CHAPTER

-I

IHTBODUCTION
The study of propagation behaviour of ultrasonic in liquid systems and solids is now rather well

waves estab-

lished as an effective means for examining certain

physical

properties of the materials. It is particularly well adapted to examining changes in such physical properties while occur. eters they

The data obtained from ultrasonic propagation paramvie., Ultrasonic velocity and absorption and its helps terms to

variation with concentration of one of the components to understand the nature of molecular interaction in

of some physical parameters.

Owing to the sensitivity

very low population densities at high energy states, ultrasonic methods methods are have been preferred and these to ultrasonic the other relaxaresonance extensively molecules

reported

to be complementary

techniques (Wyn-jones et al., 1966) like dielectric tion, etc., infrared In spectroscopy, nuclear magnetic are

other words

ultrasonic studies analysis of empirical

used in the conformational (Bergelson formulae

1960).

organic and

Several

semiempirical velocity and a and brief

have

been

developed

correlating parameters

absorption account of

with other molecular

theoretical aspects are given below.

1.1 Tbeoretiaal bswats: 1.1.1 T e m of sound propala tiaa : ho

Propagation

of sound waves in a medium may be

treated

as a series of compressions and rarefactions traveling along the direction of propagation such that the molecular of planes The

the medium are displaced from their mean position.

( E ) and velocity ( C ) of the waves are

displacement

related

by the wave equation,

It

is assumed here that the compressions and The wave

rarefacequation (0=)

tions are both reversible and adiabatic.

may be rewritten using the isoentropic compressibility and density

( p )

of the medium as,

comparing the equation ( 1 . 1 ) and ( 1 . 2 ) it is evident that

c2 =
Thus

[oD,]-~

...

(1.3)
of

in the limit of the above assumptions the velocity

the

sound

waves depends only on Bs and

( P)

(Jack Blitz

1963).
1.1.2 Rao's number:

An empirical formula relating the ultrasonic velocity C with volume V has been suggested by of his empirical work as Rao (1940) on the basis

where

is known as Rao's number which

is

independent In

of

temperature for unassociated organic liquids. plots

mixtures, are

of R with concentration of one of the components linear except in systems like water and

generally where The

alcohol

there is a strong association between the

molecules. one of

linear dependency of R on the mole fraction of

the components may be of some practical use in computing the sound velocity from known liquid mixtures. value of density or vice versa in concentration indi-

If the variation of R with

of one of cates a

the components is non-linear, it generally strong association between the molecules.

1 . 1 . 3 Jacobson ' free lenptb theory: s

Kittel

(1946) has applied Tonk's equation of state

to

wave propagation in liquids. The molar volume V is

divided

into two parts, one part Vo which is the volume of geometric closest able packing of molecules and the second part is Va=(V-Yo). The Tonk's equation of availfor

volume

state

liquid is given

by

The velocity of ultrasonic wave in a liquid is given by relation

where P is the change in pressure due to the sound wave

and

(p)

