explained many
properties of liquid water. Gel model visualises water as an infinitely and randomly
branched gel of hydrogen bonds. This model explains the melting and boiling transitions that
define the liquid phase of water. This model also explained density maximum of water,
super cooled state of water and I.R Raman spectra of water.
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1.3.1 Structure of water
Water exhibit peculiar and unique properties compared to other liquids. Water shows
a density maximum at 3.980C, sound velocity maximum at 740C. Water [44] and heavy
water [45] exhibit positive temperature coefficient of sound velocity. It means that sound
velocity increases with rise in temperature. Randall [44] observed that water has a large
positive temperature coefficient of sound velocity at room temperature and ∂u/∂t becomes
zero at 740C. Beyond 740C water behaves like other common pure liquids and ∂u/∂t is
negative. Water is odourless neutral liquid. Water possesses very high melting and boiling
points compared to other hydrides of VIA group of periodic table [46].
In water (H2O) molecule, single electron of each of hydrogen atom is shared with one
of the six outer shell electrons of oxygen forming covalent hydrogen bonds. Four electrons
of oxygen are organized into two non-bonding pairs. Thus oxygen atom in H2O is
surrounded by four electron pairs that would ordinarily tend to arrange themselves as far as
possible, so that repulsions (electrostatic) between pairs of electrons are minimal. This
results in a tetrahedral geometry in which the angle between electron pairs is 1090. But non-
bonding pairs of electrons of oxygen remain closer to the oxygen atom; as such exert
stronger repulsion against two covalent bonding pairs. As a result two hydrogen atoms are
pushed closer together. As such tetrahedral geometry is distorted and H-O-H bond angle
decreases to 104.50.
Oxygen is highly electronegative. This implies that the charge distribution due to
electron pairs participating in covalent bond between hydrogen and oxygen atoms is not
symmetrical. Negative charge density is more near oxygen atom and less near hydrogen
atom. This charge displacement constitutes an electrical dipole with positive end on
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hydrogen atom and negative end at oxygen atom. Thus we say that due to difference in
electro-negativity between hydrogen and oxygen atoms, partial electric charges are
developed in water molecule. The structure of water molecule as given below:
1.3.2 Hydrogen bonding
According to Pimental et al [47] a "hydrogen bond exists when a hydrogen atom is
bonded to two or more other atoms". Generally, the hydrogen bond refers to the entire group
of three or more atoms, which are involved in a configuration X-H-Y, where X and Y may
be like or unlike atoms (F, 0, N, Cl etc.,). One of the two bonds X-H or H-Y may be stronger
(covalent bond) than the other bond (hydrogen bond). The hydrogen bond is often described
as a strong electrostatic dipole-dipole interaction. Hydrogen bonding is found with strong
electronegative atoms like F, 0, N, Cl, etc. Increasing the electro negativity of an atom
increases its power of forming hydrogen bonds. In almost all hydrogen bonds the hydrogen
atom nearer to one of the two adjacent electronegative atoms than to the other. The variation
of ultrasonic velocity data in liquid mixtures or solid liquid solutions gives a clue to the
intermolecular association through hydrogen bonding where such possibility exists.
Partial positive charge on hydrogen atom of one water molecule is electro-statically
attracted by the partial negative charge of the oxygen atom of a neighbouring water
molecule. This process is called hydrogen bonding. Hydrogen bond is somewhat longer than
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O-H covalent bond. Hydrogen bond length is 117pm and O-H covalent bond length is 99pm.
This means that hydrogen bond is considerably weak compared to covalent bond. Hydrogen
bond is so weak that a given hydrogen bond cannot survive for more than a time fraction of
10-9 seconds.
Some of the structural features of water common to most of the models may be
utilized to explain ultrasonic behaviour of aqueous solutions.
1. Water can be considered as a mixture of hydrogen bonded clusters and dense monomers
in dynamic equilibrium.
2. Rise in temperature promotes rupture of hydrogen bonds. This favours breakdown of
hydrogen bonded structures increasing the population of non-hydrogen bonded monomer
H2O molecules in the solution.
1.3.3 Hydration of ions
Water molecules interact strongly with ions, formed by dissolving electrolytes in
water. Owing to high dipole moment of water, H2O molecules closest to the dissolved ions
are strongly attached to it, forming inner or primary hydration sheath. Cations attract
negative ends of H2O molecules. A critical view about the nature of the state of ions and
water dipoles in a solution has been envisaged by Bockris [48]. He suggested the term
primary hydration should be used for identifying the solvent molecules near to ion that have
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lost translational degrees of freedom and move as one entity with the ion during its
Brownian motion. Secondary hydration is termed to refer to the solvent molecules not
included in the primary hydration shell, but that undergo significant electrostatic interaction
with primary hydration shell. The ordered structure in primary shell creates, through
hydrogen bonding, a region in which the surrounding water is also somewhat ordered. The
outer hydration shell or secondary hydration shell is called cybotactic region.
1.4 Review of literature on previous work
Ultrasonic and thermodynamic measurements in liquids and liquid mixtures find
extensive application to study the nature of intermolecular forces. A review of research work
carried out on large number of liquid mixtures is given by Nomoto [49] and Schaaffs [50].
Liquid mixtures can be broadly divided into two groups, viz., I and II. In group I, the
velocity variation with concentration of the solute is non-linear, whereas group II exhibits
velocity maximum or minimum [51]. The ultrasonic studies in liquids and liquid mixtures
were interpreted using Jacobson's free length theory and Schaaffs' collision factor theory.
The excess parameters, i.e., the difference between molecular and physical properties of the
solvent are proportional to the strength of the interaction between unlike molecules in a
mixture. In this section brief review of the relevant literature pertaining to liquid
mixtures/solutions is given below.
In view of the above, present review of experimental work is concentrated on the
studies of various acoustic, thermodynamic and transport parameters, theoretical evaluation
of sound velocities, viscosities and studies using excess parameters on liquid
mixtures/solution of amides, acrylic esters, alcohols, anilines, citrates, chloro alkanes etc.,
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1.4.1 Literature survey on non aqueous – non electrolytes and electrolyte liquid
mixtures/solutions
Prakash et al [52] made excess free volume studies in the binary mixtures benzene +
ethanol, benzene + iso-propanol, benzene + methanol, benzene + n-hexane, carbon
tetrachloride + o-xylene, carbon tetrachloride + p-xylene, carbon tetrachloride + m-xylene,
toluene + o-xylene, toluene + p-xylene and toluene + m-xylene. They explained the observed
positive and negative deviations on the basis of molecular interaction forces. Ramaswamy
and Anbanathan [53] evaluated sound velocities using Nomoto's relation and ideal mixing
relation for the binary mixtures dioxane with methanol, ethanol, iso-propanol and n-
butanol; carbon tetrachloride with aniline, pyridine, quiniline, N,N-dimethyl aniline,
benzene, chlorobenzene and cyclohexane, benzyl alcohol with methanol, ethanol, n-propanol
and n-butanol.
Varadarajan and Bharathi [54] evaluated free volume, internal pressure and several
other parameters in the binary liquid mixtures of propylene glycol in n-butyl acetate, ethy
acrylate, iso-amyl acetate, and acetone, acetophenone and diacetone alcohol at 350 C and
explained the results. Islam and Quadri [55] investigated the binary mixtures aniline + iso-
propyl alcohol, aniline + iso-butyl alcohol, aniline + iso-amyl alcohol and aniline +toluene.
They computed several parameters for binary mixtures. They evaluated sound velocities
using isothermal compressibility values and compared them with experimental values.
