Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
*) Laboratory of Thermodynamics and Physico-chemical Hydrodynamics, Faculty of Chemistry, University of Sofia, Sofia,
Bulgaria
*) Institute of Geology, Bulgarian Academy of Sciences, Sofia, Bulgaria
Abstract: The effect of the micelles on the dynamic surface tension of micellar
surfactant solutions is studied experimentally by means of the maximum bubble
pressure method. Different frequencies of bubbling ranging approximately be-
tween 1 and 30 s- 1 are applied. The time dependence of the surface tension is
calculated using a dead time correction. Water solutions of two types of sur-
factants with different concentrations are investigated: sodium dodecyl sulfate
and nonylphenol polyglycol ether. The surface tension relaxes more quickly in
the presence of micelles. The characteristic times of relaxation of the surface
tension seem to be in the millisecond range. The time constants observed
experimentally are explained in terms of the theory of surfactant diffusion
affected by micellization kinetics.
GL 967
lliev and Dushkin, Dynamic surface tension o f micellar solutions: Part 1 371
balance across the bubble surface gives [16] (see Appendix) tension of an air/water interface, aged for time t. Afterwards
the bubble expands spontaneously during the second stage.
1 ( 2ApgRc~ The pressure inside then drops and the bubble leaves the
= 2 Rc APmax 1 3ZIPmax, / , (2) capillary. The duration of the second stage is termed dead
time, ta. Hence, to determine the net time of the surface age,
where the second term in parentheses accounts for the gravi-
we should use the formula
tation. Let us introduce the Egtv6s number Eo
Eo = 3 p g R ~ / 2 c r . t = t v - - td
In this way, Eq. (2) becomes where t~ = v-t is total time, measured experimentally.
To derive an expression for ta, Feinerman [7] has considered
y = 1 - (2/3)Eo(y)y, (3) Poiseulle flow of the air in the capillary. In this way he has
where, in view of Eq. (1): obtained the approximate formula
y = 2cr/RoApg(H -- h) .
Equation (3) can easily be solved by means of the method of t a = ReAP L R c A P \ R c ] +3\Re/ J
asymptotic expansions [17]. The formal solution of Eq. (3) valid at R b >> Ro. Here ~t~ is the air viscosity; Lo is the capillary
reads length; R u is the radius of the bubble during the stage of
y=l+ ~ ( - - 2 / 3 ) kEok(y) . (4) spontaneous expansion. Equation (8) shows that t e may de-
k=l pend on the geometrical parameters of the capillary and on the
surfactant concentration through o. Garrett and Ward [12]
The value of cr can be obtained with an appropriate accuracy
have experimentally proved this statement by using an elec-
from Eq. (4) by an iterative procedure.
tronic counter, an oscilloscope, and a high-speed cinecamera.
Let us compare Eq. (4), written in the form
They have established that t a does not depend manifestly on v.
y = 1.0 -- 0.6667Eo + 0.4444Eo 2 (5) In their experiment t a is around 19 ms for distilled water and t d
is around 25 ms for SDS solution with concentration ~ = 7
with other equations, available in the literature. The equation x 10 .6 mol/cm 3. Their capillary has a radius 10 .2 cm. Since
of Bendure [3] reads L c and R b a r e unknown in our experiment, we had to perform
y = 0.9995 + 0.0136Eo ~/2 direct measurements of t d.
To do so, we visualized (as in I5, 12, 21]) the pulsations of
-- 0.1113Eo 3/2 + 0.5647Eo 2 , (6) the pressure when bubbles are blown away. We replaced the
while the equation of Johnson and Lane [18] is water manometer, which is too inert for this purpose, with a
sensitive pressure transducer. The signal from the transducer is
y = 1.0 - 0.6622Eo - 0.0603Eo 3/2 + 0.5631Eo 2 . (7) amplified and depicted on the oscilloscope screen. The signal
Equations (6) and (7) are obtained numerically by interpo- has a saw-like form, corresponding to the changes in the
lation of the tables of Sugden [19]. The exact analytical pressure. Hence, t is the time interval, which AP needs to reach
solution of the problem, Eq. (5), explains why the contribution its maximum value P. . . . while t a is the time interval, during
of the odd powers of Eo 1/2 in Eqs. (6) and (7) is negligible. which AP drops down to its initial value. In this way the
Another solution of the Laplace equation for the capillary bubbling frequency was measured from the screen with an
pressure was found recently by Holcomb and Zollweg [20]. At accuracy 0.1 s - t .
small Eo their equation yields (cf. Eq. (5)) We measured ta at different v for distilled water and several
SDS solutions. We found that the dead time does not depend
y = 1 - 0.6689Eo . notably on the bubbling frequency (ta varied between 15 and
In most experiments with MBP-method Eo ~ 1 (y ~ 1), i.e., 25 ms). The results are plotted in Fig. 2. It is seen that with
the gravitational effect in Eq. (2) is negligible. For example, in increasing the frequency the contribution of t d increases in
our experiment Eo varies between 3.8 x 10 .4 for pure water comparison with total time t v = v - t The data for t d are too
(or = 72 dyn/cm) to 7.9 x 10-4 for micellar solutions of SDS scattered, because the dead time was measured with an accur-
(rr = 35 dyn/cm). Subsequently, the dynamic surface tension is acy of 5 ms, due to the low dividing ability of the oscilloscope
calculated in all cases by means of Eqs. (1) and (2). The screen. That is why the dependence of ta on the concentration,
accuracy in measuring the surface tension is better than predicted by Eq. (8), cannot be observed. The linear fit of the
0.2 dyn/cm. experimental data in Fig. 2 is t/G = 0 . 9 9 2 1 7 - 0.01824v.
