A Correlation for Phase Behavior of Nonionic Surfactants

M. BOURREL, 1 J. L. SALAGER, 2 R. S. SCHECHTER, AND W. H. WADE

Departments of Chemistry and Petroleum Engineering, University of Texas at Austin,
Austin, Texas 78712
Received November 20, 1979; accepted January 30, 1980
In previous studies, the s ystematics of variation of phase behavior of oil/water/surfactant systems
have been detailed for anionic surfactants. The present study details the behavior of such systems
with nonionic surfactants, including the variables: temperature, alcohol type and concentration,
added electrolyte, ethylene oxide number of the surfactant, alkane molecular weight for the oil
phase, and the hydrophobic molecular weight for the surfactant.
INTRODUCTION

Waterflooding is a standard technique for

improving the efficiency of oil recovery
from a reservoir; yet, half the oil remains
thermodynamically trapped as dispersed
droplets. If the interfacial tension between
oil and water can be reduced sufficiently,
then additional oil droplets may be displaced (1). Surfactant solutions have been
formulated to attain these required ultralow
interfacial tensions (2). Furthermore, it has
been shown that these tensions are often observed for conditions such that the oil/water/
surfactant mixtures separate into three
distinct phases (3), and recent studies (4, 5)
have documented the equivalency of these
two approaches.
When three-phase systems form, the surfactant is located largely in the phase of
density intermediate between that of water
and oil and hence is called the middle
phase. Winsor (6) called such systems with
the thermodynamically stable middle-phase
microemulsion in equilibrium with both
excess oil and water phases Type III.
1 Present address: Societe Nationale Elf Aquitaine,
Lacq, France.
2 Present address: Universidad de los Andes,
Merida, Venezuela.

Type I systems are those for which the

surfactant is in the aqueous phase (microemulsion in equilibrium with excess oil) and
Type II systems consist of microemulsion
(surfactant in oil) in equilibrium with excess
water. Of course, in each system residual
surfactant exists in all the various equilibrium phases.
It is possible to effect a I ~ I I I ~ I I
transition (or the reverse) by changing any
one of a number of system variables. For
the case of anionic surfactants, extensive
studies of this transition have been conducted and a correlation between the
salinity, oil, water/oil ratio, alcohol type and
concentration, surfactant structure, and
temperature has been established (5). All
of these parameters change the relative
affinity of the surfactant for the oil and
water and therefore tend to influence the
system type. The correlation shows that the
system is particularly sensitive to the
salinity and often a small increase of this
parameter can promote the I ~ III ~ II
transition. Temperature, on the other hand,
does not strongly influence anionic surfactant partitioning (5). A similar quantitative study of nonionic phase behavior has
not yet been reported. However, a first
qualitative study of the effect of some of

451

Journal of Colloid and Interface Science, Vol. 75, No. 2, June 1980

0021-9797/80/060451-11502.00/0
Copyright 1980by AcademicPress,Inc.
All rightsof reproductionin any formreserved.

452

BOURREL

these variables on nonionic systems has

been reported (7). Moreover, Shinoda and
co-workers (8-15) have detailed some differences between nonionics and anionics
with regard to phase behavior. Their work
deals with a "surfactant phase" which is
the middle phase described above. This
surfactant phase is observed at the socalled phase inversion temperature (PIT),
which thus corresponds to an "optimum
temperature" defined by the intersection of
the oil-microemulsion and water-emulsion interfacial tension curves (11).
The purpose of this paper is to show the
quantitative influence of the relevant parameters such as the nature of the oil, the type
and concentration of alcohol and surfactant,
temperature and salinity on the phase behavior and interfacial tensions of systems
containing nonionic surfactants, to find a
correlation between these parameters and to
contrast the observations with those reported previously using anionic surfactants.

