Alteration of Surface-Tension Profiles

Due to Adsorption
Rick D. Gdanski and Gary P. Funkhouser
Halliburton Energy Services, Inc. USA
Presented at the 2004 Tekna International Oil Field Chemistry Symposium, Geilo, Norway,
March 28-31

Abstract
A study was conducted using static adsorption tests to measure the surface-tension
profiles and critical micelle concentration (CMCs) of several surfactants both before and after
adsorption. CMCs after adsorption were found to range from 2 to 30 times higher than before
adsorption. It is thought that unreacted starting materials may be responsible for the low CMCs
of commonly used commercial products. These unreacted, low-solubility starting materials are
likely present at only low concentrations, but they induce a lowered CMC. The adsorption
process apparently establishes an adsorbed layer (or perhaps bilayer) that can accommodate the
unreacted oily materials, thereby purifying the surfactant remaining in solution and raising the
apparent CMC. It was found that the post-adsorption surface-tension profiles correlated better
with the profiles from column flow experiments than did the pre-adsorption surface-tension
profiles. As such, selection of commercial surfactants based on out-of-the-bottle CMCs may be
misleading. Furthermore, estimating the partitioning of a surfactant between oil and water based
on these CMCs may also be problematic.

Introduction
A laboratory study was undertaken to model surfactant adsorption and desorption during
flow through porous media. The purpose of the model was to link surfactant selection with
surface-tension reduction during injection and flowback of fluids in sandstone formations.
Surfactants are often used with the intention of imparting low surface-tension properties at the
leading edge of injected fluids. In addition, surface-tension reduction can be desirable on
flowback for minimizing emulsions. However, recent work1 has shown that depletion of even
nonionic surfactants by adsorption may make it extremely difficult to keep active chemicals at
the leading edge of injected fluids. Furthermore, in subsequent laboratory flow tests, surfacetension profiles of desorbing surfactants did not follow the expected behavior. These results
indicate a difference in the surface-tension profiles and CMCs of surfactants tested out of the
bottle compared to out of the column.
A laboratory study of the adsorption and desorption properties of many typical
stimulation chemicals was undertaken. The chemicals included a range of alcohols, mutual
solvents, a few types of water-soluble polymers, a range of nonionic surfactants, a cationic
surfactant, some anionic surfactants, and some phosphonate scale inhibitors. The preferred
method for determining key parameters describing the adsorption/desorption process depends on
the magnitude of the adsorption. Strongly adsorbing materials can utilize the classical
depletion method. Weakly adsorbing materials present a more difficult experimental challenge.
Flow testing through a 3-ft column packed with sand and kaolinite provided the sensitivity

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Alteration of Surface-Tension Profiles Due to Adsorption

required to measure the adsorption properties of weakly adsorbing materials. The delay in the
appearance of the test chemical in the effluent and the shape of the effluent profile during
adsorption and subsequent desorption provided the key parameters for the process.
The mathematics for the Langmuir and modified-Langmuir2 isotherms has been
successfully applied to many types of adsorbing chemicals in our laboratory. The same
mathematics was used for understanding static adsorption depletion experiments as well as flow
experiments. A further development for the flow experiments was the incorporation of kinetic
desorption.3 Kinetic desorption typically becomes more important as the strength of the
adsorption increases. The strength of adsorption is associated with the solution concentration of
the material at the center point (50% surface coverage) of the adsorption isotherm; it is not
related to the amount adsorbed, as is sometimes reasoned. The development of mathematics and
advanced modeling code was required for some materials that co-adsorbed with other
compounds or adsorbed in a multilevel fashion.

