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ULTRASONIC STUDIES ON MOLECULAR INTERACTIONS IN

CERTAIN BINARY AND TERNARY SYSTEMS

THESIS

Submitted to the
UNIVERSITY OF MADRAS

in partial fulfillment of the requirement


for the award of the degree of
DOCTOR OF PHILOSOPHY
in
PHYSICS

by
P.A. ABDUL MAHABOOB, M.Sc., B.Ed.,

Under the Guidance of

Dr. T. IRUSAN, M.Sc., M.Phil., Ph.D., Dr. V. KANNAPPAN, M.Sc., Ph.D.,


Supervisor F.I.C.S., F.A.S.C.,
Reader in Physics (Retd.) Co-Supervisor
P.G. & Research Department of Physics Reader in Chemistry
Presidency College P.G. & Research Department of Chemistry
Chennai – 600 005 Presidency College, Chennai – 600 005

Post Graduate and Research Department of Physics,


Presidency College (Autonomous), Chennai – 600 005, INDIA

NOVEMBER 2006
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ACKNOWLEDGEMENT

‘Gratitude is a rare flower which only noble hearts pluck to offer it to God’.

With grateful hearts, I acknowledge with gratitude, the innumerable graces and

blessings I received from the Almighty and for His guidance throughout my life.

I consider myself very fortunate to have Dr. T. IRUSAN, Reader (Retd.),

Post Graduate & Research Department of Physics, Presidency College

(Autonomous), Chennai – 600 005, as my research guide. It is my great

pleasure and duty to express my sincere thanks for his guidance and advice for

the successful completion of this thesis.

I wish to express my heartful gratitude and respect to my co-guide

Dr. V. KANNAPPAN, M.Sc., Ph.D., FICS, AIC., Reader, Post Graduate &

Research Department of Chemistry, Presidency College (Autonomous),

Chennai – 600 005, for having suggested the present investigation which has

immense practical applications in various branches of science and for his

committed inspiring guidance and constant encouragement. His deep interest in

research, his humane touch and positive approach have made my period of

research an educative one.


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I wish to thank Dr. S. JELANI, Deputy Secretary, UGC, (SERO)

Hyderabad and Dr. P. RAJAGOPALAN, Former Dean, College Development

Council, University of Madras, Chennai for the award of teacher fellowship

under FIP for two years.

I express my gratitude to Dr. S. Ramanathan, Principal, Presidency

College (Autonomous), Chennai for providing the necessary facilities for

carrying out my research.

I acknowledge with gratitude the Management, the Principal,

Mr. A. Khader Basha of The New College, Chennai, for allowing me to carry

out the experimental work in the college.

I owe my special thanks to Dr. M.G. Mohamed Kamil, Head of the

Department of Physics, The New College, Chennai, for his constant support,

encouragement and allowing me to do my research in the department. I also

thank all the staff, teaching and non-teaching members, in the department for

their cooperation, help and encouragement.

My sincere thanks are due to Dr. R.K. Natarajan, Head of the

Department of Physics, Presidency College (Autonomous), Chennai, for his

support shown during my research work.


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My special thanks are due to Mr. S.J. Askar Ali, Senior Lecturer in

Chemistry, The New College (on FIP), for his brotherly and friendly support

which made my research easier.

I acknowledge with gratitude Dr. M.M. Abdul Kamal Nazer, Reader in

Chemistry, Dr. T.K. Shabeer, Reader in Chemistry and Mr. A. Khaja

Mohideen, Senior Lecturer in Chemistry, The New College, for their valuable

help and encouragement rendered to me in various ways, while doing my work.

I wish to thank Mr. S. Chidambara Vinayagam, Mrs. N. Indra Gandhi,

Mrs. B.S. Shanthi, and Mrs. K. Parameswari, Teacher Fellows in the

Department of Chemistry, Presidency College, for their support and

encouragement. My thanks are also due to Mr. Y. Christurajan and

Mr. P. Balu, Research Scholars in the same department for their help and

encouragement. My special thanks are to Mr. M. Vanjinathan, Research

scholar, Department of Polymer Science, University of Madras for his help and

cooperation. I also thank Mr. M. Arunkumar and Mrs. G.S. Gayathri, M.Phil.

students in Chemistry, Mr. B. Aijaz Mohamed and Mr. K.T. Shameer, P.G.

students in Chemistry, The New College, for their help.


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I express my gratitude to Dr. (Sr.) R. Jaya Santhi, Reader in Chemistry,

Auxilium College, Vellore, Dr. S. Mahendran, Reader in Chemistry, and

Dr. D. Roop Singh, Reader in Chemistry, Presidency College, for their

cooperation and help. My special thanks are due to Dr. S. Jayakumar, Reader

in Physics, Vivekananda College, Dr. Shanaz Ahmed, Head of the Department

of Physics, JBAS College for Women, Chennai and Mrs. P.E. Akilandeswari,

Senior Lecturer in Physics, JBAS College for Women, Chennai for their support

in carrying out my research.

My special thanks are due to Mr. S.L. Balaji, A. Thirumal Marugan,

Mr. P.M. Khaleelur Rahman, Mr. A. Rahmathullah, Mr. K. Basheer Ahmed,

Mr. S.M. Abdul Aziz and Mr. Md. Kaleemuddin Sayeed for their

encouragement and support.

I am grateful to Dr. A.K.W. Anwar Ali, former Head, Department of

Physics, The New College for his cooperation and support. I also thank

Dr. B. Kamalaharan, Dr. M. Shanmugam, Dr. P. Sivakumar,

Dr. U. Ponnambalam, former Heads, Department of Physics, Presidency

College, for their support and cooperation.

My sincere thanks are also due to Dr. G. Md. Farhathullah,

Dr. M. Jailani, former Principals of The New College and

Dr. R.S. Raghavan, former Principal of Pachaiyappa’s College, for their

encouragement to carryout my research.


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I also thank the teaching and non-teaching staff of other departments of

The New College and Presidency College for their support in various ways. My

thanks are also due to the store keepers of both the colleges for their

cooperation and timely help.

Thanks are also due to the Trustees of ILM Educational Trust, Chennai

for their cooperation and invaluable blessings.

My heartful thanks are due to my departed paternal uncle

Mr. P.A. Khaja Khaleel Rahman, for his blessings and constant

encouragement, without which this project would have been very difficult. I

record my sincere gratitude to my parents Mr. P.A. Akbar Ali &

Mrs. S.M.A. Mymoon Akbar, my wife Mrs. S.A. Shabnam Mahaboob and my

uncles (Late) Mr. P.M. Sheriff Ali, Mr. P.M. Syed Aminuddin, Mr. P.M.

Basheer Ahmed, Mr. P.M. Abdul Sathar, Mr. S.M.A. Shahul Hameed and

Mr. S.A. Abdul Azeez, and my aunts and all my relatives for their prayerful

support and help, which guided me in all situations.

P.A. ABDUL MAHABOOB


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Dedicated to:
All the Members,
Relatives and
Friends of

Penna Family
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CONTENTS

Chapter Title Page Number

1. Introduction 14

2. Experimental methods 57

3. Theory and calculations 69

4. Ultrasonic investigations of molecular interactions 83


in binary liquid mixtures

5. Determination of stability constants for the charge transfer 121


complexes of certain hydrocarbons and iodine in n-hexane
solution by ultrasonic method

6. Determination of stability constants for the charge transfer 159


complexes of certain hydrocarbons and iodine monochloride
in n-hexane solution by ultrasonic method

7. Ultrasonic studies on the charge transfer complexes of iodine 195


and certain phenols at 303 K

8. Determination of stability constants for charge transfer 238


complexes of iodine monochloride and certain phenols at 303 K

9. Determination of the formation constants for the charge 280


transfer complexes of certain ethers and iodine
monochloride in different solvents

10. Summary 321

Annexure 328
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LIST OF ABBREVIATIONS AND SYMBOLS USED IN THIS THESIS

C : Concentration

U : Ultrasonic velocity

ρ : Density

η : Viscosity

κ : Adiabatic compressibility

α/f2 : Absorption coefficient

χU : Molecular interaction parameter

τ : Relaxation time

Lf : Free length

Vf : Free volume

πi : Internal pressure

CE : Cohesive energy

Z : Acoustic impedance

Va : Available volume

LJP : Lenard Jones Potential

UE : Excess ultrasonic velocity

ηE : Excess viscosity

κE : Excess adiabatic compressibility

VfE : Excess free volume

LfE : Excess free length

ZE : Excess acoustic impedance


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Va E : Excess available volume

∆G : Gibb’s free energy of formation

∆G# : Gibb’s free energy of activation

CT : Charge transfer

K : Formation / Stability constant

α : Polarizability

µ : Dipole moment

ε : Dielectric strength

Fig. : Figure

BZ : Benzene

CTC : Carbon tetrachloride

BBZ : Bromobenzene

CBZ : Chlorobenzene

MCL : m-Cresol

OCL : o-Cresol

PCL : p-Cresol

PL : Phenol

PYR : Pyridine

IO : Iodine

IC : Iodine monochloride

MST : Mesitylene

PXL : p-Xylene

MXL : m-Xylene
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OXL : o-Xylene

TL : Toluene

ANT : Anthracene

BIP : Biphenyl

NAP : Naphthalene

CVL : Carvacrol

DPE : Diphenyl ether

CAN : 4-Chloroanisole

ANS : Anisole

DOX : 1,4-Dioxane
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Chapter 1
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CHAPTER - 1

INTRODUCTION

This thesis deals with the measurement of ultrasonic velocities,

densities and viscosities of binary and ternary mixtures to understand the

intra and intermolecular interactions between the molecules of components.

Excess thermodynamic parameters are calculated for certain binary systems.

In ternary systems, the stability constant values are calculated for the

donor-acceptor complexes using the nine aromatic hydrocarbons as donors

and iodine and iodine monochloride as acceptors in n-hexane solution at 303

K. The main aim of these investigations is to investigate the effect of structure

of donor and acceptor on the stability of this type of complexes. The stability

constant values are also calculated for the charge transfer complexes of four

ethers and iodine in four different solvents of different polarities. Similar

investigations are also made with iodine monochloride as acceptor with a view

to study the influence of solvent properties and acceptor properties on the

stability of this type of complexes.

The study of molecular interactions and the variations in these

interactions due to structural changes has been carried out by various

experimental techniques such as infrared1, nuclear magnetic resonance2,3 and

Raman4 spectra and dielectric property measurement5. The complete


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understanding of the nature of intermolecular and intramolecular interaction

may not be possible by any single method. A number of workers have

reported the study through ultrasonic method6-10.

The successful application of acoustical methods to physico-chemical

investigation of solutions has become possible after the development of

adequate theoretical approaches and methods for precise ultrasonic velocity

measurements. Lagemann and Dunbar11 pointed out the sound velocity

approach for the qualitative estimation of interaction in liquids. A parallel

measurement of sound velocity and density of solution allows one to obtain

information about their volume, elastic properties and changes in their

properties. Complex formation in liquid mixtures has been extensively studied

by ultrasonic methods by many workers. The formation of hydrogen bond in

solutions and its effect on physical properties of the mixtures have received

much attention.

1.1. ULTRASONICS

Ultrasonics is the science of acoustics and the technology of sound.

The frequency range of ultrasonic waves is greater than 20 kHz up to several

MHz, which is beyond the audible limit. The upper limit for gases is around 5

MHz and for liquids is 500 MHz. Low amplitude waves are more pronounced

at frequencies between 2 to 10 MHz. The waves whose frequencies are lower

than the audible limit are called infrasonics. But human ears do not respond
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to either of these frequencies. The ultrasonic technique is used for different

investigations due to the following advantages:

• At higher frequencies, the high absorption coefficient values are

easily measurable.

• Shorter wavelengths occur at higher frequencies, so that plain

wave conditions are more easily realized which is especially

important for the smaller specimens.

• Frequencies associated with relaxation phenomena often fall

within the ultrasonic range and therefore they can be easily

focused.

The study of acoustics had its beginning with the Greek philosopher

Pythagoras in 600 BC. He laid the foundation for the use of stringed

instruments, which are notable contributions to the science of acoustics. It is

believed that Galileo was the first to start the modern studies of acoustics. In

1638, he showed that pitch is associated with vibration, which was

considered to be the second milestone in the science of acoustics. He elevated

the study of vibration to scientific standards by successful correlation of pitch

with frequency of sound source. Investigations in high frequency waves did

not emerge until 19th century.


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The era of modern ultrasonics began only in the early twentieth century

with Langevin’s use of high-frequency acoustic waves and quartz resonators

for submarine detection in 1917. From then on, slow but steady progress was

made in the measurements of propagation constants of materials. Early

landmarks included Pierce’s quartz-driven ultrasonic interferometer12 in 1925

and the discovery in 1932 by Debye and Sears and also by Lucas and

Biquard of the ultrasonic diffraction grating. An important event during

1930s was the pioneering work of Sokolov in 1934 on ultrasonic flaw

detection.

Ever since, the field has grown enormously with wide applications in

science, medicine and other areas. Graff13 investigated physical, chemical and

biological effects of ultrasounds on macromolecules, microorganisms and

cells. Stokes14 made the first attempt in medical imaging using ultrasonics.

The explosive rate of development in high frequency digital and

computer techniques has opened new avenues for using ultrasonic

equipments for laboratory study and industrial purposes15-17. The

applications of ultrasonics in various fields have been illustrated in fig.1.1.


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1.2. PRODUCTION OF ULTRASONIC WAVES

The devices that generate and detect ultrasonic waves are called

transducers. Active transducers or transmitters are those that convert

electrical energy into ultrasonic energy and passive transducers or receivers

are those, which do the reverse18-21. Transducers use any one of the following

techniques: (a) capacitive, (b) magnetostrictive, (c) electrostatic, or

(d) piezoelectric devices22,23. The various transducers are listed below.

• Magnetostrictive transducer

• Electromagnetic transducer

• Pneumatic transducer

• Mechanical transducer and

• Piezoelectric transducer

1.2.1. Magnetostrictive Transducer

In 1847, Joule19 observed that a change in length occurs in a rod of a

ferromagnetic substance such as nickel, when a magnetic field is applied

along its length. This change in length is proportional to the strength of the

field and is irrespective of the direction in which the

field is applied. This effect is known as magnetostriction.


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1.2.2. Electromagnetic Transducer

This type of transducers uses attractive forces of electromagnets, which

are used to generate vibrations. They are used for obtaining high amplitude

vibrations at frequencies usually below the ultrasonic range.

1.2.3. Pneumatic Transducer

Pneumatic transducers such as whistles are useful at frequencies

extending to a lower ultrasonic range to produce small particle sprays of

liquids, which may be used in burners, coating materials and certain type of

bulk cleaners. They are also used to dry materials and to break up foams

obtained from various chemical processes.

1.2.4. Mechanical Transducer

The mechanical transducers are devices, which are actuated

mechanically. They are used to obtain high amplitude, often-high intensity,

vibrations at low sonic frequencies. A typical example is the sonic pile driver

in which counterbalanced eccentrics are used to generate vibrations in a

direction parallel to the axis of the pile.

1.2.5. Piezoelectric Transducer

This is a widely used method for the generation of ultrasonic waves. In

this method, a pair of opposite faces of a piezoelectric crystal is subjected to

pressure, which develops opposite electric charges in other pair of opposite


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faces. The sign of the charge changes when the faces are subjected to tension

instead of pressure. Curie brothers in 1880 found that certain crystals like

quartz, tourmaline and Rochelle’s salt will develop electric charge, when

mechanical pressure or tension is applied on the face of the crystal. Their

experiments showed that there is a certain relation between the mechanical

pressure applied and the nature of charge developed, and the sign of the

charge changed when the pressure was changed to tension. Quartz crystals

have been widely used for generating ultrasonic vibrations in solids and

liquids, since they possess high mechanical impedance.

1.3. DETECTION OF ULTRASONIC WAVES

Ultrasonic waves propagated through a medium can be detected in a

number of ways24. Some of the methods employed are given below.

1.3.1. Kundt’s tube method

Ultrasonic waves can be detected with the help of Kundt’s tube. At the

nodes, lycopodium powder is collected in the form of heaps. The average

distance between two adjacent heaps is equal to half the wavelength. This

method cannot be used if the wavelength of ultrasonic waves is very small. In

the case of a liquid medium, instead of lycopodium powder, powdered coke is

used to detect the position of nodes.


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1.3.2. Sensitive flame method

A narrow sensitive flame is moved along the medium. At the position of

the antinode, the flame is steady. At the position of the node, the flame

flickers because there is change in pressure. In this way, positions of nodes

and antinodes can be found in a medium. The average distance between two

adjacent nodes is equal to half the wavelength. If the value of the frequency of

the ultrasonic wave is known, the velocity of the ultrasonic wave through the

medium can be calculated.

1.3.3. Thermal detectors

This is the most commonly used method of detection of ultrasonic

waves. In this method, a fine platinum wire is used. This wire is moved

through the medium. At the position of nodes, due to alternate compressions

and rarefactions, adiabatic changes in temperature take place. The resistance

of the platinum wire changes with respect to time. This can be detected with

the help of Callendar and Griffith’s bridge arrangement. At the position of the

antinodes, the temperature remains constant and the resistance of the

platinum wire remains constant. This will be indicated by the undisturbed

balanced position of the bridge.

1.3.4. Quartz crystal receiver

Just as quartz or Rochelle’s salt crystals are used for the generation of

ultrasonic waves, they can also be used as detectors of ultrasonic waves.


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When ultrasonic waves are incident on quartz or a Rochelle’s salt crystal,

alternating electromotive force of the same frequency as the ultrasonic waves

is generated. This voltage is very small in magnitude and a radio frequency

amplifier can be employed to amplify the received signal, which may be

detected by a superheterodyne receiver and displayed on the screen of an

oscilloscope. This is the universal method for the detection of ultrasonics.

1.4. REVIEW OF THEORETICAL ULTRASONIC STUDIES

Ultrasonic velocity is an important and essential physical parameter

having structural dependence. Kneser25 proposed the first theory of

ultrasonic absorption in liquids. Depending on excess absorption

phenomenon, Pinkerton26 gave a useful classification in liquids. Several

theories were proposed to study the ultrasonic velocities in binary and

ternary mixtures. They are Flory’s theory27, Jacobson’s free length theory28,

Schaaffs’ collision factor theory23, Junjie’s empirical relation22, Nomoto’s

equation29, Narasimhan and Manikam’s combined equation30, Vandael ideal

mixing relation31, Patterson theory33 and Flory-Patterson theory27,32,33. These

have been recently used34 to obtain the ultrasonic velocity in quaternary

liquid mixtures. These theories have been tested35. Based on the additivity of

internal energies, the sound velocity in a liquid mixture was determined by

Kudriavstev36,37. But the above theories do not explain in detail, all the

phenomena of ultrasonic wave propagation through liquid media and also the

state of individual components in a mixture.


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Ultrasonic velocity measurements are used in understanding the

molecular interactions in pure liquids and binary / ternary mixtures since

the deviations from the linear dependence of velocity and compressibility on

the mole fractions provide an insight into the physico-chemical properties of

liquid mixtures such as molecular association and dissociation as well as the

strength of interaction between the components. The molecular interaction

studies have been made on liquid mixtures. The non-linear variation of

velocity and other thermodynamic acoustical parameters, adiabatic

compressibility (β), absorption coefficient (α/f2), relaxation time (τ),

intermolecular free length (Lf), free volume (Vf) and internal pressure (πi)

explained the deviation from ideality based on the strength of interaction38-45.

Moore and Fort46 measured the ultrasonic velocity, density and

adiabatic compressibility and other acoustical parameters for fourteen liquid

mixtures. In order to substantiate the molecular interaction between the

interacting molecules, the sign and magnitude of the excess parameters were

used. Excess parameters, regarded as more suitable parameters such as

excess ultrasonic velocity UE, excess viscosity ηE, excess compressibility βE,

excess impedance ZE, excess free length LfE and excess free volume VfE have

been calculated and employed. The observed results in the variation of the

excess thermodynamic parameters of the mixtures were used to explain the

structure-making and structure-breaking47 properties of the liquid mixtures.


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Most of the papers dealing with the excess thermodynamic functions are

based on works of Moore and Fort46.

The presence of dispersion forces makes a positive contribution to the

excess values47. Similarly, a dipole-dipole, dipole-induced dipole charge

transfer and hydrogen bonding interaction make a negative contribution by

the following excess parameters UE, ηE, βE, LfE and VfE make positive

contribution by ZE indicating the presence of a strong interaction between

components. On the other hand, the above excess parameters with negative

ZE are attributed to weak interaction. Further, the magnitudes of these excess

parameters were used to study the strength of interaction47.

1.5. INVESTIGATION OF MOLECULAR INTERACTIONS

The structure of a molecule determines its function. In turn, the

forces between the atoms determine the structure of the molecule. The

interactions between the atoms in a molecule are classified as strong or weak,

depending on whether or not the interaction can be disrupted by weak forces

like thermal motion. The primary structure of the macromolecules is made of

strong interactions such as the covalent bonds. Higher order structures like

secondary, ternary and quaternary structures are governed by weak forces

and can, therefore, be disrupted by relatively small increase in temperature or

a change of pH etc. Strong interactions are implicated mainly in the formation

of the chemical structure, and to some extent in the formation of the


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molecular structure. Weak interactions, on the other hand, not only help to

determine the three-dimensional structure but also are involved in the

interactions between different molecules. Any interaction within a molecule or

between molecules can be understood as a sum of the interactions between

pairs of atoms.

Hydrogen bonds and van der Waals’ interactions are classified as weak

forces. Van der Waals’ forces act between all atoms and ions in all solids but

the effect cannot be felt in the presence of strong interactions like covalent,

ionic or metallic bonds. Van der Waals’ forces are basically electrostatic in

nature. In that, they involve interaction between electric dipoles. There are

three components of the van der Waals’ forces namely, the permanent dipoles

in the molecule, the dipoles induced by an external electric field, and the one

induced by the London-dispersion effect. The relative contribution of each to

the total force varies and depends on the type of the molecule. The hydrogen

bonds are weaker than covalent bonds but are stronger than van der Waals’

bond48.

In general, when two liquids are mixed together the structure of each of

the two liquids is the same. The components change structurally in both

aqueous and non-aqueous solutions. The phenomenon of preferential

interaction between unlike molecules (solvation) or similar ones (association)

is observed, depending on the degree of affinity between the components.


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1.5.1. Pure liquids

According to Eyring et al49,50 molecules in a liquid state are so loosely

packed as to leave some free space in-between them. This free space and its

dependent properties are related to the molecular structure and may show

some interesting features about the interaction, which may occur when two

or more organic liquids are mixed. A sound wave is regarded as travelling

with gas kinetic velocity through space and infinite velocity through rest of

the path. A good deal of work has been reported50-55 on the sound velocity and

adiabatic compressibility in pure liquids and binary liquid-liquid mixtures.

Chennarayappa et al56 have analysed in terms of the structure-

making and structure-breaking effects of the components and the influence of

alcohol chain length. Isentropic compressibilities have extensive applications

in characterizing aspects of the physico-chemical behaviour of liquid

mixtures, such as molecular association, dissociation and complex formation.

Krishnamurthy and Subba Rao57, Prakash et al58, Dhanalakshmi et al59 and

many others have carried out ultrasonic studies of aqueous and non-aqueous

solutions.

1.5.2. Binary liquid system

Extensive investigations have been carried out on intermolecular

interactions in both binary and ternary liquid systems, using various


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methods like infrared, nuclear magnetic resonance, Raman method, magnetic

susceptibility and ultrasonic methods60-62. Measurement of ultrasonic velocity

and other acoustical properties can be related to physico-chemical behaviour

and molecular interactions in a number of binary systems63-65. Nomoto29

made successful attempts to evaluate sound velocity in binary liquid

mixtures. Prakash et al has carried out theoretical evaluation of ultrasonic

velocity and its correlation to molecular association in binary liquid

mixtures66. Seghal and Porter studied the non-linear parameter for alcohol-

water mixtures and based on this parameter, they have discussed the

intermolecular interactions67. Anwar Ali and co-workers carried out

investigations on the interactions of ion-solvent system by ultrasonic method.

For example, they measured ultrasonic velocity of sodium chloride in aqueous

dimethylformamide mixtures and explained the results on the basis of solute-

solvent, ion-solvent molecular interactions and the arrangement of ions in the

solution68. The ultrasonic studies of binary liquid mixtures of methanol,

acetone with cinnamaldehyde as a function of concentration were studied by

Tabhane et al69. Kannappan and Jaya Santhi70 carried out investigation on

the interactions of induced dipole-dipole interactions and intermolecular

interactions71 in binary systems.

1.5.3. Ternary liquid systems

Ultrasonic velocity in liquids has been an experimental tool for gaining

insight into the nature of the liquid state. Literature survey shows that
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various acoustical and thermodynamic parameters have been extensively

used to study the molecular interactions in ternary liquid mixture. The

formation of charge transfer complexes has been established by

spectrophotometric, X-ray diffraction72-76, NMR spectroscopy77, magnetic78,

dipole moment79, IR and Raman spectra studies. Even though spectroscopic

techniques are powerful tools for investigating the nature of molecular

complexes, these methods do not give satisfactory results on stability

constants especially in the case of weak interacting systems where ultrasonic

technique is found to be the most pioneering tool. Using this technique,

stability constant was calculated by many workers80,81. Kannappan and

Hemalatha82 studied the molecular interactions of certain aromatic

compounds with 1-chlorobenzotriazole in solution.

The isentropic compressibility and its deviations in different mixtures

have been compared with Redlich-Kister theoretical equation and the results

were found to be satisfactory83-89. Presence of electrolyte and non-electrolyte

produces different types of interactions between the molecules of solute and

the solvent. The effect of addition of an electrolyte on the formation of charge

transfer complexes of benzyl chloride and bromobenzene with o-cresol in an

inert non-polar solvent was studied using dielectric technique90-93. The

complex has been interpreted in terms of dipole moment, interaction

dielectric constant and interaction molar polarization94-96.


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1.5.4. Polymer systems

Polymer blends are physical mixtures of two structurally different

polymers that interact through weak secondary forces with no covalent

bonds. The choice of a suitable solvent for a given polymer plays an important

role in deciding the end use. This depends on the nature of interaction

between the polymer and the solvent97. Solvents can form secondary bonds

with the polymer chains, can penetrate, replace the interchain secondary

bonds and thereby pull apart and dissolve linear and branched polymers98. It

was stated by Napper99 that the high molecular weight polymer, in general, do

not participate from solution in moderately poor solvent, in the same manner

as that single electrolytes do. Recently, Kannappan and others have used

ultrasonic velocity measurements to determine glass transition temperatures

of polymers100.

1.5.5. Soaps and detergents

Ultrasonic measurements provide interesting information on the

specificity of the ion-solvent interaction related to the structure of solute and

on the reciprocal effects that arise in the solvents. However, ultrasonic

studies on soaps and detergents have not drawn adequate attention to give

more information on the soap-solvent interaction114. A number of workers101-

104 used ultrasonic measurements for the determination of ion-solvent

interaction and the results were found to be in good agreement with those

computed by other techniques like NMR2, IR105,106 and Raman4 studies.


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Mehrotra et al studied different types of soaps like yttrium

soap107, didymium soap108, lanthanum soap109, terbium soap110 and thorium

soap111 solutions. They evaluated the Critical Micelle Concentration (CMC) of

soaps and the types of interactions present in these soap solutions80,81,112.

1.6. CHARGE TRANSFER COMPLEXES

The term ‘charge transfer’ has a wide common usage to describe the

weak interactions between electron donors and electron acceptors. This

terminology is retained in the present work although it must be emphasized

that the term cannot be taken to imply that transfer of charge is the major

mode of binding in these cases. In this type of complexes, a pair of molecules

known as electron donor and electron acceptor is involved. These charge

transfer complexes have unique absorption bands in the ultraviolet-visible

region.

The compositions of donor-acceptor complexes could not be isolated at

ordinary temperatures in pure state since they are mostly unstable. But they

exist only in solutions in equilibrium with their components. The rates of

formation of complexes in solution are generally so rapid that kinetic studies

of the reactions cannot be made, at least by ordinary procedures. The heats of

interactions are generally small that the forces of coordination are much

feebler than those established in the formation of covalent bonds113. That is,
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the degree to which electron transfer from the donor component to the

acceptor component takes place is much less than that ordinarily occurs

when new compounds are formed114. Charge transfer forces are relatively of

long-range type compared to the chemical forces115. Thus, typical distances

between molecules in these complexes are 3.2 to 3.4 Ao, whereas chemical

bond lengths are less than 1.5 Ao.

1.6.1. Types of donors

The donor components are grouped into two categories. They are

π-donors and n-donors.

π−donors

These types of donors include alkenes, alkynes, aromatic hydrocarbons

and their substitution products. These adducts which they form are called

π-complexes116. Here the electron transfer takes place when a π-donor

coordinates with an acceptor. The term ‘outer complex’ has also been used114

in describing adducts of this kind to emphasize that the acceptor does not

make deep penetration into the π−orbital.

n-donors

These donors include a large group of substances in which there are

non-bonded electrons (lone pairs) available for coordination. Alcohols, organic

iodides and nitrogen bases are examples for these.


34

1.6.2. Types of acceptors

In the similar way, acceptors are also grouped into two categories. They

are inorganic acceptors, π-acids and other organic acceptors.

Inorganic acceptors

Complexes of a wide variety of inorganic acceptors have been

reported117. Some of this type of acceptors are chlorine, bromine, iodine,

iodine monochloride, oxygen, salts of copper (I), silver (I) & mercury (II),

aluminium bromide and hydrogen halides.

π−Acids and other organic acceptors

A variety of organic compounds which function as dienophiles in the

Diels-Alder reaction, such as ethylenes with highly electronegative

substituents, chloranil, tetracyanoethylene, polynitro aliphatic, polynitro

aromatic substances, tetranitromethane in very dilute solution, nitrobenzene,

2,4,7-trinitroflurenone and 1,3,5-tricyanobenzene are some of the acceptors.

1.6.3. Types of charge transfer complexes

Charge transfer complexes may be classified according to the types of

interacting orbitals118.
35

π-donors which supply electrons and π-acceptors in which it is a

π-orbital which accepts the bonding electron, and it is then delocalized over

the orbitals of adduct. The charge transfer complexes of this type are usually

strong complexes.

Complexes are formed between σ-donors and σ-acceptors in which the

bonding involves the σ−orbitals of the reactants. This type of complexes is

relatively weak.

n-donors, where the locus of the bonding electron tends to be localized

within the reactant molecule. Tertiary nitrogen is an example of this type. On

this basis, there are six types of charge transfer complexes. They are π−π, π−σ,

σ−π, n-π, n-σ and σ-σ type of complexes.

1.6.4. Methods to determine the stability of complexes

A number of experimental procedures have been adopted in

investigating equilibria established between donor-acceptor complexes and

the components in solution. They are discussed below.

Solubility method

Equilibrium constants for the formation of complexes of a number of

aromatic substances (donors) with silver ion (acceptor) in aqueous solution

have been evaluated from the results of solubility studies119. It is not possible
36

to vary the activity or concentration of the saturating substance when it is a

liquid or a solid. Thus, when this procedure is used, there is uncertainty as

regards the number of donor molecules which are incorporated in the

complex. The uncertainty does not apply when a gaseous solution is used

since the pressure of the gaseous component and hence, its concentration in

solution can be varied. The evaluation of equilibrium constants for the

interaction of silver ion with olefins by gas chromatography is an interesting

adaptation of the gas solubility for investigating complex stabilities120,121.

Distribution measurements

This method has proved convenient in making quantitative studies of

certain types of donor-acceptor complexes. It involves measurement of

distribution of one component, usually the donor, between a liquid phase in

which only that component is appreciably soluble and a liquid phase which

contains both the donor and the acceptor and all of the complex. This is the

procedure, which has been used by Winstein and Lucas122 in investigating

the coordination of silver ion with unsaturated compounds in aqueous

medium. This method permits variation in the concentrations of both the free

donor and free acceptor. Procedures of this kind can, therefore, be applied in

establishing the true formulae of the complexes.


37

Spectrophotometric methods

Benesi and Hildebrand123 have developed spectrophotometric method of

determination of the equilibrium constant K and the molar extinction

coefficient (absorptivity) εDA, (usually at the maximum for the charge transfer

band) of a donor-acceptor complex (DA) in solution. This along with

Mulliken’s114,124 formulation of these complexes as of the charge transfer type

has opened the floodgate to research in this area.

For a 1:1 complex formed according to the reaction,

D + A DA

the equilibrium constant, often referred to as the association constant

or stability constant is given as

K = CDA/CD CA -------------- (1.1)

Where, CDA, CD and CA are the equilibrium concentrations of DA (donor-

acceptor complex), D (donor) and A (acceptor) respectively.

The absorption spectrum of a charge transfer complex is markedly

different from the individual spectrum of the free donor and the acceptor.

This makes it possible to determine the equilibrium constant of complexes in

solution using spectroscopic methods. The optical densities (absorbances) d,

at the complex absorption maximum are measured for a series of solutions of

varying concentrations of donor, in which the donor is present in large excess

compared to the acceptor. Generally, the measurements are made against


38

blanks, which are identical with the reaction mixtures except that they

contain no acceptor. Under this condition, the equation (1.1) reduces to

K = CDA/(CAo - CDAo)CDo ---------------- (1.2)

where CAo and CDo indicate the sum of the concentrations of the free and

complexed A and D.

In the simple case, in which only the complex absorbs significantly at

the wavelength of the measurements, the optical densities (d) are related to

the concentration of complex and the unit cell path length by the equation

d = εDA CDA -------------- (1.3)

Stipulating the condition that CDo >> CAo and neither A nor D absorbs

in the region of the charge transfer band, the equation (1.3) changes to the

form

CAo/d = 1/KεDA CDo + εDA -------------- (1.4)

The equation (1.4) is generally called as Benesi-Hildebrand equation. In the

charge transfer spectra of donor-acceptor complexes, Mulliken noted that

increase in stability constant value which normally results when donor

ionization potentials decrease should be accompanied by an increase in the

dipole moment and in the oscillator strength of the charge transfer transition.

A spectrophotometric study of the donor-acceptor system according to the

method of Benesi and Hildebrand leads to the conclusion that a complex with

K = 0 and εDA = ∞ is formed. Three different cases in which charge transfer

absorption results (a) solely from photo-excitation of complexes, (b) partly


39

from photo-excitation of complexes and partly from contact charge transfer

and (c) entirely from contact charge transfer. Regardless of the relative

contribution of complex absorption and contact charge transfer absorption to

the measured optical densities, the ratios of the intercepts and slopes of these

plots should provide stability constant values which are the sums of the

equilibrium constants for all complexes in solution.

Ketelaar125 has modified the Benesi-Hildebrand equation wherein there

is no precondition regarding the absorbances of the acceptor and donor at the

wavelength of the measurement.

CAo/(d-dA) = 1/KεDA CDo + 1/(εDA-εA) -------------- (1.5)

The Benesi-Hildebrand method requires an extrapolation to high

concentration region. As an alternative, Scott126 has suggested a

rearrangement of the expression which requires an extrapolation to the low

concentration region.

Foster-Hammick and Wardley127 have suggested the following equation

for a 1:1 complex

d/CDo = - Kd + KCAo εDA ------------- (1.6)

According to this equation, a plot of (d/CDo)n against ‘d’ should be linear if the

complex is of stoichiometry n:1 which results from the equilibrium

nD + A ADn
---------- (1.7)
40

A special feature of this method is to ensure the absence of higher order

complexes under the concentration conditions usually applied for 1:1

complexes. The Rose-Drago equation128

K-1 = d/εDA - CAo – CDo + CAo CDo εDA/d ---------- (1.8)

can be applied to any donor-acceptor systems that absorb in the visible or

ultraviolet region provided a 1:1 complex is formed and the donor does not

absorb in the relevant region of the study. Thus, this method can be used as

a general method to determine the equilibrium constant. Using the

experimental observations and choosing εDA randomly, K-1 is determined for

each value of εDA. The point of intersection of the curves drawn from K-1 and

εDA gives K-1. But the selection of εDA values at random, and that too for each

set of experimental data, renders this graphical method laborious and

sometimes more difficult to apply. In many cases, R-D plots show a wide

scatter in the values of K and εDA evaluated.

Person129 is of the opinion that the equimolar method of determining

the equilibrium constant should preferably be used since the errors involved

in the evaluation of K and εDA by this method are minimal. This condition

further favours the formation of 1:1 complexes.

Other methods

Equilibrium constants for the interaction can be calculated on the basis

of the changes in rate constants for the slow reactions113, which take place
41

when the reactant concentrations are varied. Maxima or minima are observed

in plots of physical properties vs compositions of donor and acceptor

mixtures. Thus, freezing point-composition diagrams are commonly used as

bases for establishing the formulae of the complexes113 from the locations of

these maxima and minima. The physical property such as surface tension130

is determined as a function of component composition. A procedure for the

evaluation of enthalpies of interaction, which is based on the results of

cryoscopic measurements131 has also been suggested. If the donor, the

acceptor, or the complex is an ion, the complex formation constant may be

evaluated by the use of appropriate electrochemical cells132,133. The

conductometric method has also been used in determining equilibrium

constants for formation of σ complexes, ArH2+F- and in solutions of

polymethylbenzenes in hydrogen fluoride134.

1.6.5. Factors affecting equilibrium constant

Solvent effect

A polar medium facilitates formation of charge transfer complexes.

However, a strong charge transfer complex in a solvent of high dielectric

strength is likely to dissociate and become ionized118. But, majority of organic

molecular complexes are formed from neutral donors and acceptors without

appreciable changes in polarization of the components. When such complexes

are produced in solution, the interacting substances must be subjected to

some desolvation. Overall, the complex is less solvated than its free
42

components. When a saturated hydrocarbon solvent is replaced by a

substance which itself can serve as a donor or an acceptor, the complex

generally becomes more dissociated. Studies show that iodine-naphthalene

complex decreases in stability as the solvent varies in the order n-heptane >

cyclohexane > carbon tetrachloride > n-hexane > chloroform135.

Temperature effect

The association constant of the complex decreases with increase in

temperature as the complexation equilibrium is accompanied by evolution of

heat. The effect is due to the thermal motion disorienting the partners of the

complex118.

Acceptor effect

It is difficult to make an extensive comparison of acceptor strengths

because of wide variations in solvents and temperatures which have been

used for complex formation. Generally, the acceptor strengths of organic

substances are enhanced by substituents, which are electron-withdrawing

and diminished by substituents which are electron-releasing in character.

Donor effect

Comparison of donor strengths is very complicated because of its wide

variations with respect to acceptors and solvents. The donor strength of

organic compounds generally decreases in the following order:

alkenes < mono substituted ring compounds < multi ring donors
43

1.6.6. Applications of charge transfer complexes

Purification and separation of organic compounds

A number of methods of purification of organic substances have been

devised which are based on the differences in the capacities of the

components of a mixture to interact with a particular donor and acceptor.

Unsaturated substances are sometimes separated from other materials

through complex formation with silver nitrate136.

Optical resolution

A variety of racemates have been resolved through the formation of

complexes with optically active complexing agents. With 1-phenyl-2-

aminopropane as the active amine in the complexing agent, a partial

resolution of cis-trans-1, 5-cyclooctadiene has been accomplished137. The

latter has been completely resolved using the platinum complex prepared

from active α-methylbenzylamine138.

Analytical procedures

Certain useful procedures for identifying an organic compound have

been described which are based on the observation of some characteristic

physical property (melting point, colour, etc.) of a molecular complex derived

from the unknown. The Kofler139 microscopic technique is well suited for the

identification of compounds which are available in very limited quantity.

Other analytical procedures are based on spectrophotometric studies of

complexes.
44

The Z value as a measure of solvent polarity

Charge transfer transition energy of the complex in a particular solvent,

designated as Z, be adopted as an empirical measure of solvent polarity140-142.

The Z value increases as the capacity of the medium to provide for ionization

increases.

Applications in biological systems

As noted by Kosower143 certain of many intermolecular interactions

which occur in biological systems may be of the type which lead to the

formation of complexes which can undergo charge transfer transition. Donor-

acceptor complexes are considered to have important functions in promoting

energy transformations in processes such as photosynthesis144,145 and

muscle-contraction146 as presented by Kearns and Calvin147. A three-

component complex of carotene (donor-carotene-acceptor) has also been

discussed as a possible medium for donor-acceptor exchanges in

photosynthesis148,149.

The relationship of complexes to reaction mechanism

There are some reactions in solutions in which catalytic action takes

place through complex formation or in which two or more of the reactants

undergo donor-acceptor interaction to form complexes which may or may not

be true reaction intermediates. Many of the reported effects of changes in


45

medium on reactivity can be ascribed to difference in the capacities of the

various solvents to form complexes with one or more reactants somewhere

along the reaction coordinates150.

Nucleophilic substitution reactions

An interesting case of catalysis through complex formation in a

nucleophilic substitution reaction has been described by Colter and Wang151.

The rate of acetolysis of 2,4,7-trinitro-9-fluorenyl-p-toluenesulfonate is

enhanced by hexamethylbenzene, phenanthrene and anthracene.

Presumably, these donors interact more strongly with the electron deficient

activated complex of the trinitrofluorene derivative than with acceptor in the

ground state. Hexamethylbenzene, which is a poor donor for steric reasons,

does not increase the acetolysis rate.

Electrophilic aromatic substitutions and related reactions

Aryl ethers undergo electrophilic substitution reactions with the

halogens and the mechanism involves the formation of transient charge

transfer complexes between the aromatic molecules and halogens152-156.

Complexes are generally considered to play an important part in Friedel-

Crafts reactions. H.C. Brown et al157 discussed the role of reaction

intermediates of adducts of the organic halide and the catalyst and also of the

aromatic reactant and the attacking electrophile. In some instances, the

complex itself serves as the electrophilic reagent. This seems to be the case
46

for the alkylation of aromatic substances with 3,4-dichlorobenzyl chloride in

nitrobenzene with aluminium chloride as the catalyst158.

Reactions with radical intermediates

Aromatic π-complexes in which the acceptors are themselves radicals

have been proposed as intermediates in free radical reactions. The reaction of

a phenyl radical with toluene in solution at room temperature to form mixture

of methyldiphenyls proceeds by way of a π-complex of phenyl radical and

toluene159.

