Professional Documents
Culture Documents
THESIS
Submitted to the
UNIVERSITY OF MADRAS
by
P.A. ABDUL MAHABOOB, M.Sc., B.Ed.,
NOVEMBER 2006
2
3
4
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.
pleasure and duty to express my sincere thanks for his guidance and advice for
Dr. V. KANNAPPAN, M.Sc., Ph.D., FICS, AIC., Reader, Post Graduate &
Chennai – 600 005, for having suggested the present investigation which has
research, his humane touch and positive approach have made my period of
Mr. A. Khader Basha of The New College, Chennai, for allowing me to carry
Department of Physics, The New College, Chennai, for his constant support,
thank all the staff, teaching and non-teaching members, in the department for
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
Mohideen, Senior Lecturer in Chemistry, The New College, for their valuable
Mr. P. Balu, Research Scholars in the same department for their help and
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.
cooperation and help. My special thanks are due to Dr. S. Jayakumar, Reader
of Physics, JBAS College for Women, Chennai and Mrs. P.E. Akilandeswari,
Senior Lecturer in Physics, JBAS College for Women, Chennai for their support
Mr. S.M. Abdul Aziz and Mr. Md. Kaleemuddin Sayeed for their
Physics, The New College for his cooperation and support. I also thank
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
Thanks are also due to the Trustees of ILM Educational Trust, Chennai
Mr. P.A. Khaja Khaleel Rahman, for his blessings and constant
encouragement, without which this project would have been very difficult. I
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
Dedicated to:
All the Members,
Relatives and
Friends of
Penna Family
10
CONTENTS
1. Introduction 14
2. Experimental methods 57
Annexure 328
11
C : Concentration
U : Ultrasonic velocity
ρ : Density
η : Viscosity
κ : Adiabatic compressibility
τ : Relaxation time
Lf : Free length
Vf : Free volume
πi : Internal pressure
CE : Cohesive energy
Z : Acoustic impedance
Va : Available volume
ηE : Excess viscosity
CT : Charge transfer
α : Polarizability
µ : Dipole moment
ε : Dielectric strength
Fig. : Figure
BZ : Benzene
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
13
OXL : o-Xylene
TL : Toluene
ANT : Anthracene
BIP : Biphenyl
NAP : Naphthalene
CVL : Carvacrol
CAN : 4-Chloroanisole
ANS : Anisole
DOX : 1,4-Dioxane
14
Chapter 1
15
CHAPTER - 1
INTRODUCTION
In ternary systems, the stability constant values are calculated for the
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
investigations are also made with iodine monochloride as acceptor with a view
solutions and its effect on physical properties of the mixtures have received
much attention.
1.1. ULTRASONICS
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
than the audible limit are called infrasonics. But human ears do not respond
17
easily measurable.
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
believed that Galileo was the first to start the modern studies of acoustics. In
The era of modern ultrasonics began only in the early twentieth century
for submarine detection in 1917. From then on, slow but steady progress was
and the discovery in 1932 by Debye and Sears and also by Lucas and
detection.
Ever since, the field has grown enormously with wide applications in
science, medicine and other areas. Graff13 investigated physical, chemical and
cells. Stokes14 made the first attempt in medical imaging using ultrasonics.
The devices that generate and detect ultrasonic waves are called
are those, which do the reverse18-21. Transducers use any one of the following
• Magnetostrictive transducer
• Electromagnetic transducer
• Pneumatic transducer
• Piezoelectric transducer
along its length. This change in length is proportional to the strength of the
are used to generate vibrations. They are used for obtaining high amplitude
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
vibrations at low sonic frequencies. A typical example is the sonic pile driver
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
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
Ultrasonic waves can be detected with the help of Kundt’s tube. At the
distance between two adjacent heaps is equal to half the wavelength. This
the antinode, the flame is steady. At the position of the node, the flame
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
waves. In this method, a fine platinum wire is used. This wire is moved
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
Just as quartz or Rochelle’s salt crystals are used for the generation of
ternary mixtures. They are Flory’s theory27, Jacobson’s free length theory28,
liquid mixtures. These theories have been tested35. Based on the additivity of
Kudriavstev36,37. But the above theories do not explain in detail, all the
phenomena of ultrasonic wave propagation through liquid media and also the
intermolecular free length (Lf), free volume (Vf) and internal pressure (πi)
interacting molecules, the sign and magnitude of the excess parameters were
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
Most of the papers dealing with the excess thermodynamic functions are
the following excess parameters UE, ηE, βE, LfE and VfE make positive
components. On the other hand, the above excess parameters with negative
forces between the atoms determine the structure of the molecule. The
strong interactions such as the covalent bonds. Higher order structures like
molecular structure. Weak interactions, on the other hand, not only help to
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
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
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
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
many others have carried out ultrasonic studies of aqueous and non-aqueous
solutions.
