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STABILITY OF E M U L S I O N S OF W A T E R IN OIL
I. T H E CORRELATION B E T W E E N ELECTROKINETIC
POTENTIAL A N D STABILITY
W. Albers I and J. Th. G. Overbeek
van 't Hoff Laboratory, University of Utrecht, Netherlands
Received January 21, 1959
ABSTRACT
E x p e r i m e n t s on W / 0 emulsions of m o d e r a t e c o n c e n t r a t i o n , stabilized with oilsoluble, ionizing stabilizers, show t h a t in these emulsions no correlation exists bet w e e n s t a b i l i t y against flocculation a n d electrokinetic potential. Although, according to t h e o r e t i c a l calculations, energy barriers of over 15 kT are present, if t h e
radius of t h e dispersed globules is a b o u t 1 ~ a n d the electrokinetic p o t e n t i a l exceeds 25 my., t h e y a p p a r e n t l y do not p r e v e n t lasting c o n t a c t between particles. All
our emulsions flocculate rapidly, even in t h e presence of a surface p o t e n t i a l considerably higher t h a n 25 my.
A r a t h e r p r o n o u n c e d a n t i c o r r e l a t i o n exists between the zeta p o t e n t i a l a n d coalescence. I t is explained as a consequence of the free m o b i l i t y of the stabilizing
molecules in t h e interface.
T h e good stabilization against coalescence caused b y some oleates of p o l y v a l e n t
metals is due to the f o r m a t i o n of a t h i c k film of partial hydrolyzates in the interface.
INTRODUCTION
502
= ~o~ ~ aS~R,
503
4~
15kT
T
~d
FIG. 1. P o t e n t i a l e n e r g y of i n t e r a c t i o n b e t w e e n t w o g l o b u l e s w i t h r a d i u s a -- 1
in oil as a f u n c t i o n of t h e d i s t a n c e d b e t w e e n t h e s u r f a c e s . T h e s u r f a c e p o t e n t i a l
~0 = 25 m y . ; dielectric c o n s t a n t of t h e oil e = 2.3. I = C o u l o m b r e p u l s i o n ; I I v a n der W a a l s ' a t t r a c t i o n .
M A T E R I A L S AND E X P E R I M E N T A L M E T H O D S
504
I,
distance between the inner wall of the bulb and the electrodes. Thus
trouble by conduction of the electric current alongside the glass walls
of the cell is diminished. This has been proved to be effective because by
measurements on pure benzene a specific conductivity lower than 10-14
t~-1 cm. -1 was obtained. This is small as compared with the specific conductivities of the solutions of soaps of polyvalent metals and other ionic
stabilizers in benzene, which are in the order of 10-1 t~-1 cm. -~
A Philips d.-c.-electronic Voltmeter-pH meter G.M. 4491 was used to
determine the potential in the circuit.
The electrophoresis measurements were carried out in the cylindrical
cell as described by van der Minne and Hermanie (13). During these
measurements the applied voltage never exceeded 100 v./cm, to prevent
electrostatic induction effects that would otherwise disturb the electrophoresis measurements.
The emulsions were prepared b y adding water slowly to the solution of
505
RESULTS
--
6~r~ '
506
TABLE I
Correlation between the Electrokinetic Potential ~ and the Stability against Coalescence
in Water-in-Benzene Emulsions Stabilized by the Oleates of
Polyvalent Metal8 and Some Other Stabilizers
1
/'-potential
= ~0 potential (my.)
Ca-didodecylsalicylate
Ba-oleate
Mn-oleate
Ca-oleate
Zn-oleate
Al-oleate
Mg-petroleum sulfonate
Ba-petroleum sulfonate
Zn-petroleum sulfonate
Ni-oleate
Cd-oleate
Sr-oleate
Fem-oleate
Mg-oleate
Pb-oleate
CuH-oleate
130
0
70
20
50
45
A few hours
3ome days
80
32
2210
15
110-20 days
Several months
507
508
ALBERS A N D O V E R B E E K
TABLE II
The Composition of the Hydrolysis Products of the Oleates in the
Interracial Film with Low Potential
1
Theoretical
oleates
Hydrolysis
products
Mg-oleate:
Mg 4.14
C 73.68
H 11.26
O 10.92
CuH-oleate:
Cu 10.16
C 69.06
H 10.55
O I0.23
67.06
10.41
7.45
67.02
10.55
14.98
Mg-O1OHorMg(OH):MgOl~ complex
24.25 4- 0.25
46.87
6.35
22.53
Cu-OIHCO3.CuCO3
Fem-oleate :
Fe 6.21
C 72.08
H 11.01
O 10.70
10.08 4- 0.17
53.26
7.33
29.33
23.96
45.28
6.41
24.35
or (CuCO3)2.HOI
complex
a or b
10.75 9.86
48.37 53.06
7.10 7.89
33.78 29.19
(a) Fe(HCO~)~.tIO1 complex or
(b) (Fe(I-ICO3)~)7.(ttO1)8 complex in
O1 = oleate HO1 = oleie acid
which
509