CHAPTER , 2

EXPERIMENTAL TECHNIQUES

2.1 V i s c e s i t v Mtasureroents :

Because of the importance of v i s c o s i t y in

sc i e n c e and t ec h n ol o g y, numerous instruments known

as viscom ete rs f o r measuring i t have been de ve lo ped

t o s u i t d i f f e r e n t need s. There a r e two types o f

methods used to determine v i s c o s i t y .

i) capillary Flow Method-^-^

Almost i n v a r i a b l y , v i s c o m e t e r s used f o r

measurement on l i q u i d electrolytes have been of

c a p i l l a r y ty pe . Measurements w i t h t h e s e vi scometer;

depend f o r t h e i r i n t e r p r e t a t i o n on a r e l a t i o n s h i p

between the r a t e o f f l o w o f l i q u i d s under a p p l i e d

p r e s s u r e and dimensions o f c a p i l l a r y t u b e through

which they are f o r c e d . Such a r e l a t i o n s h i p a r i s e

from the work of Hagen - P o i s e u i l l e and has been

giv e n as
 71

X = -t t i ^ ( P o - P 3 1 . . . (2.1)
8 V I

where i s the volume of l i q u i d f l o w i n g through

the tube in time *t' , *Pq * and * P * a re the

p r e s s u r e s at the two ends, *R' is its r a d i u s and

•1’ its le n g th .

C a p i l l a r y v i s c o m e t e r can be b r o a d l y grouped as

(A) Viscometer f o r a b s o l u t e v i s c o s i t y measurement,

( B) Vi scome ter f o r r e l a t i v e v i s c o s i t y measurement.

The measurement i n s e c t i o n A are no rm al ly on ly

used f o r the e s t a b l is h m e n t f o r c o n t r o l of a p p l i e d

p r e ss u re as w e l l as p r e c i s e knowledge of c a p i l l a r y

dimensions. Type B v i s c o m e t e r s a r e t h o s e in which

measurements are made r e l a t i v e to a pri ma ry st a n d a rd

l i q u i d o r to d e r iv e d se con dar y s t a n d a r d ,

ii) F a l l i n g B a l l Method-*-*

The f a l l i n g b a l l method c o n s i s t s of c y l i n d r i c a l

tube f i l l e d with the f l u i d of unknown v i s c o s i t y .

 12

A b a l l of s u i t a b l e d e n s i t y and r a d i u s is allowed to

fa ll a lo n g the a x i s of t u b e . The time a t which t he

b a l l pas s es r e g u l a r l y sp ac e d h o r i z o n t a l c a l i b r a t i o n

marks i s recorded and i s f u r t h e r r e l a t e d t o the

v i s c o s i t y of the f l u i d throu gh s u i t a b l e mathematical

equations.

In the pre se nt s t u d y , the c a p i l l a r y f l o w method

was employed to determine t h e v i s c o s i t y o f f l u i d a t

v a r i o u s t em p era tu re s. The u s u a l form o f t h i s simple,

ye t a c c u r a t e apparatus known a s Ubbelohde

p
v i s c o m e te r f o r comparing v i s c o s i t i e s o f d i f f e r e n t

liquids i s as shown i n f i g u r e 2 , 1 ,

The l e f t hand limb o f the U t ub e i s essen tially

a p i p e t t e wi th two d e f i n i n g marks *A* and *B* and

a c a p i lla r y resistance 'C;’ through which the l i q u i d

co n ta in e d in bu lb f l o w s under g r a v i t y back i n t o

the ’ E* in the r i g h t hand li m b . The Ubbelohde

v i s c o m e te r used in p r e s e n t i n v e s t i g a t i o n d i f f e r s from