mixtures66. Seghal and Porter studied the non-linear parameter for alcohol-
water mixtures and based on this parameter, they have discussed the
insight into the nature of the liquid state. Literature survey shows that
30
have been compared with Redlich-Kister theoretical equation and the results
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
of polymers100.
studies on soaps and detergents have not drawn adequate attention to give
interaction and the results were found to be in good agreement with those
The term ‘charge transfer’ has a wide common usage to describe the
that the term cannot be taken to imply that transfer of charge is the major
region.
ordinary temperatures in pure state since they are mostly unstable. But they
interactions are generally small that the forces of coordination are much
feebler than those established in the formation of covalent bonds113. That is,
33
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
between molecules in these complexes are 3.2 to 3.4 Ao, whereas chemical
The donor components are grouped into two categories. They are
π−donors
and their substitution products. These adducts which they form are called
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
n-donors
In the similar way, acceptors are also grouped into two categories. They
Inorganic acceptors
iodine monochloride, oxygen, salts of copper (I), silver (I) & mercury (II),
interacting orbitals118.
35
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.
relatively weak.
this basis, there are six types of charge transfer complexes. They are π−π, π−σ,
Solubility method
have been evaluated from the results of solubility studies119. It is not possible
36
complex. The uncertainty does not apply when a gaseous solution is used
since the pressure of the gaseous component and hence, its concentration in
Distribution measurements
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
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
Spectrophotometric methods
coefficient (absorptivity) εDA, (usually at the maximum for the charge transfer
D + A DA
different from the individual spectrum of the free donor and the acceptor.
blanks, which are identical with the reaction mixtures except that they
where CAo and CDo indicate the sum of the concentrations of the free and
complexed A and D.
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
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
dipole moment and in the oscillator strength of the charge transfer transition.
method of Benesi and Hildebrand leads to the conclusion that a complex with
and (c) entirely from contact charge transfer. Regardless of the relative
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
concentration region.
According to this equation, a plot of (d/CDo)n against ‘d’ should be linear if the
nD + A ADn
---------- (1.7)
40
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
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
sometimes more difficult to apply. In many cases, R-D plots show a wide
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
Other methods
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
bases for establishing the formulae of the complexes113 from the locations of
these maxima and minima. The physical property such as surface tension130
Solvent effect
molecular complexes are formed from neutral donors and acceptors without
some desolvation. Overall, the complex is less solvated than its free
42
complex decreases in stability as the solvent varies in the order n-heptane >
Temperature effect
heat. The effect is due to the thermal motion disorienting the partners of the
complex118.
Acceptor effect
Donor effect
alkenes < mono substituted ring compounds < multi ring donors
43
Optical resolution
latter has been completely resolved using the platinum complex prepared
Analytical procedures
from the unknown. The Kofler139 microscopic technique is well suited for the
complexes.
44
The Z value increases as the capacity of the medium to provide for ionization
increases.
which occur in biological systems may be of the type which lead to the
photosynthesis148,149.
Presumably, these donors interact more strongly with the electron deficient
intermediates of adducts of the organic halide and the catalyst and also of the
complex itself serves as the electrophilic reagent. This seems to be the case
46
toluene159.
The total (free and complexed) reactant concentrations for the reaction
formation of the complex serves only to reduce the concentrations of the free
Polymerization processes
of olefins and it has been suggested that complexes play a vital role as
reaction intermediates161.
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
a platinum-olefin complex.
48
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57
Chapter 2
58
CHAPTER - 2
EXPERIMENTAL METHODS
their purification techniques and details of the instruments used are outlined
briefly.
are usually employed. They are: (a) Pulse method, (b) Interferometer method
Ultrasonic Interferometer
the ultrasonic velocity in pure liquids and liquid mixtures1 with high degree of
Working Principle
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
The acoustic resonance gives rise to electric reaction on the generator driving
the quartz crystal and maximum anode current flows through the generator.
again. Using the micrometer screw attached to the reflector, the distance
measured value of wavelength (λ), the ultrasonic velocity (U) can be calculated
where ‘ν’ is the frequency of the generator which is used to excite the crystal
Description
They are:
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
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
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
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
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
± 0.1 K), water is circulated at any desired constant temperature through the
The density of the pure liquids, liquid mixtures, detergents, dyes and
Specific gravity bottle was standardized using double distilled water. The
thermostat for 15 minutes. The density of liquid and liquid mixtures can be
(accuracy ± 0.001 g), Mw is the mass of water and ρw is the density of water at
63
± 0.1 K with temperature set at required value. An electronic stop watch was
± 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
literature2.
thermostat.
2.1.4. Thermostat
2.2. MATERIALS
2.2.1. Solids
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.
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
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.
desired concentration.
66
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
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
22 4-Chloroanisole 198
23 Anisole 154
24 1,4-Dioxane 101
68
REFERENCES
2. Lide, D.R., CRC Handbook of Chemistry and Physics, 81st Edn., CRC
Press, Inc., 2001.
