SOME PECULIARITIES OF THE POLYTHERMS OF THE SURFACE

TENSION OF WATER AND AQUEOUS SOLUTIONS

A. N. Kirgintsev and L. N. Efanov UDC 532.6 +546.212 +54- 145.3

In [1] it was shown that the p o l y t h e r m of the d e r i v a t i v e of the l o g a r i t h m of the v i s c o s i t y with r e s p e c t

to the r e c i p r o c a l of the t e m p e r a t u r e (activation energy) of the v i s c o s i t y of w a t e r contains p e r i o d i c b r e a k s
at a t e m p e r a t u r e i n t e r v a l of ~6 ~ We m a y a s s u m e that analogous p h e n o m e n a w i l l a l s o be o b s e r v e d on the
p o l y t h e r m s of o t h e r p r o p e r t i e s . To c l a r i f y this question, we p e r f o r m e d p r e c i s e m e a s u r e m e n t s of the s u r -
face t e n s i o n of w a t e r and of an aqueous solution of NaC1 with a c o n c e n t r a t i o n of 0.77 M.

EXPERIMENTAL

Of all the m e t h o d s of m e a s u r i n g the s u r f a c e t e n s i o n , the m o s t a c c u r a t e is now c o n s i d e r e d to be the

method of the g r e a t e s t p r e s s u r e of g a s bubbles; however, the m o s t s e n s i t i v e is the c a p i l l a r y meth~d. The
a c c u r a c y of the l a t t e r is l i m i t e d by the quality of the c a p i l l a r i e s used, s i n c e it n e c e s s i t a t e s c a p i l l a r i e s with
a c o n s t a n t d i a m e t e r along the length, the p r e p a r a t i o n of which is a c o m p l e x t e c h n i c a l p r o b l e m . U r a z o v s k i i
and Chetaev [2] have p r o p o s e d a v a r i a t i o n of the c a p i l l a r y method, in which c a p i l l a r i e s with constant d i a m -
e t e r a r e not r e q u i r e d . The e s s e n c e of t h e i r p r o p o s a l c o n s i s t s of a c o m p e n s a t i o n for changes in the l e v e l of
tiquid in the c a p i l l a r y by changing the depth of i m m e r s i o n of the c a p i l l a r y . Since the e q u i l i b r i u m p o s i t i o n
of the m e n i s c u s at a given t e m p e r a t u r e is d e t e r m i n e d by the d i f f e r e n c e of the l e v e l s of liquid in the c a p i l -
l a r y and v e s s e l with liquid, it is always p o s s i b l e to move the v e s s e l in such a way that the m e n i s c u s r e -
m a i n s at the s a m e l e v e l in the c a p i l l a r y , s t r i c t l y fixed in the v i s u a l field of the m i c r o s c o p e . This method
does not p e r m i t a d e t e r m i n a t i o n of the a b s o l u t e v a l u e s of the s u r f a c e t e n s i o n with high a c c u r a c y ; however,
its change with the t e m p e r a t u r e can be d e t e r m i n e d r a t h e r a c c u r a t e l y .

A s c h e m e of the a p p a r a t u s is shown in F i g . 1. In the w o r k we used c a p i l l a r i e s with a d i a m e t e r of

0.1-0.3 ram, which e n s u r e d a height of r i s e of the liquid of 100-150 ram. A KM-6 c a t h e t o m e t e r was used
to o b s e r v e the p o s i t i o n of the m e n i s c u s , and it p e r m i t t e d a r e c o r d i n g to the p o s i t i o n of the m e n i s c u s with
an a c c u r a c y of ~=0.003 ram. In w o r k on this i n s t r u m e n t , e r r o r s might a r i s e on account of i n a c c u r a t e e s t a b -
l i s h m e n t of the m e n i s c u s and on account of i n a c c u r a c i e s in the moving s y s t e m . To t e s t the e s t a b l i s h m e n t
of the m e n i s c u s , b e f o r e each e x p e r i m e n t at c o n s t a n t t e m p e r a t u r e the m e n i s c u s was brought up to the z e r o
m a r k a l a r g e n u m b e r of t i m e s (always f r o m the top down). To t e s t the a c c u r a c y of the moving s y s t e m , the
c a p i l l a r y 3 with t h e r m o s t a t i c sheathing 2 was fixed d i r e c t l y on the t e s t tube with the liquid. The c a t h e t o -
m e t e r was b r o u g h t up to the m e n i s c u s of the liquid in the c a p i l l a r y . Then the e n t i r e moving s y s t e m was
e s t a b l i s h e d at v a r i o u s heights with the aid of a m i c r o m e t r i c s c r e w ; t h e s e heights w e r e fixed a c c o r d i n g to
the r e a d i n g s of the m i c r o m e t r i c s c r e w and c a t h e t o m e t e r . The r e s u l t s a r e p r e s e n t e d in F i g . 2. In all the
e x p e r i m e n t s the e r r o r did not e x c e e d the i n d i c a t e d v a l u e s of the e r r o r , =~0.003 ram.