The Diels-Alder reaction

The total (free and complexed) reactant concentrations for the reaction

of a diene such as 9,10-dimethylanthracene with maleic anhydride drops as

the dienophile concentration of the medium is increased. This can be

explained on the assumption that either a complex which is in equilibrium

with the reactants is a direct precursor of the product or alternately that

formation of the complex serves only to reduce the concentrations of the free

components which are the actual participants in the slow step160.


47

Polymerization processes

Under certain conditions, silver salts function as catalysts for polymerization

of olefins and it has been suggested that complexes play a vital role as

reaction intermediates161.

Other types of reactions

A solution of stannous chloride and chloroplatinic acid in methanol

constitutes a homogenous catalytic medium for the hydrogenation of ethylene

and acetylene162. Stannous chloride also induces the formation of Zeise’s salt

from K2PtCl4 and ethylene in 1.5 M hydrochloric acid. It is presumed that the

catalytic activity of the tin-platinum salt mixture is related to the formation of

a platinum-olefin complex.
48

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117. Andrews, L.J. and Keefer, R.M., Advances in Inorganic Chemistry and
Radiochemistry, Vol. 3, Academic Press, Inc., New York, 1961, 91.
54

118. Cissy Johnson, Hendrik Keyzer, Joseph Molnar, Gutmann Gutmann and Felix
Gutmann, Charge Transfer Complexes in Biological Systems, Marcel Dekker,
1997.

119. Andrews, L.J. and Keefer, R.M., J. Am. Chem. Soc., 71, 1949, 3644;
72, 1950, 3113, 5034.

120. Muhs, M.A. and Weiss, F.T., J. Am. Chem. Soc., 84, 1962, 4697.

121. Gil-Av, E. and Herling, J., J. Phys. Chem., 66, 1962, 1208.

122. Winstein, S. and Lucas, H. J., J. Am. Chem. Soc., 60, 1938, 836.

123. Benesi, H.A. and Hildebrand, J.H., J. Am. Chem. Soc., 71, 1949, 2703.

124. Mulliken, R.S., J. Am. Chem. Soc., 74, 1952, 811.

125. Ketelaar, J.A.A., Van de Stolpe, C., Goudsmit, A. and Dzcubas, W., Recl. Trav.
Chim. Pays-Bas Belg., 71, 1952,1104.

126. Scott, R.L., Recl. Trav. Chim. Pays-Bas Belg. 75, 1956, 787.

127. Foster, R., Hammick, Le. and Wardley, A.A., J. Chem. Soc., 1953, 3817.

128. Rose, N.J. and Drago, R.S., J. Am. Chem. Soc., 81, 1959, 6138.

129. Person, W.B., J. Am. Chem. Soc., 87, 1965, 167.

130. Cagnoli, N., Ann. Chim. (Rome), 48, 1958, 839, 1122.

131. De Maine, P.A.D., Can. J. Chem., 38, 1960, 1635.

132. Rossotti, F.J.C. and Rossotti, H., The Determination of stability constants, Mc
Graw-Hill, New York, 1961.

133. Cabani,S. and Scrocco, E., J. Inorg. and Nuclear Chem., 8, 1958, 332.

134. Kilpatrik, M. and Luborsky, F.E., J. Am. Chem. Soc., 75, 1953, 577.

135. De Maine, P.A.D. and Peone, J. Jr., J. Mol. Spectr., 4, 1960, 262.

136. Nichols, P.L., J. Am. Chem. Soc., 74, 1952,1091.

137. Cope, A.C., Ganellin, C.R. and Johnson, H.W., and Jr., J. Am. Chem. Soc., 84,
1962, 3191.
55

138. Cope, A.C., Ganellin, C.R. and Johnson, H.W., Jr., Van Auken, T.V. and
Winkler, H.J.S., ibid., 85,1963, 3276.

139. Kofler, L. and Kofler, A., Mikromethoden zur Kennzeichnung Organische.


Stoffe und Stoffegemische, Innsbruk, Univ. Wagner, 1948.

140. Kosower, E.M. and Klinedinst, E.P., J. Am. Chem. Soc., 78, 1956, 3493.

141. Kosower, E.M. ibid., 78, 1956, 5700.

142. Kosower, E.M. ibid., 80, 1958, 3253.

143. Kosower, E.M., J. Am. Chem. Soc., 78, 1956, 3497.

144. Calvin, M., Rev. Modern Physics, 31, 1949, 147.

145. Arnold, W. and Clayton, R.K., Proc. Nat’l. Acad.Sci. U.S., 46, 1960, 769.

146. Szent, A., Gyorgyi, Radiation Res. Suppl., 2, 1960, 4.

147. Kearns, D.R. and Calvin, M., J. Am. Chem. Soc., 83,1961, 2110.

148. Platt. J.R., Science, 129, 1959, 372.

149. Rosenberg, B., J. Chem. Phys., 34, 1961, 812.

150. Leffler, J.E. and Grunwald, E., Rates and Equilibria of Organic Reactions, John
Wiley & Sons, Inc., Newyork, 1963, 50.

151. Cotler, A.K. and Wang, S.S., J. Am. Chem. Soc., 85, 1963, 114.

152. De la mare, P.B.D. and Ridd, J.H., ‘Aromatic Substitution: Nitration and
Halogenation’, Baterworth’s Scientific Publications, London, 1959.

153. Berliner, E., Prog. Phys. Org. Chem., 2, 1964, 253.

154. Stock, L.M. and Brown, H.C., Advan. Phys. Org. Chem., 1, 1963, 35.

155. Norman, R.O.C and Taylor, R., ‘Electrophilic substitutions in Benzenoid


Compounds,’ American Elsevier Publishing Co., New York, 1965.

156. Marino, G., Tetrahedron, 21, 1965, 843.

157. Brown, H.C., Pearsall. H.W., Eddy, L.P., Wallace, W.J., Grayson, M. and
Nelson, K.L., Ind. Eng. Chem., 45, 1953,1462.
56

158. Brown, H.C. and Grayson, M., J. Am. Chem. Soc., 75, 1953, 6285.

159. Jacquiss, M.T. and Szwarc, M., Nature, 170, 1952, 312.

160. Andrews, L.J. and Keefer, R.M., ibid., 77, 1955, 6284.

161. Salomon, G., Rec. Trav. Chim., 68,1949, 903.

162. Cramer, R.D., Jenner, E.L., Lindesy, R.V., Jr. and Stolberg, U.G., J. Am. Chem.
Soc., 85, 1963, 1691.
57

Chapter 2
58

CHAPTER - 2

EXPERIMENTAL METHODS

In this chapter, the materials employed in the present investigation,

their purification techniques and details of the instruments used are outlined

briefly.

2.1. EXPERIMENTAL TECHNIQUES & INSTRUMENTATION

2.1.1. Ultrasonic Velocity Measurement for Liquids

For the measurement of ultrasonic velocity, the following techniques

are usually employed. They are: (a) Pulse method, (b) Interferometer method

and (c) Continuous wave method.

Ultrasonic Interferometer

The ultrasonic interferometer is a simple and direct device to determine

the ultrasonic velocity in pure liquids and liquid mixtures1 with high degree of

accuracy. It is known for its easy operation and reliability. Measurement of

ultrasonic velocity is based on accurate determination of the wavelength of

sound waves in the medium.

Working Principle

Ultrasonic waves of known frequency (ν) are produced by a quartz

crystal fixed at the bottom of a diode walled cell. The experimental liquid is
59

taken in this cell and ultrasonic waves are passed into the medium. A

movable metallic plate kept parallel to the quartz crystal reflects the waves. A

fine micrometer screw is provided to raise or lower the reflector plate. When

the distance between the metal reflector and the quartz crystal equals the

whole multiples of wavelength, stationary waves are formed in the medium.

The acoustic resonance gives rise to electric reaction on the generator driving

the quartz crystal and maximum anode current flows through the generator.

When the distance is increased or decreased exactly by one half of the

wavelength (λ/2) or integral multiple of it, anode current becomes maximum

again. Using the micrometer screw attached to the reflector, the distance

moved can be measured to an accuracy of 0.001 mm (Fig. 2.1). From the

measured value of wavelength (λ), the ultrasonic velocity (U) can be calculated

using the relation,

U = νλ ms-1 -------------- (2.1)

where ‘ν’ is the frequency of the generator which is used to excite the crystal

whose value is 2 x 106 hertz.

Description

The ultrasonic interferometer consists of two important parts.

They are:

1. The high frequency generator and

2. The measuring cell


60
61

The high frequency generator is designed to excite the quartz crystal

fixed at the bottom of the measuring cell, at its resonant frequency to

generate ultrasonic waves in the experimental solution filled in the measuring

cell. A fine micrometer screw of least count 0.001 mm is fixed at the top to

observe the changes in the current flow. Two knobs, namely, adjust and gain,

are provided on the panel of the high frequency generator to pass the current

through micro-ammeter and the changes in the anode current can be

measured from the micro-ammeter.

The measuring cell is a specially designed double walled cylinder for

maintaining the temperature of the experimental liquids constant throughout

the experiment. By raising or lowering the reflector plate using micrometer,

the effective length of the liquid column is varied. The micro-ammeter shows

maxima and minima for increase or decrease of distance between the plate

and the crystal. The distance of separation between a successive maxima and

minima in the anode current is equal to half the wavelength of ultrasonic

wave in pure liquid or liquid mixture. By noting the initial and final position

of the micrometer for one complete oscillation (maxima and minima), one can

determine the distance (d) moved by the parallel reflector. The number of

successive maxima and minima (n) are counted as a distance. The distance

moved by the micrometer screw gives the wavelength as

λ = 2d/n ------------------- (2.2)


62

Using the above relation, the ultrasonic velocity of the liquids and liquid

mixtures can be calculated using the relation 2.1. The accuracy in the

measurement of ultrasonic velocity is ± 0.1 ms-1. The instrument model F-81

was supplied by M/s Mittal Enterprises, New Delhi.

There are facilities to measure the ultrasonic velocities at different

temperatures of the liquid. For this, the measuring cell is specially designed

with a double walled cylinder provided with an inlet and outlet for the

circulation of water, to maintain the temperature of the experimental liquids

constant throughout the experiment. By using Juloba thermostat (accuracy

± 0.1 K), water is circulated at any desired constant temperature through the

outer wall of the cell.

2.1.2. Density Measurements

The density of the pure liquids, liquid mixtures, detergents, dyes and

enzyme solutions can be determined by relative measurement method.

Specific gravity bottle was standardized using double distilled water. The

temperature is maintained constant by immersing the bottle in Juloba

thermostat for 15 minutes. The density of liquid and liquid mixtures can be

calculated using the formula

ρ = (Mρw/Mw ) ----------------- (2.3)

Where M is the mass of the liquid or liquid mixtures

(accuracy ± 0.001 g), Mw is the mass of water and ρw is the density of water at
63

the experimental temperature. Density of water at different temperatures is

taken from the literature2.

2.1.3. Viscosity Measurements

The capillarity viscometric method, which is based on Poiseuille’s law,

is commonly employed for the measurement of viscosity. In the present work,

Ostwald viscometer is employed. The viscometer is filled with the

experimental solution. The flow time at different temperatures is measured by

placing the viscometer in a thermo-stated water bath with an accuracy of

± 0.1 K with temperature set at required value. An electronic stop watch was

employed to measure the time of flow.

The absolute value of coefficient of viscosity of the solution (η) can be

calculated using the formula

η = (ρsts/ρwtw ) ηw ---------------- (2.4)

where η = ρs – density of the solution; ts – flow rate of the solution;

ρw – density of water; tw – flow rate of water and ηw – coefficient of viscosity of

water. The accuracy of viscosity in this method is

± 0.001 Nsm-2.

The following precautions were taken for getting accurate and reproducible

results.

• Care was taken while mounting the viscometer to see that the capillary

is always held in vertical position.


64

• All measurements are made at a constant temperature with an

accuracy of ± 0.1 K, since viscosity is highly temperature sensitive. The

viscosity of water at a given temperature has been taken from

literature2.

• The solutions are equilibrated with thermostat for 15 minutes, so that

the experimental solution attains the same temperature of the

thermostat.

2.1.4. Thermostat

The temperature of the solution under study is maintained constant

using the electronic Juloba thermostat. This thermostat is equipped with a

heater, a stirrer, a thermometer and a regulator. The temperature was

maintained at 303 K for all the systems with an accuracy of ± 0.1 K.

2.2. MATERIALS

2.2.1. Solids

Iodine (Merck GR grade) was purified by sublimation. The hydrocarbons

naphthalene, biphenyl and anthracene were AnalaR grade samples and were

used as such.
65

2.2.2. Water

Water used in the present study is triple distilled water of high purity.

It is obtained by redistilling the double distilled water over alkaline potassium

permanganate in an all glass quick-fit distillation set up.

2.2.3. Solvents and Liquids

The liquids used in the present investigation along with their boiling

points are given in Table 2.1. All the liquids mentioned here are AnalaR grade

samples and they are purified by usual

methods3,4 before use. The boiling points of these liquids agreed well with the

literature values indicating that the liquids used in the present studies are of

high purity.

Solutions of iodine and iodine monochloride in different solvents are

prepared as follows. A stock solution of 0.1 M was prepared by dissolving

accurately weighed solid donor in their respective solvents. This stock

solution was diluted to get the required concentration. Equimolar

concentrations of donor and acceptor were mixed to obtain mixtures of

desired concentration.
66

Table 2.1. Physical constants of certain compounds

Boiling
S. No. Compound
Point (oC)

1 Water 100

2 Ethanol 78.5

3 Bromobenzene 156.2

4 Chlorobenzene 132

5 Iodine monochloride 97

6 o-Cresol 464

7 p-Cresol 474.9

8 m-Cresol 202.5

9 Phenol 180

10 Carvacrol 237

11 Dichloromethane 40

12 Chloroform 62

13 Carbon tetrachloride 76.5

14 n-Hexane 68.7

15 Mesitylene 164.7

16 p-Xylene 137.5

17 m-Xylene 139.3

18 o-Xylene 138.5
67

19 Benzene 80.1

20 Toluene 110.6

21 Diphenyl ether 259

22 4-Chloroanisole 198

23 Anisole 154

24 1,4-Dioxane 101
68

REFERENCES

1. Gooberman, G.L., Ultrasonics Theory and Applications, The English


Univ. Press, London, 1968.

2. Lide, D.R., CRC Handbook of Chemistry and Physics, 81st Edn., CRC
Press, Inc., 2001.

3. Vogel, A.L., Textbook of Practical Organic Chemistry, 5th Edn., John


Wiley, New York, 1989.

4. Riddick, J.A., Bunger, W.B. and Sakano, T.K., Techniques in Chemistry,


Vol. II, Organic Solvents, 4th Edn., John Wiley, New York, 1990..
69

Chapter 3
70

CHAPTER - 3

THEORY AND CALCULATIONS

This chapter contains the formulae employed in the calculation of

various acoustical parameters. The theoretical background in computing

acoustical, thermodynamic, molecular and surface properties is given here.

3.1. ULTRASONIC VELOCITY (U)

Numerous methods have been reported in the literature for computing

ultrasonic velocity1-3. The ultrasonic velocity determined by interferometer

method is considered as more reliable and precise. In this instrument, we can

determine the wavelength (λ) of the ultrasonic wave in liquid and liquid

mixtures. The expression used to determine the ultrasonic velocity is

U = νλ ms-1 --------------- (3.1)

Where, ‘ν’ is the frequency of the generator which is used to excite the crystal.

In the present investigation, a constant frequency (2 MHz) interferometer was

employed and hence ‘ν’ value is 2 x 106 hertz.

κ)
3.2. ADIABATIC COMPRESSIBILITY (κ

Adiabatic compressibility is a measure of intermolecular association or

dissociation or repulsion. Singh and Kalsh4 showed that the adiabatic

compressibility should be independent of temperature and pressure for

unassociated and weakly associated molecules. It also determines the


71

orientation of the solvent molecules around the liquid molecules. The

structural arrangement of the molecule affects the adiabatic compressibility.

It can be calculated using the equation5

κ = 1/U2ρ kg-1 ms-2 ------------- (3.2)

Where, U is the ultrasonic velocity and ρ is the density of the solution.

α/f2)
3.3. ABSORPTION COEFFICIENT (α

The absorption coefficient also called attenuation coefficient, is

characteristic of the medium and it also depends on the external conditions

like temperature, pressure and the frequency of measurement. It is a

measure of spatial rate of decrease in the intensity level on ultrasonic waves.

Treating the propagation of sound as an adiabatic phenomenon and following

Stoke’s theory, absorption may be taken as being proportional to the viscosity

of the medium and the square of the frequency. It can be calculated from the

viscosity (η) using the relation6

8Π 2η
(α/f2) = Nps2m-1 --------------- (3.3)
3ρU 3
72

χ U)
3.4. MOLECULAR INTERACTION PARAMETER (χ

The molecular interaction parameter can be computed using the

following formula7:

U exp
χU = −1 ------------------ (3.4)
U ideal

Where, Uexp is the observed ultrasonic velocity of the experimental solution

and Uideal is the ultrasonic velocity of the ideal mixture of the components in

the solution under study.

The sign of the molecular interaction parameter predicts the strength of

the interaction between the molecules in the solution. If χU value is negative,

then the interaction will be stronger between the molecules and the

interaction will be weak if the value of χU is positive. Thus, from the value of

this parameter, we can assess intermolecular attraction.

3.5. RELAXATION TIME (ττ)

Relaxation time and absorption coefficient are directly correlated. The

absorption of a sound wave is the result of the time lag between the passing

of the ultrasonic wave and the return of the molecules to their equilibrium

position. It is calculated using the relation8


τ= s ---------------------------------------- (3.5)
3ρU 2
73

3.6. FREE LENGTH (Lf)

The free length is the distance between the surfaces of the neighbouring

molecules. Generally, when the ultrasonic velocity increases, the value of the

free length decreases. The decrease in intermolecular free length indicates the

interaction between the solute and solvent molecules due to which the

structural arrangement in the neighbourhood of constituent ions or

molecules gets affected considerably. The intermolecular free length has been

calculated using the following formula given by Jacobson9,10

K
Lf = A° --------------------- (3.6)

Where, K is Jacobson’s constant. This constant is a temperature dependent

parameter whose value at any temperature (T) is given by (93.875 + 0.345T) x

10-8.

3.7. FREE VOLUME (Vf)

Free volume is defined as the average volume in which the centre of the

molecules can move inside the hypothetical cell due to the repulsion of

surrounding molecules. Free volume can be calculated by different methods.

Chellaiah et al11, Erying et al12, Kinacid et al13,

Mc Leod14 and Hildebrand15 have made a few approaches in calculating the

free volume. Suryanarayana and Kuppusamy16 on the basis of dimensional

analysis, obtained an expression for free volume in terms of experimentally

measurable parameters like ultrasonic velocity and viscosity and is given by


74

Vf = [Meff U/Kη]3/2 m3 ---------------- (3.7)

Where, Meff is the effective molecular weight, which is expressed as

Meff = (X1M1 + X2M2 + X3M3). Where, X and M are the mole fraction and

molecular weight of the individual component in the mixture respectively. K is

the temperature independent constant and its value is 4.28 x 109.

πi)
3.8. INTERNAL PRESSURE (π

Internal pressure is a fundamental property of a liquid, which provides

an excellent basis for examining the solution phenomenon and studying

various properties of the liquid state. It is a measure of the change in the

internal energy of liquid or liquid mixtures, as it undergoes a very small

isothermal change. It is a measure of cohesive or binding forces between the

solute and solvent molecules.

The internal pressure16 of the liquid mixture is obtained from the

experimental values of ultrasonic velocity, density and viscosity using

πi = bRT (Kη/U)1/2 (ρ2/3/Meff)7/6 atm -------------- (3.8)


75

3.9. COHESIVE ENERGY (CE)

The concept of molar cohesive energy has been used by several

researchers17-20 for comparing the interaction in the liquid mixtures. It is

usually given as a product of internal pressure (πi) and molar volume (Vm)

CE = πi x Vm kJmol-1 ---------------- (3.9)

A molecule containing strong polar groups exerts corresponding strong

attractive forces on its neighbours. If the intermolecular forces are small, the

cohesive energy is low and the molecules have relatively flexible chains.

3.10. ACOUSTIC IMPEDANCE (Z)

Sound travels through materials under the influence of sound

pressure. Since, molecules or atoms of a liquid are bound elastically to one

another, the excess pressure results in a wave propagating through the

liquid21. The acoustic impedance is given by the product of ultrasonic velocity

and density as shown below:

Z = U x ρ kg m-2s-1 ----------------- (3.10)

Acoustic impedance is important in the determination of acoustic

transmission and reflection at the boundary of two materials having different

acoustic impedance. It is also useful in the designing of ultrasonic

transducers and for assessing absorption of sound in a medium.


76

3.11. AVAILABLE VOLUME (Va)

The available volume is a direct measure of compactness in the liquid

and the strength of attraction between the molecules of a liquid or a liquid

mixture. It can be calculated from Schaaf’s relation

Va = Vm (1 – U/U ∞ ) m3 --------------- (3.11)

Where, Vm is the molar volume which is equal to (Meff/ρ) and

U ∞ = 1600 ms-1

3.12. LENARD JONES POTENTIAL (LJP)

The Lenard Jones Potential is given by22

LJP ≈ 6Vm/Va -------------- (3.12)

Where, Vm represents the molar volume and Va represents the available

volume.

3.13. FREE ENERGY OF FORMATION (∆G)

The free energy of formation is calculated using the relation

∆G = - RT ln K kJmol-1 ------------- (3.13)

Where, R is the gas constant, T is the temperature in kelvin and K is the

formation constant.
77

3.14. FREE ENERGY OF ACTIVATION (∆G#)

The free energy of activation is calculated by

∆G# = - KB T ln (h/τ KB T) kJmol-1 ------------- (3.14)

Where, KB is Boltzmann constant (1.3806 x 10-23 JK-1), T is the temperature,

h is Planck constant (6.626 x 10-34 Js) and τ is the relaxation time.

3.15. STABILITY CONSTANT (K)

Marwein and Bhatt23 have proposed an equation to calculate the

stability constants of donor-acceptor complexes in binary liquids, which

generally gives concentration dependent formation constant values. Recently,

we have proposed an equation to calculate the formation constant values of

the charge transfer complexes, appreciable to weak complexes and in very

dilute solutions24,25. The stability constant is calculated using the relation

K = Y/(b-y)2 dm3mol-1 ---------------- (3.15)

Where, Y = (a – k1/2b)/(k – k1/2);

k = x/y.

x = difference between Ucal and Uobs at lower concentration ‘a’,

y = difference between Ucal and Uobs at higher concentration ‘b’ and

Ucal = the ultrasonic velocity of the mixture calculated from the mole fractions

of the components using additive principle.

This equation can be used to calculate stability constant values for different

combinations of concentrations ‘a’ and ‘b’.


78

3.16. EXCESS THERMODYNAMIC PARAMETERS

The excess thermodynamic parameters which play a major role in

understanding the nature of molecular interaction in liquid mixtures have

been studied by several workers26-28. The excess thermodynamic parameters

are defined as the difference between the experimental and ideal mixture

values. It gives a measure of the non-ideality of the system as a consequence

of associative or of other interactions29.

The excess values of the parameters have been computed from the

following expressions30:

Excess ultrasonic velocity:

UE = Uexp – (X1U1 + X2U2) ms-1 ---------------- (3.16)

Where, U1 and U2 are the ultrasonic velocities of solute and solvent and Uexp

is the ultrasonic velocity of the mixture. X1 and X2 are the mole fractions of

the solute and solvent.

Excess viscosity:

ηE = ηexp – (X1η1 + X2η2) Nsm-2 --------------- (3.17)

Where, η1 and η2 are the viscosities of solute and solvent, and ηexp is the

viscosity of the mixture.


79

Excess adiabatic compressibility:

κE = κexp – (X1κ1 + X2κ2) kg-1ms2 ------------- (3.18)

Where, κ1 and κ2 are the adiabatic compressibility values of solute and

solvent and κ exp is the adiabatic compressibility of the mixture calculated

using the Laplace relation

κ = 1/U2 ρ.

Excess free volume:

VfE = Vf(exp) – (X1Vf1 + X2Vf2) m3 ----------------- (3.19)

Where, Vf1 and Vf2 are the free volumes of solute and solvent and Vf(exp) is the

free volume of the mixture.

Excess free length:

LfE = Lf(exp) – (X1Lf1 + X2Lf2) m -------------- (3.20)

Where, Lf1 and Lf2 are the free lengths of solute and solvent and Lf(exp) is Lf

value of the mixture.

Excess acoustic impedance:

ZE = Zexp – (X1Z1 + X2Z2) kg-2s-1 -------------- (3.21)

Where, Z1 and Z2 are the acoustic impedance values of solute and solvent and

Z(exp) is Z value of the mixture.


80

Excess available volume:

VaE = Va(exp) – (X1Va1 + X2 Va2) m3 --------------------------- (3.22)

Where, Va1 and Va2 are the acoustic impedance values of solute and solvent

and Va (exp) is Va value of the mixture.

Forte and More31 suggested that the negative contribution to excess

value indicates strong molecular interactions due to dipole-dipole, dipole-

induced dipole, charge transfer and hydrogen bonding.


81

REFERENCES

1. Bhatt, S.S. and Singh, D.P., Ind. J. Pure & Appl. Phys., 21, 1983, 506.

2. Marwein and Bhatt, S.N., Thermochemica Acta, 118, 1987, 277.

3. Thabane, Y.A., Mulay, V.D., Ghose, S. and Khasare, S.B., Acustica, 81C,
1993, 187.

4. Singh, D.P. and Kalsh, S.C., Acoustics Letters, 14(10), 1991, 206.

5. Rajan Dass, Prakash, K., Muhuri and Dilip K. Hazra, Acoustics Letters,
18(4), 1994, 69.

6. Hassun, S.K., British Polymer. J., 17(4), 1985, 330.

7. Jayakumar, S., Karunanidhi, N. and Kannappan, V., Ind. J. Pure & Appl.
Phys., 34, 1996, 761.

8. Subhi Kemal Hassun, Acoustics Letters, 11(10), 1988, 195.

9. Jacobson, B., Acta Chemica Scand., 5, 1951, 1214., 6, 1952, 1485.

10. Jacobson, B., J. Chem. Phys., 20, 1952, 927.

11. Chellaiah, N. and Sebesan, R., Ind. J. Pure & Appl. Phys., 32, 1994, 315.

12. Erying, H. and Hischfelder, J. Phys. Chem., 41, 1937, 249.

13. Kinacid, J. and Erying, H., J. Chem. Phys., 6, 1938, 620.

14. Mc Leod, D.B., Trans Farad. Soc., 41, 1945, 771.

15. Hildebrand, J.H., J. Am. Chem. Soc., 71, 1949, 2703.

16. Suryanarayana, C.V. and Kuppusamy, J., J. Acoust. Soc. Ind., 4, 1976, 75.

17. Rao, A.V., Venkateswaralu, P., Raman, G.K. and Rajulu, A.V., Acta
Polym. 43, 1992, 185.

18. Aruna, P., Natarajan, S. and Suryanarayana, C.V., Ind. J. Tech., 29,
1991, 537.

19. Rajendran, V., Ind. J. Pure & Appl. Phys., 34, 1996, 52.

20. Kannappan, V. and Kothai, S., Ind. J. Pure & Appl. Phys., 40, 2002, 17.
82

21. Kannappan, V. and Kothai, S., J. Acous. Sci. Ind., 29, 2001, 169.

22. Jayakumar, S., Ph.D. Thesis, University of Madras, 1999.

23. Marwein, B.L. and Bhatt, S.N., Acustica, 58, 1985, 243.

24. Kannappan, V. and Kothai, S., Advances of Ultrasonics., 2001, 124.

25. Kannappan, V. and Kothai, S., J. Pure & Applied Ultrasonics., 2002, 24.

26. Jiri Polak., Canad. J. Chem., 48, 1970, 2457.

27. Golla Narayanaswamy., Canad. J. Chem., 58, 1980, 229.

28. Prakash, O. and Darbari, S., Acoustics Letters, 12(2), 1988, 35.

29. Anwar Ali, Anil Kumar Nain, Vinod Kumar Sharma and Shakil Ahmad,
Acoustics Letters, 24(1), 2000, 9.

30. Rajaguru, P. and Jayaraj, Acoustics Letters, 13(8), 1990, 142.

31. Forte, R.J. and More, W.R., Trans. Faraday Soc., 61, 1963, 2102.
83

Chapter 4
84

CHAPTER – 4

ULTRASONIC INVESTIGATIONS OF MOLECULAR


INTERACTIONS IN BINARY LIQUID MIXTURES

4.1. INTRODUCTION

In the recent past, ultrasonic studies on various organic liquid mixtures

have been extensively studied. There is a rapid growth in the number of

research publications in this field1-10. This is due to the fact that the optical

methods cannot detect and assess all types of interactions, especially weak

interactions in liquid mixtures. The important physico chemical properties

like adiabatic compressibility, heat capacity, coefficient of expansion and

critical temperature may be obtained from ultrasonic velocity, density and

viscosity data. The molecular interactions in pure and binary liquid mixtures

can be analysed using ultrasonic velocity measurements which are of

considerable interest for the physicists in the last few decades11-21. Excess

free length (LfE) can be used to access the molecular interactions in binary

liquids and a comparison of the sign of LfE with excess volume (VE) or with

other thermodynamic parameters has been made by several workers22-26.

4.1.1. Types of molecular interactions

There are five types of molecular interactions between the component

molecules in binary liquid mixtures. The strength of these interactions is in

the order
85

ion-ion > ion-dipole > dipole-dipole > dipole-induced dipole >

induced dipole-induced dipole.

The factors that influence the strength of the molecular interactions are

described below:

The strength of ionic attraction depends on the charge and inter-ionic

distance. This can be obtained using Born-Lande equation

Z + Z −e2
E= --------------- (4.1)
4Π ε o r

The attraction of one ion by another is completely independent of direction

but sizes and charge number determine the ion-ion interaction energy. On

the contrary, ion-dipole forces may be thought as ‘directional’ in that they

result in preferred orientations of molecules. The potential energy of an ion-

dipole interaction is given by

Z ± µr
E= ---------------- (4.2)
4Π ε o r 2

Where, ‘ Z ± ’ is the charge on the ion and ‘r’ is the distance between ion and

‘µr’ is the molecular dipole. Ion-dipole interactions are similar to ion-ion

interaction except that they are more sensitive to distance [( 12 ) instead of ( 1 )]


r r

and seems to be some what weaker.

The energy of the interaction of the dipoles may be expressed as

− 2 µ1 µ 2
E= ---------------- (4.3)
4Π ε o r 3

This energy corresponds to head to tail arrangement as shown below (Fig.4.1).


86

- + - +

Fig. 4.1. Dipole – dipole attraction

+ -

- +

Fig. 4.2. Dipole – dipole interaction

An alternate arrangement is anti-parallel arrangement (Fig.4.2) which will be

more stable if the molecules are not too ‘fat’. At moderate temperature and in

the gas phase, there will be a tendency for internal motion to randomize the

orientation of dipoles and the energy of interaction will be considerably

reduced. However, in liquid mixtures at room temperature, the dipole-dipole

interaction energy is greater than that in gas phase containing the same

molecular components. Dipole-dipole interactions tend to be even weaker

than ion-dipole interaction and fall off more rapidly with distance ( 13 ) and
r

they are decreasing in character.

There may be two types of interactions in liquid mixtures containing

polar and non-polar molecules as components. They are dipole-dipole and


87

dipole-induced dipole interactions. The dipolar molecules disturb the electron

cloud of the non-polar molecule and this type of polarization of neutral

species will depend upon the inherent polarizability (of systems), α , and on

the polarizing field offered by the dipole. This interaction energy is much

weaker than the energy of dipole-dipole interaction. The interaction energy is

much weaker than the energy of dipole-dipole interaction. The energy of

interaction if given by

− µ 2α
E= -------------- (4.4)
r6

Where, ‘ µ ’ is the dipole moment of inducing dipole. Since the energy varies

inversely with high power of ‘r’, they are effective only at very short distances.

Even in molecules which have no permanent dipole, instantaneous

dipoles will arise as a result of momentary imbalances in electron

distribution. These dipoles are capable of inducing dipoles in adjacent

molecules. Induced dipole-induced dipole attractions are extremely short

ranged and weak. The energy of such interactions may be expressed as

− 2µ α
E= ------------ (4.5)
r6

Where, ‘ µ ’ is the mean instantaneous dipole or

− 3Iα 2
E= ---------------- (4.6)
4r 6

Where, ‘ α ’ is the polarizability and ‘I’ is the internal energy of the species.

London forces are external short range in action (depending upon ( 16 )) and
r
88

the weakest of all attractive forces of interest to chemists and physicists. As a

result of the ‘ α 2 ’ term, London force increases rapidly with molecular size or

more properly molar volume and the number of polarizable electrons.

At extremely short distances, the electronic clouds of the interacting

molecules begin to overlap and Pauli repulsion becomes extremely large. The

repulsive energy is given by

+k
E= ---------------- (4.7)
rn

Where, ‘k’ is a constant and ‘n’ may have various values (usually ‘n’ may take

values from 5 to 10). Repulsive energies come into play only at extremely

short distances.

4.2. Results and Discussion

In this chapter, the results obtained in the ultrasonic velocity

investigations of the following six binary systems are presented and

discussed.

1. Benzene – carbon tetrachloride

2. Bromobenzene – chlorobenzene

3. Ethanol – water

4. Ethanol – p-cresol

5. Ethanol – phenol

6. Ethanol – pyridine
89

Benzene and carbon tetrachloride are non-polar and there are only

induced dipole-induced dipole interactions in the mixture of benzene and

carbon tetrachloride. However, dipole-dipole attraction exists in

bromobenzene-chlorobenzene system. Phenols are dipolar molecules and they

are associated through hydrogen bonding which is evident from the

spectra27-30. Four binary systems are chosen such that they contain ethanol

as the common component and the second component is varied. In these four

systems, the variation in the intermolecular attraction is mainly due to the

second component. Thus, acoustical studies are made on six binary liquid

mixtures such that different types of molecular attractions could be assessed.

The acoustical parameters were calculated for benzene-carbon

tetrachloride and bromobenzene-chlorobenzene systems of various

compositions, from ultrasonic velocities, densities and viscosities at 303 K

and they are given in Tables 4.1 – 4.4. The data for the other four systems at

303 K are given in Tables 4.5 – 4.12. These data are discussed in the light of

molecular interactions between the components which exist in the six binary

liquid systems.

4.2.1. Ultrasonic Velocity (U)

The ultrasonic velocity (U) increases with increase in mole fraction of

benzene in benzene – carbon tetrachloride system but decreases with

increase in mole fraction of bromobenzene in bromobenzene – chlorobenzene

system. This suggests that there are different types of molecular interactions
90

between the components in these binary mixtures. Fig. 4.1 contains the plots

of ultrasonic velocity vs mole fraction of the first components. The linear

variation in the ultrasonic velocity values in these systems suggests that

these systems behave almost ideally. The curve obtained in the case of

bromobenzene-chlorobenzene system is steeper than that of benzene-carbon

tetrachloride system which indicates that slightly stronger dipole-dipole

interactions exist in the former while weak induced dipole-induced dipole

interactions exist in the latter.

In the case of ethanol-water, ethanol-p-cresol, ethanol-phenol and

ethanol-pyridine systems, the ultrasonic velocity decreases with increase in

mole fraction of ethanol (Fig. 4.7). It is seen that in the case of ethanol-water

system, the ultrasonic velocity increases, reaches a maximum and then

decreases with increase in the mole fraction of ethanol. The increase in

ultrasonic velocity indicates that water molecules behave as structure breaker

for ethanol clusters. The decrease in velocity at higher mole fraction shows

that the molecules of the components are strongly attracted by hydrogen

bond. In other three systems, the extent of intermolecular hydrogen bond

between the components increases with increase in the mole fraction of the

second component.
91

κ)
4.2.2. Adiabatic Compressibility (κ

The adiabatic compressibility (κ) values for various compositions of six

binary mixtures have been computed from the measured values of ultrasonic

velocities and densities (Tables 4.1, 4.3, 4.5, 4.7, 4.9 and 4.11). The plots of

adiabatic compressibility vs mole fraction of the first component are given in

Fig.4.2 for benzene-carbon tetrachloride and bromobenzene-chlorobenzene

systems. In both the cases the value of compressibility decreases with

increase in concentration indicating strong molecular interaction over a wide

range of concentration. Slightly steeper curve obtained in bromobenzene-

chlorobenzene system shows that the molecular attractions (dipole-dipole) in

these systems are slightly stronger than induced dipole-induced dipole

attractions in benzene-carbon tetrachloride system.

In the case of mixtures of ethanol- water, ethanol-p-cresol, ethanol-

phenol and ethanol-pyridine, the plots in Fig. 4.8 show that there is an

increase in compressibility with an increase in concentration except in

ethanol-water system. This indicates strong molecular interactions between

ethanol and molecules of other components and the intramolecular

attractions become weak among each component. A comparison of the values

of ‘κ’ in these three mixtures suggests that their compressibilities are in the

order:

Ethanol-pyridine > ethanol-p-cresol > ethanol-water > ethanol-phenol.


92

It may be noted that in the case of ethanol-water mixture, the compressibility

decreases to a minimum value and then increases. This indicates a stronger

dipole-dipole interaction even at lower concentration and water acts as

structure breaker for ethanol.

4.2.3. Absorption coefficient (α/f2)

The absorption coefficient (α/f2) values in a system can be used to

ascertain the variation in intermolecular attraction and also to establish the

existence of similar types of interaction in different binary systems. In the

binary systems studied, the absorption coefficient values increase with

increase in the mole fraction of the first component in three systems namely,

bromobenzene-chlorobenzene, ethanol-water and ethanol-pyridine systems,

while it decreases in other systems (Tables 4.1, 4.3, 4.5, 4.7, 4.9 and 4.11).

This trend suggests that different types of molecular interaction exist in these

binary systems.

4.2.4. Molecular Interaction Parameter (χU)

The molecular interaction parameter (χU) values are calculated and

presented in Tables 4.1, 4.3, 4.5, 4.7, 4.9 and 4.11 for the six binary systems.

These values are negative for benzene-carbon tetrachloride and

bromobenzene-chlorobenzene mixtures indicating the presence of attractive

forces. In benzene-carbon tetrachloride system, the molecular interaction


93

parameter values are more negative. Plots of ‘χU’ vs X1 are presented in

Fig.4.3. It is interesting to note that in bromobenzene-chlorobenzene system,

molecular interaction parameter values are more negative than those for

benzene-carbon tetrachloride system. Further, the molecular interaction

parameter values are minimum at X1 = 0.4 – 0.6 suggesting that the two types

of interactions are concentration dependent and hence, the distance between

the component molecules. It may be noted that molecular interaction

parameter values are more negative for binary mixtures of bromobenzene-

chlorobenzene than those in benzene-carbon tetrachloride mixtures. Thus,

dipole-dipole attractions are stronger than induced dipole-induced dipole

attractions. Similar plots for the other four systems are given in Fig. 4.9.

Molecular interaction parameter values are positive and a maximum

molecular interaction parameter value is obtained for each system. In

ethanol-water system, molecular interaction parameter value is the highest at

X1 = 0.2. Thus, stronger intermolecular hydrogen bonding is present in this

system even at lower concentration. In the other cases, the maximum ‘χU’

values are observed at X1 = 0.4 – 0.6 and molecular interactions are stronger

in this concentration range in these binary systems.

4.2.5. Relaxation Time (τ)

The values of relaxation time (τ) are calculated for the six binary

systems from coefficient of viscosity, density and ultrasonic velocity values.


94

The relaxation time values are given in Tables 4.1, 4.3, 4.5, 4.7, 4.9 and 4.11.

There are only slight variations in relaxation time values in bromobenzene-

chlorobenzene and benzene-carbon tetrachloride systems. In these two

systems, there is only a slight increase in the molecular interactions with

concentration. However, in the case of ethanol-water and ethanol-pyridine

systems, relaxation time values increase significantly with increase in

concentration and the interaction between the molecules of components is

stronger than the attractive forces between the molecules of each component.

But in the case of other two systems, relatively weaker interactions exist

between the molecules of the two components and stronger intermolecular

interactions exist between the molecules of each component.

4.2.6. Free Length (Lf)

The free length (Lf) of a system is a measure of intermolecular attraction

between the components in binary mixtures. The increase in free length

indicates weakening of intermolecular interaction. From the data in Tables

4.1 and 4.3, it is seen that free length remains constant in the case of

benzene-carbon tetrachloride and bromobenzene-chlorobenzene systems. The

free length values for various compositions of the four binary mixtures are

given in Tables 4.5, 4.7, 4.9 and 4.11. In the case of binary systems of

ethanol with water, p-cresol, phenol and pyridine, the free length values

increase with increase in concentration of ethanol. This shows that the


95

intramolecular attraction weakens at higher concentration and intermolecular

attractions between ethanol and water molecules dominate at higher

concentration.

4.2.7. Internal Pressure (πi)

The internal pressure (πi) in a binary mixture is a measure of

intermolecular attraction between the components. The internal pressure

values for various compositions for all the six systems have been obtained

from the equation suggested by Suryanarayana31. The internal pressure

values for benzene-carbon tetrachloride system and bromobenzene-

chlorobenzene system are given in Tables 4.1 and 4.3 respectively. The

internal pressure values increase slightly with increase in concentration for

both the systems indicating the existence of relatively weak interactions in

these two systems.

The internal pressure values for the binary mixtures of ethanol with

water, p-cresol, phenol and pyridine are given in Tables 4.5, 4.7, 4.9 and 4.11

and the corresponding plots are given in Fig.4.10. It is seen that the internal

pressure is maximum for ethanol-water mixture suggesting strong

intermolecular hydrogen bonding which may be due to the high polarity of

water. The slight increase in internal pressure value with concentration in

other systems indicates the existence of molecular interactions in these

systems.
96

4.2.8. Cohesive Energy (CE)

The cohesive energy (CE) in a liquid is indicative of the attractive force

existing between the molecules. When two liquids are mixed, there is

molecular attraction between the molecules of components and hence, the

cohesive energy is high. The cohesive energy values for all the binary systems

are given in Tables 4.1, 4.3, 4.5, 4.7, 4.9 and 4.11. The corresponding plots

are given in Figs. 4.4 and 4.11. The value of cohesive energy decreases with

increase in concentration in the case of benzene-carbon tetrachloride which

may be due to weak induced dipole-induced dipole interaction in the system.

