Journal of Colloid and Interface Science 227, 1–6 (2000)
doi:10.1006/jcis.2000.6810, available online at http://www.idealibrary.com on
Surface Pressure, Hysteresis, Interfacial Tension, and CMC of Four
Sorbitan Monoesters at Water–Air, Water–Hexane,
and Hexane–Air Interfaces
Leena Johanna Peltonen1 and Jouko Yliruusi
Department of Pharmacy, Pharmaceutical Technology Division, University of Helsinki, Helsinki FIN-00014, Finland
Received March 2, 1999; accepted March 6, 2000
The purpose of this study was to investigate the interfacial prop-
erties of sorbitan monoesters (Span 20, 40, 60, and 80). The sur-
face pressure was investigated at the water–air interface using a
Langmuir–Blodgett apparatus. Interfacial tensions at n-hexane–
air and water–n–hexane interfaces were measured by a du Nouy
tensiometer. The effects of different surface-active agents and their
concentrations on the interfacial properties of surfactant films were
determined. With saturated sorbitan monoesters the lengthening of
the hydrocarbon chain increases the collapse pressure and molecu-
lar area at the water–air interface. Unsaturated Span 80 had a lower
collapse pressure and a larger molecular area than its saturated
counterpart Span 60. Under compression–expansion cycles, all sor-
bitan monoesters showed hysteresis effects. At the n-hexane–air in-
terface there were no differences in the interfacial tension between
different sorbitan monoesters. At the water–n-hexane interface, dif-
ferences in CMCs were small, but the surface excess of Span 80 was
markedly smaller and the molecular area larger than the corre-
sponding values of other sorbitan monoesters. °C 2000 Academic Press
Key Words: interfacial tension; surface pressure; CMC; liquid–
liquid interface; n-hexane; sorbitan monoesters.
INTRODUCTION
Despite the wide use of sorbitan esters, rather few studies have
been conducted on their interfacial tension and surface pressure.
Interfacial film strength is an important contributor to emulsion
stability, and there are some articles on the evaluation of emul-
sion stability by surface tension measurements (1, 2). To our
knowledge, all the studies of sorbitan esters concern only a few
members of the sorbitan ester family. Span 20, sorbitan mono-
laurate (3–6), and Span 80, sorbitan monooleate (4–10), are the
most widely used, but also Span 40, sorbitan monopalmitate
(7), and Span 83, sorbitan sesquioleate, or Span 85, sorbitan tri-
oleate, have been used a few times (5–7). There is no article on
systematic research on the surface and interfacial properties of
sorbitan esters.
1 To whom correspondence should be addressed at the Department of
Pharmacy, Pharmaceutical Technology Division University of Helsinki, P.O.
Box 56 (Viikinkaari 5), FIN-00014 University of Helsinki, Finland. E-mail:
leena.peltonen@helsinki.fi.
1 0021-9797/00 $35.00
In this study, the behavior of sorbitol surfactants with differ-
ent alkyl chain lengths or structures was analyzed. Four sorbitan
monoesters (Span 20, Span 40, Span 60, sorbitan monostearate,
and Span 80) which differ from each other by the length (Span
20, 40, and 60) or the structure (Span 60 and 80) of the hydrocar-
bon chain were tested. Dynamic surface pressure and hysteresis
of the spread films of sorbitol surfactants were measured at the
water–air interface by the Langmuir–Blodgett technique. CMCs
of the surface-active agents in the water–n-hexane system were
determined with the aid of interfacial tension measurements us-
ing a du Nouy tensiometer. Also interfacial tensions of surface-
active agents in n-hexane against air were measured.
MATERIALS AND METHODS
Materials
All chemicals were used as received. The surface-active
agents Span 20, Span 40, Span 60, and Span 80 were all pur-
chased from Fluka Chemie AG, Switzerland. Some physical
properties of sorbitan monoesters are summarized in Table 1.
The structure of sorbitan monoesters is presented in Fig. 1.