Purnachandra Rao [56] investigated binary mixtures of N,N-dimethyl formamide and N,N-
dimethyl acetamide with aliphatic esters at 303.15 K and computed isentropic
compressibility. The results were explained on the basis of effects of carbon chain length and
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chain boundary of esters studied ultrasonic velocity and absorption in aqueous ammonium
on the specific interactions between unlike molecules.
Anwar Ali and Anil Kumar Nain [57] studied binary mixtures of formamide with 2-
propanol, 1,2-propanediol, 1,2,3-propanetriol over the entire composition range at 308 K.
Isentropic compressibility, free length, relative association, acoustic impedance, deviation of
isentropic compressibility, excess volume, deviation in sound velocity, excess acoustic
impedance were computed. Results were discussed in terms of molecular interactions
between molecules of component liquids. Amalendu Pal and Harsha Kumar [58] studied the
binary mixtures of dipropylene glycol monomethy ether with methanol, 1-propanol, 1-
pentanol and 1-heptanol at 298.15 K. Free length, adiabatic compressibility, available
volume, Rao's number, acoustic impedance, relative association, molecular association,
Vander Waals constant etc., were determined. They concluded the existence of strong
interactions between unlike molecules in the solutions on the basis of observed sharp
increase in acoustic impedance and Rao's number with composition of mixture. Collision
factor theory, free length theory, Nomoto's relation, Junjie’s theory were employed for
theoretical evaluation of sound velocities in the mixtures.
Anwar Ali et al [59] studied molecular interactions in binary mixtures of acetonitrile
with formamide, N,N-dimethyl formamide and N,N-dimethyl acetamide at 308.15 K.
Deviation in isentropic compressibility, excess free length and excess volume were
computed and used to study intermolecular interactions. Further theoretical values of
ultrasonic velocities were calculated using free length theory, Collision factor theory,
Nomoto's relation and ideal mixing relation. Subramanyam Naidu et al [60] investigated
excess internal pressure, excess free length, excess molar volume, excess activation energy
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and excess enthalpy in the binary mixtures of 3-methoxy acetophenone and 4-chloro
acetophenone with dimethyl sulphoxide as common component. The results were discussed
in terms of dipole-dipole interactions, charge transfer interactions and dispersive forces. The
investigations were carried out in the temperature range to 30 and 500 C. Ultrasonic
velocities were evaluated using free length theory, collision factor theory, Van Dael and
Junjie equations and compared with experimental values.
Bhadja et al [61] investigated poly ( R, R’, 4,4’-cyclohexylidene diphenyl
phosphorochloridate), DMF solutions at 30, 35 and 400 C. Acoustic impedance, Vander
Waals constant, Rao's number, free volume, isentropic compressibility, relaxation strength
and internal pressure were evaluated. The results suggested presence of powerful structure
making polymer – DMF interactions. Solvation number increased with concentration
indicating powerful polymer solvent interactions over polymer-polymer interactions.
Satyanarayana Rao et al [62] studied binary mixtures consisting of o-chlorophenol, o-cresol
and m-cresol with N,N-dimethyl acetamide at 308.15, 313.15, 318.15 and 323.15 K over the
entire composition range. Various excess parameters such as excess molar volume, excess
viscosity, excess adiabatic compressibility, and excess free length and Grunberg–Nissan
interaction parameter were computed. From their analysis of the results, the authors
concluded the absence of strong specific interactions in the systems.
Subramanyam Naidu and Ravindra Prasad [63] studied binary liquid mixtures
dimethyl sulphoxide + acetonitrile and dimethyl sulphoxide + N,N-dimethyl formamide at
30,40 and 500 C. Sound velocities were theoretically evaluated using the free length theory,
collision factor theory and these theoretical values were compared with experimental values.
Adiabatic compressibility, excess adiabatic compressibility, excess free length and excess
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molar volume were calculated and intermolecular interactions were studied in terms of
variation of excess parameters with concentration. Sastry and George [64] investigated
thermo physical properties of non-electrolytic mixtures of methyl methacrylate and branched
alcohols (propan-2-ol, 2-methyl propan-2-ol, butan-2-ol and 2-methy propan-2-ol) at 298.15
and 308.15 K. Relative association, solvation number and excess adiabatic compressibility
were evaluated over the entire composition range. The mixture viscosities were analysed in
terms of Grunberg- Nissan, McAllister and Auslander equations. Sound velocities were
analysed using free length theory, collision factor theory, Junjie's theory and Nomoto's
relation. Molecular interactions were studied in the light of variation of excess
compressibility with concentration. The conclusions drawn were supplemented by variation
of relative association and solvation number. Oswal et al [65] investigated isentropic
compressibility and excess isentropic compressibility’s of 14 binary mixtures containing tri
alkyl amines with alkanes and mono-alkyl amines at 303.15 K over the entire composition
range. The magnitude and sign of the evaluated values were interpreted in terms of
molecular interactions and interstitial accommodation. Further experimental values of speeds
of sound analyzed in terms of collision factor theory, free length theory and Prigogine-Flory-
Patterson statistical theory of solutions.
Sridevi et al [66] investigated binary liquid mixtures o-chloro aniline + o-chloro
phenol, N,N-diethyl aniline + o-chloro phenol and N,N-diethyl aniline + o-cresol at 34,37,40
and 430 C over entire composition range of the mixtures. Excess molar volume and excess
compressibility were evaluated and found to be negative in the mixtures. Excess
compressibility values have been compared with corresponding theoretical values as
suggested by Barker. The results were explained in terms of molecular interaction due to
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hydrogen bonding. Arul and Palaniappan [67] investigated 1-butanol in pyridine with
benzene at 303 K and evaluated adiabatic compressibility, free length, free volume and
internal pressure. From the variation of excess parameters of free volume and internal
pressure concluded that associative nature of alcohol disturbs the molecular symmetry
available in benzene molecule.
Savitha Jyostna and Satyanarayana [68] studied binary mixtures of acetophenone,
propiophenone, paramethyl acetophenone and parachloro acetophenone with acetonitrile
over the entire range of composition at 308.15 K. Deviations in sound velocity, adiabatic
compressibility and free length were evaluated. On the basis of variation of these parameters,
specific interactions between unlike molecules were predicted. Deviation in adiabatic
compressibility data was fitted to Redlich–Kister type polynomial equation. Mehra [69]
investigated binary liquid mixtures of hexadecane with 1-pentanol, 1-hexanol and 1-heptanol
at 298, 308 and 318 K over entire composition range. Adiabatic compressibility, free length,
molar sound velocity, acoustic impedance, deviation of adiabatic compressibility, excess free
length, excess viscosity, excess activation energy and interaction parameter were computed.
All the excess functions were fitted to Redlich-Kister type equation. The variation of
computed parameters with concentration was used to discuss nature and extent of molecular
interactions in the mixtures.
Wankhede et al [70] studied the binary mixtures of propylene carbonate with ethanol,
n-propanol and n-butanol at 298.15, 303.15 and 308.15 K. They evaluated excess adiabatic
compressibility, excess free length, excess acoustic impedance and deviation in refractive
index to study molecular interactions in the mixtures. They fitted excess parameters to
Redlich-Kister polynomial equation. Adel S. Al-Jimaz et al [71] studied the binary mixtures
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of chloro benzene with n-alkanols (C6-C10) from 298.15 to 313.15 K. They computed
isentropic compressibility, excess isentropic compressibility, and excess molar volume,
deviation in viscosity and deviation in speed of sound from the experimentally measured
values of sound velocity, density and viscosity. Excess parameters were fitted to polynomial
relation to estimate the coefficients and standard error. They also computed theoretical
velocities using collision factor theory and free length theory. Satyanarayana et al [72]
studied the binary mixtures of chloro ethanes and chloro ethenes with N-methyl acetamide at
308.15 K. They evaluated deviations in sound velocity, isentropic compressibility, free
length and relative association. The variation of calculated parameters indicated non-specific
interactions between unlike molecules. Deviations in computed parameters were fitted to
Redlich-Kister polynomial equation.