Experimental Method
Column Method. The column for the experiment consisted of a 3-ft Hassler sleeve used
extensively for previous research efforts. The 1.5-in. diameter column consisted of 1.5-in. long
filtrose filters at the inlet and outlet and a 32.5-in. long unconsolidated pack of sand, clay, and
silica flour in the middle. The clay provided the large surface area required for adsorption, and
the silica flour reduced the permeability of the pack to improve the pressure response during
flow. For this study, a mixture of 1870 g of Oklahoma No. 1 sand, 220 g of kaolinite having a
surface area of 13 m2/g, and 110 g of silica flour were blended in a Hobart mixer for 1 hr. The
solids were dampened with 60 mL of 6% sodium chloride (NaCl) to prevent dusting during the
dry-mixing process. The mixture was then packed into the column until full, and the remainder
was weighed.
During packing, a filtrose end piece was first inserted in the column. The sand, clay, and
silica flour mixture was added to the column in approximately 50 mL stages and tamped firmly
in place. About 1800 to 2000 g of the mixture was loaded into the column before the second
filtrose end piece was inserted. The column was then placed into an oven, and all connections
were secured. The oven temperature was set at the desired temperature and the column was
equilibrated for at least 2 days with a continual flow of 6% NaCl brine (>3 L) before a flow test
was conducted. The columns were characterized by stable permeabilities that ranged from 20 to
50 md, a dispersion constant of 0.15, approximately 28% porosities, and pore volumes (PV) of
the columns that ranged from 300 to 350 mL.
Samples of the effluent were collected at appropriate intervals. Each sample consisted of
10 mL for compositional analysis. All samples were analyzed for surface tension and TOC total
organic carbon (TOC) content. Selected samples were extracted and analyzed for component
identification using NMR and FT-IR analytical techniques. Ultraviolet-visible light (UV-Vis)
spectroscopy was used for concentration analysis where appropriate.
Depletion Method. Static adsorption tests were conducted using the depletion method.
An initial stock solution was prepared with an appropriate amount of commercial grade material
and 6.0 g NaCl made up to 100 mL in deionized water to give about 0.15 M surfactant. The stock
solution was adjusted, when necessary, to approximately pH 6.5 to 7.5. The initial stock solution
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Alteration of Surface-Tension Profiles Due to Adsorption

was used to prepare secondary stock solutions (4 to 16 in number) with a range of concentration
from approximately 1.0E-4 to 2.0E-2 M, depending on the anticipated adsorption capacity. A
sample of each secondary stock solution was saved, its pH measured, and its surface tension
measured. The five secondary stock solutions of lowest concentration were diluted 1:10 and the
surface tensions measured. The CMC was determined using a regression routine. Separate
depletion tests (4 to 16 in number) were prepared by pipetting 25 mL of a secondary stock
solution into a 50 mL plastic centrifuge tube containing 10.00 g of kaolinite having a surface
area of 13 m2/g. The centrifuge tubes were placed in an 85F water bath, removed and shaken
every few hours, and allowed 2 days to reach equilibrium.
The literature indicates that the mass plateau of adsorption is reached very quickly for
surfactants (possibly within seconds) but may require several hours of molecular rearrangement
to achieve the thermodynamically preferred adsorbed structure.4 As such, 2 days was considered
more than sufficient to assure equilibrium. The tubes were then centrifuged for 10 min at full
speed, the liquid decanted and filtered through 0.45-micron Nalgene filters, and the pH
measured. In some experiments, surface tensions were measured and CMC determined using a
regression routine. Samples of the initial stock solution, the secondary stock solutions, and the
final solutions after depletion were analyzed for TOC analysis to determine surfactant
concentrations. When applicable, UV-Vis spectroscopy was used to determine surfactant
concentrations.