Hexane (purity ≥99%, Fluka Chemie AG, Switzerland) was
used as a spreading agent in surface pressure measurements and
also as the oil phase in oil–air and water–oil measurements. The
water used was ultrapure Millipore water.
Surface Pressure
The surface pressure was measured by a computer-
controlled Langmuir–Blodgett instrument (KSV Minitrough,
KSV, Finland; Fig. 2). The measurement itself was made by the
Wilhelmy plate method, placing the plate partly under the sur-
face of the subphase and recording the force with which the plate
was pulled downward by the surface film. This force was mea-
sured using electrobalance. By adjusting movable barriers, the
area available to the film could be modified. When the film area
diminished molecules lying flat on the liquid surface were forced
into more vertical positions where they required less space. The
ease of compressing the film and the area per molecule at a given
pressure represent how readily a molecule tolerates the presence
of its neighbors.
Copyright °C 2000 by Academic Press
All rights of reproduction in any form reserved.
2 PELTONEN AND YLIRUUSI

TABLE 1
Some Physical Parameters of Sorbitan Monoesters

Span 20 Span 40 Span 60 Span 80

HLB 8.6 6.7 4.7 4.3

Mw (g/mol) 346 403 431 429
δo (cal/cm3 )1/2 13.52 12.58 11.59 11.38
Cw /Co 85 0.43 1.7 × 10−3 5.5 × 10−4

Note. (All values are from the literature): HLB (hydrophilic–lipophilic

FIG. 1. The structure of sorbitan monoesters. R is –OOC(C11 H23 ) for
Span 20, –OOC(C15 H31 ) for Span 40, –OOC(C17 H35 ) for Span 60, and
–OOC(C17 H33 ) for Span 80 (12).
The trough was made out of a solid piece of PTFE and the
barriers of hydrophilic material, Delrin, which ensured that the
film did not go under the barrier. The barrier position was con-
trolled by a servo-controlled DC motor. The motor moved the
barrier holder using a tooth belt. The position of the barrier was
measured using an optical encoder. The trough was glued to an
aluminum base plate, in which there were water channels for
thermostation of the subphase. Thermostation was performed
using a circulator connected to the trough.
Before each measurement, the trough and the barriers were
washed with pure ethanol and rinsed carefully with ultrapure
Millipore water. This washing and rinsing was done twice. Also
all the glassware used was cleaned twice with ethanol and then
rinsed several times with Millipore water before use. The barriers
were moved to the ends of the trough manually, and the trough
was filled with Millipore water (45 ml). The barriers were driven
manually to the center, and the water surface between the bar-
riers was cleaned with a suction pipette. After that the barriers
were driven to the starting position and the Wilhelmy plate was
settled so that one-third of the plate was under the water surface.
In that position the surface pressure value was zeroed and the
balance, from Ref. 12), Mw (molecular weight, 11), δo (solubility parameter,
13, 14), Cw /Co (water–oil partition coefficient, 13, 14).
film was deposited. As a control test, a blank compression with-
out a film was measured. During this measurement, which took
50 min, the pressure developed did not exceed 0.15 mN/m. The
dynamic values were measured continuously for at least 50 min
without disturbing the interface. The hysteresis measurements
took approximately 9 h.
An ethanol–hexane mixture (1 : 9 v/v) in which surface-active
agents were dissolved was used as a spreading solution. This
spreading solution (20 to 50 µl) was then deposited on the water–
air interface. The measurement was started 10 min later to en-
sure that all the ethanol–hexane solvent had vaporized from the
surface. In order to ensure that 10 min waiting time was long
enough, a control test was run out: without starting the measure-
ment the differences in surface pressure were monitored for 2 h
after the film was deposited on the water–air interface. All the
measurements were run five times and the results were calcu-
lated as the mean of these five different measurements. With all
the sorbitan monoesters the standard deviation in surface pres-
sure measurements was less than 0.5 mN/m.
The dimensions of the trough were such that the total surface
area of 6930 mm2 (231 × 30 mm) was available for compres-
sion. The measurement rate (rate of the barriers) was 2 mm/min
(=2 mm2 /s).

