28

CHAPTER – 1

Introduction and review of literature

29

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.,

30

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.

31

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].

32

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.

33

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

34

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.

35

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

36

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

37

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

38

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.,

39

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

40

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

41

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

42

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

43

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

44

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

45

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

46

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

47

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

48

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

References

[1] Ali A, Abida, Hyder S and Nain A K, Indian J. Physics., 76B (2002) 661.

[2] Satyanarayana Rao T, Veeraiah N and Rambabu C, Indian J. Pure & Appl. Phys., 40

(2002) 850.

[3] Oswal S L, Oswal O S and Phalak R P, J. Sol. Chem., 27 (1998) 507.

[4] Rajasekhar J and Naidu P R, J. Chem. Engg. Data., 41 (1996) 373.

[5] Adidharma H and Radosz M, Fluid Phase Equilib. 161 (1999) 1.

[6] Temperley H N V, 'Physics of simple liquids' (1968), North Holland Publishing

Company, Amsterdam.

[7] Hildebrand J H and Scott R L, 'Solubility of non-electrolytes', 3rd Ed., Reinhold

Publishing Corp., New York (1950).

[8] Hildebrand J H and Scott R L, 'Regular Solutions' Prentice Hall, Englewood Cliffs, N. J.

(1962).

[9] Lennard-Jones J E and Devonshire A F, Proc. Roy. Soc. (London), A 163 (1937) 63, A

164 (1938) 1.

[10] Kihara T, Rev. Mod. Phys., 25 (1953) 83157.

[11] Haman S D and Lambert J A, Australian J. Chem., 1 (1954) 1.

[12] Barker J A, Proc. Roy. Soc. (London)., A259 (1961) 442.

[13] Prigogine I and Garikian G,Physica., 16 (1950) 239.

[14] Prigogine I, Bellemans A and Methot V, 'The molecular theory of solutions', North

Holland Pub. Co., Amsterdam. (1957).

[15] Prigogine I and Methot V, J. Chem. Phys., 20 (1952) 49.

[16] Eyring H and John M S, 'Significant liquid structures', John Wiley, New York. (1969).

72

[17] Barker J A, Lattice Theories of Liquid State, Pergamon Press, Oxford (1963).

[18] Panayiotou C and Sanchez I C, J. Phys. Chem. 95 (1991) 90.

[19] Barker J A, 'Lattice theories of liquid state', Pergmon, Oxford., (1963).

[20] Rowlinson J S, 'Lattice theories of liquid state', Vol. I. McMillan, New York. (1963).

[21] Longuet-Higgins H C, Proc. Roy. Soc. (London), A205 (1951) 247.

[22] Pitzer K S, J. Chem. Phys., 7 (1939) 583.

[23] Prigogine I, Bellemans A and Englert Chowoles A, J. Chem. Phys., 24 (1956) 516.

[24] Balescu R, Bull. Acad. Belg. Cl. Sci., 41 (1955) 242.

[25] Barker J A, J. Chem. Phys., 19 (1951) 1430, 20 (1952) 1526.

[26] Brown W B, Phil. Trans., A250 (1957)175, 221.

[27] Salsburg Z W, Woztowicz P J and Kirkwood J G, J. Chem. Phys., 26 (1957)1533.

[28] Salsburg Z W, Woztowicz P J and Kirkwood J G, J. Chem. Phys., 27 (1957) 505.

[29] Durov V A, Khim Zh Fiz, Russ. J. Phys. Chem 67 (1993) 264.

[30] Durov V A, J. Mol. Liq. 78 (1998) 51.

[31] Durov V A, J. Therm. Anal. Cal., 62 (2000) 15.

[32] Durov V A, In Concentrated and Saturated Mixtures (monograph in Russian), pp.170–

254, Science Publ., Moscow (2002).

[33] Durov V A, J. Mol. Liq., 103–104 (2003) 41.

[34] Prigogine I and Defay P, Chemical Thermodynamics, Longmans Green, London

(1954).

[35] Prausnitz J M, Lichtenthaler R N and De Azevedo R N, Molecular Thermodynamics of

Fluid-Phase Equilibria, 2nd ed., Prentice-Hall, Englewood Cliffs, New York (1986).

[36] Schuster P, Zundel G and Sandorfy S, The Hydrogen Bond: Recent Development in

73

Theory and Experiment, Vols. 1–3, North Holland, Amsterdam (1976).