Wankhede et al [73] studied the binary mixtures of 2,4,6-trimethyl-1,3,5-trioxane
with methyl acetate, ethyl acetate and 1- butyl acetate over the entire mole fractions at
(298.15, 303.15 and 308.15) K. They studied the variation of excess molar volume and
viscosity deviations and these values were fitted to Redlich-Kister polynomial equation.
Kannappan et al [74] studied the solutions of iodine mono chloride in the equimolar mixtures
of diphenyl ether / 4-chloroanisole / anisole / 1,4-diaxone and dichloromethane /
chloroform/carbon tetrachloride/n-hexane. They evaluated isentropic compressibility,
classical absorption coefficient, internal pressure, cohesive energy, excess energy of
activation and viscous relaxation time. The results indicated formation of charge transfer
complexes in these systems.
Jaime Wisnaik et al [75] studied excess molar volumes in the ternary systems tolune
+ butyl acrylate + methyl methacrylate and its binaries at 298.15 K in the whole composition
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range. The corresponding data were correlated with the Redlich-Kister equation and with a
series of Legender polynomials. Sanjeevan J Kharat and Pandharinath S Nikam [76]
investigated the binary system aniline + benzene and ternary system aniline + benzene +
N,N-dimethyl formamide at 298.15, 303.15, 308.15 and 313.15 K. From the experimentally
determined values of density and viscosity they calculated excess volume and deviation of
viscosity in the mixtures. The excess parameters were fitted to Redlich-Kister polynomial
equation. The results were discussed in terms of molecular interactions. Hossein A Zarei
[77] investigated the binary mixtures of acetic acid with n-alkanols (C1-C4) at 298.15 K. He
evaluated excess molar volume, partial molar volume and excess partial molar volume in the
mixtures. Redlich-Kister polynomial equation was fitted to excess properties computed.
Anil Kumar Nain [78] studied the binary mixtures of formamide with ethanol, 1-
propanol, 1,2–ethanediol and 1,2–propanediol at different temperatures and calculated
deviations of different parameters. The variation of these parameters with composition and
temperature of the mixtures discussed in terms of molecular interactions in these mixtures.
Furthermore, he also examined the dependence of the deviations of the parameters obtained
by using Eyring viscosity equation on composition of the mixtures. Kannappan et al [79]
studied adiabatic compressibility, free length, free volume, internal pressure, viscous
relaxation time and Gibbs free energy in the mixtures of benzamide with propan-2-ol, butan-
1-ol, 1-pentanol and n-hexanol in 1,4-dioxane at 303, 308 and 313 K. These results support
the occurrence of complex formation through hydrogen bonding in these ternary mixtures.
Fushan Chen [80] investigated binary mixtures of N,N-dimethyl acetamide +
benzene/toluene/ethyl benzene at different temperatures. The excess volume values were
computed and are used to study intermolecular interactions. Further these values are fitted to
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Redlich-Kister type polynomial equation. Shipra Baluja et al [81] measured ultrasonic
velocity, density and viscosity of some Schiff bases of 4-amino benzoic acid in 1,4-dioxane
and N,N-dimethyl formamide at 308.15 K. Most of the calculated acoustic and
thermodynamic parameters suggested predominance of solute solvent interactions in the
studied systems. Thiyagarjan et al [82] investigated binary systems of cyclohexane +
ethanol, 1-propanol. Weak dispersive type intermolecular interactions were confirmed in the
systems. Thirumaran et al [83] made acoustic studies in ternary mixtures 1–alkanols in p-
xylene with nitrobenzene at 303 K. Excess values of adiabatic compressibility, acoustic
impedance and internal pressure are evaluated, and concluded that the existence of strong
dipole-dipole interactions through hydrogen bonding between nitrobenzene and 1-alkanols.
Followed by, the donor–acceptor complex formation observed between p-xylene and
nitrobenzene molecules. Moses Ezhil raj et al [84] investigated the binary mixture containing
dimethyl formamide and methanol at different temperatures 303-323 K. He evaluated the
excess valves of adiabatic compressibility, molar compressibility, molar sound relaxation
strength and their excess values. The variation of these parameters with composition of
mixture were explained on the basis of the dipole induced dipole interactions and hydrogen
bonding. The complex formation through inter molecular hydrogen bonding was confirmed
from the FTIR spectra.
Thirumaran et al [85] studied n-alkanols in toluene with nitrobenzene at 303 K.
Adiabatic compressibility, free volume, and internal pressure values are evaluated from
measured values of ultrasonic velocity, density and viscosity. From the variation of excess
parameters they concluded that there exists dipole-dipole interaction through hydrogen
bonding between nitrobenzene and 1–alkanols and also donor–acceptor complex formation
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is observed between toluene and nitrobenzene molecules. C.M. Kinart et al [86] measured
viscosities of binary mixtures of sulfolane with ethylene glycol, di-ethylene glycol, tri-
ethylene glycol and tetra-ethylene glycol at 303.15 K. The deviations in viscosities were
discussed in terms of inter molecular interactions and structure of studied binary mixtures.
They also correlated the experimental viscosity values with the values obtained from Hind et
al, Grunberg and Nissan, Frenkal and Mc. Allister equations.
Anil Kumar Nain et al [87] investigated the densities and volumetric properties of
binary mixtures of ethyl acryl ate with 1-butanol, 2–butanol, 2-methyl-1propanol, and 2-
methyl-2-proponal at different temperatures. They evaluated excess molar volume, partial
molar volumes and excess partial molar volumes at infinite dilution. The variation of these
parameters with composition and temperature of the mixtures have been discussed in terms
of molecular interactions, indicating the presence of specific interactions between ester and
alkanol molecules.
Thiurumaran and Sudha [88] investigated organic ternary mixtures of benzene,
chloro benzene and nitrobenzene with N,N-dimethyl formamide in cyclohexane at 303 K.
They calculated adiabatic compressibility, free length, free volume, Gibbs free energy and
acoustic impedance. The excess values of these parameters discussed in the light of
molecular interaction in the mixtures. Raja Gopal and Chenthilnath [89] calculated excess
available volume, excess free volume, excess free energy of activation, deviations in
isentropic compressibility and ultrasonic speed in the binary liquid mixtures of 2-methyl 2-
propanol with ketones at 298.15, 303.15 and 308.15 K. The variations of these properties
with composition and temperature discussed in terms of molecular interactions between
unlike molecules of the mixtures. Viscosity data was correlated with semi-empirical
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relations like Grunberg and Nissan, Hind and Ubbelohde, Katti and Chaudhri and Heric-
Brewer. Almasi and Iloukhani [90] investigated the binary mixtures of acetophenone and 2-
alkanols at 298.15 K. They evaluated excess molar volume, viscosity deviation and
refractive index deviations and correlated by the Redlich-Kister type function. The
experimental results were used to test the applicability of Prigogine – Flory – Patterson
(PFP) theory.
Ranjith Kumar et al [91] evaluated excess molar volume, deviation in viscosity and
deviation in isentropic compressibility for the binary mixtures of amines with N-methyl
acetamide at 308.15 K. These properties were fitted to the Redlich-Kister polynomial and the
results of excess parameters discussed in terms of molecular interactions. Pandiyan et al [92]
measured densities and speeds of sound of binary mixtures formed by aniline or N-methyl
aniline or N-ethyl aniline with di-isopropyl ether (DIPE) at a temperature of (303.15, 313.15,
and 323.15) K and atmospheric pressure. From these values isentropic compressibility’s,
excess molar volumes and excess isentropic compressibility’s were calculated. The results
have been used to investigate molecular interactions and structural effects in these mixtures.
