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ADSORPTION AND INTERFACIAL, TENSION IN EMULSION

a a
N. Garti & M. Katz
a
Casali Institute of Applied Chemistry The Hebrew University of Jerusalem , Jerusalem,
91904, Israel
Published online: 27 Mar 2007.

To cite this article: N. Garti & M. Katz (1985) ADSORPTION AND INTERFACIAL, TENSION IN EMULSION, Journal of Dispersion
Science and Technology, 6:2, 149-158, DOI: 10.1080/01932698508943940

To link to this article: http://dx.doi.org/10.1080/01932698508943940

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 J. DISPERSION SCIENCE AND TECHNOLOGY, 6(2), 149-158 (1985)

ADSORPTIOK AND 1!\'fERFACIAL,TENSION IN BllJLSION

N. Garti and M. Katz

Casali Institute of Applied Chemistry
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The Hebrew University of Jerusalem

Jerusalem 91904, Israel

ABSTRACT

This report is an attempt to study adsorption and reduction of

interfacial tension caused by adsorption of nonionic ethox)'lated non)"l
phenols in emulsion. In order to study these phenomenon a method for
estimating adsorption and interfacial tension in emulsion vas developed.
It has been found, in contrast to a concept which appears in literature,
that there is no correlation between values of interfacial tension as
measured in emulsified and separated o i l-water systems. Yet, there seems
to be a significant correlation between adsorption values as measured in
emulsified and separated oil-water systems. In addition it has been
found that the values of maxirnwn adsorption of the emulsifiers as measured
in t he separated 0; Ivwat er- system correlate linearly with HiB values of
these emulsifiers. Such correlation may indicate possible dependance of
HLB \alues on emulsifier's adsorption to the interface.

1~1"RODUCTION

Fmulsifiers are surface active agents and are characterized by

their tendency to adsorb to interfaces, thus causing the interface to alter
its characteristics, e.g. interfacial tension, electric cha.rge , mechanical
strength etc. There is a concept, which appears in the lit.erature, stating
that interfacial tension, between separated liquid phases (oil and water)
contributes to the stability of the emulsion which is obtained from these two
phases. This concept is based on the fact that the Ins tahi Litv of an
emulsion is a result of a large interface and a positive ir..terfacial tension.
It is concluded that the lowering of interfacial tension will result in
l
greater emulsion stability. In order to prove this concept Adamson brings
an example in \~lich the reduction of interfacial tension in the system

149

Copyright © 1985 by Marcel Dekker, Inc. o193-1691/85/0602.Q14913.50/0

 ISO GARTI AND KATZ

paraffinic oil, oleic acid and water, caused by the addition of sodium
hydroxide which also leads to the formation of a more stable emulsion.
An attempt to confirm this concept was made by Yasukatsu Tamai
2
using ethoxylated nonyl phenols as emulsifiers. In this experiment 0.1%
of emulsifier solutions were prepared, interfacial tension between paraffinic
oil and water were measured and stability of emulsion was estimated. The
results show that at the required HLB maximum gtability and minimum interfacial
Downloaded by [University of Sussex Library] at 23:39 09 February 2015

tension were obtained. Yet it must be added that no significant data is

available concerning the interfacial tension on droplets in emulsion.
This report is an attempt to examine adsorption and interfacial tension
in emuls ion, Therefore, several assumpt ions ,..ere laid:

(a) the behaviour of an oil droplet is as of a continuous phase.

(b) adsorption of the emulsifier to air-water and oil-water interfaces
in the emulsion is dependent on the emulsifier concentration in
water only.
(c) throughout the experiment the concentration of the emulsifier
in the oil, the water and the co-existing interfaces in the
emulsion do not change.
Cd) the existence of a dispersed phase does not interfere with
surface tension measurements.