[37] Nemathy G and Sheraga H A, J. Chem. Phys., 36 (1962) 3382, 41 (1969) 680.

[38] Vand V and Senior W A, J. Chem. Phys., 43 (1965) 1878.

[39] Jhon M S, Grosh J, Ree T and Eyring H, J. Chem. Phys., 44 (1966) 1456.

[40] Jhon M S, Van Artsdalen E R, Ghosh J and Eyring H, J. Chem. Phys., 47 (1967) 2231.

[41] Angell C A, J. Phys. Chem., 75 (1971) 3698.

[42] Weres O and Rice S A, J. Amer. Chem. Soc., 94 (1971) 8983.

[43] Gibbs J H, Cohen C, Fleming P and Posoroff H, J. Sol. Chem., 2 (1973) 277.

[44] Randall R, Bur. Stand. J. Res., 8 (1932) 79.

[45] Pancholy M, J. Acous. Soc. Amer., 25 (1953) 1003.

[46 Tamn K and Haddenhorst H C, Acustica, 4 (1954 ) 653.

[47] Pimental G C and M'Cledlan A L, "The Hydrogen Eons', W.H.Freeman Co., San

Francisco, (1959).

[48] Bockris J O' M, Quart. Rev. Chem. Soc. Lond., 3(1949)173

[49] Nomoto O, Soc Jpn., 11 (1956) 827.

[50] Schaaffs W, Acoustica, 4 (1954) 636.

[51] Nomoto O, J Chem. Soc. Jpn., 8 (1953) 553.

[52] Prasad N, Prakash O, Singh S and Prakash S, Ultrasonics (GB), 16 (1978) 77.

[53] Ramaswamy K and Anbanathan D, J. Acous. Soc. India., 13 (1985) 192.

[54] Varadarajan R and Bharathi G, J. Pure and Appl. Ultrason., 9 (1987) 1.

[55] Islam R M and Quadri S K, Acoust. Letts., 11 (1988) 219.

[56] Purnachandra Rao K, Ultrasonics., 28 (1990) 120

[57] Anwar Ali and Anil Kumar Nain, Indian J. Pure & Appl. Phys., 39 (2001) 421.

74

[58] Amalendu Pal and Harsha Kumar, Indian J. Phys., 75B (2001) 419.

[59] Anwar Ali, Anil Kumar Nain, Narender Kumar and Mohammad Ibrahim, J. Pure and

Appl. Ultrason., 24 (2002) 27.

[60] Subramanyam Naidu P, Prabhakara Rao N and Ravindra Prasad K, J. Pure and Appl.

Ultrason., 24 (2002) 36.

[61] Bhadja D R, Patel Y V and Parsania P H, J. Pure and Appl. Ultrason., 24 (2002) 47.

[62] Satyanarayana Rao T, Veeraiah N and Rambabu C, Indian J. Pure & Appl. Phys., 40

(2002) 80.

[63] Subramanyam Naidu P and Ravindra Prasad K, J. Pure and Appl. Ultrason., 24 (2002)

18.

[64] Sastry N V and George J, Int. J. Thermophys., 24 (2003) 1089.

[65] Oswal S L, Patel S G, Gardas R L and Ghael, Fluid Phase equlib, 215 (2004) 61.

[66] Sridevi U, Samatha K and Sarma A V, J. Pure and Appl. Ultrason., 26 (2004) 1.

[67] Arul G and Palaniappan L, Indian J. Pure & Appl. Phys., 43 (2005) 755.

[68] Savitha Jyostna T and Satyanarayana M, Indian J Pure & Appl. Phys., 43 (2005) 591.

[69] Mehra R, Z. Phys. Chem., (Germany), 219 (2005) 425.

[70] Wankhede D S, Wankhede N N, Lande M K and Arbat B R, Indian J. Pure & Appl.

Phys., 44 (2006) 909.

[71] Adel S. Al-Jimaz, Jasem A Al-Kandary and Abdul-Haq M. Abdul-Latif, J. Chem. Eng.

Data., 52 (2006) 206.

[72] Satyanarayana B, Savitha Jyostna T and Satyanarayana N, Indian J. Pure & Appl.

Phys., 44 (2006) 587.

[73] Wankhede N N, Wankhede D S , Lande M K and Arbad B R, J. Chem. Thermodyn., 38

75

(2006) 1664.