Results and Discussion

Alkoxylated Terpene. The surface-tension profiles of an alkoxylated terpene, both
before and after adsorption, are shown in Figure 1. Surface tensions after adsorption were
determined from the depletion tests. The apparent CMC shifted higher by a factor of 7 after
adsorption. Such a shift can most readily be explained by a change in composition of the
surfactant solution. A change in solution composition for a nonionic surfactant is not too
surprising because they are definitely multicomponent surfactants. The typical alkoxylated
surfactant can easily have a broad range for the number of alkoxylates on the original alcohol.
For example, a nonionic surfactant with a nominal loading of 10 ethylene oxides (EO) can easily
have 25 different molecules ranging from 1 EO to 25 EOs on the original alcohol.5 In fact, for
surfactants based on aliphatic alcohols, 1 to 2% unreacted alcohol is often present. For example,
analysis of a C6-EO6 sample showed 2% unreacted alcohol and 15 separate ethoxylates. The
alkoxylate distributions in the various samples of these experiments were not determined.
However, it is suspected that the lower alkoxylated materials likely preferentially partitioned into
the adsorbed surfactant layer, thereby raising the CMCs of the final solutions. In fact, the
literature shows clear evidence of such an enrichment process.6

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Fig. 1Alkoxylated terpene surface-tension profiles in 6% NaCl.

At the beginning of the study, it was not anticipated that the CMC would shift during the
adsorption process. However, the shift in the CMC did resolve an issue with regards to the
adsorption isotherm. Figure 2 reports the results from the 30 depletion experiments, the
regression fit of the modified Langmuir isotherm, the CMCs both before and after adsorption,
and surface tensions observed after adsorption. Classical theory anticipates that the CMC will
occur at concentrations near or above the adsorption plateau. However, the CMC before
adsorption was located at approximately 25% of the plateau and was clearly difficult to
understand. The CMC after adsorption was located at nearly 90% of the adsorption plateau, and
so was in better agreement with expectations.

Fig. 2Alkoxylated terpene on kaolinite in 6% NaCl at 85F.

C10-EO10. The surface-tension profiles of an ethoxylated decyl alcohol in 5% HCl, both
before and after adsorption, are shown in Figure 3. The surface tensions after adsorption were
measured on samples collected from a column flow test.

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Alteration of Surface-Tension Profiles Due to Adsorption

Fig. 3C10-EO10 surface-tension profiles in 5% HCl.

The apparent CMC shifted higher by a factor of 6 after adsorption. Such a shift can most
readily be explained by a change in composition of the surfactant solution due to the adsorption
process. The ethoxylated distributions in the various samples of these experiments were not
determined. However, it is suspected that the lower ethoxylated materials likely preferentially
partitioned into the adsorbed surfactant layer, thereby raising the CMCs of the final solutions.
The adsorption isotherm for C10-EO10 was originally determined in 6% NaCl as a
starting point for the adsorption isotherm in 5% HCl for the column flow experiments. Figure 4
reports the results from the 14 depletion experiments, the regression fit of the modified Langmuir
isotherm with a zero-intercept (the point of apparent near-zero adsorption, Cz), and the surfacetension profile before adsorption for C10-EO10. The CMC is located at approximately 15% of
the adsorption plateau. At the time of the determinations, surface tensions after adsorption were
not yet being measured.

Fig. 4C10-EO10 on kaolinite in 6% NaCl at 85F.

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A flow experiment was conducted in the 3-ft column on 10% kaolinite at 150F using
C10-EO10 in 5% HCl. The zero-intercept modified Langmuir isotherm that best fit the effluent
surfactant profile is shown in Figure 5. Based on the experimental design, four effluent samples
were chosen to calculate the apparent adsorption capacity as a function of solution concentration.
Those data are also reported in Figure 5 for comparison to the optimized flow test isotherm and
show good agreement. The surface-tension profile from the experiment was much higher than
expected. Therefore, 11 effluent samples, chosen for surface-tension measurements, were used to
construct the profile and determine the CMC after adsorption. Those data are reported in Figures
3 and 5. The evaluation of this experiment eventually led to the measurement of surface tensions
after adsorption in the depletion experiments.
The CMC after adsorption (Figure 5) was located at approximately 95% of the plateau
adsorption. This location is consistent with classical expectations and is located better than the
CMC before adsorption at approximately 55% of plateau. The plateau adsorption capacity from
5% HCl at 150F was approximately three times higher than from 6% NaCl at 85F. However,
the strength of adsorption, or the solution concentration at 50% of plateau, was about the same
for both solutions at approximately 3E-4 M.