The speed of sound in present mixtures has been estimated using several theoretical models
to determine their relative predicting ability in terms of pure component properties. Rajgopal
and Chenthilanth [93] studied the binary mixtures of 2-methyl-2-propanol (2M2P) with
Acetonitrile (AN), Propionitrile (PN) and Butyronitrile (BN) including those of pure liquids
over the entire composition range at temperatures 298.15, 303.15 and 308.15 K. The excess
molar volume calculated from density data and other volumetric properties, partial molar
volumes, and partial molar volumes at infinite dilution of each component have been
calculated using two different approaches. Furthermore, other excess thermodynamic
49
properties such as deviations in isentropic compressibility, ultrasonic speed and viscosity,
excess intermolecular free length, excess acoustic impedance and excess free energy of
activation are calculated. The variations of these parameters with composition and
temperature show the presence of a weak interaction between the participating components
in these mixtures.
Gyan Prakash Dubey and Krishan Kumar [94] measured densities, viscosities and
speeds of sound for the binary liquid mixtures containing Diethylenetriamine with 2-methyl-
1-propanol, 2-propanol and 1-butanol at different temperatures. Using this data excess molar
volumes and deviations in isentropic compressibility and speed of sound has been evaluated.
Viscosity data were used to compute deviations in viscosity and excess Gibbs energy of
activation of viscous flow. A Redlich–Kister type equation was applied to fit the excess
molar volumes and deviations in isentropic compressibility, speed of sound and viscosity
data. The viscosity data have been correlated with the equations of Grunberg–Nissan,
Tamura–Kurata, Heric–Brewer and of Hind et al. Iloukhani and Khatereh Khanlarzadeh [95]
studied quaternary system consisting of 1-chloro butane(1) + butyl amine(2) + butyl
acetate(3) + iso butanol (4), related ternary systems of 1-chloro butane(1) + butyl amine(2) +
butyl acetate(3), 1-chloro butane(1) + butyl acetate(3) + iso-butanol(4), and butyl amine(2) +
butyl acetate(3) + iso-butanol(4), and binary systems of 1-chloro butane(1) + butyl acetate(3)
and butyl amine(2) + butyl acetate(3) at 298.15 K and ambient pressure. Excess molar
volumes, for the mixtures were derived and correlated as a function of mole fraction by
using the Redlich–Kister and the Cibulka equations for binary and ternary mixtures,
respectively. From the experimental data, partial molar volumes, and excess partial molar
volumes, were also calculated for binary systems. The experimental results of the constituted
50
binary mixtures have been used to test the applicability of the Prigogine–Flory–Paterson
(PFP) theory.
Pandiyan et al [96] investigated binary mixtures formed by N,N-dimethyl aniline
(DMA) or N,N-diethyl aniline (DEA) with Di-isopropyl ether (DIPE) or oxolane over the
entire range of composition at a temperature of (303.15, 313.15 and 323.15) K and
atmospheric pressure. The density and velocity values are used to calculate isentropic
compressibility’s, Rao's molar sound functions, intermolecular free lengths, specific acoustic
impedances, excess molar volumes, excess isentropic compressibility’s, excess
intermolecular free lengths, and excess specific acoustic impedances. The results have been
used to investigate molecular interactions and structural effects in these mixtures. Kiki
kurnia et al [97] studied binary mixtures containing the protic ionic liquid
bis(2hydroxyethyl) methylammonium formate[BHEMF] with methanol, ethanol, and 1-
propanol at four different temperatures (293.15, 303.15, 313.15, and 323.15) K and
atmospheric pressure. Excess molar volume and viscosity deviations for the binary system
were calculated. The calculated results were fitted to a Redlich-Kister equation to obtain the
coefficients and estimate the standard deviations between the experimental and calculated
quantities.
C.M. Kinart et al [98] studied the binary mixtures of 2-butoxyethanol with ethylene
glycol, di-ethylene glycol, tri-ethylene glycol and tetra-ethylene glycol at different
temperatures. The deviations in the viscosity have been calculated from the experimental
data. The viscosity data, at T=298.15 K, were correlated with equations of Hind et al and
Grunberg and Nissan. The results are discussed in terms of intermolecular interactions and
structural properties of studied binary mixtures.
51
Pandiyan et al [99] studied the thermodynamic and acoustic properties of binary
mixtures of di-isopropyl ether or oxolane with 2- or 3-chloroanilines at 303.15, 313.15 and
323.15 K. The ρ and u values were used to calculate isentropic compressibility’s, Rao's
molar sound function, intermolecular free length, specific acoustic impedance, excess molar
volume, excess isentropic compressibility’s, excess intermolecular free lengths and excess
specific acoustic impedances. These results were used to explain the molecular interactions
and structural effects in these mixtures. Radhey Shyam Sah et al [100] measured the density,
viscosity, speed of sound and refractive index of the binary mixture of 2-methoxyethanol (2-
ME) + diethylether, 2-ME + dichloromethane (DCM) and diethyl ether + DCM and the
ternary mixture of 2-ME + diethylether + DCM at 298.15 K and atmospheric pressure over
the entire composition range. These results were used to calculate excess molar volume,
viscosity deviation and deviation in isentropic compressibility, excess Gibbs free energy of
activation and excess molar refraction for the above systems. The calculated quantities were
further fitted to the Redlich–Kister equation to estimate the binary fitting parameters and
root mean square deviations from the regression lines. Shashi Singh et al [101] investigated
the values of the density and ultrasonic velocity for binary mixtures of butylamine with 1-
butanol and with tert-butanol at temperatures of 293.15, 303.15 and 313.15 K over the entire
mole fraction range. From these data, the excess molar volumes, deviations in isentropic
compressibility, excess internal pressures, and excess molar enthalpies were calculated. All
of the excess functions were fitted to Redlich-Kister polynomial relations to estimate the
adjustable parameters along with the standard deviations of the fits. The variations of these
excess functions with mole fraction of butylamine have been examined.
52
In our laboratory, Sreekanth et al [102,103] measured densities and viscosities of
mixtures of iso-propanol, iso-butanol and iso-amylalcohol with equimolar mixture of ethanol
and N,N-dimethyl acetamide and density, ultrasonic speed in the mixtures of iso-propanol
(IPA), iso-butanol(IBA) and iso-amyl alcohol(IAA) with equimolar mixture of ethanol and
formamide (EMM), including those of pure liquids were measured over the entire range of
composition at temperature 308.15 K. Deviations in viscosity, excess molar volume, excess
Gibb’s free energy of activation of viscous flow and deviations in ultrasonic speed,
isentropic compressibility, excess acoustic impedance and excess free length were calculated
from the experimental values of densities, viscosities and velocities. Excess properties fitted
to the Redlich–Kister type polynomial equation and the corresponding standard deviations
were calculated. The variations of these properties with composition of solution were
discussed in terms of molecular interactions between unlike molecules of the mixtures. The
experimental data of viscosity were correlated to empirical relations of Grunberg–Nissan,
Hind–McLaughlin, Katti–Chaudhary and Heric–Brewer for the systems studied.
Anjali Awasthi and Asshees Awasthi [104] measured the viscosity (η) of formamide
(FA) with 2-methoxyethanol (2-ME) and 2-ethoxyethanol (2-EE) at 303.15, 308.15, 313.15,
318.15 and 323.15 K over the entire composition range. From the experimental viscosity
data, viscosity deviations (Δη) of binary mixtures were evaluated and fitted to the Redlich–
Kister equation. The Δη values are positive over the entire range of composition.