IGEPAL CO EON = 6.32

WOR= 4
'3 gpdl SURFACTANT
3gpdl SEe- BUTANOL
I gpdl ISOPENTANOL

6gpdl Noel

8O
*~ 70
ttl

~o
ne
W
n
'~

][

Trr

4O

5O

I0

EXPERIMENTAL

TECHNIQUES

Aqueous solutions of a variety of surfactants, C.P. NaC1 (KC1 and CaCI2 were
used on occasion), and various alcohols
were equilibrated with n-alkanes of differing
carbon number (ACN). The systems were
sealed in glass tubes which were shaken
each day after recording the phase volumes.
In 3 or 4 days the phase volumes attained constancy.
All aqueous concentrations are in grams
per deciliter and purities have been previously given (7). The water/hydrocarbon
ratio (WOR) was four for all systems.
Generally, 3 g/dl of sec-butanol in addition to other alcohols was used to facilitate the attainment of equilibrium, since it
is a general observation that demacroemulsification is promoted when the alcohol
concentration is high.
The spinning drop tensiometer (16) was
employed for interfacial tension measurements (always at 28C).
The GAF Corporation provided the nonionic surfactants in 100% active form. The
nonylphenols were designated as Igepal CO
with average ethylene oxide numbers
(EON) of 1.5, 4, 5, 6, 7.5, 9, and 10.5. In
addition ethoxylated octylphenols (Igepal
CA) were studied with an average of 1 to 9
EO units per mole of octylphenol. GAF
tridecyloxyethanols--the Emulphogene ser i e s - c o n t a i n i n g 3 to 9.75 EO units were
also used as received. These samples have
well-characterized HLB values (17) and
have been the subjects of previous studies
in this laboratory (18).
Following the procedure used by others
(4, 14, 19, 20), surfactants were mixed to
obtain intermediate EON, assuming a linear
mole fraction mixing rule. The validity of this
procedure has been discussed earlier (7).
RESULTS

15
ACN

F l o . 1. P h a s e b e h a v i o r w i t h t e m p e r a t u r e
a l k a n e c a r b o n n u m b e r ( A C N ) as v a r i a b l e s .

ET AL.

and

Journal of Colloid and Interface Science, Vol. 75, No. 2, June 1980

Because of the well-documented decrease

of solubility of nonionics at elevated temperatures the phase behavior is as shown in
Fig. 1 for a nonylphenol with an average

NONIONIC

6.32 moles of EO. With increased temperature transitions occur in the sequence
I ~ III ~ II. The phase transition temperatures are obviously dependent on the oilphase alkane but will also be seen to depend on the nature and concentration of the
other components of the system. For example, when the EO content of the surfactant increases, its solubility in the water
increases and the boundaries move toward
higher temperatures.
As mentioned earlier, the three-phase
regime of the type of systems studied here
is always associated with a minimum of
interfacial tension. From this standpoint it
must be possible to define an optimum temperature for minimum tension which is
closely related to the phase inversion temperature (PIT) defined by Shinoda (8, 9).
The temperature effect on the phase behavior will be discussed later in more
detail.
Figure 2 shows the middle-phase region
obtained by varying EON at constant
temperature. Increasing EON is plotted in

gpdlIGEPAL
CO
glxllSEC-BUTANOL
glxll IS(]:~NTANOL/~
gpdlNaCl

,/
,~/~~

o
tel
EON- EON~

ACN

12

453

SURFACTANTS

16

FIG. 2. Phase behavior with ethylene oxide number

(EON) and ACN as variables with optimum EON
(EON*) as defined in the text.

[] MICROE[MULSION/WATER
0 MICRCEMULSION/OIL

i"

z
o
to
I--

Ig

3tixll IGEPALCOEON=5.0
3~odlSEC-SUTN~Ot.