However, in bromobenzene-chlorobenzene system, cohesive energy

increases with increase in the mole fraction of bromobenzene. This suggests

that intermolecular interaction increases with the concentration of

bromobenzene which may be due to existence of stronger dipole-dipole

attraction in this system.

In ethanol-water and ethanol-pyridine systems, cohesive energy value

increases with increase in concentration of ethanol. This is due to strong

intermolecular attraction between the molecules of the components. However,

in the case of systems containing phenol and p-cresol, there is a decrease in

cohesive energy values. Phenols are associated liquids and ethanol molecules
97

may disrupt the association due to intermolecular attraction. Consequently,

the cohesive energy decreases.

4.2.9. Free Volume (Vf) and Available Volume (Va)

The free volume (Vf) and available volume (Va) values are calculated and

presented in Tables 4.1 – 4.12 for all the binary systems investigated. It is

found that for all the systems at 303 K, free volume increases with increase in

concentration except for bromobenzene-chlorobenzene and ethanol-pyridine

mixtures. But the calculated available volume increases with increase in

concentration for all the systems except bromobenzene-chlorobenzene

system.

4.2.10. Excess Parameters

The excess acoustical parameters can be used to find out the extent of

deviation from ideal behaviour in binary liquid mixtures. These values are

calculated for all the six binary systems for different mole fractions at 303K.

These values are presented in Tables 4.2, 4.4, 4.6, 4.8, 4.10 and 4.12 and the

corresponding plots are given in Figs. 4.5, 4.6, 4.12 and 4.13. It may be

pointed out that the excess adiabatic compressibility (κE), excess free length

(LfE) and excess available volume (VaE) are negative for almost all compositions

of ethanol with water, p-cresol, phenol and pyridine. This indicates that the

attractive forces between the molecules of components are stronger than the

intramolecular attractions in each component. Further, excess acoustical


98

parameters are more negative for binary mixtures containing equimolar

concentrations of the two components suggesting that the attractive forces

are significant at moderate concentration. It may be pointed out here that

excess acoustic impedance increases at higher mole fractions of the first

component in all the systems except bromobenzene-chlorobenzene and

benzene-carbon tetrachloride system. This indicates that at higher

concentration, the repulsive forces may dominate and the two systems

bromobenzene-chlorobenzene and benzene-carbon tetrachloride differ from

the other four in the intermolecular attraction.

4.3. CONCLUSION

The various acoustical parameters such as adiabatic compressibility,

absorption coefficient, relaxation time, free length, free volume, internal

pressure, cohesive energy, acoustic impedance and available volume, have

been evaluated from the measured ultrasonic velocity, density and viscosity

values for the six binary mixtures. The value of molecular interaction

parameter (χU) indicates the strength of molecular interactions. The excess

thermodynamic parameters such as excess ultrasonic velocity, excess

compressibility, excess free volume, excess free length and excess impedance

have been determined for all the six binary liquid mixtures. These acoustical

properties and their trend with concentration suggest that very weak

interactions of induced dipole-induced dipole type are present in benzene-


99

carbon tetrachloride system, while relatively strong dipole-dipole attraction

exists in bromobenzene-chlorobenzene binary system. In the other four

systems containing ethanol as common component, strong intermolecular

hydrogen bonds are present and ethanol acts as structure breaker for water

clusters. In ethanol-pyridine system, there are strong dipole-dipole

attractions. However, in ethanol-phenol and ethanol-p-cresol systems,

ethanol molecules break the intramolecular hydrogen bonds present in the

phenolic compounds and with increase in the mole fraction of ethanol, there

are strong intermolecular attractions between ethanol and phenol molecules.


100

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TABLE 4.1

ULTRASONIC VELOCITY (U), DENSITY (ρ


ρ), VISCOSITY (η
η), ADIABATIC COMPRESSIBILITY (κ α/f2),
κ),ABSORPTION COEFFICIENT (α
MOLECULAR INTERACTION PARAMETER (χ χU), RELAXATION TIME (ττ), FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (ππi),
AND COHESSIVE ENERGY (CE) VALUES AT VARIOUS MOLE FRACTIONS OF BENZENE - CARBON TETRACHLORIDE SYSTEM

Temperature : 303 K
Mole Fraction
of first U ρ η /10-4 κ /10
/
-9
α/f2 /10-15 χU /10-3 τ /10-13 Lf Vf /10-7 πi CE
Component -1 -3 -2 -1 2 -1 2 -1 o 3
(X1) ms kg m Nsm kg ms Npm s ms s A m atm kJ mol-1
0.000 906.0 1590.1 8.67 0.77 19.3 0.0 8.9 0.5 2.3 3865 37.9
0.108 939.6 1502.9 8.69 0.75 18.3 -13.5 8.7 0.5 2.2 3900 38.3
0.214 957.4 1435.9 8.45 0.76 17.6 -55.9 8.6 0.5 2.2 3948 38.3
0.318 982.4 1367.9 8.09 0.76 16.4 -79.5 8.2 0.5 2.2 3956 38.0
0.421 1009.8 1298.0 7.75 0.76 15.2 -95.8 7.8 0.5 2.3 3962 37.7
0.521 1049.0 1227.8 7.36 0.74 13.7 -89.4 7.3 0.5 2.3 3937 37.1
0.620 1080.2 1157.1 7.01 0.74 12.6 -95.8 6.9 0.5 2.4 3938 36.8
0.718 1122.8 1086.6 6.70 0.73 11.5 -82.3 6.5 0.5 2.4 3936 36.5
0.813 1161.4 1016.1 6.34 0.73 10.5 -75.0 6.2 0.5 2.5 3931 36.2
0.907 1210.6 944.8 6.00 0.72 9.4 -50.6 5.8 0.5 2.5 3921 35.8
1.000 1276.8 864.7 5.65 0.70 8.3 0.0 5.3 0.5 2.6 3860 35.3

Plots : Fig. 4.1 U vs Mole Fraction; Fig. 4.3 χU vs Mole Fraction;


Fig. 4.2 κ vs Mole Fraction; Fig. 4.4 CE vs Mole Fraction;
103

TABLE 4.2

ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va), LENARD JONES POTENTIAL (LJP),
EXCESS ULTRASONIC VELOSITY (UE), EXCESS VISCOSITY (η
ηE), EXCESS ADIABATIC COMPRESSIBILITY (κ
κE),
EXCESS FREE LENGTH (LfE), EXCESS FREE VOLUME (VfE), EXCESS ACOUSTICAL IMPEDANCE (ZE) AND EXCESS
AVAILABLE VOLUME (VaE) VALUES AT VARIOUS MOLE FRACTIONS OF BENZENE - CARBON TETRACHLORIDE SYSTEM
Temperature : 303 K
Mole Fraction
of first Z /105 Va /10-5 LJP UE ηE /10-5 κE /10-12 VfE/10-8 LfE/10-13 ZE /105 VaE /10-6
Component (X1) kg-2s-1 m3 ms-1 Nsm-2 kg-1ms2 m3 m kg-2s-1 m3
0.000 14.4 4.2 0.8 - - - - - - -
0.108 14.1 4.0 1.5 -6.4 3.35 -6.34 -1.1 -2.3 0.1 0.6
0.214 13.7 3.8 1.9 -27.9 4.20 5.77 -1.8 2.1 0.1 1.6
0.318 13.4 3.7 2.5 -41.6 3.89 9.37 -1.8 3.5 0.1 2.2
0.421 13.1 3.5 3.3 -52.1 3.66 13.24 -1.8 4.9 0.1 2.7
0.521 12.9 3.2 4.4 -50.3 2.93 3.56 -1.3 1.4 0.2 2.5
0.620 12.5 3.0 5.5 -55.8 2.51 9.68 -1.3 3.6 0.2 2.8
0.718 12.2 2.7 7.1 -49.3 2.48 4.57 -1.2 1.8 0.2 2.4
0.813 11.8 2.5 8.9 -46.1 1.89 9.65 -1.0 3.6 0.1 2.2
0.907 11.4 2.2 11.7 -31.9 1.51 7.56 -0.8 2.8 0.1 1.5
1.000 11.0 1.8 16.7 - - - - - - -

E
Plots : Fig.4.5 U vs Mole Fraction;
E
Fig.4.6 Z vs Mole Fraction;
104

TABLE 4.3

ULTRASONIC VELOCITY (U), DENSITY (ρ


ρ), VISCOSITY (η
η), ADIABATIC COMPRESSIBILITY (κ α/f2),
κ),ABSORPTION COEFFICIENT (α
MOLECULAR INTERACTION PARAMETER (χ χU), RELAXATION TIME (ττ), FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (ππi),
AND COHESSIVE ENERGY (CE) VALUES AT VARIOUS MOLE FRACTIONS OF BROMOBENZENE - CHLOROBENZENE SYSTEM
Temperature : 303 K

Mole Fraction

of first U ρ η /10-4 κ /10


/
-9
α/f2 /10-15 χU /10-3 τ /10-13 Lf Vf /10-7 πi CE
Component (X1) ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s Ao m3 atm kJ mol-1
0.000 1241.7 1102.0 7.28 0.59 9.1 0.0 5.7 0.5 3.0 3411 35.3
0.097 1225.6 1005.2 6.63 0.66 9.4 -8.6 5.9 0.5 3.6 2949 34.7
0.195 1214.8 1036.9 6.81 0.65 9.6 -8.5 5.9 0.5 3.6 2935 34.8
0.294 1201.2 1071.7 7.14 0.65 10.1 -13.0 6.2 0.5 3.5 2966 35.2
0.393 1190.8 1103.0 7.35 0.64 10.4 -12.1 6.3 0.5 3.5 2959 35.3
0.493 1179.2 1138.7 7.46 0.63 10.5 -13.2 6.3 0.5 3.5 2943 35.2
0.593 1168.6 1170.3 7.66 0.63 10.8 -12.4 6.4 0.5 3.5 2936 35.3
0.694 1159.2 1203.8 7.95 0.62 11.2 -9.5 6.6 0.5 3.4 2950 35.6
0.795 1149.6 1235.9 8.25 0.61 11.6 -6.7 6.7 0.5 3.3 2961 35.9
0.897 1139.4 1271.3 8.46 0.61 11.8 -4.9 6.8 0.5 3.3 2963 36.0
1.000 1130.8 1494.0 9.90 0.52 12.1 0.0 6.9 0.5 2.7 3463 36.9

Plots : Fig. 4.1 U vs Mole Fraction; Fig. 4.3 χU vs Mole Fraction;


Fig. 4.2 κ vs Mole Fraction; Fig. 4.4 CE vs Mole Fraction;
105

TABLE 4.4

ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va), LENARD JONES POTENTIAL (LJP),
EXCESS ULTRASONIC VELOSITY (UE), EXCESS VISCOSITY (η
ηE), EXCESS ADIABATIC COMPRESSIBILITY (κ
κE),
EXCESS FREE LENGTH (LfE), EXCESS FREE VOLUME (VfE), EXCESS ACOUSTICAL IMPEDANCE (ZE) AND
EXCESS AVAILABLE VOLUME (VaE) VALUES AT VARIOUS MOLE FRACTIONS OF BROMOBENZENE - CHLOROBENZENE SYSTEM
Temperature : 303 K

Mole Fraction

of first Z /105 Va /10-5 LJP UE ηE /10-5 κE /10-12 VfE/10-8 LfE/10-13 ZE /105 VaE /10-6
Component (X1) kg-2s-1 m3 ms-1 Nsm-2 kg-1ms2 m3 m kg-2s-1 m3
0.000 13.7 2.3 13.8 - - - - - - -
0.097 12.3 2.7 12.6 -5.3 -9.02 80.04 6.1 31.9 -1.7 3.6
0.195 12.6 2.8 11.9 -5.2 -9.88 77.64 6.5 31.2 -1.7 3.7
0.294 12.9 2.9 11.1 -7.9 -9.11 77.21 5.5 31.2 -1.8 4.0
0.393 13.1 3.0 10.5 -7.3 -9.61 76.36 5.7 31.1 -1.8 4.2
0.493 13.4 3.1 9.8 -7.8 -11.09 75.04 6.4 30.8 -1.8 4.3
0.593 13.7 3.2 9.3 -7.3 -11.77 75.74 6.6 31.2 -1.9 4.4
0.694 14.0 3.3 8.8 -5.5 -11.48 74.78 6.1 31.0 -2.0 4.4
0.795 14.2 3.4 8.3 -3.9 -11.17 75.45 5.7 31.4 -2.0 4.5
0.897 14.5 3.5 7.8 -2.8 -11.77 75.70 5.9 31.6 -2.1 4.5
1.000 16.9 3.1 7.5 - - - - - - -

E
Plots : Fig.4.5 U vs Mole Fraction;
E
Fig.4.6 Z vs Mole Fraction;
106

TABLE 4.5

ULTRASONIC VELOCITY (U), DENSITY (ρ


ρ), VISCOSITY (η
η), ADIABATIC COMPRESSIBILITY (κ α/f2),
κ),ABSORPTION COEFFICIENT (α
MOLECULAR INTERACTION PARAMETER (χ χU), RELAXATION TIME (ττ), FREE LENGTH (Lf), FREE VOLUME (Vf),
INTERNAL PRESSURE (π
πi), AND COHESSIVE ENERGY (CE) VALUES AT VARIOUS MOLE FRACTIONS OF ETHANOL - WATER SYSTEM
Temperature : 303 K
Mole Fraction
of first U ρ η /10-4 κ /10
/
-9
α/f2 /10-15 χU /10-3 τ /10-13 Lf Vf /10-7 πi CE
-1 -3 -2 -1 2 -1 2 -1 o 3
Component (X1) ms kg m Nsm kg ms Npm s ms s A m atm kJ mol-1
0.000 1510.0 995.7 7.98 0.44 6.1 0.0 4.7 0.4 0.2 25701 47.1
0.033 1563.2 873.4 8.27 0.47 6.5 89.6 5.2 0.4 0.2 22221 48.8
0.072 1596.4 863.2 9.82 0.45 7.4 158.6 6.0 0.4 0.2 22274 52.3
0.117 1611.2 851.7 11.97 0.45 8.8 207.6 7.2 0.4 0.2 22581 57.2
0.171 1584.0 837.9 13.63 0.48 10.8 199.9 8.6 0.4 0.2 22181 61.1
0.236 1530.2 821.4 14.33 0.52 12.8 158.6 9.9 0.5 0.2 20869 63.4
0.317 1470.4 804.8 14.45 0.57 14.9 116.7 11.1 0.5 0.2 19030 64.4
0.419 1401.6 783.4 14.00 0.65 17.1 72.9 12.1 0.5 0.2 16738 64.4
0.553 1333.2 763.1 12.84 0.74 18.7 46.7 12.6 0.5 0.2 14058 62.6
0.736 1267.2 739.3 11.35 0.84 19.8 53.2 12.7 0.6 0.3 11244 59.6
1.000 1136.0 789.0 8.91 0.98 20.3 0.0 11.7 0.6 0.5 8955 53.0
Plots : Fig. 4.7 U vs Mole Fraction; Fig. 4.10 πi vs Mole Fraction;
Fig. 4.8 κ vs Mole Fraction; Fig. 4.11 CE vs Mole Fraction;
Fig. 4.9 χU vs Mole Fraction;
107

TABLE 4.6

ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va), LENARD JONES POTENTIAL (LJP),
EXCESS ULTRASONIC VELOSITY (UE), EXCESS VISCOSITY (η
ηE), EXCESS ADIABATIC COMPRESSIBILITY (κ
κE),
EXCESS FREE LENGTH (LfE), EXCESS FREE VOLUME (VfE), EXCESS ACOUSTICAL IMPEDANCE (ZE) AND
EXCESS AVAILABLE VOLUME (VaE) VALUES AT VARIOUS MOLE FRACTIONS OF ETHANOL - WATER SYSTEM
Temperature : 303 K
Mole Fraction

of first Z /105 Va /10-5 LJP UE ηE /10-5 κE /10-12 VfE/10-8 LfE/10-13 ZE /105 VaE /10-6
Component (X1) kg-2s-1 m3 ms-1 Nsm-2 kg-1ms2 m3 m kg-2s-1 m3
0.000 15.0 0.1 93.7 - - - - - - -
0.033 13.7 0.0 247.9 65.6 0.03 10.03 0.1 -29.3 -1.1 -1.0
0.072 13.8 0.0 2653.7 113.3 0.18 -24.80 -0.4 -27.7 -0.8 -2.1
0.117 13.7 0.0 -870.1 145.0 0.39 -51.65 -0.8 -25.8 -0.6 -3.0
0.171 13.3 0.0 587.0 138.0 0.55 -57.50 -1.2 -23.6 -0.7 -3.4
0.236 12.6 0.1 124.5 108.6 0.61 -48.57 -1.4 -20.8 -1.0 -3.4
0.317 11.8 0.3 61.1 79.0 0.62 -37.51 -1.5 -17.5 -1.3 -3.3
0.419 11.0 0.5 35.4 48.4 0.56 -17.86 -1.6 -13.2 -1.5 -3.0
0.553 10.2 0.7 23.0 30.1 0.43 -2.83 -1.5 -7.6 -1.5 -2.5
0.736 9.4 1.1 15.8 32.4 0.27 3.27 -1.1 0.0 -1.2 -1.8
1.000 9.0 1.7 7.7 - - - - - - -

E
Plots : Fig.4.12 U vs Mole Fraction;
E
Fig.4.13 Z vs Mole Fraction;
108

TABLE 4.7

ULTRASONIC VELOCITY (U), DENSITY (ρ


ρ), VISCOSITY (η
η), ADIABATIC COMPRESSIBILITY (κ α/f2),
κ),ABSORPTION COEFFICIENT (α
MOLECULAR INTERACTION PARAMETER (χ χU), RELAXATION TIME (ττ), FREE LENGTH (Lf), FREE VOLUME (Vf),
πi), AND COHESSIVE ENERGY (CE) VALUES AT VARIOUS MOLE FRACTIONS OF ETHANOL - p-CRESOL
INTERNAL PRESSURE (π
SYSTEM
Temperature : 303 K
Mole
Fraction
of first U ρ η /10-4 κ /10
/
-9
α/f2 /10-15 χU /10-3 τ /10-13 Lf Vf /10-7 πi CE
Component -1 -3 -2 -1 2 -1 2 -1 o 3
(X1) ms kg m Nsm kg ms Npm s ms s A m atm kJ mol-1
0.000 1450.4 1034.0 90.15 0.46 75.1 0.0 55.3 0.4 0.1 11152 118.2
0.166 1447.0 888.7 50.64 0.54 49.4 71.0 36.3 0.5 0.2 8502 94.8
0.309 1425.6 876.1 41.65 0.56 43.1 109.9 31.2 0.5 0.2 8599 88.4
0.434 1398.2 857.1 29.36 0.60 32.9 132.5 23.4 0.5 0.3 7992 76.7
0.544 1372.0 838.3 23.04 0.63 28.0 150.2 19.5 0.5 0.3 7802 70.1
0.642 1337.4 817.5 18.97 0.68 25.5 147.2 17.3 0.5 0.4 7786 65.9
0.729 1303.4 797.9 15.50 0.74 23.1 139.0 15.2 0.5 0.4 7723 61.7
0.807 1269.8 775.1 12.89 0.80 21.3 125.9 13.7 0.6 0.5 7684 58.3
0.878 1229.2 751.8 10.61 0.88 20.0 95.3 12.4 0.6 0.6 7609 55.0
0.942 1192.6 730.1 9.62 0.96 20.4 67.3 12.4 0.6 0.5 7893 54.4
1.000 1136.0 789.0 8.91 0.98 20.3 0.0 11.7 0.6 0.5 8955 53.0
Plots : Fig. 4.7 U vs Mole Fraction; Fig. 4.10 πi vs Mole Fraction;
Fig. 4.8 κ vs Mole Fraction; Fig. 4.11 CE vs Mole Fraction;
Fig. 4.9 χU vs Mole Fraction;
109

TABLE 4.8

ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va), LENARD JONES POTENTIAL (LJP),
EXCESS ULTRASONIC VELOSITY (UE), EXCESS VISCOSITY (ηηE), EXCESS ADIABATIC COMPRESSIBILITY (κ
κE),
E E E
EXCESS FREE LENGTH (Lf ), EXCESS FREE VOLUME (Vf ), EXCESS ACOUSTICAL IMPEDANCE (Z ) AND
EXCESS AVAILABLE VOLUME (VaE) VALUES AT VARIOUS MOLE FRACTIONS OF ETHANOL - p-CRESOL SYSTEM
Temperature : 303 K
Mole Fraction
of first Z /105 Va /10-5 LJP UE ηE /10-5 κE /10-12 VfE/10-8 LfE/10-13 ZE /105 VaE /10-6
Component (X1) kg-2s-1 m3 ms-1 Nsm-2 kg-1ms2 m3 m kg-2s-1 m3
0.000 15.0 1.0 51.2 - - - - - - -
0.166 12.9 1.1 49.7 48.8 -2.60 -9.02 0.1 -24.5 -1.1 -0.4
0.309 12.5 1.1 42.0 72.4 -2.34 -59.61 -0.2 -18.4 -0.6 -0.9
0.434 12.0 1.2 34.6 84.3 -2.55 -89.77 0.0 -13.1 -0.4 -0.9
0.544 11.5 1.3 29.1 92.7 -2.29 -110.30 0.2 -8.4 -0.2 -1.0
0.642 10.9 1.4 23.6 88.8 -1.90 -111.07 0.2 -4.2 -0.2 -0.7
0.729 10.4 1.5 19.4 82.1 -1.54 -102.64 0.4 -0.5 -0.2 -0.4
0.807 9.8 1.5 16.1 73.1 -1.17 -81.11 0.6 2.8 -0.3 -0.1
0.878 9.2 1.7 12.9 54.7 -0.83 -37.77 1.0 5.8 -0.5 0.5
0.942 8.7 1.7 10.6 38.2 -0.40 11.44 0.6 8.5 -0.6 0.8
1.000 9.0 1.7 7.7 - - - - - - -
E
Plots : Fig.4.12 U vs Mole Fraction;
E
Fig.4.13 Z vs Mole Fraction;
110

TABLE 4.9

ULTRASONIC VELOCITY (U), DENSITY (ρ


ρ), VISCOSITY (η
η), ADIABATIC COMPRESSIBILITY (κ α/f2),
κ),ABSORPTION COEFFICIENT (α
MOLECULAR INTERACTION PARAMETER (χ χU), RELAXATION TIME (ττ), FREE LENGTH (Lf), FREE VOLUME (Vf),
INTERNAL PRESSURE (π
πi), AND COHESSIVE ENERGY (CE) VALUES AT VARIOUS MOLE FRACTIONS OF ETHANOL - PHENOL SYSTEM
Temperature : 303 K
Mole Fraction
of first U ρ η /10-4 κ /10
/
-9
α/f2 /10-15 χU /10-3 τ /10-13 Lf Vf /10-7 πi CE
-1 -3 -2 -1 2 -1 2 -1 o 3
Component (X1) ms kg m Nsm kg ms Npm s ms s A m atm kJ mol-1
0.000 1454.8 1066.0 52.75 0.44 42.3 0.0 31.2 0.4 0.1 10223 91.4
0.144 1458.4 925.0 39.08 0.51 35.8 71.4 26.5 0.4 0.2 8739 83.5
0.274 1436.2 903.8 31.71 0.54 31.1 103.2 22.7 0.5 0.3 8521 77.3
0.393 1406.8 882.0 24.55 0.57 26.3 119.8 18.7 0.5 0.3 8118 70.1
0.502 1379.0 857.3 18.14 0.61 21.2 134.3 14.8 0.5 0.4 7522 62.2
0.602 1346.2 834.2 16.48 0.66 21.3 136.2 14.5 0.5 0.4 7742 61.3
0.694 1316.0 812.2 14.13 0.71 20.1 138.1 13.4 0.5 0.5 7731 58.6
0.779 1279.6 786.9 12.30 0.78 19.6 125.0 12.7 0.6 0.5 7769 56.7
0.858 1234.8 762.7 10.94 0.86 20.0 92.8 12.5 0.6 0.5 7920 55.6
0.932 1200.4 736.9 9.55 0.94 19.7 74.9 12.0 0.6 0.6 7951 54.0
1.000 1136.0 789.0 8.91 0.98 20.3 0.0 11.7 0.6 0.5 8955 53.0
Plots : Fig. 4.7 U vs Mole Fraction; Fig. 4.10 πi vs Mole Fraction;
Fig. 4.8 κ vs Mole Fraction; Fig. 4.11 CE vs Mole Fraction;
Fig. 4.9 χU vs Mole Fraction;
111

TABLE 4.10

ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va), LENARD JONES POTENTIAL (LJP),
EXCESS ULTRASONIC VELOSITY (UE), EXCESS VISCOSITY (η
ηE), EXCESS ADIABATIC COMPRESSIBILITY (κ
κE),
EXCESS FREE LENGTH (LfE), EXCESS FREE VOLUME (VfE), EXCESS ACOUSTICAL IMPEDANCE (ZE) AND
EXCESS AVAILABLE VOLUME (VaE) VALUES AT VARIOUS MOLE FRACTIONS OF ETHANOL - PHENOL SYSTEM AT 303.15 K
Temperature : 303 K
Mole Fraction
of first Z /105 Va /10-5 LJP UE ηE /10-5 κE /10-12 VfE/10-8 LfE/10-13 ZE /105 VaE /10-6
Component (X1) kg-2s-1 m3 ms-1 Nsm-2 kg-1ms2 m3 m kg-2s-1 m3
0.000 15.5 0.8 53.1 - - - - - - -
0.144 13.5 0.8 54.8 49.5 -0.74 -12.23 1.2 -24.8 -1.1 -1.0
0.274 13.0 0.9 45.6 68.8 -0.90 -54.44 1.0 -19.3 -0.7 -1.3
0.393 12.4 1.0 36.7 77.4 -1.10 -82.11 1.1 -14.4 -0.5 -1.2
0.502 11.8 1.1 30.4 84.2 -1.26 -100.25 1.8 -9.8 -0.4 -1.2
0.602 11.2 1.2 24.8 83.3 -0.99 -106.04 1.3 -5.6 -0.3 -1.0
0.694 10.7 1.3 20.8 82.4 -0.82 -106.22 1.2 -1.8 -0.3 -0.9
0.779 10.1 1.4 17.0 73.2 -0.63 -86.94 1.1 1.8 -0.3 -0.5
0.858 9.4 1.6 13.3 53.6 -0.42 -45.65 0.8 5.1 -0.5 0.2
0.932 8.8 1.7 11.0 42.6 -0.24 -3.39 0.8 8.1 -0.6 0.4
1.000 9.0 1.7 7.7 - - - - - - -

E
Plots : Fig.4.12 U vs Mole Fraction;
E
Fig.4.13 Z vs Mole Fraction;
112

TABLE 4.11

ULTRASONIC VELOCITY (U), DENSITY (ρ


ρ), VISCOSITY (η
η), ADIABATIC COMPRESSIBILITY (κ α/f2),
κ),ABSORPTION COEFFICIENT (α
MOLECULAR INTERACTION PARAMETER (χ χU), RELAXATION TIME (ττ), FREE LENGTH (Lf), FREE VOLUME (Vf),
INTERNAL PRESSURE (π
πi), AND COHESSIVE ENERGY (CE) VALUES AT VARIOUS MOLE FRACTIONS OF ETHANOL - PYRIDINE
SYSTEM
Temperature : 303 K

Mole Fraction

of first U ρ η /10-4 κ /10


/
-9
α/f2 /10-15 χU /10-3 τ /10-13 Lf Vf /10-7 πi CE
kJ mol-
Component (X1) ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s Ao m3 atm 1

0.000 1393.0 981.0 7.71 0.53 7.6 0.0 5.4 0.5 3.1 3213 35.9
0.133 1371.8 846.9 6.77 0.63 8.1 19.2 5.7 0.5 3.2 3092 36.2
0.257 1348.2 832.6 6.64 0.66 8.6 32.1 5.9 0.5 2.7 3414 36.9
0.372 1327.6 817.0 6.60 0.69 9.1 47.0 6.1 0.5 2.4 3766 37.9
0.479 1304.4 801.9 6.68 0.73 9.9 55.2 6.5 0.5 2.0 4183 39.3
0.580 1282.6 784.9 6.74 0.77 10.7 63.1 7.0 0.6 1.7 4611 40.6
0.674 1261.6 769.7 6.89 0.82 11.7 69.9 7.5 0.6 1.4 5109 42.3
0.763 1235.0 752.7 7.08 0.87 13.1 64.7 8.2 0.6 1.2 5663 44.2
0.847 1206.0 736.1 7.34 0.93 14.9 52.8 9.1 0.6 0.9 6299 46.5
0.926 1180.6 721.7 7.53 0.99 16.7 44.6 10.0 0.6 0.8 6966 48.6
1.000 1136.0 789.0 8.91 0.98 20.3 0.0 11.7 0.6 0.5 8955 53.0
Plots : Fig. 4.7 U vs Mole Fraction; Fig. 4.10 πi vs Mole Fraction;
Fig. 4.8 κ vs Mole Fraction; Fig. 4.11 CE vs Mole Fraction;
Fig. 4.9 χU vs Mole Fraction;
113

TABLE 4.12

ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va), LENARD JONES POTENTIAL (LJP),
EXCESS ULTRASONIC VELOSITY (UE), EXCESS VISCOSITY (η
ηE), EXCESS ADIABATIC COMPRESSIBILITY (κ
κE),
EXCESS FREE LENGTH (LfE), EXCESS FREE VOLUME (VfE), EXCESS ACOUSTICAL IMPEDANCE (ZE) AND
EXCESS AVAILABLE VOLUME (VaE) VALUES AT VARIOUS MOLE FRACTIONS OF ETHANOL - PYRIDINE SYSTEM
Temperature : 303 K
Mole Fraction
of first Z /105 Va /10-5 LJP UE ηE /10-5 κE /10-12 VfE/10-8 LfE/10-13 ZE /105 VaE /10-6
Component (X1) kg-2s-1 m3 ms-1 Nsm-2 kg-1ms2 m3 m kg-2s-1 m3
0.000 13.7 1.4 33.4 - - - - - - -
0.133 11.6 1.6 29.1 13.0 -0.11 41.39 4.1 -28.4 -1.4 1.9
0.257 11.2 1.7 25.1 21.2 -0.14 18.29 3.1 -22.8 -1.2 1.9
0.372 10.8 1.7 22.2 30.1 -0.16 -0.64 2.3 -17.6 -1.1 1.7
0.479 10.5 1.7 19.5 34.6 -0.16 -11.31 1.2 -12.7 -1.0 1.6
0.580 10.1 1.7 17.2 38.7 -0.17 -15.76 0.8 -8.1 -0.9 1.5
0.674 9.7 1.7 15.4 41.9 -0.16 -17.13 0.5 -3.8 -0.8 1.2
0.763 9.3 1.8 13.3 38.1 -0.15 -2.91 0.3 0.2 -0.8 1.3
0.847 8.9 1.8 11.4 30.6 -0.14 21.93 0.3 4.0 -0.8 1.4
0.926 8.5 1.8 9.9 25.5 -0.13 46.03 0.8 7.6 -0.8 1.3
1.000 9.0 1.7 7.7 - - - - - - -

E
Plots : Fig.4.12 U vs Mole Fraction;
E
Fig.4.13 Z vs Mole Fraction;
Fig. 4.1 Plots of Ultrasonic Velocity vs Mole Fraction of first component

1300

1200
U, ms -1

1100

1000
BZ-CTC BBZ-CBZ
900
0.0 0.2 0.4 0.6 0.8 1.0
Mole Fraction of first component X1

Fig. 4.2 Plots of Adiabatic compressibility vs Mole Fraction of first


component

0.8
κ /10 , kg-1 ms 2

0.7
-9

0.6

BZ-CTC BBZ-CBZ
0.5
0.0 0.2 0.4 0.6 0.8 1.0
Mole Fraction of first component X1
115

Fig. 4.3 Plots of Molecular interaction parameter vs Mole Fraction of


first component

Temperature : 303 K
0
-20
-1

-40
χ U /10 , ms

-60
-3

-80
-100
BZ-CTC BBZ-CBZ
-120
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Mole Fraction of first component X 1

Fig. 4.4 Plots of Cohessive Energy vs Mole Fraction of first component

40

38
CE, kJ mol-1

36

34
BZ-CTC BBZ-CBZ
32
0.0 0.2 0.4 0.6 0.8 1.0
Mole Fraction of first component X1
116

Fig. 4.5 Plots of Excess Ultrasonic velocity vs Mole Fraction of first


component

Temperature : 303 K
0

-25
UE, ms -1

-50

BZ-CTC BBZ-CBZ
-75
0.0 0.2 0.4 0.6 0.8 1.0
Mole Fraction of first component X1

Fig. 4.6 Plots of Excess Acoustic impedance vs Mole Fraction of first


component

Temperature : 303 K
1

0
ZE /105, kg-2 s-1

-1

-2
BZ-CTC BBZ-CBZ
-3
0.0 0.2 0.4 0.6 0.8 1.0
Mole Fraction of first component X 1
117

Fig. 4.7 Plots of Ultrasonic Velocity vs Mole Fraction of first


components
Temperature : 303 K
1700
EL-Water
EL-PCL
EL-PL
EL-PYR
1500
U, ms -1

1300

1100
0.0 0.2 0.4 0.6 0.8 1.0
Mole Fraction of first component X1

Fig. 4.8 Plots of Adiabatic Compressibility vs Mole Fraction of first


components

1.2
EL-Water
EL-PCL
EL-PL
1.0
2
κ /10 , kg ms

EL-PYR
-1

0.8
-9

0.6

0.4
0.0 0.2 0.4 0.6 0.8 1.0
Mole Fraction of first component X1
118

Fig. 4.9 Plots of Molecular interaction parameter vs Mole Fraction of


first components

250
EL-Water
EL-PCL
200 EL-PL
EL-PYR
-1
χ U /10 , ms

150
-3

100

50

0
0.0 0.2 0.4 0.6 0.8 1.0
Mole Fraction of first component X1

Fig. 4.10 Plots of Internal Pressure vs Mole Fraction of first components

EL-Water
EL-PCL
22000 EL-PL
EL-PYR
17000
πi, atm

12000

7000

2000
0.0 0.2 0.4 0.6 0.8 1.0
Mole Fraction of first component X1
119

Fig. 4.11 Plots of Cohessive Energy vs Mole Fraction of first


components

130
EL-Water
EL-PCL
110 EL-PL
CE, kJ mol-1

EL-PYR
90

70

50

30
0.0 0.2 0.4 0.6 0.8 1.0
Mole Fraction of first component X1

Fig. 4.12 Plots of Excess Ultrasonic velocity vs Mole Fraction of first


components

160
EL-Water
EL-PCL
120 EL-PL
EL-PYR
UE, ms -1

80

40

0
0.0 0.2 0.4 0.6 0.8 1.0
Mole Fraction of first component X1
120

Fig. 4.13 Plots of Excess Acoustic impedance vs Mole Fraction of first


components

Temperature :303 K
0.0

-0.4
ZE /105, kg-2 s -1

-0.8

EL-Water
-1.2 EL-PCL
EL-PL
EL-PYR
-1.6
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Mole Fraction of first component X1
121

Chapter 5
122

CHAPTER – 5

DETERMINATION OF STABILITY CONSTANTS FOR THE


CHARGE TRANSFER COMPLEXES OF CERTAIN
HYDROCARBONS AND IODINE IN n-HEXANE SOLUTION
BY ULTRASONIC METHOD

5.1. INTRODUCTION

Aromatic hydrocarbons are rich in π-electron and favour the formation

of charge transfer complexes with electron deficient molecules. This may be

due to the intermolecular attractive forces or through dipole-dipole

interaction with electron deficient molecules. The halogenation reactions are

widely employed by synthetic organic chemists in the preparation of several

insecticides and pharmaceuticals1-5. Both kinetic and non-kinetic methods

have been employed to establish the mechanism of this reaction6-8. It has

been suggested that halogen combines with donor molecule to form donor-

acceptor complexes. There is equilibrium between the complex and the donor

and acceptor molecules involved in the complexation. Thus, the formation of

charge transfer complex is the first step in halogenation. These donor-

acceptor complexes are called π-complexes. The formation of π−complexes

with halogens and several homocyclic aromatic compounds have been well

established by UV spectroscopy9-11. Among halogens, iodine has basic

character and it can function as an effective electron acceptor. It may form

charge transfer complexes with electron donors like aromatic hydrocarbons12.


123

Polynuclear aromatic hydrocarbons (PAH) are potential carcinogens.

Among these, derivatives of anthracene, phenanthrene, benzo(a)pyrene are

the most health hazardous chemicals. Studies in the fresh water trout

demonstrated that trout liver microsomes actively biotransformed PAH

carcinogens into a variety of electrophilic metabolites and catalysed binding of

activated PAH molecule to DNA13. Carcinogenic polycyclic aromatic

hydrocarbons are thus metabolically activated and bind covalently to DNA,

RNA and protein in systems in which they induce biological effects14. In both

mouse skin and rodent embryo cell cultures, the carcinogenic activity of a

hydrocarbon is directly correlated with the amount of the hydrocarbon bond

to DNA and to a specific protein, namely, the h-protein15.

Recently, ultrasound has been used to detect donor-acceptor complexes

in solutions. Bhatt and co-workers16,17 have determined formation or stability

constants of charge transfer complexes by ultrasonic method. The limitation

of this method is that it can be applied to binary systems in moderate

concentrations. Further, the formation constants were found to be

concentration dependent18. Based on the assumptions of Marwein and Bhatt,

Kannappan et al19-21 showed that the deviation from ideal behaviour of any

physical properties is due to charge transfer complex formed. They deduced

the equation to calculate formation constants of charge transfer (CT)

complexes even in dilute solutions containing the donor and acceptor in non-
124

polar solvents. They applied this equation to a large number of donor-

acceptor complexes22-24.

This chapter contains the results obtained in the investigation of

charge transfer complexes of iodine (acceptor) and six monocyclic aromatic

hydrocarbons and three polynuclear aromatic hydrocarbons (donors) in n-

hexane solution at 303 K. Here, the positive end of iodine dipole polarizes the

π-electron cloud of the polynuclear aromatic hydrocarbons25-33. The six

monocyclic aromatic hydrocarbons used as donors are mesitylene, o-xylene,

m-xylene, p-xylene, benzene and toluene while the three polynuclear aromatic

hydrocarbons are anthracene, biphenyl and naphthalene. The structures of

these donor molecules are given below.

CH3 CH3
CH3

H 3C CH3
CH3 CH3
Mesitylene p - Xylene m - Xylene

CH3
CH3
CH3

o - Xylene Benzene Toluene


125

Anthracene Biphenyl Naphthalene

The acoustical parameters such as adiabatic compressibility (κ),

absorption coefficient (α/f2), molecular interaction parameter (χU), relaxation

time (τ), free length (Lf), free volume (Vf), internal pressure (πi), cohesive energy

(CE), acoustic impedance (Z), available volume (Va), Lenard Jones Potential

(LJP) and Gibb’s free energy of activation (∆G#) are calculated at various

concentrations. The interactions between the donor and acceptor molecules

have been studied from the variation of acoustical parameters with the

concentration of donor. The stability constant (K) values are calculated for all

the nine systems in n-hexane at 303 K. From the calculated values of K, the

free energies of formation (∆G) are computed to ascertain their

thermodynamic stability.

5.2. Results and Discussion

The ultrasonic velocities (U), densities (ρ) and viscosities are determined

for n-hexane solutions containing equimolar concentrations of iodine and

each of six homocylic hydrocarbons namely, mesitylene, p-xylene, m-xylene,

o-xylene, toluene and benzene at 303 K. Tables 5.1 - 5.12 contain the

calculated acoustical parameters for the following systems. Plots of ultrasonic

velocity vs concentration for all the six systems are given in Fig. 5.1. It is
126

evident from these plots that ultrasonic velocity (U) increases in all the

systems uniformly with increase in concentration except in mesitylene and

m-xylene systems. The increasing trend in ultrasonic velocity suggests that

the complexation increases with increase in concentration. In the case of

mesitylene and m-xylene even at lower concentration, the complexation is

significant. The measured values of ultrasonic velocity, density and viscosity

values for the three polynuclear hydrocarbons are presented in Tables 5.13 –

5.18 and the corresponding plots are given in Fig. 5.6. The ultrasonic velocity

decreases with increase in concentration in the case of biphenyl and

naphthalene. This shows that the complexation is significant even at lower

concentration in these two systems. In the case of anthracene, the ultrasonic

velocity is found to be a minimum in the concentration range 0.004 and

0.008M. Thus, the donor-acceptor complex formation is significant in this

concentration range for this system.

The adiabatic compressibility (κ) and free length (Lf) values for the nine

systems are calculated at different concentrations and are given in

Tables 5.1 – 5.18. In a given system, the adiabatic compressibility and free

length values generally remain constant at lower concentrations and

increases slightly at moderate concentrations. The same trend is followed in

all the six monocyclic hydrocarbon systems which are given in Fig. 5.2. The

slight increase in the values of adiabatic compressibility and free length at

higher concentration may be due to the formation of charge transfer


127

complexes. In the case of polynuclear hydrocarbons, for iodine-anthracene

system, the adiabatic compressibility values are least at lower and higher

concentrations which indicates that the complexation is maximum in those

concentrations. For iodine-biphenyl system, the adiabatic compressibility

increases with increase in concentration, which shows that complexation is

maximum at lower concentrations. But the adiabatic compressibility values

remain almost constant in the case of iodine-naphthalene system. The plots

are given in Fig. 5.7. The values of adiabatic compressibility and free length of

pure components are given in Table 5.20. There is a weak bond between the

donor and acceptor molecules. Hence, the compressibility of charge transfer

complex is slightly greater than that of pure component. It may be pointed

out here that the compressibility coefficient in the concentration range

studied for almost all the systems are slightly greater than that of n-hexane.

