cfiapterf

m t x* o dsxGfc xoxi

1

1.1 U l t r a s o n i c s :

E l a s t i c waves of f r e q u e n c i e s beyond the a u d i b i l i t y r a n g e of

normal human e a r , a r e c a l l e d u l t r a s o n i c waves or i-'trasound.

9 U l t r a s o u n d f r e q u e n c y r a n g e e x t e n d s from 1600 Hz t o 10 Hz. I t s

upper l i m i t d o es not depend upon any i n t r i n s i c p h y s i c a l p r o p e r t y of

u l t r a s o n i c waves of such high trequencies.but on the t e c h n i c a l

p o s s i b i l i t y of p r o d u c i n g such waves.

1.2 U l t r a s o n i c a p p l i c a t i o n s :

U l t r a s o n i c waves have a c q u i r e d the s t a t u s of an i m p o r t a n t

p r obe f o r t h e s t u d y of s t i u c t u r e a nd p r o p e r t i e s of m a t t e r .In b a s i c

s c i e n c e s , t h e s e waves a r e used t o p r o v i d e i n f o r m a t i o n on the

? b e h a v i o u r of m i c r o s c o p i c p a r t i c l e of m a t t e r . Through the h i g h e r

o r d e r e l a s t i c c o n s t a n t s i n v o l v e d in the p r o p a g a t i o n of t h e s e waves,

an i n s i g h t i n t o t h e i n t e r a c t i o n in s o l i d i s o b t a i n e d . The a b s o r p t i o n

and d i s p e r s i o n of waves p r o v i d e i n f o r m a t i o n about r e l a x a t i o n

1-3 p r o c e s s e s in l i q u i d

The u l t r a s o n i c waves a r e b e i n g used f o r d e t e c t i o n of f l a w s ,

t e s t i n g of ma t e r i a 1 s , niechan i ca 1 c l e a n i n g of s u r f a c e s e t c . In medical

s c i e n c e s , the waves a r e b e i n g used tu d e t e r m i n e s t r u c t u r e and

b e h a v i o u r of b i o mo 1 ecu 1os, to d e t e c t hone f r a c t u r e s , t u m o u r s . f o e t a l

c o n d i t i o n s and f o r p h y s i o t h e r a p y . b l o o d l e s s s u r g e r y , c a r d i o l o g y ,

g y n e c o l o g y e t c . P r e s e n t day a p p l i c a t i o n s of u l t r a s o n i c s a r e emerging

m a n i f o l d in the f i e l d of f o r e n s i c s c i e n c e s , s p a c e r e s e a r c h and in

war f a r e .

1.3 U l t r a u o n i c wave p r o p o g a t i o n in f l u i d :

The u l t r a s o n i c v e l o c i t y and a b s o r p t i o n c o e f f i c i e n t

measurement have f u r n i s h e d , method f o r s t u d y i n g m o l e c u l a r and

s t r u c t u r a l p r o p e r t i e s of f l u i d . There e x i s t s c l o s e r e l a t i o n s h i p

between t h e u l t r a s o n i c v e l o c i t y and chemical or s t r u c t u r a l

c h a r a c t e r i s t i c s of m o l e c u l e s of f l u i d . T h i s g i v e s a p r o p e r t y of

b a s i c i m p o r t a n c e t o sound v e l o c i t y in m o l e c u l a r t h e o r y of f l u i d .

Upto 1930 u l t r a s o n i c v e l o c i t y d a t a in very few l i q u i d s was

a v a i l a b l e . The improvement of e x p e r i m e n t a l t e c h n i q u e s made the

i n v e s t i g a t i o n m a n i f o l d , both q u a l i t a t i v e l y and q u a n t i t a t i v e l y .

1.4 U l t r a s o n i c Parameters:

a) A d i a b a t i c C o m p r e s s i b i l i t y :

Two i m p o r t a n t p a r a m e t e r s a s r e g a r d s t o u l t r a s o n i c waves a r e

t h e i r v e l o c i t i e s and a b s o r p t i o n c o e f f i c i e n t s . By s i m p l y m e a s u r i n g

u l t r a s o n i c v e l o c i t y and d e n s i t y of l i q u i d , many a c o u s t i c a l

p a r a m e t e r s can be c a l c u l a t e d , which throw l i g h t on the m o l e c u l a r

b e h a v i o u r of the l i q u i d . The u l t r a s o n i c v e l o c i t y u i s g i v e n by

u 2 = ( d P / d ^ ) s

° r 2 1/u = ( l/^> ) ( d P / d ? ) s

= *a? or

6a = 1 / u ^ 1.1

where P i s t h e p r e s s u r e , ^ i s t h e d e n s i t y of l i q u i d and 6a i s the

a d i a b a t i c c o m p r e s s i b i l i t y . So with t h e e x p e r i m e n t a l d e t e r m i n a t i o n of

u l t r a s o n i c v e l o c i t y and d e n s i t y , /3a can be c a l c u l a t e d .