A U-8 t h e r m o s t a t , in which the p r o p e l l e r m i x t u r e was r e p l a c e d by a t u r b i n e , w a s used for t e m p e r a -

t u r e c o n t r o l . A 2 0 - l i t e r v e s s e l , equipped with a m i x e r , w a s p l a c e d between the t h e r m o s t a t and the i n s t r u -
ment. This m a d e it p o s s i b l e to obtain s t a b i l i t y of the t e m p e r a t u r e during the m e a s u r e m e n t s (15-30 rain) of
no l o w e r than 0.01 ~ A t h e r m i s t o r , the r e s i s t a n c e of which w a s m e a s u r e d with a M T B - t y p e r e s i s t a n c e
b r i d g e , was used to m e a s u r e the t e m p e r a t u r e . Since the s i n g u l a r i t i e s on the p o l y t h e r m of the p r o p e r t y in
p r i n c i p l e might be c a u s e d by s i n g u l a r i t i e s on the c h a r a c t e r i s t i c of the m e a s u r i n g i n s t r u m e n t , a s p e c i a l ex-
p e r i m e n t w a s conducted p r e l i m i n a r i l y to check on the R v e r s u s T c h a r a c t e r i s t i c of the t h e r m i s t o r . The
e l e c t r i c a l c i r c u i t of the e x p e r i m e n t is p r e s e n t e d in F i g . 3. The t h e r m i s t o r (RT) , around which an insulating
n i c h r o m e w i r e was wound, w a s p l a c e d in a g l a s s tube, c l o s e d on both ends with r u b b e r s t o p p e r s , which was
i m m e r s e d in an i c e - w a t e r m i x t u r e . The r e s i s t a n c e of the t h e r m i s t o r (R0oC = 8700~) was m e a s u r e d with a
b r i d g e of the MTB type with an e r r o r of • 0.05 ~ . A c u r r e n t , the s t r e n g t h of which I w a s m e a s u r e d with a
Institute of Inorganic Chemistry, Siberian Department of the Academy of Sciences of the USSR.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 571-577, March, 1967.
Original article submitted September 15, 1964.

551
 P-300 p o t e n t i o m e t e r (R2 - s t a n d a r d r e s i s t a n c e coil) with an e r r o r of • 0.001
mA, w a s p a s s e d through the n i c h r o m e w i r e . The value of the c u r r e n t was
: { e s t a b l i s h e d with the aid of a b a t t e r y of r e s i s t o r s (R1). A f t e r s o m e t i m e had
e l a p s e d , the t h e r m a l s y s t e m of the t h e r m i s t o r b e c a m e s t a t i o n a r y . The
f-
equation of the t h e r m a l b a l a n c e in this c a s e w i l l be the following in a f i r s t
/2 a p p r o x i m a t i o n (without c o n s i d e r i n g the c u r r e n t through the t h e r m i s t o r )

j3 I2Rn -~- k F A t (1)