FIG. 2. The block diagram of the Langmuir–Blodgett surface balance measurement station. The Wilhelmy plate is connected to the microelectronic feedback
system for surface pressure control. The force was measured using the electrobalance, but there is also a microelectronic feedback system for surface pressure
control (modified from Ref. 15).
 INTERFACIAL PROPERTIES OF SORBITAN ESTERS
Before the film balance work with the chosen surface-active
agents the technique was checked against a pressure–area
isotherm found in the literature: stearic acid (16). Occasionally
throughout this work, the validity of the technique was checked
with this standard. The complete spreading of film-forming ma-
terial was ensured by changing the spreading solution (chloro-
form, hexane, hexane–ethanol (9 : 1)) and the depositing method
of the film onto the water surface. All these above-mentioned
measurements were reproducible, which is believed to prove that
the film-forming material was spread completely on the water
surface.
Interfacial Tension
The interfacial tension was measured with a du Nouy ten-
siometer (KSV Sigma 70, KSV, Finland) with a platinum ring.
The interfacial tension was calculated from the maximum force
needed to separate the ring from the interface.
Several dilutions of each surface-active agent were made in
hexane. For the interfacial tension measurements, 10 ml of each
dilution was needed. The interfacial tension of surface-active
agent in hexane against air was measured first. Five measure-
ments were made at 5-min intervals from the same sample and
means and standard deviations were calculated.
Second, the interfacial tension between hexane and water was
measured with the surface-active agents dissolved in the hexane
phase. Water was settled as a lower phase, and the surface-active
agent–hexane solution was gently poured onto the water phase.
The system was not stirred to avoid emulsification. The phases
were allowed to stabilize for 30 min before the measurement (the
surface-active agent in the hexane phase). Again, five different
measurements were carried out at 30-min intervals in order to
ensure a sufficently long stabilization time. Thirty minutes of
stabilization was determined by measuring the interfacial ten-
sion as a function of the age of the interface until a constant
value was reached.
From the results of the interfacial tension measurements
CMCs were extrapolated. The instrument was calibrated against
Millipore water. All the surface pressure and interfacial tension
measurements were taken at room temperature (22.0 ± 0.5◦ C).
RESULTS
Water–Air Interface
The shapes of the curve of the dynamic surface pressure of
sorbitan monoesters (Fig. 3) at the water–air interface are sim-
ilar to those of alkyldimethylphosphine oxides (also nonionic
surface-active agents (17)). The collapse pressure of saturated
sorbitan monoesters is lowered by shortening the hydrocarbon
chain. This lowering is more obvious between 12 (Span 20) and
16 (Span 40) carbon atoms than between 16 and 18 (Span 60)
carbon atoms. Also the collapse pressure is more determinable
with Span 40 and 60, while with Span 20 and 80 the collapse
point is not so clear.
3
FIG. 3. The surface pressure–molecular area curves of sorbitan monoesters
(T = 295 K).
The shape of the Span 40 and 60 curves is also steeper, which
implies that these molecules tolerate compression better and are
more readily associated with each other than Span 20 and 80.
The increase in surface pressure with increasing alkyl chain
length indicates that the compounds derive the surface activity
primarily from the alkyl group. In a monolayer, sorbitan mo-
noester molecules are oriented so that each hydrocarbon chain
lies on the oil side of the interface and each sorbitan ring lies
on the aqueous phase (6). The significant increment in collapse
pressure between Span 20 and Span 40 suggests that lengthen-
ing of the hydrocarbon chain from 12 to 16 carbon atoms dom-
inates the molecular properties in this region. It was observed
earlier that emulsifier molecules cannot be associated readily
unless the hydrocarbon chains contain at least 8 carbon atoms
(6). With 12 carbon atoms (Span 20) the polarity, caused by the
shorter fatty acid chain length, has been reported to result in
aqueous phase solubilization, which apparently hinders interfa-
cial molecular interactions (5). Diethanolamine derivatives, also
nonionic surface-active agents, have been noticed to behave as
sorbitan monoesters: the longer the alkyl chain, the higher the
collapse pressure observed and the larger the molecular area
(18).