3

b) Rao's C o n s t a n t :

4 P a r t h a s a r a t h y d e r i v e d a number of e m p e r i c a l r u l e s f o r

u l t r a s o n i c v e l o c i t y v a r i a t i o n in d i f f e r e n t homologous s e r i e s and

5 6 d i f f e r e n t o r g a n i c g r o u p i n g . Rao ' e s t a b l i s h e d a r e l a t i o n between

sound v e l o c i t y and molar volume f o r the f i r s t time. The r a t i o of

t e m p e r a t u r e c o e f f i c i e n t of v e l o c i t y (du/dT>/u and e x p a n s i o n

c o e f f i c i e n t (dV/dT)/V a r e p r a c t i c a l l y same f o r a l l the u n a s s o c i a t e d

o r g a n i c l i q u i d s which g i v e e m p e r i c a l r u l e s a s

1 /^ V.u = R 1.2

where V i s t h e molar volume and R i s c o n s t a n t f o r a g i v e n l i q u i d

c a l l e d a s Rao's c o n s t a n t or m o l e c u l a r sound v e l o c i t y . For

u n a s s o c i a t e d l i q u i d , R i s 3. The v a l u e of R u n d e r g o e s r e g u l a r

i ncrement among members of a homologous s e r i e s of compounds. In a

s e r i e s , i t i s p o s s i b l e t o e x p r e s s R a s a l i n e a r f u n c t i o n of the

m o l e c u l a r w e i g h t , t h a t i s

R = a.M + b 1.3

where th e c o n s t a n t s a and b, c h a r a c t e r i s e t h e s e r i e s .

c) Physical S i g n i f i c a n c e of Rao's c o n s t a n t :

T e m p e r a t u r e dependence of Rao's c o n s t a n t R, d e r i v e d on

7 t h e o r e t i c a l c o n s i d e r a t i o n s , was used by J o h a r i t o g e t the r a n g e of

8 Q r e p u l s i v e f o r c e c o n s t a n t in some l i q u i d s . Tabhane *" i n t r o d u c e d

p h y s i c a l c o n c e p t of Rao's c o n s t a n t in e x p l a i n i n g the f o r m a t i o n of

o b s e r v e d c o m p l e x e s of CCI4 with benzene. The exponent of r e p u l s i v e

4

f o r c e |) in l i q u i d c a n be der i v e r j u s i n g r e l a t i o n

-V/2 = < ( d u / d T ) / u J / { idV/cIT) /V)

t h e v a l u e o f y was u s e d t o o b t a i n R v a l u e s a t d i f f e r e n t t e m p e r a t u r e

u s i n g r e l a t i o n

R u = u . V 1.4

5 Rao a s s u m e d O =6 and h e n c e i n e q u a t i o n ( 1 . 4 ) t h e v a l u e s o f O =-3 i s

u s e d t o o b t a i n R a o ' s c o n s t a n t

R6 = u Z / 6 . V 1.5

The v a r i a t i o n of R5 i s l i n e a r and t e m p e r a t u r e i n d e p e n d e n t , w h i 1 e t h a t

of RJJ c a n b e t a k e n a s an i n d i c a t i o n of m o l e c u l a r a s s o c i a t i o n of

l i q u i d s .

d) v a n d e r W a a l s ' C o n s t a n t :

v a n d e r W a a l s ' e q u a t i o n i s s t a t e d a s

<P + a/V") ( V b) -- RT 1.6

i n w h ich " b " i s known a s van der W a a l s ' c o n s t a n t , w h i c h i s n o r m a l l y

c a l c u l a t e d f r o m c r i t i c a l t e m p e r a t u r e T(, and c r i t i c a l p r e s s u r e P c

f r o m t h e e q u a t i o n s

b = ( R . T C ) / 8 P C or b =•- Vc/3 1.7

10 S c h a a f f ' s h a s made i t e a s y t o c a l c u l a t e 'b' from u l t r a s o n i c

v e l o c i t y r a t h e r t h a n f r o m c r i t i c a l c o n s t a n t s . He d e v e l o p e d t h e

f o r m u l a M - 2 = 2 1 - ' '

b = - j 1 - ' RT/Mu ) [ 1 • ( Hu / :-iRT) J - 1 1.8

5 i i K h a s a r e ~~ m o d i f i e d the e q u a t i o n of s t a t e f o r hard s p h e r e f l u i d

m i x t u r e . In pure l i q u i d 'b' can be c a l c u l a t e d u s i n g r e l a t i o n

(i - In'' h V ( !>"' ' <'"' 1 )

where "N? = N̂ /V = number d e n s i t y ; 0 ~ p a c k i n g f a c t o r ,

~c , RS

1 .9

1 • 1 (THT/MiT) 2 '• V

where, R i s c o r r e c t e d mean r a d i u s . R -> the r a d i u s of hard s p h e r e ,

S -> the s u r f a c e a r e a and T = Cp/Cv.

T h i s vander w a l l s ' m o l e c u l a r volume p a r a m e t e r "b" g i v e s an

i d e a of r e l a t i v e s i z e s of d i f f e r e n t m o l e c u l e s .

1.5 M o l e c u l a r I n t e r a c t i o n T e c h n i q u e s :

The s t u d y of m o l e c u l a r i n t e r a c t i o n in l i q u i d s p r o v i d e s

v a l u a b l e i n f o r m a t i o n r e g a r d i n g i n t e r n a l s t r u c t u r e , i n t e r n a l

p r e s s u r e . m o l e c u l a r a s s o c i a t i o n , c o m p I ex f o r m a t i o n e t c . The v a r i o u s

e x p e r i m e n t a l t e c h n i q u e s a v a i l a b l e to s t u d y them a r e NMR, microwaves,

u l t r a v i o l e t and i n f r a r e d s p e c t r o s c o p y and u l t r a s o n i c s . While NMR

t e c h n i q u e r e f l e c t s t h e e f f e c t on the p r o t o n b e a r i n g m o l e c u l e s . The

microwave a b s o r p s i o n , p r o v i d e s i n f o r m a t i o n t h r o u g h the d i e l e c t r i c

c o n s t a n t , n e u t r o n and X-ray s c a t t e r i n g , h e l p s in the s t u d y of

m o l e c u l a r motion. The s p e c t r o s c o p i c t e c h n i q u e s p r o v i d e u s e f u l

i n f o r m a t i o n on i t i t e r mo 1 ecu 1 ar i n t e r a c t i o n , when i n t e r a c t i o n e n e r g i e s

i n v o l v e d a r e l a r g e r . a s such,weak m o l e c u l a r i n t e r a c t i o n s cannot be

r e s o l v e d from the o b s e r v e d s p e c t r a . T h e u l t r a - s o n i c t e c h n i q u e s on the

o t h e r hand r e v e a l weak i n t e r a c t i o n s due to i t s u s e f u l w a v e l e n g t h