Ostw ald and Cannon-Fenske viscometers i n the p r o v i s i o n

of a suspended l e v e l 'H* a t the j u n c t i o n of the

c a p i l l a r y and the b u l b *G‘ , This f e a t u r e , which i s

ob t a in e d by exposing suspended l e v e l t o the atmosphere,

ensures t h a t the l i q u i d i s s u i n g from t h e c a p i l l a r y

D <-

C <-

H
 73

adhers as a f i l m t o the w a l l of the b u l b 'G ‘ . It

i s claimed that t h i s device eliminates l o a d i n g and

surface tension e r r o r s . A d e f i n i t e volume of l i q u i d

is employed and d e l i v e r e d i n t o the * F ’ from a

c a lib ra te d pipette. The q u a n t i t y of l i q u i d sh ou ld be

such t h a t when the l i q u i d is sucked up i n t o the l e f t

hand limb u n t i l the meniscus stands above the mark

'A ' then the meniscus on the r i g h t st a nd s a t the

bottom of the b u l b ’E ’ . T h is liqu id is released

from t h i s p o s i t i o n and a l l o w e d t o f l o w back, when t h e

meniscus passes mark * A ' , a st op watch i s started

and when i t reaches mark ' B ’ the watch i s stopped

and the time of out f l o w is noted. The watch i s

w i th an accuracy of 0.01 s e c . The volume f lo w n from

'A* to 'B ' intime *t' is giv e n by the e qu a t i o n 2 . 1 .

The dete rmina tion of a b s o l u t e v i s c o s i t y o f a

l i q u i d w i t h the h e lp of e qu ati on 2.1 does involve

w i th the ac cur ate measurement of 'P ' = po -p , 'H ’

and ’ t ' . I t is u s u a l l y s u f f i c i e n t t o compare the

v i s c o s i t y of l i q u i d w i t h t h a t o f w a t e r o r o t h e r

stand ard l i q u i d s by measuring the time taken f o r

equal volumes of the two l i q u i d s t o f l o w through

 74

same c a p i l l a r y under p r e s s u r e due t o t h e i r own

weights. The d e n s i t i e s o f both l i q u i d s a r e known.

The a b s o l u t e v i s c o s i t y o f the l i q u i d can then be

ob t a in e d knowing the v i s c o s i t y of t h e st a n d a rd

liqu id.

The f o r c e d r i v i n g the l i q u i d th r o u g h the

c a p i l l a r y in the vi sc om e r i s equ al t o h x x g

where *h* i s mean d i f f e r e n c e of l e v e l of l i q u i d in •

t he two limbs of t h e t u b e , » i s t h e d e n s i t y of

t h e l i q u i d and ‘ g ’ the g r a v i t a t i o n a l c o n s t a n t . The

r e s i s t a n c e t o " f l o w depends on the dimensions o f the

c a p i l l a r y which a r e c o n s t a n t and on t he v i s c o s i t y

of the l i q u i d . If now t he same volume of a second

l i q u i d o f known v i s c o s i t y i s i n t r o d u c e d i n t o the t u b e ,

t he mean d i f f e r e n t of l e v e l o f t he two l i q u i d s'urface

w i l l a l s o be h , so t h a t the d r i v i n g f o r c e i s now

h X ^^x g . Thus, the d r i v i n g f o r c e i s proportional

t o the d e n s i t i e s of the l i q u i d s w h i l e the r e s i s t a n c e

is proportional to t h e i r v i s c o s i t i e s . S i n c e the

r a t e of f l o w i s p r o p o r t i o n a l t o f o r c e / r e s i s t a n c e , the

times of out f l o w (tj^ and t 2 ) f o r the same volume o f

the two l i q u i d s a r e i n t he i n v e r s e r a t i o i,e .

 75

to.
OY

.1 .'.. - - . u .a

Thus if the a b s o l u t e v i s c o s i t y of one l i q u i d i s

known, t h a t of the g iv e n l i q u i d can be determined.

S in c e the r a t e of f l o w through a c a p i l l a r y tube

depends on and 'rl* (internal radius of c a p i l l a r y )

can vary from 0.2 t o 2 mm, Ubbelohde v i s c o m e t e r can

4
be made to cover a range of 10 in v i s c o s i t y .