w h e r e R n is the r e s i s t a n c e of the n i c h r o m e w i r e ; F is the s u r f a c e of heat
t r a n s f e r between the t h e r m i s t o r and the i c e - w a t e r mixture; At is the t e m -
p e r a t u r e d i f f e r e n c e of the t h e r m i s t o r and the i c e - w a t e r m i x t u r e .
The r e s i s t a n c e of the t h e r m i s t o r is r e l a t e d to its t e m p e r a t u r e by the
equation [3]
log R = A~ + Bz t / T (2)
Fig. 1. Scheme of ap-
paratus for determining Combining (1) and (2) and t r a n s f o r m i n g , we obtain
the d e p e n d e n c e of the
s u r f a c e t e n s i o n upon Y ~__-A I % R ~ a I / T 2 (3)
the t e m p e r a t u r e : 1) hi 2
stand; 2) sheathing of
w h e r e A l o g R and /xI2 a r e the change in log R and that in 12, r e s p e c t i v e l y ,
c a p i l l a r y ; 3) c a p i l l a r y ;
when the t e m p e r a t u r e of the t h e r m i s t o r is changed by AT. F i g u r e 4 p r e -
4) t e s t tube with i n v e s t i -
s e n t s the dependence of Y upon the t e m p e r a t u r e (AT =1~ F r o m this it is
gated liquid; 5) sheathing
evident that, at l e a s t within the l i m i t s of 20 ~, the c h a r a c t e r i s t i c of the t h e r m -
of t e s t tube; 6) u p p e r
i s t o r to m e a s u r e the t e m p e r a t u r e cannot be the c a u s e of the s i n g u l a r i t i e s on
base; 7) m i c r o m e t r i c
the i s o t h e r m s of the p r o p e r t i e s .
screw.
T h e r e is no need to u s e the a b s o l u t e v a l u e s of the t e m p e r a t u r e to de-
t e c t s i n g u l a r i t i e s on the p o l y t h e r m s of the p r o p e r t i e s . The value of any
monotonic and continuous function of the t e m p e r a t u r e , for e x a m p l e , the l o g a r i t h m of the t h e r m i s t o r r e s i s t -
ance [see Eq. (2)], can be u s e d f o r this p u r p o s e . To o p e r a t e with m o r e usual q u a n t i t i e s , we c a l i b r a t e d the
t h e r m i s t o r , i.e., d e t e r m i n e d the value of the c o n s t a n t s A and B in its Eq. (2). F o r this p u r p o s e , during the
e n t i r e e x p e r i m e n t s i m u l t a n e o u s d e t e r m i n a t i o n s w e r e m a d e of the t h e r m i s t o r r e s i s t a n c e and the t e m p e r a -
t u r e a c c o r d i n g to a t h e r m o m e t e r with a s c a l e m a r k e d off in d i v i s i o n s of 0.1 ~ Then A and B w e r e d e t e r -
m i n e d a c c o r d i n g to a l l the v a l u e s of l o g R and t by the method of l e a s t s q u a r e s ; they w e r e used to c a l c u l a t e
the t e m p e r a t u r e . Thus, we obtain a value of the t e m p e r a t u r e with a b s o l u t e a c c u r a c y of at l e a s t 0.1 ~ but
the change in the t e m p e r a t u r e is d e t e r m i n e d with f a r g r e a t e r a c c u r a c y , c o r r e s p o n d i n g to the a c c u r a c y of
the m e a s u r e m e n t of the r e s i s t a n c e , or, m o s t often, to the s t a b i l i t y of the t e m p e r a t u r e in the t h e r m o s t a t .

In our w o r k we did find the a b s o l u t e v a l u e s of the s u r f a c e tension, always o p e r a t i n g with the r e a d i n g s

of the m i c r o m e t r i c s c r e w h. This value is r e l a t e d to the s u r f a c e t e n s i o n ~ by the s i m p l e function
h - ~ - - A -{- 2 a / r g p (4)

w h e r e A is a constant; r is the r a d i u s of the c a p i l l a r y ; g is the a c c e l e r a t i o n of the f o r c e of g r a v i t y ; p is the

d e n s i t y of the liquid. Since a change in the t e m p e r a t u r e c a u s e s a g r e a t e r change in the s u r f a c e tens ion than
in the d e n s i t y (at 20 ~ a change in the t e m p e r a t u r e of 1 ~ c a u s e s a change in the d e n s i t y of w a t e r of 0.02% and
in the s u r f a c e t e n s i o n of 0.2%), the change in the value of h is p r o p o r t i o n a l with a good a p p r o x i m a t i o n to the
change in the s u r f a c e tension.
F o r the s a k e of b r e v i t y , we s h a l l h e n c e f o r t h c a l l the dependence of h upon t the p o l y t h e r m of the s u r -
face t e n s i o n . F o r the d e t e c t i o n of s i n g u l a r i t i e s on the p o l y t h e r m s , we used the method of d i f f e r e n t i a l d e -
r i v a t i v e s , which, in our opinion, is m o r e o b j e c t i v e . The d i f f e r e n t i a l d e r i v a t i v e of the s u r f a c e t e n s i o n f was
d e t e r m i n e d a c c o r d i n g to the f o r m u l a
5h
At (5)