Chapter 3
70
CHAPTER - 3
determine the wavelength (λ) of the ultrasonic wave in liquid and liquid
Where, ‘ν’ is the frequency of the generator which is used to excite the crystal.
κ)
3.2. ADIABATIC COMPRESSIBILITY (κ
α/f2)
3.3. ABSORPTION COEFFICIENT (α
of the medium and the square of the frequency. It can be calculated from the
8Π 2η
(α/f2) = Nps2m-1 --------------- (3.3)
3ρU 3
72
χ U)
3.4. MOLECULAR INTERACTION PARAMETER (χ
following formula7:
U exp
χU = −1 ------------------ (3.4)
U ideal
and Uideal is the ultrasonic velocity of the ideal mixture of the components in
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
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
4η
τ= s ---------------------------------------- (3.5)
3ρU 2
73
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
molecules gets affected considerably. The intermolecular free length has been
K
Lf = A° --------------------- (3.6)
Uρ
10-8.
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
Meff = (X1M1 + X2M2 + X3M3). Where, X and M are the mole fraction and
πi)
3.8. INTERNAL PRESSURE (π
usually given as a product of internal pressure (πi) and molar volume (Vm)
attractive forces on its neighbours. If the intermolecular forces are small, the
cohesive energy is low and the molecules have relatively flexible chains.
U ∞ = 1600 ms-1
volume.
formation constant.
77
k = x/y.
Ucal = the ultrasonic velocity of the mixture calculated from the mole fractions
This equation can be used to calculate stability constant values for different
are defined as the difference between the experimental and ideal mixture
The excess values of the parameters have been computed from the
following expressions30:
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
Excess viscosity:
Where, η1 and η2 are the viscosities of solute and solvent, and ηexp is the
κ = 1/U2 ρ.
Where, Vf1 and Vf2 are the free volumes of solute and solvent and Vf(exp) is the
Where, Lf1 and Lf2 are the free lengths of solute and solvent and Lf(exp) is Lf
Where, Z1 and Z2 are the acoustic impedance values of solute and solvent and
Where, Va1 and Va2 are the acoustic impedance values of solute and solvent
REFERENCES
1. Bhatt, S.S. and Singh, D.P., Ind. J. Pure & Appl. Phys., 21, 1983, 506.
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.
7. Jayakumar, S., Karunanidhi, N. and Kannappan, V., Ind. J. Pure & Appl.
Phys., 34, 1996, 761.
11. Chellaiah, N. and Sebesan, R., Ind. J. Pure & Appl. Phys., 32, 1994, 315.
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.
23. Marwein, B.L. and Bhatt, S.N., Acustica, 58, 1985, 243.
25. Kannappan, V. and Kothai, S., J. Pure & Applied Ultrasonics., 2002, 24.
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.
31. Forte, R.J. and More, W.R., Trans. Faraday Soc., 61, 1963, 2102.
83
Chapter 4
84
CHAPTER – 4
4.1. INTRODUCTION
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
viscosity data. The molecular interactions in pure and binary liquid mixtures
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
the order
85
The factors that influence the strength of the molecular interactions are
described below:
Z + Z −e2
E= --------------- (4.1)
4Π ε o r
but sizes and charge number determine the ion-ion interaction energy. On
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
− 2 µ1 µ 2
E= ---------------- (4.3)
4Π ε o r 3
- + - +
+ -
- +
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
interaction energy is greater than that in gas phase containing the same
than ion-dipole interaction and fall off more rapidly with distance ( 13 ) and
r
species will depend upon the inherent polarizability (of systems), α , and on
the polarizing field offered by the dipole. This interaction energy is much
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.
− 2µ α
E= ------------ (4.5)
r6
− 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
result of the ‘ α 2 ’ term, London force increases rapidly with molecular size or
molecules begin to overlap and Pauli repulsion becomes extremely large. The
+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.
discussed.
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
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
second component. Thus, acoustical studies are made on six binary liquid
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.
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
these systems behave almost ideally. The curve obtained in the case of
mole fraction of ethanol (Fig. 4.7). It is seen that in the case of ethanol-water
for ethanol clusters. The decrease in velocity at higher mole fraction shows
between the components increases with increase in the mole fraction of the
second component.
91
κ)
4.2.2. Adiabatic Compressibility (κ
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
phenol and ethanol-pyridine, the plots in Fig. 4.8 show that there is an
of ‘κ’ in these three mixtures suggests that their compressibilities are in the
order:
increase in the mole fraction of the first component in three systems namely,
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.
presented in Tables 4.1, 4.3, 4.5, 4.7, 4.9 and 4.11 for the six binary systems.
molecular interaction parameter values are more negative than those for
parameter values are minimum at X1 = 0.4 – 0.6 suggesting that the two types
attractions. Similar plots for the other four systems are given in Fig. 4.9.