2 .2 Practical D etails :

A visc ome ter was s e l e c t e d having a f l o w time of

150-700 seconds^ I t was f i r s t t h r o u g h l y c le a n e d

w i t h warm chromic a c i d so t h a t t h e r e were no o b s t r u -

-ctions in the c a p i l l a r y and the l i q u i d ran c l e a r l y

without l e a v i n g drops b e h in d . I t was then t h r o u g h l y

washed by drawing d i s t i l l e d wa te r thr ough i t followed

by d i s t i l l e d acetone and f i n a l l y was d r i e d by

 76

a s p i r a t i n g c lea n hot a i r through i t . Compressed a i r

was not used because f o r e i g n p a r t i c l e s or traces of

o i l might cause s e r i o u s errors. The v i s c o m e t e r was

fastned accurately v e r t i c a l in a g la s s sided

thermostat as shown in f i g u r e 2 . 2 . The mark ‘A ’ was

w e l l below the s u r f a c e of w a t e r . A p i e c e of rubber

tubing, cleaned i n t e r n a l l y to remove d u s t , was

att a c h e d to the tube 'A* and used when sucking the

l i q u i d i n t o the l e f t hand li m b. The tempera tur e of

the thermostat was c o n t r o l l e d w i t h i n 0.01 A

mechanical s t i r r e r was used to maintain a uniform

temperature of the t h e r m o s t a t , A s u it a b le quantity

of the l i q u i d under i n v e s t i g a t i o n , usually^S c .c.,

measured e x a c t l y , was i n t r o d u c e d i n t o the v is c o m e t e r

w it h a p i p e t t e and a l l o w e d 10-15 minutes to reach

the temperature o f the t he r m os t a t. The l i q u i d was

then sucked up and r e l e a s e d and the time of out f l o w

between the marks was determined wi th a st op watch

r ea d in g t o 0.01 second. The de t e rm i n at i o n was

rep e at e d a number of times ( u s u a l l y 5-6 t i m e s ) . The

different readings did not d e v i a t e from the mean by

more than 0.2 second. To determine the i n f l u e n c e o f

temperature on v i s c o s i t y , the time of out f l o w was

F'3- e - r

X- -

J
'v
j V
 77

measured a t the i n t e r v a l of 5 between 25 and

A small e r r o r may a r i s e i n th e se measurements

due to the change of volume of the l i q u i d owing to

expansion but t h i s may be n e g l e c t e d p r o v i d e d t h a t

during the out f l o w p e r i o d , the l o w e r meniscus l i e s

i n s i d e the bulb 'E* so t h a t the change of level is

small.

F or the purpose of calculatin g v is c o s it i'^ ^

densities of l i q u i d s a t v a r i o u s tempera tur es were

required. These were determined by means of a

pycnometer.

The vi sc om e te r was c a l i b r a t e d s e p e r a t e l y a t each

temperature with e x a c t l y same volume o f a l i q u i d of

known v i s c o s i t y and d e n s i t y , u su a lly water, the

v i s c o s i t y of which was taken as 0,8937 cp, a t 25 ^C,

From the d e n s i t i e s and times o f f l o w , absolute

viscosities of the s o l v e n t mixtures and e l e c t r o l y t e

s o l u t i o n s were c a l c u l a t e d w it h the h e l p of e qu ati on

( 2 .2 ).

2 .3 D e n s i t y Measurements ;

The d e n s i t y of a l i q u i d o r s o l u t i o n is defined
 78

as " the mass pe r u n i t volume and i s generally

—3
e x p r e ss e d as gem in C.G.S. u n i t s o r more a p p r o -

- p r i a t e l y as Kgm" in 3 .1 . units. Densities of

liq u id s are g e n e r a l l y measured e i t h e r by w e ig h i n g

a d e f i n i t e volume of the l i q u i d i n a d e n s i t y b o t t l e

o r pycnometer or by de te rm in in g buoyancy a c t i o n on

a ’ sinker' immersed in a l i q u i d ( P r i n c i p l e of

Archem ed es), Small changes of d e n s i t y a r e sometimes

determined by measuring the r a t e of r i s e of o r f a l l

of a small immersed q u a r t z f l o a t o r p r e - a r r a n g e d

overall density. Where s u f f i c i e n t l i q u i d i s

available, the d e n s i t y can be determined, approxi-

-mately, by means of hydrometers.

For present study pycnometer was used f o r the

d e n s i t y de te rm in ati on, hence a b r i e f s u r v e y of

various pycnometers i s given.

When only small q u a n t i t i e s of l i q u i d a re

available, or where g r e a t e r a c cu r ac y i s required, the

d e n s i t y of liq u id is b e s t determined by means of

vessels of a c c u r a t e l y d e f i n e d volume, called

pycnometers. These a r e made i n v e r y v a r y i n g sha pes .