w h e r e At and Ah a r e the d i f f e r e n c e s of the v a l u e s of the t e m p e r a t u r e s and heights of the r i s e of the liquid

in the c a p i l l a r y . The e r r o r f was d e t e r m i n e d a c c o r d i n g to the f o r m u l a

552
 ::r8 ~ R, PJoo ]
~h-fO#
~i~ -:y.+,,-- .~.r,+~.~.,,~7_.T.~..-=..-"~."~..~ r . +'+''-
! I I P I I I I I I I
t# z,# 3.# 4# 4oh GI G2
Fig. 2 Fig. 3

F i g . 2. V e r i f i c a t i o n of a c c u r a c y of moving s y s t e m of a p p a r a t u s for m e a s u r e m e n t
of s u r f a c e tension: h) r e a d i n g s of m i c r o m e t r i c s c r e w ; Ah) d i f f e r e n c e of c a t h e t o m -
e t e r r e a d i n g s c o r r e s p o n d i n g to a 0 . l - r a m change in the height of the m e n i s c u s a c -
c o r d i n g to the m i c r o m e t r i c s c r e w . The d a s h e d lines show the l i m i t of the e r r o r of
the m e a s u r e m e n t , m a d e up of the e r r o r in the a c c u r a c y of a d j u s t m e n t of the m e n i s -
cus (• 0.003 ram) and the e r r o r of the c a t h e t o m e t e r r e a d i n g (• 0.003 mm).
F i g . 3. E l e c t r i c a l c i r c u i t of e x p e r i m e n t for v e r i f y i n g continuity of the t e m p e r a t u r e
c h a r a c t e r i s t i c of the t h e r m i s t o r .

-F
o,~ l- ~- I , I ' ?

y.M 8

1. I :1
20r
r
g:e~_ I
z,6 47 3~#log R g~ Jo 3 g oG

Fig. 4 Fig. 5

F i g . 4. Dependence of the d e r i v a t i v e of the s q u a r e of the c u r r e n t

s t r e n g t h with r e s p e c t to the l o g a r i t h m of the r e s i s t a n c e upon the t e m -
perature.
F i g . 5. Dependence of the d e r i v a t i v e of the s u r f a c e t e n s i o n of f r e s h l y
d i s t i l l e d w a t e r on the t e m p e r a t u r e . In F i g s . 5-8, the v e r t i c a l d a s h e d
lines c o r r e s p o n d to the t e m p e r a t u r e of the m i n i m a of f r e s h l y r e d i s -
t i l l e d w a t e r . The h o r i z o n t a l l i n e s c l o s e to the X - a x i s denote the t e m -
p e r a t u r e of t r a n s i t i o n f r o m i s t e p to a n o t h e r in the e x p e r i m e n t of
Q u r a s h i and A h s a n u l l a h .

-+- S t \
(6)
w h e r e ~h is the e r r o r in the m e a s u r e m e n t of the height of the m e n i s c u s , • 0.003 ram; 6t is the e r r o r in the
t e m p e r a t u r e m e a s u r e m e n t , • 0.01 ~ In F i g s . 5-8, the v e r t i c a l l i n e s c o r r e s p o n d to the e r r o r of the m e a s u r e -
m e n t s , c a l c u l a t e d a c c o r d i n g to Eq. (6).

