3.

THEORETICAL ASPECTS

3.1 INTRODUCTION

Modern technological developments are in some way or other

depends on the development of new dielectric compounds. Therefore, a

handy treatise providing the basic physical properties governing the

behavior of dielectric liquids and its mixtures has to be given before

developing the new compounds. These physical properties, depends on

their composition, the structure of the substance and other external

factors which affects the dielectric liquids initiated the researchers to

conduct research work in this field. Various investigations already been

made in this field provided the knowledge about the molecular structure

and structural change of the mixture and the characteristic nature of the

dielectric liquids. This knowledge helps one to proceed research work in

the field of dielectric liquids and liquid mixtures. The theoretical

investigation plays a major role in the field of investigation of

Ultrasonic parameters.

The theoretical evaluation of sound velocity in liquid mixtures is

of considerable interest. The theoretical evaluation of sound velocity

based on molecular models in liquid mixtures has been used to correlate

with the experimental findings and to know the thermodynamics of the

mixtures. The comparisons of theoretical and experimental results also

provide better understanding about the velocity of the various

thermodynamic, empirical, semi-empirical and statistical theories. The

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various theories, which are used to calculate the ultrasonic velocity in

the multi-components mixtures, are

i. Nomoto’s relation

ii. Van Deal ideal mixing relation

iii. Collision factor theory.

3.1.1 Nomoto’s Relation

Nomoto1 established an empirical formula for sound velocity (U)

in binary liquid mixtures based on the assumption of the linearlty of the

molar sound velocity namely,

Rmix = X1R1 + X2R2 (3.1)

Where R1 and R2 are the molar sound velocities whose mole fractions

are X1 and X2 respectively. The molar sound velocity (R) also known

as Rao’s constant is related to sound velocity (U) and density (ρ) by the

relation.

R = (M/ ρ)U⅓ (3.2)

The additive molar volume (Vmix) is givenby

Vmix = X1V1 + X2V2 (3.3)

Hence the sound velocity in binary mixtures, Umix given by

Umix = (Rmix/ Vmix)3

Umix = {[ X1R1 + X2R2] / [ X1V1 + X2V2]} (3.4)

Where Rmix is the molar sound velocity and Vmix is the molar voume of

the mixtures.

3.1.2. Van – Deal Method

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 Van Deal2 relation has been employed successfully in the study

of acoustical behavior of binary liquid mixtures. According to his

assumption, the adiabatic compressibility (βS) of the mixture is given by

the relation.

βS(im) = φ1(Y1/Yim) βS(1) + φ2(Y2/Yim) βS(2) (3.5)

where φ and Y represent volume fraction and specific heat ratio

respectively. To avoid complication, richardson3 abd Balndamer and

Wadington4 assumed the following relation for βS(im) as

βS(im) = φ1βS(1)) + φ2βS(2) (3.6)

but the relation is true only for the ideal mixture and the condition

Y1 = Y2 = Y(im) is satisfied. Eq (3.6) can be transformed to linear

combination of mole fractions. By assuming V1 = V2

βS(im) = X1βS(1)) + X2βS(2) (3.7)

On the basis of Eq (3.7) Van-Deals expression for sound velocity in

binary mixtures may be written as

1 1 X1 X2
• = +
X 1M 1 + X 2 M 2 U (im )
2
M 1U 1
2
M 2U 2
2

(3.8)

Where M1 and M2,U1 and U2 are molecular weights and sound velocities

of the first and second component respectively.

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3.1.3 Collision Factor Theory

Schaff’s on the basis of collision factor theory, gave the

following relations for second velocity in liquids.

U = U∞.S.rf

U = U∞.S.(B/V) (3.9)

Where U∞ = 1600ms1

S is collision factor and rf is space filling factor, rf = B/V

B is actual volume of the molecule per mole and V is molar volume.

Nutsch – Khunkies extended the concept to binary liquid mixtures as

( X 1 B1 + X 2 B2 ) (3.10)
U mix = U∞( X 1 S1 + X 1 S 2 ) *
Vm

The actual volume of the molecule per mole for pure component was

calculated using for pure component was calculated using the relation.

B = (4π/3)rm3N (3.11)

Where n is Avagadro number,

rm is the molecular radius, cn be calculated from the following relation

1 Vσ 1 / 4
d 5/ 2 = * (3.12)
7.2 x1019 Tc1/ 4

In example (3.12) d is the molecular diameter V, σ and Tc stands

for molar volume, surface tension and critical temperature respectiviely.

