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Emulsion Stability: Determination from Turbidity

S. R. REDDY a AND H. S. FOGLER


Department o f Chemical Engineering, The University o f Michigan, Ann Arbor, Michigan 48109
Received December 19, 1979; accepted May 16, 1980

A novel technique for studying the stability of emulsions has been developed. Owing to the
fact that emulsion turbidity is a function of particle concentration and size, the stability of emul-
sions can be determined by measuring the change in turbidity with time. The relationship between
turbidity and particle size and concentration is derived for a polydispersed emulsion. The
stability of acoustically prepared emulsions determined by measuring the initial mean particle size
and changes in emulsion turbidity is compared with the stability determined from scanning
electron microscope measurements of the particle growth rate. The agreement between the two
methods is excellent.

INTRODUCTION and Void (1) and Bagchi and Void (3) used
this approximate method for comparing the
A novel method for studying emulsion
stabilities of nonaqueous suspensions. The
stability to flocculation has been developed.
turbidity of suspensions containing very
Emulsion stability is determined by measur-
coarse particles varies inversely with par-
ing the turbidity as a function of time.
ticle size. Hiemenz and Void (4) and Bagchi
This method can be applied to many oil-in-
and Vold (5) used the turbidity method
water emulsions by measuring the changes
for determining the size of very coarse
in emulsion turbidity, which is very easy and
particles. The turbidity of an emulsion
inexpensive. The turbidity of an emulsion is
containing very fine and polydispersed
a function of particle size and concentra-
particles is a complex function of particle
tion. Therefore, the change in turbidity indi-
size and concentration. In this study, a
cates the change in particle size and concen-
turbidity method is developed for deter-
tration. In an unstable emulsion, particle
mining the stability of emulsions containing
concentration and size change with time due
polydispersed small particles. Results ob-
to coagulation and coalescence of particles.
tained from the turbidity method are com-
The turbidity method has not been pre-
pared with direct particle size measure-
viously used for determining the stability
ments made by using a scanning electron
factor, W, of an electrostatically stabilized
microscope.
emulsion. The turbidity technique has been
used (1, 2) to determine approximately the
THEORY
stability of suspensions by assuming that
turbidity is directly proportional to particle The optical density or turbidity, z, of an
concentration. This assumption can lead to emulsion containing monodispersed par-
erroneous stability factors or aggregation ticles is given by the relationship (6, 7)
rate constants as will be shown later. Dunn
ln(Io/I)
i Presently at General Motors Research Labora-
,r - - - - K 1 r a Z N , [1]
l
tories, Fuels and Lubricants Department, Warren,
Mich. 48090. where I0 and I = the intensity of the in-
101
0021-9797/81/010101-04502.00/0
Copyright© 1981by AcademicPress, Inc.
Journal of Colloidand Interface Science, Vol.79, No. 1, January 1981 All rightsof reproductionin any formreserved.
102 REDDY AND FOGLER

cident and transmitted light, respectively; Solving the equation for the ratio of initial
a = the particle radius; l = scattering path turbidity, z0, to the turbidity at any time, ~-,
length; N = the concentration of particles; assuming no creaming (i.e. 49 = 490)
and K = the total scattering coefficient de-
•o _ (ao/X)" ° (a3~2) [9]
fined as
(a/x)" (a~/Oo
K = Ko(a/h) m, [2]
Assuming a/fi0 = (a312)/((a312)o) and sub-
w h e r e K0 = the size-independent c o m - stituting into Eq. [9],
p o n e n t of the scattering coefficient, and
"to (ao)-,o-lX-, .....
m = the e x p o n e n t of the wavelength, )% - [10]
T (a) m-i
d e p e n d e n t on particle size and refractive
index. In emulsion stability studies, it is desir-
By measuring the turbidity at different able to determine the ratio of initial particle
w a v e l e n g t h s , the value of m can be deter- concentration to the particle concentration
mined f r o m the slope of a l o g - l o g plot of at any time, No~N, as a function of time.
~- vs h according to the equation In the absence of any creaming the ratio
~- = constant ()k) m. [3] N o / N can be related to Zo/Z using the rela-
tionship
F o r a polydispersed system, the turbidity
No 63
is given b y - [11]
N ~
"r = 7r ~ K~a2Ni, [4]
i Solving Eq. [10] for ~ and substituting
in Eq. [11],
w h e r e Ki = Ko(ai/h) "~.
The equation can be further simplified NON _ ~L1[ Xm-rtl°(ao)m°-lTo/___~ ]3/.,-~. [12]
to a useful f o r m b y evaluating K~ at an
a v e r a g e particle radius, 6:
F o r a special case w h e n the particles are
K~ = Ko(~t/h)". [5] very large, mo = m = 0, Eq. [12] reduces to
Then
"f = 7rKo(~l/h) m ~ a~Ni. [6] No
i