This also confirms the formation of a weak complex between iodine and

aromatic hydrocarbons. This is also supported by the higher free length

values in all the systems compared to the free length in pure components.

Further, both adiabatic compressibility and free length values of all the

systems are almost constant at the concentrations investigated. This suggests

that similar types of complexes are formed in these systems.

The molecular interaction parameter (χU) in respect of ultrasonic

velocity values are calculated for six monocyclic aromatic systems and the

values are presented in Tables 5.1, 5.3, 5.5, 5.7, 5.9 and 5.11. Plots of
128

molecular interaction parameter vs concentration for the aromatic monocyclic

systems are given in Fig. 5.3 while Fig. 5.8 contains similar plots for iodine–

polynuclear hydrocarbon systems. It is found that molecular interaction

parameter values are large negative for iodine-mesitylene and iodine-p-xylene

systems indicating that the extent of deviation from ideal behaviour is more

in these two systems which may probably due to complex formation. The

interaction parameter values are either positive or small negative depending

upon concentration in the iodine-m-xylene and iodine-o-xylene systems.

Relatively weaker interactions persist between donor and acceptor molecules

in these two systems and they are concentration dependent. In iodine-

benzene and iodine-toluene systems, the molecular interaction parameter

values are positive indicating a positive deviation in these two systems.

Further, relatively weak interactions are present in these two systems. It may

be pointed out that the molecular interaction parameter values are large

positive in iodine-biphenyl system, small positive in iodine-naphthalene

system and the values are both positive and negative in iodine-anthracene

system. This suggests that iodine forms a strong complex with anthracene.

The absorption coefficient (α/f2) and relaxation time (τ) values are

characteristic of the species present in solution. These values are given for

the nine systems in Tables 5.1, 5.3, 5.5, 5.7, 5.9, 5.11, 5.13, 5.15 and 5.17.

The constant values indicate that similar types of molecular interactions

between the donor and acceptor are present in these nine systems and
129

similar types of charge transfer complexes are formed in all the nine systems

investigated.

The values of free volume (Vf), acoustic impedance (Z) and available

volume (Va) are given in Tables 5.2, 5.4, 5.6, 5.8, 5.10, 5.12, 5.14, 5.16 and

5.18. These are characteristic of the charge transfer complexes in the system

investigated. These are calculated from ultrasonic velocity and viscosity

values. It is found that the free volume and available volume do not change

significantly in these nine systems. Thus, complexation between iodine and

aromatic hydrocarbons does not influence available volume and free volume

values.

The internal pressure (πi) values for the six monocyclic hydrocarbons

are calculated and listed in Tables 5.2, 5.4, 5.6, 5.8, 5.10, and 5.12. The

internal pressure is a measure of cohesive forces between the component

molecules. The internal pressure values are generally found to decrease with

increase in concentration and then start increasing. Thus, the acceptor

polarizes the donor molecules at lower concentration and form complexes at

moderate concentrations. The plots of internal pressure vs concentration is

given in Fig. 5.4. The variation of internal pressure with concentration for

polynuclear aromatic hydrocarbons indicates that the complexation is

significant even at lower concentration as indicated by the high values of

internal pressure in these systems. Tables 5.14, 5.16 and 5.18 give the values
130

of internal pressure for the polynuclear aromatic hydrocarbons. The

corresponding plots are given in Fig. 5.9. The acoustic impedance (Z) is

almost constant (Tables 5.2, 5.4, 5.6, 5.8, 5.10, 5.12, 5.14, 5.16 and 5.18) for

all the systems and does not vary significantly with concentration. This

suggests the existence of similar type of complexes in these systems.

The cohesive energy (CE) in liquid mixtures is an indicative of the force

of attraction between the component molecules. These values for the six

monocyclic systems are given in Tables 5.2, 5.4, 5.6, 5.8, 5.10 and 5.12, and

their corresponding plots are given in Fig. 5.5. The cohesive energy values are

found to be almost constant for a given system indicating similar type of

cohesive forces in that system. However, it varies slightly from one system to

another depending upon the strength of molecular interactions. The cohesive

energy is found to be almost constant for iodine-anthracene and iodine-

naphthalene, where it is found to decrease in the case of iodine-biphenyl

system with concentration. These values are given in Tables 5.14, 5.16 and

5.18 and the corresponding plots are given in Fig. 5.10. Thus, the cohesive

energy values in the nine systems also suggest the complexation between

iodine and aromatic hydrocarbons.

The formation constant (K) is a measure of stability of charge transfer

complex. The formation constant values are calculated for the nine systems

and the mean values are presented in Table 5.19. The formation constant
131

values are calculated from the ultrasonic velocities. It may be noted that the

stability constant values are constant at different concentrations for a

particular system. The free energy of formation values are also computed

from the stability constant values and they are also listed in Table 5.19. It is

found that the formation constant values for these complexes are influenced

by the structure of the donor molecules. In general, the formation constant

values for polycyclic aromatic hydrocarbon are greater than those for

benzenoid systems. This is justified because, polynuclear aromatic

hydrocarbons are richer in π-electrons than monocyclic benzene derivatives

and the former can function as more effective π-electron donor than the

monocyclic aromatic hydrocarbons. Among the benzene derivatives,

mesitylene forms more stable complex with iodine than other monocyclic

aromatic hydrocarbons. This is due to the presence of three electron releasing

methyl substituents in this molecule. Similarly, xylenes also form relatively

more stable complexes with iodine than benzene and toluene. Among xylenes,

o-xylene forms a less stable complex than the other two isomeric xylenes

which may be due to steric reason. Among polynuclear aromatic

hydrocarbons, biphenyl and naphthalene contain less π-electron density and

they form less stable charge transfer complexes with iodine than with

anthracene.
132

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33. Kothai, S., Ph.D. Thesis, University of Madras, 2003.


TABLE 5.1

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
2
ABSORPTION COEFFICIENT (α α/f ), MOLECULAR INTERACTION PARAMETER (χ χ U)
AND RELAXATION TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE - MESITYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 τ /10-13


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s

0.001 1050.8 634.6 3.27 1.43 11.7 -14.3 6.2


0.002 1056.6 635.0 3.27 1.41 11.5 -3.5 6.2
0.003 1054.0 635.6 3.27 1.42 11.6 -8.6 6.2
0.004 1050.0 633.9 3.28 1.43 11.7 -16.2 6.3
0.005 1048.5 634.1 3.27 1.43 11.8 -19.2 6.3
0.006 1048.9 634.3 3.27 1.43 11.7 -18.6 6.2
0.007 1049.7 633.3 3.30 1.43 11.8 -17.3 6.3
0.008 1049.1 637.2 3.29 1.43 11.7 -18.6 6.2
0.009 1048.9 634.4 3.29 1.43 11.8 -19.1 6.3
0.010 1047.6 633.9 3.28 1.44 11.8 -21.7 6.3

Plots : Fig. 5.1 U vs Concentration; Fig. 5.3 χU vs Concentration;


Fig. 5.2 κ vs Concentration;
135

TABLE 5.2

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va) AND LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE - MESITYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C Lf Vf /10-7 πi CE Z /105 Va /10-5 LJP


M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 5.2 2349 32.3 6.7 4.7 4.5
0.002 0.7 5.3 2341 32.2 6.7 4.6 4.7
0.003 0.7 5.2 2346 32.3 6.7 4.6 4.6
0.004 0.8 5.2 2347 32.4 6.7 4.7 4.5
0.005 0.8 5.2 2347 32.4 6.6 4.7 4.4
0.006 0.8 5.2 2344 32.3 6.7 4.7 4.4
0.007 0.8 5.1 2352 32.5 6.6 4.7 4.4
0.008 0.7 5.2 2356 32.4 6.7 4.7 4.4
0.009 0.8 5.2 2349 32.4 6.7 4.7 4.4
0.010 0.8 5.2 2345 32.4 6.6 4.7 4.4

Plots : Fig. 5.4 πi vs Concentration;


Fig. 5.5 CE vs Concentration;
136

TABLE 5.3

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
2
ABSORPTION COEFFICIENT (α α/f ), MOLECULAR INTERACTION PARAMETER (χ χ U)
AND RELAXATION TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE - PARA XYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10 -4
κ /10 -9 2
α/f /10 -15
χU /10-3 τ /10-13
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s

0.001 1050.4 636.4 3.32 1.42 11.8 -15.0 6.3


0.002 1052.8 636.6 3.32 1.42 11.7 -10.7 6.3
0.003 1053.1 636.9 3.30 1.42 11.7 -10.3 6.2
0.004 1053.5 635.9 3.30 1.42 11.7 -9.7 6.2
0.005 1054.3 635.6 3.29 1.42 11.6 -8.3 6.2
0.006 1053.5 637.1 3.30 1.41 11.7 -10.0 6.2
0.007 1054.1 634.9 3.28 1.42 11.6 -9.0 6.2
0.008 1053.1 638.2 3.30 1.41 11.6 -11.1 6.2
0.009 1055.4 635.8 3.31 1.41 11.6 -6.9 6.2
0.010 1057.2 635.4 3.31 1.41 11.6 -3.7 6.2

Plots : Fig. 5.1 U vs Concentration; Fig. 5.3 χU vs Concentration;


Fig. 5.2 κ vs Concentration;
137

TABLE 5.4

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va) AND LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE - PARA XYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C Lf Vf /10-7 πi CE Z /105 Va /10-5 LJP


M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 5.1 2370 32.5 6.7 4.7 4.5
0.002 0.7 5.1 2366 32.5 6.7 4.6 4.5
0.003 0.7 5.2 2360 32.4 6.7 4.6 4.6
0.004 0.7 5.2 2357 32.4 6.7 4.6 4.6
0.005 0.7 5.2 2350 32.3 6.7 4.6 4.6
0.006 0.7 5.2 2358 32.4 6.7 4.6 4.6
0.007 0.7 5.2 2344 32.3 6.7 4.6 4.6
0.008 0.7 5.2 2358 32.3 6.7 4.6 4.6
0.009 0.7 5.2 2352 32.4 6.7 4.6 4.6
0.010 0.7 5.2 2350 32.4 6.7 4.6 4.7

Plots : Fig. 5.4 πi vs Concentration;


Fig. 5.5 CE vs Concentration;
138

TABLE 5.5

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
2
ABSORPTION COEFFICIENT (α α/f ), MOLECULAR INTERACTION PARAMETER (χ χ U)
AND RELAXATION TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE - META XYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 τ /10-13


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s

0.001 1057.2 636.8 3.37 1.41 11.8 -2.2 6.3


0.002 1061.2 636.8 3.37 1.39 11.7 5.2 6.3
0.003 1057.8 637.6 3.36 1.40 11.7 -1.4 6.3
0.004 1058.5 636.1 3.36 1.40 11.7 -0.2 6.3
0.005 1058.3 635.8 3.36 1.40 11.7 -0.8 6.3
0.006 1058.1 637.0 3.36 1.40 11.7 -1.3 6.3
0.007 1056.1 635.4 3.34 1.41 11.7 -5.2 6.3
0.008 1052.4 638.8 3.38 1.41 11.9 -12.3 6.4
0.009 1052.5 636.4 3.37 1.42 11.9 -12.3 6.4
0.010 1050.8 635.4 3.36 1.43 12.0 -15.6 6.4

Plots : Fig. 5.1 U vs Concentration; Fig. 5.3 χU vs Concentration;


Fig. 5.2 κ vs Concentration;
139

TABLE 5.6

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va) AND LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE - META XYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C Lf Vf /10-7 πi CE Z /105 Va /10-5 LJP


M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 5.0 2382 32.7 6.7 4.6 4.7
0.002 0.7 5.0 2377 32.6 6.8 4.6 4.8
0.003 0.7 5.0 2379 32.6 6.7 4.6 4.7
0.004 0.7 5.1 2372 32.6 6.7 4.6 4.7
0.005 0.7 5.1 2372 32.6 6.7 4.6 4.7
0.006 0.7 5.1 2374 32.6 6.7 4.6 4.7
0.007 0.7 5.1 2364 32.5 6.7 4.6 4.7
0.008 0.7 5.0 2388 32.7 6.7 4.6 4.5
0.009 0.7 5.0 2378 32.7 6.7 4.6 4.5
0.010 0.7 5.0 2376 32.7 6.7 4.7 4.5

Plots : Fig. 5.4 πi vs Concentration;


Fig. 5.5 CE vs Concentration;
140

TABLE 5.7

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
2
ABSORPTION COEFFICIENT (α α/f ), MOLECULAR INTERACTION PARAMETER (χ χ U)
AND RELAXATION TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE - ORTHO XYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 τ /10-13


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s

0.001 1058.0 637.5 3.36 1.40 11.7 -0.7 6.3


0.002 1058.8 637.2 3.35 1.40 11.6 0.6 6.2
0.003 1063.4 637.1 3.36 1.39 11.5 9.2 6.2
0.004 1059.2 637.1 3.35 1.40 11.6 1.1 6.3
0.005 1056.0 637.8 3.37 1.41 11.8 -5.1 6.3
0.006 1058.0 636.5 3.38 1.40 11.8 -1.5 6.3
0.007 1060.0 636.7 3.38 1.40 11.7 2.1 6.3
0.008 1061.2 637.1 3.38 1.39 11.7 4.2 6.3
0.009 1062.4 635.9 3.36 1.39 11.6 6.3 6.2
0.010 1058.8 638.7 3.39 1.40 11.7 -0.7 6.3

Plots : Fig. 5.1 U vs Concentration; Fig. 5.3 χU vs Concentration;


Fig. 5.2 κ vs Concentration;
141

TABLE 5.8

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va) AND LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE - ORTHO XYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C Lf Vf /10-7 πi CE Z /105 Va /10-5 LJP


M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 5.1 2378 32.6 6.7 4.6 4.7
0.002 0.7 5.1 2372 32.5 6.7 4.6 4.7
0.003 0.7 5.1 2370 32.5 6.8 4.5 4.9
0.004 0.7 5.1 2371 32.5 6.7 4.6 4.8
0.005 0.7 5.0 2381 32.6 6.7 4.6 4.6
0.006 0.7 5.0 2381 32.7 6.7 4.6 4.7
0.007 0.7 5.0 2376 32.6 6.7 4.6 4.8
0.008 0.7 5.0 2377 32.6 6.8 4.6 4.8
0.009 0.7 5.1 2365 32.6 6.8 4.6 4.9
0.010 0.7 5.0 2383 32.7 6.8 4.6 4.7

Plots : Fig. 5.4 πi vs Concentration;


Fig. 5.5 CE vs Concentration;
142

TABLE 5.9

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
2
ABSORPTION COEFFICIENT (α α/f ), MOLECULAR INTERACTION PARAMETER (χ χ U)
AND RELAXATION TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE - TOLUENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 τ /10-13


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s

0.001 1059.6 637.3 3.41 1.40 11.8 2.3 6.3


0.002 1061.7 636.4 3.40 1.39 11.7 6.1 6.3
0.003 1061.2 637.7 3.38 1.39 11.6 5.0 6.3
0.004 1060.1 637.5 3.37 1.40 11.7 2.8 6.3
0.005 1061.5 635.6 3.35 1.40 11.6 5.3 6.2
0.006 1064.9 638.2 3.36 1.38 11.5 11.6 6.2
0.007 1066.2 637.4 3.37 1.38 11.5 13.9 6.2
0.008 1064.5 637.1 3.36 1.39 11.5 10.5 6.2
0.009 1062.4 638.6 3.38 1.39 11.6 6.4 6.3
0.010 1062.6 637.2 3.36 1.39 11.6 6.6 6.2

Plots : Fig. 5.1 U vs Concentration; Fig. 5.3 χU vs Concentration;


Fig. 5.2 κ vs Concentration;
143

TABLE 5.10

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va) AND LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE - TOLUENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C Lf Vf /10-7 πi CE Z /105 Va /10-5 LJP


M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 5.0 2393 32.8 6.8 4.6 4.8
0.002 0.7 5.0 2386 32.7 6.8 4.6 4.8
0.003 0.7 5.0 2380 32.6 6.8 4.6 4.8
0.004 0.7 5.1 2377 32.6 6.8 4.6 4.8
0.005 0.7 5.1 2363 32.5 6.7 4.6 4.8
0.006 0.7 5.1 2370 32.5 6.8 4.5 4.9
0.007 0.7 5.1 2369 32.5 6.8 4.5 5.0
0.008 0.7 5.1 2364 32.5 6.8 4.5 4.9
0.009 0.7 5.1 2378 32.6 6.8 4.5 4.9
0.010 0.7 5.1 2366 32.5 6.8 4.6 4.9

Plots : Fig. 5.4 πi vs Concentration;


Fig. 5.5 CE vs Concentration;
144

TABLE 5.11

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
2
ABSORPTION COEFFICIENT (α α/f ), MOLECULAR INTERACTION PARAMETER (χ χ U)
AND RELAXATION TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE - BENZENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 τ /10-13


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s

0.001 1058.1 639.4 3.41 1.40 11.8 -0.5 6.3


0.002 1059.2 638.2 3.40 1.40 11.8 1.4 6.3
0.003 1058.4 638.7 3.40 1.40 11.8 -0.3 6.3
0.004 1058.9 637.8 3.39 1.40 11.8 0.5 6.3
0.005 1061.1 637.9 3.37 1.39 11.6 4.5 6.3
0.006 1064.4 639.8 3.37 1.38 11.5 10.6 6.2
0.007 1059.7 639.7 3.40 1.39 11.8 1.6 6.3
0.008 1067.7 640.1 3.36 1.37 11.3 16.6 6.1
0.009 1068.1 638.7 3.36 1.37 11.4 17.2 6.1
0.010 1068.0 638.7 3.37 1.37 11.4 16.9 6.2

Plots : Fig. 5.1 U vs Concentration; Fig. 5.3 χU vs Concentration;


Fig. 5.2 κ vs Concentration;
145

TABLE 5.12

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va) AND LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE - BENZENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C Lf Vf /10-7 πi CE Z /105 Va /10-5 LJP


M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 4.9 2401 32.8 6.8 4.6 4.7
0.002 0.7 5.0 2393 32.8 6.8 4.6 4.8
0.003 0.7 5.0 2394 32.7 6.8 4.6 4.7
0.004 0.7 5.0 2386 32.7 6.8 4.6 4.7
0.005 0.7 5.1 2378 32.6 6.8 4.6 4.8
0.006 0.7 5.1 2377 32.5 6.8 4.5 4.9
0.007 0.7 5.0 2394 32.7 6.8 4.6 4.8
0.008 0.7 5.1 2370 32.4 6.8 4.5 5.0
0.009 0.7 5.1 2366 32.4 6.8 4.5 5.0
0.010 0.7 5.1 2368 32.4 6.8 4.5 5.0

Plots : Fig. 5.4 πi vs Concentration;


Fig. 5.5 CE vs Concentration;
146

TABLE 5.13

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
2
ABSORPTION COEFFICIENT (α α/f ), MOLECULAR INTERACTION PARAMETER (χ χ U)
AND RELAXATION TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE - ANTHRACENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 τ /10-13


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s

0.001 1060.3 638.3 3.37 1.39 11.6 3.4 6.3


0.002 1060.0 639.1 3.39 1.39 11.7 2.4 6.3
0.003 1060.2 637.3 3.39 1.40 11.7 2.4 6.3
0.004 1056.9 636.5 3.41 1.41 11.9 -4.2 6.4
0.005 1061.2 638.1 3.41 1.39 11.8 3.5 6.3
0.006 1060.3 636.1 3.39 1.40 11.8 1.4 6.3
0.007 1059.2 636.9 3.38 1.40 11.8 -1.0 6.3
0.008 1058.0 635.4 3.38 1.41 11.8 -3.7 6.3
0.009 1061.6 639.3 3.39 1.39 11.6 2.7 6.3
0.010 1060.8 639.5 3.41 1.39 11.8 0.8 6.3

Plots : Fig. 5.6 U vs Concentration; Fig. 5.8 χU vs Concentration;


Fig. 5.7 κ vs Concentration;
147

TABLE 5.14

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va) AND LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE - ANTHRACENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C Lf Vf /10-7 πi CE Z /105 Va /10-5 LJP


M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 5.0 2382 32.6 6.8 4.6 4.8
0.002 0.7 5.0 2391 32.7 6.8 4.6 4.8
0.003 0.7 5.0 2383 32.7 6.8 4.6 4.8
0.004 0.7 4.9 2393 32.9 6.7 4.6 4.7
0.005 0.7 5.0 2391 32.8 6.8 4.6 4.8
0.006 0.7 5.0 2377 32.7 6.7 4.6 4.8
0.007 0.7 5.0 2377 32.7 6.7 4.6 4.8
0.008 0.7 5.0 2371 32.7 6.7 4.6 4.7
0.009 0.7 5.0 2380 32.6 6.8 4.6 4.8
0.010 0.7 5.0 2389 32.7 6.8 4.6 4.8

Plots : Fig. 5.9 πi vs Concentration;


Fig. 5.10 CE vs Concentration;
148

TABLE 5.15

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
2
ABSORPTION COEFFICIENT (α α/f ), MOLECULAR INTERACTION PARAMETER (χ χ U)
AND RELAXATION TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE - BIPHENYL SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 τ /10-13


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s

0.001 1088.1 679.7 3.78 1.24 11.3 56.9 6.3


0.002 1086.2 679.6 3.74 1.25 11.3 53.0 6.2
0.003 1084.4 679.3 3.74 1.25 11.4 49.2 6.2
0.004 1082.0 677.1 3.75 1.26 11.5 44.4 6.3
0.005 1079.6 675.1 3.67 1.27 11.4 39.5 6.2
0.006 1077.3 674.6 3.65 1.28 11.4 34.9 6.2
0.007 1075.3 665.7 3.52 1.30 11.2 30.8 6.1
0.008 1072.8 666.7 3.55 1.30 11.3 25.8 6.2
0.009 1070.1 667.7 3.56 1.31 11.4 20.4 6.2
0.010 1065.7 668.0 3.54 1.32 11.5 11.8 6.2

Plots : Fig. 5.6 U vs Concentration; Fig. 5.8 χU vs Concentration;


Fig. 5.7 κ vs Concentration;
149

TABLE 5.16

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va) AND LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE - BIPHENYL SYSTEM

Solvent : n-hexane Temperature : 303 K

C Lf Vf /10-7 πi CE Z /105 Va /10-5 LJP


M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 4.4 2596 33.3 7.4 4.1 5.8
0.002 0.7 4.5 2585 33.2 7.4 4.1 5.7
0.003 0.7 4.5 2585 33.3 7.4 4.1 5.6
0.004 0.7 4.4 2583 33.4 7.3 4.1 5.5
0.005 0.7 4.6 2553 33.1 7.3 4.2 5.4
0.006 0.7 4.6 2547 33.0 7.3 4.2 5.4
0.007 0.7 4.8 2481 32.6 7.2 4.3 5.3
0.008 0.7 4.8 2496 32.8 7.2 4.3 5.2
0.009 0.7 4.7 2501 32.8 7.1 4.3 5.1
0.010 0.7 4.8 2499 32.8 7.1 4.3 5.0

Plots : Fig. 5.9 πi vs Concentration;


Fig. 5.10 CE vs Concentration;
150

TABLE 5.17

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
2
ABSORPTION COEFFICIENT (α α/f ), MOLECULAR INTERACTION PARAMETER (χ χ U)
AND RELAXATION TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE - NAPHTHALENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 τ /10-13


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s

0.001 1058.8 664.1 3.51 1.34 11.7 0.7 6.3


0.002 1064.3 665.2 3.53 1.33 11.6 10.8 6.3
0.003 1064.7 665.6 3.52 1.33 11.5 11.3 6.2
0.004 1064.4 665.8 3.53 1.33 11.6 10.4 6.2
0.005 1064.9 665.9 3.51 1.32 11.5 11.1 6.2
0.006 1064.8 666.0 3.51 1.32 11.5 10.7 6.2
0.007 1065.1 666.1 3.50 1.32 11.4 10.9 6.2
0.008 1061.2 666.7 3.49 1.33 11.5 3.3 6.2
0.009 1065.8 667.4 3.52 1.32 11.5 11.7 6.2
0.010 1063.2 666.6 3.51 1.33 11.5 6.5 6.2

Plots : Fig. 5.6 U vs Concentration; Fig. 5.8 χU vs Concentration;


Fig. 5.7 κ vs Concentration;
151

TABLE 5.18

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va) AND LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE - NAPHTHALENE SYSTEM

Solvent : n-hexane Temperature : 303 K

C Lf Vf /10-7 πi CE Z /105 Va /10-5 LJP


M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 4.7 2497 32.8 7.0 4.4 4.7
0.002 0.7 4.7 2501 32.8 7.1 4.3 4.9
0.003 0.7 4.8 2496 32.8 7.1 4.3 4.9
0.004 0.7 4.7 2499 32.8 7.1 4.3 4.9
0.005 0.7 4.8 2492 32.7 7.1 4.3 4.9
0.006 0.7 4.8 2492 32.7 7.1 4.3 4.9
0.007 0.7 4.8 2488 32.7 7.1 4.3 4.9
0.008 0.7 4.8 2489 32.7 7.1 4.4 4.8
0.009 0.7 4.8 2494 32.7 7.1 4.3 5.0
0.010 0.7 4.8 2489 32.7 7.1 4.4 4.9

Plots : Fig. 5.9 πi vs Concentration;


Fig. 5.10 CE vs Concentration;
152

TABLE 5.19

MEAN VALUES OF GIBB'S FREE ENERGY OF FORMATION (∆G), MEAN VALUES OF


GIBB'S FREE ENERGY OF ACTIVATION (∆G#) AND MEAN VALUES FORMATION CONSTANT (K)
OF HYDROCARBON COMPOUNDS WITH IODINE IN n-HEXANE SOLUTIONS

Solvent : n-hexane Temperature : 303 K


#
∆G ∆G K
Donor kJ mol-1 kJ mol-1 dm mol-1
-3

Mesitylene -9.5 3.8 44.9


p-Xylene -9.5 3.8 43.0
m-Xylene -9.1 3.8 37.6
o-Xylene -8.8 3.8 32.7
Toluene -8.5 3.8 28.7
Benzene -8.2 3.8 25.5
Anthracene -10.2 3.8 58.3
Biphenyl -9.3 3.8 41.1
Naphthalene -8.6 3.8 30.7
153

TABLE 5.20

ADIABATIC COMPRESSIBILITY (κ) AND FREE LENGTH (Lf) OF PURE COMPONENTS

Temperature : 303 K
component κ /10-9 Lf
kg-1ms2 Ao

n-Hexane 1.35 0.73


Mesitylene 0.67 0.51
p-Xylene 0.66 0.51
m-Xylene 0.69 0.52
o-Xylene 0.65 0.51
Toluene 0.69 0.52
Benzene 0.68 0.52
Anthracene 0.16 0.41
Biphenyl 0.42 0.25
Naphthalene 0.27 0.33
Fig. 5.1 Plots of Ultrasonic velocity vs Concentration

Solvent : n-hexane Temperature : 303 K


1070
IO-MST IO-PXL
IO-MXL IO-OXL
IO-BZ IO-TL
1065

1060
U, m s -1

1055

1050

1045
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M

Fig. 5.2 Plots of Adiabatic compressibility vs Concentration

Solvent : n-hexane Temperature : 303 K


1.45
1.44
1.43
1.42
2
κ /10 , kg ms

1.41
-1

1.40
-9

1.39
1.38
IO-MST IO-PXL
1.37 IO-MXL IO-OXL
IO-BZ IO-TL
1.36
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M
155

Fig. 5.3 Plots of Molecular interaction parameter vs Concentration

Solvent : n-hexane Temperature : 303 K


20.0
IO-MST IO-PXL
15.0 IO-MXL IO-OXL
IO-BZ IO-TL
10.0
5.0
-1
χ U /10 , ms

0.0
-3

-5.0
-10.0
-15.0
-20.0
-25.0
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M

Fig. 5.4 Plots of Internal pressure vs Concentration

Solvent : n-hexane Temperature : 303 K


2410
IO-MST IO-PXL IO-MXL
2400 IO-OXL IO-BZ IO-TL

2390

2380
πi , atm

2370

2360
2350

2340
2330
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M
156

Fig. 5.5 Plots of Cohessive energy vs Concentration

Solvent : n-hexane Temperature : 303 K


32.9

32.8

32.7

32.6
CE, kJ mol-1

32.5

32.4

32.3
IO-MST IO-PXL
32.2 IO-MXL IO-OXL
IO-BZ IO-TL
32.1
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M

Fig. 5.6 Plots of Ultrasonic velocity vs Concentration

Solvent : n-hexane Temperature : 303 K


1090
IO-ANT
1085 IO-BIP
IO-NAP
1080

1075
U, ms -1

1070

1065

1060

1055
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M
157

Fig. 5.7 Plots of Adiabatic compressibility vs Concentration

Solvent : n-hexane Temperature : 303 K


1.43
2
κ /10 , kg ms
-1

1.31
-9

IO-ANT
IO-BIP
IO-NAP
1.19
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M

Fig. 5.8 Plots of Molecular interaction parameter vs Concentration

Solvent : n-hexane Temperature : 303 K


60
IO-ANT
50 IO-BIP
IO-NAP
40
-1
χ U/10 , ms

30
-3

20

10
0

-10
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M
158

Fig. 5.9 Plots of Internal pressure vs Concentration

Solvent : n-hexane Temperature : 303 K


2600
IO-ANT
IO-BIP
2550 IO-NAP

2500
πi , atm

2450

2400

2350
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M

Fig. 5.10 Plots of Cohessive energy vs Concentration

Solvent : n-hexane Temperature : 303 K


33.6
IO-ANT
IO-BIP
IO-NAP

33.2
-1
CE, kJ mol

32.8

32.4
0.000 0.002 0.004 0.006 0.008 0.010

Concentration, M
159

Chapter 6
160

CHAPTER – 6

DETERMINATION OF STABILITY CONSTANTS OF CHARGE


TRANSFER COMPLEXES BETWEEN IODINE
MONOCHLORIDE AND CERTAIN AROMATIC
HYDROCARBONS IN n-HEXANE

6.1. INTRODUCTION

Ultrasound has been used to detect donor-acceptor complexes in

solution1,2. Prakash et al3 have determined stability constants of charge

trasfer complexes by ultrasonic methods. Jaya Santhi2 used ultrasound to

determine the stability constants of donor-acceptor complexes between

carbonyl compounds and tetrachloroethylene in n-hexane solution.

Kannappan et al have investigated the interactions in charge transfer

complexes of chloroform and carboxyl compounds in sloution.

The donor-acceptor complex formation is biologically important. Oxygen

transfer in blood involves reversible complexation between haeme and

oxygen. It has been suggested that the carcinogenic activity of certain

chemicals is due to the complexes formed between these chemicals and DNA

and consequent occurrence of DNA repairs result in the formation of

cancerous cell4,5. Bacteria obtain energy to grow by transforming electrons

from donor to acceptor. These microorganisms get energy through their

cellular machinery. The complexation reactions are of interest not only


161

because they allow organisms to obtain energy, but also because they involve

in the natural biodegradation of organic contaminants6,7. Kannappan and

Kothai8-11 have made investigation on charge transfer complexes formed

using iodine as acceptor.

Iodine monochloride is an important interhalogen compound. It is

mainly used as iodinating agent and in the determination of iodine value of oil

under the trade name Wijs’ solution. It is a polar compound and iodine is the

positive end of the dipole. It acts as a Lewis acid and forms additional

products with olefins12. It is a dark brown liquid and it is highly corrosive,

although it is neither a potential carcinogen nor a suspected carcinogen. It

was once used in small doses to cure pregnancy goitre but as it was proved to

be fatal in few cases, it was abandoned13. It can be used to synthesise iodo

compounds from alkenes and it is also used as an iodinating agent for

aromatic compounds, in which iodine monochloride acts as an electrophile.

In both the addition and substitution reactions, it is suggested that a

transient intermediate, namely, π complex is formed. The formation of such π

complexes has been detected in typical cases14. Recently, Al Mokhtar

Lambabhi et al have detected several charge transfer complexes formed

between iodine monochloride and carbonyl compounds by ultraviolet

spectroscopic method15. Equilibrium constants and Gibb’s energy changes for

the formation of 1:1 charge transfer complexes were also determined with a

view to compare the basicity of the carbonyl compounds. They also found that
162

the basicity of carbonyl compounds towards iodine monochloride is enhanced

with respect to that exhibited towards iodine. As a consequence, the

substituent’s effect on the Gibb’s energy is twice larger in iodine

monochloride than in iodine complexes. In the previous chapter, the

formation constants of iodine with aromatic hydrocarbons are reported. In

order to compare those results, the formation constants for charge transfer

complexes of iodine monochloride with nine aromatic hydrocarbons are

determined and the results obtained in their ultrasonic studies are reported

in this chapter and discussed.

The acoustical parameters such as adiabatic compressibility (κ),

absorption coefficient (α/f2), molecular interaction parameter (χU), relaxation

time (τ), free length (Lf), internal pressure (πi), cohesive energy (CE), acoustical

impedance (Z), Lenard Jones Potential (LJP) and Gibb’s free energy of

activation (∆G#) are calculated at various concentrations. The interaction

between the donor and acceptor molecules has been studied from the

variation of acoustical parameters with concentration. The stability constant

(K) values are calculated for all the nine complexes in n-hexane at

303 K.

6.2. RESULTS AND DISCUSSION

The acoustical parameters along with measured ultrasonic velocities,

densities and viscosities for six monocyclic aromatic hydrocarbons and three
163

polynuclear hydrocarbons at 303 K are given in Tables 6.1 – 6.18. These data

are discussed in the light of molecular interaction and complexation between

the components. Their corresponding plots are given in Figs. 6.1 – 6.10.

The ultrasonic velocity (U) increases slightly with concentration in the

case of all systems except in o-xylene-iodine monochloride, anthracene-iodine

monochloride and benzene-iodine monochloride systems. Further, there is a

characteristic concentration for each system at which the ultrasonic velocity

is a maximum. Even in the three systems in which ultrasonic velocity

decreases initially, there is an increase in velocity at a particular

concentration. These observations establish the formation of charge transfer

complexes between iodine monochloride and the aromatic hydrocarbons. This

is also suggested by the slight increase in density and viscosity at these

concentrations. Plots of ultrasonic velocity vs concentration for the

monocyclic systems are given in Fig. 6.1 while Fig. 6.6 contains similar plots

for polycyclic systems.

Adiabatic compressibility (κ) values are computed from ultrasonic

velocity and density for all the systems and are given in Tables 6.1 – 6.18.

Plots of adiabatic compressibility vs concentration are presented in Fig. 6.2

for monocyclic aromatic systems while similar plots for polycyclic systems are

given in Fig. 6.7. It may be pointed out here that whether adiabatic

compressibility increases or decreases at low concentration, the value is

found to be a minimum at the same concentration at which the ultrasonic


164

velocity, density and viscosity values are at maximum. This trend in adiabatic

compressibility in all the nine systems suggests that complexation between

iodine monochloride and aromatic hydrocarbon is a maximum at a specific

concentration which is characteristic of the system.

Thus, minimum values of stability constant are observed for systems

containing benzene derivatives in the concentration range 0.003 M and

0.006 M which indicate the maximum complexation in this concentration

range. In the case of anthracene, the adiabatic compressibility value

decreases between 0.008 M and 0.01 M. This shows maximum complexation

at this concentration for anthracene system. A similar trend is seen in the

case of biphenyl and naphthalene also. The values are listed in Tables 6.13,

6.15 and 6.17; the corresponding plots are given in Fig. 6.7.

The molecular interaction parameter (χU) is indicative of the extent of

deviation of ultrasonic velocity from ideal behaviour. These values can be

used to assess the strength of molecular attraction between the donor and

acceptor in non-polar medium like n-hexane. Tables 6.1, 6.3, 6.5, 6.7, 6.9

and 6.11 give the values of molecular interaction parameter, and the

corresponding plots are given in Fig. 6.3 for the six monocyclic hydrocarbons.

These molecular interaction parameter values vary with concentration

indicating that the extent of deviation from ideal behaviour and the extent of

complexation are both concentration dependent. For monocyclic systems, the

molecular interaction parameter values are positive except that for benzene.
165

The molecular interaction parameter values are generally positive, but

negative in the concentration from 0.003 M to 0.007 M in the case of

polynuclear aromatic hydrocarbons except for anthracene system. This

positive value indicates that iodine monochloride-biphenyl and iodine

monochloride-naphthalene complexes may be less stable than that of iodine

monochloride-anthracene complex. The plots of molecular interaction

parameter vs concentration for polycyclic systems are presented in Fig. 6.8.

The absorption coefficient (α/f2) and relaxation time (τ) values are

almost constant for a given system, indicating that they are characteristic

properties of the complex. These values are given in Tables 6.1, 6.3, 6.5, 6.7,

6.9, 6.11, 6.13, 6.15 and 6.17. However, the slight difference in absorption

coefficient values for different systems is indicative of different strength in

molecular interactions between the donor and acceptor in systems studied.

The free length (Lf) values are given in Tables 6.2, 6.4, 6.6, 6.8, 6.10,

6.12, 6.14, 6.16 and 6.18. These values are calculated from ultrasonic

velocity and viscosity values and they are used to detect and analyze the

intermolecular attraction between the molecules of the components in the

system. It may be pointed out here that the free length values are almost

constant for each system and independent of concentration. Thus, the iodine

monochloride molecules form similar type of complexes with the aromatic

hydrocarbon. It may be possible that the positive end of the dipole in iodine
166

monochloride may attract the π-electron cloud and the molecular axis of

iodine monochloride may be perpendicular to the plane of the aromatic

hydrocarbon molecule. The free length values are slightly greater than those

for pure components, indicating the iodine monochloride-aromatic

hydrocarbon complex formation.

The internal pressure (πi) is a measure of binding forces between the

solute and solvent molecules. The internal pressure values are calculated

from the values of ultrasonic velocity, density and viscosity. The internal

pressure values for the six monocyclic hydrocarbons are presented in Tables

6.1, 6.3, 6.5, 6.7, 6.9, and 6.11. The corresponding plots are given in Fig. 6.4.

The internal pressure values are maximum at concentration range 0.003 M -

0.004 M indicating maximum complexation in this concentration range. The

variation of internal pressure with concentration for polynuclear aromatic

hydrocarbons indicates that the complexation is maximum at higher values of

concentration. Tables 6.13, 6.15 and 6.17 contain the values of internal

pressure for the polynuclear aromatic hydrocarbon stystems. The

corresponding plots are given in Fig. 6.9.

The cohesive energy (CE) in liquid mixtures indicates the forces of

attraction between the component molecules. The values of cohesive energy

for all the nine systems are given in Tables 6.2, 6.4, 6.6, 6.8, 6.10, 6.12, 6.14,

6.16 and 6.18. The corresponding plots are given in Figs. 6.5 and 6.10. The
167

cohesive energy value is maximum at a specific concentration which is

characteristic of the system.

The values of acoustic impedance (Z), free volume (Vf) and available

volume (Va) are presented in Tables 6.2, 6.4, 6.6, 6.8, 6.10, 6.12, 6.14, 6.16

and 6.18. It is found that the acoustic impedance, free volume and available

volume do not change significantly in these nine systems. Thus, complexation

between iodine monochloride and aromatic hydrocarbons does not influence

acoustic impedance, available volume and free volume values. This indicates

that there is formation of similar complexes in these systems.

The formation constants (K) can be used to compare stabilities of the

charge transfer complexes. In all the nine systems, the donor is the aromatic

hydrocarbon molecule which is a π-electron donor and so it is expected that

the extension of conjugation of the π-electron system should increase the

stability constant values. The mean values of formation constants are

calculated and presented in Table 6.19. The formation constant is almost a

constant for a particular system, indicating that it is characteristic of the

system and independent of concentration. From the values of stability

constant, the stability of charge transfer complexes are found to be in the

order

ICl-mesitylene > ICl -p-xylene > ICl -m-xylene >

ICl -o-xylene > ICl-toluene > ICl -benzene


168

In the case of monocyclic aromatic hydrocarbons, and in polycyclic

aromatic systems, it is in the order

ICl -anthracene > ICl -biphenyl > ICl -naphthalene

This trend can be explained as follows. In toluene molecule, the presence of

electron releasing methyl group enhances the basicity of the donor molecule.

Hence, the stability constant for iodine monochloride-toluene complex is

slightly greater than that of iodine monochloride-benzene charge transfer

complex. This is also supported by the higher values for charge transfer

complexes of iodine monochloride and xylenes, which contain two methyl

substituents. Among xylenes, p-xylene complex is more stable than m-xylene

complex which is slightly more stable than o-xylene complex. This may be

due to steric reason. Of the three charge transfer complexes of iodine

monochloride and polycyclic aromatic hydrocarbons, iodine monochloride-

anthracene complex is the most stable. This may be due to the maximum

π-electron density in anthracene. Biphenyl with twelve π electrons has greater

π-electron density than naphthalene with only ten π electrons. Hence, the

formation constant of iodine monochloride-biphenyl complex is greater than

that of iodine monochloride-naphthalene complex.

It may be of interest to compare the formation constants of iodine-

aromatic hydrocarbons with those of iodine monochloride-aromatic

hydrocarbon complexes. It is found that the order of stability is in the same

order among the nine systems for both iodine and iodine monochloride as
169

acceptors. Further, the complexes formed between iodine monochloride and

aromatic hydrocarbons are more stable than the complexes formed between

iodine and the same donors. Similar observations were made by Al Mokhtar

Lambabhi and coworkers15 in the study of complexes of carbonyl compounds

(donors), iodine and iodine monochloride (acceptors). The negative value of

Gibb’s free energy of formation (∆G) also supports the formation of

thermodynamically stable complexes in the nine systems.


170

REFERENCES

1. Kannappan, V. and Mahendran, S., National Symposium on Acoustics., 32, 2000.

2. Jaya Santhi, R., Ph.D. Thesis, University of Madras, 2002.

3. Prakash, S., Prasad, N., Singh, R. and Prakash, O., Acustica., 34, 1975, 121.

4. Szent-Gyorgyi, A., Introduction to a Sub-Molecular Biology., Academic Press, New


York, 1960.

5. Pfeiffer, P., Organische Molekullirbindungen., 2ndEdn., Ferdinand Enke, Stuttgart,


1927.