is

the corresponding change in density of

the

medium

under adiabatic conditions. Kittel

Using equation ( 1 . 5 ) and ( 1 . 6 ) liquid

showed that the ultrasonic velocity ( C ) in a

is given by

where

~~~~~~d is the ratio of specific heats

at constant

pressure to the constant volume. linear relation between Va and V.

Equation ( 1 . 7 ) indicates a

Jacob5on ( 1 9 5 1 ) suggested that the adiabatic compressibility of a liquid can be better understood in terms of the

intermolecular free length which is the distance between the surface of the molecules, hereafter designated as Lf. Lf

is
per

related to the available volume Va and the surface molecule Y through the relation of Syrine et a1

area
(1997)

as

where Y is equal to (36 x N v,~)"~,

( N is Avogadro's number

and Vo is the volume at absolute zero).

The

intermolecular

free length depends on the type of packing and the extent of association in a given liquid. From the study of adiabatic compressibility and Lf in

the case of non-associated organic liquids, Jacobson has shown that the plot of log,.?I

(1951)

against log Lf is a linear

one suggesting a relation of the type

uhere K and X are constants and the values of the constants X and log

K are 2.082 and 7.097 C.G.S units at 20'C

The free length Lf the free

in

the

case of non-associated liquids. lated using equation

calculength

(1.8) agrees with

calculated

using equation (1.9) and the

maximum

deviation uncer-

being approximately 3% and this is attributed to the tainties The of the parameters in equation (1.8). computation of the free length for

mixtures

of

liquids from molar volumes has been extended (Jacobson 1851) by revising the definition Lf = 2Va / Y as

where

X A , XB and

vOA ,vOB

represent the mole fractions and and

volumes

at absolute zero of the liquid components A

respectively and Vn stands for molar volume of the mixture.

YA

and YB are surface areas of the molecules of the compofree length computed from the crhpressibility

nents. The data

according to the equation (1.9)agrees well with that for mixtures from molar volumes, the average

calculated error

being

less than one percent. This constitutes the the applicability and utility of

strongest evidence of

equation (1.9) for liquid mixtures.

I . 1 . 4 Tbeory of I n t e r n a l pressure :

Rlchards
(1873)

(1925), Hilderbrand (1950) and the importance of

Vander

Waals

suggested

internal pressure Pi

which

indicates the strength of attractive forces between The terms a/vZ in Vander Waals equation

the molecules.

being the measure of the attractive forces of the molecules is called the cohesive or internal pressure and is of very

great importance in the study of the properties of liquids. Intermolecular forces give a liquid its cohesion. The

attractive forces mainly comprises of dipole

hydrogen

bonding,

dipole, multipolar and over

dispersion very small

interactions. intermolecular process under

Repulsive forces acting

distances paly a minor role in the cohesion

normal circumstances. Cohesion creates a pressure of 1 0 to ~

104 atmospheres within a liquid. Dissolved solutes experi-

ence sure

some of this pressure and the amount of internal presincreases whenever they interact with solvent through

hydrogen bonding, charge transfer, Coulombic or Vander Waals interaction. pressure" the Thus a solute is subjected to

"structural

from the solvent and a "Chemical pressure" from hence the solution sol-

interaction with the solvent and

exists vent.

under a higher internal pressure than the pure

A liquid undergoing a small isothermal-volume expansion

does work against the cohesive forces which causes a change in the internal energy U . The function (6U/6V)T is known as ther-

the internal pressure P i . From Maxwell's equation of modynamics (Moelwyn - Hughes 1964
)

it follows that

i . e . ,Internal pressure = Kinetic pressure sure

External

pres-

The term (bP/bT), in the equation is called the thermal pressure coefficient and it is equal to a/@ where a is

the co-efficient of thermal expansion and D is the

isother-

mal compressibility. As a/R has a large value and as such P can be neglected in comparison to T(bP/bT),. Hence the

equation reduces to

since RiSo = r O,,

this equation also can be expressed as

where r is the ratio of the specific heat at constant pressure to constant volume. Extensive pressure study of literature shows that internal

in liquid solution seems to be such single factor

which varies due to all the interaction of type 1 - 1 , 2 - 2 and

1 - 2 where 1 and 2 are constituents of mixtures
1978).

(Srinivasan, of ionic

It

is

also known that many

properties

solution may be derived in terms of without

intermolecular forces charge or

appealing to the concepts of electrical

ionic radii.

1.2 Theow of Ultrasonic Absorption:

When a plane progressive wave passes through the system

each

small volume

in the system is subjected

to

time

dependent perturbation. The study of Ultrasonic absorption is to understand how the system responds to the perturbation and relaxes when the perturbation passes on. The Ultrasonic attenuation in fluid media are attributed mainly due to following causes. the