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
The values of relaxation time (τ) are calculated for the six binary
The relaxation time values are given in Tables 4.1, 4.3, 4.5, 4.7, 4.9 and 4.11.
stronger than the attractive forces between the molecules of each component.
But in the case of other two systems, relatively weaker interactions exist
4.1 and 4.3, it is seen that free length remains constant in the case of
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
concentration.
values for various compositions for all the six systems have been obtained
chlorobenzene system are given in Tables 4.1 and 4.3 respectively. The
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
systems.
96
existing between the molecules. When two liquids are mixed, there is
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
cohesive energy values. Phenols are associated liquids and ethanol molecules
97
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
system.
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
concentration, the repulsive forces may dominate and the two systems
4.3. CONCLUSION
been evaluated from the measured ultrasonic velocity, density and viscosity
values for the six binary mixtures. The value of molecular interaction
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
hydrogen bonds are present and ethanol acts as structure breaker for water
phenolic compounds and with increase in the mole fraction of ethanol, there
REFERENCES
1. Seshagiri Rao, M.G. and Ramachandra Rao, B., Ind. J. Pure & Appl. Phys., 3,
1965, 208.
2. Bhatti, S.S., Virk, J.S. and Singh, D.P., Acustica, 50, 1982, 291.
4. Singh, D.P. and Kalsh, S.C., Acoustics letters, 14(10), 1991, 206.
5. Pandey, J.D., Gyan Prakash Dubey, B.P. Shukla and Dubey, Pramana. J. Phys., 15,
1991, 497.
6. Ramanjappa, T., Sivakumar, K.V. and Rajagopal, E., Acustica, 73, 1991, 42.
7. Ramanjappa, T., Murahari Rao and Rajagopal, E., Ind. J. Pure & Appl. Phys., 31,
1993, 348.
8. Acharya, S., Dash, S.K. and Swain, B.B., Acoustics letters, 21(3), 1997, 52.
9. Syal, V.K., Baljeet, S. and Chauhan, S., Ind. J. Pure & Appl. Phys., 37,
1999, 366.
10. Ali, A., Nain, A.K., Sharma, V.K. and Ahmad, S., J. Acous. Soc. Ind., 28, 2000, 283.
11. Sati, R., Choudhary, S.N., Singh, K.M., Mishra, V.K., Acustica, 78, 1993, 55.
12. Subramanyam, T.V.S. and Viswanatha Sarma., Acustica, 79, 1993, 88.
13. Chauhan, M.S., Kumar, A. and Chauhan, S., Acoustics letters, 21, 1998, 228.
14. Samatha, K., Hari Babu, V.V. and Sree Rama Murthy, J., Acustica, 84, 1998, 169.
15. Vijaya Kumar Naidu, B., Sadasiva Rao, A. and Chowdoji Rao., J. Acous. Soc. Ind., 28,
2000, 297.
16. Nikam, P.S., Kapade, V.M. and Mehdi Hasan., Ind. J. Pure & Appl. Phys., 38,
2000, 170.
17. Kannappan, V., Xavier Jesu Raja, S. and Jaya Shanthi, R., Ind. J. Pure & Appl. Phys.,
41, 2003, 690.
18. Amalendu Pal and Suresh Kumar, J. Ind. Chem. Soc., 81, 2004, 1019.
101
19. Prabhavathi, C.L., Sivakumar, K., Venkateswarlu, P. and Raman, G.K., Ind. J. Chem.,
43A, 2004, 294.
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21. Kannappan, V., and Jaya Shanthi, R Ind. J. Pure & Appl. Phys., 43, 2005, 750.
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Chem., 28A, 1989, 217.
23. Roshan Abraham, Abdul Khadar, M. and Asokan, C.V., Acoustics letters, 20(11),
1997, 236.
24. Sadasiva Rao, A., Vijaya Kumar Naidu, B. and Chowdoji Rao, K., J. Acous. Soc. Ind.,
28, 2000, 301.
25. Pitchai J.Victor, Debasish Das and Dilip K. Hazra, J. Ind. Chem. Soc., 81, 2004, 1045.
26. Amalendu Pal and Anil Kumar, Ind. J. Chem., 43A, 2004, 722.
27. Adgoankar, C.S. and Mulay, N.N., Ind. J. Pure & Appl. Phys., 25, 1987, 281.
28. Singh, D.P., Rarajit Kan, Harkiram Ham, Mohan Joshi and Jasbir Singh, J. Chem. Soc.
Faraday Trans., 89(21), 1993, 1737.