6. Foster, R., Molecular Complexes, Vol.1, Science, London, 1973.

7. Tabhane, P., Ind. J. Pure and Appl. Phys., 20, 1977, 89.

8. Kannappan, V. and Kothai, S., J. Acous. Soc. Ind., 29, 2001, 169.

9. Kannappan, V. and Kothai, S., Ind. J. Pure and Appl. Phys., 40, 2002, 17.

10. Kannappan, V. and Kothai, S., J. Acous. Soc. Ind., 30, 2002, 76.

11. Kothai, S., Ph.D. Thesis, University of Madras, 2003.

12. De la mare, P.P.D., Electrophilic Halogenation, Chapter 10, Cambridge University


Press, London, 1976.

13. Material safety data sheet No. 12775, Baker Inc., 2006.

14. Amitha, N., Ph.D. Thesis, University of Madras, 1978.

15. Al Mokhtar Lambabhi, Widad Bouab, Muhamed Essaffar, Manual Alcami, Manual
Yanex and Jose-Luis, M, Abboud, New. J. Chem., 25, 2001, 509.
TABLE 6.1

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
2
ABSORPTION COEFFICIENT (α α/f ), MOLECULAR INTERACTION PARAMETER (χ χU) AND RELAXATION
TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - MESITYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K


C U ρ -4
η /10 -9
κ /10 2
α/f /10 -15
χU /10-3 τ /10-13
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s
0.001 1061.5 638.7 3.37 1.39 11.6 6.0 6.2
0.002 1060.0 638.5 3.36 1.39 11.6 3.1 6.2
0.003 1065.2 642.1 3.40 1.37 11.5 13.0 6.2
0.004 1063.2 637.8 3.36 1.39 11.5 9.1 6.2
0.005 1059.2 640.3 3.39 1.39 11.7 1.5 6.3
0.006 1059.6 642.7 3.40 1.39 11.7 2.2 6.3
0.007 1060.2 636.2 3.36 1.40 11.7 3.3 6.3
0.008 1060.8 643.5 3.39 1.38 11.6 4.4 6.2
0.009 1063.8 639.8 3.39 1.38 11.6 10.0 6.2
0.010 1062.8 637.2 3.38 1.39 11.6 8.1 6.3

Plots : Fig. 6.1 U vs Concentration; Fig. 6.3 χU vs Concentration;


Fig. 6.2 κ vs Concentration;
172

TABLE 6.2

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va), LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - MESITYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K


-7 5
C Lf Vf /10 πi CE Z /10 Va /10-5 LJP
M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 5.0 2382 32.6 6.8 4.5 4.8
0.002 0.7 5.1 2379 32.5 6.8 4.6 4.8
0.003 0.7 5.0 2397 32.6 6.8 4.5 5.0
0.004 0.7 5.1 2373 32.5 6.8 4.5 4.9
0.005 0.7 5.0 2393 32.7 6.8 4.6 4.8
0.006 0.7 5.0 2402 32.7 6.8 4.5 4.8
0.007 0.7 5.1 2370 32.6 6.7 4.6 4.8
0.008 0.7 5.0 2400 32.6 6.8 4.5 4.8
0.009 0.7 5.0 2384 32.6 6.8 4.5 4.9
0.010 0.7 5.1 2376 32.6 6.8 4.5 4.9

Plots : Fig. 6.4 πi vs Concentration;


Fig. 6.5 CE vs Concentration;
173

TABLE 6.3

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
ABSORPTION COEFFICIENT (α α/f2), MOLECULAR INTERACTION PARAMETER (χ χU) AND RELAXATION
TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - PARA XYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K


C U ρ -4
η /10 -9
κ /10 2
α/f /10 -15
χU /10-3 τ /10-13
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s
0.001 1062.2 641.2 3.34 1.38 11.4 7.3 6.1
0.002 1059.0 639.9 3.37 1.39 11.7 1.2 6.3
0.003 1065.8 645.0 3.41 1.36 11.5 14.1 6.2
0.004 1062.0 646.7 3.43 1.37 11.6 6.8 6.3
0.005 1061.2 638.2 3.37 1.39 11.6 5.3 6.2
0.006 1061.8 644.8 3.42 1.38 11.7 6.3 6.3
0.007 1059.2 642.1 3.40 1.39 11.7 1.4 6.3
0.008 1060.8 646.8 3.42 1.37 11.7 4.4 6.3
0.009 1060.6 643.4 3.41 1.38 11.7 3.9 6.3
0.010 1065.0 638.2 3.38 1.38 11.5 12.2 6.2

Plots : Fig. 6.1 U vs Concentration; Fig. 6.3 χU vs Concentration;


Fig. 6.2 κ vs Concentration;
174

TABLE 6.4

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va), LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - PARA XYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K


-7 5
C Lf Vf /10 πi CE Z /10 Va /10-5 LJP
M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 5.1 2375 32.3 6.8 4.5 4.9
0.002 0.7 5.0 2388 32.6 6.8 4.6 4.7
0.003 0.7 5.0 2406 32.6 6.9 4.5 5.0
0.004 0.7 4.9 2420 32.7 6.9 4.5 4.8
0.005 0.7 5.1 2378 32.6 6.8 4.6 4.8
0.006 0.7 4.9 2413 32.7 6.8 4.5 4.8
0.007 0.7 5.0 2403 32.7 6.8 4.5 4.8
0.008 0.7 4.9 2418 32.7 6.9 4.5 4.8
0.009 0.7 5.0 2406 32.7 6.8 4.5 4.8
0.010 0.7 5.1 2377 32.6 6.8 4.5 4.9

Plots : Fig. 6.4 πi vs Concentration;


Fig. 6.5 CE vs Concentration;
175

TABLE 6.5

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
ABSORPTION COEFFICIENT (α α/f2), MOLECULAR INTERACTION PARAMETER (χ χU) AND RELAXATION
TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - META XYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K


C U ρ -4
η /10 -9
κ /10 2
α/f /10 -15
χU /10-3 τ /10-13
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s

0.001 1061.8 641.3 3.38 1.38 11.6 6.6 6.2


0.002 1062.4 638.8 3.37 1.39 11.6 7.7 6.2
0.003 1059.4 641.0 3.37 1.39 11.6 2.0 6.2
0.004 1060.8 643.2 3.39 1.38 11.6 4.6 6.3
0.005 1061.2 635.9 3.36 1.40 11.6 5.3 6.3
0.006 1065.2 640.4 3.37 1.38 11.5 12.8 6.2
0.007 1066.0 639.2 3.38 1.38 11.5 14.3 6.2
0.008 1062.8 643.0 3.39 1.38 11.5 8.2 6.2
0.009 1062.3 641.9 3.40 1.38 11.6 7.2 6.3
0.010 1062.4 636.3 3.35 1.39 11.5 7.4 6.2

Plots : Fig. 6.1 U vs Concentration; Fig. 6.3 χU vs Concentration;


Fig. 6.2 κ vs Concentration;
176

TABLE 6.6

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va), LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - META XYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K


C Lf Vf /10-7 πi CE Z /105 Va /10-5 LJP
M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 5.0 2390 32.5 6.8 4.5 4.8
0.002 0.7 5.1 2382 32.6 6.8 4.5 4.9
0.003 0.7 5.0 2389 32.6 6.8 4.5 4.8
0.004 0.7 5.0 2401 32.6 6.8 4.5 4.8
0.005 0.7 5.1 2370 32.6 6.7 4.6 4.8
0.006 0.7 5.1 2381 32.5 6.8 4.5 5.0
0.007 0.7 5.1 2379 32.5 6.8 4.5 5.0
0.008 0.7 5.0 2394 32.5 6.8 4.5 4.9
0.009 0.7 5.0 2395 32.6 6.8 4.5 4.9
0.010 0.7 5.1 2363 32.5 6.8 4.6 4.9

Plots : Fig. 6.4 πi vs Concentration;


Fig. 6.5 CE vs Concentration;
177

TABLE 6.7

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
ABSORPTION COEFFICIENT (α α/f2), MOLECULAR INTERACTION PARAMETER (χ χU) AND RELAXATION
TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - ORTHO XYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K


C U ρ -4
η /10 -9
κ /10 2
α/f /10 -15
χU /10-3 τ /10-13
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s
0.001 1069.2 639.0 3.38 1.37 11.4 20.7 6.2
0.002 1067.0 640.2 3.37 1.37 11.4 16.4 6.2
0.003 1061.4 640.8 3.40 1.39 11.7 5.7 6.3
0.004 1059.8 644.2 3.42 1.38 11.7 2.7 6.3
0.005 1065.2 637.4 3.38 1.38 11.5 12.9 6.2
0.006 1067.4 642.5 3.40 1.37 11.4 17.0 6.2
0.007 1062.5 639.7 3.42 1.38 11.7 7.6 6.3
0.008 1062.7 642.2 3.40 1.38 11.6 8.0 6.2
0.009 1061.2 643.1 3.40 1.38 11.6 5.1 6.3
0.010 1062.8 636.9 3.37 1.39 11.6 8.1 6.2

Plots : Fig. 6.1 U vs Concentration; Fig. 6.3 χU vs Concentration;


Fig. 6.2 κ vs Concentration;
178

TABLE 6.8

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va), LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - ORTHO XYLENE SYSTEM

Solvent : n-hexane Temperature : 303 K


-7 5
C Lf Vf /10 πi CE Z /10 Va /10-5 LJP
M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 5.1 2378 32.5 6.8 4.5 5.1
0.002 0.7 5.1 2379 32.4 6.8 4.5 5.0
0.003 0.7 5.0 2398 32.7 6.8 4.5 4.8
0.004 0.7 4.9 2414 32.7 6.8 4.5 4.8
0.005 0.7 5.1 2378 32.6 6.8 4.5 5.0
0.006 0.7 5.0 2394 32.6 6.9 4.5 5.0
0.007 0.7 5.0 2397 32.7 6.8 4.5 4.9
0.008 0.7 5.0 2396 32.6 6.8 4.5 4.9
0.009 0.7 5.0 2400 32.6 6.8 4.5 4.8
0.010 0.7 5.1 2372 32.6 6.8 4.5 4.9

Plots : Fig. 6.4 πi vs Concentration;


Fig. 6.5 CE vs Concentration;
179

TABLE 6.9

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
ABSORPTION COEFFICIENT (α α/f2), MOLECULAR INTERACTION PARAMETER (χ χU) AND RELAXATION
TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - TOLUENE SYSTEM

Solvent : n-hexane Temperature : 303 K


C U ρ -4
η /10 -9
κ /10 2
α/f /10 -15
χU /10-3 τ /10-13
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s
0.001 1063.1 638.7 3.41 1.39 11.7 9.1 6.3
0.002 1061.4 638.6 3.39 1.39 11.7 5.8 6.3
0.003 1060.1 639.0 3.39 1.39 11.7 3.3 6.3
0.004 1059.8 638.7 3.40 1.39 11.8 2.7 6.3
0.005 1064.0 637.6 3.39 1.39 11.6 10.6 6.3
0.006 1063.0 639.5 3.39 1.38 11.6 8.7 6.3
0.007 1060.0 636.4 3.38 1.40 11.7 3.0 6.3
0.008 1060.4 639.9 3.38 1.39 11.7 3.7 6.3
0.009 1064.0 636.9 3.40 1.39 11.7 10.5 6.3
0.010 1060.0 635.9 3.37 1.40 11.7 2.8 6.3

Plots : Fig. 6.1 U vs Concentration; Fig. 6.3 χU vs Concentration;


Fig. 6.2 κ vs Concentration;
180

TABLE 6.10

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va), LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - TOLUENE SYSTEM

Solvent : n-hexane Temperature : 303 K


-7 5
C Lf Vf /10 πi CE Z /10 Va /10-5 LJP
M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 5.0 2395 32.7 6.8 4.5 4.9
0.002 0.7 5.0 2387 32.6 6.8 4.5 4.8
0.003 0.7 5.0 2390 32.7 6.8 4.6 4.8
0.004 0.7 5.0 2394 32.7 6.8 4.6 4.8
0.005 0.7 5.0 2383 32.7 6.8 4.5 4.9
0.006 0.7 5.0 2389 32.6 6.8 4.5 4.9
0.007 0.7 5.0 2378 32.6 6.7 4.6 4.8
0.008 0.7 5.0 2389 32.6 6.8 4.5 4.8
0.009 0.7 5.0 2383 32.7 6.8 4.5 4.9
0.010 0.7 5.1 2373 32.6 6.7 4.6 4.8

Plots : Fig. 6.4 πi vs Concentration;


Fig. 6.5 CE vs Concentration;
181

TABLE 6.11

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
2
ABSORPTION COEFFICIENT (α α/f ), MOLECULAR INTERACTION PARAMETER (χ χU) AND RELAXATION
TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - BENZENE SYSTEM

Solvent : n-hexane Temperature : 303 K


C U ρ -4
η /10 -9
κ /10 2
α/f /10 -15
χU /10-3 τ /10-13
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s
0.001 1067.2 637.2 3.39 1.38 11.5 16.9 6.2
0.002 1062.4 637.0 3.39 1.39 11.7 7.7 6.3
0.003 1062.0 637.9 3.42 1.39 11.8 6.9 6.3
0.004 1060.0 636.0 3.39 1.40 11.8 3.1 6.3
0.005 1064.0 637.6 3.38 1.39 11.6 10.6 6.2
0.006 1062.5 638.6 3.41 1.39 11.7 7.7 6.3
0.007 1060.8 636.7 3.37 1.40 11.7 4.5 6.3
0.008 1059.8 640.4 3.40 1.39 11.7 2.5 6.3
0.009 1058.7 636.1 3.39 1.40 11.8 0.4 6.3
0.010 1057.6 635.0 3.34 1.41 11.7 -1.7 6.3

Plots : Fig. 6.1 U vs Concentration; Fig. 6.3 χU vs Concentration;


Fig. 6.2 κ vs Concentration;
182

TABLE 6.12

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va), LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - BENZENE SYSTEM

Solvent : n-hexane Temperature : 303 K


-7 5 LJP
C Lf Vf /10 πi CE Z /10 Va /10-5
M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 5.1 2377 32.6 6.8 4.5 5.0
0.002 0.7 5.0 2384 32.7 6.8 4.5 4.9
0.003 0.7 4.9 2398 32.8 6.8 4.5 4.8
0.004 0.7 5.0 2382 32.7 6.7 4.6 4.8
0.005 0.7 5.1 2378 32.6 6.8 4.5 4.9
0.006 0.7 5.0 2393 32.7 6.8 4.5 4.9
0.007 0.7 5.0 2378 32.6 6.8 4.6 4.8
0.008 0.7 5.0 2397 32.7 6.8 4.5 4.8
0.009 0.7 5.0 2382 32.7 6.7 4.6 4.7
0.010 0.7 5.1 2364 32.5 6.7 4.6 4.7

Plots : Fig. 6.4 πi vs Concentration;


Fig. 6.5 CE vs Concentration;
183

TABLE 6.13

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
ABSORPTION COEFFICIENT (α α/f2), MOLECULAR INTERACTION PARAMETER (χ χU) AND RELAXATION
TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - ANTHRACENE SYSTEM

Solvent : n-hexane Temperature : 303 K


C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 τ /10-13
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s
0.001 1066.0 638.2 3.37 1.38 11.5 14.3 6.2
0.002 1061.6 637.2 3.39 1.39 11.7 5.7 6.3
0.003 1059.2 636.9 3.36 1.40 11.7 0.9 6.3
0.004 1058.8 638.9 3.39 1.40 11.8 -0.1 6.3
0.005 1058.4 637.1 3.37 1.40 11.7 -1.2 6.3
0.006 1059.6 639.4 3.37 1.39 11.7 0.8 6.3
0.007 1058.8 638.8 3.37 1.40 11.7 -1.0 6.3
0.008 1064.4 640.8 3.39 1.38 11.5 9.4 6.2
0.009 1064.0 643.2 3.42 1.37 11.6 8.3 6.3
0.010 1062.8 636.8 3.39 1.39 11.7 5.8 6.3

Plots : Fig. 6.6 U vs Concentration; Fig. 6.8 χU vs Concentration;


Fig. 6.7 κ vs Concentration;
184

TABLE 6.14

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va), LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - ANTHRACENE SYSTEM

Solvent : n-hexane Temperature : 303 K


-7 5 LJP
C Lf Vf /10 πi CE Z /10 Va /10-5
o 3
M A m atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 5.1 2376 32.5 6.8 4.5 5.0
0.002 0.7 5.0 2384 32.7 6.8 4.6 4.8
0.003 0.7 5.1 2376 32.6 6.7 4.6 4.8
0.004 0.7 5.0 2391 32.7 6.8 4.6 4.7
0.005 0.7 5.0 2378 32.6 6.7 4.6 4.7
0.006 0.7 5.0 2383 32.6 6.8 4.6 4.8
0.007 0.7 5.0 2382 32.6 6.8 4.6 4.7
0.008 0.7 5.0 2384 32.6 6.8 4.5 4.9
0.009 0.7 5.0 2401 32.7 6.8 4.5 4.9
0.010 0.7 5.0 2377 32.7 6.8 4.6 4.9

Plots : Fig. 6.9 πi vs Concentration;


Fig. 6.10 CE vs Concentration;
185

TABLE 6.15

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
ABSORPTION COEFFICIENT (α α/f2), MOLECULAR INTERACTION PARAMETER (χ χU) AND RELAXATION
TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - BIPHENYL SYSTEM

Solvent : n-hexane Temperature : 303 K


C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 τ /10-13
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s
0.001 1061.3 638.9 3.36 1.39 11.6 5.6 6.2
0.002 1059.2 637.4 3.38 1.40 11.7 1.5 6.3
0.003 1057.7 638.4 3.37 1.40 11.7 -1.4 6.3
0.004 1060.8 636.7 3.36 1.40 11.6 4.3 6.2
0.005 1062.4 636.8 3.34 1.39 11.5 7.3 6.2
0.006 1058.4 639.5 3.36 1.40 11.7 -0.4 6.3
0.007 1060.8 638.6 3.38 1.39 11.7 4.0 6.3
0.008 1065.2 643.3 3.39 1.37 11.5 12.3 6.2
0.009 1066.6 638.0 3.35 1.38 11.4 14.8 6.2
0.010 1063.2 637.2 3.36 1.39 11.5 8.3 6.2

Plots : Fig. 6.6 U vs Concentration; Fig. 6.8 χU vs Concentration;


Fig. 6.7 κ vs Concentration;
186

TABLE 6.16

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va), LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - BIPHENYL SYSTEM

Solvent : n-hexane Temperature : 303 K


C Lf Vf /10-7 πi CE Z /105 Va /10-5 LJP
M Ao m3 atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 5.1 2378 32.5 6.8 4.5 4.8
0.002 0.7 5.0 2384 32.7 6.8 4.6 4.8
0.003 0.7 5.0 2383 32.6 6.8 4.6 4.7
0.004 0.7 5.1 2371 32.5 6.8 4.6 4.8
0.005 0.7 5.1 2365 32.5 6.8 4.6 4.9
0.006 0.7 5.1 2382 32.6 6.8 4.6 4.7
0.007 0.7 5.0 2381 32.6 6.8 4.6 4.8
0.008 0.7 5.0 2393 32.5 6.9 4.5 5.0
0.009 0.7 5.1 2363 32.4 6.8 4.5 5.0
0.010 0.7 5.1 2367 32.5 6.8 4.5 4.9

Plots : Fig. 6.9 πi vs Concentration;


Fig. 6.10 CE vs Concentration;
187

TABLE 6.17

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ
κ),
2
ABSORPTION COEFFICIENT (α α/f ), MOLECULAR INTERACTION PARAMETER (χ χU) AND RELAXATION
TIME (ττ) AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - NAPHTHALENE SYSTEM

Solvent : n-hexane Temperature : 303 K


C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 τ /10-13
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 s
0.001 1063.5 637.3 3.35 1.39 11.5 9.7 6.2
0.002 1059.7 636.4 3.31 1.40 11.5 2.3 6.2
0.003 1057.7 636.6 3.35 1.40 11.7 -1.6 6.3
0.004 1056.7 635.0 3.35 1.41 11.7 -3.7 6.3
0.005 1053.6 635.0 3.35 1.42 11.8 -9.7 6.3
0.006 1052.7 634.1 3.34 1.42 11.9 -11.5 6.3
0.007 1052.6 633.1 3.33 1.43 11.8 -11.9 6.3
0.008 1063.2 634.9 3.32 1.39 11.4 8.0 6.2
0.009 1061.2 637.5 3.35 1.39 11.6 4.0 6.2
0.010 1058.8 638.1 3.38 1.40 11.7 -0.7 6.3

Plots : Fig. 6.6 U vs Concentration; Fig. 6.8 χU vs Concentration;


Fig. 6.7 κ vs Concentration;
188

TABLE 6.18

FREE LENGTH (Lf), FREE VOLUME (Vf), INTERNAL PRESSURE (π


πi), COHESSIVE ENERGY (CE),
ACOUSTICAL IMPEDANCE (Z), AVAILABLE VOLUME (Va), LENARD JONES POTENTIAL (LJP),
AT VARIOUS CONCENTRATIONS OF IODINE MONOCHLORIDE - NAPHTHALENE SYSTEM

Solvent : n-hexane Temperature : 303 K


-7 5 LJP
C Lf Vf /10 πi CE Z /10 Va /10-5
o 3
M A m atm kJ mol-1 kg-2 s-1 m3
0.001 0.7 5.1 2371 32.5 6.8 4.5 4.9
0.002 0.7 5.2 2357 32.3 6.7 4.6 4.8
0.003 0.7 5.1 2374 32.6 6.7 4.6 4.7
0.004 0.7 5.1 2368 32.6 6.7 4.6 4.7
0.005 0.7 5.1 2371 32.6 6.7 4.6 4.6
0.006 0.7 5.1 2367 32.6 6.7 4.7 4.5
0.007 0.7 5.1 2359 32.6 6.7 4.7 4.5
0.008 0.7 5.2 2350 32.4 6.8 4.6 4.9
0.009 0.7 5.1 2369 32.5 6.8 4.6 4.8
0.010 0.7 5.0 2382 32.6 6.8 4.6 4.7

Plots : Fig. 6.9 πi vs Concentration;


Fig. 6.10 CE vs Concentration;
189

TABLE 6.19

MEAN VALUES OF GIBB'S FREE ENERGY OF FORMATION (∆G), MEAN VALUES OF


GIBB'S FREE ENERGY OF ACTIVATION (∆G#) AND MEAN VALUES FORMATION CONSTANT (K)
OF HYDROCARBON COMPOUNDS WITH IODINE MONOCHLORIDE IN n-HEXANE SOLUTIONS

Solvent : n-hexane Temperature : 303 K


∆G ∆G# K
DONOR kJ mol-1 kJ mol-1 dm-3 mol-1
mesitylene -9.9 3.8 50.4
p-xylene -9.7 3.8 46.9
m-xylene -9.6 3.8 45.1
o-xylene -9.4 3.8 41.4
toluene -9.0 3.8 35.1
benzene -8.7 3.8 32.2
anthracene -11.3 3.8 90.5
biphenyl -10.8 3.8 74.1
naphthalene -10.0 3.8 52.5
Fig. 6.1 Plots of Ultrasonic velocity vs Concentration

1070 Solvent : n-hexane Temperature : 303 K


IC-MST IC-PXL IC-MXL
1068 IC-OXL IC-BZ IC-TL

1066
U, m s -1

1064

1062

1060

1058

1056
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M

Fig. 6.2 Plots of Adiabatic compressibility vs Concentration

1.42 Solvent : n-hexane Temperature : 303 K

IC-MST IC-PXL
1.41 IC-MXL IC-OXL
IC-BZ IC-TL
2

1.40
κ /10 , kg ms
-1

1.39
-9

1.38

1.37

1.36
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M
191

Fig. 6.3 Plots of Molecular interaction parameter vs Concentration

Solvent : n-hexane Temperature : 303 K


25
IC-MST IC-PXL
IC-MXL IC-OXL
20 IC-BZ IC-TL

15
-1
χ U /10 , ms

10
-3

-5
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M

Fig. 6.4 Plots of Internal pressure vs Concentration

Solvent : n-hexane Temperature : 303 K


2440
IC-MST IC-PXL IC-MXL
IC-OXL IC-BZ IC-TL
2420
πi , atm

2400

2380

2360
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M
192

Fig. 6.5 Plots of Cohessive energy vs Concentration

32.9

32.8

32.7
CE, kJ mol-1

32.6

32.5

IC-MST IC-PXL
32.4 IC-MXL IC-OXL
IC-BZ IC-TL
32.3
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M

Fig. 6.6 Plots of Ultrasonic velocity vs Concentration

Solvent : n-hexane Temperature : 303 K


1068

1064

1060
U, ms-1

1056

1052 IC-ANT
IC-BIP
IC-NAP
1048
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M
193

Fig. 6.7 Plots of Adiabatic compressibility vs Concentration

1.44
IC-ANT
IC-BIP
IC-NAP
1.42
2
κ /10 , kg ms
-1

1.40
-9

1.38

1.36
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M

Fig. 6.8 Plots of Molecular interaction parameter vs Concentration

14

9
-1

4
χ U /10 , ms
-3

-1

-6
IC-ANT
-11 IC-BIP
IC-NAP
-16
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M
194

Fig. 6.9 Plots of Internal pressure vs Concentration

Solvent : n-hexane Temperature : 303 K

2390
πi , atm

2365

IC-ANT
IC-BIP
IC-NAP
2340
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M

Fig. 6.10 Plots of Cohesive energy vs Concentration

32.8
IC-ANT
IC-BIP
IC-NAP
32.7
CE, kJ mol-1

32.6

32.5

32.4

32.3
0.000 0.002 0.004 0.006 0.008 0.010 0.012

Concentration, M
195

Chapter 7
196

CHAPTER – 7

ULTRASONIC STUDIES ON THE CHARGE TRANSFER


COMPLEXES OF IODINE AND CERTAIN PHENOLS AT 303 K

7.1. INTRODUCTION

Phenols are important class of aromatic compounds and they are

widely used in the manufacturer of several dyes and drugs1. They undergo

electrophilic substitution reactions2-4 with several electrophiles. In these

reactions, it is suggested that the first step is the formation of a loose

complex between phenol and the electrophile. It may be pointed out that

phenol undergoes electrophilic substitution more easily than benzene. Thus,

phenolic group activates the benzene ring in electrophilic substitution

reaction. Phenols may form complexes with electron deficient species.

Venkateswarlu and coworkers investigated the donor abilities of phenols

and their tendency to form change transfer complexes with

π acceptors5. They also studied the charge transfer spectra, stability and

thermodynamic parameters of charge transfer complexes of phenols with

2,3-dichloro-5,6-dicyano-p-benzoquinone6 (DDQ). Literature Survey reveals

that DDQ forms charge transfer complexes with phenols and produces a

characteristic colour in methanol7,8, but the colour fades with time

indicating that these complexes are unstable and soon turn into other
197

products. It has been reported that charge transfer complexes can be

stabilized for a longer time in solvents of low polarity at low temperatures

and under low donor concentration9,10.

Iodine is an important halogen which functions as acceptor. It forms

complexes with several π as well as n electron donors. Complexes of iodine

with carbon tetrachloride and olefins are well known11. Optical methods

have been used to determine the formation constant of these complexes. A

mixture of iodine and phenols at low concentration is used as antiseptic and

disinfectant. Iodine can form change transfer complexes with phenols. In

this chapter, ultrasonic studies have been carried out to determine the

formation constants of iodine and phenols at 303 K. Ultrasonic velocity,

density and viscosities are measured for systems containing equimolar

concentrations of donor (phenol) and acceptor (iodine) in solution. Wide

concentration range of 1x10-3 – 20x10-3 M has been chosen to study the

influence of concentration on the complexation. The donors used in the

present study are phenol, o-cresol, p-cresol, m-cresol and carvacrol. Less

polar liquids like n-hexane, carbon tetrachloride, chloroform and

dichloromethane are used as solvents in the present investigation. In order

to establish the formation of CT complexes in these systems, acoustical

parameters like adiabatic compressibility, free length, molecular interaction

parameter, internal pressure and cohesive energy are also computed and

reported.
198

7.2 Results and Discussion

The measured ultrasonic velocity (U) for iodine - phenol systems in

dichloromethane along with density and viscosity values are presented in

Table 7.1 – 7.5. Plots of ultrasonic velocity vs concentration are given Fig

7.1. It is found that the ultrasonic velocity in general decreases with

increase in concentration, and density increases with concentration.

However, there is no significant change in viscosity. This observation shows

that iodine forms a charge transfer complex with phenols. The ultrasonic

velocity, density and viscosity values for the five systems in chloroform are

in Tables 7.6 – 7.10, while the values in carbon tetrachloride are given in

Figs. 7.11 - 7.15. Tables 7.16 – 7.20 contain the measured values ultrasonic

velocity, density and viscosity for iodine-phenol systems in n-hexane at 303

K. It may be noted that in each solvent, the ultrasonic velocity is minimum

at a characteristic concentration the complexation may be maximum at this

concentration. This is as supported by the higher density value at this

concentration.

Adiabatic compressibility (κ) values are calculated for different

iodine-phenol systems in four solvents at various concentrations and they

are given in Tables 7.1 – 7.20. Plots of adiabatic compressibility vs

concentration for the twenty systems are given in Figs. 7.2, 7.7, 7.12 and

7.17. It is seen from the data in the Tables and Plots in the figures that
199

adiabatic compressibility values decrease with concentration and it is

minimum at a characteristic concentration for each system. Thus, extent of

complex formation is concentration dependent and there is a specific

concentration for each system at which complexation is maximum. Thus,

the trend in adiabatic compressibility values also establishes the formation

of charge transfer complexes between phenols and iodine in the four

solvents.

Free length (Lf) values are computed for all the systems and presented

in Tables 7.1 – 7.20. It is found that the free length values in the mixtures

containing donor and acceptor are slightly greater than those of pure

components (Table 7.22). This may be due to the association of phenols and

iodine. Further, the free length values are found to be almost constant in all

the systems suggesting the formation of similar complexes in these systems.

Attenuation constant (α/f2) values are calculated from the measured

ultrasonic velocity, density and viscosity for all the systems. Generally, the

absorption coefficient value increases slightly with increase in concentration

may be due to increase in the extent of complexation with increase in

concentration.

Molecular interaction parameter (χU) with respect to velocity in a

liquid mixture is indicative of the extent of deviation from ideal behaviour.


200

This indication may be due to the formation of a charge transfer complex

between the components of the mixture. Molecular interaction parameter

values are calculated from the observed ultrasonic velocity values and ideal

mixing values of the mixtures containing the donor and the acceptor. These

values are given in Tables 7.1 - 7.20. Figures 7.3, 7.8, 7.13 and 7.18

contain the plots of molecular interaction parameter vs concentration for the

twenty systems. It is found that molecular interaction parameter values are

either positive or negative depending upon the system and concentration.

Thus, charge transfer complexes are formed between iodine and phenols.

Further, decrease in molecular interaction parameter values at higher

concentration suggests that the degree of complexation increases with

increase in concentration. Large negative values of molecular interaction

parameter are observed at a specific concentration for each system. Hence,

maximum complexation is expected at characteristic concentration for each

system.

Internal pressure (πi) in a liquid system is indicative of the

intermolecular attractive forces between the component molecules. In binary

and ternary liquid mixtures internal pressure value is a measure of

attractive forces between components. Internal pressure values are

calculated for all the systems (Table 7.1 – 7.20). Plots of internal pressure vs

concentration are given in Figs. 7.4, 7.9, 7.14, and 7.19 for all the twenty

systems investigated. It is found that internal pressure values in the


201

solution containing donor and acceptor are different from the internal

pressure values of the component liquids (Table 7.22). There are attractive

forces between iodine and phenol molecules in the ternary mixtures as the

internal pressure values are also different from the internal pressure values

of the solvents. This may be due to the formation of charge transfer

complexes between iodine and phenol. Increase in internal pressure values

in a given system with increase in concentration suggests that the extent of

complexation increases with concentration. It may be noted that in a given

system, internal pressure value is higher at a specific concentration. Thus,

the extent of complexation is maximum at a particular concentration which

is characteristic of the system.

Cohesive energy (CE) in a liquid mixture is also a measure of

intermolecular molecular forces between the component molecules.

Cohesive energy values are computed for all the twenty systems and they

are listed in Tables 7.1 – 7.20. Plots of cohesive energy against

concentration are presented in Figs. 7.5, 7.10, 7.15 and 7.20. It is evident

from the data in the Tables and the plots in the Figures that the cohesive

energy values are close to the cohesive energy values of pure solvents (Table

7.22). This is justified because the solvent is the major component in all the

systems. However, the cohesive energy values differ slightly from the

cohesive energy values of pure solvents indicating the presence of

intermolecular attractive forces. Cohesive energy generally decreases with


202

increase in concentration and it is minimum for a given system at a

particular concentration. This observation also suggests that the extent of

complexation is maximum at characteristic concentration.

The main aim of the present work is to evaluate the formation

constants (K) of charge transfer complexes formed between iodine (acceptor)

and five structurally different phenols (donors) in four different solvents. The

effect of substituent in phenol and the influence of polarity of the medium

can be investigated by calculating formation constant values for the twenty

systems. Bhatt et al have suggested a method to compute stability constant

values for the complexes formed in binary mixtures from the measured

ultrasonic velocity12. However, this method has the limitation that it can be

applied to charge transfer complexes which are relatively stable and in

solutions of moderate concentration13. Recently, Kannappan and coworkers

have derived an equation to calculate the formation constants of even weak

complexes14,15. This equation has been successfully applied to several

ternary mixtures to calculate the formation constants of complexes16,17. In

the present work, the equation suggested by Kannappan is used to calculate

the formation constant of charge transfer complexes formed between iodine

and phenols in four different solvents. Less polar solvents with low dielectric

constants are used in the present work so that the charge transfer

complexes are not destabilised by the solvents due to solvation.


203

The mean stability constant values for all the twenty charge transfer

complexes are shown in table 7.21. The stability of the complexes depends

upon the structure of the phenol and the order of stability according to the

structure of donor is

o-cresol > p-cresol > m–cresol > phenol > carvacrol

The effect of substituents on the stability of the iodine-phenol charge

transfer complex is attributed to the interaction of substituents with the π-

orbitals of the benzene ring of phenol. The hyperconjucative and inductive

effect of methyl group and isopropyl group perturb the resonance in benzene

ring and boost the energy level of the donor and bring it closer to the LUMO

of iodine and this enhances the stability of the complex. Since the inductive

effect and hyper conjugative effect are possible in ortho and para isomers of

cresols, these two phenols form more stable complexes with phenol. In the

case of m-cresol, only inductive effect is possible and hence, the charge

transfer complex of iodine and m-cresol is slightly less stable than those of

ortho and para isomers. In the case of carvacrol, the presence of both

methyl and isopropyl groups in the benzene ring may contribute to the

stability but the presence of bulky isopropyl group and methyl substituted

higher approach of acceptor (iodine) molecule and this steric effect

predominates over the milder inductive effect. This is indicated by the

smaller stability constant value of iodine-carvacrol complex than those of

iodine and other phenols used as donors in the present work.


204

The formation of charge transfer complex between iodine and phenol

involves the polarization of π-electronic cloud by the acceptor. Thus, there is

induced dipole created in the charge transfer complex besides the

permanent dipole present in phenol. In order to establish this, the solvent

effect on the stability of the charge transfer complexes is investigated. The

formation constants are evaluated in four less polar solvents. These solvents

differ in the dielectric constant only slightly. The extent of solvation may be

greater for a given complex in a solvent of higher dielectric constant. It is

found that for a given charge transfer complex, the formation constants are

slightly greater in the slightly polar solvents like chloroform and

dichloromethane and less in non-polar solvents like n–hexane and carbon

tetrachloride.

The free energy of formation (∆G) values are computed from the mean

values of stability constant and they are presented in Table 7.21 along with

the relaxation time (τ). The free energy of formation is negative for all the

complexes indicating the formation of stable complexes between iodine and

all the phenols. Relaxation time values are found to be constant and

independent of concentration for a given system. Since free energy of

formation and relaxation time values are intrinsic properties of a complex,

these values do not depend upon the concentration. It may be noted that,

the relaxation time differs slightly from those of donor systems and also

relaxation time values of pure solvents.


205

REFERENCES

1. Francis A Carey, Organic Chemistry, 5th Edn., Tata McGraw Hill Publishing
Comapany Ltd., New Delhi, 2005.

2. March, J., Advanced Organic Chemistry, 4th Edn., John Wiley, New York, 1992.

3. Robert Thornton Morrison and Robert Neilson Boyd, Organic Chemistry, 6th Edn.,
Prientice Hall of India Pvt. Ltd., New Delhi, 2006.

4. Pine Stanely, H., Hendrickson, B., Cran, D.J. and Hammond, G.S., Organic
Chemistry, McGraw Hill, GB, 1989.

5. Shanta, M., Suresh, T. and Venkateshwarlu, G., Ind. J. Chem., 37(A), 1998, 1119.

6. Vinodkumar, T, Veeraiah, T. and Venkateshwarlu, G., Proc. Indian Acad. Sci.


(Chem. Sci.), 112, 2000, 119.

7. Becker, H.D., J. Org. Chem., 30, 1965, 982.

8. Hewgill, F.R. and Howie, G. B., Aust. J. Chem., 31, 1978, 907.

9. Rappoport, Z., J. Chem. Soc., 1963, 4498.

10. Rappoport, Z. and Harowitz, A., J. Chem. Soc., 1964, 1348.

11. De la mare, P.P.D., Electrophilic Halogenation, Chapter 10, Cambridge University


Press, London, 1976.