During the e x p e r i m e n t , the t e m p e r a t u r e was always v a r i e d f r o m higher to l o w e r , to avoid wetting

h y s t e r e s i s . The m e a s u r e m e n t s w e r e p e r f o r m e d , as a r u l e , at i n t e r v a l s of 0.6 +1.0% A f t e r a change in the
t e m p e r a t u r e of the t h e r m o s t a t , we w a i t e d a d e f i n i t e t i m e , so that the c a p i l l a r y and liquid in the t e s t tube
would a s s u m e the e s t a b l i s h e d t e m p e r a t u r e . A f t e r this, the v a l u e of h was r e c o r d e d (the r e a d i n g of the
m i e r o m e t r i c s c r e w ) . A f t e r 5 and 10 min, the m e a s u r e m e n t s w e r e r e p e a t e d . If the t e m p e r a t u r e and p o s i -
tion of the m e n i s c u s w e r e unchanged during this t i m e , then the m e a s u r e m e n t at a given t e m p e r a t u r e was
c o n s i d e r e d c o m p l e t e d . If the t e m p e r a t u r e changed m o r e than the e s t a b l i s h e d l i m i t or the p o s i t i o n of the
m e n i s c u s changed, the m e a s u r e m e n t s w e r e r e p e a t e d until coinciding r e s u l t s w e r e obtained. The total d u r a -
tion of the e x p e r i m e n t on the r e c o r d i n g of one p o l y t h e r m w a s 12-16 h.

553
 -f
-F r j I f -ujuj- ~ .
'II3 ~ - J- i f z : z: J
0,06~-
- 1 I z o)g- : z
o,o6~: i

o,io~ ~ I _ ~ f O,fJ~ I T I • I r : : il T I: I I ,

26 gO J# ~ 26 3# ~

Fig. 6 Fig. 7
F i g . 6. Dependence of the d e r i v a t i v e of the s u r f a c e t e n s i o n of "old" w a t e r upon the
t e m p e r a t u r e : 1,2) s t o r a g e for a week; 3) s t o r a g e for 3 d a y s .
F i g . 7. Dependence of the d e r i v a t i v e of the s u r f a c e t e n s i o n on the t e m p e r a t u r e of
" m e l t e d " w a t e r (1, 2) and 0.7 M solution of NaC1 (3), p r e p a r e d in " m e l t e d " w a t e r .

In the c o u r s e of the m e a s u r e m e n t s it was found that the n a t u r e of the p o l y t h e r m depends to a sub-

s t a n t i a l d e g r e e upon the p r e h i s t o r y of the p r e p a r a t i o n ; t h e r e f o r e s a m p l e s with d i f f e r e n t p r e h i s t o r i e s w e r e
used in the e x p e r i m e n t s . F i g u r e 5 p r e s e n t s the dependence of the d i f f e r e n t i a l d e r i v a t i v e of the s u r f a c e
t e n s i o n upon the t e m p e r a t u r e for t h r e e s a m p l e s of f r e s h l y r e d i s t i l l e d w a t e r . The s a m p l e s w e r e c o l l e c t e d
d i r e c t l y f r o m the d i s t i l l e r and p l a c e d i m m e d i a t e l y in the i n s t r u m e n t for m e a s u r e m e n t of the s u r f a c e ten-
sion. The t o t a l t i m e f r o m s a m p l e c o l l e c t i o n to the beginning of the m e a s u r e m e n t s was 70-75 rain. At the
s a m e t i m e , the pH v a l u e s w e r e d e t e r m i n e d on the L P - 5 tube p o t e n t i o m e t e r (at e q u i l i b r i u m with aiI') with
an a c c u r a c y of 9 0.05 pH unit, and the e l e c t r i c conductivity was a l s o d e t e r m i n e d with an a c c u r a c y of •
In all t h r e e e x p e r i m e n t s , the pH value w a s 5.6, the s p e c i f i c e l e c t r i c conductivity 3 910 -~ ~ - t . F r o m F i g . 5
it is evident that the d e r i v a t i v e of the s u r f a c e t e n s i o n of w a t e r with r e s p e c t to the t e m p e r a t u r e is not con-
s t a n t , but r e p r e s e n t s a s i n u s o i d a l c u r v e with an i n t e r v a l between m i n i m a of ~3 ~ The t e m p e r a t u r e s of the
m i n i m a in d i f f e r e n t e x p e r i m e n t s , conducted with d i f f e r e n t c a p i l l a r i e s , coincide with the l i m i t s of the ex-
p e r i m e n t a l e r r o r ; h o w e v e r , the t e m p e r a t u r e s of the m a x i m a , as well as the a m p l i t u d e s of the s i n e c u r v e s in
d i f f e r e n t e x p e r i m e n t s , d i f f e r , i.e., only the t e m p e r a t u r e s of the m i n i m a a r e p r o d u c e d . The s a m e r e s u l t s
w e r e a l s o obtained in o t h e r e x p e r i m e n t s with f r e s h l y r e d i s t i l l e d w a t e r .

