The Relationship of Structure to Properties in Surfactantsl

MILTON J. ROSEN, Department of Chemistry, Brooklyn College,

City University of New York, Brooklyn, New York 11210

ABSTRACT be obtained by an examination of their molecular structure.

Changes in the various structural units present in The characteristic structural feature of surface-active
surfactants strongly affect the interracial properties agents is a molecular structure containing a group which has
shown by these materials. Such properties as surface a strong attraction for the solvent (called the lyophilic
tension reduction, micelle formation, wetting, foam- group) together with a group which has very little attrac-
ing and defoaming, detergency, and dispersion of tion for the solvent (the lyophobic group). When used in
solids all show marked changes with variations in water the terms are hydrophilic and hydrophobic, respec-
both the hydrophilic and hydrophobic portions of tively. The hydrophobic group is usually a long chain
the surfactant molecule, reflecting the processes hydrocarbon residue, occasionally an halogenated or oxy-
occurring on a molecular level. Changes in these genated hydrocarbon residue; the hydrophilic group is an
properties caused by such factors as the length and ionic or highly polar group. Molecules containing both
nature of the hydrophobic group, branching or Iyophilic and lyophobic groupings are called amphipathic
unsaturation in the hydrophobic group, the nature of molecules; a surfactant, therefore, is an amphipathic mole-
the hydrophilic group and its position in the mole- cule. When an amphipathic molecule is dissolved in water,
cule, and the presence or absence of an ionic charge its hydrophobic group distorts the water structure in such
are described and explained in terms of the molecular fashion as to decrease the entropy of the system, with the
processes involved. result that some of the molecules are expelled from the
bulk of the solvent and are adsorbed at the interfaces
surrounding the solution; the hydrophilic group, however,
INTRODUCTION AND DEFINITION OF TERMS keeps them in solution and prevents them from separating
A surface-active agent is a substance which, when out as another phase. In addition their amphipathic nature
present at low concentration in a system, has the property causes the molecules adsorbed at the interfaces to be
of adsorbing onto the surfaces or interfaces of the system oriented, usually with the hydrophilic portions turned
and of altering to a marked degree the surface or interfacial towards' the water and the hydrophobic portions oriented
free energies of those surfaces (or interfaces). The term away from the water. This orientation is a very important
"interfaces" indicates a boundary between any two immis- factor in determining the change in the properties of the
cible phases; the term "surface" denotes an interface where interface produced by the surfactant upon adsorption
one phase is a gas, usually air. there. The properties of an interface with adsorbed mole-
The interfacial free energy is the minimum amount of cules may vary greatly, depending upon the particular
work required to create that interface. The interfacial free orientation of these molecules with respect to it.
energy per unit area is what we measure when we determine As in all molecules, changes in the structural character-
the interfacial tension between two phases. It is the istics of the various groupings in the amphipathic molecule
minimum amount of work required to create unit area of (in this case the hydrophilic and hydrophobic portions),
the interface or to expand it by unit area. When we measure particularly their relative size, shape, and position with
the surface tension of a liquid, we are measuring the respect to each other, result in changes in the properties of
interfacial free energy per unit area of the boundary the molecule. This discussion will be confined to the effect
between the liquid and the air above it. When we expand an of structural changes on certain interfacial phenomena in
interface, therefore, the minimum work required to create aqueous media-surface tension reduction, wetting, foaming
the additional amount of that interface is the product of and defoaming, detergency, and dispersion of solids.
the interfacial tension times the increase in area of the
interface; Wmin = "/I x A. A surface-active agent, therefore, SURFACE TENSION
is a substance which, at low concentrations, wilt adsorb at REDUCTION IN AQUEOUS MEDIA
some o1" all of the interfaces in the system and significantly
change the amount of work required to expand those Surface tension reduction in aqueous media depends
interfaces. A common example of the action of a surface- upon the replacement of water molecules at the surface by
active agent is the lowering of the surface tension of water surface-active molecules from the interior of the solution;
when a detergent is added to it. In this case the detergent the adsorption at the surface of surfactant molecules results
molecules are adsorbed at the liquid-air interface and in a lowering of the surface tension of the water. For our
purposes it is necessary to distinguish between the effi-
reduce the work required to expand that surface.
ciency of a surfactant, measured by the concentration of
Since in many processes surfaces or interfaces are
surfactant required to produce some significant reduction
expanded greatly, sometimes by many orders of magnitude,
in the surface tension of the water, and its effectiveness,
i.e., in wetting, emulsification, foaming or in the dispersion
of solids, the presence of a surface-active agent which can
reduce the amount of work needed to expand the appropri-
ate interface in these systems greatly facilitates the process. Am m / v v V V ' g V b
GENERAL STRUCTURES AND
MECHANISM OF ACTION
An understanding of why surface-active agents have the
property of being adsorbed at interfaces, and how they
accomplish this lowering of the interfacial free energy, can