Hence, the dead time is given by
t a = 18.24 + 7.83/v, (9)
where v is in s-1 and ta is in milliseconds. Equation (9) differs
Dead-time correction from the empirical formula of Austin et al. [2]
td = 39.9 - 0.252v. (10)
There are two stages of formation of a bubble on the tip of a
capillary [3]. During the first stage the bubble grows until the Equation (10) is obtained for a capillary having different radius
maximum pressure APmax is reached and a hemispherical form (R c = 5 x 10 .3 cm) and probably different length L c. Both
is established. At that time or(t) corresponds to the surface Eqs. (9) and (10) are compared in Fig. 2.
lliev and Dushkin, Dynamic surface tension of micellar solutions: Part 1 373
1.0
~t
tv "'~.'._ ' ~"o , ~
0.5
Fig. 2. Frequency dependence of t/G for SDS
solutions with different concentration
(mol/cmS): 0( 9 2 x 1 0 - 6 ( O ) , 3x10 6(O),
4X 10-6(D), 6 x 10-6(11), 7X 10-6(A),
Results a n d discussion
70 o - -<~T x - 3 - o . ~ <:o- r ~ l -
~ _ _ ~ - _ ~ ~- -z~-
- D- - - - d~- - O - - OK~
r ) . . O ' -Z
- _; ~ - - ~ " - ~
g o o d a g r e e m e n t w i t h the M B P - d a t a o f o t h e r au-
40
t h o r s [11, 12], p l o t t e d also in Fig. 3 for c o n c e n t r a -
tions equal or very close to the c o n c e n t r a t i o n s used . . . . .
60
O. _ a D . _ _ O - - - O- ~D" -<'~- ,O
W i t h increasing the f r e q u e n c y v, very s h o r t times
50 b e c o m e accessible. F o r such s h o r t time intervals the
r Z__-<>---o- . . . . . . . k- ...r b u b b l e surface r e m a i n s a l m o s t clean, because the
40 , " 9 ~ ..... -,- - -- ~ - - - ~ - ~ . i r - " s u r f a c t a n t molecules d o n o t have time to a d s o r b
o n t o it. T h e r e f o r e , in this case the surface tension
30 tends to the value o f p u r e water. In the o p p o s i t e
0 10 20 30 case (low frequencies v, i.e., large t) the s u r f a c t a n t
9 (s-9 molecules have e n o u g h time to reach the b u b b l e
Fig. 3. Experimental dependence of the dynamic surface ten- surface a n d to a d s o r b o n t o it. In this w a y they
sion cr on the bubbling frequency v at different SDS concentra- sufficiently l o w e r the surface tension.
tions (mol/cm3): 2 X 10 -6 curve 1; 3 X 10 - 6 - 2; It is seen f r o m Fig. 5 t h a t at infinite times the
4• 6 _ 3; 6• 6 _ 4 ; 8 x 1 0 - 6 - 5 ; 1.2• s _ 6; surface t e n s i o n o f SDS tends to its e q u i l i b r i u m
1.6 • 10- s _ 7; 2.4 • 10- 5 _ 8; 3.2 x 10- 5 _ 9. The open circles
values (the bars o n the r i g h t h a n d side f r a m e o f the
(O) represent the data below CMC, and the filled circles (O)
are those above CMC. The data of Garrett and Ward [12] are: figure). (The e q u i l i b r i u m values are calculated by
5 • 10- 6 ( A ) and 7 x 10- 6 ( A ) - curve 4*. The data of Woolf- m e a n s o f Eq. (11).) T h e SDS m o n o m e r s are trans-
rey et al. [11] are: 2x I0-6(C]) and 8x 10-6(11) p o r t e d in s h o r t time (of the o r d e r o f milliseconds)
374 Colloid and Polymer Science, Vol. 270 9 No. 4 (1992)
40 .... _2-_ . . . . . . . . . . ; . . . . . . .
Here 8 is in dyn/cm, while 2 is in mmol/1. Equation
7O
30 0-
0 50 100 150 200 250 {d yn/cm)
60 ~
t (ms)
Fig. 5. The time dependence of the surface tension ~r of the
SDS solutions obtained by the data in Fig. 3. The bars denote so ~Q~X,
the respective equilibrium values ~ calculated by Eq. (11)
X%.L.
40
ooo--omco-- o..~_o- - - qso- . . . . . . . . o
7O ~ , 7 ~ A . ~ - _-~_ -._-22 . . . . . . . . A- -.-A CMC
/
z+O
70 -'&7-<. o
g.