12. Marwein, B.L. and Bhatt, S.N., Thermochimica Acta, 118, 1987, 277.

13. Marwein, B.L. and Bhatt, S.N., Acustica, 58, 1985, 243.

14. Kannappan, V. and Kothai, S., J. Acous. Soc. Ind., 29(1), 2001, 169.

15. Kannappan, V. and Jaya Santhi, R., Ind. J. Pure & Appl. Phys., 43,
2005, 167.

16. Kannappan, V. and Kothai, S., Ind. J. Pure & Appl. Phys., 40, 2002, 17.

17. Indra Gandhi, N., Ph.D. Thesis, University of Madras, 2006.


TABLE 7.1

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - ORTHO CRESOL SYSTEM

Solvent : dichloromethane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1058.2 1136.3 5.08 0.79 9.9 9.4 0.6 4375 33.1 12.0

0.002 1055.2 1136.2 5.08 0.79 10.0 3.6 0.6 4382 33.2 12.0

0.004 1052.8 1136.8 5.10 0.79 10.1 -1.2 0.6 4393 33.3 12.0

0.006 1050.0 1138.2 5.09 0.80 10.2 -6.7 0.6 4398 33.3 12.0

0.010 1051.4 1138.7 5.05 0.79 10.0 -4.4 0.6 4377 33.1 12.0

0.015 1048.8 1139.6 5.08 0.80 10.2 -9.9 0.6 4392 33.2 12.0

0.020 1047.6 1139.9 5.10 0.80 10.2 -12.6 0.6 4403 33.3 11.9

Plots : Fig. 7.1 U vs Concentration; Fig. 7.3 χU vs Concentration; Fig. 7.5 CE vs Concentration;
Fig. 7.2 κ vs Concentration; Fig. 7.4 πi vs Concentration;
207

TABLE 7.2

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - PARA CRESOL SYSTEM

Solvent : dichloromethane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1040.0 1137.7 5.03 0.81 10.3 -25.0 0.6 4396 33.2 11.8

0.002 1043.6 1138.1 5.05 0.81 10.3 -18.3 0.6 4397 33.2 11.9

0.004 1048.0 1137.4 5.07 0.80 10.2 -10.1 0.6 4393 33.3 11.9

0.006 1047.6 1139.2 5.09 0.80 10.2 -11.1 0.6 4403 33.3 11.9

0.010 1046.0 1139.5 5.11 0.80 10.3 -14.4 0.6 4414 33.4 11.9

0.015 1040.0 1140.0 5.07 0.81 10.4 -26.0 0.6 4408 33.3 11.9

0.020 1050.6 1140.6 5.06 0.79 10.1 -6.4 0.6 4380 33.1 12.0

Plots : Fig. 7.1 U vs Concentration; Fig. 7.3 χU vs Concentration; Fig. 7.5 CE vs Concentration;
Fig. 7.2 κ vs Concentration; Fig. 7.4 πi vs Concentration;
208

TABLE 7.3

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - META CRESOL SYSTEM

Solvent : dichloromethane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1047.8 1135.3 5.06 0.80 10.2 -10.3 0.6 4384 33.2 11.9

0.002 1049.2 1136.7 5.03 0.80 10.1 -7.8 0.6 4373 33.1 11.9

0.004 1050.0 1137.9 5.02 0.80 10.0 -6.5 0.6 4367 33.0 11.9

0.006 1051.6 1138.3 5.01 0.79 10.0 -3.6 0.6 4360 33.0 12.0

0.010 1054.8 1138.5 4.99 0.79 9.8 2.1 0.6 4342 32.9 12.0

0.015 1055.9 1138.7 4.99 0.79 9.8 3.7 0.6 4339 32.9 12.0

0.020 1047.2 1139.9 4.98 0.80 10.0 -13.3 0.6 4350 32.9 11.9

Plots : Fig. 7.1 U vs Concentration; Fig. 7.3 χU vs Concentration; Fig. 7.5 CE vs Concentration;
Fig. 7.2 κ vs Concentration; Fig. 7.4 πi vs Concentration;
209

TABLE 7.4

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - PHENOL SYSTEM

Solvent : dichloromethane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1054.4 1135.7 5.11 0.79 10.1 2.2 0.6 4393 33.3 12.0

0.002 1050.0 1136.9 5.09 0.80 10.2 -6.3 0.6 4396 33.3 11.9

0.004 1048.8 1137.8 5.05 0.80 10.1 -8.7 0.6 4385 33.2 11.9

0.006 1055.6 1136.7 5.06 0.79 9.9 4.0 0.6 4369 33.1 12.0

0.010 1055.2 1138.7 5.04 0.79 9.9 2.8 0.6 4362 33.0 12.0

0.015 1053.6 1139.0 5.03 0.79 9.9 -0.7 0.6 4360 33.0 12.0

0.020 1050.8 1139.5 5.04 0.79 10.0 -6.5 0.6 4367 33.1 12.0

Plots : Fig. 7.1 U vs Concentration; Fig. 7.3 χU vs Concentration; Fig. 7.5 CE vs Concentration;
Fig. 7.2 κ vs Concentration; Fig. 7.4 πi vs Concentration;
210

TABLE 7.5

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - CARVACROL SYSTEM

Solvent : dichloromethane Temperature : 303 K


-4 -9 2 -15 -3
C U ρ η /10 κ /10 α/f /10 χU /10 Lf πi CE Z /105
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1048.0 1134.9 5.00 0.80 10.1 -9.9 0.6 4359 33.1 11.9

0.002 1056.4 1136.2 4.97 0.79 9.8 5.9 0.6 4330 32.8 12.0

0.004 1046.8 1137.2 5.00 0.80 10.1 -12.5 0.6 4364 33.0 11.9

0.006 1049.2 1138.1 5.00 0.80 10.0 -8.1 0.6 4358 33.0 11.9

0.010 1050.0 1137.9 5.01 0.80 10.0 -7.0 0.6 4355 33.0 11.9

0.015 1043.2 1139.9 5.01 0.81 10.2 -20.3 0.6 4374 33.1 11.9

0.020 1050.0 1139.2 5.00 0.80 10.0 -7.9 0.6 4347 32.9 12.0

Plots : Fig. 7.1 U vs Concentration; Fig. 7.3 χU vs Concentration; Fig. 7.5 CE vs Concentration;
Fig. 7.2 κ vs Concentration; Fig. 7.4 πi vs Concentration;
211

TABLE 7.6

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - ORTHO CRESOL SYSTEM

Solvent : chloroform
Temperature : 303 K
-4 -9 2 -15 -3
C U ρ η /10 κ /10 α/f /10 χU /10 Lf πi CE Z /105
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 956.2 1276.4 6.05 0.86 14.3 -20.8 0.6 3650 34.6 12.2

0.002 955.2 1277.7 6.03 0.86 14.2 -23.0 0.6 3647 34.5 12.2

0.004 950.0 1277.0 6.03 0.87 14.5 -33.9 0.6 3655 34.6 12.1

0.006 962.5 1279.0 5.98 0.84 13.8 -8.7 0.6 3619 34.2 12.3

0.010 961.6 1279.3 6.00 0.85 13.9 -11.2 0.6 3626 34.3 12.3

0.015 966.4 1281.2 6.03 0.84 13.7 -2.1 0.6 3628 34.3 12.4

0.020 969.4 1281.6 6.00 0.83 13.5 3.2 0.6 3613 34.1 12.4

Plots : Fig. 7.6 U vs Concentration; Fig. 7.8 χU vs Concentration; Fig. 7.10 CE vs Concentration;
Fig. 7.7 κ vs Concentration; Fig. 7.9 πi vs Concentration;
212

TABLE 7.7

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - PARA CRESOL SYSTEM

Solvent : chloroform
Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 983.4 1278.2 6.04 0.81 13.1 35.8 0.6 3598 34.0 12.6

0.002 976.8 1278.7 6.05 0.82 13.3 21.8 0.6 3614 34.2 12.5

0.004 972.4 1279.5 6.06 0.83 13.6 12.3 0.6 3627 34.3 12.4

0.006 959.6 1279.7 6.06 0.85 14.1 -14.4 0.6 3649 34.5 12.3

0.010 962.8 1279.9 6.07 0.84 14.0 -8.3 0.6 3646 34.5 12.3

0.015 969.6 1279.5 6.04 0.83 13.6 5.0 0.6 3620 34.3 12.4

0.020 964.4 1279.8 6.02 0.84 13.8 -6.4 0.6 3623 34.3 12.3

Plots : Fig. 7.7 U vs Concentration; Fig. 7.9 χU vs Concentration; Fig. 7.11 CE vs Concentration;
Fig. 7.8 κ vs Concentration; Fig. 7.10 πi vs Concentration;
213

TABLE 7.8

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - META CRESOL SYSTEM

Solvent : chloroform
Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 970.0 1276.5 6.03 0.83 13.6 7.7 0.6 3615 34.3 12.4

0.002 973.2 1278.2 6.04 0.83 13.5 14.2 0.6 3616 34.2 12.4

0.004 971.6 1278.0 6.04 0.83 13.6 10.5 0.6 3619 34.3 12.4

0.006 960.8 1278.2 6.08 0.85 14.1 -12.1 0.6 3651 34.6 12.3

0.010 962.4 1278.6 6.13 0.84 14.1 -9.5 0.6 3660 34.6 12.3

0.015 964.4 1277.6 6.09 0.84 14.0 -6.2 0.6 3643 34.5 12.3

0.020 958.8 1279.3 6.02 0.85 14.0 -18.5 0.6 3634 34.4 12.3

Plots : Fig. 7.7 U vs Concentration; Fig. 7.9 χU vs Concentration; Fig. 7.11 CE vs Concentration;
Fig. 7.8 κ vs Concentration; Fig. 7.10 πi vs Concentration;
214

TABLE 7.9

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - PHENOL SYSTEM

Solvent : chloroform
Temperature : 303 K
-4 -9 2 -15 -3
C U ρ η /10 κ /10 α/f /10 χU /10 Lf πi CE Z /105
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 969.0 1278.5 6.04 0.83 13.6 5.6 0.6 3624 34.3 12.4

0.002 964.4 1278.2 6.09 0.84 14.0 -4.0 0.6 3647 34.5 12.3

0.004 968.4 1278.7 6.03 0.83 13.7 3.9 0.6 3623 34.3 12.4

0.006 965.6 1279.3 6.06 0.84 13.8 -2.2 0.6 3637 34.4 12.4

0.010 964.8 1279.2 6.11 0.84 14.0 -4.5 0.6 3653 34.6 12.3

0.015 967.2 1280.0 6.09 0.84 13.8 -0.4 0.6 3643 34.5 12.4

0.020 960.0 1280.5 6.06 0.85 14.1 -16.0 0.6 3646 34.5 12.3

Plots : Fig. 7.7 U vs Concentration; Fig. 7.9 χU vs Concentration; Fig. 7.11 CE vs Concentration;
Fig. 7.8 κ vs Concentration; Fig. 7.10 πi vs Concentration;
215

TABLE 7.10

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - CARVACROL SYSTEM

Solvent : chloroform
Temperature : 303 K
-4 -9 2 -15 -3
C U ρ η /10 κ /10 α/f /10 χU /10 Lf πi CE Z /105
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 964.8 1275.5 6.09 0.84 14.0 -3.1 0.6 3641 34.5 12.3

0.002 961.2 1276.5 6.08 0.85 14.1 -10.6 0.6 3648 34.6 12.3

0.004 957.4 1277.2 6.08 0.85 14.3 -18.7 0.6 3654 34.6 12.2

0.006 962.8 1278.4 6.09 0.84 14.0 -8.0 0.6 3648 34.5 12.3

0.010 968.4 1277.7 6.09 0.83 13.8 3.0 0.6 3635 34.4 12.4

0.015 957.0 1278.0 6.08 0.85 14.3 -21.2 0.6 3653 34.6 12.2

0.020 952.8 1278.2 6.06 0.86 14.4 -30.6 0.6 3652 34.6 12.2

Plots : Fig. 7.7 U vs Concentration; Fig. 7.9 χU vs Concentration; Fig. 7.11 CE vs Concentration;
Fig. 7.8 κ vs Concentration; Fig. 7.10 πi vs Concentration;
216

TABLE 7.11

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - ORTHO CRESOL SYSTEM

Solvent : carbon tetrachloride Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 894.4 1366.9 7.94 0.91 21.3 -25.5 0.6 3365 38.4 12.2

0.002 898.8 1367.6 7.96 0.91 21.1 -16.1 0.6 3362 38.3 12.3

0.004 896.8 1368.6 7.86 0.91 20.9 -20.9 0.6 3346 38.1 12.3

0.006 901.6 1367.0 7.91 0.90 20.8 -10.9 0.6 3345 38.1 12.3

0.010 898.4 1367.9 7.92 0.91 21.0 -18.9 0.6 3353 38.2 12.3

0.015 906.2 1368.1 7.93 0.89 20.5 -2.9 0.6 3342 38.1 12.4

0.020 907.6 1368.6 7.96 0.89 20.4 -1.1 0.6 3344 38.1 12.4

Plots : Fig. 7.11 U vs Concentration; Fig. 7.13 χU vs Concentration; Fig. 7.15 CE vs Concentration;
Fig. 7.12 κ vs Concentration; Fig. 7.14 πi vs Concentration;
217

TABLE 7.12

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - PARA CRESOL SYSTEM

Solvent : carbon tetrachloride Temperature : 303 K


-4 -9 2 -15 -3
C U ρ η /10 κ /10 α/f /10 χU /10 Lf πi CE Z /105
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 900.0 1365.8 8.10 0.90 21.4 -13.2 0.6 3386 38.6 12.3

0.002 901.2 1366.3 8.03 0.90 21.1 -10.7 0.6 3371 38.4 12.3

0.004 903.5 1366.5 7.98 0.90 20.8 -6.1 0.6 3355 38.3 12.3

0.006 905.2 1366.9 7.92 0.89 20.5 -2.7 0.6 3341 38.1 12.4

0.010 907.6 1367.2 7.96 0.89 20.5 1.8 0.6 3344 38.1 12.4

0.015 911.2 1367.3 8.00 0.88 20.3 8.8 0.6 3346 38.2 12.5

0.020 918.8 1367.0 8.04 0.87 19.9 24.7 0.6 3339 38.1 12.6

Plots : Fig. 7.11 U vs Concentration; Fig. 7.13 χU vs Concentration; Fig. 7.15 CE vs Concentration;
Fig. 7.12 κ vs Concentration; Fig. 7.14 πi vs Concentration;
218

TABLE 7.13

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - META CRESOL SYSTEM

Solvent : carbon tetrachloride Temperature : 303 K


-4 -9 2 -15 -3
C U ρ η /10 κ /10 α/f /10 χU /10 Lf πi CE Z /105
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 906.8 1366.5 8.00 0.89 20.6 1.8 0.6 3355 38.3 12.4

0.002 901.4 1367.2 7.95 0.90 20.9 -10.4 0.6 3355 38.2 12.3

0.004 898.0 1368.1 8.01 0.91 21.3 -18.3 0.6 3376 38.5 12.3

0.006 901.2 1369.2 7.96 0.90 20.9 -11.7 0.6 3360 38.2 12.3

0.010 898.0 1369.6 8.00 0.91 21.2 -19.7 0.6 3374 38.4 12.3

0.015 899.2 1368.8 7.98 0.90 21.1 -18.2 0.6 3367 38.3 12.3

0.020 896.8 1369.1 7.97 0.91 21.2 -24.6 0.6 3368 38.4 12.3

Plots : Fig. 7.11 U vs Concentration; Fig. 7.13 χU vs Concentration; Fig. 7.15 CE vs Concentration;
Fig. 7.12 κ vs Concentration; Fig. 7.14 πi vs Concentration;
219

TABLE 7.14

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - PHENOL SYSTEM

Solvent : carbon tetrachloride Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 914.2 1364.7 7.87 0.88 19.9 18.2 0.6 3311 37.8 12.5

0.002 906.8 1365.0 7.83 0.89 20.2 1.5 0.6 3316 37.9 12.4

0.004 912.8 1366.3 7.82 0.88 19.8 14.3 0.6 3306 37.7 12.5

0.006 911.2 1366.9 7.84 0.88 19.9 10.3 0.6 3312 37.8 12.5

0.010 912.8 1367.3 7.87 0.88 19.9 12.9 0.6 3317 37.8 12.5

0.015 904.8 1375.3 7.85 0.89 20.3 -5.9 0.6 3339 37.8 12.4

0.020 916.0 1368.5 7.86 0.87 19.7 17.7 0.6 3310 37.7 12.5

Plots : Fig. 7.11 U vs Concentration; Fig. 7.13 χU vs Concentration; Fig. 7.15 CE vs Concentration;
Fig. 7.12 κ vs Concentration; Fig. 7.14 πi vs Concentration;
220

TABLE 7.15

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - CARVACROL SYSTEM

Solvent : carbon tetrachloride Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 907.2 1365.3 7.96 0.89 20.5 2.6 0.6 3343 38.2 12.4

0.002 901.2 1366.3 7.89 0.90 20.7 -10.8 0.6 3340 38.1 12.3

0.004 909.6 1365.8 7.91 0.88 20.2 7.3 0.6 3328 38.0 12.4

0.006 907.2 1367.2 8.05 0.89 20.7 1.5 0.6 3364 38.4 12.4

0.010 908.0 1366.7 8.04 0.89 20.6 2.4 0.6 3357 38.3 12.4

0.015 901.6 1366.6 7.95 0.90 20.9 -12.8 0.6 3351 38.2 12.3

0.020 896.8 1367.3 8.02 0.91 21.4 -24.4 0.6 3374 38.5 12.3

Plots : Fig. 7.11 U vs Concentration; Fig. 7.13 χU vs Concentration; Fig. 7.15 CE vs Concentration;
Fig. 7.12 κ vs Concentration; Fig. 7.14 πi vs Concentration;
221

TABLE 7.16

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - ORTHO CRESOL SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1061.6 571.5 3.01 1.55 11.6 6.0 0.8 2088 31.9 6.1

0.002 1055.2 572.2 3.03 1.57 11.8 -6.3 0.8 2103 32.1 6.0

0.004 1049.2 572.7 3.02 1.59 12.0 -17.9 0.8 2106 32.1 6.0

0.006 1048.4 573.3 3.02 1.59 12.0 -19.8 0.8 2109 32.2 6.0

0.010 1052.0 574.2 3.02 1.57 11.9 -13.9 0.8 2102 32.1 6.0

0.015 1050.0 575.5 3.03 1.58 11.9 -18.6 0.8 2107 32.1 6.0

0.020 1052.8 576.7 3.04 1.56 11.9 -14.4 0.8 2108 32.1 6.1

Plots : Fig. 7.16 U vs Concentration; Fig. 7.18 χU vs Concentration; Fig. 7.20 CE vs Concentration;
Fig. 7.17 κ vs Concentration; Fig. 7.19 πi vs Concentration;
222

TABLE 7.17

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - PARA CRESOL SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1057.0 572.7 3.00 1.56 11.6 -2.6 0.8 2092 31.9 6.1

0.002 1050.8 572.2 2.99 1.58 11.8 -14.4 0.8 2094 32.0 6.0

0.004 1052.0 572.4 3.00 1.58 11.8 -12.5 0.8 2095 32.0 6.0

0.006 1050.4 573.0 3.02 1.58 12.0 -15.8 0.8 2106 32.1 6.0

0.010 1049.6 574.1 3.02 1.58 12.0 -17.8 0.8 2106 32.1 6.0

0.015 1048.0 575.0 3.01 1.58 12.0 -21.6 0.8 2101 32.0 6.0

0.020 1052.6 575.7 3.04 1.57 11.9 -13.7 0.8 2105 32.1 6.1

Plots : Fig. 7.16 U vs Concentration; Fig. 7.18 χU vs Concentration; Fig. 7.20 CE vs Concentration;
Fig. 7.17 κ vs Concentration; Fig. 7.19 πi vs Concentration;
223

TABLE 7.18

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - META CRESOL SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1045.6 567.6 2.96 1.61 12.0 -24.0 0.8 2078 32.0 5.9

0.002 1043.8 567.9 2.98 1.62 12.1 -27.6 0.8 2088 32.1 5.9

0.004 1048.0 568.9 2.97 1.60 11.9 -20.1 0.8 2079 31.9 6.0

0.006 1046.2 570.3 2.98 1.60 12.0 -23.9 0.8 2087 32.0 6.0

0.010 1049.2 572.3 3.00 1.59 11.9 -19.0 0.8 2095 32.1 6.0

0.015 1055.2 574.7 3.02 1.56 11.8 -8.8 0.8 2097 32.0 6.1

0.020 1056.8 576.6 3.04 1.55 11.7 -6.7 0.8 2103 32.0 6.1

Plots : Fig. 7.16 U vs Concentration; Fig. 7.18 χU vs Concentration; Fig. 7.20 CE vs Concentration;
Fig. 7.17 κ vs Concentration; Fig. 7.19 πi vs Concentration;
224

TABLE 7.19

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - PHENOL SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1053.2 572.5 3.00 1.57 11.8 -9.8 0.8 2098 32.0 6.0

0.002 1056.4 573.3 3.03 1.56 11.8 -4.0 0.8 2105 32.1 6.1

0.004 1054.4 573.7 3.05 1.57 11.9 -8.1 0.8 2116 32.2 6.0

0.006 1058.8 574.3 3.05 1.55 11.8 -0.2 0.8 2110 32.1 6.1

0.010 1052.2 575.4 3.04 1.57 11.9 -13.4 0.8 2114 32.2 6.1

0.015 1050.0 576.3 3.02 1.57 11.9 -18.5 0.8 2108 32.1 6.1

0.020 1049.1 577.1 3.03 1.57 11.9 -21.1 0.8 2110 32.1 6.1

Plots : Fig. 7.16 U vs Concentration; Fig. 7.18 χU vs Concentration; Fig. 7.20 CE vs Concentration;
Fig. 7.17 κ vs Concentration; Fig. 7.19 πi vs Concentration;
225

TABLE 7.20

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE - CARVACROL SYSTEM

Solvent : n-hexane Temperature : 303 K


-4 -9 2 -15 -3
C U ρ η /10 κ /10 α/f /10 χU /10 Lf πi CE Z /105
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1046.8 568.9 2.95 1.60 11.9 -21.8 0.8 2076 31.9 6.0

0.002 1048.4 570.0 2.99 1.60 12.0 -19.0 0.8 2090 32.0 6.0

0.004 1044.0 570.7 3.00 1.61 12.1 -27.6 0.8 2098 32.1 6.0

0.006 1042.6 571.0 2.98 1.61 12.1 -30.5 0.8 2092 32.1 6.0

0.010 1048.0 571.6 2.99 1.59 12.0 -21.2 0.8 2090 32.0 6.0

0.015 1057.2 573.5 3.01 1.56 11.7 -4.8 0.8 2086 31.9 6.1

0.020 1059.6 575.7 3.02 1.55 11.6 -1.2 0.8 2091 31.9 6.1

Plots : Fig. 7.16 U vs Concentration; Fig. 7.18 χU vs Concentration; Fig. 7.20 CE vs Concentration;
Fig. 7.17 κ vs Concentration; Fig. 7.19 πi vs Concentration;
226

TABLE 7.21

MEAN VALUES OF RELAXATION TIME (ττ), MEAN VALUES OF GIBB'S FREE ENERGY OF FORMATION (∆G) AND MEAN VALUES OF
FORMATION CONSTANT (K) FOR IODINE - PHENOLS CHARGE TRANSFER COMPLEXES IN DIFFERENT SOLVENTS AT 303 K

Solvent :- Dichloromethane Chloroform Carbon tetrachloride n-Hexane


-13 -13 -13 -13
τ /10 ∆G K τ /10 ∆G K τ /10 ∆G K τ /10 ∆G K
kJ kJ kJ kJ
DONOR s mol-1 dm-3 mol-1 s mol-1 dm-3 mol-1 s mol-1 dm-3 mol-1 s mol-1 dm-3 mol-1

o-Cresol 5.4 -11.6 102.7 6.8 -10.6 71.0 9.5 -9.7 50.9 6.3 -8.6 32.8

p-Cresol 5.4 -11.2 90.0 6.7 -10.6 69.5 9.5 -9.8 49.2 6.3 -8.4 28.7

m-Cresol 5.3 -11.2 84.7 6.8 -10.4 65.1 9.6 -9.7 48.2 6.4 -8.1 27.0

Phenol 5.3 -10.9 82.1 6.8 -10.0 56.9 9.2 -9.5 45.0 6.3 -7.9 23.0

Carvacrol 5.3 -10.8 77.7 6.9 -9.9 54.6 9.5 -9.0 36.4 6.3 -7.0 15.8
227

TABLE 7.22

FREE LENGTH (Lf), INTERNAL PRESSURE (π


πi)
AND COHESIVE ENERGY (CE) FOR PURE LIQUIDS

COMPONENT τ /10-13 Lf πi CE
s Ao atm kJ mol-1

Dichloromethane 4.91 0.52 5017 32.6

Chloroform 6.74 0.54 4271 35.1

Carbon tetrachloride 9.46 0.55 4004 39.2

n-Hexane 6.23 0.73 2481 32.7

o-Cresol 27.21 0.41 8081 84.4

p-Cresol 12.15 0.48 4909 52.0

m-Cresol 51.63 0.42 10844 114.8

Phenol 26.02 0.42 9393 83.6

Carvacrol 83.29 0.45 8614 134.4


Fig. 7.1 Plots of Ultrasonic velocity vs Concentration

Solvent : dichloromethane Temperature : 303 K


1065

1055
U, m s -1

1045

IO-OCL IO-PCL
IO-MCL IO-PL
IO-CVL
1035
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 7.2 Plots of Adiabatic compressibility vs Concentration

Solvent : dichloromethane Temperature : 303 K


0.82

0.81
2
κ /10 , kg ms
-1

0.80
-9

0.79

IO-OCL IO-PCL IO-MCL


IO-PL IO-CVL
0.78
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
229

Fig. 7.3 Plots of Molecular interaction parameter vs Concentration

Solvent : dichloromethane Temperature : 303 K


20.0
IO-OCL IO-PCL
IO-MCL IO-PL
10.0 IO-CVL
-1

0.0
χ U /10 , ms
-3

-10.0

-20.0

-30.0
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 7.4 Plots of Internal pressure vs Concentration

Solvent : dichloromethane Temperature : 303 K


4420

4400

4380
πi , atm

4360

4340
IO-OCL IO-PCL IO-MCL
IO-PL IO-CVL
4320
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
230

Fig. 7.5 Plots of Cohessive energy vs Concentration

Solvent : dichloromethane Temperature : 303 K


33.4

33.2
CE, kJ mol-1

33.0

32.8
IO-OCL IO-PCL IO-MCL
IO-PL IO-CVL
32.6
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 7.6 Plots of Ultrasonic velocity vs Concentration

Solvent : chloroform Temperature : 303 K


990
IO-OCL IO-PCL
IO-MCL IO-PL
IO-CVL
980

970
U, m s -1

960

950

940
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
231

Fig. 7.7 Plots of Adiabatic compressibility vs Concentration

Solvent : chloroform Temperature : 303 K


0.88

0.86
2
κ /10 , kg ms
-1

0.84
-9

0.82
IO-OCL IO-PCL IO-MCL
IO-PL IO-CVL
0.80
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 7.8 Plots of Molecular interaction parameter vs Concentration

Solvent : chloroform Temperature : 303 K


40.0
IO-OCL IO-PCL
IO-MCL IO-PL
IO-CVL
20.0
-1
χ U /10 , ms

0.0
-3

-20.0

-40.0
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
232

Fig. 7.9 Plots of Internal pressure vs Concentration

Solvent : chloroform Temperature : 303 K


3680

3660

3640
πi , atm

3620

3600

IO-OCL IO-PCL IO-MCL


3580 IO-PL IO-CVL
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 7.10 Plots of Cohessive energy vs Concentration

Solvent : chloroform Temperature : 303 K


34.8

34.6
CE, kJ mol-1

34.4

34.2

IO-OCL IO-PCL IO-MCL


34.0 IO-PL IO-CVL

0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
233

Fig. 7.11 Plots of Ultrasonic velocity vs Concentration

Solvent : carbon tetrachloride Temperature : 303 K


920

910
U, m s -1

900

IO-OCL IO-PCL
IO-MCL IO-PL
IO-CVL
890
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 7.12 Plots of Adiabatic compressibility vs Concentration

Solvent : carbon tetrachloride Temperature : 303 K


0.92

0.91

0.90
2
κ /10 , kg ms
-1

0.89
-9

0.88

0.87 IO-OCL IO-PCL IO-MCL


IO-PL IO-CVL
0.86
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
234

Fig. 7.13 Plots of Molecular interaction parameter vs Concentration

Solvent : carbon tetrachloride Temperature : 303 K


30.0
IO-OCL IO-PCL
IO-MCL IO-PL
20.0 IO-CVL

10.0
-1
χ U /10 , ms

0.0
-3

-10.0

-20.0

-30.0
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 7.14 Plots of Internal pressure vs Concentration

Solvent : carbon tetrachloride Temperature : 303 K


3400
IO-OCL IO-PCL IO-MCL
IO-PL IO-CVL
3380

3360
πi , atm

3340

3320

3300
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
235

Fig. 7.15 Plots of Cohessive energy vs Concentration

Solvent : carbon tetrachloride Temperature : 303 K


38.8
IO-OCL IO-PCL IO-MCL
38.6 IO-PL IO-CVL

38.4
CE, kJ mol-1

38.2

38.0

37.8

37.6
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 7.16 Plots of Ultrasonic velocity vs Concentration

Solvent : n-hexane Temperature : 303 K

1060
U, m s -1

1050

IO-OCL IO-PCL
IO-MCL IO-PL
IO-CVL
1040
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
236

Fig. 7.17 Plots of Adiabatic compressibility vs Concentration

Solvent : n-hexane Temperature : 303 K


1.62
IO-OCL IO-PCL
IO-MCL IO-PL
IO-CVL
1.60
2
κ /10 , kg ms
-1

1.58
-9

1.56

1.54
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 7.18 Plots of Molecular interaction parameter vs Concentration

Solvent : n-hexane Temperature : 303 K


IO-OCL IO-PCL
5.0 IO-MCL IO-PL
IO-CVL

-5.0
-1
χ U /10 , ms
-3

-15.0

-25.0

-35.0
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
237

Fig. 7.19 Plots of Internal pressure vs Concentration

Solvent : n-hexane Temperature : 303 K

2115

2100
πi , atm

2085

IO-OCL IO-PCL IO-MCL


IO-PL IO-CVL
2070
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 7.20 Plots of Cohessive energy vs Concentration

Solvent : n-hexane Temperature : 303 K


IO-OCL IO-PCL IO-MCL
32.3 IO-PL IO-CVL
CE, kJ mol-1

32.1

32.0

31.8
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
238

Chapter 8
239

CHAPTER – 8

DETERMINATION OF STABILITY CONSTANTS FOR


CHARGE TRANSFER COMPLEXES OF IODINE
MONOCHLORIDE AND CERTAIN PHENOLS AT 303 K

Introduction

The chemistry of phenolic group plays essential role in organic

synthesis as a pivotal functional group useful in a number of

transformations1-3. Phenols possess antifungal and antiviral properties and

they are used as effective antiseptic and disinfectant at low concentration4.

Halogens (X2) and interhalogen compounds (X-Y) form donor-acceptor

complexes of the type B…... X2 and B……XY with a wide range of Lewis

bases B5-7. These charge transfer (CT) complexes, first proposed by

Mulliken8 are now recognized to play a key role in many chemical and

biological processes. Consequently, many studies in spectral,

thermodynamic and other aspects have been reported in the literature, but

a few of them include a theoretical analysis of the results5,6,9. Although the

CT complexes are formed to be stable in solvents of low dielectric constants,

there is need for further work on the role of solvent in determining the

stability of CT complexes. Phenols form donor-acceptor complexes with

halogens, 2,3-dichloro-4,5dicyano-p-benzoquinone10 (DDQ),


240

tetracyanoethylene11 (TCN) and chloronil12 Kirsch et al have studied the

structure of these complexes by 1R studies11,12.

This chapter contains the results obtained in the ultrasonic

investigation of CT complexes formed between iodine monochloride and five

phenols. Studies are made in four different less polar and non polar

solvents, namely, dichloromethane, chloroform, carbon tetrachloride and n-

hexane. Ultrasonic velocities, densities and viscosities are measured in

solutions containing equimolar concentrations of phenol (donor) and iodine

mono-chloride (acceptor). Acoustical parameters such as adiabatic

compressibility, free length, internal pressure, cohesive energy and acoustic

impedance values are calculated from the measured properties. The

measurements and calculations have been made in order to establish the

formation of CT complex between iodine monochloride and phenol. In order

to asses the attraction between the donor and acceptor, formation constants

of the complexes are calculated using the equation proposed by

Kannappan13,14. This method is better than Bhatt’s15 method as the latter

can be used only for systems in which strong CT complexes are formed in

binary systems.

The measured ultrasonic velocities for the twenty systems along with

other acoustical properties are listed in Tables 8.1 – 8.20. Fig. 8.1 contains

the plots of ultrasonic velocity vs concentration for the five systems in


241

dichloromethane solution. It is found that the ultrasonic velocity decreases

with concentration, reaches a minimum at a specific concentration and then

increases with increase in concentration. A similar trend is observed in all

the media (Figs. 8.6, 8.11 and 8.16). These observations indicate that there

are interactions between iodine monochloride and phenol molecules even in

dilute solution. The interaction is found to be the maximum at a specific

concentration, which is characteristic of the solvent. This is also supported

by the increase in density with concentration in dilute solution. The density

is also higher at a characteristic concentration. At this concentration, the

viscosity is also found to be high.

Adiabatic compressibility (κ) values are calculated for the twenty

systems from the measured ultrasonic velocity and density values. Plots of

adiabatic compressibility against concentration in dichloromethane solvent

are given in Fig. 8.2. Similar plots for other solvents are given in Figs. 8.7,

8.12 and 8.17. The trend in adiabatic compressibility values with

concentration is the reverse of the trend observed in velocity values.

Adiabatic compressibility is found to be high at the concentration at which

the extent of complexation is a maximum. The increase in adiabatic

compressibility at a specific concentration also establishes the formation of

a CT complex between iodine monochloride and phenol. This is also

supported by the observation that free length values in the systems are

different from those in pure components (Chapter 7, Table 7.22). It is seen


242

that the free length is found to be constant for a given system. The values

are slightly greater than those of pure components. This confirms the

formation CT complexes between iodine monochloride and phenols.

Acoustic impedance (Z) is indicative of repulsive forces between the

component molecules. These values are given for all the systems in

Tables 8.1 – 8.20. It is formed that the acoustic impedance varies only

slightly with concentration. The slight decrease in acoustic impedance in the

mixtures containing donor-acceptor establishes the presence of attractive

forces between iodine monochloride and phenol molecules. This confirms

the formation of CT complexes between iodine monochloride and phenols.

Molecular interaction parameters (χU) with respect to velocity are a

measure of deviation from ideal behaviour and it can be used to establish

the formation of CT complexes. In the present investigation, molecular

interaction parameter values are calculated for all the systems at different

concentrations (Tables 8.1 – 8.20) and plots of molecular interaction

parameters against concentration are illustrated in Figs. 8.3, 8.8, 8.13 and

8.18. The positive and negative values of molecular interaction parameter in

almost all the systems establish the formation of CT complexes between

iodine monochloride and phenols in the four solvents investigated.

Molecular interaction parameter value is found to be large negative at a

specific concentration in each system. This observation also establishes that


243

the extent of complexation depends upon concentration and it is maximum

at a characteristic concentration.

Internal pressure (πi) in binary and ternary liquid mixtures can be

used to assess the deviation from ideal behaviour which may arise due to

intermolecular forces. The values of internal pressure are calculated for all

the systems and plots of internal pressure vs concentration are given in

figures 8.4, 8.9, 8.14 and 8.19. It is found that the internal pressure values

in ternary mixtures are different from that in pure components (Chapter 7,

Table 7.22). This indicates that there is a deviation from ideal behaviour in

all the systems which may be due to the formation of CT complexes between

iodine monochloride and phenols. In each system, internal pressure value is

relatively high at a particular concentration, suggesting that the

complexation is maximum at a specific concentration. This concentration

depends upon the solvent. Thus, the stability of this type of complexes is

influenced by the nature of the solvent.

Cohesive energy (CE) is another acoustical parameter that can be

used to assess the intermolecular attraction and CT complex formation in

liquid mixtures. Cohesive energy values for the twenty systems are

calculated and presented in Tables 8.1 – 8.20. The variation of cohesive

energy with concentration depends upon the nature of components in the

ternary mixtures. However, cohesive energy is high at a specific


244

concentration. Thus, intermolecular attraction in the systems studied is

maximum at that concentration. Plots of cohesive energy against

concentration for all the systems are illustrated in Figs. 8.5, 8.10, 8.15 and

8.20. Thus, the variation in the acoustical parameters establishes the

formation of a donor-acceptor complex between iodine monochloride and

phenols and the stability of the complex depends upon the concentration

and structure of phenols.

The effect of phenol structure and the influence of solvent on the

stability of the CT complex are also investigated in the present investigation.

The stability constants (K) of the complexes between iodine monochloride

and five structurally different phenols are calculated by the method of

Kannappan. The mean values of stability constant for the twenty systems in

four different solvents are summarised in Table 8.21. The change in the

values of stability constant with the structure of phenol is explained first.

The mean values of formation constant (Table 8.21) in a given solvent

suggest that the stability of complexes of iodine monochloride with phenols

is in the order:

Carvacrol < phenol < m-cresol < p-cresol < o-cresol

This order is the same as that between iodine and phenols. The presence of

methyl substituent at ortho and para positions of phenol, enhances the

stability of the complex as this substituent increases the π-electron density

of the benzene ring by inductive and hyper conjugative effects. In the case of
245

m-cresol, only +I effect operates and hence, it forms a more stable complex

with iodine monochloride than with phenol. The stability constant of o-

cresol-iodine monochloride complex is greater than that of p-cresol-iodine

monochloride complex as the electron releasing methyl substituents in

o-cresol is near the complexation site. Carvacrol-iodine monochloride

complex is the least stable among the five systems. This may be due to

steric effect of the presence of both iso-propyl and methyl substituents near

the complexation site in the ring.

The CT complexes are generally stable in less polar solvents as polar

solvents will destabilize the complex due to solvation of donor and acceptor

molecules as these are also polar compounds. The formation constants are

calculated for iodine monochloride-phenol complexes in four different

solvents to study the influence of solvent on the stability of these complexes.

The data are presented in Table 8.21. It is found that for a given system, the

stability constant increases with increase in the dielectric constant of the

medium. Thus the stability constant of o-cresol-iodine monochloride is the

highest in dichloromethane which has a dielectric constant (ε) of about 9

while the stability constant is the least in n-hexane which has a dielectric

constant of 1.89. This trend can be explained as follows: Phenol is a dipolar

molecule and iodine monochloride is also a polar molecule. When iodine

monochloride forms CT complex with phenol, the donor molecule is further

polarised. The increase in polarization leads to greater solvation in a solvent


246

of slightly higher dielectric constant and hence, among the less polar

solvents stability constant increases with increase in the dielectric constant

of the medium.

It is also worth comparing the stability constants of iodine monochloride-

phenol complexes (Table 8.21) with those of iodine-phenol complexes

(Chapter 7, Table 7.21). Comparison of the data presented in these two

tables shows that iodine forms a less stable complex with phenol than

iodine monochloride. This may be due to greater polarizing power of iodine

monochloride than that of iodine. Iodine monochloride is more polar than

iodine and it is a more effective Lewis acid than iodine. Another aspect

which is interesting to note is that the influence of methyl substituents in

phenol is more significant in iodine monochloride-phenol systems than in

iodine-phenol systems. This is better illustrated by comparing the difference

in the stability constants of iodine-phenol system and iodine-o-cresol

system and also by the difference between the stability constant values of

iodine monochloride-phenol and iodine monochloride-o-cresol systems. This

difference is more in the case of systems containing iodine than in the case

of systems containing iodine monochloride. This observation indicates the

extended selectivity relationship may be applicable to the complexation

process which involves equilibrium between donor and acceptor. This

principle was proposed by Brown and Nelson16,17 for electrophilic

substitution reaction which is a rate process. According to this principle,


247

the more reactive the attacking species, the less selective in electrophilic

substitution. When partial rates are considered, the less reactive

electrophile is better in distinguishing the substrates with different rates

than the more reactive electrophile. In the present case, iodine is a less

effective acceptor than iodine monochloride. It is more effective in

distinguishing the stabilities of complexes with phenols which are

structurally different.
248

REFERENCES

1. Carruthers, W., Some Modern Methods of Organic Synthesis, 3rd Edn., Cambridge
University Press, Cambridge, 1984.

2. House, H.O., Modern Synthetic Methods, 2nd Edn., Benjamin Cummins, Menlo Park,
1972.

3. March, J., Advanced Organic Chemistry, 4th Edn., John Wiley, New York, 1992.

4. Francis A Carey, Organic Chemistry, 5th Edn., Tata McGraw Hill Publishing
Comapany Ltd., New Delhi, 2005.

5. Legon, A.C., J. Chem. Soc., Faraday Trans., 91, 1995, 1881.

6. Raby, C., Claud, J., Buxereaud, J and Moesch, C., Bull. Soc. Chim. Fr., 1981, 5.

7. Drago, R.S. and Wenz, D.A., J. Am. Chem. Soc., 84, 1962, 526.

8. Mulliken, R.S., J. Am. Chem. Soc., 72, 1950, 600.

9. Abboud, J.L.M., Mo, O., de Paz, J.L.G., Yanez, M., Esseffar, M., Bouab, W., El
Mouhtadi, M., Mokhlisse, R., Ballesteros, E., Herreros, M., Homan, H., Lopez
Mardomingo, C. and Notario, R., J. Am. Chem. Soc., 115, 1993, 12468.