I presented at the AOCS Short Course, "Update on Detergents

and Raw Materials," Lake Placid, New York, June 1971. FIG. 1. A. Efficient ~ reducer. B. Effective 3' reducer.

293
294 3OURNAL OF THE AMERICANOIL CHEMISTS~SOCIETY VOL. 49

65f . . . . . . . . . . . . I ..... "I ............. I ! ............... i ......... .__

@SO3Na
6o

55
._0
¢B
50

O
, k,
,- 45

C16
40
C~
35 l. . . . . . . . I., I . . . . . . C v¢

1.0 2.0 3,0 4.0 5.0

Concentration [10-3 Mol / I ]
YIG. 2. Surface tension of aqueous solutions o[ sodium p-(n-alkyl)benzenesutfonates at "/5 C as a function of their concentration.

measured by the minimum value to which it can lower the The lower efficiency of ionic surfactatnts compared to
surface tension, since these two often run counter to each nonionics can be explained in similar fashion. Since the
other. surfactant molecules are adsorbed at the surface in oriented
Efficiency increases with increase in the length of the fashion, there is greater repulsion between the similarly
hydrophobic portion; effectiveness usually decreases (1,2). charged ionic heads there than when the molecules are
Efficiency decreases with increased branching or unsatura- dissolved in random fashion in the bulk phase. The presence
tion of the hydrophobic portion and with movement of the of an ionic hydrophilic group therefore increases the free
hydrophilic group from a terminal to an increasingly central energy of the molecule at the surface relative to that in the
position in the hydrophobic chain; effectiveness increases interior with a consequent decrease in the proportion of
with these changes (2). Therefore a surfactant with a long, molecules at the surface.
straight hydrophobic group and with a terminally located On the other hand the effectiveness of a surfactant-the
hydrophilic group will lower the surface tension of water minimum value to which it can depress surface tension of
more efficiently, but much less effectively, than a shorter the water--depends to a large extent upon the cohesiveness
chain homolog, or one with a branched chain, or one with a of the hydrophobic groups in the surface-active molecules.
centrally located hydrophilic group (Fig. 1). The lower their cohesiveness, the lower the attainable
Efficiency is also decreased by electrostatic repulsion surface tension. The minimum value to which a surfactant
between ionized hydrophilic groups, with the result that can depress the surface tension of water appears to
ionic surfactants are usually much less efficient than approach that of the parent hydrophobe (4). Since
nonionics, although not necessarily more effective. When branched chain hydrocarbons have lower cohesive forces
counterqons are strongly associated with the surfactant than straight chain hydrocarbons with the same number of
ions, however, especially where the couter-ion is itself a carbons, surfactants having branched chain hydrophobic
surface-active ion, efficiency is greatly improved (3). groups can reduce the surface tension of water to lower
The explanation for all these effects is that efficiency is values than their straight chain analogs. For the same reason
a reflection of the concentration of surfactant at the surfaetants with dimethylsilicone hydrophobic groups can
surface relatNe to that in the bulk of the solution, and tNs depress the surface tension of water to lower values than
is determined by the free energy change involved in the those with hydrocarbon chains and those with fluorocarbon
transfer of a surfactant molecule from the interior to lhe chains can depress it to even lower values.
surface, Since for each additional carbon atom in the The effectiveness of a particular surfactant in reducing
hydrophobic chain of the dfssolved surfactant there is a the surface tension of water depends also upon another
corresponding decrease in the entropy of the molecule, and phenomenon characteristic of amphipathic molecules in
thus an increase in its free energy in the bulk phase relative aqueous solu tion-micellization.
to that at the surface, the proportion of molecules of Surface-active agents, when dissolved in water at very
surfactant at the surface, and hence its efficiency, increases low concentrations, are present as individual molecules.
with increased length of the hydrophobic chain. Branching However as the amount of surface-active agent in solution is
of the hydrocarbon chain, on the other hand, or positioning increased, a critical concentration is reached, the value of
of the hydrophilic group in a more central location in the which is dependent upon the structure of the surfactant, at
molecule, reduces the effective length of the chain and its which point an increase in the am~3unt of dissolved
entropic effect in solution with a consequent decrease in its surfactant causes no significant increase in the amount of
efficiency. molecularly dispersed material. Instead the additional mate-
MAY, 1972 ROSEN: SURFACTANT STRUCTURE AND PROPERTIES 295