In comparisons of surface pressure–molecular area curves of
Span 60 (saturated) and 80 (unsaturated), the molecular area
of Span 80 is larger than that of Span 60. With Span 80 there
is a discontinuity point at approximately 33 Å2 and 23 mN/m.
Surface areas above this discontinuity point are larger with Span
80 than with Span 60. When stearic and oleic acids are compared
(Span 60 is a sorbitan ester of stearic acid and Span 80 a sorbitan
ester of oleic acid), the surface pressure–molecular area curves
behave in the same way, the molecular area of stearic acid being
smaller at the same surface pressure compared to that of oleic
acid (19).
When measurements are made after 4 h of stabilization instead
of 10 min, the discontinuity point is more obvious with Span 20
and 80 (Fig. 4), though the shift to the left is not so dramatic
with Span 20. With Span 80 the discontinuity point after 4 h
4 PELTONEN AND YLIRUUSI
FIG. 4. The surface pressure–molecular area curves of sorbitan monoesters,
the effect of waiting time before starting the measurement: the dashed line is 4 h
before measurement and the solid line is 10 min before measurement.
of stabilization is approximately 23 Å2 and 30 mN/m. It was
noticed earlier that Span 80 has a tendency to form a stronger
film given sufficient time (4). With Span 40 and 60 a small shift
to the left can also be seen, but the shape of the curve is similar
(Fig. 4).
Hysteresis
All the sorbitan monoesters showed hysteresis effects when
the monolayers were subjected to compression–expansion
cycles (Figs. 5–8). Between each following compression–
expansion cycle there was a shift to the left. This means that
material is lost from the surface during compression. However,
that material is not respread on the surface during the expansion.
This loss of material is probably due to the fact that sorbitan mo-
noesters, though practically insoluble in water, are dispersible
in the water phase during the compression process (20).
In the beginning of the expansion the surface pressure falls
strongly with all sorbitan monoesters, with Span 20 close to
0 mN/m. The collapse pressure of Span 40 and 60 and the dis-
FIG. 5. The hysteresis of Span 20: the numerals are the numbers of the
compression–expansion cycle.
FIG. 6. The hysteresis of Span 40: the numerals are the numbers of the
compression–expansion cycle.
continuity point of Span 20 did not fall as the hysteresis ad-
vanced. With Span 80 the shape of the curve changed, and the
drop of the surface pressure was more obvious as the hystere-
sis advanced. This is partly caused by the great excess of Span
80 which was injected to the interface in order to have hys-
teresis in the same molecular area as all the other sorbitan mo-
noesters. That caused the surface pressure during the first com-
pression to be consistently above the discontinuity point (Figs. 3
and 8).
One reason for the strong drop in surface pressure in the be-
ginning of expansion may be the molecular orientation, e.g.,
flipping of hydrocarbon tails from a horizontal to a vertical po-
sition. Relaxation may also be partly due to the redistribution
of unequally distributed molecules resulting from the disturbing
effects of compression (21).
The area of hysteresis decreased markedly between the
successive compression curves, the difference between the first
and the second cycle being the greatest. Similar behavior was
reported previously with dipalmitoyl lecithin (22) and stearic
acid (21).
FIG. 7. The hysteresis of Span 60: the numerals are the numbers of the
compression–expansion cycle.
 INTERFACIAL PROPERTIES OF SORBITAN ESTERS
FIG. 8. The hysteresis of Span 80: the numerals are the numbers of the
compression–expansion cycle.
Oil–Air Interface
All the sorbitan monoesters were soluble in n-hexane, by
slight warming for Span 40 and Span 60, and CMC could not
been determined. Sorbitan monoesters, too, have no effect on
the interfacial tension of n-hexane against air. Similar behavior
was noticed in earlier studies with mineral oil (5). The surface
tension of mineral oil against air did not change after the addi-
tion of the Spans. This phenomenon has been explained by the
fact that in the absence of a hydrophilic phase there is no driving
force for interfacial adsorption and multilayer formation.