[74] Kannappan V, Askar Ali S J and Abdul Mahabood P A, Indian J. Pure & Appl. Phys.,

44 (2006) 903.

[75] Jaime Wisniak, Isabel Villarreal, Rene. D.Pralta and Homero Soto., J. Chem.

Thermodyn., 39 (2007) 88.

[76] Sanjeevan J Kharat and Pandharinath S Nikam, J. Mol. Liq., 131-132 (2007) 81.

[77] Hossein A Zarei, J. Mol. Liq., 130 (2007) 74.

[78] Anil Kumar Nain, J. Mol. Liq., 140 (2008)108.

[79] Kannappan A N, Kesavaswamy R and Ponnuswamy V, American J. Of Engineering

and applied Sciences., 1 (2008) 95.

[80] Fushan Chen, Jiang Wu and Zhen Wang, J. Mol. Liq., 140 (2008) 6.

[81] Shipra Baluja, Nayan Vekariya and Jag dish Movaliya, Iran. J. Chem. Chem. Eng., 27

(2008) 129.

[82] Thiyagarajan R and Palaniappan L, Indian J. Pure & Appl. Phys., 46 (2008) 852.

[83] Thirumaran S and Saradha Devi S. App. Sci Research., 1 (2009) 128.

[84] Moses Ezhil Raj A, Resmi L B, Bena Jyothi V, Jayachandran M and Sanjeeviraja C,

Fluid Phase Equili., 281 (2009) 78.

[85] Thirumaran S and Jaya Kumar J, Indian J. Pure & Appl. Phys, 47 (2009) 265.

[86] Cezary M Kinart, Marta Maj and Wojciech J, Kinart, Phy. Chem. Liq., 47 (2009) 487.

[87] Anil Kumar Nain, Rajini Sharma, Anwar Ali and Swaritha gopal, J. Mol. Liq., 144

(2009) 138.

[88] Tirumaran S and Sudha S, J. Chem. and Pharm Research., 2 (2010) 327.

[89] Rajagopal K and Chenthilanath S, J. Mol. Liq., 155 (2010) 20.

76

[90] Almasi and Iloukhani, J.Chem. Eng. Data, 55 (2010) 1416.

[91] Rajith Kumar, Asra Banu, Savitha Jyostna and Satyanarayana N, Phys. Chem. Liq., 48

(2010) 78.

[92] Pandiyan V, Vasantharani P, Oswal S L and Kannappan A N, J. Chem. Eng. Data.,

56(2) (2011) 269.

[93] Rajagopal K and Chenthilanth S, J. Mol. Liq., 160 (2011) 72.

[94] Gyan Prakash Dubey and Krishan Kumar, Thermochim. Acta, 524 (2011) 7.

[95] Iloukhani H and Khanlarzadeh K, J. Chem. Eng. Data, 56 (2011) 4244.

[96] Pandiyan V, Oswal S L and Vasantharani P, Thermochim. Acta., 518 (2011) 36.

[97] Karnia K A, Abdul Mutalib M I, Murugesan T and Ariwahjoedi B, J. Sol. Chem., 40

(2011) 818.

[98] Kinart C M, Klimczak M and Kinart W, Phys. Chem. Liq., 49 (2011) 181.

[99] Pandiyan V, Oswal S L, Malek N I and Vasantharani P, Thermochim. Acta., 524 (2011)

140.

[100] Radhey Shyan Sah and Roy M N, Phy. Chem. Liq., 49 (2011) 133.

[101] Singh S, Parveen S, Shukla D, Yasminm M, Gupta M and Shukla J P, J. Sol. Chem.,

40 (2011) 889.

[102] Sreekanth K, Kumar D S, Kondaiah M and Rao D K, Physica B., 406 (2011) 854.

[103] Sreekanth K, Kumar D S, Kondaiah M, Rao D K, J. Chem. Pharm. Res., 3 (2011) 29.

[104] Awasthi A and Awasthi A, Thermochimica Acta., 537 (2012) 57.

[105] Xu Y, Yao J, Wang C and Haoran L, J. Chem. Eng. Data., 57 (2012) 298.

[106] Juarez-Camacho E P, Manriquez-Ramirez M E, Reza-San German C M and Zuniga-

Moreno A, J. Sol. Chem., 41 (2012) 1575.