Furthermore, Gibbs free energy of activation (ΔG), enthalpy of activation (ΔH*), entropy of
activation (ΔS*) and excess Gibbs free energy of activation (ΔG*E) of viscous flow have
also been evaluated by using Eyring viscosity equation. The results were discussed in terms
of molecular interactions due to physical, chemical and structural effects between the unlike
53
molecules. Yingjie Xu et al [105] have determined densities and viscosities for the binary
mixtures of n-butylammonium acetate ionic liquid (NBAC) with methanol, ethanol, n-
propanol, and n-butanol at temperatures of (293.15, 298.15, 303.15, 308.15, and 313.15) K
under atmospheric pressure. Excess molar volumes (VE), viscosity deviations (Δη), and
refractive index deviations (ΔnD) were obtained from the experimental data and fitted with
the Redlich–Kister equation. The correlation results were in good agreement with the
experimental data, and optimal fitting parameters were presented. The results were
interpreted in terms of interactions and structural factors of NBAC + alkanols mixtures.
Elizabeth P. Juarez-Camacho et al [106] studied the volumetric properties for the
trihexyltetradecylphosphonium bromide (CYPHOS IL 102) + N,N-dimethyl formamide
(DMF) binary system at temperatures from T=293.15 to 313.15 K and ambient pressure
(p=0.7 atm). Densities were measured by means of a vibrating tube densimeter (VTD).
Excess molar volumes were fitted to a Redlich–Kister type equation. Gerson A. Rodriquez et
al [107] were investigated molar volumes, excess molar volumes, and partial molar volumes
for glycerol formal + propylene glycol mixtures from density measurements at temperatures
from (278.15 to 313.15) K. Mixture compositions were varied in 0.05 in mass fraction of
both components. Excess molar volumes were fitted to the Redlich–Kister equation and
compared with literature values for other systems. The system exhibits positive excess
volumes probably due to increased non-specific interactions. The effect of temperature on
the different volumetric properties studied was also analyzed. Arivazhagan et al [108]
measured ultrasonic velocity, density and viscosity of the binary mixtures ethanol + butyl
acrylate and ethanol + butyl methacrylate over the entire composition range at 303 K. The
excess values have fitted to Redlich–Kister type polynomial. Analysis of the results, they
54
showed specific interaction between the mixtures constituents exist. Das et al [109]
calculated excess molar volumes and viscosity deviations for N,N-dimethyl
acetamide + dimethyl formamide binary mixtures at 298.15, 308.15 and 318.15 K from
experimental density and viscosity data. The experimental values were used to test the
applicability of the correlative reduced Redlich–Kister equation and the recently proposed
Herraez equation. Their correlation ability at different temperatures, and the use of different
number of parameters, was discussed for the case of limited experimental data.
Sreekanth et al [110,111] have measured ultrasonic velocity, density, viscosity of
mixtures of N,N-dimethyl acetamide with equimolar mixture of ethanol+iso-propyl
alcohol/iso-butyl alcohol/iso-amyl alcohol at (T = 308.15, 313.15, and 318.15) K and
ultrasonic velocities, densities for three binary mixture systems of 2-chloroaniline (CA) with
ethyl acrylate (EA), butyl acrylate (BA), and 2-ethylhexyl acrylate (EHA) over the entire
mole fraction range at the temperature 308.15 K. Using the experimental data, various
thermo acoustic parameters such as deviations in ultrasonic velocity, isentropic
compressibility, viscosity, excess molar volume, excess Gibb’s free energy of activation for
viscous flow, deviations in ultrasonic velocity, the excess molar volumes, deviations in
excess molar volume, and deviations in isentropic compressibility, excess intermolecular
free lengths and excess acoustic impedances were measured. The deviation and excess
functions were fitted to the Redlich–Kister type polynomial equation. The influence of
temperature on the observed negative and positive values of deviation and excess
thermodynamic properties were explained in terms of molecular interactions. The above
liquid mixtures were performed in our laboratory.
55
Kermanpour et al [112] measured density and viscosity of binary mixtures of iso-
butanol + 1-propanol, iso-butanol + 2-propanol and 3-amino-1-propanol + 1-propanol over
the entire composition range and at temperatures range (293.15 to 333.15) K. The excess
molar volumes and viscosity deviations were correlated by the Redlich-Kister and
McAllister equations, respectively. Ion Ion et al [113] have measured the density and
refractive index of the diluted binary mixture of active carbon and exfoliated graphite nano
platelets dispersed in N,N-dimethyl formamide at different temperatures and the ultrasound
speed through these materials was determined. The results were used to identify molecular
interactions in the mixtures, including structural changes of exfoliated graphite nano
platelets in polar solvents. Micael et al [114] studied the densities and viscosities for binary
mixtures 2-butanol +iso-butanol, 2-butanol + tert-butanol and iso-butanol + tert-butanol at
temperatures between (308.15 and 343.15) K over the entire composition range. Excess
molar volumes, viscosity deviation and energies of activation were measured from the
experimental measurements.
A.K. Nain et al [115] measured the densities of binary mixtures of butyl acrylate with
1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol, including those of the
pure liquids, over the entire composition range at temperatures of (288.15, 293.15, 298.15,
303.15, 308.15, 313.15, and 318.15) K and atmospheric pressure. From the experimental
data, the excess molar volume, partial molar volumes, and excess partial molar volumes
were calculated over the whole composition range. The excess molar volume values were
found to be positive over the whole composition range for all the mixtures and at each
temperature studied, indicating the presence of weak (non-specific) interactions between
butyl acrylate and alkanol molecules. Priyanka Yadav et al [116] were measured densities
56
and ultrasonic velocities for binary liquid mixtures of ethyl acetoacetate (EAA) with
chloroform (CHCl3) and dimethyl sulphoxide (DMSO) over the entire composition range.
These experimental values were used to calculate the adiabatic compressibility,
intermolecular free length, excess molar volume, excess adiabatic compressibility and excess
intermolecular free length for the liquid mixtures. In all the excess parameters, a positive
deviation was observed in CHCl3–EAA binary mixture, whereas a slight negative deviation
was found for EAA–DMSO binary liquid mixture. These deviations were explained in terms
of molecular interactions between like and unlike molecules.
Firdosa Nabi et al [117] have been derived excess molar volumes by using viscosity
data for the binary mixtures of styrene (STY) with dimethylsulfoxide (DMSO), acetone
(ACT), chlorobenzene (CB), and ethanol (EA) at different temperatures. From the literature
data of viscosities, entropies and enthalpies of activation of viscous flow have been
determined. Moreover, theoretical values of viscosities and ultrasonic speeds of the binary
mixtures were calculated using different empirical relations and theories. The results were
discussed in terms of deviations in experimentally and theoretically calculated values. The
sign and magnitude of these parameters were found to be sensitive towards interactions
prevailing in the studied systems. Hosseinali Zarei et al [118] were obtained excess molar
volumes and viscosity of the ternary mixture of N,N-dimethyl acetamide (1) + N-methyl
formamide (2) + propane-1,2-diol (3) and their binary mixtures from density and viscosity
measurements over the entire mole fraction range at temperatures (293.15 to 333.15) K.
Negative trend were observed for the VmE values of the binary mixtures in the whole
composition range except for N-methyl formamide (2) + propane-1,2-diol (3) mixture in the
N-methyl formamide rich region. Also, negative VmE values were observed for the ternary
57
mixture except a few mole fractions in accordance with their binary mixtures. Effect of
rising temperature on the trend of the VmE values is not the same for the mixtures. The
results were interpreted based on the strength of specific interaction, size and shape of
molecules. The experimental data of excess molar volumes were correlated with the
Redlich–Kister and the Cibulka equations for the binary and ternary mixtures, respectively.