The surface tension of liquid has been evaluated using the relation.

Σ = 6.3 x 10-4 x ρ x U3/2 (3.13)

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3.2 Molar sound Velocity

An empirical relation relating the ultrasonic velocity U with the

molar volume v has been suggested by Rao, on the basis of his

experimental work as,

R = U1/3 V (3.14)

Where r is known as rao’s constant. It is also known as molar sound

velocity. For liquid mixtures the plots of r with mole fractions are

generally found to be linear expecting in water – alcohol system where

there is a possibility of association through hydrogen bonding. The

linear dependency of R on the mole fraction may be of practical use in

computing the sound velocity from known value of density or the

density from known value of sound velocity in liquid mixtures. The non-

linear variation of R with the variation of concentration of one of the

components generally indicates a strong association between the

molcules10.

The molar volume V of a binary mixture is calculated using the

relation,

X 1M 1 + X 2 M 2
V = (3.15)
ρ12

Where X1 and X2 are the concentration of the first and second liquid in

moles M1 and M2 are their corresponding molecular weights. Ρ12 is the

density of the solution.

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3.3 Molar Compressibility

Wada11 based on his experimental work has established a

relation between the isentropic compressibility and molar volune called

wada’s relation given by

B = Vβs(-1/7) (3.16)

Where B is called Wada’s constant or Molar compressibility.

According to Wada, the quality ‘B’ should be a pressure

independent quantity and depends on temperature of the pure liquid.

Wada’s constant has a linear dependence on the mole fraction for all

known binary mixtures except those for the water alcohol systems.

3.4 Specific Acoustic Impedance

Study of acoustic impedance throws light on solute-solvent

interactions. It is given by

Z = ρU (3.17)

Where ρ – density of the solution

U – Ultrasonic velocity

3.5 Molar sound volume

Schaff’s Kulnkies and Woelk (1962) made a critical study of

Rao’s equation and showed that the fundamental physical involved in

sound transmission is the actual volume of the molecule and molar

sound volume is given by relation.

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 1/ 3
U 1
φ= V (3.18)
U ∞ ( 4 / 3)πs

Where u is the ultrasonic velocity,

U∞ has been equaled to 1600ms-1 by Schaff’s

S is the collision factor of the molecule and v is the molar volume.

3.6 Excess parameters

Values12 of the excess thermodynamic parameters GE were

evaluated from the relation

GE = G- GE (3.19)

Here, Gidl is the ideal value given by

Gidl = ΣiXiGi (3.20)

The degree of intermolecular attraction is given by

2
U exp
α= −1 (3.21)
U im2

3.7 Approximation in the Theoretical Methods

In Nomoto’s method, it is assumed that there is no change in

volume on mixing the liquids. Therefore it is not effectively taking the

interaction between the components into account.

In the ideal mixing method of Van Deal, it is assumed that V1 =

V2 = Vim. Further, the molar volumes of the components are assumed to

29
be equal which may make it very approximate. Therefore, strong

interaction between the liquids in a mixture may give rise to large

deviation of the calculation values from the experimental values.

Collision factor theory has the limitation that the sound velocity

should be less than 1600ms-1. The theory fails when U exceeds

1600ms-1. CFT involves the velocity ratio U/U∞ where U∞ is assigned an

empirical value of 1600ms-1.

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 Reference

1. Nomoto J. Phys. Soc, 13 1528 (1958)

2. Van Deal W (1978) Thermodynamic Properties and velocity of sound

(London: Buterworth)ch.5.

3. Richardson E (1962) ultrasonic physics (Amsterdam, Elsevier)

4. Blandamer M J and Wadington D, J phys. Chem. 74, 2569 (1970).

5. Schaff’s W, Z phys, 114 (1975) 110; 115 (1975) 69.

6. Schaff’s W, Molecular Acoustic Chapter X1 and X11 (Springer,

Berline) (1963).

7. Nutsch-Kuhunkies R, Acoustica 15, 383 (1965).

8. Chaturvedi CV & Pratap S. Acoustica 42, 60 (1979).

9. A Verbach N. Experimental 4, 473 (1948).

10. Vigoureux P Ultrasonics (1952)

11. Wada Y Jol. Phy. Soc. Japan 4, 2180 (1949).

12. Jacobson B. Cata. Chem. Scand, 5, 1214.

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