29. Singh, D.P. and Jasbir Singh, J. Chem. Soc. Faraday Trans., 89(21), 1993, 3955.
30. Gunasekaran, S., Varadhan, S.R. and Karunanidhi, N., Oriental J. Chem., 11, 1995, 27.
31. Suryanarayana, C.V., Ind. J. Pure & Appl. Phys., 27, 1989, 751.
TABLE 4.1
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
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
Mole Fraction
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
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
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
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
Mole Fraction
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
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
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
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
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
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
1300
1100
0.0 0.2 0.4 0.6 0.8 1.0
Mole Fraction of first component X1
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
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
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
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
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
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
5.1. INTRODUCTION
been suggested that halogen combines with donor molecule to form donor-
acceptor complexes. There is equilibrium between the complex and the donor
with halogens and several homocyclic aromatic compounds have been well
the most health hazardous chemicals. Studies in the fresh water trout
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
Kannappan et al19-21 showed that the deviation from ideal behaviour of any
complexes even in dilute solutions containing the donor and acceptor in non-
124
acceptor complexes22-24.
hexane solution at 303 K. Here, the positive end of iodine dipole polarizes the
m-xylene, p-xylene, benzene and toluene while the three polynuclear aromatic
CH3 CH3
CH3
H 3C CH3
CH3 CH3
Mesitylene p - Xylene m - Xylene
CH3
CH3
CH3
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
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
thermodynamic stability.
The ultrasonic velocities (U), densities (ρ) and viscosities are determined
o-xylene, toluene and benzene at 303 K. Tables 5.1 - 5.12 contain the
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
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
The adiabatic compressibility (κ) and free length (Lf) values for the nine
Tables 5.1 – 5.18. In a given system, the adiabatic compressibility and free
all the six monocyclic hydrocarbon systems which are given in Fig. 5.2. The
system, the adiabatic compressibility values are least at lower and higher
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
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
values in all the systems compared to the free length in pure components.
Further, both adiabatic compressibility and free length values of all the
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
systems are given in Fig. 5.3 while Fig. 5.8 contains similar plots for iodine–
systems indicating that the extent of deviation from ideal behaviour is more
in these two systems which may probably due to complex formation. The
Further, relatively weak interactions are present in these two systems. It may
be pointed out that the molecular interaction parameter values are large
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.
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
values. It is found that the free volume and available volume do not change
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
molecules. The internal pressure values are generally found to decrease with
given in Fig. 5.4. The variation of internal pressure with concentration for
internal pressure in these systems. Tables 5.14, 5.16 and 5.18 give the values
130
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
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
cohesive forces in that system. However, it varies slightly from one system to
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
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
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
values for polycyclic aromatic hydrocarbon are greater than those for
and the former can function as more effective π-electron donor than the
mesitylene forms more stable complex with iodine than other monocyclic
more stable complexes with iodine than benzene and toluene. Among xylenes,
o-xylene forms a less stable complex than the other two isomeric xylenes
they form less stable charge transfer complexes with iodine than with
anthracene.
132
REFERENCES
1. Ando, T., Sumi, S., Kawate, T., Ichihara, J. and Hanafusa, T., J. Chem. Soc. Chem.
Commun., 1984, 439.
2. Coleman, A.J. and Saunders, J.E., Ultrasound Med. Biol., 15, 1989, 213.
3. Toy, M.S., Carter, M.K. and Passel, T.O., Environ. Technol., 11, 1990, 837.
4. Jayakumar, S., Karunanithi, K. and Kannappan, V., Ind. J. Pure & Appl. Phys., 34,
1996, 761.
5. Tigran, V., Chalikian, Jens Volker, Don Anafi and Kenneth J. Breslauer, J. Mol. Biol.,
274, 1997, 237.
7. March, J., Advanced Organic Chemistry, 4th Edn., John Wiley, New York, 1992.
8. Pine Stanely, H., Hendrickson, B., Cran, D.J. and Hammond, G.S., Organic Chemistry,
McGraw Hill, GB, 1989.
9. Kannappan, V., Nanjan, M.J. and Ganesan, R., Actacincia indica, 4, 1982, 196.
11. Kannappan, V., Nanjan, M.J. and Ganesan, R., Z. Physik Chem. (Neuefolge),
Frankfurt,, 91, 1984, 183.
12. Kannappan, V. and Kothai, S., Ind. J. Pure & Appl. Phys., 40, 2002, 17.
13. Ahokas, A.T., Saarni, H., Nebert, D.W. and Pelkonen, O., Chem. Biol. Interact.,
25, 1979, 103.
14. Baird, W.M. and Diamond, L., Int. J. Cancer., 22, 1978, 189.
15. Boobis, A. and Nebert, D.W., Advances in Enzyme Regulations, Ed. Weber, G.,
Pergmoun Press, Oxford and New York, 55, 1977, 339.