1.2.1 C l a s s i cal absorption :

The propagation of Ultrasonic wave through a thin layer of medium suffers a fractional loss of energy. If I and are the intensities of the ultrasound before and

I,

after

passing through a layer of thickness X then,

where

a*

is defined as the absorption coefficient of

the

medium and is generally expressed in nepers per

centimeter.

The classical absorption arises because the propagating wave loses energy in overcoming the shear viscosity (Qs) and represented

thermal conductivity ( K ) of liquids. It may be as

It

is written as follows in the form of

Stroke's

Kirchoff

equation,

where the

p is the density of the medium,

C is the velocity
is

in the

medium,

is the ratio of specific heats, C v

specific heat at constant volume. As generally ultrasonic for liquid the thermal conductivity of most of the liquids small, its contribution to the attenuation is of

waves is negligible (-10-20 metals.

se~.-~ctn-l) except to shear

However the attenuation due

viscosity will have significant contribution (-10-l1 aek . - 2 cm-1) .

1 . 2 . 2 Excess a b s o r p t i o n :

The classical absorption may be calculated theoretically using the relation (1.14) as a sum of shear viscosity and thermal conductivity contributions. But in many licluids the

experimentally measured ultrasonic absorption is found to be higher tween than the classical absorption. The difference be-

these two absorption is termed as

excess

absorption

(a/f2)ex.

1 . 2 . 3 Molecular a b s o r p t i o n :

For

most

of the liquids the than the

experimentally

measured

absorption is higher

(a/f2)classical a b a o m t f o n . The

This excess absorption is due to molecular relaxation.

molecular relaxation arises either due to thermal relaxation or structural relaxation or both.
1 . 2 . 4 ibe-1
~laXdtf0.0;

During

adiabatic compression of a unit volume

of

the

system by ultrasonic sound waves, the total enerw is made up of many different contributions such as and intermolecular translational, (structural) from acoustic delay.

vibrational, rotational energies.

The translational energy derived

waves is passed from one molecule to another without

A

part of this energy may be converted into rotational or equilibrium beThis

vibrational energy during collision. The tween

the three energy states is gradually restored. energy from external to

transfer of freedom

internal degrees of to
be

requires finite time and the medium is said This phenomenon is termed as thermal the attenuation of sound waves.

relaxing. which

relaxation Rotational commonly

causes

isomerism

and vibrational relaxation are the most

observed types of thermal relaxation.

1.2.5S t r u c t u r a l r e l a x a t f on.

This

type of relaxation first proposed by Hall

(1948)

to explain the excess absorption in water which could not be explained on the basis of thermal relaxation alone. tural Struc-

relaxation occurs in liquids like water, alcohol and

other similar polywric liquids where inter-molecular forces are fairly strong. In these liquids, the molecules are

assumed The

to be in two structurally lag in exchange of energy

different between

arrangements. two different

time

structural arrangements is termed as structural relaxation. If the structural fluctuation perturbs the of the components of a molecular relaxation equilibrium then equito

process,

the thermodynamic coefficient depends not only on the librium

thermodynamic variables, but also on the extent

which the reaction has proceeded towards its local rium.

equilibfunc-

The bulk modulus for example becomes a complex

tion of acoustic frequency ( w ) as given below: 0 = and hence

om+

0 / l+jC ,

...

(1.15)

Bo = 0 + Dr ,

where T represents the relaxation time and 0 the ,

contribu-

tion to B caused by relaxational effect and is the compressibility at high frequency and j = 4-1, Do is the bility at low frequency. The one significance of cornpresai-

a,,

0 and 0 , ,

can be in

realised two

if

considers

that the liquids can exists

energy

states(1) and ( 2 ) having energy values W l and W2 respectively. For the lower state W 1 the volume is larger than Sor

the higher state W2. for the higher state.

Here 8 represents the compressibility , At lower frequencies where there is

sufficient time for a complete transfer of energy from state

(1)

to

state ( 2 ) , Br will be equal to 1, B is 3. ,

the At

comvery to

pressibility high flow

which corresponds to the lower state.

frequencies where there is no time for any , from state ( 1 ) to ( 2 ) D is equal to 0. that by a
( 1 ) and ( 2 ) were

energy Hall

(1948)

considered separated

states

of and

equilibrium obtained an

potential barrier of AF

expression for the relaxation time T as given below

where
Rg

0 = ,

shear viscosity, V = molar volume of the

liquid,

= gas constant, T = absolute temperature and K = Boltzman

constant.

1.2.6 Volume V f s c o s f t r :
In order to explain the excess absorption in in some to

liquids, volume shear the the viscosity.

viscosity was introduced

addition