i o4

I glxll
|

No Cl

12

,
16

ACN

FIG. 3. Interfacial tension as a function of ACN

with the appropriate phases as noted.
the negative direction along the ordinate in
order to maintain the same relative positions
of Types I, II, and III systems as in Fig.
1. Thus, increasing the temperature or decreasing EON both increase the oil-phase
affinity of the surfactant.
The three-phase region was extensively
mapped by series of interfacial tension
measurements varying both ACN and EON.
Typical results are shown in Figs. 3 and 4.
The interfacial tensions between excess oil
and the surfactant phase and excess water
and the surfactant phase cross at a point
near the left boundary of the three-phase
region in the ACN scan (Fig. 3) but near
the center of the three-phase region in the
EON scan (Fig. 4). The center crossing
is the common observation with anionics
involving salinity scans (5, 21, 22); therefore, it was decided to characterize the
three-phase region by defining an optimum
EON (EON*) as being that in the center of
the three-phase range. As with anionic
salinity scans, defining such an EON* perJournal of Colloid and Interface Science, Vol. 75, No. 2, June 1980

454

BOURREL

[] MICR(Tr_MUL
SION/ WATER
0 MICROEMULSlON/ OIL

~,,

. ~ 5 PHASES

I0"~

J
z
_o

I.-

I-

3 gpI

IO-I

3 gpdl SEC-BUTANOL
I gl~ll No CI
OIL PHASE: OCTANE

5.0

52

5.4
EON

5.6

5.8

6.0

FI6. 4. Interfacial tension as a function of EON

with the appropriate phases as noted.
mits the three-phase region to be located by
a straight line such as shown in Fig. 2.
Although not shown, phase behavior
studies were also performed on ethoxylated
octylphenols (Igepal CA series) and ethoxylated tridecanol (Emulphogene BC). EON*/
ACN lines are found to have the same
slope (-0.15) as for the Igepal CO series,
in agreement with the previous results of
Hayes et al. (23).
In the following sections, the effect of
alcohols, salts, surfactant nature and concentration, and temperature with regard to
the EON* line will be examined.

ET AL.

data sets were obtained for various conditions of salinity and surfactant and alcohol
nature and concentration at room temperature (28C). The first observation is that
EON* is shifted toward higher EON by the
same amount for each ACN. This means
that if isopentanol is added, the affinity of
the surfactant for the oil is increased and
this must be compensated by increasing
EON to maintain a balanced system. The
second observation is that the shift is proportional to the alcohol concentration and is
independent of the other parameters defining the system: surfactant nature and
concentration and salinity as summarized
in Fig. 6. The different points belonging to
the same straight line relating to isopentanol refer to the different systems where
the shift was observed.
In the same figure one notes that n-pentanol and hexanol give even more dramatic
positive shifts. On the contrary, the lowmolecular-weight alcohols have an opposite

3 9Pdt SURFACTANTIGEPALCO
3 gpdl SEC"BUTANOL
3 gpdl No CI
o
5
z
o
b.I

Alcohol Effects
Alcohols have commonly been added as
cosurfactants to adjust the optimum salinity
of anionic formulations (5, 7). It is, therefore, of interest to examine the effect of
alcohols on phase behavior when the surfactant is nonionic.
Figure 5 shows the effect of isopentanol
concentration on EON*/ACN. Many more
Journal of Colloid and Interface Science, Vol. 75, No. 2, June 1980

ACN

12

F I G . 5. T h e i n f l u e n c e o f i s o p e n t a n o l o n E O N * / A C N .

455

NONION1C SURFACTANTS
-0.2

0.2

~0.4
..r
o
0.6
~0.a
ll~ ID
Z
O
1.2
I.~ L4

n-HEXANOL

1.6
L8

\ 0 n-PEN~TANO
\L
2
ALCOHOLCONCENTRATION(glxll)

FIG. 6. T h e e f f e c t o f a v a r i e t y of a l c o h o l s on
E O N * as a f u n c t i o n o f a l c o h o l c o n c e n t r a t i o n .

effect on EON*, but the effect is small

compared with that for high-molecularweight alcohols. The see-butanol effect has
been checked in two different co-alcohol
environments and has been found identical
in both cases.
This classification of the alcohols into
two groups depending on their effect on the
phase behavior of nonionic surfactants is
in agreement with observations on anionic
surfactants (24). Table 1 summarizes the
coefficient found for the EON*/alcohol
concentration dependence.