6

r a n g e . Moreover. u l t r a s o n i c p a r a m e t e r s a r e d i r e c t l y r e l a t e d t o a

l a r g e number of m o l e c u l a r and thermodynamic p a r a m e t e r s . S i n c e

v a r i o u s l i q u i d s t a t e t h e o r i e s a r e b a s e d upon tnermodynamic

c o n s i d e r a t i o n s , u l t r a s o n i c a b s o r p t i o n c o e f f i c i e n t s and v e l o c i t i e s

p r o v i d e means t o s t u d y them.

1.6 Review of e a r l i e r work.

a ) O r g a n i c l i q u i d s and t h e i r m i x t u r e s :

The u l t r a s o n i c measurement, have been c a r r i e d out in a l a r g e

number of m i x t u r e s of u n a s s o c i a t e d . a s s o c i a t e d and u n a s s o c i a t e d , two

12-16 a s s o c i a t e d t y p e s of l i q u i d s by v a r i o u s w o r k e r s . The d a t a on

more than 90 m i x t u r e s have been p r e s e n t e d by La n d o f f . The

u l t r a s o n i c v e l o c i t y and r e l a t e d thermodynamic p r o p e r t i e s such a s

a d i a b a t i c c o m p r e s s i b i l i t y , vander waa1s* c o n s t a n t , f r e e volume, Uada

c o n s t a n t . r e l a t i v e a s s o c i a t i o n , thermal p r e s s u r e c o e f f i c i e n t e t c .

have been c a l c u l a t e d in b i n a r y l i q u i d m i x t u r e s by a number of

workers . E x c e s s thermodynamic p a r a m e t e r s throw l i g h t on

24 25 26 27 intermo1 e c u l a r i n t e r a c t i o n . R a s t o g i J a i n , Naidu , T u r r u e l ,

28 29 3r)

S h e s h a d r i and many o t h e r s s t u d i e d the i n t e r a c t i o n in b i n a r y

l i q u i d m i x t u r e s from t h e knowledge of e x c e s s thermodynamic

f u n c t i o n s and some a c o u s t i c a l p a r a m e t e r s . U l t r a s o n i c a b s o r p t i o n

36- 38 measurement s t u d y has been done by many workers phase

39 40

t r a n s i t i o n s t u d y i s a l s o g o i n g on . J o h r i s t u d i e d t he u . s .

v e l o c i t y and p h a s e t r a n s i t i o n of TBA by the measurement of d e n s i t y

and v i s c o s i t y a t d i f f e r e n t t e m p e r a t u r e s near t he s o l i d i f i c a t i o n

7

41 p o i n t . Dhake s t u d i e d the r e f r a c t i v e i n d i c e s and p h a s e t r a n s i t i o n

of l i q u i d c r y s t a l a t d i f f e r e n t t e m p e r a t u r e . A t t e m p t s a r e now b e i n g

made t o s t u d y the v a r i o u s b i o l o g i c a l s y s t e m s f o r b e t t e r

42-43 u n d e r s t a n d i n g of b i o m o l e c u l e s . I n r e c e n t y e a r s many a t t e m p t s a r e

b e i n g c a r r i e d out t o s t u d y t h e m o l e c u l e s which r e s e m b l e the

b i o l o g i c a l s y s t e m s . i n o r d e r t o u n d e r s t a n d t h e i r b e h a v i o u r

i n d i r e c t 1 y .

b) Recent U l t r a s o n i c Work:

Study of u l t r a s o n i c v e l o c i t y measurement i s s t i l l g o ing on a s

44 r e c e n t l y r e p o r t e d by Subba Rao a l o n g with t h e e x c e s s s p e c i f i c

45 a c o u s t i c impedence s t u d y . The s t u d y of Nagbhushanam of e x c e s s

sound v e l o c i t y b e h a v i o u r of d e c a n - l - 0 1 + n - a l k a n e s and + branched

a l k a n e s have shown t h e a p p l i c a b i l i t y of e x c e s s sound v e l o c i t y

p a r a m e t e r a s a p o t e n t i a l p robe t o i n v e s t i g a t e t h e s o l u t e - s o l v e n t

i n t e r a c t i o n in b i n a r y m i x t u r e s . T h e y c a l c u l a t e d t h e o r e t i c a l v e l o c i t y

from CFT and FLT and showed t h a t the f r e e l e n g t h v a r i e s a s t h e s i z e

of m o l e c u l e s of both t h e components in m i x t u r e s . The l i t e r a t u r e

18 46-52 r e v e a l s l a r g e amount of work ' on c o m p a r i s o n of FLT and CFT

f o r wide r a n g e of s y s t e m s . T r e a t i n g a l 1 t h e m o l e c u l e s a s s p h e r i c a l

such a s N.methyl formamide, N.N.dimethyl formamide, nonane, dec a n e ,

53 h e x a d e c a n e e t c . H a l d a r c a l c u l a t e d the hard c o r e m o l e c u l a r d i a m e t e r

54 and Mandal a l s o c o n s i d e r e d a n i s o t r o p i c m o l e c u l e s a s e q u i v a l e n t hard

s p h e r e s and deduced the c o m p r e s s i b i l i t y e q u a t i o n t o j u s t i f y the

p r i n c i p l e of c o r r e s p o n d i n g s t a t e s in l i q u i d s . T h i s e q u a t i o n has been

8

compared with Mm ("jni,iti,(ii and ill HI l i n ^ ' i i Ktpi.it i • i it of s t a t e .