2 ....
! ..........
| ......... " | ' ~" ' ' ' ' I ................

60

55

5O
tj
¢#
45 - CH--~SO3Na
I
C
= 40
O
,Na
e-

~" 3 5
¢J
¢0
--CH-CH-CH-CH--@~3Na
.._A I t I

= 30
o~
I
25 . . . . . . i ....... i. i I ........... I __

1.0 2.0 3.0 4.0 5.0

Concentration [10-3Mol/I]
FIG. 3. Surface tension of aqueous solutions of sodium p-dodecylbenzenesulfonates at 75 C as a function of thei~ concentration.

riat dissolves to form a polymeric form of the surfactant number of carbon atoms; and (f) ionized hydrophilic group.
known as a micelle. This concentration is known as the These are all structural factors which prevent the close
cntical concentration for micelle formation (cmc). Micelli- packing o f hydrophobic groups.
zation provides a mechanism alternative to expulsion to the The decreased effectiveness of longer chain surfactants
interfaces for removing hydrophobic groups from contact in reducing the surface tension of water, compared to
with water molecules and thereby reducing the free energy shorter chain or branched chain homologs, is therefore a
of the system. reflection of the increased micellization tendency of the
Since the amount of molecularly dispersed surfactant former. Figure 2 illustrates this and, in addition, the
does n o t increase significantly above the cmc, those increase in efficiency with increased chain length. Figure 3
interfacial properties which depend upon molecularly dis- illustrates the greater efficiency of a straight chain (C 12)
persed surfactant reach their ultimate value and do not surfactant over isomeric branched chain surfactants at low
change significantly above the cmc. On the other hand, concentrations and its lower effectiveness compared to the
since miceiles appear in significant numbers only at the latter.
cmc, those properties which depend upon the presence of
micelles in the solution first become significant at the cmc. WETTING
Since reduction in surface tension depends upon the Good wetting agents characteristically have either a
presence at the surface of molecularly dispersed molecules, branched chain structure with a centrally located hydro-
this property shows no significant change once micelliza- philic group or a shorter chain hydrophobic group with a
tion starts. Since the miceltes compete ,,vith the interfaces terminally located hydrophitic group (Fig. 4).
for the surfactant molecules, structural factors in surfactant Wetting depends upon effective reduction of the surface
molecules which cause miceltization before the interfacial tension under dynamic conditions, i.e., as the wetting liquid
properties have reached their maximum possible values will spreads over the substrate, the surface-active molecules
prevent those maximum values f r o m b e i n g attained, i.e.,
decrease the effectiveness of the molecule. On the other
hand structural factors which inhibit micellization will
increase the probability of interfacial properties reaching
their maximum potential values and increase the effective-
ness of the molecule.
Some of the structural factors which inhibit micelliza-
tion (increase the cmc) are: (a) Decrease in the overall
length of the hydrophobic group; (b) branching in the
hydrophobic group; (c) unsaturation in the hydrophobic
group; (d) moving the hydrophilic group towards the center
of the hydrophobic group; (e) substitution of two short
A/X/X/Vb
hydrophobic groups for one long one with the same FIG, 4, Wetting agents.
296 JOURNAL OF THE AMERICANOIL CHEMISTS' SOCIETY VOL. 49

c,
/vvvvvx
FIG. 6. Foaming agent.
restoring force restoring force

A/x/XA/X/X/X/X
C s, s ~2>~ FIG. 7. Detergent.
C t ~ ,=.