16. Marvein, B.L. and Bhatt, S.N., Acustica, 58, 1985, 242.
17. Marvein, B.L. and Bhatt, S.N., Thermochimica Acta., 118, 1987, 277.
18. Mehrotra, K.N., Chauhan, M. and Shukla, R.K., Phys. Chem. Liq., 21, 1990, 239.
19. Kannappan, V. and Kothai, S., J. Acous. Soc. Ind., 29, 2001, 169.
133
20. Kannappan, V. and Jaya Santhi, R., J. Acous. Soc. Ind., 29, 2001, 192.
21. Kannappan, V., Jaya Santhi, R. and Malar, E.J.P., Phys. Chem. Liq., 40(4), 2002, 507.
22. Kannappan, V. and Kothai, S., J. Acous. Soc. Ind., 30, 2002, 76.
24. Kannappan, V. and Jaya Santhi, R., Ind. J. Chem., 43(A), 2004, 1431.
25. De la mare, P.B.D. and Robertson, P.W., J. Chem. Soc., 1943, 279.
26. Keefer, R.H., Ottenberg, A. and Andrews, L.J., J. Am. Chem. Soc., 78, 1956, 255.
27. Brown, T.L. and Kuboto, M., J. Am. Chem. Soc., 83, 1961, 4175.
30. Rao, C.N.R., Chaturvedi, G.C. and Bhat, S.N., J. Mol. Spectroscopy, 33, 1970, 554.
31. Ulrich, K. and Purt, H., J. Mol. Structure, 218, 1990, 45.
TABLE 5.2
TABLE 5.3
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
TABLE 5.4
TABLE 5.5
TABLE 5.6
TABLE 5.7
TABLE 5.8
TABLE 5.9
TABLE 5.10
TABLE 5.11
TABLE 5.12
TABLE 5.13
TABLE 5.14
TABLE 5.15
TABLE 5.16
TABLE 5.17
TABLE 5.18
TABLE 5.19
TABLE 5.20
Temperature : 303 K
component κ /10-9 Lf
kg-1ms2 Ao
1060
U, m s -1
1055
1050
1045
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
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
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
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
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
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
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
30
-3
20
10
0
-10
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
158
2500
πi , atm
2450
2400
2350
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
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
6.1. INTRODUCTION
chemicals is due to the complexes formed between these chemicals and DNA
because they allow organisms to obtain energy, but also because they involve
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
was once used in small doses to cure pregnancy goitre but as it was proved to
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
order to compare those results, the formation constants for charge transfer
determined and the results obtained in their ultrasonic studies are reported
time (τ), free length (Lf), internal pressure (πi), cohesive energy (CE), acoustical
impedance (Z), Lenard Jones Potential (LJP) and Gibb’s free energy of
between the donor and acceptor molecules has been studied from the
(K) values are calculated for all the nine complexes in n-hexane at
303 K.
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
the components. Their corresponding plots are given in Figs. 6.1 – 6.10.
monocyclic systems are given in Fig. 6.1 while Fig. 6.6 contains similar plots
velocity and density for all the systems and are given in Tables 6.1 – 6.18.
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
velocity, density and viscosity values are at maximum. This trend in adiabatic
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.
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.
indicating that the extent of deviation from ideal behaviour and the extent of
molecular interaction parameter values are positive except that for benzene.
165
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
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
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
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
hydrocarbon molecule. The free length values are slightly greater than those
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.
concentration. Tables 6.13, 6.15 and 6.17 contain the values of internal
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
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
acoustic impedance, available volume and free volume values. This indicates
charge transfer complexes. In all the nine systems, the donor is the aromatic
order
electron releasing methyl group enhances the basicity of the donor molecule.
complex. This is also supported by the higher values for charge transfer
complex which is slightly more stable than o-xylene complex. This may be
anthracene complex is the most stable. This may be due to the maximum
π-electron density than naphthalene with only ten π electrons. Hence, the
order among the nine systems for both iodine and iodine monochloride as
169
aromatic hydrocarbons are more stable than the complexes formed between
iodine and the same donors. Similar observations were made by Al Mokhtar
REFERENCES
3. Prakash, S., Prasad, N., Singh, R. and Prakash, O., Acustica., 34, 1975, 121.
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.
13. Material safety data sheet No. 12775, Baker Inc., 2006.
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
TABLE 6.2
TABLE 6.3
TABLE 6.4
TABLE 6.5
TABLE 6.6
TABLE 6.7
TABLE 6.8
TABLE 6.9
TABLE 6.10
TABLE 6.11
TABLE 6.12
TABLE 6.13
TABLE 6.14
TABLE 6.15
TABLE 6.16
TABLE 6.17
TABLE 6.18
TABLE 6.19
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
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
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
2400
2380
2360
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
192
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
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
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
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
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
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
7.1. INTRODUCTION
widely used in the manufacturer of several dyes and drugs1. They undergo
complex between phenol and the electrophile. It may be pointed out that
π acceptors5. They also studied the charge transfer spectra, stability and
that DDQ forms charge transfer complexes with phenols and produces a
indicating that these complexes are unstable and soon turn into other
197
with carbon tetrachloride and olefins are well known11. Optical methods
this chapter, ultrasonic studies have been carried out to determine the
present study are phenol, o-cresol, p-cresol, m-cresol and carvacrol. Less
parameter, internal pressure and cohesive energy are also computed and
reported.