C o m p r e s s i b i l i t y and o t h e r thermodynamic p a r a m e t e r in t e t r a a l k y l -

ammoniun-iodide, e t h e l e n e , c a r b o n a t e s o l u t i o n a t d i f f e r e n t

55-57 t e m p e r a t u r e s have been c a r r i e d out r e c e n t l y by P a n k a j " and

o t h e r s .

V o l u m e t r i c and u l t r a s o n i c b e h a v i o u r of some ch1 o r o e t h e n e s and

58 59 c h 1 o r o e t h a n e s have been c a r r i e d by Reddy and P r a k a s h . From the

v a r i a t i o n of e x c e s s volumes and e x c e s s i s e n t r o p i c c o m p r e s s i b i l i t i e s

59 e t c , d i f f e r e n t i n t e r a c t i o n s a r e r e p o r t e d . P r a k a s h s t u d i e d b i n a r y

s y s t e m s of d i - c h 1 oromethane with a r o m a t i c h y d r o c a r b o n s and

i n t e r p r e t e d t h e r e s u l t on t h e b a s i s of e x c e s s thermodynamic

R O

p a r a m e t e r . Govindappa r e p o r t e d t he u l t r a s o n i c v e l o c i t i e s of

m i x t u r e s of b e n z e n e , t o 1une,xy1enes,chromo,bromo and n i t r o b enzenes

with 1 - c h 1 o r o b u t a n e and a n a l y s e d t he r e s u l t in ter m s of CFT and FLT

t h e o r i e s , s h o w i n g t h a t t h e t h e o r i e s a g r e e well f o r t h e s e s y s t e m s . The

d i p o 1 e - d i p o 1 e or d i p o l e induced d i p o 1 e i n t e r a c t i o n between u n l i k e

m o l e c u l e s a r e e x p l a i n e d from the e x c e s s c o m p r e s s i b i l i t y p a r a m e t e r . R 1

Recent e x p e r i m e n t a l i n v e s t i g a t i o n in t h i s l a b o r a t o r y have shown

t h a t d e r i v e d p a r a m e t e r s such a s a d i a b a t i c c o m p r e s s i b i l i t y 6B, the

vander w a a l s p a r a m e t e r b and t h e i r d e v i a t i o n s from a d d i t i v e r u l e

p r o v i d e a b e t t e r i n s i g h t i n t o the m o l e c u l a r p r o c e s s e s and t h e s e

e x c e s s p a r a m e t e r s can be used t o d e t e r m i n e t he r e l a t i v e s t r e n g t h of

homo and h e t e r o m o l e c u l a r i n t e r a c t i o n s in b i n a r y l i q u i d m i x t u r e s .

R a v i e h a n d r a n h.n, i.tudind u . u . vt. h><-i I y urn) * b s u i p t l u n in

aq u e o u s e l e c t r o y l i c s o l u t i o n of ammonium c h l o r i d e , ammonium d i h y d r o

0

p h o s p h a t , and ammonium oxaI a t e , r e c e n t 1y u s i n g p u l s e echo t e c h n i q u e

and non l i n e a r i n c r e a s e in u l t r a s o n i c v e l o c i t y and d e c r e a s e in

o b s e r v e d a b s o r p t i o n a r e d i s c u s s e d on the b a s i s of F l i c k e r i n g c l u s t e r

model and H a l l s two s t a t e model f o r 1 i q u i d . U 1 t r a s o n i c A b s o r p t i o n

62 s t u d i e s of Endo in e l e c t r o l y t e s of h i g h s o l u b i l i t y l i k e NaCl,

NaBr,NaI,KC1,KBr and Kl shows a d e c r e a s e in a b s o r p t i o n with i n c r e a s e

in c o n c e n t r a t ion.The a b s o r p t i o n s t u d i e s of B a r r e t t i n d i c a t e the

d e c r e a s e of a b s o r p t i o n i s h i g h e r f o r NaBr and NaI whereas the

a b s o r p t i o n of NaCl and KC1 s o l u t i o n r e m a i n s c o n s t a n t on t h e o r e t i c a l

b a s i s . A b s o i p t i o n , d i s p e r s i o n and r e l a x a t i o n a r e s t u d i e d in c a r b o n -

d i s u l p h i d e in terms of t h e complex and f r e q u e n c y dependent bulk

v i s c o s i t y c o e f f i c i e n t of t h e l i q u i d by Narasimham and t h e l a r g e

a b s o r p t i o n in c a r b o n d i s u 1 p h i d e i s a c c o u n t e d f o r , by i t s bulk

v i s c o s i t y . A b s o r p t i o n and d i s p e r s i o n of c o m p r e s s i o n a 1 waves in l i q u i d

a r e c l o s e l y a s s o c i a t e d with the bulk v i s c o s i t y of the l i q u i d which

3 1 becomes complex and f r e q u e n c y dependent under t h e a c t i o n of

u l t r a s o n i c waves.