10. Vinodkumar, T, Veeraiah, T. and Venkateshwarlu, G., Proc. Indian Acad. Sci.
(Chem. Sci.), 112, 2000, 119.

11. Volkman, B., Kirsch, J., Proc. Ind. Acad. Sci., 97, 1988, 229.

12. Harsh, D. and Kirsch, J., Proc. Ind. Acad. Sci., 97, 1988, 223.

13. Kannappan, V. and Jaya Santhi, R., J. Acous. Soc. Ind., 29, 2001, 192.

14. Kannappan, V., Jaya Santhi, R. and Malar, E.J.P., Phys. Chem. Liq., 40(4), 2002, 507.

15. Marwein, B.L. and Bhatt, S.N., Acustica, 58, 1985, 243.

16. Brown, H.C. and McGray, C.W., J. Am. Chem. Soc., 77, 1955, 2300.

17. Brown, H.C. and Nelson, K.L., J. Am. Chem. Soc., 75, 1953, 6292.
TABLE 8.1

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - ORTHO CRESOL SYSTEM

Solvent : dichloromethane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1060.4 1136.7 5.10 0.78 9.9 13.7 0.6 4378 33.1 12.1

0.002 1050.0 1137.6 5.11 0.80 10.2 -6.2 0.6 4408 33.3 11.9

0.004 1049.0 1138.0 5.08 0.80 10.2 -8.1 0.6 4397 33.3 11.9

0.006 1048.0 1137.8 5.08 0.80 10.2 -10.1 0.6 4396 33.3 11.9

0.010 1052.0 1138.2 5.08 0.79 10.1 -2.7 0.6 4390 33.2 12.0

0.015 1056.0 1137.9 5.08 0.79 10.0 4.6 0.6 4379 33.2 12.0

0.020 1050.1 1138.4 5.09 0.80 10.2 -6.8 0.6 4394 33.3 12.0

Plots : Fig. 8.1 U vs Concentration; Fig. 8.3 χU vs Concentration; Fig. 8.5 CE vs Concentration;
Fig. 8.2 κ vs Concentration; Fig. 8.4 πi vs Concentration;
250

TABLE 8.2

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - PARA CRESOL SYSTEM

Solvent : dichloromethane Temperature : 303 K


-4 -9 2 -15 -3
C U ρ η /10 κ /10 α/f /10 χU /10 Lf πi CE Z /105
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1055.2 1137.1 5.06 0.79 10.0 3.8 0.6 4374 33.1 12.0

0.002 1054.3 1137.9 5.07 0.79 10.0 2.1 0.6 4382 33.1 12.0

0.004 1049.9 1138.3 5.06 0.80 10.1 -6.3 0.6 4386 33.2 12.0

0.006 1048.0 1136.9 5.06 0.80 10.2 -10.0 0.6 4388 33.2 11.9

0.010 1050.2 1137.5 5.07 0.80 10.1 -5.9 0.6 4387 33.2 11.9

0.015 1058.8 1137.9 5.06 0.78 9.9 10.4 0.6 4365 33.0 12.0

0.020 1061.2 1138.0 5.04 0.78 9.7 14.9 0.6 4348 32.9 12.1

Plots : Fig. 8.1 U vs Concentration; Fig. 8.3 χU vs Concentration; Fig. 8.5 CE vs Concentration;
Fig. 8.2 κ vs Concentration; Fig. 8.4 πi vs Concentration;
251

TABLE 8.3

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - META CRESOL SYSTEM

Solvent : dichloromethane Temperature : 303 K


-4 -9 2 -15 -3
C U ρ η /10 κ /10 α/f /10 χU /10 Lf πi CE Z /105
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1052.0 1137.8 5.03 0.79 10.0 -2.3 0.6 4372 33.1 12.0

0.002 1056.0 1138.1 5.04 0.79 9.9 5.2 0.6 4367 33.0 12.0

0.004 1062.8 1139.3 5.04 0.78 9.7 18.1 0.6 4357 32.9 12.1

0.006 1052.4 1139.0 5.05 0.79 10.0 -1.8 0.6 4378 33.1 12.0

0.010 1058.8 1138.5 5.05 0.78 9.8 10.2 0.6 4363 33.0 12.1

0.015 1058.0 1139.0 5.06 0.78 9.9 8.5 0.6 4370 33.0 12.1

0.020 1051.4 1140.4 5.08 0.79 10.1 -4.2 0.6 4393 33.2 12.0

Plots : Fig. 8.1 U vs Concentration; Fig. 8.3 χU vs Concentration; Fig. 8.5 CE vs Concentration;
Fig. 8.2 κ vs Concentration; Fig. 8.4 πi vs Concentration;
252

TABLE 8.4

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - PHENOL SYSTEM

Solvent : dichloromethane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1057.0 1136.9 5.04 0.79 9.9 7.2 0.6 4361 33.0 12.0

0.002 1055.0 1137.3 5.05 0.79 9.9 3.3 0.6 4372 33.1 12.0

0.004 1053.0 1139.0 5.05 0.79 10.0 -0.5 0.6 4379 33.1 12.0

0.006 1050.0 1139.1 5.07 0.80 10.1 -6.3 0.6 4393 33.2 12.0

0.010 1046.0 1139.3 5.07 0.80 10.2 -14.0 0.6 4403 33.3 11.9

0.015 1042.0 1139.3 5.04 0.81 10.3 -21.7 0.6 4393 33.2 11.9

0.020 1057.6 1140.0 5.02 0.78 9.8 7.6 0.6 4355 32.9 12.1

Plots : Fig. 8.1 U vs Concentration; Fig. 8.3 χU vs Concentration; Fig. 8.5 CE vs Concentration;
Fig. 8.2 κ vs Concentration; Fig. 8.4 πi vs Concentration;
253

TABLE 8.5

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - CARVACROL SYSTEM

Solvent : dichloromethane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1070.0 1138.4 5.06 0.77 9.5 32.1 0.5 4348 32.9 12.2

0.002 1056.0 1138.5 5.05 0.79 9.9 5.3 0.6 4373 33.1 12.0

0.004 1052.4 1139.4 5.05 0.79 10.0 -1.7 0.6 4381 33.1 12.0

0.006 1050.0 1139.5 5.06 0.80 10.1 -6.3 0.6 4391 33.2 12.0

0.010 1049.2 1139.5 5.08 0.80 10.1 -7.9 0.6 4396 33.2 12.0

0.015 1054.8 1140.1 5.10 0.79 10.0 2.5 0.6 4394 33.2 12.0

0.020 1057.1 1140.6 5.09 0.78 9.9 6.7 0.6 4384 33.1 12.1

Plots : Fig. 8.1 U vs Concentration; Fig. 8.3 χU vs Concentration; Fig. 8.5 CE vs Concentration;
Fig. 8.2 κ vs Concentration; Fig. 8.4 πi vs Concentration;
254

TABLE 8.6

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - ORTHO CRESOL SYSTEM

Solvent : chloroform
Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 971.4 1278.5 6.06 0.83 13.6 10.7 0.6 3627 34.3 12.4

0.002 962.6 1279.0 6.08 0.84 14.0 -7.6 0.6 3651 34.5 12.3

0.004 966.0 1276.8 6.10 0.84 13.9 -0.8 0.6 3646 34.5 12.3

0.006 965.2 1278.5 6.12 0.84 14.0 -2.6 0.6 3656 34.6 12.3

0.010 979.2 1276.4 6.11 0.82 13.4 26.2 0.6 3624 34.3 12.5

0.015 967.4 1279.2 6.09 0.84 13.8 1.1 0.6 3642 34.4 12.4

0.020 977.6 1279.6 6.01 0.82 13.2 21.9 0.6 3602 34.1 12.5

Plots : Fig. 8.6 U vs Concentration; Fig. 8.8 χU vs Concentration; Fig. 8.10 CE vs Concentration;
Fig. 8.7 κ vs Concentration; Fig. 8.9 πi vs Concentration;
255

TABLE 8.7

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - PARA CRESOL SYSTEM

Solvent : chloroform
Temperature : 303 K
-4 -9 2 -15 -3
C U ρ η /10 κ /10 α/f /10 χU /10 Lf πi CE Z /105
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 971.3 1277.0 6.07 0.83 13.6 10.5 0.6 3627 34.4 12.4

0.002 972.0 1278.8 6.06 0.83 13.6 11.9 0.6 3626 34.3 12.4

0.004 975.2 1277.3 6.03 0.82 13.4 18.5 0.6 3608 34.2 12.5

0.006 968.8 1279.1 6.05 0.83 13.7 5.1 0.6 3629 34.3 12.4

0.010 960.0 1278.9 6.06 0.85 14.1 -13.3 0.6 3649 34.5 12.3

0.015 955.0 1278.7 6.04 0.86 14.3 -23.8 0.6 3650 34.5 12.2

0.020 949.2 1278.8 6.02 0.87 14.5 -35.9 0.6 3655 34.6 12.1

Plots : Fig. 8.6 U vs Concentration; Fig. 8.8 χU vs Concentration; Fig. 8.10 CE vs Concentration;
Fig. 8.7 κ vs Concentration; Fig. 8.9 πi vs Concentration;
256

TABLE 8.8

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - META CRESOL SYSTEM

Solvent : chloroform
Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 978.0 1277.0 6.16 0.82 13.6 24.5 0.6 3641 34.5 12.5

0.002 964.0 1278.0 6.11 0.84 14.0 -4.7 0.6 3656 34.6 12.3

0.004 962.8 1278.5 6.10 0.84 14.0 -7.4 0.6 3653 34.6 12.3

0.006 966.8 1279.1 6.07 0.84 13.8 0.7 0.6 3640 34.4 12.4

0.010 968.8 1279.0 6.08 0.83 13.7 4.5 0.6 3637 34.4 12.4

0.015 962.9 1279.3 6.09 0.84 14.0 -8.1 0.6 3651 34.5 12.3

0.020 961.2 1280.3 6.10 0.85 14.1 -12.0 0.6 3660 34.6 12.3

Plots : Fig. 8.6 U vs Concentration; Fig. 8.8 χU vs Concentration; Fig. 8.10 CE vs Concentration;
Fig. 8.7 κ vs Concentration; Fig. 8.9 πi vs Concentration;
257

TABLE 8.9

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - PHENOL SYSTEM

Solvent : chloroform
Temperature : 303 K
-4 -9 2 -15 -3
C U ρ η /10 κ /10 α/f /10 χU /10 Lf πi CE Z /105
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 960.0 1277.3 6.04 0.85 14.1 -12.9 0.6 3640 34.5 12.3

0.002 962.0 1278.7 6.06 0.85 14.0 -8.8 0.6 3646 34.5 12.3

0.004 980.6 1279.3 6.09 0.81 13.3 29.7 0.6 3619 34.2 12.5

0.006 995.0 1279.8 6.06 0.79 12.6 60.0 0.6 3586 33.9 12.7

0.010 982.0 1280.3 6.03 0.81 13.1 32.1 0.6 3601 34.0 12.6

0.015 974.8 1279.6 6.00 0.82 13.3 16.6 0.6 3604 34.1 12.5

0.020 973.6 1279.0 5.98 0.82 13.3 13.7 0.6 3599 34.0 12.5

Plots : Fig. 8.6 U vs Concentration; Fig. 8.8 χU vs Concentration; Fig. 8.10 CE vs Concentration;
Fig. 8.7 κ vs Concentration; Fig. 8.9 πi vs Concentration;
258

TABLE 8.10

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - CARVACROL SYSTEM

Solvent : chloroform
Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 977.6 1277.4 6.03 0.82 13.3 23.7 0.6 3603 34.1 12.5

0.002 973.2 1278.3 6.05 0.83 13.5 14.4 0.6 3619 34.2 12.4

0.004 971.2 1278.5 6.07 0.83 13.6 10.1 0.6 3629 34.3 12.4

0.006 964.4 1278.4 6.06 0.84 13.9 -4.2 0.6 3638 34.4 12.3

0.010 966.4 1278.2 6.06 0.84 13.8 -0.4 0.6 3634 34.4 12.4

0.015 963.2 1278.6 6.05 0.84 13.9 -7.4 0.6 3635 34.4 12.3

0.020 978.8 1278.2 6.04 0.82 13.2 24.7 0.6 3602 34.1 12.5

Plots : Fig. 8.6 U vs Concentration; Fig. 8.8 χU vs Concentration; Fig. 8.10 CE vs Concentration;
Fig. 8.7 κ vs Concentration; Fig. 8.9 πi vs Concentration;
259

TABLE 8.11

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - ORTHO CRESOL SYSTEM

Solvent : carbon tetrachloride Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 913.8 1368.8 7.99 0.87 20.1 17.4 0.6 3342 38.0 12.5

0.002 898.0 1368.6 7.94 0.91 21.1 -17.6 0.6 3361 38.3 12.3

0.004 911.6 1369.2 7.95 0.88 20.1 12.1 0.6 3339 38.0 12.5

0.006 907.4 1369.1 7.96 0.89 20.5 2.5 0.6 3351 38.1 12.4

0.010 905.6 1368.3 7.94 0.89 20.5 -2.1 0.6 3347 38.1 12.4

0.015 896.8 1369.0 7.93 0.91 21.1 -22.1 0.6 3363 38.3 12.3

0.020 895.6 1370.1 7.99 0.91 21.3 -25.4 0.6 3381 38.4 12.3

Plots : Fig. 8.11 U vs Concentration; Fig. 8.13 χU vs Concentration; Fig. 8.15 CE vs Concentration;
Fig. 8.12 κ vs Concentration; Fig. 8.14 πi vs Concentration;
260

TABLE 8.12

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - PARA CRESOL SYSTEM

Solvent : carbon tetrachloride Temperature : 303 K


-4 -9 2 -15 -3
C U ρ η /10 κ /10 α/f /10 χU /10 Lf πi CE Z /105
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 919.0 1365.9 7.90 0.87 19.6 29.0 0.6 3311 37.8 12.6

0.002 920.8 1367.6 7.93 0.86 19.5 33.0 0.6 3315 37.8 12.6

0.004 897.2 1367.8 7.95 0.91 21.1 -19.5 0.6 3363 38.3 12.3

0.006 902.8 1367.7 7.96 0.90 20.8 -7.4 0.6 3356 38.2 12.3

0.010 904.0 1368.8 7.98 0.89 20.8 -5.1 0.6 3361 38.2 12.4

0.015 902.3 1366.1 7.97 0.90 20.9 -9.3 0.6 3358 38.3 12.3

0.020 905.2 1367.3 7.98 0.89 20.7 -3.4 0.6 3357 38.2 12.4

Plots : Fig. 8.11 U vs Concentration; Fig. 8.13 χU vs Concentration; Fig. 8.15 CE vs Concentration;
Fig. 8.12 κ vs Concentration; Fig. 8.14 πi vs Concentration;
261

TABLE 8.13

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - META CRESOL SYSTEM

Solvent : carbon tetrachloride Temperature : 303 K


-4 -9 2 -15 -3
C U ρ η /10 κ /10 α/f /10 χU /10 Lf πi CE Z /105
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 916.3 1366.9 7.98 0.87 19.9 23.0 0.6 3333 38.0 12.5

0.002 913.2 1368.8 7.96 0.88 20.1 15.9 0.6 3337 38.0 12.5

0.004 905.4 1369.6 7.93 0.89 20.5 -1.6 0.6 3348 38.1 12.4

0.006 901.5 1369.0 7.94 0.90 20.8 -10.5 0.6 3356 38.2 12.3

0.010 900.4 1369.6 7.95 0.90 20.9 -13.4 0.6 3362 38.2 12.3

0.015 904.0 1369.1 7.96 0.89 20.7 -6.2 0.6 3356 38.2 12.4

0.020 896.5 1368.3 7.96 0.91 21.2 -23.3 0.6 3371 38.4 12.3

Plots : Fig. 8.11 U vs Concentration; Fig. 8.13 χU vs Concentration; Fig. 8.15 CE vs Concentration;
Fig. 8.12 κ vs Concentration; Fig. 8.14 πi vs Concentration;
262

TABLE 8.14

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - PHENOL SYSTEM

Solvent : carbon tetrachloride Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 900.0 1366.5 7.97 0.90 21.0 -13.1 0.6 3362 38.3 12.3

0.002 901.2 1368.3 7.98 0.90 21.0 -10.6 0.6 3364 38.3 12.3

0.004 905.8 1368.5 7.98 0.89 20.6 -0.7 0.6 3356 38.2 12.4

0.006 915.2 1369.6 7.97 0.87 20.0 19.8 0.6 3338 38.0 12.5

0.010 918.4 1369.4 7.95 0.87 19.7 26.4 0.6 3329 37.9 12.6

0.015 924.2 1368.3 7.95 0.86 19.3 38.8 0.6 3317 37.8 12.6

0.020 902.4 1369.1 7.95 0.90 20.8 -10.3 0.6 3359 38.2 12.4

Plots : Fig. 8.11 U vs Concentration; Fig. 8.13 χU vs Concentration; Fig. 8.15 CE vs Concentration;
Fig. 8.12 κ vs Concentration; Fig. 8.14 πi vs Concentration;
263

TABLE 8.15

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - CARVACROL SYSTEM

Solvent : carbon tetrachloride Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 909.2 1367.3 7.93 0.88 20.3 7.2 0.6 3337 38.0 12.4

0.002 915.2 1368.8 8.01 0.87 20.1 20.4 0.6 3344 38.1 12.5

0.004 916.0 1368.9 7.97 0.87 19.9 21.9 0.6 3336 38.0 12.5

0.006 911.8 1368.7 7.93 0.88 20.1 12.3 0.6 3333 37.9 12.5

0.010 910.9 1367.6 7.94 0.88 20.2 9.8 0.6 3336 38.0 12.5

0.015 901.2 1367.7 7.96 0.90 20.9 -12.2 0.6 3358 38.3 12.3

0.020 910.0 1368.0 7.96 0.88 20.3 6.6 0.6 3343 38.1 12.4

Plots : Fig. 8.11 U vs Concentration; Fig. 8.13 χU vs Concentration; Fig. 8.15 CE vs Concentration;
Fig. 8.12 κ vs Concentration; Fig. 8.14 πi vs Concentration;
264

TABLE 8.16

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - ORTHO CRESOL SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1060.0 571.2 2.99 1.56 11.5 3.1 0.8 2083 31.8 6.1

0.002 1053.8 571.0 3.00 1.58 11.8 -8.7 0.8 2092 32.0 6.0

0.004 1056.8 571.1 3.00 1.57 11.7 -3.2 0.8 2089 32.0 6.0

0.006 1062.0 570.7 2.99 1.55 11.5 6.5 0.8 2080 31.8 6.1

0.010 1056.0 570.5 2.98 1.57 11.7 -5.2 0.8 2079 31.9 6.0

0.015 1043.2 570.2 2.97 1.61 12.1 -29.6 0.8 2086 32.0 5.9

0.020 1048.4 569.6 2.96 1.60 11.8 -20.3 0.8 2073 31.9 6.0

Plots : Fig. 8.16 U vs Concentration; Fig. 8.18 χU vs Concentration; Fig. 8.20 CE vs Concentration;
Fig. 8.17 κ vs Concentration; Fig. 8.19 πi vs Concentration;
265

TABLE 8.17

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - PARA CRESOL SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1045.4 571.0 2.97 1.60 12.0 -24.3 0.8 2091 32.0 6.0

0.002 1052.4 571.2 2.98 1.58 11.8 -11.2 0.8 2087 31.9 6.0

0.004 1055.6 571.2 2.99 1.57 11.7 -5.2 0.8 2087 31.9 6.0

0.006 1050.4 571.5 2.99 1.59 11.9 -15.1 0.8 2091 32.0 6.0

0.010 1052.8 571.5 2.99 1.58 11.8 -10.7 0.8 2089 32.0 6.0

0.015 1060.8 570.6 2.98 1.56 11.5 4.2 0.8 2073 31.8 6.1

0.020 1065.8 570.3 2.97 1.54 11.3 13.5 0.8 2064 31.7 6.1

Plots : Fig. 8.16 U vs Concentration; Fig. 8.18 χU vs Concentration; Fig. 8.20 CE vs Concentration;
Fig. 8.17 κ vs Concentration; Fig. 8.19 πi vs Concentration;
266

TABLE 8.18

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - META CRESOL SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1053.4 571.1 2.97 1.58 11.7 -9.3 0.8 2083 31.8 6.0

0.002 1053.6 571.0 2.94 1.58 11.6 -9.0 0.8 2073 31.7 6.0

0.004 1051.2 571.2 2.93 1.58 11.6 -13.7 0.8 2070 31.7 6.0

0.006 1049.6 571.0 2.98 1.59 11.9 -16.8 0.8 2088 32.0 6.0

0.010 1050.4 571.5 3.00 1.59 11.9 -15.7 0.8 2093 32.0 6.0

0.015 1057.6 571.8 2.97 1.56 11.6 -2.5 0.8 2077 31.8 6.0

0.020 1056.0 572.5 2.97 1.57 11.6 -5.9 0.8 2076 31.7 6.0

Plots : Fig. 8.16 U vs Concentration; Fig. 8.18 χU vs Concentration; Fig. 8.20 CE vs Concentration;
Fig. 8.17 κ vs Concentration; Fig. 8.19 πi vs Concentration;
267

TABLE 8.19

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
α/f2), MOLECULAR INTERACTION PARAMETER (χ
COEFFICIENT (α χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - PHENOL SYSTEM

Solvent : n-hexane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1050.8 567.1 2.96 1.60 11.8 -14.2 0.8 2072 31.9 6.0

0.002 1047.8 567.4 2.96 1.61 11.9 -19.9 0.8 2074 31.9 5.9

0.004 1050.8 568.4 2.97 1.59 11.8 -14.4 0.8 2077 31.9 6.0

0.006 1052.0 567.8 2.97 1.59 11.8 -12.3 0.8 2074 31.9 6.0

0.010 1053.2 568.0 2.97 1.59 11.8 -10.4 0.8 2073 31.9 6.0

0.015 1054.2 568.7 2.96 1.58 11.7 -8.9 0.8 2071 31.8 6.0

0.020 1061.6 569.3 2.98 1.56 11.5 4.7 0.8 2068 31.8 6.0

Plots : Fig. 8.16 U vs Concentration; Fig. 8.18 χU vs Concentration; Fig. 8.20 CE vs Concentration;
Fig. 8.17 κ vs Concentration; Fig. 8.19 πi vs Concentration;
268

TABLE 8.20

ULTRASONIC VELOCITY (U), DENSITY (ρ ρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE) AND ACOUSTIC IMPEDANCE (Z) AT VARIOUS CONCENTRATIONS
OF IODINE MONOCHLORIDE - CARVACROL SYSTEM

Solvent : n-hexane Temperature : 303 K


-4 -9 2 -15 -3
C U ρ η /10 κ /10 α/f /10 χU /10 Lf πi CE Z /105
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1

0.001 1049.2 567.0 2.95 1.60 11.8 -17.2 0.8 2069 31.9 5.9

0.002 1048.0 567.2 2.95 1.61 11.9 -19.5 0.8 2072 31.9 5.9

0.004 1047.6 567.6 2.96 1.61 11.9 -20.4 0.8 2074 31.9 5.9

0.006 1057.6 567.9 2.96 1.57 11.6 -1.7 0.8 2067 31.8 6.0

0.010 1054.4 568.4 2.95 1.58 11.6 -8.0 0.8 2064 31.8 6.0

0.015 1053.2 569.1 2.96 1.58 11.7 -10.6 0.8 2068 31.8 6.0

0.020 1056.8 570.0 2.97 1.57 11.6 -4.2 0.8 2068 31.8 6.0

Plots : Fig. 8.16 U vs Concentration; Fig. 8.18 χU vs Concentration; Fig. 8.20 CE vs Concentration;
Fig. 8.17 κ vs Concentration; Fig. 8.19 πi vs Concentration;
269

TABLE 8.21

MEAN VALUES OF RELAXATION TIME (ττ)MEAN VALUES OF GIBB'S FREE ENERGY OF FORMATION (∆G) AND MEAN VALUES OF FORMATION
CONSTANT (K) FOR IODINE MONOCHLORIDE - PHENOLS CHARGE TRANSFER COMPLEXES IN DIFFERENT SOLVENTS AT 303 K

Solvent :- Dichloromethane Chloroform Carbon tetrachloride n-Hexane


-13 -13 -13 -13
τ /10 ∆G K τ /10 ∆G K τ /10 ∆G K τ /10 ∆G K
kJ kJ kJ kJ
DONOR s mol-1 dm-3 mol-1 s mol-1 dm-3 mol-1 s mol-1 dm-3 mol-1 s mol-1 dm-3 mol-1

o-Cresol 5.4 -12.7 158.8 6.7 -11.0 84.1 9.5 -10.3 60.3 6.3 -9.6 45.6

p-Cresol 5.3 -12.2 125.3 6.8 -10.9 75.5 9.4 -10.0 55.7 6.3 -9.1 39.4

m-Cresol 5.3 -12.1 123.0 6.8 -10.8 73.2 9.5 -10.0 55.3 6.2 -8.6 36.4

Phenol 5.3 -12.0 118.9 6.6 -10.5 65.9 9.4 -9.9 51.9 6.3 -8.8 33.9

Carvacrol 5.3 -11.3 90.3 6.7 -10.3 62.1 9.4 -9.6 49.2 6.3 -7.8 22.1
Fig. 8.1 Plots of Ultrasonic velocity vs Concentration

Solvent : dichloromethane Temperature : 303 K


1075
IC-OCL IC-PCL
IC-MCL IC-PL
IC-CVL
1065
U, m s -1

1055

1045

1035
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 8.2 Plots of Adiabatic compressibility vs Concentration

Solvent : dichloromethane Temperature : 303 K


0.82

0.81

0.80
2
κ /10 , kg ms
-1

0.79
-9

0.78

0.77 IC-OCL IC-PCL


IC-MCL IC-PL
IC-CVL
0.76
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
271

Fig. 8.3 Plots of Molecular interaction parameter vs Concentration

Solvent : dichloromethane Temperature : 303 K


40
IC-OCL IC-PCL
IC-MCL IC-PL
30 IC-CVL

20
-1
χ U /10 , ms

10
-3

-10

-20

-30
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 8.4 Plots of Internal pressure vs Concentration

Solvent : dichloromethane Temperature : 303 K


4420
IC-OCL IC-PCL
IC-MCL IC-PL
IC-CVL
4400
πi , atm

4380

4360

4340
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
272

Fig. 8.5 Plots of Cohessive energy vs Concentration

Solvent : dichloromethane Temperature : 303 K


33.4
IC-OCL IC-PCL IC-MCL
IC-PL IC-CVL

33.2
CE, kJ mol-1

33.0

32.8
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 8.6 Plots of Ultrasonic velocity vs Concentration

Solvent : chloroform Temperature : 303 K


1000
IC-OCL IC-PCL
IC-MCL IC-PL
990 IC-CVL

980
U, m s -1

970

960

950

940
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
273

Fig. 8.7 Plots of Adiabatic compressibility vs Concentration

Solvent : chloroform Temperature : 303 K


0.88

0.86
2
κ /10 , kg ms

0.84
-9 -1

0.82

0.80
IC-OCL IC-PCL
IC-MCL IC-PL
IC-CVL
0.78
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 8.8 Plots of Molecular interaction parameter vs Concentration

Solvent : chloroform Temperature : 303 K


70
IC-OCL IC-PCL
IC-MCL IC-PL
50 IC-CVL

30
-1
χ U /10 , ms

10
-3

-10

-30

-50
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
274

Fig. 8.9 Plots of Internal pressure vs Concentration

Solvent : chloroform Temperature : 303 K


3680
IC-OCL IC-PCL
IC-MCL IC-PL
IC-CVL
3660

3640
πi , atm

3620

3600

3580
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 8.10 Plots of Cohessive energy vs Concentration

Solvent : chloroform Temperature : 303 K


34.8

34.6
CE, kJ mol-1

34.4

34.2

34.0 IC-OCL IC-PCL


IC-MCL IC-PL
IC-CVL
33.8
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
275

Fig. 8.11 Plots of Ultrasonic velocity vs Concentration

Solvent : carbon tetrachloride Temperature : 303 K


930

920
U, m s -1

910

900

IC-OCL IC-PCL IC-MCL IC-PL IC-CVL


890
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 8.12 Plots of Adiabatic compressibility vs Concentration

Solvent : carbon tetrachloride Temperature : 303 K


0.92

0.91

0.90
2
κ /10 , kg ms

0.89
-1

0.88
-9

IC-OCL
0.87 IC-PCL
IC-MCL
0.86 IC-PL
IC-CVL
0.85
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
276

Fig. 8.13 Plots of Molecular interaction parameter vs Concentration

Solvent : carbon tetrachloride Temperature : 303 K


50
IC-OCL IC-PCL IC-MCL
40 IC-PL IC-CVL

30

20
-1
χ U /10 , ms

10
-3

-10

-20

-30
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 8.14 Plots of Internal pressure vs Concentration

Solvent : carbon tetrachloride Temperature : 303 K


3400
IC-OCL IC-PCL IC-MCL
IC-PL IC-CVL
3380

3360
πi , atm

3340

3320

3300
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
277

Fig. 8.15 Plots of Cohessive energy vs Concentration

Solvent : carbon tetrachloride Temperature : 303 K


38.6
IC-OCL IC-PCL
IC-MCL IC-PL
IC-CVL
38.4
CE, kJ mol-1

38.2

38.0

37.8

37.6
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 8.16 Plots of Ultrasonic velocity vs Concentration

Solvent : n-hexane Temperature : 303 K


1070
IC-OCL IC-PCL
IC-MCL IC-PL
IC-CVL

1060
U, m s -1

1050

1040
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
278

Fig. 8.17 Plots of Adiabatic compressibility vs Concentration

Solvent : n-hexane Temperature : 303 K


1.62
IC-OCL IC-PCL IC-MCL IC-PL IC-CVL

1.60
2
κ /10 , kg ms
-1

1.58
-9

1.56

1.54
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 8.18 Plots of Molecular interaction parameter vs Concentration

Solvent : n-hexane Temperature : 303 K


15

5
-1

-5
χ U /10 , ms
-3

-15

-25
IC-OCL IC-PCL
IC-MCL IC-PL
IC-CVL
-35
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
279

Fig. 8.19 Plots of Internal pressure vs Concentration

Solvent : n-hexane Temperature : 303 K


IC-OCL IC-PCL IC-MCL
IC-PL IC-CVL

2090
πi , atm

2075

2060
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M

Fig. 8.20 Plots of Cohessive energy vs Concentration

Solvent : n-hexane Temperature : 303 K


IC-OCL IC-PCL IC-MCL IC-PL IC-CVL
32.1
CE, kJ mol-1

31.9

31.8

31.6
0.000 0.005 0.010 0.015 0.020 0.025

Concentration, M
280

Chapter 9
281

CHAPTER – 9

DETERMINATION OF FORMATION CONSTANTS FOR THE


CHARGE TRANSFER COMPLEXES OF CERTAIN ETHERS
AND IODINE MONOCHLORIDE IN DIFFERENT SOLVENTS

9.1. INTRODUCTION

Aryl ethers undergo electrophilic substitution reaction with halogens.

The reaction mechanism involves the formation of charge transfer complex

between aryl ether and halogen1-5. The formation of charge transfer complex

has been established by spectrophotometric methods, and the stability

constant values have been reported6-8. It may be pointed out that aryl ethers

and heterocyclic aromatic compounds can function as π- and n-electron

donors, since ethereal oxygen in aryl ethers, and heteroatom in heterocyclic

aromatic compounds contain lone pair of electrons. It has been found that

aliphatic and aromatic ethers form charge transfer complexes with acceptors

like iodine, iodine monochloride and tetrachloroethylene9-11.

Ultrasonic velocity measurements can be used to detect charge transfer

(CT) complexes in solution. Bhat and coworkers12 proposed an equation to

calculate the formation constants of complexes in binary mixtures at

moderate concentration. However, this method can be used only for relatively

strong donor-acceptor complexes. Recently, Kannappan et al modified Bhatt’s


282

equation and deduced another equation based on the assumption that the

deviation from ideal behaviour may be due to complex formation. This method

has been successfully used by several workers13-16 to calculate the formation

constants of complexes in solution.

This chapter deals with solvent and structural effects on the stability of

CT complexes formed between iodine monochloride (acceptor) and ethers

(donors) and identification of molecular property which is primarily

responsible for complex formation. The following four ethers were used as

donors in the present investigation:

Diphenyl ether, 4-chloroanisole, anisole and 1,4-dioxane.

The structures of ethers used as donors are given below:

Cl O
O CH3
diphenyl ether 4-chloroanisole

CH3 O
O
O

anisole 1,4-dioxane
283

The four solvents (medium) used in this investigation are:

Dichloromethane, chloroform, carbon tetrachloride and n-hexane.

These solvents are less polar and have low dielectric constants. It may be

pointed out that CT complexes are stable only in less polar solvents. The

formation constants are determined for the above sixteen systems at 303 K.

9.2. RESULTS AND DISCUSSION

The measured values of ultrasonic velocity, density, viscosity and

computed values of adiabatic compressibility, absorption coefficient,

molecular interaction parameter, free length, internal pressure, cohesive

energy, acoustic impedance, Lenard Jones Potential, relaxation time, free

energy of formation, free energy of activation and formation constants for

charge transfer complexes of iodine monochloride and four ethers in four

different solvents at 303 K are presented in Tables 9.1 – 9.17.

9.2.1. Ultrasonic Velocity (U)

The plots of ultrasonic velocity vs concentration are given in Fig. 9.1 for

the four systems in dichloromethane, while Fig. 9.6 contains similar plots for

chloroform solvent at 303 K. In these eight systems, the ultrasonic velocity

uniformly decreases with increase in concentration suggesting negative

deviation form ideal behaviour. The curves are steeper in systems containing

diphenyl ether, anisole and 1,4-dioxane as donors. These ethers may form

strong complexes with iodine monochloride as compared to 4-chloroanisole.


284

Plots of ultrasonic velocity vs concentration for the four systems in carbon

tetrachloride are given in Fig. 9.11 while similar plots for n-hexane solvent

are given in Fig. 9.16. The variation of ultrasonic velocity with concentration

in these two solvents is interesting to note. In carbon tetrachloride medium,

the ultrasonic velocity increases with increase in concentration in systems

containing anisole as donor. But the ultrasonic velocity decreases with

increase in concentration in systems in which 4-chloroanisole and diphenyl

ether are donors. Further, in 1,4-dioxane system, the ultrasonic velocity

decreases with increase in concentration, reaches a minimum at a particular

concentration and then increases. These observations also suggest that there

is deviation from ideal behaviour in the case of the four systems in carbon

tetrachloride solution. In n-hexane medium, the decrease in ultrasonic

velocity is observed in systems containing diphenyl ether and 1,4-dioxane

while increase in velocity is observed in systems in which anisole and

4-chloroanisole are used as donors. Thus, in the sixteen systems the

ultrasonic velocity depends upon the concentration and structure of donor.

9.2.2. Adiabatic Compressibility (κ)

The adiabatic compressibility values for various compositions of four

systems in each solvent have been calculated from the measured values of

ultrasonic velocities and densities. In the case of dichloromethane and

chloroform solvents, the adiabatic compressibility decreases with increase in

concentration for all the ethers as shown in the Figs. 9.2 and 9.7. This
285

indicates that there is considerable formation of donor-acceptor complexes for

all the ethers in these two solvents. In the case of carbon tetrachloride, there

is a decrease in adiabatic compressibility with increase in concentration for

diphenyl ether and 4-chloroanisole which is quite reverse in the case of the

other two as shown in Fig. 9.12. In the case of n-hexane medium, the

decreasing trend is observed for diphenyl ether and 1,4-dioxane, indicating

the formation of charge transfer complexes at higher concentration. But the

trend is quite opposite in the case of 4-chloroanisole and anisole as indicated

in Fig. 9.17.

α/ 2)
9.2.3. Absorption Coefficient (α/f

The absorption coefficient depends on the type of molecular species and

it is a measure of intermolecular attraction. In all these systems, there is

strong attraction between the electrophile iodine monochloride and ethers

which act as electron donors. It is found that in a given medium, the

absorption coefficient values are almost constant for all the ethers, indicating

that it is intrinsic property of the CT complex. However, these values are

different for different systems.

9.2.4. Molecular Interaction Parameter (χU)

The molecular interaction parameter is indicative of the extent of

deviation from ideal behaviour which may be due to the formation of charge
286

transfer complex. It can be used to assess the strength of molecular

attraction between the donor and acceptor in solution. Both positive and

negative values are obtained for all these systems in all the four media. This

suggests that some systems exhibit a positive deviation while others show a

negative deviation from ideal behaviour. These observations establish that in

all the systems, charge transfer complexes are formed. Plots of molecular

interaction parameter vs concentration are given in Figs. 9.3, 9.8, 9.13

and 9.18.

9.2.5. Relaxation Time (τ) and Free Length (Lf)

The relaxation time can be calculated from coefficient of viscosity,

density and ultrasonic velocity of the mixtures. The mean values of relaxation

time for each system are given in Table 9.17. It is found that the relaxation

time value is a constant for a particular system in a given solvent. This

indicates that there is formation of CT complex in all the systems and similar

complexes are formed.

The free length values are also found to be constant for all the systems

in a medium. It is found that these values do not vary much when the

solvents are different. It may be noted that the free length values are different

from those of pure components and this also establishes the formation of CT

complexes between iodine monochloride and ethers.


287

9.2.6. Internal Pressure

The internal pressure (πi) in binary mixtures is a measure of

intermolecular attraction between molecules of the components. The plots of

internal pressure vs concentration for all the four systems in

dichloromethane are shown in Fig. 9.4. The internal pressure increases first

and then decreases with increase in concentration for

4-chloroanisole and 1,4-dioxane. It is quite opposite in the case of diphenyl

ether and anisole. The same trend is almost seen in the case of chloroform

medium also. The plots of internal pressure vs concentration are given in Fig.

9.9. In the case of carbon tetrachloride and n-hexane, the internal pressure

values are found to be almost constant, and there is only a slight variation in

internal pressure, for all the systems. Figures 9.14 and 9.19 contain the plots

of internal pressure vs concentration in carbon tetrachloride and n-hexane

media respectively. There is one common observation in all the systems.

Whether the internal pressure value increases or decreases with increase in

concentration, the internal pressure is the highest at a particular

concentration which is characteristic of the system. This indicates that the

extent of complexation depends upon the structure of donor, the medium and

also the concentration.

9.2.7. Cohesive Energy (CE)

The cohesive energy in a liquid mixture is a measure of potential energy

of attraction between the molecules of the components. The interaction


288

between the molecules in a system can be assessed from cohesive energy

values. Plots of cohesive energy vs concentration for all the four ethers in

dichloromethane are given in Fig.9.5. It has been observed that cohesive

energy increases initially and then decreases in the case of 4-chloroanisole

and 1,4-dioxane but in the case of diphenyl ether and anisole it decreases

and then increases with increase in concentration. It is seen in general, that

the cohesive energy value is high at a particular concentration in each

system. This is similar to the variation in internal pressure value with

concentration. Thus, the extent of complexation is concentration dependent.

Plots of cohesive energy vs concentration are given in Figs. 9.10, 9.15 and

9.20.

9.2.8. Acoustic Impedance (Z)

The acoustic impedance for all the systems in a particular solvent is

found to be constant. Thus, acoustic impedance values vary with change in

medium, which may be due to difference in the stability of the CT complexes

in different media.

9.2.9. Lenard Jones Potential (LJP)

The Lenard Jones Potential values are computed for all the systems in

all the four solvents. The Lenard Jones Potential is found to be almost a

constant for all the ethers in a particular solvent. But the value increases

with change in solvent in the following order: n-hexane > dichloromethane >
289

chloroform > carbon tetrachloride. Since Lenard Jones Potential is a measure

of repulsive forces, which suggests that the repulsive forces operate

significantly in solvents of higher dielectric constant.

9.2.10. Free Energy of Formation (∆G)

The free energy of formation can be calculated from the formation

constant value. The free energy of formation values are determined for all the

sixteen systems (Table 9.17). The negative values of free energy of formation

for all the systems in all the solvents suggest that the donor-acceptor

complexes formed in all these systems are thermodynamically stable. The

values of free energy of formation in different solvents indicate that the

stability depends upon the solvent which is in the following order:

Dichloromethane > chloroform > carbon tetrachloride > n-hexane.

9.2.11. Free Energy of Activation (∆G#) and Relaxation Time (τ)

The constant values of free energy of activation and relaxation time for

all the systems in each solvent indicate the formation of similar type of

complexes.

9.2.12. Formation Constant (K)

The formation constants of CT complexes for various ethers and iodine

monochloride in different solvents are calculated and tabulated (Fig.9.17). It

may be noted that the formation constant values are almost constant for a
290

given system at a given temperature, indicating that the formation constant

depends on the structure of ethers. By comparing the values of formation

constants of four ethers in each solvent, the ease of complexation with iodine

monochloride and ethers is found to be in the order:

Diphenyl ether > 4-chloroanisole > anisole > 1,4-dioxane.

During the complexation between ether and iodine monochloride, ethereal

oxygen donates electron which is attracted by positive end of dipole in iodine

monochloride. The diphenyl ether contains electron releasing phenyl groups

on either side of the donor. Therefore, it forms relatively more stable complex

with iodine monochloride. In 4-chloroanisole, chlorine in the para position to

methoxy group releases electron by mesomeric effect although it withdraws

electrons by -I effect. But mesomeric effect is stronger than inductive effect.

However, in anisole molecule, the resonance effect is limited although

methoxy group is directly attached to a phenyl ring. In 1,4-dioxane molecule,

no mesomeric effect is possible and hence, the stability constant value is the

least in this case.

9.3. Correlation of stability constants with molecular properties

The complex formation is influenced by the molecular properties such

as polarizability (α), dipole moment (µ) and dielectric constant (ε) of donor

molecules17,18. These parameters for the four ethers are listed in Table 9.18.

The formation constant increases with increase in polarizability of donor

molecules. Therefore, increase in polarizability of donor increases the ease of

complexation. Further, formation constant increases with increase in dipole


291

moment of donor in three systems. However, in the case of diphenyl ether, the

formation constant is abnormally high even though it has a low dipole

moment. This may be due to rich π-electrons in diphenyl ether. It is also

found that the stability constant increases with increase in dielectric constant

of donor molecules except diphenyl ether. The greater stability constant of

diphenyl ether may be due to increase in π electron density in the two

neighbouring phenyl rings. These correlations of formation constant with

molecular properties indicate that, it is the polarizability factor, which

predominantly determines the ease of complexation. Thus, the acceptor

molecule first polarizes the donor molecule during the formation of a charge

transfer complex. The stability of charge transfer complex is also affected by

the polarity of the medium. As the dielectric constant of the medium

increases, the stability constant of the charge transfer complex also

increases.
292

REFERENCES

1. De la Mare, P.B.D.and Ridd, J.H., Aromatic Substitution: Nitration and Halogenation,


Baterworth’s Scientific Publications, London, 1959.

2. Stock, L.M. and Brown, H.C., Advan. Phys. Org. Chem., 1, 1963, 35.

3. Berliner, E., Prog. Phys. Org. Chem., 2, 1964, 253.

4. Norman, R.O.C.and Taylor, R., Electrophilic substitutions in Benzenoid Compounds,


American Elsevier Publishing Co., New York, 1965.

5. Marino, G., Tetrahedron, 21, 1965, 843.

6. Dewar, M.J.S., Kubba, V.P. and Petit, R., J. Chem. Soc., 1958, 3073.

7. Abraham, R.J., Sheppard, R.C., Thomas, W.A. and Turner, S., Chem. Common.,
1965, 43.

8. Winn, M. and Bordwell, F.G., J. Org. Chem., 32, 1967, 1810.

9. Mahendran, S., Ph.D. Thesis, University of Madras, 2002.

10. Kothai, S., Ph.D. Thesis, University of Madras, 2003.

11. Indra Gandhi, N., Ph.D. Thesis, University of Madras, 2006.

12. Marwein, B.L. and Bhat, S.N., Acustica, 58, 1985, 243.

13. Kannappan, V. and Jaya Santhi, R., J. Acous. Soc. Ind., 29, 2001, 192.

14. Kannappan, V. and Kothai, S., J. Acous. Soc. Ind., 30, 2002, 76.

15. Kannappan, V., Jaya Santhi, R. and Malar, E.J.P., Phys. Chem. Liq., 40, 2002, 507.

16. Kannappan, V. and Jaya Santhi, R. and Xavier Jesu Raja,S., Phys. Chem. Liq., 14(2),
2003, 133.

17. Timmernian, J., Physico-chemical constants fo pure organic compounds, Elsevier,


Regensburg, Germany, 1950.