When the w a t e r is s t o r e d , the p i c t u r e b e c o m e s l e s s d e f i n i t e - t h e a m p l i t u d e of the " s i n e c u r v e s " de-

c r e a s e s , and the i n t e r v a l s between m i n i m a b e c o m e i r r e g u l a r (Fig. 6). F i g u r e 6 p r e s e n t s t y p i c a l r e s u l t s
of e x p e r i m e n t s with s a m p l e s of w a t e r s t o r e d for a w e e k a f t e r d i s t i l l a t i o n (curves 1, 2) and for t h r e e days
a f t e r d i s t i l l a t i o n (curve 3) in a c o v e r e d f l a s k of J e n a g l a s s . No change in the pH and e l e c t r i c conductivity
w a s d e t e c t e d in this c a s e . On c u r v e s 1 and 2, m i n i m a can be noted with an i n t e r v a l of 6 ~ at t e m p e r a t u r e s
coinciding with the t e m p e r a t u r e s of t r a n s i t i o n between the s t e p s in the e x p e r i m e n t s of Q u r a s h i and Ahsanul-
lah. However, the a m p l i t u d e of the " s i n e c u r v e s " only v e r y s l i g h t l y e x c e e d s the e r r o r of the m e a s u r e m e n t s ;
t h e r e f o r e , it is i m p o s s i b l e to s p e a k m o r e or l e s s d e f i n i t e l y of p e r i o d i c s i n g u l a r i t i e s in this c a s e .

A d i f f e r e n t p i c t u r e is p r e s e n t e d by s a m p l e s of " m e l t e d " w a t e r . W a t e r taken f r o m the d i s t i l l e r w a s

f r o z e n in a r e f r i g e r a t o r in a c o v e r e d b e a k e r for weighing. The t i m e f r o m c o l l e c t i o n of the s a m p l e until its
c o m p l e t e s o l i d i f i c a t i o n w a s an a v e r a g e of 2 h. A f t e r 10-12 h, the weighing b o t t l e with ice w a s r e m o v e d
f r o m the r e f r i g e r a t o r and p l a c e d on an e l e c t r i c hot p l a t e , w h e r e the ice m e l t e d c o m p l e t e l y in a p e r i o d of
~10 rain, the w a t e r w a s w a r m e d up to r o o m t e m p e r a t u r e and p l a c e d in the i n s t r u m e n t for m e a s u r e m e n t of
the s u r f a c e tension. The m e a s u r e m e n t s of the pH and e l e c t r i c conductivity of m e l t e d w a t e r r e v e a l e d no
d i f f e r e n c e between it and f r e s h l y r e d i s t i l l e d w a t e r . The e x p e r i m e n t a l r e s u l t s a r e p r e s e n t e d in Fig. 7 (1, 2).
In t h i s c a s e , the p o l y t h e r m r e p r e s e n t s a s t r a i g h t line, a l m o s t p a r a l l e l to the X - a x i s .
E n t i r e l y analogous r e s u l t s w e r e obtained when the s u r f a c e t e n s i o n of a 0.77 M solution of NaC1 was
m e a s u r e d . The solutions w e r e p r e p a r e d in the following way. To w a t e r taken d i r e c t l y f r o m the d i s t i l l e r we
added a w e i g h e d amount of the s a l t , and the solution was p l a c e d in a t h e r m o s t a t with a t e m p e r a t u r e of 60 ~
A f t e r 1 h the s o l u t i o n was r e m o v e d f r o m the t h e r m o s t a t , and p a r t of it was p l a c e d in an i n s t r u m e n t for de-
t e r m i n a t i o n of the s u r f a c e tension. The t o t a l t i m e f r o m c o l l e c t i o n of the s a m p l e f r o m the d i s t i l l e r until the
beginning of the e x p e r i m e n t s was 140-150 rain. The r e s u l t s of the e x p e r i m e n t a r e p r e s e n t e d in Fig. 8 (curve
1). Another p o r t i o n of the s a m e solution was left f o r a week at r o o m t e m p e r a t u r e in a c o v e r e d J e n a g l a s s
f l a s k . The r e s u l t s of the m e a s u r e m e n t s of the s u r f a c e t e n s i o n of this p o r t i o n of the solution a r e p r e s e n t e d
in F i g . 8 (curve 2). The a m p l i t u d e of the ~sine c u r v e s " in this c a s e is 1.5 t i m e s s m a l l e r than in the f r e s h l y
p r e p a r e d solution.