Manukonda et al [119] have measured densities (ρ), viscosities (η), and ultrasonic
speeds (u) for binary mixtures of N,N-diethyl aniline (N,N-DEA) with acetone (AC), methyl
ethylketone (MEK), methyl propylketone (MPK), diethylketone (DEK), and
methylisobutylketone (MIBK) and their pure liquids at (303.15 and 308.15) K over the
entire composition range. These experimental data have been used to calculate the excess
molar volume (VE), deviation in ultrasonic speeds (Δu), deviation in isentropic
compressibility (Δks), deviation in intermolecular free length (ΔLf), deviation in acoustic
impedance (ΔZ), excess Gibbs free energy of activation of viscous flow (G∗E) and deviation
in viscosity (Δη). The variation of these properties with composition of the mixtures
suggests dipole -dipole interactions and charge transfer complex formation between N,N-
diethyl aniline and dipolar ketones. The viscosity data were correlated using three equations:
Grunberg and Nissan, Katti & Chaudhri and Hind et al.
1.4.2 Literature survey on aqueous – electrolytes and non electrolyte liquid
solutions/mixtures
Suryanarayana and Kuppusami [120] computed free volume and internal pressure of
large number of pure liquids and the results were in good agreement with the values already
reported in literature. Suryanarayana and Kuppusami [121] studied the aqueous solutions of
sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, sodium sulphate,
58
potassium sulphate, zinc sulphate, copper sulphate, potassium iodide, lead nitrate, tri-methyl
ammonium chloride and glucose in a wide range of concentrations including saturation.
They studied variation of internal pressure and free volume with concentration and
temperature and obtained quantitative relations between them. They concluded from their
study that free volume, internal pressure and temperature are the key thermodynamic
parameters characterizing the liquid state. Krishna Moorthy et al [122] investigated the role
of free volume in the behaviour of dimethyl formamide + water mixtures. They used
equations developed by Suryanarayana and Kuppusami for calculating free volume. Pande
and Pandey [123] studied free volume in the aqueous solutions of t-butanol, n-propanol,
ethylene glycol and glycerol. They used Eyring and Kincaid equations to evaluate free
volume in aqueous solutions at 250 C.
Manohara Murthy et al [124] studied excess values of molar sound velocity and
compressibility of water + N-methyl formamide and water + DMF at 250. Destabilization of
hydrogen bonded structure of water and formation of 3:1 water amide complexes was
proposed by them to explain the results. Manohara Murthy and Nagabhushanam [125]
studied the binary mixtures water + methanol, ethanol, tetrahydrofuran and evaluated excess
free volumes at 298.15. The results were explained in terms of modifications of hydrogen
bonded structure of water by the solutes. Pillai et al [126] studied aqueous solutions of
dimethyl sulphoxide and computed free volume and adiabatic compressibility. They studied
variation of free volume and adiabatic compressibility with concentration and explained the
results on the basis of molecular interactions. Dhanalakshmi and Lalitha [127,128]
investigated aqueous solutions of nickel nitrate, cobaltous chloride and cupric nitrate. They
studied relationships between internal pressure/free volume and equivalent conductance.
59
They verified that internal pressure and free volume are the key thermodynamic parameters
characterizing the thermodynamic state of liquid systems. Rajagopalan and Tewari [129]
determined adiabatic compressibility, free volume, and internal pressure in water + methanol
mixtures at 0,15,25,30 and 400 C. They verified relationship between free volume and
internal pressure for different mole fractions of methanol.
Dhanalakshmi and Lalitha [130] calculated internal pressure, free volume and
equivalent conductance of aqueous solutions of magnesium chloride at different
temperatures. They verified qualitative relationship between internal pressure, free volume
and equivalent conductance with evaluated concentration and temperature. Suryanarayana
[131] evaluated internal pressure in 22 liquids. He specifically discussed the applicability of
equations used in this investigation, for evaluating free volume and internal pressure in case
of water. Jha and Jha [132] studied partial molar volume and partial molar compressibility of
aqueous solutions of zinc sulphate, cadmium sulphate, zinc nitrate, cadmium nitrate and
cadmium chloride. Ramakrishna et al [133] investigated dilute solutions of water in t-
butanol, secondary butanol, iso-butanol, p-dioxane, dimethyl sulphoxide and ethylene glycol
at 250C. The results were discussed on the basis of water - water; water – non electrolyte
interactions leading to formation of non-electrolyte complexes.
Sravana Kumar et al [134] investigated aqueous solutions of sodium potassium
tartarate and potassium antimony tartarate at 35,45 and 550C. They evaluated free volume
and internal pressure and studied molecular interactions in the light of variation of evaluated
parameters with concentration and temperature. These authors also verified that free volume
and internal pressure are the key thermodynamic parameters characterising the liquid state of
these systems. Rajendra [135] studied adiabatic compressibility, free length, acoustic
60
impedance and relative association of tetra-alkyl ammonium bromides in dioxane-water
mixtures at 303.15 K. Sravana kumar et al [136] investigated aqueous solutions of
acrylamide and N,N-methylene bis–acrylamide at 35,45 and 550C. Structure making and
breaking properties of the non-electrolyte solutes were studied in the light of variation of
free volume and internal pressure with temperature and concentration of the solute.
Subramanyam Naidu and Ravindra Prasad [137] made an ultrasonic study of salts of sodium
in their aqueous solutions. Ragouramane and Srinivasa Rao [138] carried out ultrasonic
velocity studies on the influence of electrolytes on molecular interactions in aqueous
solutions of ethylene glycol. Ishwar Bhatt and Shivakumar [139] studied acoustic and
solvation behaviour of potassium thiocynate in water, DMSO (dimethyl suphoxide), DMF
(dimethyl formamide) and their mixtures. They evaluated adiabatic compressibility, apparent
molar compressibility, free length, acoustic impedance, relative association and solvation
number.
Venkata Ramana et al [140] studied dilute solutions of water in n-propanol, iso-
propanol, glycerol, formamide, N-methyl formamide, dimethyl formamide, tetra hydro
furan, propylene glycol. They studied molecular interactions in the light of variation of
excess velocity. Varadarajan et al [141] investigated aqueous solutions of potassium acetate.
They used Padova's model and made solvation studies in the system. Ravichandran [142]
studied the effect of urea on the micelles of aqueous surfactants i.e. sodium oleate and
sodium taurocholate at 303 K. Adiabatic compressibility, free length and classical absorption
coefficient were calculated and the results were discussed on the basis of micelle formation
and structure breaking nature of urea. Dash et al [143] studied the acoustic behaviour of the
solutions of potassium ferro and ferricyanides in water + alcohol mixtures at 303.15, 308.15
61
and 313.15 K. Basing on the thermo-acoustic parameters ion-solvent interactions and
different structural effects have been studied. Govindarajan et al [144] studied solutions of
gallicacid in aqueous methanol and aqueous acetone. Acoustic impedance, adiabatic
compressibility, free volume, internal pressure, available volume, classical absorption
coefficient, viscous relaxation time, free length, molecular interaction parameter and
cohesive energy were calculated. Solute-solute interactions were studied in terms of
variation of the above parameters.
Ramanathan and Ravichandran [145] investigated mixtures of ammonium sulphate
and ammonium chloride in water at 303 K. Adiabatic compressibility, free length and
acoustic impedance were calculated. Ultrasonic velocity versus concentration (mole fraction)
graph exhibited dips at a composition of 60:40. The observed variation of ultrasonic velocity
and other parameters were discussed. Kannappan and Jayasanthi [146] investigated aqueous
solutions of isomeric butyl alcohols (n-butanol, iso-butanol, s-butanol, t-butanol) at 298 K.