18. McClellan, A.L., Tables of experimental dipole moments, W.H. Freeman & Company,
San Francisco and London, 1963.
TABLE 9.1

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - DIPHENYL ETHER SYSTEM

Solvent : dichloromethane Temperature : 303 K

C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105 LJP


M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 1052.0 1261.4 5.61 0.72 10.0 -2.4 0.5 4944 33.7 13.3 4.5
0.002 1050.0 1258.1 5.59 0.72 10.1 -6.2 0.5 4931 33.7 13.2 4.5
0.003 1049.6 1259.2 5.60 0.72 10.1 -7.1 0.5 4937 33.8 13.2 4.4
0.004 1049.0 1257.6 5.59 0.72 10.1 -8.3 0.5 4928 33.7 13.2 4.4
0.005 1048.6 1256.8 5.55 0.72 10.1 -9.1 0.5 4909 33.6 13.2 4.4
0.006 1048.0 1261.0 5.63 0.72 10.2 -10.3 0.5 4952 33.8 13.2 4.4
0.007 1047.2 1258.9 5.60 0.72 10.2 -11.9 0.5 4935 33.8 13.2 4.4
0.008 1046.4 1260.3 5.61 0.72 10.2 -13.5 0.5 4943 33.8 13.2 4.3
0.009 1046.0 1258.1 5.65 0.73 10.3 -14.4 0.5 4956 34.0 13.2 4.3
0.010 1045.2 1259.7 5.61 0.73 10.2 -16.0 0.5 4940 33.8 13.2 4.3

Plots : Fig. 9.1 U vs Concentration; Fig. 9.3 χU vs Concentration; Fig. 9.5 CE vs Concentration;
Fig. 9.2 κ vs Concentration; Fig. 9.4 πi vs Concentration;
294

TABLE 9.2

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - 4-CHLOROANISOLE SYSTEM

Solvent : dichloromethane Temperature : 303 K


C U ρ η /10 -4
κ /10 -9 2
α/f /10 -15
χU /10 -3
Lf πi CE Z /105 LJP
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 1054.8 1261.4 5.70 0.71 10.1 3.0 0.5 4978 34.0 13.3 4.6
0.002 1054.4 1262.9 5.60 0.71 9.9 2.2 0.5 4936 33.6 13.3 4.6
0.003 1054.0 1262.6 5.67 0.71 10.1 1.4 0.5 4964 33.8 13.3 4.6
0.004 1053.2 1261.1 5.64 0.71 10.1 -0.2 0.5 4950 33.8 13.3 4.6
0.005 1052.8 1262.6 5.67 0.71 10.1 -1.0 0.5 4964 33.9 13.3 4.5
0.006 1052.0 1263.2 5.68 0.72 10.2 -2.6 0.5 4974 33.9 13.3 4.5
0.007 1051.6 1264.1 5.69 0.72 10.2 -3.4 0.5 4980 33.9 13.3 4.5
0.008 1050.8 1264.7 5.68 0.72 10.2 -5.0 0.5 4976 33.9 13.3 4.5
0.009 1050.4 1263.8 5.66 0.72 10.2 -5.8 0.5 4966 33.9 13.3 4.5
0.010 1049.6 1265.3 5.62 0.72 10.1 -7.4 0.5 4955 33.8 13.3 4.4

Plots : Fig. 9.1 U vs Concentration; Fig. 9.3 χU vs Concentration; Fig. 9.5 CE vs Concentration;
Fig. 9.2 κ vs Concentration; Fig. 9.4 πi vs Concentration;
295

TABLE 9.3

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - ANISOLE SYSTEM

Solvent : dichloromethane Temperature : 303 K


C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105 LJP
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 1052.8 1256.6 5.61 0.72 10.1 -0.8 0.5 4931 33.8 13.2 4.5

0.002 1050.8 1257.9 5.62 0.72 10.1 -4.7 0.5 4941 33.8 13.2 4.5

0.003 1050.6 1257.8 5.61 0.72 10.1 -5.1 0.5 4937 33.8 13.2 4.5

0.004 1048.8 1256.7 5.58 0.72 10.1 -8.6 0.5 4925 33.7 13.2 4.4

0.005 1048.0 1258.6 5.59 0.72 10.1 -10.2 0.5 4933 33.7 13.2 4.4

0.006 1047.4 1259.1 5.58 0.72 10.1 -11.4 0.5 4929 33.7 13.2 4.4

0.007 1047.2 1257.7 5.43 0.73 9.9 -11.8 0.5 4862 33.3 13.2 4.4

0.008 1047.0 1258.5 5.56 0.72 10.1 -12.2 0.5 4919 33.7 13.2 4.4

0.009 1046.6 1256.9 5.54 0.73 10.1 -13.1 0.5 4908 33.6 13.2 4.3

0.010 1044.8 1258.4 5.57 0.73 10.2 -16.5 0.5 4926 33.7 13.1 4.3

Plots : Fig. 9.1 U vs Concentration; Fig. 9.3 χU vs Concentration; Fig. 9.5 CE vs Concentration;
Fig. 9.2 κ vs Concentration; Fig. 9.4 πi vs Concentration;
296

TABLE 9.4

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - 1,4 DIOXANE SYSTEM

Solvent : dichloromethane Temperature : 303 K


C U ρ η /10 -4
κ /10 -9 2
α/f /10 -15
χU /10 -3
Lf πi CE Z /105 LJP
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 1052.9 1257.1 5.61 0.72 10.0 -0.6 0.5 4930 33.7 13.2 4.5
0.002 1051.8 1258.2 5.67 0.72 10.2 -2.8 0.5 4960 33.9 13.2 4.5
0.003 1052.4 1258.1 5.66 0.72 10.2 -1.7 0.5 4956 33.9 13.2 4.5
0.004 1050.2 1258.0 5.66 0.72 10.2 -5.9 0.5 4961 33.9 13.2 4.5
0.005 1048.0 1257.5 5.68 0.72 10.3 -10.1 0.5 4972 34.0 13.2 4.4
0.006 1048.2 1260.6 5.71 0.72 10.3 -9.8 0.5 4992 34.1 13.2 4.4
0.007 1046.6 1261.0 5.66 0.72 10.3 -12.8 0.5 4971 33.9 13.2 4.3
0.008 1046.0 1259.0 5.64 0.73 10.3 -14.0 0.5 4961 33.9 13.2 4.3
0.009 1045.6 1257.8 5.65 0.73 10.3 -14.8 0.5 4961 34.0 13.2 4.3
0.010 1045.2 1258.2 5.64 0.73 10.3 -15.6 0.5 4960 34.0 13.2 4.3

Plots : Fig. 9.1 U vs Concentration; Fig. 9.3 χU vs Concentration; Fig. 9.5 CE vs Concentration;
Fig. 9.2 κ vs Concentration; Fig. 9.4 πi vs Concentration;
297

TABLE 9.5

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - DIPHENYL ETHER SYSTEM

Solvent : chloroform
Temperature : 303K
C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105 LJP
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 964.8 1411.2 6.70 0.76 13.9 -3.0 0.5 4088 35.0 13.6 2.1
0.002 964.4 1410.8 6.75 0.76 14.0 -4.0 0.5 4101 35.2 13.6 2.1
0.003 964.0 1412.2 6.72 0.76 14.0 -5.0 0.5 4096 35.1 13.6 2.1
0.004 963.9 1410.6 6.70 0.76 13.9 -5.3 0.5 4085 35.0 13.6 2.1
0.005 963.6 1411.8 6.71 0.76 14.0 -6.1 0.5 4093 35.1 13.6 2.1
0.006 962.8 1412.2 6.73 0.76 14.0 -7.8 0.5 4101 35.1 13.6 2.1
0.007 962.4 1413.5 6.78 0.76 14.2 -8.8 0.5 4119 35.3 13.6 2.1
0.008 961.6 1412.5 6.74 0.77 14.1 -10.6 0.5 4104 35.2 13.6 2.0
0.009 960.8 1413.2 6.73 0.77 14.1 -12.4 0.5 4104 35.1 13.6 2.0
0.010 960.0 1413.1 6.80 0.77 14.3 -14.1 0.5 4126 35.3 13.6 2.0

Plots : Fig. 9.6 U vs Concentration; Fig. 9.8 χU vs Concentration; Fig. 9.10 CE vs Concentration;
Fig. 9.7 κ vs Concentration; Fig. 9.9 πi vs Concentration;
298

TABLE 9.6

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - 4-CHLOROANISOLE SYSTEM

Solvent : chloroform
Temperature : 303K
C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105 LJP
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 966.4 1411.7 6.71 0.76 13.9 0.3 0.5 4088 35.0 13.6 2.2
0.002 966.0 1412.8 6.72 0.76 13.9 -0.6 0.5 4094 35.1 13.6 2.1
0.003 965.2 1412.4 6.73 0.76 13.9 -2.4 0.5 4098 35.1 13.6 2.1
0.004 964.8 1413.2 6.77 0.76 14.0 -3.3 0.5 4111 35.2 13.6 2.1
0.005 964.4 1413.5 6.77 0.76 14.0 -4.2 0.5 4113 35.2 13.6 2.1
0.006 964.0 1412.4 6.73 0.76 14.0 -5.2 0.5 4097 35.1 13.6 2.1
0.007 963.2 1412.1 6.70 0.76 14.0 -6.9 0.5 4090 35.0 13.6 2.1
0.008 962.4 1412.6 6.73 0.76 14.1 -8.7 0.5 4103 35.1 13.6 2.1
0.009 962.0 1411.8 6.73 0.77 14.1 -9.6 0.5 4101 35.2 13.6 2.0
0.010 961.6 1412.2 6.73 0.77 14.1 -10.5 0.5 4101 35.1 13.6 2.0

Plots : Fig. 9.6 U vs Concentration; Fig. 9.8 χU vs Concentration; Fig. 9.10 CE vs Concentration;
Fig. 9.7 κ vs Concentration; Fig. 9.9 πi vs Concentration;
299

TABLE 9.7

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - ANISOLE SYSTEM

Solvent : chloroform
Temperature : 303K
C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105 LJP
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 967.6 1412.1 6.64 0.76 13.6 2.8 0.5 4064 34.8 13.7 2.2
0.002 966.8 1414.3 6.72 0.76 13.8 1.0 0.5 4095 35.0 13.7 2.2
0.003 966.4 1412.2 6.75 0.76 13.9 0.1 0.5 4101 35.1 13.6 2.2
0.004 965.2 1413.0 6.70 0.76 13.9 -2.5 0.5 4089 35.0 13.6 2.1
0.005 964.8 1412.9 6.67 0.76 13.8 -3.5 0.5 4079 34.9 13.6 2.1
0.006 964.0 1412.8 6.72 0.76 14.0 -5.2 0.5 4098 35.1 13.6 2.1
0.007 963.2 1413.0 6.72 0.76 14.0 -7.0 0.5 4098 35.1 13.6 2.1
0.008 962.4 1413.7 6.73 0.76 14.0 -8.8 0.5 4105 35.1 13.6 2.1
0.009 962.0 1414.1 6.67 0.76 13.9 -9.7 0.5 4089 35.0 13.6 2.0
0.010 961.2 1414.0 6.72 0.77 14.1 -11.5 0.5 4103 35.1 13.6 2.0

Plots : Fig. 9.6 U vs Concentration; Fig. 9.8 χU vs Concentration; Fig. 9.10 CE vs Concentration;
Fig. 9.7 κ vs Concentration; Fig. 9.9 πi vs Concentration;
300

TABLE 9.8

ULTRASONIC VELOCITY (U), DENSITY (ρ


ρ), VISCOSITY (η
η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - 1,4-DIOXANE SYSTEM
Solvent : chloroform
Temperature : 303K
C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105 LJP
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 967.6 1411.3 6.75 0.76 13.9 2.8 0.5 4098 35.1 13.7 2.2
0.002 966.0 1411.2 6.75 0.76 13.9 -0.6 0.5 4099 35.1 13.6 2.1
0.003 965.6 1410.6 6.73 0.76 13.9 -1.5 0.5 4093 35.1 13.6 2.1
0.004 965.2 1412.8 6.80 0.76 14.1 -2.5 0.5 4119 35.3 13.6 2.1
0.005 964.0 1411.4 6.82 0.76 14.2 -5.0 0.5 4125 35.3 13.6 2.1
0.006 963.6 1411.6 6.81 0.76 14.2 -6.0 0.5 4124 35.3 13.6 2.1
0.007 962.4 1410.9 6.78 0.77 14.2 -8.5 0.5 4115 35.3 13.6 2.1
0.008 961.6 1410.8 6.80 0.77 14.3 -10.3 0.5 4123 35.3 13.6 2.0
0.009 960.8 1410.8 6.77 0.77 14.2 -12.0 0.5 4116 35.3 13.6 2.0
0.010 960.4 1411.9 6.75 0.77 14.2 -12.9 0.5 4113 35.2 13.6 2.0

Plots : Fig. 9.6 U vs Concentration; Fig. 9.8 χU vs Concentration; Fig. 9.10 CE vs Concentration;
Fig. 9.7 κ vs Concentration; Fig. 9.9 πi vs Concentration;
301

TABLE 9.9

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - DIPHENYL ETHER SYSTEM

Solvent : carbon tetrachloride


Temperature : 303 K
C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105 LJP
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 908.8 1515.0 8.78 0.80 20.3 6.5 0.6 3759 38.7 13.8 0.9
0.002 908.0 1514.2 8.81 0.80 20.4 4.5 0.6 3768 38.8 13.7 0.9
0.003 907.2 1513.5 8.79 0.80 20.5 2.5 0.6 3763 38.7 13.7 0.9
0.004 907.2 1514.4 8.83 0.80 20.5 2.4 0.6 3773 38.8 13.7 0.9
0.005 906.4 1513.2 8.80 0.80 20.5 0.4 0.6 3767 38.8 13.7 0.8
0.006 905.6 1514.6 8.83 0.81 20.6 -1.5 0.6 3776 38.9 13.7 0.8
0.007 904.8 1514.2 8.84 0.81 20.7 -3.5 0.6 3779 38.9 13.7 0.8
0.008 904.4 1514.2 8.86 0.81 20.8 -4.5 0.6 3784 38.9 13.7 0.8
0.009 904.0 1514.9 8.79 0.81 20.6 -5.6 0.6 3770 38.8 13.7 0.8
0.010 903.2 1515.1 8.84 0.81 20.8 -7.5 0.6 3784 38.9 13.7 0.8

Plots : Fig. 9.11 U vs Concentration; Fig. 9.13 χU vs Concentration; Fig. 9.15 CE vs Concentration;
Fig. 9.12 κ vs Concentration; Fig. 9.14 πi vs Concentration;
302

TABLE 9.10

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - 4-CHLOROANISOLE SYSTEM

Solvent : carbon tetrachloride


Temperature : 303 K
C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105 LJP
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 906.8 1516.7 8.91 0.80 20.7 2.1 0.6 3795 39.0 13.8 0.8
0.002 906.4 1516.9 8.85 0.80 20.6 1.0 0.6 3783 38.9 13.7 0.8
0.003 906.2 1517.7 8.89 0.80 20.7 0.4 0.6 3794 38.9 13.8 0.8
0.004 905.6 1516.2 8.90 0.80 20.8 -1.0 0.6 3794 39.0 13.7 0.8
0.005 905.2 1515.9 8.94 0.81 20.9 -2.1 0.6 3803 39.1 13.7 0.8
0.006 904.0 1515.8 8.84 0.81 20.8 -4.8 0.6 3785 38.9 13.7 0.8
0.007 903.2 1516.7 8.87 0.81 20.9 -6.8 0.6 3794 39.0 13.7 0.8
0.008 902.4 1518.2 8.90 0.81 21.0 -8.7 0.6 3804 39.0 13.7 0.8
0.009 901.6 1516.0 8.92 0.81 21.1 -10.6 0.6 3806 39.1 13.7 0.7
0.010 900.8 1517.3 8.95 0.81 21.2 -12.5 0.6 3817 39.2 13.7 0.7

Plots : Fig. 9.11 U vs Concentration; Fig. 9.13 χU vs Concentration; Fig. 9.15 CE vs Concentration;
Fig. 9.12 κ vs Concentration; Fig. 9.14 πi vs Concentration;
303

TABLE 9.11

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - ANISOLE SYSTEM

Solvent : carbon tetrachloride


Temperature : 303 K
C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105 LJP
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 899.6 1513.0 8.73 0.82 20.8 -13.8 0.6 3765 38.8 13.6 0.7
0.002 900.4 1513.4 8.69 0.82 20.7 -12.2 0.6 3756 38.7 13.6 0.7
0.003 901.2 1513.5 8.74 0.81 20.7 -10.6 0.6 3764 38.8 13.6 0.7
0.004 902.0 1514.0 8.72 0.81 20.6 -9.0 0.6 3761 38.7 13.7 0.8
0.005 902.4 1514.4 8.77 0.81 20.7 -8.3 0.6 3772 38.8 13.7 0.8
0.006 903.4 1513.8 8.81 0.81 20.8 -6.2 0.6 3777 38.9 13.7 0.8
0.007 903.6 1514.0 8.76 0.81 20.6 -6.0 0.6 3766 38.8 13.7 0.8
0.008 904.0 1512.5 8.75 0.81 20.6 -5.2 0.6 3760 38.7 13.7 0.8
0.009 904.4 1513.4 8.69 0.81 20.4 -4.5 0.6 3749 38.6 13.7 0.8
0.010 905.0 1512.5 8.72 0.81 20.5 -3.3 0.6 3753 38.6 13.7 0.8

Plots : Fig. 9.11 U vs Concentration; Fig. 9.13 χU vs Concentration; Fig. 9.15 CE vs Concentration;
Fig. 9.12 κ vs Concentration; Fig. 9.14 πi vs Concentration;
304

TABLE 9.12

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - 1,4-DIOXANE SYSTEM

Solvent : carbon tetrachloride


Temperature : 303 K
C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105 LJP
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 907.6 1522.1 9.05 0.80 20.9 3.8 0.6 3833 39.2 13.8 0.9
0.002 907.2 1522.1 9.03 0.80 20.9 2.8 0.6 3828 39.2 13.8 0.9
0.003 906.8 1521.2 9.00 0.80 20.9 1.8 0.6 3823 39.2 13.8 0.8
0.004 905.6 1521.7 9.02 0.80 21.0 -1.0 0.6 3830 39.2 13.8 0.8
0.005 906.0 1521.5 8.99 0.80 20.9 -0.3 0.6 3822 39.1 13.8 0.8
0.006 907.6 1522.3 9.03 0.80 20.9 3.1 0.6 3830 39.2 13.8 0.9
0.007 909.6 1521.2 9.02 0.79 20.7 7.4 0.6 3821 39.1 13.8 0.9
0.008 912.0 1522.2 9.02 0.79 20.5 12.6 0.6 3818 39.1 13.9 1.0
0.009 912.4 1521.4 9.02 0.79 20.5 13.3 0.6 3816 39.1 13.9 1.0
0.010 912.8 1522.3 9.03 0.79 20.5 14.1 0.6 3819 39.1 13.9 1.0

Plots : Fig. 9.11 U vs Concentration; Fig. 9.13 χU vs Concentration; Fig. 9.15 CE vs Concentration;
Fig. 9.12 κ vs Concentration; Fig. 9.14 πi vs Concentration;
305

TABLE 9.13

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - DIPHENYL ETHER SYSTEM

Solvent : n-hexane
Temperature : 303 K
C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105 LJP
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 1052.8 625.2 3.27 1.44 11.8 -10.4 0.8 2322 32.4 6.6 4.5
0.002 1051.6 625.4 3.28 1.45 11.9 -12.8 0.8 2328 32.5 6.6 4.5
0.003 1050.4 626.0 3.26 1.45 11.8 -15.1 0.8 2322 32.4 6.6 4.5
0.004 1049.2 626.3 3.27 1.45 11.9 -17.4 0.8 2327 32.5 6.6 4.4
0.005 1048.0 625.8 3.26 1.45 11.9 -19.8 0.8 2322 32.4 6.6 4.4
0.006 1047.8 627.0 3.27 1.45 11.9 -20.2 0.8 2329 32.5 6.6 4.4
0.007 1047.6 626.6 3.26 1.45 11.9 -20.7 0.8 2324 32.4 6.6 4.4
0.008 1047.2 626.8 3.26 1.45 11.9 -21.5 0.8 2323 32.4 6.6 4.4
0.009 1046.8 626.8 3.26 1.46 11.9 -22.3 0.8 2325 32.5 6.6 4.4
0.010 1046.4 627.2 3.27 1.46 12.0 -23.1 0.8 2329 32.5 6.6 4.3

Plots : Fig. 9.16 U vs Concentration; Fig. 9.18 χU vs Concentration; Fig. 9.20 CE vs Concentration;
Fig. 9.17 κ vs Concentration; Fig. 9.19 πi vs Concentration;
306

TABLE 9.14

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - 4-CHLOROANISOLE SYSTEM

Solvent : n-hexane
Temperature : 303 K
C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105 LJP
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 1050.8 631.2 3.34 1.43 12.0 -14.2 0.8 2365 32.7 6.6 4.5
0.002 1051.6 631.9 3.33 1.43 11.9 -12.7 0.8 2360 32.6 6.6 4.5
0.003 1053.2 632.0 3.34 1.43 11.9 -9.8 0.7 2361 32.6 6.7 4.6
0.004 1054.0 632.4 3.33 1.42 11.8 -8.3 0.7 2358 32.6 6.7 4.6
0.005 1054.4 632.5 3.33 1.42 11.8 -7.6 0.7 2358 32.6 6.7 4.6
0.006 1055.6 632.7 3.34 1.42 11.8 -5.4 0.7 2362 32.6 6.7 4.6
0.007 1056.0 632.7 3.36 1.42 11.8 -4.7 0.7 2364 32.7 6.7 4.6
0.008 1056.4 632.9 3.33 1.42 11.7 -4.0 0.7 2354 32.5 6.7 4.7
0.009 1057.2 633.7 3.36 1.41 11.8 -2.5 0.7 2366 32.7 6.7 4.7
0.010 1057.6 633.8 3.34 1.41 11.7 -1.8 0.7 2359 32.6 6.7 4.7

Plots : Fig. 9.16 U vs Concentration; Fig. 9.18 χU vs Concentration; Fig. 9.20 CE vs Concentration;
Fig. 9.17 κ vs Concentration; Fig. 9.19 πi vs Concentration;
307

TABLE 9.15

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - ANISOLE SYSTEM

Solvent : n-hexane
Temperature : 303 K
C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105 LJP
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 1048.8 634.1 3.29 1.43 11.8 -17.9 0.8 2358 32.5 6.7 4.4
0.002 1050.2 634.7 3.31 1.43 11.9 -15.4 0.7 2365 32.5 6.7 4.5
0.003 1051.0 634.9 3.31 1.43 11.8 -13.9 0.7 2362 32.5 6.7 4.5
0.004 1051.6 634.8 3.32 1.42 11.8 -12.9 0.7 2363 32.5 6.7 4.5
0.005 1052.0 634.1 3.32 1.42 11.8 -12.2 0.7 2360 32.5 6.7 4.5
0.006 1052.4 635.0 3.30 1.42 11.7 -11.5 0.7 2356 32.4 6.7 4.5
0.007 1052.8 634.9 3.31 1.42 11.7 -10.8 0.7 2359 32.5 6.7 4.5
0.008 1054.0 635.7 3.32 1.42 11.7 -8.6 0.7 2361 32.5 6.7 4.6
0.009 1054.4 635.4 3.32 1.42 11.7 -7.9 0.7 2362 32.5 6.7 4.6
0.010 1055.2 635.1 3.33 1.41 11.7 -6.5 0.7 2361 32.5 6.7 4.6

Plots : Fig. 9.16 U vs Concentration; Fig. 9.18 χU vs Concentration; Fig. 9.20 CE vs Concentration;
Fig. 9.17 κ vs Concentration; Fig. 9.19 πi vs Concentration;
308

TABLE 9.16

ULTRASONIC VELOCITY (U), DENSITY (ρρ), VISCOSITY (η


η), ADIABATIC COMPRESSIBILITY (κ κ), ABSORPTION
2
COEFFICIENT (α
α/f ), MOLECULAR INTERACTION PARAMETER (χ χU), FREE LENGTH (Lf), INTERNAL PRESSURE (ππi),
COHESIVE ENERGY (CE), ACOUSTIC IMPEDANCE (Z) AND LENARD JONES POTENTIAL (LJP) AT VARIOUS
CONCENTRATIONS OF IODINE MONOCHLORIDE - 1,4-DIOXANE SYSTEM

Solvent : n-hexane
Temperature : 303 K
C U ρ η /10-4 κ /10-9 α/f2 /10-15 χU /10-3 Lf πi CE Z /105 LJP
M ms-1 kg m-3 Nsm-2 kg-1ms2 Npm-1s2 ms-1 Ao atm kJ mol-1 kg-2 s-1
0.001 1056.4 636.1 3.4 1.4 11.81 -3.63 0.7 2381 32.7 6.7 4.7
0.002 1055.6 635.8 3.3 1.4 11.76 -5.19 0.7 2372 32.6 6.7 4.6
0.003 1055.2 636.4 3.3 1.4 11.73 -5.99 0.7 2370 32.5 6.7 4.6
0.004 1054.4 637.0 3.4 1.4 11.80 -7.54 0.7 2378 32.6 6.7 4.6
0.005 1054.0 635.9 3.3 1.4 11.80 -8.33 0.7 2373 32.6 6.7 4.6
0.006 1052.8 635.6 3.3 1.4 11.81 -10.64 0.7 2369 32.6 6.7 4.5
0.007 1054.4 636.3 3.3 1.4 11.81 -7.67 0.7 2375 32.6 6.7 4.6
0.008 1055.2 635.9 3.3 1.4 11.77 -6.21 0.7 2371 32.6 6.7 4.6
0.009 1054.4 636.7 3.4 1.4 11.83 -7.76 0.7 2378 32.6 6.7 4.6
0.010 1053.6 636.8 3.3 1.4 11.81 -9.31 0.7 2374 32.6 6.7 4.6

Plots : Fig. 9.16 U vs Concentration; Fig. 9.18 χU vs Concentration; Fig. 9.20 CE vs Concentration;
Fig. 9.17 κ vs Concentration; Fig. 9.19 πi vs Concentration;
309

TABLE 9.17

MEAN VALUES OF RELAXATION TIME (t), MEAN VALUES OF GIBB'S FREE ENERGY
OF FORMATION (∆G) AND MEAN VALUES OF FORMATION CONSTANT (K) FOR
IODINE - PHENOLS CHARGE TRANSFER COMPLEXES IN DIFFERENT SOLVENTS AT 303 K

Solvent :- Dichloromethane Chloroform


-13 -13
τ /10 ∆G ∆G# K τ /10 ∆G ∆G# K
DONOR kJ mol- kJ kJ kJ dm-3
s 1
mol-1 dm-3 mol-1 s mol-1 mol-1 mol-1

Diphenyl ether 5.4 -13.8 3.4 236.7 6.9 -13.3 4.0 197.8
4-Chloroanisole 5.4 -10.6 3.4 72.2 6.8 9.7 4.0 53.8
Anisole 5.4 -10.5 3.4 69.6 6.8 -9.7 4.0 51.2
1,4-Dioxane 5.5 -9.7 3.4 52.1 6.9 -9.0 4.1 42.6

Solvent :- Carbon tetrachloride n-Hexane


-13 # -13
τ /10 ∆G ∆G K τ /10 ∆G ∆G# K
DONOR kJ kJ kJ
kJ mol- dm-3
s 1
mol-1 dm-3 mol-1 s mol-1 mol-1 mol-1

Diphenyl ether 9.5 -10.0 4.9 57.9 6.3 -9.3 3.8 47.6
4-Chloroanisole 9.6 -9.7 5.0 48.6 6.3 -9.2 3.8 40.0
Anisole 9.4 -9.2 4.9 38.5 6.3 -8.9 3.8 35.4
1,4-Dioxane 9.6 -9.0 5.0 36.1 6.3 -8.6 3.8 32.0
310

TABLE 9.18

POLARIZABILITY (α), DIPOLE MOMENT (µ) AND DIELECTRIC STRENGTH (ε)


DIELECTRIC STRENGTH (ε) OF DONORS OF SOLVENTS

Donor α/10-30 µ ε Solvent ε


m3 Debye

Diphenyl ether 20.86 1.03 2.68 Dichloromethane 9.08

4-Chloroanisole 14.75 1.62 7.84 Chloroform 4.81

Anisole 13.07 1.08 4.30 Carbon tetrachloride 2.24

1,4-Dioxane 10.00 0.00 2.22 n-Hexane 1.89


Fig. 9.1 Plots of Ultrasonic velocity vs Concentration

Solvent : dichloromethane Temperature : 303 K


1056
IC-DPE
IC-CAN
1054 IC-ANS
IC-DOX
1052
-1
U, m s

1050

1048

1046

1044
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M

Fig. 9.2 Plots of Adiabatic compressibility vs Concentration

0.730 Solvent : dichloromethane Temperature : 303 K

0.726
2
κ /10 , kg ms

0.722
-9 -1

0.718
IC-DPE
0.714 IC-CAN
IC-ANS
IC-DOX
0.710
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
312

Fig. 9.3 Plots of Molecular interaction parameter vs


Concentration

Solvent : dichloromethane Temperature : 303 K


IC-DPE
2 IC-CAN
IC-ANS
-2 IC-DOX
χ U/10-3, ms-1

-6

-10

-14

-18
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M

Fig. 9.4 Plots of Internal pressure vs Concentration

5000 Solvent : dichloromethane Temperature : 303 K

4980
4960
4940
πi, atm

4920
4900 IC-DPE
IC-CAN
4880
IC-ANS
4860 IC-DOX

4840
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
313

Fig. 9.5 Plots of Cohesive energy vs Concentration

34.2

34.0
CE, kJ mol-1

33.8

33.6
IC-DPE
IC-CAN
33.4 IC-ANS
IC-DOX

33.2
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M

Fig. 9.6 Plots of Ultrasonic velocity vs Concentration

Sovent : chloroform Temperature : 303 K


968
IC-DPE
IC-CAN
966 IC-ANS
IC-DOX

964
U, m s -1

962

960

958
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
314

Fig. 9.7 Plots of Adiabatic compressibility vs Concentration

Sovent : chloroform
0.772

0.768
2
κ /10 , kg ms

0.764
-9 -1

0.760
IC-DPE
IC-CAN
0.756
IC-ANS
IC-DOX
0.752
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M

Fig. 9.8 Plots of Molecular interaction parameter vs


Concentration

Sovent : chloroform Temperature : 303 K


5.0
IC-DPE
IC-CAN
0.0 IC-ANS
-1

IC-DOX
χ U /10 , ms

-5.0
-3

-10.0

-15.0

-20.0
0.000 0.005 0.010 0.015
Concentration, M
315

Fig. 9.9 Plots of Internal pressure vs Concentration

Sovent : chloroform
4130

4120

4110
π i, atm

4100

4090
IC-DPE
4080
IC-CAN
4070 IC-ANS
IC-DOX
4060
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M

Fig. 9.10 Plots of Cohesive energy vs Concentration

35.4 Sovent : chloroform

35.2
CE, kJ mol-1

35.0

34.8
IC-DPE IC-CAN
IC-ANS IC-DOX
34.6
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
316

Fig. 9.11 Plots of Ultrasonic velocity vs Concentration

Sovent : carbon tetrachloride Temperature : 303 K


916
IC-DPE IC-CAN
IC-ANS IC-DOX
912

908
U m s-1

904

900

896
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M

Fig. 9.12 Plots of Adiabatic compressibility vs Concentration

Sovent : carbon tetrachloride Temperature : 303 K


0.82

0.81
2
κ /10 , kg ms
-1

0.80
-9

0.79

IC-DPE IC-CAN
IC-ANS IC-DOX
0.78
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
317

Fig. 9.13 Plots of Molecular interaction parameter vs


Concentration

Sovent : carbon tetrachloride


15
IC-DPE IC-CAN
IC-ANS IC-DOX
9

3
χ U, ms-1

-3

-9

-15
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M

Fig. 9.14 Plots of Internal pressure vs Concentration

Sovent : carbon tetrachloride Temperature : 303 K


3840

3820

3800
π i, atm

3780

3760
IC-DPE IC-CAN
IC-ANS IC-DOX
3740
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
318

Fig. 9.15 Plots of Cohesive energy vs Concentration

Sovent : carbon tetrachloride Temperature: 303 K


39.4

39.2
CE, kJ mol -1

39.0

38.8

38.6
IC-DPE IC-CAN
IC-ANS IC-DOX
38.4
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M

Fig. 9.16 Plots of Ultrasonic velocity vs Concentration

Sovent : n-hexane Temperature : 303 K


1060
IC-DPE IC-CAN
IC-ANS IC-DOX

1056
U, m s -1

1052

1048

1044
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
319

Fig. 9.17 Plots of Adiabatic compressibility vs Concentration

Sovent : n-hexane Temperature : 303 K


1.46
2

1.44
κ /10 , kg ms
-9 -1

1.42

IC-DPE IC-CAN
IC-ANS IC-DOX
1.40
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M

Fig. 9.18 Plots of Molecular interaction parameter vs


Concentration

Solvent : n-hexane Temperature : 303 K

0 IC-DPE IC-CAN
IC-ANS IC-DOX

-5
-1

-10
χ U, ms

-15

-20

-25
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
320

Fig. 9.19 Plots of Internal pressure vs Concentration

Solvent : n-hexane Temperature : 303 K


2400

2380

2360
πi , atm

2340

2320
IC-DPE IC-CAN IC-ANS IC-DOX
2300
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M

Fig. 9.20 Plots of Cohesive energy vs Concentration

Solvent : n-hexane
32.8
IC-DPE IC-CAN
IC-ANS IC-DOX
32.7
CE, kJ mol-1

32.6

32.5

32.4

32.3
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
321

Chapter 10
322

CHAPTER – 10

SUMMARY

This thesis deals with ultrasonic studies on binary and ternary liquid

systems. The main aim of the present investigation is to distinguish

different types of intermolecular forces of attraction. The formation

constants of donor acceptor complexes formed between iodine and several

organic compounds are determined through ultrasonic velocity

measurement. Similar studies are also made in ternary systems containing

iodine monochloride and several organic compounds in n-hexane medium at

303 K. In the first chapter, the nature of ultrasound, measurement of

ultrasonic velocity and applications of ultrasound in various fields are

briefly outlined. The present work deals with charge transfer complexes and

hence, different types of donors, acceptors and donor-acceptor complexes

are indicated. The methods employed for the determination of such

complexes and the factors which influence the formation of CT complexes

are also described in this chapter.

The experimental details including materials used, their purification

and instrumental details are explained in the second chapter. The relevant

equations employed for computing the acoustical parameters and excess

properties are presented in the third chapter.


323

Ultrasound scan in liquid mixtures can be used to distinguish

different types of intermolecular attraction. In order to establish this,

ultrasonic velocity measurements were made in the following binary liquid

mixtures:

Benzene-carbon tetrachloride, bromobenzene-chlorobenzene,

ethanol-water, ethanol-p-cresol, ethanol-phenol and ethanol-pyridine.

The acoustical properties, excess functions and their trend with

concentration suggest that weak interactions of induced dipole-induced

dipole are present in benzene-carbon tetrachloride system while relatively

strong dipole-dipole attraction exists in bromobenzene-chlorobenzene binary

system. In the other four systems containing ethanol as common

component, ethanol behaves as structure breaker for water clusters and

strong intermolecular hydrogen bonds are present in this system at

moderate concentration. In ethanol-pyridine system, there are strong dipole-

dipole attractions. However, in ethanol-phenol and ethanol-p-cresol

systems, ethanol molecules break the intermolecular hydrogen bonds

present in the phenolic compounds and with increase in the mole fraction of

ethanol, there are strong intermolecular attractions between ethanol and

phenol molecules. The results obtained in these investigations are presented

in fourth chapter and discussed.


324

The fifth chapter deals with the ultrasonic investigations of charge

transfer complexes of iodine with six benzene derivatives and three

polynuclear aromatic hydrocarbons. Benzene derivatives used as donors are

benzene, toluene, o-xylene, m-xylene, p-xylene and mesitylene while the

polynuclear aromatic hydrocarbons are naphthalene, biphenyl and

anthracene. The ultrasonic velocity values and other acoustical properties

vary with concentration and these variations establish the formation of

donor-acceptor complexes between iodine and all the nine aromatic

hydrocarbon molecules. The trend in formation constant and free energy of

formation values suggests that the presence of methyl substituent in

benzene enhances the stability of the complex. Steric effect also plays a role

in the complexation and this is evident from stability constant and free

energy of formation values of ortho isomer of xylene as compared to those of

para and meta xylenes. Further, polynuclear aromatic hydrocarbon

molecules are rich in π electrons and hence, they form more stable

complexes than benzene derivatives. Among the polynuclear aromatic

hydrocarbon molecules, the stability constants of the complexes are in the

following order:

anthracene > biphenyl > naphthalene

Iodine monochloride is a dipolar molecule and the positive end of the

dipolar molecule may be attracted by π electrons of aromatic hydrocarbon

molecules. In the sixth chapter, stability constants for the CT complexes of


325

iodine monochloride and six benzene derivatives as well as three polycyclic

hydrocarbons are reported. These values are determined by ultrasonic

method. The acoustical properties also establish the formation of CT

complexes in these systems. It is found that the stability constant, free

energy of formation and relaxation time are constant for a given system and

differ from one system to another. The influence of substituents is found to

be similar to that observed in iodine complexes of these donor molecules. It

is also found that iodine monochloride forms more stable complexes with

aromatic hydrocarbons than with iodine.

Seventh chapter deals with the ultrasonic studies on the charge

transfer complexes of iodine and five phenolic derivatives. Acoustical

properties are calculated for the five systems in four different solvents with a

view to study the influence of solvent polarity on the stability of this type of

CT complexes. The variations in the acoustical properties with concentration

establish the formation of CT complexes between iodine and the five

phenols. The trend in the formation constant values indicates that the

presence of electron releasing group like methyl enhances the stability of the

complex. However, when bulky groups like isopropyl is adjacent to the

phenolic group, the stability constant is found to decrease. Slight increase

in polarity of the medium increases the stability of the CT complexes formed

in the five systems.


326

Eighth chapter contains the results obtained in the ultrasonic

investigation of CT complexes formed between iodine monochloride and five

phenols. Studies are made in four different less polar and non-polar

solvents namely, dichloromethane, chloroform, carbon tetrachloride and n-

hexane. The stability constants of the complexes formed between iodine

monochloride and phenols are calculated by the method of Kannappan. The

trend in the values of formation constants is explained with the known

structural effects. In a given solvent, the trend in the stability constants

indicates that the order of stability is:

o-Cresol > p-cresol > m-cresol > phenol > carvacrol

This order is similar to the trend in the stability constants of iodine

and phenols. The influence of dielectric constant of the medium on the

stability of this type of complexes is also studied. The stability constant of a

particular iodine monochloride-phenol complex increases with increase in

dielectric constant of the solvent.

Iodine monochloride can form CT complexes with ethers. Ethers can

function as n electron donors and in the case of aryl ethers, they can

function as π electron donors also. The results obtained in the ultrasonic

investigation of CT complexes formed between iodine monochloride and four

ethers are summarized in ninth chapter. Formation constants are reported

for CT complexes of iodine monochloride and four ethers in four solvents.


327

The trend in stability constants is explained with the structural effects. The

stabilities of these complexes are influenced by the dielectric constant of the

solvent. It is found that stability constant increases with increase in the

dielectric strength of the medium. The stability constants of the sixteen CT

complexes are correlated with the molecular properties of donor molecules.

Polarizability of donor correlates with the formation constants.

The conclusions drawn from the results obtained in all the

investigations and the important findings of the present studies are

summarized in the tenth chapter.


328

Annexure
329

LIST OF PUBLICATIONS
1. Arunkumar, M., Shabeer, T.K., Abdul Mahaboob, P.A., Jayakumar,
S., Kannappan, V. and Ulagendran, V., ‘Acoustical studies on
binary liquid mixtures’ Journal of Acoustical Society of India, Vol.
32, 2004, pp 142.

2. Kannappan, V., Askar Ali, S.J. and Abdul Mahaboob, P.A.,


‘Determination of stability constant of charge transfer
complexes of iodine monochloride and certain ethers in solution
at 303 K by ultrasound method’ Indian Journal of Pure & Applied
Physics, Vol. 44, December, 2006

3. Kannappan, V., Irusan, T., Abdul Mahaboob, P.A., and Askar Ali,
S.J. ‘Solvent effect on the stability constants of charge transfer
complexes of iodine and certain ethers at
303 K’ Journal of Molecular Liquids (Communicated)
330

LIST OF PAPERS PRESENTED

1. ‘Determination of stability constant of charge transfer


complexes of iodine and certain ethers in solution at 303
K’ ‘ALPS 2006’ - International Conference on Recent
Advancements in Chemistry, sponsored by Department of
Science and Technology, held at Auxilium College, Vellore,
Tamilnadu State during 5th and 6th January, 2006.

2. ‘Determination of stability constant of charge transfer


complexes of iodine monochloride and certain ethers in
solution at 303 K’ ‘ALPS 2006’ - International Conference on
Recent Advancements in Chemistry, sponsored by Department
of Science and Technology, held at Auxilium College, Vellore,
Tamilnadu State during 5th and 6th January, 2006.

3. ‘Ultrasonic studies on charge transfer complexes of iodine


monochloride and polynuclear aromatic hydrocarbons in
n-hexane solution at 303 K’ - ‘Newchemlinks 2006’ -
National Conference on Eco-, Sono- and Nanochemistry &
Recent Advancements in Chemistry, sponsored by Department
of Science and Technology, New Delhi held at The New College,
Chennai, Tamilnadu State during 20th and 21st December,
2006.
331

4. ‘Determination of stability constant of charge transfer


complexes of ethanolamines with tetrachloroethylene in
dimethyl sulphoxide solution by ultrasound method at
303 K’ - ‘Newchemlinks 2006’ - National Conference on Eco-,
Sono- and Nanochemistry & Recent Advancements in
Chemistry, sponsored by Department of Science and
Technology, New Delhi held at The New College, Chennai,
Tamilnadu State during 20th and 21st December, 2006.

5. ‘Determination of stability constant of charge transfer


complexes of polynuclear aromatic hydrocarbons with
iodine in n-hexane 303 K’ – ‘RAMS – 2006’ – National
Conference on Recent Advancements in Materials Science,
Sponsored by UGC, RKM Vivekananda College, Chennai,
Tamilnadu State during 29th and 30th December, 2006.

6. ‘Ultrasonic studies on charge transfer complexes of carbon


tetrachloride and ethanolamines in dimethyl sulphoxide
solution at 303 K’ - ‘RAMS – 2006’ – National Conference on
Recent Advancements in Materials Science, Sponsored by
UGC, RKM Vivekananda College, Chennai, Tamilnadu State
during 29th and 30th December, 2006.
332
333

Indian Journal of Pure & Applied Physics


Vol. 44, December 2006, pp. 903-908

Determination of stability constants of charge transfer complexes of


iodine monochloride and certain ethers in solution at 303 K by ultrasonic
method

V Kannappan, S J Askar Ali & P A Abdul Mahaboob


Postgraduate and Research Department of Chemistry, Presidency College (Autonomous), Chennai 600 005
Received 21 February 2006; revised 22 March 2006; accepted 24 October 2006

Ultrasonic velocities (U), densities (ρ), and coefficient of viscosities (η) are measured for solutions
containing iodine monochloride (ICl) and one of the following ethers in equimolar concentration in the range
0.001-0.01M at 303 K. The diphenyl ether, 4-chloroanisole, anisole and 1,4-dioxane are used as donors and the
dichloromethane, chloroform, carbon tetrachloride and n-hexane have been used as solvents. Acoustical
parameters such as adiabatic compressibility (β), absorption coefficient (α/f2), internal pressure (πi) and
cohesive energy (CE) values are calculated from the measured values of U, ρ and η. The trend in the acoustical
parameters establishes the formation of charge transfer complexes between iodine monochloride (acceptor) and
ethers (donors). The stability constants (K) are calculated for these complexes. The free energy changes (∆G)
for the formation of these complexes are also calculated from K values. The formation constants with
polarizability, dielectric strength and dipole moment of the donor and solvent molecules have been correlated.
The free energy of activation (∆G#) and viscous relaxation time (τ) are found to be almost constant for these
complexes indicating the formation of similar charge transfer complexes in these systems.

Keywords: Ultrasonic velocity, Formation constants, Donor-acceptor complexes, Iodine monochloride, Ethers
IPC Code: B01J19/10