V a r i o u s e q u a t i o n s of s t a t e f o r hard s p h e r e have come forw a r d .

R e c e n t l y K h a s a r e m o d i f i e d an e q u a t i o n of s t a t e and found t h a t

t h e r e i s a c l o s e a greement with computer s i m u l a t i o n r e s u l t . S.S.

64 B h a t t i has made u l t r a s o n i c s t u d y and c a l c u l a t e d a c o u s t i c a l

65 p a r a m e t e r s of l i q u i d on hard s p h e r e model. Sharma t e s t e d the

v a l i d i t y of an e q u a t i o n of s t a t e of r e a l f l u i d s and d e r i v e d the

e x p r e s s i o n s f o r v a r i o u s a c o u s t i c a l p a r a m e t e r s t o r e l a t e them with

G r u n e i s e n p a r a m e t e r . It i s c o n c l u d e d from t h e s e s t u d i e s t h a t l i q u i d

10

f l u o r i n e can be d e s c r i b e d s a t i s f a c t o r i l y by r i g i d model with

66 a t t r a c t i v e i n t e r a c t i o n s . G o p a l a Rao f o r m u l a t e d an e q u a t i o n of

s t a t e f o r a s q u a r e well f l u i d and v a r i o u s thermodynamic p a r a m e t e r s .

E x t e n d i n g the F l o r y ' s e q u a t i o n t o m i x t u r e s of u n r e l a t e d t y p e of

36 E m o l e c u l e s . S a b e s a n c a l c u l a t e d e x c e s s e n t h a l p y v a l u e H e x c e s s

*E 2

a c t i v a t i o n e n e r g y of v i s c o u s flow G and a/f and found

e x p e r i m e n t a l r e s u l t s in good agreement s u g g e s t i n g t h a t F l o r y ' s

e q u a t i o n c o u l d be e x t e n d e d t o m i x t u r e s of u n r e l a t e d t y p e . The

a c t i v a t i o n co e f f i c i e n t s f o r v i s c o u s f o r c e s have a l s o been o b t a i n e d

14 u s i n g E y r i n g ' s r a t e t h e o r y .The pseudo G r u n e i s e n p a r a m e t e r i s

69-71 c a l c u l a t e d by Pandey which c h a r a c t e r i s e s t h e l a t t i c e

b e h a v i o u r and t h e dimens ion 1 e s s measure of t h e change in e n t r o p y

with volume or the thermal p r e s s u r e . Pseudo G r u n e i s e n p a r a - m e t e r have

been s t u d i e d in o r d e r t o i n v e s t i g a t e t h e i n t e r n a l s t r u c t u r e and

q u a s i c r y s t a 1 1 i n e p r o p e r t i e s of pure l i q u i d s and l i q u i d metal 14

a l l o y s U l t r a s o n i c s t u d i e s of l i q u i d c r y s t a l have been r e p o r t e d 72-77

by l a r g e number of w o r k e r s . The u l t r a s o n i c s v o 1 u m e t r i c , o p t i c a 1 ,

d i e l e c t r i c , s p e c t r o s c o p i c and thermal p r o p e r t i e s of l i q u i d c r y s t a l

41 have been s t u d i e d by Dhake . These s t u d i e s a r e i n t e r e s t i n g and

e x p l a i n p r e t r a n s i t i o n a 1 and t r a n s i t i o n a l e f f e c t of t h e r m o t r o p i c

l i q u i d c r y s t a 1 . B i o 1 o g i c a 1 m a t e r i a l s l i q u i d or s o l i d , h a v e been

84 i n v e s t i g a t e d by S i n g h f o r a d u l t e r a t i o n due t o i t s a d v e r s e e f f e c t

on human b e i n g s . An u . s . d o u b 1 e - p r o b e - t h r o u g h - t r a n s m i s s i o n t e c h n i q u e

has been d e v e l o p e d and u s e d t o d e t e c t a d u l t e r a t i o n in b i o l o g i c a l and

b i o l o g i c a l l y s i g n i f i c a n t m a t e r i a l s , t h i s t e c h n i q u e has an a d v a n t a g e

of no e n e r g y l o s s due t o r e f l e c t i o n or a b s o r p t i o n e t c .

11

1.7 Remarks and O r i e n t a t i o n of P r e s e n t Work.

Many t h e o r i e s have been a p p l i e d t o l i q u i d m o l e c u l e s and

e q u a t i o n of s t a t e have been d e r i v e d . U l t i r a a t e aim of a l l s t u d i e s i s

to g e t the p a r a m e t e r s c l i a i a c t e i s i n g t h e l i q u i d s t a t e and the

m o l e c u l a r f o r c e s e x i s t i n g between d i f f e r e n t t y p e s of component

m o l e c u l e s in the m i x t u r e of two or t h r e e l i q u i d s . The r e c e n t s t u d i e s -70

of Tabhane have shown t h a t t h e n a t u r e of v e l o c i t y vs c o m p o s i t i o n

c u r v e s a r e smooth with a p o s i t i v e or n e g a t i v e c o n c a v i t y when any of

the AA, AB or BB i n t e r a c t i o n s p r e d o m i n a t e . The hydrogen bonded

complex f o r m a t i o n in a number of s y s t e m s has been i n d i c a t e d by a

peak in v e l o c i t y and c o r r e s p o n d i n g d i p in c o m p r e s s i b i l i t y vs

79 c o n c e n t r a t i o n c u r v e s , with t h e h e l p of a c o u s t i c a l and

thermodynamic p a r a m e t e r s . T h r o u g h e x c e s s v a 1 u e s , v a r i o u s a t t e m p t s have

been made t o a n a l y s e t h e i n t e r a c t i o n s or complex f o r m a t i o n .