They computed adiabatic compressibility, free length, molecular interaction parameter,
available volume, cohesive energy, internal pressure, Rao's number and classical absorption
coefficient at various mole fractions of alcohol. They found strong intermolecular hydrogen
bonding between alcohol and water molecules and that the strength of the bond depends on
the length of alkyl chain and branching in alkyl group.
Maria M Palaiologou et al [147] measured ultrasonic velocity and density in the
binary mixtures of dimethyl sulphoxide with water, methanol, ethanol, 1-propanol, 2-
propanol, acetone and cyclohexane at 293.15 K and 313.15 K. They computed excess
volume, deviation in velocity of sound and excess isentropic compressibility to study
molecular interactions in the systems investigated. They fitted excess parameters to the
62
Redlich-Kister polynomial equation. Jan Zielkiewicz [148] investigated binary liquid
mixtures N,N-dimethyl acetamide + water/methanol/ethanol and their ternary mixtures N,N-
dimethyl acetamide + methanol + water and N,N-dimethyl acetamide + ethanol + water. He
evaluated excess volumes, standard deviations and examined the possibility of predicting the
ternary results from the binary ones. Kharat [149] studied aqueous solutions of sodium
acetate at different temperatures and calculated apparent molar isentropic compressibility,
limiting apparent molar isentropic compressibility, apparent molar volume, partial molar
volume, solute-solvent interaction parameter, and Helper’s constant. From these parameters
he concluded that sodium acetate is water structure maker. Roy et al [150] measured
densities, viscosities and speeds of sound for the ternary mixtures of water + N,N-dimethyl
formamide + mono alkanols at different temperatures. From the experimental measurements
excess isentropic compressibility’s, excess molar volumes, viscosity deviation and energy
index evaluated. These results were discussed in terms of molecular package and specific
interaction predominated by hydrogen bonding. Roy et al [151] evaluated apparent molar
volumes, viscosity B–coefficients and adiabatic compressibility’s of some mineral sulfates
in aqueous binary mixtures of formamide at different temperatures. Their studies reveal that
ion-ion interactions are predominant over ion – solvent interactions in all the aqueous binary
mixtures of formamide at all the temperatures and also the sulfates were found to act as
structure makers in the solvent mixtures studies. Furthermore, the activation parameters of
viscous flow were determined and successfully discussed by the application transition state
theory.
Pankaj K Singh and Bhatt [152] studied the solutions of poly vinyl acetate in acetic
acid at concentration range 0.5% to 2.0% and in temperature range 350C to 550C various
63
acoustic parameters like adiabatic compressibility, acoustic impedance relaxation time and
ultrasonic attenuation were evaluated. From these parameters they concluded that there were
strong polymer–solvent interactions existing at higher concentration range. Rajgopal and
Jaya balakrishnan [153] measured ultrasonic speeds of 4-aminobytyric acid aqueous
salbutamol sulphate solutions at different temperatures with different concentrations. They
measured isentropic compressibility, change in compressibility, relative change in isentropic
compressibility and apparent molar compressibility. These parameters were used to interpret
the solute-solute and solute-solvent interaction in the solutions. Yasmin Akhtar and Ibrahim
[154] measured the densities and ultrasonic velocities of glycine (0.01–0.09 M) in aqueous
NaCl and MgCl2 (0.02 and 0.06 M) solutions at 303 K. From these experimental data
adiabatic compressibility, apparent molar volume, apparent molar adiabatic compressibility,
partial molar volume and partial molar adiabatic compressibility at infinite dilution were
calculated for all the ternary systems. The data have been interpreted in terms of solute–
solute and solute–solvent interactions.
Rajagopal and Edwin Gladson [155] were studied the apparent molal volumes,
apparent molal compressibilities and viscosity A and B-coefficients of potassium fluoride in
aqueous solutions of dimethyl sulfoxide (DMSO), have been evaluated at T = 303.15,
308.15, 313.15 and 318.15 K from density, velocity and viscosity data, respectively. The
standard partial molal volumes, standard partial molal volumes of transfer, standard partial
molal compressibilities and standard partial molal compressibilities of transfer were
determined and interpreted in terms of solute–solvent interactions. Banipal et al [156]
measured the densities, sound velocities and viscosities of glycine, dl-α-alanine, dl-α-amino-
n-butyric acid, l-valine, and l-leucine, in aqueous solutions (0.1, 0.5, 1.0, and 1.5) mol · kg−1
64
of manganese chloride tetrahydrate, MnCl2·4H2O at different concentrations using a
vibrating-tube digital densimeter, ultrasonic multi frequency interferometer and ubbelohde
type capillary viscometer attached with automatic viscosity measuring unit, respectively,
within the temperature range (288.15 to 318.15) K. Partial molar volume, partial molar
adiabatic compressibility’s and viscosity B-coefficients were determined from these
measurements. The data were discussed in terms of hydration of hydrophobic and
hydrophilic parts of amino acids in these solutions.
Deosarkar [157] measured the density, viscosity and ultrasonic velocity of some
substituted pyrazoles viz. 5-(2-hydroxyphenyl)-3-(pyridin-3-yl)-4-benzoylpyrazol, 5-(2-
hydroxyphenyl)-3-(3-nitrophenyl)-4-(3-pyridinoyl)-pyrazol, 5-(2-hydroxyphenyl)-3-(3-
nitrophenyl)-4-benzoylpyrazol and 5-(2-hydroxyphenyl)-3-phenyl-4-(3-pyridinoyl)-pyrazole
in 70: 30 (vol/vol) acetone-water mixture at 298, 303, 308, and 313 K for 0.01 mol
dm−3 concentration of pyrazoles. The acoustical parameters such as adiabatic
compressibility, relative association, specific acoustic impedance, apparent molar volume,
apparent molar adiabatic compressibility and intermolecular free length were calculated
from the experimental densities and velocities. The changes in acoustical properties have
been used to interpret the molecular interactions in solutions. Aiju Chen et al [158] studied
densities and viscosities of the pseudo binary system 7-hydroxy-4-methylcoumarin+
(ethanol or 1-propanol) +water at temperatures of (293.15, 298.15, 303.15, 308.15 and
313.15) K and refractive indices of this system at T = 298.15 K as a function of the molality
of 7-hydroxy-4-methylcoumarin. The calculated parameters and their variation tendencies
were expounded in terms of the interactions between solutes and solvents.
65
Chunli Liu et al [159] have measured densities of l-alanine and l-serine in aqueous
solutions of N,N-dimethyl formamide (DMF) at 298.15 K with an Anton Paar Model
densimeter. Apparent molar volumes, standard partial molar volumes, standard partial molar
volumes of transfer and hydration numbers have been determined for the amino acids. The –
CH3 group of l-alanine has much more influence on the volumetric properties. Mohammed
Toghi et al [160] have measured density, speed of sound and viscosity values of {poly
ethylene glycol di-methyl ether 2000 (PEGDME2000) + poly ethylene glycol 400
(PEG400) + water}, ((PEGDME2000) + water) and ((PEG400) + water) solutions at
T = (293.15, 298.15, 303.15, 308.15, and 313.15) K. From these measurements, values of
the excess molar volume, excess molar isentropic compression, excess Gibbs free energy of
activation of viscous flow and deviation of viscosity were calculated. Eyring-modified
Wilson and Eyring-NRTL models have been used to correlate the viscosity values of binary
and ternary solutions. The apparent specific volumes at infinite dilution values for the binary
and ternary solutions were also determined from the density data at dilute range. These
values were used to obtain some information regarding the segment–solvent and segment–
segment interactions.