n\TERIALS AND "IEmODS

The materials used were dionized water, paraffinic oil and e thoxyl a ted
nonyl phenols produced by ICI Ltd. Wilton, Middlesbrough, Cleveland. Using
a Fisher tensiometer model 21 and a 6 em circl~ference Pt-Ir ring surface
and interfacial tension measurements were carried out on various ethoxylated
nonyl phenols solutions. The results served for both calculating adsorption
in the separated oil-water system and as calihration curves for calculating
adsorption in emulsion and estimating interfacial tension on droplets in
emulsion. Adsorption in the separated oil-water system was calculated
using the slope of interfacial tension V8PSUS log concentration curve
according to the Gibbs equation assuming that in the linear portion of
the curve, adsorption is constant within experimental error and at its
~1Ximum value. Calculation of adsorption in emulsions was made in the
following manner. Using a Silverson homogenizer, o/w emulsions were
prepared. The emulsions were allowed to cream for approximately two hours
until a sufficient volume of translucent solution appeared. In a sample
 ADSORPTION AND INTERFACIAL TENSION IN EMULSION lSI

t-
E E
u
~ <,
c; c:

-~
c-, >-
u u
-;:
: log C
~
r"',,--
log W
I
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~
E~
e.i --
u
I
I
»: I
log C

Figure 1: A graphical display of the method for estimating adsorption

and interfacial tens ion in emulsions.

of this solution surface tension was measured. The value cf surface tension
in emulsion (Y are in correlation with concentration (c) of the emulsifier
e)
in the solution according to the calibration curve. Thus the weight of
emulsifier adsorbed in emulsion is given by

re = W - C'Y/100

where Wis the total "eight of emulsifier in the emulsion, C is its "eight
percent in solution and Y is the volume of water. The emulsifier's
concentration C also fitted an interfacial tension in the calibration
cury·e. This interfacial tension value (Yie) is assumed to be an estlination
of interfacial tension or droplets in emulsion. The method is graphically
displayed in Figure 1.

RESULTS .~ DISCUSSION
Figure Z shows the plot of surface tension (Yf) ve~sus log concentration
(e) expressed by weight percent curves for ethoxylated nonyl phenols ,;ith
6, 10 and 15 EO units are sho,;n. The linear portion of the curves is
expressed in equations shown in Table L
 152 GARTI AND KATZ

•
& n=6
• n=IO
o n=15
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........----.
c
Figure 2: Surface tension \YfJ versus log concentration (c) in wt~,
for ethoxylated nonyl phenol solutions.

TABLE 1
Equations expressing log C as derived from surface tensions
of ethoxylated nonyl phenols (EO) solutions at 20°C

Number of EO units Equation

6 -log C = (vf + 31.96)/23.89
10 -Log C = (y f + 10.12)/18.50
15 -log C = (yf 8.00)/14.75

From these results (}C values adsorption (y) and area per molecule (5),
values were calculated on basis of the results presented in Table 1 and
are given in Table 5. Log (}C values were found to correlate linearly
wi th number of EO and values were found to correlate linearly wi th 2nd root
of EO nl~ber. This phenomenon was described in a number of publications 3- 5.
Figure 3 shows curves of interfacial tension (Yi) versus log concentration (C),
for ethoxylated nonyl phenols with 6, 10 and 15 EO. The linear portion of
the curve is expressed in equations given in Table 3.
 ADSORPTION AND INTERFACIAL TENSION IN EMULSION 153

TABLE 2

Experimental and calculated concentrations (in wt%)

of ethoxylated nonyl phenol wi th 6 EO units
expressing the deviation from the equation in ~~able 1
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Experimental CalcUlated
4
ColO (I<t%) CoI 04 (,<1:%) 6CoI04(wt%)
Y f dyn/cm

9.21 40.0 9.72 -0.51

5.86 45.5 5.72 +0.14
3.07 52.0 3.06 +0.01
2.93 52.0 3.06 -0.13
1. 54 59.0 1. 56 -0.02

•
E 20
•
• n=6
u
<, • n= 10
,.,
c o n=15
"0

>-. 10

-3 -2
log C

Figure 3: Interfacial tension (y.) versus log concentration (c) in wt%,

for ethoxylated nonyl Iphenol sOlutions.
 154 GARTI AND KATZ

TABLE 3

Equations expressing the interfacial tensions (Yi) as derived from

emulsifier concentrations for ethoxylated nonyl phenols (EO) at 20D C

Number of EO un i ts Equation

6 Yi -(20.17 + 12.14 log C)

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10 Yi -(18.54 + 11.15 log C)