1 9 P r a ka s h Rtudiod a c m K l n physi rr> ^hornir.»l prnpurt it><s of t he b i n a r y

m i x t u r e s of e l e c t r o n d o n a t i n g h y d r o c a r b o n s with t e t r a c h I o r o e t h a n e

which throw l i g h t on s t r e n g t h of i n t e r a c t i o n . U l t r a s o n i c i n v e s t i -

42 g a t i o n of ki d n e y s t o n e s has been done by S i n g h s u g g e s t i n g t h a t the

s t u d y would h e l p in d e t e r m i n i n g t he d e s i g n p a r a m e t e r s to d e v e l o p a

t e c h n i q u e f o r the kidney d i s i n t e g r a t i o n .

In r e c e n t y e a r s u . s . s t u d i e s a r e b e i n g c a r r i e d out on

84-85 v a r i e t y of l i q u i d s r e s e m b l i n g b i o - f l u i d s . B i o - f l u i d s a r e

g e n e r a l l y made up of long c h a i n m o l e c u l e s c o n s i s t i n g of a r o m a t i c ,

h e t e r o c y c l i c compounds e t c . T h e y a r e b i g g e r in s i z e and c o m p l i c a t e d

J. (^

in s t r u c t u r e . A review of l i t e r a t u r e shows l a r g e amount of work on

79 81 o r g a n i c l i q u i d s " but s c a n t y work on b i o - 1 i q u i d s . T h e r e f o r e i t was

t h o u g h t w o r t h w h i l e to u n d e r t a k e u . s . i n v e s t i g a t i o n on some b i o l i q u i d s

To u n d e r s t a n d the b e h a v i o u r of b i o - me 1 ecu 1 e s , repr t-sen t a t i ve , ar omat i c

h e t e r o c y c l i c and a,^-unsaturated c a r b o n y l compounds have been

s e l e c t e d f o r i n v e s t i g a t i o n . The p r e s e n t t h e s i s , p r e s e n t s the r e s u l t s

of e x p e r i m e n t a l and t h e o r e t i c a l u l t r a s o n i c i n v e s t i g a t i o n of

s y s t e m s , a c e t o n e + m e t h y l m e t h a c r y l a t e . a c e t o n e + c i n n a m a l d e h y d e , a c e t o n e *

a c r o l e i n , a c e t o n e + a c r y 1 o n i t r i lg, and a c e t o n e + p y r i d i n e . T h e a c e t o n e i s

a b i o - m o l e c u l e and a l i p h a t i c in n a t u r e . I t i s p r e s e n t in normal

u r i n e but in d i a b e t e s and s t a r v a t i o n c o n d i t i o n , i t s ammount i s

l a r g e l y i n c r e a s e d . I t i s the p r o d u c t of d e c o m p o s i t i o n of c e l l u l o s e

in human body. It i s a l s o found in wood s p i r i t . Cinnama1dehyde,

a c r o l e i n , a c r y l o n i t r i l methy1-methacry1 a t e a r e a , ^ - u n s a t u r a t e d

c a r b o n y l compounds.They a r e compounds of s p e c i a l i n t e r e s t in b i o ­

m e d i cal t e c h n o l o g y and i n d u s t r i e s . P y r i d i n e i s a s t a b l e h e t e r o c y c l i c

compound.Groups and d e r i v a t i v e s of p y r i d i n e l i k e compouds a r e found

in body s y s t e m .

To u n d e r s t a n d the b e h a v i o u r of t h e s e b i o - l i q u i d s , namely

cinnama1dehyde, methy1methacry1 a t e , a c r o l e i n , a e r y 1 o n i t r i I e and

p y r i d n e in m i x i t u r e with p o l a r l i q u i d a c e t o n e a s s o l v e n t , have been

s e l e c t e d f o r e x p e r i m e n t a l and t h e o r e t i c a l u l t r a s o n i c s t u d i e s in

p r e s e n t i n v e s t i g a t i o n . In a m o l e c u l e s c o n t a i n i n g d i f f e r e n t r a d i c a l s ,

t h e r e l a t i v e o r i e n t a t i o n of t h e r a d i c a l s i s e x p e c t e d t o p l a y an

i m p o r t a n t r o l e in the i n t e r a c t i o n of t h e s e m o l e c u l e s with o t h e r

p o l a r and non p o l a r m o l e c u l e s . In the p r e s e n t s y s t e m a c e t o n e ,

cinnama1dehyde, methy1 methacry1 a t e , a c r o l e i n a r e oxygen b e a r i n g

m o l e c u l e s , w h i l e p y r i d i n e and a e r y l o n i t r i l e a r e n i t r o g e n b e a r i n g

m o l e c u l e s . A c o m p a r i s o n of u l t r a s o n i c p a r a m e t e r of above compound in

m i x t u r e with p o l a r s o l v e n t a c e t o n e was t h o u g h t w o r t h w h i l e . I t was

a l s o i n t e n d e d t o s t u d y whether t h e s e r a d i c a l s in a, j S - u n s a t u r a t e d

c a r b o n y l compounds have s p e c i f i c r o l e t o p l a y in intermo1 ecu 1ar

i n t e r a c t i o n in b i n a r y l i q u i d m i x t u r e s . M o s t of the e a r l i e r

t h e o r e t i c a l u l t r a s o n i c work i s d i r e c t e d in p r e d i c t i n g u l t r a s o n i c