554
 The following experiments w e r e conducted with
solutions p r e p a r e d in m e l t e d w a t e r . Aweighed amount
was f r o z e n in a r e f r i g e r a t o r . Then a weighed amount
of salt was poured into the flask with ice, and the
flask was placed for 1 h in a t h e r m o s t a t with a tem-
O..gSb- ~ - f I~ t
' L._~l I I I I 1.~ p e r a t u r e of 60 ~ after which the p o l y t h e r m of the s u r -
ZO 2,5" 30 "8 face tension of the solution was r e c o r d e d . T~qoical
Fig. 8. Dependence of the derivative of the s u r - r e s u l t s a r e presented in Fig. 7 (3). Just as for melted
face tension of a 0.77 M solution of NaC1 on the w a t e r , the polytherm r e p r e s e n t s a straight line.
t e m p e r a t u r e : 1) f r e s h l y p r e p a r e d solution; 2)
DISCUSSION OF RESULTS
solution s t o r e d for 1 week after preparation.
1. On the polytherm of the s u r f a c e tension of
f r e s h l y redistilled w a t e r and solutions p r e p a r e d in it,
t h e r e are periodic singularities. The period of the singularities on the polytherms of f r e s h l y distilled wa-
ter is 3 ~ In the Handbook l i t e r a t u r e [4], the dependence of the s u r f a c e tension upon the t e m p e r a t u r e is
cited with an e r r o r of the s u r f a c e tension of =L0.05 d y n / c m , and with an e r r o r of the t e m p e r a t u r e of • 0.1 ~
In the e a s e of differential differentiation, at intervals of AT =1 ~ the e r r o r Jr, determined according to
f o r m u l a (6), is • 87% in the c a s e of such e r r o r s of the initial quantities. In Fig. 5 the g r e a t e s t amplitude
of the "sine c u r v e s " is observed on c u r v e 2, w h e r e the m a x i m u m value of the derivative of the a r i t h m e t i c
mean is 67%. This quantity is s m a l l e r than the e r r o r calculated according to the Table data. Consequently,
our data do not contradict the l i t e r a t u r e data. T h e r e is at p r e s e n t too little experimental m a t e r i a l to be
able to speak with a s s u r a n c e of the theory of this phenomenon. We might a s s u m e that the periodic singu-
larities m a y be due to a change in the quality of the aggregates in the liquid [5].
2. F r o m the results of our experiments it follows that the polytherm of the s u r f a c e tension of freshly
redistilled w a t e r differs significantly f r o m the p o l y t h e r m of the s u r f a c e tension of melted water. The de-
pendence of the p r o p e r t i e s of w a t e r upon the method of its products was noted long ago by biologists ac-
cording to the effects of water on various biological specimens [6-8]; however, insofar as we know, no dif-
f e r e n c e in the p h y s i c o c h e m i c a l p r o p e r t i e s of f r e s h l y distilled and melted w a t e r had yet been detected. In
our opinion, these phenomena a r e associated with a r e a r r a n g e m e n t of the s t r u c t u r e of water, which m a y
consist of transition f r o m the state of aggregation c h a r a c t e r i s t i c of f r e s h l y distilled w a t e r to a s t r u c t u r e
of the type of ice, c h a r a c t e r i s t i c of melted w a t e r .
3. The reproducibility of the periodic singularities on the p o l y t h e r m s of the s u r f a c e tension of f r e s h -
ly distilled w a t e r and of solutions p r e p a r e d in it is c o m p a r a t i v e l y low. In various experiments, the t e m p e r -
atures of the minima are reproducible, but the t e m p e r a t u r e s of the m a x i m a and amplitude of the sine c u r v e s
are not reproducible. The causes of the poor reproducibility of the polytherms, in our opinion, lie in the
dependence of the nature of the p o l y t h e r m s upon the p r e h i s t o r y of the sample and averaging of the d e r i v a -
tive. Actually, our investigations show that the type of p o l y t h e r m of the derivative depends substantially
upon the p r e h i s t o r y of the sample. The possibility remains that in addition to the p a r a m e t e r s of the p r e -
h i s t o r y monitored (method of production of sample, time of its storage, etc.), the sample might also be
substantially influenced by factors that a r e not considered in the usual physieoehemieal experiment, since
their influence, as a rule, is exceptionally s m a l l . However, in certain c a s e s these f a c t o r s may significantly
change the c o u r s e of the p r o c e s s . Thus, for example, s o l a r activity, which is not usually c o n s i d e r e d in a
physicoehemical experiment, has a substantial influence upon the coagulation of sols [9]. All these con-
s i d e r e d f a c t o r s lead to the fact that the samples in one s e r i e s of experiments may differ f r o m one another.
The latter c i r c u m s t a n c e is responsible for the poor reproducibility of the periodic curve. Averaging of the
derivative also might be a cause of low reproducibility, since in certain c a s e s , when the derivative changes
sharply, the value of the differential derivative m a y differ f r o m the true value of the derivative at a given
point.