The pycnometer in v e n t e d by Spe ng el and m o d i f i e d by

 79

Ostwald i s very p o p u l a r f o r a c c u r a t e d e n s i t y

measurement. Perking, B o n s f i e l d and many o t h e r

a l t e r e d forms of pycnometers. Most of the

pycnometers are o f s i n g l e c a p i l l a r y and u s u a l l y used

t o determine the d e n s i t y of l i q u i d a t f i x e d tem p e ra -

-ture.

A b i c a p i l l a r y pycnometer ( F i g . 2 . 3 ) having a

volume o f 10-12 c . c , was chosen f o r the p r e s e n t work.

T h i s a l l o w e d an a c c u r a c y of about 5 u n i t s in 5^^ p l a c e

of dec imals, which was q u i t e s u f f i c i e n t f o r our

pu rp os es. The pycnometer was washed t h r o u g h l y w i t h

hot chromic a c id t o remove o b s t r u c t i o n s in the

cap illary. This e n a b l e d a smooth f l o w o f liqu id

wi thou t drops s t i c k i n g be h in d . T h i s was f u r t h e r

f o l l o w e d by washing i t w i t h d i s t i l l e d w a t e r and

acetone and then d r i e d w i t h a stream o f warm a i r

from hot b lo we r. I t was f u r t h e r weighed a c c u r a t e l y

on VrV€*iljfyh^l3nce having a s e n s i t i v i t y o f 0.1 mg.

The pycnometer was f i l e d w i t h a i r f r e e t r i p l y

d i s t i l l e d water by d i p p i n g the end of ‘A* limb w i t h

the w a te r taken i n b e a k e r of 15-20 ml. volume.

Water f i l l e d upto mark i n limb *B* by c a p i l l a r y

action. The pycnometer was weighed a g a i n t o o b t a i n

 A

Fig 2. ?- B(cQ.pillary P y o o o m e t e r
 80

the mass of water taken i n pycnometer.

The pycnometer was mounted a c c u r a t e l y v e r t i c a l

in a g l a s s si de d t h e r m o s t a t . The temperature of

the thermostat was c o n t r o l l e d w i t h i n Oirt ° C . The

h eig h t o f water in limbs *A* and ' B ' sa y hj^ and h2

were noted at v a r i o u s t e m p e r a t u r e s . From the known

densities of water a t v a r i o u s tem pe rat ure s and the

weights of the w a te r taken in pycnometer, correspon-

- d i n g volumes of w a t e r were c a l c u l a t e d .

The volumes were p l o t t e d a g a i n s t t he t o t a l

he ig h t ( hj^ + h2 ) of w a t e r l e v e l s yielding a

straight lin e. T h i s s e r v e d as a c a l i b r a t i n g curve

f o r pycnometer,

Pycnometer was removed from the th e rm os ta t

and c le a n e d as ab ov e . I t was f i l l e d w i t h ex perime-

-n tal l i q u i d s and mounted in the t h e r m o s t a t . The

procedure was r ep e at e d t o f i n d the t o t a l h e ig h ts

(hj^ + h2 ) f o r e x p e r im e n ta l l i q u i d s at various

te m pe rat ure s. From t h e i r t o t a l h e i g h t s the

c or re sp on di n g volume of liquids under i n v e s t i g a t i o n

were ob t a in e d from the c a l i b r a t i o n curve and the

co r re sp on di n g d e n s i t i e s determined.
 81

2.4 U l t r a s o n i c V g l o c i t v Measurements ;

The pr o p a g a t io n of u l t r a s o n i c waves i n l i q u i d s
Q 12
and mixtures a re conducted by d i f f e r e n t method .

An u l t r a s o n i c i n t e r f e r o m e t e r i s a s im pl e and d i r e c t

devic e to determine the u l t r a s o n i c v e l o c i t y (U) in

l i q u i d s wi th a high de gr ee of a c cu r a c y .

The p r i n c i p l e used i n the measurement of ’U ’ is

based on the a c c u r a t e d e t e r m i n a t i o n o f the w avelen gth

i n a medium. U l t r a s o n i c waves of known f re q u e n c y ( f )

a re produced by a q u a r t z c r y s t a l f i x e d a t the bottom

o f the c e l l . These waves a r e r e f l e c t e d by a movable

m etallic p l a t e kept p a r a l l e l to the q u a r t z c r y s t a l .