198
Table 7.1 – 7.5. Plots of ultrasonic velocity vs concentration are given Fig
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
concentration.
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
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
ultrasonic velocity, density and viscosity for all the systems. Generally, the
concentration.
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
Thus, charge transfer complexes are formed between iodine and phenols.
system.
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
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
Cohesive energy values are computed for all the twenty systems and they
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
and five structurally different phenols (donors) in four different solvents. The
values for the complexes formed in binary mixtures from the measured
ultrasonic velocity12. However, this method has the limitation that it can be
and phenols in four different solvents. Less polar solvents with low dielectric
constants are used in the present work so that the charge transfer
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
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
formation constants are evaluated in four less polar solvents. These solvents
differ in the dielectric constant only slightly. The extent of solvation may be
found that for a given charge transfer complex, the formation constants are
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
all the phenols. Relaxation time values are found to be constant and
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
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.
8. Hewgill, F.R. and Howie, G. B., Aust. J. Chem., 31, 1978, 907.
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.
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
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
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
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
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
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
Solvent : chloroform
Temperature : 303 K
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
Solvent : chloroform
Temperature : 303 K
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
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
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
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
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
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
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
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
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
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
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
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
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
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
COMPONENT τ /10-13 Lf πi CE
s Ao atm kJ mol-1
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
0.81
2
κ /10 , kg ms
-1
0.80
-9
0.79
Concentration, M
229
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
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
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
970
U, m s -1
960
950
940
0.000 0.005 0.010 0.015 0.020 0.025
Concentration, M
231
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
0.0
-3
-20.0
-40.0
0.000 0.005 0.010 0.015 0.020 0.025
Concentration, M
232
3660
3640
πi , atm
3620
3600
Concentration, M
34.6
CE, kJ mol-1
34.4
34.2
Concentration, M
233
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
0.91
0.90
2
κ /10 , kg ms
-1
0.89
-9
0.88
Concentration, M
234
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
3360
πi , atm
3340
3320
3300
0.000 0.005 0.010 0.015 0.020 0.025
Concentration, M
235
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
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
1.58
-9
1.56
1.54
0.000 0.005 0.010 0.015 0.020 0.025
Concentration, M
-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
2115
2100
πi , atm
2085
Concentration, M
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
Introduction
complexes of the type B…... X2 and B……XY with a wide range of Lewis
Mulliken8 are now recognized to play a key role in many chemical and
thermodynamic and other aspects have been reported in the literature, but
there is need for further work on the role of solvent in determining the
phenols. Studies are made in four different less polar and non polar
to asses the attraction between the donor and acceptor, formation constants
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 media (Figs. 8.6, 8.11 and 8.16). These observations indicate that there
systems from the measured ultrasonic velocity and density values. Plots of
are given in Fig. 8.2. Similar plots for other solvents are given in Figs. 8.7,
supported by the observation that free length values in the systems are
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
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
interaction parameter values are calculated for all the systems at different
parameters against concentration are illustrated in Figs. 8.3, 8.8, 8.13 and
at a characteristic concentration.
used to assess the deviation from ideal behaviour which may arise due to
intermolecular forces. The values of internal pressure are calculated for all
figures 8.4, 8.9, 8.14 and 8.19. It is found that the internal pressure values
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
depends upon the solvent. Thus, the stability of this type of complexes is
liquid mixtures. Cohesive energy values for the twenty systems are
concentration for all the systems are illustrated in Figs. 8.5, 8.10, 8.15 and
phenols and the stability of the complex depends upon the concentration
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
is in the order:
This order is the same as that between iodine and phenols. The presence of
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
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
solvents will destabilize the complex due to solvation of donor and acceptor
molecules as these are also polar compounds. The formation constants are
The data are presented in Table 8.21. It is found that for a given system, the
while the stability constant is the least in n-hexane which has a dielectric
of slightly higher dielectric constant and hence, among the less polar
of the medium.
tables shows that iodine forms a less stable complex with phenol than
iodine and it is a more effective Lewis acid than iodine. Another aspect
system and also by the difference between the stability constant values of
difference is more in the case of systems containing iodine than in the case
the more reactive the attacking species, the less selective in electrophilic
than the more reactive electrophile. In the present case, iodine is a less
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.
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.