Water–Oil Interface
From the results of the interfacial tension measurements at
the water–n-hexane interface (Fig. 9), the surface excess, 0,
was calculated by means of the Gibbs’ adsorption isotherm
1 dγ
0=− × , [1]
RT d ln c
FIG. 9. The effect of concentration of sorbitan monoesters on interfacial
tension at water–n-hexane interface. The error bars are within the symbols.
5
TABLE 2
Molecular Area of Sorbitan Monoesters
Span 20 Span 40 Span 60 Span 80
a
A (A2 ) 40 37 38 46
where R is the gas constant, T absolute temperature, γ interfacial
tension, and c concentration. From the surface excess, the area
per molecule, A, just below the CMC was calculated according
to
1
A= , [2]
0N
where N is Avogadro’s number. The molecular area values are
summarized in Table 2.
Table 2 shows that Span 40 had the smallest molecular
area though the differences between saturated sorbitan mo-
noesters were small. Unsaturated Span 80 shows a larger area
per molecule.
Generally it has been noticed that for a homologous series
of nonionic surfactants the increase in the hydrophobic chain
length increases the apparent CMC at the oil–water interface (4).
However, with our surface-active agents the differences in CMC
were quite small (all the CMCs approximately 0.0070 mg/ml);
in all our research, especially those between 16 and 18 saturated
carbon atoms seemed to be not so dominant. The reason for this
may be the small difference in the hydrophobic chain length,
only two carbon atoms, between these two surface-active agents.
CONCLUSIONS
Interfacial tension and surface pressure techniques can be used
to determine the interactions in the presence and the absence
of different surface-active agents (23–38). These measurements
have appeared to be useful, for example, in preformulation stud-
ies on emulsifier films: the stronger the interfacial film, the more
stable the resultant emulsion.
In this study, the effect of the concentration of various sur-
factants (Span 20, 40, 60, and 80) on the interfacial proper-
ties of surfactant films were determined. With saturated sorbitan
monoesters the lengthening of the hydrocarbon chain increases
the collapse pressure and molecular area at the water–air inter-
face, but unsaturation of the hydrocarbon chain lowers the col-
lapse pressure and increases the molecular area. All the sorbitan
monoesters used showed hysteresis effects under compression–
expansion cycles. With these sorbitan monoesters, unsaturation
of the hydrocarbon chain seemed to be more dominant in deter-
mining the interfacial properties at the water–n-hexane interface
than in determining the hydrocarbon chain length. The differ-
ences between the saturated 16 and 18 carbon atoms in the chain
were especially small.
Some interfacial properties of sorbitan monoesters were
highlighted, but in this area of research there are still many
6 PELTONEN AND YLIRUUSI
phenomena that are not understood or explained as yet. Work
currently under way in our laboratory aims at further clarifying
these properties of sorbitan ester-type surfactant systems.
REFERENCES
1. Ishii, F., Takamura, A., and Ogata, H., J. Pharm. Pharmacol. 40, 89 (1988).
2. Takamura, A., Ishii, F., Noro, S., Tanifuji, M., and Nakajima, S., J. Pharm.
Sci. 73, 91 (1984).
3. Phares, R. E., Jr., J. Pharm. Sci. 54, 408 (1965).
4. Wan, L. S. C., and Lee, P. F. S., Can. J. Pharm. Sci. 8, 136 (1973).
5. Opawale, F. O., and Burgess, D. J., J. Colloid Interface Sci. 197, 142 (1998).
6. Boyd, J., Parkinson, C., and Sherman, P., J. Colloid Interface Sci. 41, 359
(1972).
7. Rabiskova, M., Song, J., Opawale, F. O., and Burgess, D. J., J. Pharm.
Pharmacol. 46, 631 (1994).