Salt Effects
Figure 7 is one example of such data sets
obtained for systems showing the effect of
NaC1 on middle-phase behavior. It can be
seen that NaC1 has the same effect on
EON* as adding isopentanol; that is, the
optimum is shifted toward higher EON by
the same amount for every alkane. This
means that NaC1 enhances partitioning of
the surfactant into the oil phase. Similar
effects were noted for CaCI2 and KC1.
Figure 8 displays the linear variation in
EON* resulting from variation in the elec-

trolyte concentration. The different symbols belonging to a given straight line

once again refer to data obtained under a
variety of conditions emphasizing that the
effect of added electrolyte is independent
of the other variables.
It can also be seen that the effects are of
the same order of magnitude for NaC1 and
CaC12, which is quite different from that
observed for sulfonates (25), which are
particularly sensitive to the presence of
bivalent ions. The influence of the electrolyte is summarized in Table I by the slope
of the straight lines of Fig. 8. When salinity
is expressed in grams per deciliter, NaC1
has a somewhat larger effect than CaC12,
KCI having a smaller effect. When salinity
is expressed in moles per liter, the contrary
is observed.
These results are consistent with Shinoda
and Takeda's observations on the effect of
salt on both the cloud point and the phase
inversion temperature (12).

Surfactant Concentration Effects

Complex mixtures of anionic surfactants
show a dependence of phase behavior and
TABLE I
C o r r e l a t i o n for O p t i m u m P h a s e B e h a v i o r
of Nonionic Surfactants
Surfactant

k ( E O N , g/dl)
a (EON)
C ( E O N , g/dl)

Ethoxylated
nonylphenol

Ethoxylated
octylphenol

Ethoxylated
tridecanol

0.15
6.65
0.057

0.15
6.35
--

0.14
4.34
--

Alcohol
IsoC, OH
or 2-C40I-[
m (EON/g/dl)

IsoC~OH n-CsOH n-C60H

-0.05

0.5

0.58

0.98

Salt

b (EON/g/dl)
b (EON/mole/liter)

NaCI

CaCI2

KCI

0.13
0.77

0.10
1.11

0.09
0.69

Journal of Colloid and Interface Science, Vol. 75, No. 2, June 1980

456

BOURREL ET AL.
factants is sensitive to temperature. The
solubility of nonionic surfactants in water is
due to hydrogen bonding, which in turn is a
very sensitive function of the temperature.
Thus, increasing temperature may be expected to have the same effect as increasing
salinity or increasing the concentration of a
high-molecular-weight alcohol. Figure 10
shows the temperature effect on EON*/
ACN. Near room temperature, EON* is a
linear function of ACN of near constant
slope. H o w e v e r , at elevated temperatures
there is a measurable decrease in slope and
curvature can develop (data for these systems are not shown). The average temperature coefficient is also given in Table I.

2 gpdl IGEPALCO
3 qpdl SEC-BUTANOL
I Ilpdl ISOPENTANOL

f...
0

o ~i

[]

I g~i

3 ~t

DISCUSSION

12

16

ACN

FIG. 7. The influenceof salinity(NaC1)on EON*/ACN.

interfacial tension on surfactant concentration. Increased concentrations require a decreased ACN for optimization. To the extent that ethoxylated nonionics are also
complex mixtures one would expect that increased concentration would require a
larger value of EON*. Figure 9 supports
this contention. The value of the shift in
EON* due to surfactant concentration is
plotted taking the value Of 3 g/dl of surfactant as a reference. The different points
refer to different system formulations, as
indicated on the figure. Unlike the observed
alcohol and salt effects, EON* shifts with
surfactant concentration are nonlinear and
hard to quantify at this time but are consistent with those reported by Arai and
Shinoda (13) on the effect on PIT (which
was found to be depressed at higher surfactant concentrations).

Temperature Effects
As was seen in Fig. 1, the phase behavior of systems containing nonionic surJournal of Colloid and Interface Science, Vol. 75, No. 2, June 1980

With the exception of surfactant concentration dependence, all the results previously presented can be summarized in a
simple linear equation:
a - EON* = kACN - ~ i m i A i
-

bS

c(T

28),

[1]

where A~ and S are the alcohol and salt

O.0

O 0.4

~0.8

Cl

~'CaCl2
1.2 ~

NaCI
i

i
4

i
8

12

SALT CONCENTRATION~pdl)
FIG. 8. The comparison of salt effects for KCI, CaC|2,

and NaCI on phase behavior.