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
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
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
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
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
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
Solvent : chloroform
Temperature : 303 K
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
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
Solvent : chloroform
Temperature : 303 K
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
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
Solvent : chloroform
Temperature : 303 K
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
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
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
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
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
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
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
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
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
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
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
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
1055
1045
1035
0.000 0.005 0.010 0.015 0.020 0.025
Concentration, M
0.81
0.80
2
κ /10 , kg ms
-1
0.79
-9
0.78
Concentration, M
271
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
4380
4360
4340
0.000 0.005 0.010 0.015 0.020 0.025
Concentration, M
272
33.2
CE, kJ mol-1
33.0
32.8
0.000 0.005 0.010 0.015 0.020 0.025
Concentration, M
980
U, m s -1
970
960
950
940
0.000 0.005 0.010 0.015 0.020 0.025
Concentration, M
273
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
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
3640
πi , atm
3620
3600
3580
0.000 0.005 0.010 0.015 0.020 0.025
Concentration, M
34.6
CE, kJ mol-1
34.4
34.2
Concentration, M
275
920
U, m s -1
910
900
Concentration, M
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
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
3360
πi , atm
3340
3320
3300
0.000 0.005 0.010 0.015 0.020 0.025
Concentration, M
277
38.2
38.0
37.8
37.6
0.000 0.005 0.010 0.015 0.020 0.025
Concentration, M
1060
U, m s -1
1050
1040
0.000 0.005 0.010 0.015 0.020 0.025
Concentration, M
278
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
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
2090
πi , atm
2075
2060
0.000 0.005 0.010 0.015 0.020 0.025
Concentration, M
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
9.1. INTRODUCTION
between aryl ether and halogen1-5. The formation of charge transfer complex
constant values have been reported6-8. It may be pointed out that aryl ethers
aromatic compounds contain lone pair of electrons. It has been found that
aliphatic and aromatic ethers form charge transfer complexes with acceptors
moderate concentration. However, this method can be used only for relatively
equation and deduced another equation based on the assumption that the
deviation from ideal behaviour may be due to complex formation. This method
This chapter deals with solvent and structural effects on the stability of
responsible for complex formation. The following four ethers were used as
Cl O
O CH3
diphenyl ether 4-chloroanisole
CH3 O
O
O
anisole 1,4-dioxane
283
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.
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
deviation form ideal behaviour. The curves are steeper in systems containing
diphenyl ether, anisole and 1,4-dioxane as donors. These ethers may form
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
concentration and then increases. These observations also suggest that there
is deviation from ideal behaviour in the case of the four systems in carbon
systems in each solvent have been calculated from the measured values of
concentration for all the ethers as shown in the Figs. 9.2 and 9.7. This
285
all the ethers in these two solvents. In the case of carbon tetrachloride, there
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
in Fig. 9.17.
α/ 2)
9.2.3. Absorption Coefficient (α/f
absorption coefficient values are almost constant for all the ethers, indicating
deviation from ideal behaviour which may be due to the formation of charge
286
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
all the systems, charge transfer complexes are formed. Plots of molecular
and 9.18.
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
indicates that there is formation of CT complex in all the systems and similar
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
dichloromethane are shown in Fig. 9.4. The internal pressure increases first
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
extent of complexation depends upon the structure of donor, the medium and
values. Plots of cohesive energy vs concentration for all the four ethers in
and 1,4-dioxane but in the case of diphenyl ether and anisole it decreases
Plots of cohesive energy vs concentration are given in Figs. 9.10, 9.15 and
9.20.
in different media.
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
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
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.
may be noted that the formation constant values are almost constant for a
290
constants of four ethers in each solvent, the ease of complexation with iodine
on either side of the donor. Therefore, it forms relatively more stable complex
no mesomeric effect is possible and hence, the stability constant value is the
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.
moment of donor in three systems. However, in the case of diphenyl ether, the
found that the stability constant increases with increase in dielectric constant
molecule first polarizes the donor molecule during the formation of a charge
increases.
292
REFERENCES
2. Stock, L.M. and Brown, H.C., Advan. Phys. Org. Chem., 1, 1963, 35.
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.
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.
18. McClellan, A.L., Tables of experimental dipole moments, W.H. Freeman & Company,
San Francisco and London, 1963.
TABLE 9.1
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
1050
1048
1046
1044
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
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
-6
-10
-14
-18
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
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
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
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
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
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
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
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
908
U m s-1
904
900
896
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
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
3
χ U, ms-1
-3
-9
-15
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Concentration, M
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
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
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
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
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
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
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
briefly outlined. The present work deals with charge transfer complexes and
and instrumental details are explained in the second chapter. The relevant
mixtures:
present in the phenolic compounds and with increase in the mole fraction of
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
molecules are rich in π electrons and hence, they form more stable
following order:
energy of formation and relaxation time are constant for a given system and
is also found that iodine monochloride forms more stable complexes with
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
phenols. The trend in the formation constant values indicates that the
presence of electron releasing group like methyl enhances the stability of the
phenols. Studies are made in four different less polar and non-polar
function as n electron donors and in the case of aryl ethers, they can
The trend in stability constants is explained with the structural effects. The
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.
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
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