77

[107] Rodriquez G A, Delgado D R, Martinez F, Abolghassemi Fakhree M A and Jouyban

A, J. Sol. Chem., 41 (2012) 1477.

[108] Arivazhagan G, Mahalakshmi M and Jeenathus Zahira S A, Indian J. Phys., 86 (2012)

493.

[109] Das D, Barhoumi Z, Dhouibi N, Sanhoury M A M K and Ouerfelli N, Phy. Chem.

Liq., 50 (2012) 712.

[110] Sreekanth K, Kondaiah M, Kumar D S, and Rao D K, J. Therm. Anal. Calorim., 110

(2012) 1341.

[111] Sreekanth K, Kondaiah M, Kumar D S and Rao D K, J. Sol. Chem., 41(2012) 1088.

[112] Kermanpour F, Niakan H Z and Sharifi T, J. Chem. Eng. Data., 58 (2013)1086.

[113] Ion I, Sirbu F and Catrinel Ion A, J. Chem. Eng. Data., 58 (2013) 1212.

[114] Bravo-Sanchez M G, Iglesias-Silva G A and Estrada-Baltazar A, J. Chem. Eng. Data.,

58 (2013) 2538.

[115] Nain A K, J. Sol. Chem., 42 (2013) 1404.

[116] Yadav P, Kumar M and Yadav R, Phys. Chem. Liq., 52 (2014) 331.

[117] Nabi F, Jesudason C G, Malik M A and Al-Thabaiti S A, Chem. Eng. Commu., 200

(2013) 77.

[118] Zarei H, Golroudbari S A and Behroozi M, J. Mol. Liq., 187 (2013) 260.

[119] Manukonda G S, Ponneri V, Kasibhatta K S and Sakamuri S R B, Arabian J. Chem.,

http://dx.doi.org/10.1016/j.arabjc.2013.09.042.

[120] Suryanarayana C V and Kuppusami J, J. Acous. Soc. India., 9 (1981) 4.

[121] Suryanarayana C V and Kuppusami J, J. Acous. Soc. India., 4 (1976) 75.

[122] Krishnamoorthy K, Pillai S O and Kuppusami J, J. Acous. Soc. India, 5 (1977) 80.

78

[123] Pande P and Pandey B D, J.Phys.,Part-B., 56 (1982) 325.

[124] Manohara Murthy N, Sivakumar K V, Rajagopal E and Subramanyam S V, Acoust.

Letts., 6 (1983) 28.

[125] Manohara Murthy N and Nagabhushanam G, Acoust. Letts., 8 (1984) 100.

[126] Pillai S O, Natarajan S, Palanisamy P K and Murugesan V, J. Acous. Soc. India., 13

(1985) 107.

[127] Dhanalakshmi A and Lalitha V, J. Acous. Soc. India., 12 (1984) 32.

[128] Dhanalakshmi A and Lalitha V, J. Acous. Soc. India., 13 (1985) 124.

[129] Rajagopalan S and Tiwari S A, Acustica., 58 (1985) 98.

[130] Dhanalakshmi A and Lalitha V, J. Chem. Phys., 88 (1988) 405.

[131] Suryanarayana C V, Indian J. Pure & Appl. Phys., 27 (1989) 751.

[132] Jha D K and Jha B L, Indian J. Pure & Appl. Phys., 28 (1990) 346.

[133] Ramakrishna V, Rajagopal E and Manohara Murthy N, Acoust. Letts.,14 (1991) 14.

[134] Sravana Kumar D, Subramanyam Naidu P and Ravindra Prasad K, J. Pure and Appl.

Ultrason., 15 (1995) 11.

[135] Rajendran V, Indian J. Pure & Appl. Phys., 32 (1994) 523.

[136] Sravana Kumar D, Subramanyam Naidu P and Ravindra Prasad K, J. Pure and Appl.

Ultrason., 17 (1995) 24.

[137] Subramanyam Naidu P and Ravindra Prasad K, J. Pure and Appl. Ultrason., 18 (1996)

30.

[138] Ragouramane D and Srinivasa Rao A, Indian J. Pure Appl. Phys, 36 (1998)777.

[139] Ishwar Bhatt J and Shiva Kumar H R, Indian J. Pure Appl. Phys, 38 (2000)306.

[140] Venkata Ramana G, Rajagopal E and Manohara Murthy N, Indian J. Pure and Appl.