Mehra and Brij [161] determined density, viscosity, sound speed and refractive index
of lactose with mixed solvent of N,N-dimethyl formamide-water or (DMF–H2O) from
0.1050 to 1.045 m at different temperatures using bicapillary pycnometer, Ostwald’s
viscometer, Abbe’s refractometer and single frequency ultrasonic interferometer at 2 MHz
frequency respectively. The derived parameters like apparent molal volume, free volume,
intermolecular free length, acoustic relaxation time, Gibb’s free energy, internal pressure,
Rao’s constant, Wada’s constant, adiabatic compressibility, acoustic impedance, absorption
66
coefficient and molar refractivity were calculated from experimental data. They concluded
that solute–solvent interactions are stronger at all the temperatures in the mixtures.
1.5 Scope of the present work
Acrylic esters are important industrial chemicals and are widely used as precursors in
the production of technically important special type polymers. Amides, relevant liquid
systems for the study of molecular interactions, are among the most common solvents used
in chemical reactions and in many industrial processes and important model systems for the
investigation of peptide and protein interactions in biological systems. Binary liquid
mixtures containing glycols are used in the pharmaceutical, cosmetic and food industries.
Propionic acid is a naturally occurring carboxylic acid and it is used as food preservative
(calcium and sodium propionate). It is also useful as an intermediate in the production of
other chemicals, especially polymers, plastics, cosmetics. Aromatic anilines N,N-dimethyl
aniline, N,N-diethyl aniline are used as intermediates to manufacture dyes, vanillin, and as a
stabilizer for calorimetric peroxidase determination. Alkanols are of interesting simple
examples of biological and industrial important amphiphilic materials. Dimethyl sulfoxide
is a highly polar (μ = 4.06 D) self-associated solvent, is an important solvent in chemistry,
biotechnology, and medicine and it is able to participate in hydrogen bonding.
Dichloromethane used as a cleaning agent, paint remover and in extraction technology;
paraffin extraction, recovery of specialty pharmaceuticals. 1,2-Dichloroethane mostly used
in the production of vinyl chloride which is used to make a variety of plastic and vinyl
products including polyvinyl chloride. Tri potassium citrate is used to control uric acid
kidney stones. When orally administered it is rapidly absorbed and excreted in urine as
67
carbonate. Tri-sodium citrate is used as food additive and as a preservative. In blood
transfusions it is used as anticoagulant.
In view of growing interest and importance of the chemicals in the industrial purpose
the result of an ultrasonic velocity, density and viscosity to study the related acoustical
parameters of above chemicals are presented in this work. However, no effort has been made
to collect the ultrasonic velocity, density and viscosity data on prepared binary and ternary
(equimolar) mixtures in the previous literature. Therefore studies of acoustic, volumetric and
transport properties of following systems are made in the present study. Moreover, the study
intends to provide the information on the molecular interactions between the constituent
liquid molecules for the prepared binary and ternary (equimolar) liquid systems.
Binary systems:
1. N,N-dimethyl formamide with acrylic esters at 308.15 K
a) N,N-dimethyl formamide + methyl acrylate
b) N,N-dimethyl formamide + ethyl acrylate
c) N,N-dimethyl formamide + butyl acrylate
d) N,N-dimethyl formamide + 2-ethyl hexyl acrylate
2. Propionic acid with anilines at 303.15, 313.15 and 323.15 K
a) Propionic acid + N,N-dimethyl aniline
b) Propionic acid + N,N-diethyl aniline
68
3. Aqueous tripotassium citrate and trisodium citrate of 0.1 m with methanol at
308.15 K.
a) Aqueous tripotassium citrate + methanol
b) Aqueous trisodium citrate + methanol
4. Aqueous ethylene glycol and propylene glycol of different molalities
(0.5m, 1.0m and 1.5m) with isopropyl alcohol at 308.15 K
a) Aqueous ethylene glycol + isopropyl alcohol
b) Aqueous propylene glycol + isopropyl alcohol
5. Dichloromethane or 1,2-dichloroethane with N,N-dimethyl formamide or dimethyl
sulfoxide at 308.15 K
a) Dichloromethane + N,N-dimethyl formamide
b) Dichloromethane + dimethyl sulfoxide
c) 1,2-dichloroethane + N,N-dimethyl formamide
d) 1,2-Dichloroethane + dimethyl sulfoxide
6. Ethylene glycol with amides at 308.15 K
a) Ethylene glycol + formamide
b) Ethylene glycol + N,N-dimethyl formamide
c) Ethylene glycol + N,N-dimethyl acetamide
69
Ternary (equimolar) systems:
1) Equimolar mixture of N,N-dimethyl acetamide + ethyl acrylate with butanols at
308.15 K.
a) (N,N-dimethyl acetamide + ethyl acrylate) + n-butanol
b) (N,N-dimethyl acetamide + ethyl acrylate) + iso-butanol
c) (N,N-dimethyl acetamide + ethyl acrylate) + t-butnaol
2) Equimolar mixture of N,N-dimethyl formamide +methanol/ethanol/1-propanol
(EMM) with propanoic acid at 303.15, 313.15 and 323.15 K.
a) (N,N-dimethyl formamide + methanol) + propanoic acid
b) (N,N-dimethyl formamide + methanol) + propanoic acid
c) (N,N-dimethyl formamide + methanol) + propanoic acid
In this context ultrasonic velocity (u), density (ρ), and viscosity (η), are determined in
pure and liquid mixtures and solutions. From these measured values acoustic and
thermodynamic properties like isentropic compressibility (ks), isothermal compressibility
(βT), thermal expansion coefficient (α), inter molecular free length (Lf), specific acoustic
impedance (Z), molar volume (Vm), free volume (Vf), internal pressure (πi), enthalpy (H),
viscous relaxation time (τ) and relaxation strength (α) are computed. Further deviation/
excess properties of acoustic, thermodynamic and transport parameters such as excess molar
volume ( EmV ), excess intermolecular free length ( E
fL ), excess specific acoustic impedance
(ZE), excess free volume ( EfV ), excess internal pressure ( E
i ), excess enthalpy (HE), excess
Gibbs free energy (ΔG*E), deviation in viscosity (Δη), deviation in isothermal
70
compressibility (ΔβT), deviation in thermal expansion coefficient (Δα), excess relaxation
time (τE) are evaluated from the above calculated parameters. The calculated deviation and
excess functions have been fitted to the Redlich–Kister [162] type polynomial equation, and
their corresponding standard deviations are also evaluated. Partial molar volumes m,1V , m,2V ,
excess partial molar volumes Em,1V ,
Em,2V , partial molar compressibility’s 1,mK , 2,mK , excess
partial molar compressibility’s EmK 1, ,
EmK 2, , of liquid mixture also evaluated to study the
molecular interactions exist in the liquid components.
The experimental data of ultrasonic velocity have been used to check the
applicability of theoretical velocity evaluated models such as Nomoto [163], Van Dael and
Vangeel [164], Junjie [165], Impedence relation [166], Jacobson [167], Rao’s (specific
sound velocity) [168] and experimental values of ultrasonic velocity data have been fitted to
two types of polynomial equations [169] f(x) and g(x). Further, viscosity data have also been
availed to test the applicability of standard viscosity models of Kendall and Monroe relation
[170], Grunberg-Nissan [171], Tamura and Kurata relation [172], Frenkel relation [173],
Hind-McLaughlin [174], Katti-Chaudhary [175] and Heric-Brewer [176] for all the systems
investigated at various temperatures. The results obtained are presented and analyzed to
study the molecular interactions between unlike molecules of different components of
various binary and ternary (equimolar) liquid mixtures and solutions.
71
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