One of the approaches adopted to

explain of

volume viscosity is a pseudo - lattice liquid

description this

state (Herzfeld et al, 1959). In

model. (vacant lat-

molecules lattice

jump from lattice positions to the holes

sites) and the holes jump to the neighbouring

tice sites. The presence of such holes account for the fact that the molar volume of the liquid is nearly always greater than the molar volume of the corresponding solid. is subjected to a shearing When a jump

liquid

force, molecules

between neighboring planes perpendicular to the direction of

shear.

When a liquid is compressed the molecules

jump

to

occupy holes resultin# in closer packing i.e. the holes move out on compression. This leads to a volume viscosity

nv.

The relaxation of volume viscosity (0,) and shear

viscosity

(0s) with the increase in frequency results from a kinetic

control of molecular reorganization. However, the volume viscosity cannot be independently determined. It is estimated from the ultrasonic absorption in the liquid by the

following relation:

In order to explain the ultrasonic absorption in water, Ha11 1 1 9 4 8 ) used the model of water developed by Bernal bowler (1933). According to these authors the water in two phases in which one phase in a dense monomeric and

exists water

and the other ice like structure. When the ultrasonic waves pass through water the equilibrium between these two is disturbed Hall which causes the absorption of on phases

ultrasonic the above

waves.

developed an expression based

model for the excess ultrasonic absorption as

where T is the structural relaxation time, Or is the relaxational part of the compressibility, C the ultrasonic velocity and P the density of the liquid.

The molar

structural

relaxation tima 7: was related

to the

the two

volume

and frea energy difference between

states is given as

where

= molar volume, r), = shear viscosity, Rg

gas

constant, T = absolute temperature, AF = difference between the free energy of the two states.

he'

relaxational part of the compressibility (3) 1,

was

related to the volume viscosity (pv) and the relaxation time

(T) an expression developed by Litovitz and Davis by

as

(1965)

where Oo is the static compressibility. For the viscoelastic liquids it has been found that the relaxation time (T)may be related to the static compressibility (0,) and the two viscosities

9 and ,

I, as follows )

1.3 HLLR relaxation time and hydrogen bonding:

1 . 9 . 1 Introductfon

Nuclear frequently and the

Magnetic

Resonance (NMR) technique molecular

is very

used in elucidating the

interactions Spin

molecular structure of solids and relaxation time TI and the

liquids.

lattice time T2

Spin-Spin of

interaction the nuclear these

are the two important parameters

magnetic

resonance in liquids and their mixtures and

parameters throw considerable light on the dynamic es.

A

processMagnetic

brief

account of the theory

of

Nuclear

Resonance (NMR) and relaxation mechanism is given below.

1 . 3 . 2 Theory of Nuclear Magnet1 c Resonance:

The inducing

principal

feature of the NMR method an

consists

in

transitions by the application of

appropricte

radio frequency field between the energy levels which correspond to different orientatior~sof nuclear spin in a applied moment magnetic field. The interaction of the can strong magnetic be de-

with the applied magnetic field Ho

scribed by the Hamiltonian,

where the magnetic moment

I is I

given by

7 being

the

gyromagnetic ratio and I the, nuclear

spin

operator.
If

the

magnetic field is assumed to be

along

the

axis, equation (1.23) becomes

The eigen values of the above Hamiltonian are

where

m = -I, - I + l , . . . . . + I . The (21+1) fold degeneracy

of

the ground state is removed by the application of the strong magnetic field. The energy difference between successive

levels is +fiHo. between levels

l'hc selection rule governing the transition is m =

1 . A quantum of energy

h?

can

therefore excite transitions between energy levels if it has *,he same magnitude as the level spacing:

For protons, in a magnetic field of 5 0 gauss, the frequency 00

of the radiation turns out to be 21.3 mega cycles.
1 . 3 . 3 Spin l a t t i c e Relaxation:

The above discussion has been limited to a single spin

interacting with

magnetic

and

radio

frequency

fields with

Nuclear magnetic resonance experiments are carried out bulk samples, and hence it is necessary to

consider the the applied

interaction of a macroscopic spin system with

radio frequency and magnetic fields. For a free spin system with I = Y in an external field Ho, it can be shown that the populations of level by the lower level exceeds that of the upper Ts is the The

the Boltzmann factor e2kH0/kTs where equilibrium temperature of the spin

thermal

system.

absorption this

of energy from the radio frequency field

causes the and

population excess to dwindle. In course of

time

populations the

of the upper and lower levels become equal This discrepancy

resonance would disappear

arises

because the spin systern is assumed to be free. there is an interaction between the spin