If the s e p a r a t i o n between these two p l a t e s is exactly

a whole m u l t i p l e of the sound wave l e n g t h , s t a n d in g

waves a r e formed in the medium. T h is a c o u s t i c

resonance gives r i s e to an e l e c t r i c r e a c t i o n on the

g e n e r a t o r d r i v i n g q u a r t z c r y s t a l and the anode c u r r e n t

of the g e n e r a t o r becomes maximum.

If the di st a n c e i s now i n c r e a s e d o r dec rea se d and

the v a r i a t i o n i s e x a c t l y one h a l f wave le n g t h ( X 2 .)

o r m u l t i p l e of i t , anode c u r r e n t becomes maximum.

From the knowledge of wave l e n g t h , ^ , the v e l o c i t y ,

 82

U can be ob ta in e d by t he r e l a t i o n

V e l o c i t y = Wave l e n g t h x f re q u e n c y

U = / \ x f --------- ( 2 . 3 )

2 .5 P r e s e n t Work :

In pre se nt i n v e s t i g a t i o n M-81 u l t r a s o n i c

i n t e r f e r o m e t e r o p e r a t i n g a t f o u r f r e q u e n c i e s was
13—18
used , The a c c u r a c y in v e l o c i t y measurements was

+ 0,1% , The i n t e r f e r o m e t e r was s u p p l i e d by M i t t a l

enterprises, New D e l h i ,

This u ltra so n ic interferom eter ( f i g . 2,4)

consists of the f o l l o w i n g parts,

A) High freq ue nc y g e n e r a t o r ,

B) Measuring c e l l .

A) The High freq ue nc y G e n e r a t o r ;

T h is interferom eter ( f i g . 2,4) is d e si g n ed to

e x c i t e the quart z c r y s t a l f i x e d a t the bottom of the

measuring c e l l a t i t s r es on an t f re q u e n c y t o g e n e r a te

u l t r a s o n i c waves i n the ex perimental l i q u i d f i l l e d in

 83

the measuring c e l l . A microammeter to ob se rv e the

changes i n c u r r e n t and two c o n t r o l s f o r the purpose

of s e n s i t i v i t y r e g u l a t i o n and i n i t i a l adjus tme nt of

the microammeter a r e p r o v i d e d on the p a n e l of the

high fre qu en cy g e n e r a t o r .

B) The Measuring C e l l ;

The measuring c e l l (F ig. 2.4) *B* is a sp ecially

designed double w a l l e d c e l l f o r m a i n t a i n i n g the

temperature of the l i q u i d c on st an t d u r in g the e x p e r i -

-ment. A f i n e micrometer screw has been p r o v i d e d a t

the top which can r a i s e o r lo w e r the r e f l e c t o r p l a t e

in the l i q u i d in the c e l l through a known d i s t a n c e .

It has q u a r t z c r y s t a l f i x e d a t i t s bottom. The

maximum c a p a c i t y o f the c e l l is 12 cc.

C) Adjustment of U l t r a s o n i c I n t e r f e r o m e t e r :

The instrument was a d j u s t e d i n the f o l l o w i n g

manner,

1) The c e l l was i n s e r t e d i n the squa re base soc ke t

and clamped to i t w it h the help o f a screw p r o v i d e d

 84

on one of its sides.

2) The knurled cap of the c e l l was unscrewed and

l i f t e d away from the do ub le w a l l e d c e l l . Exp erime-

- n t a l l i q u i d was poured i n the middle p o r t i o n of the

c e l l and the knu rled cap was screwed,

3) Water a t d e s i r e d temperature from a t her mo st at

was c i r c u l a t e d through two chutes i n d o ub le w a l l of

the c e l l .

4) The high fre qu en cy g e n e r a t o r was connected t o the

c e l l by a c o - a x i a l c a b l e .