T h e v o l u m e fraction, 49, of the dispersed H o w e v e r , Dunn and Vold (1) used the re-
p h a s e is given by lationship
4 No To
49 = ~ 7r ~ a~Ni. [7] -- - [14]
N ~-

E q u a t i o n s [6] and [7] can be c o m b i n e d to to evaluate the effect of the molecular


e x p r e s s r as a function of particle size, weight of a nonionic stabilizer on the stabil-
ity of graphon dispersions. L a w r e n c e and
a~N~ Parfitt (2) used the same method for meas-
~- - _49Ko~"
_ (a/X) m - i - uring the stability of nonaqueous dis-
(4/3)7r ~ a~N~
i persions. T h e y used an equation of the type
3 (~/X) m -d~-
- 49Ko~ , [8] - k"c 2 [15]
4 a312 dt
w h e r e a3/2 is the v o l u m e surface average for
particle radius. -dN/dt = kN 2
Journal o f Colloid and Interface Science, Vol. 79, No, 1, January 1981
EMULSION STABILITY 103

for kinetics of particle flocculation. Equa- o From Particle Size Ar~lysis o///
tion [12] can be used to determine the ~C- zx From TurbidityAnalysis
stability of an emulsion by measuring the
8 N \TJ
initial average particle size, do, and turbidity f
No % ~ "
as a function of time. The values of m are -~-6 o
determined by measuring ~-of the same sam-
ple at different k and plotting In ~- vs In h. 4
From the kinetics of flocculation
- d N / d t = k N 2, [ 16]
where k = 4kT/3tz W. O~ I 1 I I ]
10 20 30 40 50
Integrating and using the initial condition TIME (rain)
N=Noatt = 0,
FIG. 1. E m u l s i o n s t a b i l i t y d e t e r m i n e d from the
No/N = 1 + Nokt. [17] turbidity measurements.

Therefore, by plotting No/N vs t, one can


determine the stability factor. The initial at different times and diluted as required,
particle concentration and particle size is and the turbidity was measured at three
always required; however, it can be meas- different wavelengths by using a B a u s c h and
ured or it can be predicted from the method L o m b Spectronic 88 s p e c t r o p h o t o m e t e r .
of preparation o f the suspension. For ex- The value of m was obtained from the
ample, the particle size of acoustically pre- slope o f the curve of a plot o f In ~- as a
pared emulsions can be estimated from the function of In h. This curve was obtained
theory of Li and Fogler (8, 9). from a polynomial fit of the values in
The stability of acoustically prepared Table I. The ratios (No/N) at different
paraffin oil-in-water emulsions was deter- times were calculated from Eq. [12] using
mined by measuring the turbidity and initial a wavelength of 400 nm and the results are
particle size. An emulsion of 0.05 ml p r e s e n t e d in Fig. 1.
C36H74 in 60 ml water containing 4.2 F o r comparison, the ratio N o / N was also
× 10-2 g mole MgSO4/liter was prepared by c o m p u t e d by measuring the particle size as a
acoustic irradiation for 5 min at 80°C and function o f time as described below (10, 11).
stored at the same temperature. The initial The total particle concentration, N , is re-
particle size was determined by withdraw- lated to the volumetric mean particle diam-
ing a sample, freezing the particles, and eter, D3/o. F r o m a material balance on
placing them under a scanning electron the oil,
microscope. Emulsion samples were drawn
N - qb , [181
TABLEI (~'/6)(D310)3
Turbidity Data ~rFig. l"
where 4) is volume fraction of oil, and D3/0
Time is given by
(min) 400 nm 430 nm 480 nm Value of m

0 0,344 0.330 0.300 0.459 D3/0 = (f~D~ + f z D z3 + f 3 d ] + "" .)1/3, [19]


I0 0.345 0.339 0.320 0.131
20 0.301 0,304 0.300 -0.239
where f , is the fraction of particles in group
30 0.266 0.275 0.278 -0.603
45 0.232 0.240 0,243 -0.610 i with diameter D~. Emulsion particles w e r e
divided into several groups with i n c r e m e n t
" No = 3.61 × 109 p a r t i c l e s / c m ~. groupings o f equal diameter.
Journal o f Colloid and Interface Science, Vol. 79, No. 1, January 1981
104 REDDY AND FOGLER