FIG. 5. Elasticity mechanism is a stretched foam film. surface from the interior not take place before sufficient
material from the perimeter has been moved in to thicken
must diffuse rapidly to the moving boundary between the film under the influence of the surface tension gradient.
liquid and substrate and reduce the surface tension (and Therefore a surfactant which is a good wetting agent, i.e.,
ideally, also the substrate-liquid interracial tension) in that rapidly reduces the surface tension at an extended inter-
region to a low value. Therefore the structural require- face, can act as a defoamer by preventing the operation of
ments for a good wetting agent are those for an effective this film-healing mechanism.
reduction of surface tension coupled with mobility and For practical purposes, however, foam must .not only be
rapid adsorption at a new surface. Short chain or branched produced but must also show appreciable stability-
chain structures, as mentioned above, yield effective surface resistance against mechanical and thermal shock. This
tension reducers; in addition these structures are believed to requires the presence at the surface of molecules which can
be rapidly adsorbed at interfaces (5,6). The length of the pack closely to form a film with mechanical strength. For
hydrophobic group should therefore be no longer than that this purpose the hydrophobic groups should be long and
required to cause efficient adsorption or the surfactant at straight. This type of hydrophobic group also shows stow
the surface, under the conditions of use; the hydrophilic adsorption at the surface and thus promotes film elasticity.
group should have only sufficient interaction with the However since increased length of the hydrophobic group
solvent to prevent the molecule from becoming insoluble, decreases the effectiveness of the molecule for reducing the
since interaction with the solvent reduces the tendency of surface tension of the system, foaming capacity goes
the molecule to migrate to the interface. through a maximum with increase in length of the
The hydrophitic group may be ionic or a nonionic polar hydrophobic chain (9), and good goaming agents have
grouping such as two or more hydroxyl groups or a short structures of intermediate chain length (Fig. 6).
polyoxyethylene chain. Other structural factors which increase foaming capacity
are: (a) increased association of the counter-ion with the
FOAMI NG surfactant ion in ionic surfactants. This makes for decreased
Some wetting agents, especially those of low solubility electrostatic repulsion between similarly charged ionic
in water, also function as antifoaming agents. The reason for hydrophilic groups in the film with consequent closer
this is not difficult to understand. In contrast to the packing; (b) functional groups in the surfactant molecules,
requirements for wetting, which depends upon almost such as a few ether linkages between hydrophobic and
instantaneous reduction of the surface tension as the hydrophilic portions (10), which increase the interaction of
interface is extended, foaming depends upon the existence, the surfactant molecules with the water without .chan gin g
when the interface is extended, of an appreciable period of the packing of the hydrophobic tails significantly. These
time before the surface tension is reduced to its equilibrium hydratable functional groups decrease the rate of migration
value. of the surfactant to the surface and also cause the surface
The production of foam is facilitated by the lowering of film to include bound water molecules which increase its
the surface tension, since that reduces the work (W = 7A, stability.
where A = the total surface area of the bubbles in the foam) DETERGENCY
required to produce the foam. Thus initial foam height Detergency is a very complex phenomenon which
correlates welt with surface tension of the foaming solution depends on many factors and the mechanisms of which
(7). The lower the surface tension, the higher the initial vary with the nature of the soil to be removed and the
foam. substrate upon which the soil is held (t 1). However despite
However for foam to have any stability, the foam film this complexity, good detergents generally have a very long,
produced must have some elasticity, i.e., as the film thins straight hydrophobic group and a terminally located hydro-
and stretches, there must be some restoring force generated philic group (Fig. 7). Almost all studies indicate that
by the stretching process which opposes this effect and detergency is increased with increase in the length of the
prevents the stretching from continuing with eventual hydrophobic chain, subject to solubility limits (2,12,13),
rupture of the film. It is for this reason that pure liquids, and with movement of the hydrophilic group to a terminal
even with low surface tension, do not foam. In solutions of position in the molecule (2,14,15). These are structural
surface-active agents, this restoring force is believed to be factors which promote micellization and correlate well with
due to the higher surface tension which a newly increased studies which indicate that detergency becomes significant
surface shows. According to this mechanism (Fig. 5) when a only when the cmc is reached (t6,17). For oily soil and
portion of a foam film is stretched, the local concentration nonionic surfactants, detergency has been correlated with
of surfactant decreases momentarily and the surface tension solubitizing power of the surfactant (17), and solubilization
at the stretched spot becomes momentarily greater than the is welt known to be a property shown only by micelles. For
tension in the surrounding areas. This causes a surface carbonaceous soil, the increase in detergency with chain
tension gradient, radiating out from the stretched spot, length may reflect the increased adsorption of the longer
which draws liquid in from the surrounding areas counter- chain materials onto carbon particles (12) with resulting
ing the stretching of the film and thickening it (8). increased dispersion or solubilization, or both, of this type
For this mechanism to act effectively, it is essential that of soft.
the surface tension at the stretched portion not be reduced
too rapidly, i.e., that the reduction of the tension to its DISPERSION OF SOLIDS
equilibrium value by surfactant molecules migrating to the The dispersion of solids in aqueous media depends upon
MAY, 1972 ROSEN: S U R F A C T A N T S T R U C T U R E AND PROPERTIES 297