74 v e l o c i t i e s u s i n g J o c o b s o n ' s f r e e l e n g t h t h e o r y , S c h a a f f ' s

c o l l i s i o n f a c t o r t h e o r y , Nomoto's i d e a l mixing t h e o r y , F l o r y ' s

s t a t i s t i c a l t h e o r y , s c a l e d p a r t i c l e t h e o r y and v a r i o u s o t h e r

74 t h e o r i e s u s i n g e m p i r i c a l c o n s t a n t s e.g. J o c o b s o n ' s c o n s t a n t

K , S c h a a f f ' s c o l l i s i o n f a c t o r S, Nomoto's m o l e c u l a r sound v e l o c i t y ,

s h a p e f a c t o r of m o l e c u l e e t c . t h e s e t h e o r i e s were used t o g e n e r a t e

thermodynamic p a r a m e t e r s of pure and b i n a r y l i q u i d m i x t u r e s by

c o n s i d e r i n g m o l e c u l e s t o be s p h e r i c a l one. An a t t e m p t has been made

f o r t h e f i r s t t i m e , in p r e s e n t t h e s i s t o c a l c u l a t e u l t r a s o n i c

v e l o c i t y from F l o r y ' s t h e o r y and S c a l e d p a r t i c a l t h e o r y u s i n g

d i f f e r e n t m o l e c u l a r model s h a p e s such a s s p h e r i c a l , c u b i c a l ,

t e t r a h e d r a l and d i s c f o r t h e i n t e r a c t i n g m o l e c u l e in b i n a r y l i q u i d .

F u r t h e r an a t t e m p t has been made to f o r m u l a t e a more r e c e n t t h e o r y

of l i q u i d s and i t has been a p p l i e d t o t h e s y s t e m i n v e s t i g a t e d

f o r t e s t i n g f o r i t s a b i l i t y t o r e p r o d u c e v a r i o u s thermodynamic

p a r a m e t e r s of p u r e and b i n a r y l i q u i d m i x t u r e s .

R e f e r e n c e s

14

1) H e r f e i d K . F. &L i t o v i t::

2 ) J o c o b s o n B.

3 ) N a r s i mham A.V.

4 ) P a r t h s a a r t h y

5 ) M. R.Rao.

6 ) M. R.Rao

^7 > J o h i i G. V..t Mi f;hr ... Rl.

8 > T a b h a n e V.A.

9 ) T a b h a n e V.A.

10) S c h a a f f '

11) K h a s a r e 3.B.

t2 ) K r i s h n a M u orthy I-.. K u p p u s a m i J and 0 m a y o a r u p a k a m P i 1 I a i s

13) M u r l i d h a r K.Swami M.L Rao S.N.& S u b h a r a o K.

14 i Bhok h r a R.L . and Anupma Nag

15) P.S.N i k a m & Mend i h a s a n

16) G.Ra v i c h a n d r a m, A . S h r i v a s Rao. T . K . N a m b i n a r a y a n

17,i Land o f f

A b s o r p t i o n a n d d i s p e r s i o n o t u . s . w a v e s (A c e d e m i c P r e s s N e w Y o r k ) 1 959

A c t a Chem. S c a n d 6 ( 1 0 5 2 ) 1 4 6 ,

IEEE: t r a n s s o n i c s <and u l t r a s o n i c s (U.S.A) SU 16 ( 1 9 6 9 ^ 1 6 2

A b s o r p t i o n a nd d i s p e r s i o n OT U . S . wave

(A. P . ) ( 1 9 5 9 ) , 362

i n d . J . of P u r e and a p p l i e d P h y s i c s 14 t ! 94 0 > .1 09

1 nd . Chem. P h v s 9 ( 1 9 4 1 ) 6 3 2

]K)..I MI pur,. ;,|K| ..pp |,hvr. ', ( 1 9 6 4 ) 6 7 7

2 2

A c o u s t i c s 5 2 '.1982)44

S y m p o s i u m , S o I i d S t a t e P h y s i c s 1 9 8 9 .

M o l e c u l a r a k u s t i c k " s p r i n g e r B e r l i n

'. 1 9 6 3 i _ ? 2 I n d . J h u p a n d a p p l i e d p h v V o l 2 9 ( i 9 9 1 ) 1 9

<9.ir i ;.'.- l ' I nd ' 4 4 ' I 9 /'> ' , <i

P h y . R e v , A 5 3 ( 1 9 8 6 >

I nd . .J . pu r e a nd a pp I . pny . 29' 1 99 1 ) 756

i n d . J . p u r e and a p p 1 . p h v . 2 4 ( 8 6 ) 5 0 2

I n d . J . p u r e h a p p . p h v . 2 9 ( 1 9 9 1 ) 7 9 2

N u m e r i c a l d a t a and f u n c t i o n a l r e l a t i o n i n s c i e n c e a nd t e c h n o l o g y i n M o l e c u l a r A c o u s t i c s .

18) J ha D.K.and J ha B.L. I n d . J . o f p u r e and a p p l . p h y s i c s

15 19)

2 0 )

21 )

2 2 )

2 3 )

2 4 )

2 5 )

2 6 )

2 7 )

2 8 )

2 9 )

3 0 )

3 1 )

3 2 )

3 3 )

3 4 )

3 5 )

3 6 )

P r a k a s h . 0 , P r a k a s h S and S h r i v a s t a v a A.