15 1i - (15.31 + 10.11 log C)

TABLE 4
Experimental and calculated interfacial tensions
of ethoxylated nonyl phenol with 6 EO units expressing
the deviation from the equation in Table 3

Experimental Calculated
-log C Vi d,njcm Yi dynjcm 6Yi dynjcm

2.39 9.0 8.8 0.2

2.69 12.3 12.5 -0.2
2.96 15.6 15.8 -0.2
3.17 18.5 18.3 0.2
3.43 20.5 21. 5 -1.0

From these results adsorption values (r i) were calculated and are given
in Table 5. These values in Table 5 differ by~ 10% from those published
already. 3,5 The fact that the emulsifiers "ere used without any further
treatment may account for such discrepancy

Tables 6-8 list surface tensions (Y e) , calculated amounts of emulsifier

adsorbed (r e) and estimated interfacial tension (Y i e) on the droplet in
emulsions containing the different emulsifiers. The values of f calculated
e
in the manner mentioned already above, clearly show in all cases that more
than 95% of the emulsifier added is adsorbed. This is with good correlation
to adsorption values calculated from the slopes of the Y - log C curves
i
wh ich refer to the separated oi l-water system as they indicate efficient
adsorption (high emulsifier concentration per unit interface area).
 TABLE 5

Characteristic values for the

same ethoxylated nonyl phenols (at 20·C)

Xccnbc r of EO units 6 10 15

OIC (air-solution) mole/liter 4.34.10. 5 6.25 010-

5 9.85.10. 5

r (air-solution) mole/an 2 4.3 010.

10 3.3 010-
10 2.6 010.
10

S (air-solution) A°2 39 SO 63
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HLB 10.9 13.3 15

2 2.2 10 2.0.10- 10 1.8 10
f
i
(oil· sOlution) mole/an 010. 010.

TABLE 6

Surface tension (y ) interfacial tens ion (y, ) and adsorption (Ye)

in o/w emQlsions prepared with pa~~ffinic oil and
ethoxylated nonyl phenol with 6 EO units
(oil vclume fraction 6=0.2, 20°C)

li(gr) ye(tlyn/an) Yie(dyn/an) fe(gr) i' /IV(gr/gr)

0.011 48.0 20.4 0.0106 0.966
0.025 42.5 17.7 0.0244 0.976
0.051 38.0 15.3 0.0500 0.981
0.110 33.0 11.6 0.l080 0.983
0.150 32.0

TABLE 7

Surface tension fy ), interfacial tension (y, ) and

adsorption (f ')ein 0;" emulsions prepared1{hth
paraffinic oileand ethoxylated nonyl phenol with
10 EO units (oil volume fraction $=0.2, 20"C)

IV(gr) ye(dyn/an) Yie(dyn/cm) f e (gr) r /\V(gr/grJ

0.050 44 00 14.1 0.049 0.981

0.100 42.0 12.9 0.099 0.988
0.200 38.0 10.5 0.198 0.990
0.300 36.0 9.3 0.297 0.991
0.400 35.0 8.7 0.397 0.993
 156 GANTI AND KATZ

TABLE 8

Surface tension (y ), interfacial tension (y. ) and

adsorption (f ) ei n o/w emulsions prepared'$ith
paraffinic oileand ethoxylated nonyl phenol with
15 EO units (oil volume fraction ~=0.2, 20°C)

N(gr) Ye(dyn/cm) yie(dyn/on) fe(gr) r /W(gr/gr)

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0.050 46.0 10.7 0.048 0.958

0.100 44.0 9.4 0.097 0.971
0.200 43.0 8.7 0.197 0.983
0.300 42.0 8.0 0.296 0.987
0.400 39.0