79

Phys., 38 (2000) 10.

[141] Varadarajan R and Kalyana Sundaram S Maria Eugenie Pia K, J. Pure and Appl.

Ultrason., 24 (2002) 11.

[142] Ravichandran G, Indian J. Phys., 76B (2002) 277.

[143] Dash U N, Roy G S and Mohanty S, Ultra. Sci. Phys. Sci., 15 (2003) 1.

[144] Govindarajan S, Kannappan V, Naresh M D Venkataboopathy K V and Lokandan B,

J. Mol. Liq., (Netherlands), 107 (2003) 289.

[145] Ramanathan K and Ravichandran S, J. Pure and Appl. Ultrason., 26 (2004) 12.

[146] Kannappan V and Jayasanthi R, Indian J. Pure & Appl. Phys., 43 (2005)161.

[147] Marai M Palaiologou, George K Arianas and Nikos G Tsierkezos., J. Sol. Chem., 35

(2006) 1551.

[148] Jan Zielkiewicz, J.Chem. Thermodyn., 40 (2008) 431.

[149] Kharat S J, J. Mol. Liq., 140 (2008) 10.

[150] Roy M N, Chandra R and Ghosh G, Russian J. Phys Chem. A., 83 (2009) 1331.

[151] Roy M N, Chandra R and Sarkar B K, Russian J. Phys Chem. A., 83 (2009) 1737.

[152] Pankaj K. Singh and Bhatt S C, Appl. Phy. Research., 2 (2010) 35.

[153] Rajagopal and Jaya balakrishnan, Chinese Journal of Chemical Eng., 18 (2010) 659.

[154] Akhtar Y and Ibrahim S F, Arabian Journal of Chemistry., 4 (2011) 487.

[155] Rajagopal K and Edwin Gladson S, Thermochimica Acta., 20 (2011) 197.

[156] Banipal T S, Kaur J and Banipal P K, J. Chem. Thermodyn., 48 (2012) 181.

[157] Deosarkar S D, Russian J. Phy. Chem. A., 86 (2012) 1507.

[158] Chen A, Liu M, Zheng Y, Sun D, Wang B and Wang L, J. Chem. Eng. Data., 58

(2013) 2474.

80

[159] Liu C, Zhou L, Ma L and Lin R, J. Sol. Chem., 42 (2013) 1572.

[160] Mohammed Tagi Zafarani-Moattar and Tohidifar N, Fluid Phase Equilibria., 343

(2013) 43.

[161] Mehra R and Malav B B, Arabian J. Chem.,

http://dx.doi.org/10.10.1016/j.arabjc.2013.07.018.

[162] Redlich O and Kister A T, Ind. Eng. Chem., 40 (1948) 345.

[163] Nomoto O, J. Phys. Soc. Jpn., 4 [1940] 280, 13 (1958) 1528.

[164] Van Dael W and Vangeel E, Proc. Int. conf. on calorimetry and thermodynamics,

Warasa, (1955) 555.

[165] Junjie Z, J. China Univ. Sci. Techn., 14 (1984) 298.

[166] Shipra Baluja and Parsania P H, Asian J. Chem., 7 (1995) 417.

[167] Jacobson B, Theoretical study of ultrasonic velocity in binary liquid mixtures at 300C,

Acta Chem. Scand., A6 (1952) 1485-1498.

[168] Gokhale V D and Bhagavat N N, J. Pure Appl. Ultrason., 11 (1989) 21.

[169] Ali A, Nain A K, Kumar N and Ibrahmim M, J. Pure Appl. Ultrason., 24 (2002) 27.

[170] Kendall J and Monroe K P, J. Am. Chem. Soc. 39 (1917) 1787.

[171] Gurnberg L, Nissan A H, Nature., 164 (1949) 799.

[172] Tamura M and Kurata M, Bull.Chem. Soc. Jpn. 25 (1952) 32.

[173] Frenkel Ya I., Petroleum (London) 9 (1946) 27.

[174] Hind R K, Mc. Laughlin E and Ubbelohde A R, Trans. Faraday. Soc., 56 (1960) 328.

[175] Katti P K and Chaudhari M M,J. Chem. Eng. Data., 9 (1964) 442.

[176] Heric E L and Brewer J C, J. Chem. Eng. Data., 12 (1967) 574.