C h o u d h r y N.V.Naidu P.R, And C h a n d r a M o u l i J . C .

P r a k a s h 0 and S i n h a . S .

S u b b a Rao S and Gopa 1 k r i s h n a n R.

B h a t t i £.$. and S i n g h D.P.

R a s t o g i R.P. and Mi s h r a J .

J a i n D.V, G u p t a V.K. and L a r k B.S.

Nai du P.R. and Kr i s h n a n V.C.

De l m o s G . T u r r e l s

S h e s h a d r i K . P r a b h a k a r N.and K e dd v K•C.

B a t l & s m l e y G.H. and S c o t t * R. L.

P r a k a s h 0 and D a r b a r i s

A d g a o n k a r C . S . J a i o o S.N D e o g a o n k a r V.S.

N a t h J . a n d Dubey S.N.

Reddy K.S.& S r e e n i v a s a n M.and N a i d u P.R.

T a b h a n e V.A.& P a t k i B.A.

P r a k a s h O . S i n h a S and P r a k a s h S.

S a b e s a n R . V a r a d a r a i a n R, and N a t a r a j a n M.

3 7 ) S a r a f B,

A c r u s t i c a l 56 ( 1 9 8 4 ) 68

A c r u s t l e t t 6 ( 1 9 8 2 ) 56

A c o u s t i c a 54 ( 1 9 8 4 ) 2 2 3

J . A c o u s t a s o c . i n d . 7 ( 1 9 7 9 ) 5

A c o u s t i c a 5 6 ( 1 9 8 4 ) 2 9 0

J.Phy.Chem, 7 1 ( 1 9 7 7 ) 1 2 7 7

Ind.J.Chem. 8 ( 1 9 7 0 ) 8 1 5

J . P h v . S'-oc ( J a p a n ) 3 0 ( 1 9 6 5 ) 1554

T r a n s . F a r S o c . 7 0 ( 1 9 7 5 ) 5 9 0

J . |jhy . chem i e . t Neve r o 1 g e > 0 9 (, 1974 ) 109

Aug..J Chem 2 9 ( 1 9 7 6 ) 4 2.7

A c u s t i c a 6 5 ( 1 9 7 8 ) 107

l n d . J . P u r e b. A p p l . P h v . 1 7 ( 1 9 7 9 ) 3 7 5

J ( P h y ) C h e m . 8 4 ( 1 9 8 0 ) 2 1 6 6

Z e r t Fur Phy Chem 54 ( 1 9 8 1 ) 150

A c u s t i c a 5 2 ( 1 9 8 2 ) 44

A c o u s t l e t t 7 ( 1 9 6 3 ) 47

I n d . J . P u r e & a p p l . p h v . 2 6 ( 1 9 6 8 ) 504

A c o u s t L e t t 7 ( 1 9 8 3 ) 37

10 38) T.Homowski & M.Kobowsk : A c u s t i c a 76 no 4 (1 9 9 2 ) 8

39) Vigourex P. : U l t r a s o n i c (Chapman & Ha 1 1,London>1952

40) J o h r i G.K.and Mishra K.C. : A c u s t i c a 2 8 . ( 1 9 7 3 ) 301

4 1 ) D h a k e « ' ( ) , f t ' h a ^ t v J ' ? . c * n ^ : "3- ^ Cousfc--<So^ • lv^A*Q V B i n H " > H mcxVva-jo,* **• <.lt.tvsVvaifcVx T-Okaync O q g q " } l £ l

42) S i n g h V.R.Agrawal R.B. Sud S.P. : I n d . J . P u r e and appl Phv.26 (1988) 475

43) Anil S u r v a v a n s h i & V.R. S i n g h : A c u s t i c a 76 no A (.1992.* 86

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45) a ) NagBhushanarn G & N.

Monohara Murthv : I n d . J . P u r e & appl.Phy 27 ( 1 9 8 9 ) 193

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c) : J.ACULU. Sue I n d i a 12 ( 1 9 8 4 ) 32

d) " : A c u s t i c a (Ger) 65 ( 1 9 8 8 ) 295 46) P.Venketeswar i a,K.Ram

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5 8 ) V i i a y a B h a s k a r Reddy. D. Raman j a n e y u 1 u K b K r i s h n a i a h A

5 9 ) Qmprak.ash, A n i t a S h r i v a s t a u , A n j a l i S h r i v a s t a v . a n d 5. P r a k a s h

6 0 ) G o v i n d a p f i a J.Rambahu K V a n t a I e s w a r a 1 u P.and Raman G.K.

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6 2 ) Endo H . O t o n i k o Nomoto

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I n d . J . P u r e . a n d A p p l . P h y . 2 8 ( 1 9 9 0 ) 6 3 8

A c o u s t l e t t CGB) 10 ( 1 9 8 6 ) 6 3

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I n d . J . P u r e and App.Phy 24 ( 1 9 8 6 ) 306

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J . C h e m . S o c . F a r a d a y T r a n s . ( G B ) 2 ( 1 9 6 1 ) 2 1 7

I n d . J . P u r e and App.Phv.26 ( 1 9 8 8 ) 4 8 7 I n d . J . P u r e and Aop.Phy.25 ( 1 9 8 7 ) 182 I n d . J . P u r e and App.Phy.25 ( 1 9 8 7 ) 180 I n d . J . P u r e and App.Phy.29 ( 1 9 9 1 ) 5 4 7

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6 5 ) S h a r m a B.K, P a r a m a n a 14 ( 1 9 6 0 ) 4 7 7

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