NONIONIC SURFACTANTS
IGEPAL CO
3 gpdl SEC-BUT/~IOL

.,lr,
z
o
w
z

I glxII ISOPENTANOL
I gpdl Noel

I gpdl ISO~E~rrtJ~OL
:5 (jpdl NaCI

~-.6

[]

I gpdl

z
o

~ -.4
Iu-.2
z

8
~0
(.3
"<.2

In S* = K(ACN) + f(A) - o-,

/ ~3d~'lI[~.aS~IIrNTANOL

3~ 4

[2]

NaCf

L
I

centration of 3 g/dl since it was found to be

mildly concentration dependent.
For anionic surfactants, Salager et al. (5)
have shown that the optimum salinity S*
is given by:

2 gpdl ISOPENTANOL

\12]

457

6(gNO

.4.

FIG. 9. The influence of surfactant concentration

on EON*.

concentrations, respectively, m and b are

constants characteristic of each type of alcohol and salt (their values are given by the
slopes of the straight lines in Figs. 6 and 8),
a and k are constants for a given type of
surfactant, and c is the coefficient of temperature, T, restricted to the low-temperature linear regime (28 to -60C). The values
of the constants pertinent to the above
equation are listed in Table I.
Table I shows that k has the same value
for ethoxylated nonyl- and octylphenols,
almost the same value for ethoxylated tridecanol, and is independent of surfactant
concentration.
For a 28C system without alcohol and
without salt, the preferred ACN is given by
(a - EON)/k and it is of course a characteristic of the surfactant molecule. Therefore, since the hydrophilic part is represented by EON/k, a/k is a characteristic of
the lipophilic part of the surfactant. Table
I gives its value for the types of surfactants studied here, at a surfactant con-

where K = 0.16 for all the sulfonates, f(A)

is a function of alcohol type and concentration, and o- is a surfactant characteristic;
~/k has been called the extrapolated alkane
carbon number at unit salinity and no alcohol (EPACNUS), since f(A) vanishes
when the alcohol concentration goes to
zero. The EPACNUS has been studied in detail for several families of surfactants (7, 26).
The influence of molecular structure can
be evaluated from the reference wherein
it was shown that adding a CH2 group to the
lipophilic part of the molecule increases the
EPACNUS by two units, regardless of surfactant hydrophile. Moreover, adding a benzene ring to the molecule was found to
increase the EPACNUS by 32 units (equiva-

3 gpdl IGEPAL CO
3 glxII SEe-BUTANOL
I gpdl ISOPENTANOL

6
;z
0
tel

I0

12

A40

V 70
~I, 75

45
50
.

65

16

ACN

FIG. 10. The influence of temperature on EON*/ACN.

Journal of Colloid and Interface Science,

Vol. 75, No. 2, June 1980

458

BOURREL ET AL.

lent to 16 lipophilic CH2 units!) Such calculations can be carried out for nonionics;
going from ethoxylated octyl- to nonylphenol increases a by 0.3, i.e., the preferred ACN at no alcohol and no salt is increased by 0.3/0.15 = 2 (Table I). This is
identical to the results mentioned above for
anionics. Using this result, the parameter
a/k can be calculated for an ethoxylated
tridecylphenol and then, by comparison
with the results known for the ethoxylated
tridecanol, it is possible to estimate the
contribution of the benzene ring to the preferred ACN for nonionic surfactants. The
parameter a/k is found to increase by
approximately 20 units when the benzene
ring is added to the surfactant molecule.
This is equivalent to adding ten carbons
to the oil-phase ACN. The importance of
molecular structure on the properties of the
surfactants is once again found profound
and clearly molecular weight is not sufficient
to completely characterize a surfactant,
even when constancy of the hydrophilic
group is maintained.
The surfactant hydrophile effect on the
preferred ACN is taken into account by the
parameter k; it can be seen that when EON
increases by one, the preferred ACN is
shifted by 6.6 units toward lower values.
As noted previously (18), it is not surprising
that low tensions have not been widely
reported with ethoxylated surfactants since
very select values of EON are required.
The alcohol molecular weight is described
in Table I by the values of m. As mentioned above, the alcohols can be classified
in two groups depending on the direction of
the shift they produce on the optimum phase
behavior; " h e a v y " alcohols decrease the
surfactant affinity for the aqueous phase,
"light" alcohols increase this affinity. These
results are in agreement with Marszall's
(27) observations on the cloud points of
ethoxylated nonylphenols in the absence of
an oil phase. He notes that methanol,
ethanol, and propanol increase the cloud
point (that is, increase the surfactant soluJournal of Colloid and Interface Science, Vol. 75, No. 2, June 1980