the formation of energy barriers around the particles, to aid both central and terminal positions in the molecule is also
their dispersion and to prevent their coalescence when believed to inhibit this adverse orientation.
dispersed. These energy barriers may be either electrical or
REFERENCES
steric in nature. The production of an electrical barrier to
coalescence involves the adsorption of ionic surfactant 1. Kolbel, H., D. Klamann and P. Kurzendorfer, 3rd Intern. Congr.
Surface Active Agents, Cologne, 1960, 1., p. 1.
molecules onto the solid particles to give all the particles 2. Greiss, W., Fette, Seifen, Anstrichm. 57:24, 168, 236 (1955).
electrical charges of similar sign. The similarly charged 3. Rosen, M.J., D. Friedman and M- Gross, J. Phys. Chem.
particles repet each other and remain suspended, tt follows 68:3219 ( t 9 6 4 ) .
that the more ionic charges a surfactant can impart to a 4. Schwarz, E.G., and W.G. Reid, Ind. Eng. Chem. 56:26 (1964).
5. Moilliet, J.L., B. Collie and W. Black, "Surface Activity," Van
particle, the more effective it wilt be as a dispersing agent. Nostrand, Princeton, N J . , 1961, p, 156.
As a result most good dispersing agents contain multiple 6. Komor, J.A., and J.P.G. Beiswanger, JAOCS 43:435 (1966).
ionic groups. In addition dispersing agents for use with 7. Rosen, M.J., and J. Solash, Ibid. 4 6 : 3 9 9 (1969).
polar solids in aqueous media usually have hydrophobic 8. Kitchener, J.A., and C.F. Cooper, Quart. Rev. 13:71 (1959).
groups with polarizable or slightly polar structures such as 9. Kolbel, H., and P. K u h n , Angew. Chem. 71:211 (1959).
10. Gotte, E., Fette, Seifen, Anstrichm. 7 l : 2 1 9 (1969).
aromatic rings or ether linkages, or both, rather than 11. Tomlinson, F., Jr., H.R. Billica and T.H. Grindstaff, JAOCS
saturated hydrocarbon chains. The purpose of these is to 45:354 (1968).
increase the adsorption of the surfactant molecule onto the 12. Gotte, E., and M.J. Schwuger, Tenside 6:131 (1969).
solid particles and, most importantly, to prevent adsorption 13. Gray, F.W., I.J. Krems and J.F. Gerecht, JAOCS 42:998
(1965).
from occurring with "reverse orientation," that is, to 14. Dreger, E.E., G.I. Keim, G.D. Miles, L. Shedlovsky and J. Ross,
prevent adsorption with the hydrophilic group oriented Ind. Eng. Chem. 36:610 (1944).
towards the solid to be dispersed and the hydrophobic 1S. Bau mgartner, F., Ind. Eng. Chem. 46 : 1349 (1954).
group oriented towards the water. This "reverse orienta- 16. Mankowich, A.M., JAOCS 38:589 (1961).
17. Ginn, M.E., and J.C. Harris, Ibid. 38:605 (1961).
tion" would result in the flocculation of the solid, rather
than in its dispersion. Positioning of hydrophilic groups in [Received July 6, 1971 ]