The phenomena that we observed substantially exceed the experimental e r r o r , which was d i s c u s s e d
above. Our experiments once again d e m o n s t r a t e this a c c u r a c y of the m e a s u r e m e n t s . Actually, the experi-
ments with f r e s h l y redistilled w a t e r (see Fig. 5) and the experiments with melted water (see Fig. 7) were
conducted under quite identical conditions; m o r e o v e r , the experiment with melted water was followed by an
experiment with melted w a t e r . The results of the experiments with f r e s h l y distilled and melted water, how-
ever, differ substantially. This p e r m i t s a quite definite a s s e r t i o n that the periodic singularities that we
observed are p r o p e r t i e s of the liquid itself, and a r e not caused by any instrumental e r r o r s .

555
 CONCLUSIONS
1. The p o l y t h e r m s of the s u r f a c e tension of w a t e r and of an aqueous solution of NaC1 w e r e studied.
On the p o l y t h e r m s of the s u r f a c e tension of f r e s h l y r e d i s t i l l e d w a t e r and a solution of NaCI p r e p a r e d with
it, t h e r e a r e periodic s i n g u l a r i t i e s with a period of 3 ~
2. The type of p o l y t h e r m of the s u r f a c e tension of w a t e r and of an aqueous s o l u t i o n of NaC1 depends
s u b s t a n t i a l l y upon the p r e h i s t o r y of the s a m p l e .
3. The r e p r o d u c i b i l i t y of the periodic singularities is low - the period of the "sine c u r v e s " and t e m -
p e r a t u r e s of the m i n i m a a r e r e p r o d u c e d , but the amplitude and t e m p e r a t u r e s of the m a x i m a a r e not r e p r o -
duced.

LITERATURE CITED
1. M . M . Qurashi and A. K. M. Ahsanullah, Brit. J. Appl. Phys., 1_~2,65 (1961).
2. S . S . U r a z o v s k i i and P. M. Chetaev, Zh. Fiz. Khimii, 2_33, 1421 (1949).
3. A . G . Shashkov and A. S. K a s p e r o v i c h , Dynamic P r o p e r t i e s of Circuits with T h e r m i s t o r s [in Russian],
Gos~nergoizdat, Moscow (1962).
4. Technical Encyclopedia, Handbook on Physical, Chemical, and Technological Quantities [in Russian],
10 (1933), p. 23.
5. A . N . K i r g i n t s e v and L. N. Efanov, Izv. AN SSSR, Set. Khim., 1965, 625.
6. V. Saccerdoti, Arch. F a r m a c . Sperin, 5 3 , 2 4 1 (1930).
7. A . V . F a l e e v and F. T. Sukhenko, Dokl. AN SSSR, 3_~3, 300 (1941).
8. A . K . Guman, T r . Leningradskogo Obshch. E s t e s t v o i s p y t a t e l e i , 7__00,70 (1959).
9. G. P i c c a r d i , Soc. roy. belge ing et ind., M6m. N 3, 93 (1953); Chem. A b s t r s . , 4153b (1954).

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