These results seem to be in accordance wi th those publ i shed by Cockbain6

who examined adsorption of sodium dodecyl sulphate in decane-water
emulsion by means of t i.t rat ion, Direct comparison of the values of r e and
r i is rather difficult since emuls i on interface area is undefined. Yet,
one can say that, on the one hand, emulsifier wi th less EO un i ts adsorbs
more efficiently to the interface an effect which appears in both emulsions
and separated o i L'water systems. For example, for system consisting of
2
nonyl phenol "ith 6 EO units 4.3'10. 10 mole/on are adsorbed to solution-air
interface, 2.2.10- 10 mole/on 2 are adsorbed to solution-oil interface and 98~
out of O. OS gr are adsorbed in an emulsion of 20 ml oil in 80 ml water ,
Using nonyl phenol wi th 15 EO units 2.6'10- 10 mole/cm2 are adsorbed to
air-solution interface, 1.8'10- 10 mole/on 2 are adsorbed to ,oil-solution
interface and 96% out of 0.05 gr are adsorbed in an emulsion of 20 ml oil in
80 ml "ater. On the other hand, observation of interfacial tension values
shows that values wh ich are obtained directly (yi) are much lower than those
estimated on a droplet in emulsion. It also seems that the change of
interfacial tension values wi th number of EO units in the emulsifier are
in opposite direction. For example, using 0.05% solution of nonyl phenol
wi th 6 EO units a value of 3 dyn/cm was obtained directly and a value of 15.3
dy~/on "as obtained indirectly. Using 0.05% of nonyl phenol "ith 15 EO units
in solution, a value of 6 dyn/cm "as obtained directly and a value of 12 dyn/cm
was der ived indirectly.

In order to varify the as simpt ion that all the emulsifier missing in the
solution is adsorbed in the emulsion, emulsion with various oil volume
fractions and constant emulsifier weight "ere prepared and measured. The
 ADSORPTION AND INTERFACIAL TENSION IN EMULSION IS7

TABLE 9

Surface tension (y ). interfacial tension (y. ) and

adsorption (r ) e i n o/w emulsions prepared'$ith
paraffinic oileand ethoxylated nonyl phenol with
15 EO Units (W = 0.200 gr, 20°C)

~ Ye(dyn/on] yie(dyn/an) fe(gr) r /W(gr/gr)

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0.05 3S 8.6 0.197 0.983

0.10 36 9.3 0.197 0.985
0.15 37 9.9 0.198 0.988
0.20 38 10.5 0.198 0.990

results are given in Table 9 and they clearly rule out the pcssibility of
being dependent on a solubility factor.
In addition, adsorption values were found to correlate linearly
\..i th l-il...B values of the emulsifiers.
For the air-solution system it was
found that HLB 21.l7-2.4·10 10'f and for the oil-solution system it was
found that HLB 35.52-ll.3'10 10'f i. This phenomenon may indicate dependence
of HLB values on adsorption.

CO:-<CLUSION
The data obtained can be summarized in the following way:
(a) Changes in adsorption in separated and emulsified oil-water systems
bear a significant resemblance.
(b) There is a certain possibility that HLB values depend on adsorption
values.

(c) Changes of interfacial tension values in separateJ and errulsified

oil-water systems do not resemble. As a matter of fact they change
in opposite directions.
Therefore, it can be concluded that the use of interfaci.l tension data
as means for estUnating emulsion stability is incorrect. Int~rfacial tension
reduction is only one of a few changes in the interface caused by the
emulsifier when adsorbed. It would be more adequate to say that adsorption
of emulsifier to the interface causes heterogenity of 'some kiod which results
in emulsion stability. It is adsorption rather than interfacial tension
 158 GARTI AND KATZ

hTIich should be studied more thoroughly in order to obtain a fundamental

tool for estimating emulsion stability.

REFERENCES

1. A.W. Adamson, "Physical Chemi st ry of Surfaces", 3rd ed., Wiley,

New York, 1967, P. 493.
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2. Yasukat su Tama i , in "Colloid and Interface Science", Vol. II,

M. Kerker, ed., Academic Press Inc., New York, 1976, P. 257.

3. L. Hsiao, H.N. Dunning and P.B. Lorenz, J. Phys. Chem., 60,

657 (1956).

4. H. Lange, Proc. Intern. Congr. Surface Activity, 3rd, Cologne,

!.'279 (1960).

S. P. Becher, in "Nonionic Surfactants", M.J. Shick, ed . , Marcell

Dekker, Inc., New York, 1966, P. 478.

6. E.G. Cockbain, Trans. Faraday Soc., 50,874 (1954).

October 14, 1984