In reality, and to the the bring same

system

lattice, and this spin-lattice interactisn tends both the systems The into thermal equilibrium at almost

temperature. with

common temperature is

identical tempera-

the lattice temperature, since except at low

tures the heat capacity of the spin system is small compared with that of the lattice. Thus, while the radio is reducing the excess population in frequency the lower

radiation

arlrrgy state, the interactions with the lattice are to restore the excess to the original value. The time with which the equilibrium is

tending characis

teristic

approached

called the spin- lattice relaxation time T I .

1 . 3 . 4 Spin-Spin relaxatioa: A dipole - dipole interaction exists between nuclei due

to their individual magnetic dipole moment.

From a

classi-

cal point of view, each nuclear magnet finds itself not only in the steady applied field Ho, but also in a small fluctu-

ating local magnetic field HlOc produced by the neighbouring nulcear magnets. The direction of the local field differs

from one site to another and depends on the relative direction of the neighbouring nuclei in the lattice and their

magnetic quantum number m. The netic magnetic field at a point distant r,from the moment 1 is of the order of u/r3. The magfield

dipole

therefore falls off rapidly with increase in r , so that only the nearest neighbours make important contributions to H l 0 , For a value of r = 1 A end u = one nuclear magneton, we find
H~~~

v r3

5 gauss

.. .

(1.27)

The each

steady

magnetic field will not therefore be

same

for Gauss

nucleus, but will vary over a range of

several

from one nucleus to another.

It follows that the

resonance

condition will not be perfectly sharp as was for a system of free energy Hioc spins described by the equation (1.26). Instead, the levels are broadened by an amount of the order of

This spread results in a distribution of the

Larmor

precession frequencies over a range 6u0 given by 6v0

3 Hloc

uo2/h r3

lo4 sec

...

(1.28)

since the molecules tumbel around in a random fashion, with nuclear moments conferred on them, they generate very magnetic fields which are random in frequency and in small phase.

Fourier analysis of the random motion show that fraction are at or near the frequency of the nuclei that are being These motions are most effective in bringing of energy between the spin system. reabout

laxed. exchange

Since the

relative phases of the nuclei change in a time of the order of 1/6w0 the correct phasing for this spin exchange process should occur after a time interval of this order and this in turn should determine the life time of a spin state. It is

well known that a life time of 1/6w0, and this should result in a further broadening of the resonance line. These esses procthe

are characterised by a relaxation time T2 called

Spin-Spin relaxation time or transverse relaxation time T2.

1 . 3 . 5 Spin

L a t t i c e r e l a x a t i o n in l i q u i d s :

For for

non-metallic liquids the important mechanism of The

relaxation is that arising from the thermal motion

the atoms or molecules which constitute the .lattice.. atoms nuclei or molecules are regarded as vehicles from point to point. Thus each

conveying the

nuclear magnetic

moment takes part in the random translational and rotational

Brownian motion of the molecules.

In consequence, the Local

magnetic field at any point contributed by the neighbouring nuclear magnetic moments, and by any electronic magnetic fluctuating frequency induces

moments which may also be present, is a rapidly

function of time. The component at the resonance of the Fourier spectrum of this fluctuating

field

transitions between the nuclear magnetic energy

levels in field.

just the same way as does an applied radiofrequency

First a formulation is made of the energy of magnetic interaction between the ith nucleus and all the neighbouring For each

magnetic

moments, of which the jth is typical. three

neighbour, the energy is found to involve

functions

(Andrew, 1958) of the distance rij between the nucleus i and the neighbour j, the angle Bij between rij nd Ho, and the

azimuth angle 0ij of rij measured from some fixed reference direction. The three functions are
:

yOj = ( 1 - 3 ~ 0 ~ 2 rij-3~ ) 8 ~

-3 Ylj = exp(i fiij) SIN 8ij COS Bij rij ... YZj = exp(2i 0ij) SIN' Bij r-3ij
The position intensities of the Fourier spectra of these functions are then introduced

(1.29) three the

and are given

symbols Joj(J), Jlj(v) and Jzj(d) (Andrew ,1958) respectively at frequency

T.

The total intensity

for all

neighbours

of the functions Yoj is

2 Joj(i), and this is called J0(3);

similarly, J1(v) and J Z ( V ) represent the total

intensities

for the other two functions. It is found that fluctuations of the position coordinate are capable of inducing transi-

tions between the energy levels of the ith nucleus for which the magnetic quantum number, r 1 changes by unity. n ally we may regard the motion of neighbour J with Pictorifrequency field

$ as producing at nucleus i , an oscillating magnetic ,