0 No/N from Turbidity


a c c u r a t e d e t e r m i n a t i o n o f e m u l s i o n stabil-
onolysis /
Z~ N°IN [ T°/T / ity. F i g u r e 2 is a n o t h e r c a s e w h e r e t h e
s t a b i l i t y o f a n e m u l s i o n is d e t e r m i n e d b y
2~ m e a s u r i n g t h e t u r b i d i t y a n d the c o r r e s p o n d -
ing t u r b i d i t y d a t a a r e p r e s e n t e d in T a b l e II.
2C
T h e t u r b i d i t y m e t h o d w a s u s e d (10, 11) for
le investigating the stability and stability
z
% m e c h a n i s m o f a c o u s t i c a l l y f o r m e d emul-
z 12
sions. T h i s s i m p l e a n d a p p r o x i m a t e m e t h o d
can be used for determining the stability
8
of various other emulsions.
4
SUMMARY
o; I
10
I
20
I
40
I I
50
30 T h e r e l a t i o n s h i p b e t w e e n p a r t i c l e size a n d
TIME (min)
c o n c e n t r a t i o n a n d t u r b i d i t y has b e e n de-
FIG. 2. Emulsion stability determined from differ- veloped for a polydispersed system. The
ent methods. stability of acoustically prepared emulsions
o f C36Hr4 in w a t e r w e r e d e t e r m i n e d f r o m
In the absence of creaming or sedimenta- t u r b i d i m e t r y a n d f o u n d to b e in a g r e e m e n t
tion, w i t h t h e s t a b i l i t y d e t e r m i n e d b y t h e freez-
No_[ D3lo ]3 ing m e t h o d . T h e t u r b i d i m e t r y m e t h o d c a n
N L~J ' [20] be used for determining the stability of
various emulsions easily and inexpensively.
w h e r e s u b s c r i p t 0 i n d i c a t e s t h e initial v a l u e .
REFERENCES
T h e v a l u e s o f N o / N f r o m p a r t i c l e size
m e a s u r e m e n t s a r e a l s o p l o t t e d in F i g . 1. T h e 1. Dunn, V., and Vold, R. D., J. Colloid Interface
a g r e e m e n t b e t w e e n t h e t w o m e t h o d s is Sci. 54, 22 (1976).
2. Lawrence, S. G., and Parfitt, G. D., J. Colloid
e x c e l l e n t . A l s o p l o t t e d in F i g . 1 a r e N o / N
Interface Sci. 35, 675 (1971).
c a l c u l a t e d f r o m E q s . [13] a n d [14]. It is c l e a r 3. Bagchi, P., and Vold, R. D., J. Colloid Inter-
t h a t o n e c a n n o t a p p r o x i m a t e N o / N b y To/~" face Sci. 33, 405 (1970).
or assume the particles are larger and 4. Hiemenz, P. C., and Void, R. D., J. Colloid
m = 0. E q u a t i o n [12] s h o u l d b e u s e d f o r Interface Sci. 21,479 (1966).
5. Bagchi, P., and Void, R. D., J. Colloid Interface
Sci. 53, 194 (1975).
TABLE II 6. Weissberger, A. (Ed.), "Techniques of Organic
Chemistry, Physical Methods of Organic Chem-
Turbidity Data for Fig. 24 istry" Part III, pp. 2107-2145. Interscience,
Time
New York, 1960.
(min) 400 n m 450 nm 500 n m Values ofm 7. Lothian, G. F., and Chappel, F. P., J. Appl.
Chem. 1,475 (1951).
0 0.574 0.552 0.524 0.255 8. Li, M. K., and Fogler, H. S., J. Fluid Mech.
5 0.485 0.490 0.490 -0.133 88, 499 (1978).
10 0.380 0.395 0.403 0.402 9. Li, M. K., and Fogler, H. S., J. Fluid Mech.
20 0.300 0.315 0.320 -0.554 88, 513 (1978).
30 0.235 0.250 0.260 -0.606 10. Reddy, S. R., "On the Stability of Emulsions."
45 0.185 0.195 0.200 -0.556 Ph.d. thesis, The University of Michigan, 1980.
11. Reddy, S. R. and Fogler, H. S., J. Phys.
~' No = 4.35 × 109 particles/cm3. Chem. 84, 1570 (1980).

Journal of Colloid and Interface Science, VoL 79, N o . 1, J a n u a r y 1981