8. Kawashima, Y., Hino, T., Takeuchi, H., and Niwa, T., Chem. Pharm. Bull.
40, 1240 (1992).
9. Campanelli, J. R., and Wang, X., J. Colloid Interface Sci. 190, 491 (1997).
10. Criddle, D. W., and Meader, A. L., Jr., J. Appl. Phys. 26, 838 (1955).
11. Budavari, S., O’Neil, M. J., Smith, A., Heckelman, P. E., and Kinneary, J. F.
(Eds.), “The Merck Index,” 12th ed. p. 1490, Merck, Whitehouse Station,
NJ, 1996.
12. Florence, A. T., and Attwood, D., “Physicochemical Principles of Phar-
macy,” 3rd ed. Macmillan Press Ltd., Easton, Bristol, 1998.
13. Davies, J. T., and Rideal, E. K., “Interfacial Phenomena,” Academic Press,
New York, NY, 1961.
14. Schott, H., J. Pharm. Sci. 84, 1215 (1995).
15. “KSV Minitrough Instruction Manual,” Finland, 1993.
16. Cook, H. D., and Ries, H. E., Jr., J. Phys. Chem. 60, 1533 (1956).
17. Ferrari, M., Liggieri, L., Ravera, F., Amodio, C., and Miller, R., J. Colloid
Interface Sci. 186, 40 (1997).
18. Ghaicha, L., Leblanc, R. M., and Chattopadhyay, A. K., J. Phys. Chem. 96,
10948 (1992).
19. Feher, A. I., Collins, F. D., and Healy, T. W., Aust. J. Chem. 30, 511
(1977).
20. Reynolds, J. E. F. (Ed.), “Martindale, The Extra Pharmacopoeia” 30th ed.
p. 1032, Pharmaceutical Press, London, 1993.
21. Munden, J. W., Blois, D. W, and Swarbrick, J., J. Pharm. Sci. 58, 1308
(1969).
22. Galdston, M., and Shah, D. O., Biochim. Biophys. Acta 137, 255 (1967).
23. Dahanayake, M., Cohen, A. W., and Rosen, M. J., J. Phys. Chem. 90, 2413
(1986).
24. Rosen, M. J., Cohen, A. W., Dahanayake, M., and Hua, X.-Y., J. Phys.
Chem. 86, 541 (1982).
25. Nagarajan, R., and Wasan, D. T., J. Colloid Interface Sci. 159, 164 (1993).
26. Liggieri, L., Ravera, F., and Passerone, A., J. Colloid Interface Sci. 169,
238 (1995).
27. Göbel, J. G., and Joppien, G. R., J. Colloid Interface Sci. 191, 30 (1997).
28. Schott, H., J. Pharm. Sci. 58, 1521 (1969).
29. Corkill, J. M., Goodman, J. F., and Ottewill, R. H., Trans. Faraday Soc. 57,
1627 (1961).
30. Corkill, J. M., Goodman, J. F., and Harrold, S. P., Trans. Faraday Soc. 60,
202 (1964).
31. Silvestri, S., Ganguly, N., and Tabibi, E., Pharm. Res. 9, 1347 (1992).
32. Yamaguchi, T., Nishizaki, K., Itai S., Hayashi, H., and Ohshima, H., Pharm.
Res. 12, 1273 (1995).
33. Varadaraj, R., Bock, J., Valint, P., Jr., Zushma, S., and Thomas, R., J. Phys.
Chem. 95, 1671 (1991).
34. Elworthy, P. H., and Florence, A. T., J. Pharm. Pharmacol. 21, 72 (1969).
35. Elworthy, P. H., and Mysels, K. J., J. Colloid Interface Sci. 21, 331 (1966).
36. Yoon, K. A., and Burgess, D. J., Pharm. Res. 13, 433 (1996).
37. Yoon, K. A., and Burgess, D. J., J. Pharm. Pharmacol. 49, 478 (1997).
38. Mollet, C., Touhami, Y., and Hornof, V., J. Colloid Interface Sci. 178, 523
(1996).