30
. . . . t , , i , I i , . . i . . . . i . . . .
~"
-~,,,~
0 50 100 150 200 250 6O \ \
(11) was obtained in [22] by fitting experimental ies. In non-equilibrium conditions the micettes can
data, obtained by the Wilhelmy plate method. disintegrate into monomers and additionally sup-
The CMC of SDS is supposed to be 8.3 ply the bubble surface with surface active material.
• 10- s mol/cm 3" Two relaxation processes of micellization are ob-
The equilibrium surface tension data of Veranol served experimentalJy by the usual chemical relaxa-
H10 are taken from [13]. It is seen from Fig. 8 that tion methods like p-jump method [24]. The first
5(J) exhibits a minimum around CMC (CMC is process, called fast process, is attributed to the
accepted to be 5 x 10-8 mol/cm 3). The best fit of release of several monomers by a micelle in order to
the data below CMC is make it less stable. During the second process,
which is called slow process, the micelles destroy to
8 = 54.96 -- 3.7051nc - 0.7271n2c, (12)
reach their equilibrium concentration. We will de-
where ~ is in pmol/1. Figure 8 illustrates the very note the time constant of this particular relaxation
large difference between the dynamic surface ten- process by zM.
sion and the equilibrium surface tension of Veranol However, the micelles can also be transported
H10 in cornparison with the respective curves of towards the bubble surface. In such a way they can
SDS in Fig. 7. This fact, due to the weaker trans- facilitate the adsorption, thus causing t'he surface
port ability, is also observed for other surfactants tension to relax faster than in the case below CMC.
in [4, 23]. Subsequently, the difference between the dynamic
If the surfactant concentration increases, the re- surface tension r and the equilibrium one 5, shown
laxation of the surface tension becomes much in Figs. 7 and 8, can be explained by the partici-
faster (see Figs. 5 and 6). As we see, below CMC pation of the micelles in the mass transfer. If the
this may be attributed to the accumulation of transport of micelles and the micellization are
surfactant monomers in the bulk of solution. The much faster than the time intervals accessible in the
transport of material to the surface becomes more experiment, the equilibrium surface tension should
intensive and the surface equilibrates rapidly. To establish instantaneously. These processes should
describe this process more quantitatively, we will have comparable characteristic time in order that
use the equation for the monomer concentration in the effect of the micelles becomes observable. It is
the subsurface layer 9 (t) derived in the subsequent seen from Figs. 5 and 6 that the time intervals
paper [14]: covered in our experiment are between 5 and
9 (t) = g, {1 - E[(t/'~D)I/2]} . (13) 250 ms. The surface tension of SDS and Veranol
H10 above CMC changes notably until 30-40 ms.
Here, ~1 is the equilibrium monomer concentration Therefore, the characteristic time of miceltization
and E (z) = exp (z 2) erfc (z) where erfc (z) is tee erro- ~M is to be in the millisecond range. Of the same
r function complement. The characteristic diffm order should be the characteristic time of trans-
sion time c o represents the ability of the surfactant portation of the free monomers ZD, tOO, because
molecules to enhance the relaxation. The subsu> the last species act like mediators among the micel-
face concentration 9 can be obtained experb les and the surface adsorption layer.
mentally from the data of c~. Fitting these data by In this case the subsurface concentration is given
Eq. (13), we found that the values of c o for SDS by another equation derived in [15]:
range from 5.8 to 15 ms [14]. Of the same order are
also the values of c o obtained experimentally by (/)(t) = Z~ {1 -- exp( -- ~CD){blE[(k,t/co) 1/2
Garrett and Ward [12]. For Veranol H10 a suffi- - b2E[(kat/CD)I/2]}} , (14)
ciently larger value of CD, 14.7 S was computed at
concentration ~ = 3.16 x 10 -18 mol/cm 3 [15]. where bi = (1 + G)/2, b 2 = (1 - G)/2, kl =
With increasing the surfactant concentration cD (1 + G)2/4, k 2 = (1 - G)2/4 and G = (1 +
generally decreases. Hence, Eq. (13) predicts that 4CD/'CM) 1/2. Equation (14) predicts a faster relaxa-
the surface tension relaxation will really become tion than Eq. (13) depending on the ratio TD/TM. It
faster. is known from the experiments on the micellization
In addition, above CMC the rmmber of the free kinetics [24] that TM usual]y decreases with increas-
monomers r e m a i n s almost c o n s t a n t : t h e e x c e s s ing the surfactant concentration. This fact, to-
amount of surfactant added transforms into miceb gether with Eq. (14) explains qualitatively why the
376 Colloid and Polymer Science, Vol. 270 9 No. 4 (1992)
Authors' address:
Ceco D. Dushkin
I- Ro ]\0- Laboratory of Thermodynamics and Physico-chemical
Hydrodynamics
I Faculty of Chemistry
University of Sofia
Fig. 9. Sketch of an air bubble expanding on a capillary tip i Anton Ivanov Blvd.
(for notations see the text) 1126 Sofia, Bulgaria