bility in water) and butanol and pentanol depress the cloud point (that is, decrease the
surfactant solubility in water). Furthermore, the heavy alcohols are found to have
a stronger influence on the cloud point
than the light alcohols and pentanol's effect
is larger than that for butanol. Marszall
shows that all the above cloud point effects have roughly the same magnitude for
the three surfactants studied, with 8, 10, and
12 EO's per molecule. The consistency between Marszall's results and those presented above is a strong indication that the
phase behavior of nonionic surfactants, at
least concerning the effect of alcohols, is
related to the partitioning of alcohol into
the aqueous phase, even when oil is present
in the system. Furthermore, it must be
pointed out that the influence of the alcohol
nature is stronger than the influence of its
concentration in water since its effect is
more important when its molecular weight
increases although its partitioning between
oil and water becomes more favorable to the
oil. Of course, a balance between these two
competing effects must be reached for high
enough alcohol molecular weight. Similar
behavior has been observed for alcohol effects with anionic surfactants (28).
If the nonionic surfactant itself is considered as a special heavy alcohol, its concentration effect may ultimately be understood. In fact, looking at the nonionic surfactant as an alcohol leads one to think that
the concentration effect could be different,
depending on the ethylene oxide number; at
low EON, the surfactant is rather hydrophobic and will act as a heavy alcohol,
i.e., its concentration will affect the phase
behavior; at high EON, the surfactant is
hydrophilic and will act as a light alcohol,
i.e., its concentration will affect only
slightly the phase behavior, and eventually
in the opposite direction. Arai and Shinoda's
observations (13) on the influence of surfactant concentration effect on the cloud
point at different ethylene oxide number are
in agreement with this analysis. Alternately,

NONIONIC

459

SURFACTANTS

despite the quoted purity of these commercial surfactants, small amounts of unreacted oxonylphenol in the surfactant
could be the origin of an "apparent"
concentration shift if this impurity behaves
as a typical heavy alcohol.
Of course, the salt effect described by
b in Table I can be reasoned by an argument paralleling that for alcohols. As reported earlier, the magnitude of the effect on
EON* follows the order: CaCle > NaC1
> KC1 when the salt concentration is expressed in moles per liter. This result can be
correlated with the classification of the cations by their hydration numbers, and thus
to the solvation strength of water. Some
variation is found for these hydration
numbers, depending on the technique used
for their evaluation but there is a general
agreement on their classification:
Ca 2+ > Na + > K +.
The coincidence between this classification
and the observed effects on the phase
behavior provides support for considering
the mechanism of bivalent cation action on
nonionic surfactants as being similar to that
for univalent ions.
The sensitivity of the phase behavior to
the salinity can be expressed in terms of a

preferred ACN shift at constant EON.