The i n t e r f e r o m e t e r was i n i t i a l l y a d j u s t e d w i th

the help of two knobs p r o v i d e d on the hig h f re q u e n c y

generator, one marked w i t h Adj and o t h e r w it h G ain,

wi th knob marked A d j . t he p o s i t i o n of n e e d le on the

ammeter was a d j u s t e d and knob marked g a i n was used

t o , i n c r e a s e the s e n s i t i v i t y of the instrument f o r

greater deflection i f desired. The meter was used to

n o t ic e the number o f maximum d e f l e c t i o n s w h i l e m i c r o -

- m e t e r screw was moved up and down, A number of

maximum r e a d in g ^ o f anode c u r r e n t were taken and t h e i r

number ( n ) was counted. The t o t a l distance (d ) moved

by the micrometer screw thus gave the v a l u e of

wa velen gth ( /\ ) w i t h the help of f o l l o w i n g e q u a t i o n

 85

d = n --------- ( 2 . 4 )
2.

Once the wavelength ( ^ ) was known the v e l o c i t y

•U* in the l i q u i d was c a l c u l a t e d w i t h the h e l p of

equation ( 2 . 3 ) .

2 ,6 P r e c a u t io n s Taken ;

1) The g e n e r a t o r was always sw itc h e d on a f t e r

fillin g experimental l i q u i d in the c e l l .

2) A f t e r the expe rime nt, e xpe rim en tal l i q u i d was

taken out and c e l l was kept c l e a n and d r i e d .

3) The micrometer was kept open a t 25 mm a f t e r use.

4) Sudden r i s e or f a l l i n temperature of c i r c u l a t e d

l i q u i d was avoided to p r e v e n t thermal shock to the

quartz c r y s t a l .

5) While c l e a n i n g the c e l l , c a re was taken not to

s p o i l o r sc r at c h the god p l a t i n g on the q u a r t z c r y s t a l .

6) U s u a l l y 15 seconds time was giv e n f o r warming the

generator.
 86

REFERENCES

1. B i r d R B, S t e w a r t W E & L i g h t f o o t E N

” T r a n s p o r t phenomena " , John W i l e y & Son,

In c, New York, i960.

2. S c h i l l e r L & Stromung in Rohren, i n Handbuch

der expe rim en tal ph ys ik " vol, 4 p t . 4 pp 39-57

Akademic V e r l a g Gmb H, B e r l i n 1932.

3. Erk S , Zahigkeitsmessungen in Handbuch der

experimental physik " , vol. 4 pt. 4, pp 465-468

Akademic V e r l a g GmbH, B e r l i n 1932.

4. S w i n d e l l s J F, Coe J R ( J r ) S. G o d f r e y T B,

J Res N a t l Bur S td US, 48 (1952) 1 .

5. S w i n d e l l s J F, Ullraan R & Mark H, in A VVeissberger

(e d, " Technique of o r g a n i c ch em is t ry " Vo, 1

rd
" p h y s i c a l methods of o r g a n i c c h em is try " 3 ed

p t . 1 c hap ter 12, Interscience publishers, In c ,

New York 1959.

6. Dorsey N E, Phy Rev, 28 (1926) 833.

7. Bacon L R, J Franklin In st, 221 (1936) 251.

8. Kaminsky, Z physic chem ( N . F . ) , 5 (1955) 154.

 87

9, Mikhaylov I. G , R a s p o r o s t r a n i y e U1 *trazvkovykh

Voln V Zh id ko st ry akh (The p r o p a g a t i o n of

u l t r a s o n i c waves i n l i q u i d s ) G o s t e k h i z d a t 1949.

10. Kudryavtsev B B, Primeneniye U l ’ t r a a k u s t i c h e s i s -

-sledovaniy ( A p p l i c a t i o n s of u l t r a s o n i c methods

to Phy sic o -C h e m ic a l s t u d i e s ) , Gostekhizdate,

1952,

11, Bergmann L, U l * t r a z v u k (u ltrasonics) 1956.

12. P a r t h a s a r a t h y S, P r o c , I n d i a n Acad S c i ,

(1935) 497,

13, Nikam P S 8. Mehdi Hasan, I n d i a n J of Pure and

A pplied Physics, 24 (1986) 502,

14. Nikam P S & Mehdi Hasan, J Chem Eng Data,

33 (1988) 165.

15. Nikam P S & H i r a y A R, I n d i a n J P ure A p p l Phys,

29 (1991) 601,

16, Nikam P S & H i r a y A R, O r i e n t a l J Chem,

8 (1992) 237,

17, Nikam P 3 & Mehdi Hasan, A s i J Chem,

5 (1993) 319.

\^- ? s 2_
/ ^
sVi "ft ^ 3 (o