of this frequency which is capable of inducing transitions. It is further found that fluctuations of the position tions func-

Y2j at frequency 26, are capable of inducing transit

ions (Slichter, 1963). After tions calculating the total probability W of transi-

induced by molecular fluctuations, the

spin-Lattice If no be

relaxation time TI is found using the formula TI = 5 W . all the nuclear magnetic moments are identical, and

electronic magnetic moments are present, TI is found to given by

where, as usual, V and I are respectively the nuclear magnetic

gyro-

ratio and the nuclear spin number. If other mag-

netic moments, nuclear or electronic, are also present, l/T1 is given by the sum over all types of magnetic moment of

expressions similar to (1.30). Although expression (1.30) is given for general values

of

I , it has to be remembered that nuclei having I

possesses also an electric quadrupole moment. The tion between of this quadrupole moment the local electric field and the

interac-

fluctuating

gradient

constitutes another

mechanism for spin It

lattice relaxation in liquids. to find the form of We the spectral

is, necessary

intensity functions J ( d ) .

introduce a correlation time roughly takes

(Tc) which sets a time scale to the random motion. speaking to turn

(Tc) is of the order of the time a molecule through a radian, or to move through a

distance

comparable with its dimensions. It is found for the position function Yoj that

where IYoj1

is the time average of

In general, the ~ 1 ~ .
not

rorrelation time (tij) for the different neighbours are t,he same. Similar expressions to (1.31)for
J1(i')

and J 2 ( D )

are obtained by changing throughout the subscript 0 to 1 and

2 respectively.
It can be shown that the intermolecular contribution

involving rotational motion to ( l / T 1 ) for a liquid system of like spins is given by

The

determination of the correlation time (Tc) required

in

(1.32), is closely related to the problem encountered in the theory of Debye dielectric dispersion in polar liquids.

Debye assumed as an approximation that the molecule could be treated as a sphere of radius 'a' embedded in a viscous

liquid, and found a correlation time given by

where

(0)is

the viscosity of the liquid, k is

Boltzmann's The function theory is from here. differs

constant whose

and T is the absolute temperature.

correlation time is required in the Debye

COS 8 , the symmetry character of which is

that of the functions with which we of are

different concerned time

Because

this difference, the correlation

slightly, and is given by

To

evaluate

the

molecular radius, a , the

equation

derived

by

Ramamoorthy and Varadhachari (1970) using

the

concept of free volume of liquids can be used. The equation is

d , represents the molecular diameter, N , the Avaaadro ber.

num-

V,

the molar volume, a the coefficient of '

cubical

expansion, T , the temperature, R

the gas constant and k , a

constant = 1 for most of the liquids. The above equations have been developed for rotational motion and consequently apply for intramolecular relaxation. The motions involved in intramolecular relaxation are pridifferent

marily translational motions. These motions have correlation times and lead to some what

different expresby

sions for contribution of dipolar relaxation to TI given equation (1.30). Spin the

- Lattice relaxation time T1 strongly depends on

the protons (Andrew, 1958). due If the

environment of

environment of

the protons is changed

to molecular

interactions such as hydrogen bonding, the values of T1 are also significantly altered.
1.3.6 Ifydrogen bondfng:

According to exists

Pimental et a1 (1959) "A hydrogen

bond other

when a hydrogen atom is bonded to two or more

atoms".

Usually

the hydrogen bond refers to

the

entire

group of three or more atoms which are involved in a configuration X- H One

Y , where X and Y may be like or unlike atoms. the as

of

the two bonds X-H or H-Y may be stronger than The weaker of the two bonds is sometimes called

other.

hydrogen bond to distinguish it from the stronger bond which may be a covalent bond. Such a bonding situation is by X - H . . Y . Although the hydrogen bond is its bond energy that is the energy often not of a the to

indicated strong

bond,

reaction XH+Y->XHY
1 K 0

lying in most cases in the ranges 2 Hydrogen bonding is found with

cal/mole.

strong or

electronegative atoms like F , 0. N , Cl etc. The atoms X

Y is one of these electronegative atoms in the configuration

X-H..Y. Increasing the electronegativity of an atom inall two

creases its power of forming hydrogen bonds. hydrogen adjacent hydrogen

In almost the

bonds the hydrogen atom nearer to one of

electronegative atoms than to the .other.

These

bonds existing in substances containing 0-H, N-H,

F-H groups provide special properties to these substances. The hydrogen bond species varied from the highly sym-

metric ones like F-H..F to general form of A-H..B type. The variation of Ultrasonic velocity data indicates the intermolecular association through hydrogen bonding (Anbanathan

1979, Tabhane et a1 1983, Nambinarayanan et at 1983. 1985).