When the NaC1 concentration goes from 1 to
2 g/dl, the ACN is decreased by 20.9 units.
For anionic surfactants, the same change in
salinity would produce a shift of 4.3 units
according to Eq. [2], in which K = 0.16
(this shift would be higher at lower salinity).
This is a clear illustration of the reduced
influence of the salinity on nonionic phase
behavior compared to anionics. Thus EON
is much more efficient in shifting the ACN
of nonionics, being comparable to the salt
effects with anionics. For nonionic surfactants, the effect of high-molecular-weight
alcohols is larger than the salt effect, as
shown by the values of m and b in Table
I. This is in agreement with the NaCI and
pentanol effects on cloud point reported in
the literature (12, 27).
In order to check the ability of Eq. [1]
to predict the position of interfacial tension
minima, measurements have been carried
out under a variety of conditions. For example, if the scanned variable is the salinity,
everything else being kept constant, an optimum salinity is determined, as illustrated
in Table II, which must verify Eq. [1]. The
results are reported in the table and there
selected values are compared with the predictions by Eq. [1]. The agreement between

T A B L E II
Various Optimal System Formulations

EON"

ACN

(g/dl)

Isopentanol
(g/dl)

n-Hexanol
(g/dl)

NaCI
(g/dl)

CaCI
(g/dl)

6
7.5
6.31
5
5.5
6.32
5
5.6/5.53 ~
5.7/5.9
6.25/6.14 b
6.3/6.25

7
7
8
10.5/10.7 b
10.8/11.5
10.2/9.4 b
11/11.5
8
9
9
9

3
3
0
3
3
3
3
3
3
3
3

0
0
1
0
1
0
0
0
1
1
1

0
0
0
0
0
1
0
0
0
0
0

3.3/3.45 b
15/15.2 b
2.4/2.0 b
0
1
1
1
1
1
3
0

0
0
0
0
0
0
0
0
0
0
4

sec-Butanol

a 3 g/dl e t h o x y l a t e d n o n y l p h e n o l .
b Calculated.
Journal of Colloid and Interface Science, Vol, 75, No. 2, June 1980

460

BOURREL ET AL.

the experimental and calculated values, as

shown in the table, is rather good, especially
if the precision of the parameter determination of Eq. [1] is considered (-5%); for example, if there is an error of 0.1 in the a
value, it leads to an error of 0.7 in the preferred ACN determination, or to 0.1 on
EON*, or to 0.8 g/dl in the optimum salinity.
CONCLUSIONS

Nonionic surfactant systems parallel

anionic systems in that any variable tending to decrease the affinity of the surfactant
for the aqueous phase relative to that of
the oil phase will drive transitions in the
same direction.
As is logarithm optimal salinity for
anionics, EON* is a linear function of ACN,
with the slope independent of salt type and
concentration, alcohol type and concentration, and temperature (~<60C). Surfactant
structural effects can be separated into two
terms corresponding to the hydrophobic
and hydrophilic moieties of the molecule;
the lipophilic moiety is found to have a
similar effect on the phase behavior of
nonionic and anionic surfactants; the EON
of the nonionic and the temperature are
the parameters having the strongest influence on phase behavior.
Alcohols can be separated into two
groups depending on the direction of their
effect on optimum phase behavior; highermolecular-weight alcohols depress the relative affinity of nonionics (and anionics)
for water, while lower-molecular-weight alcohols have an opposite but substantially
smaller effect.
Nonionic salinity tolerance is substantially greater than that observed for anionics.
Temperature decreases relative affinity of
nonionic surfactants for water, whereas the
converse is true for anionic surfactants.
It is the only parameter affecting the two
classes of surfactants in a different way and
its effect is somewhat more complex than
that of other parameters. As opposed to
Journal of Colloid and Interface Science, Vol. 75, No. 2, June 1980

anionics, nonionic solubility is inversely

proportional to temperature.
ACKNOWLEDGMENTS
The authors express their appreciation to the Department of Energy, the Robert A. Welch Foundation, Delegation Generale a la Recherche Scientifique
et Technique, and the following oil and chemical
companies: Amoco, Ashland, Atlantic Richfield,
British Petroleum, Chevron, Continental, Elf-Aquitaine, Exxon, Gulf, Marathon, Mobil, Stepan, Suntech, Tenneco, Texaco, Union, and Witco.
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Journal of Colloid and Interface Science, Vol. 75, No. 2, June 1980