Fig. 5C10-EO10 on Kaolinite in 5% HCl at 150F.

Cocoamine Quat. The surface-tension profiles of a cocodimethylbenzyl ammonium
chloride (cocoamine quat) in 6% NaCl, both before and after adsorption, are shown in Figure 6.
The surface tensions after adsorption were obtained from the depletion tests. The apparent CMC
shifted higher by a factor of 30 after adsorption. The shift in CMC by such a large amount is
more difficult to explain than for the alkoxylated surfactants. The most reasonable explanation is
a purification process that removes very low-solubility starting materials such as unquaternized
cocodimethylamine. Specifically, it is suspected that the low-solubility materials preferentially
partition into the adsorbed surfactant layer, thereby raising the CMC of the final solution. Before
adsorption, the low-solubility materials are held in solution when the surfactant concentration is
above the real CMC. However, as the surfactant solutions are diluted, the low-solubility
materials are thought to prefer to come out of solution, thereby providing an oil drop for the
surfactant to adsorb or aggregate around. In effect, the low-solubility contaminants or unreacted
starting materials induce a lower CMC.
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Fig. 6Cocoamine quat surface-tension profiles in 6% NaCl.

The adsorption capacity of the quat on kaolinite was much higher than anticipated. As
such, the original set of 16 depletion experiments produced no useful results because the final
solution concentrations were below detection limit, even with UV-Vis techniques. An additional
four depletion experiments were conducted to determine the plateau adsorption capacity and
possibly estimate the inflection in the isotherm. Figure 7 reports the results from the four
depletion experiments, the regression fit of the modified Langmuir isotherm, the CMCs (before
and after adsorption), and the surface-tension profile observed after adsorption. The CMC after
adsorption was located at about 95% of the plateau adsorption and was much more reasonable
than the pre-adsorption location of less than 5% of the plateau.

Fig. 7Cocoamine quat on kaolinite in 6% NaCl at 85F.

C12-Ester-Sulfonate. The surface-tension profiles of a C12-ester-sulfonate in 6% NaCl,
both before and after adsorption, are shown in Figure 8. The surface tensions after adsorption
were obtained from the depletion tests. The apparent CMC shifted higher by a factor of less than
two after adsorption.

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Fig. 8C12-ester-sulfonate surface-tension profiles in 6% NaCl.

Figure 9 shows the results from the 30 depletion experiments, the regression fit of the
zero-intercept modified Langmuir isotherm, the CMCs (before and after adsorption), and the
surface-tension profile observed after adsorption. The CMC after adsorption was located at
approximately 70% of the plateau adsorption and is considerably lower than expected. An
explanation for this behavior was not readily available at this time, although it may be related to
the multi-component nature of the nominally C12 fatty acid used as starting material.

Fig. 9C12-ester-sulfonate on kaolinite in 6% NaCl at 85F.

C14-Ester-Sulfonate. The surface-tension profiles of a C14-ester-sulfonate in 6% NaCl
(before and after adsorption) are shown in Figure 10. The surface tensions after adsorption were
obtained from a column flow test. The apparent CMC shifted higher by a factor of five after
adsorption. The shift is attributed to purification by adsorption in which unsulfonated starting
material partitioned into the adsorbed surfactant layer.

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Fig. 10C14-ester-sulfonate surface-tension profiles in 6% NaCl.

Figure 11 reports the results from the 30 depletion experiments, the regression fit of the
zero-intercept modified Langmuir isotherm, the CMCs (before and after adsorption), and the
surface-tension profile observed after adsorption. The CMC after adsorption was located at
approximately 75% of the plateau adsorption and was lower than what might have been
expected. Unfortunately, because of the high concentration, data scatter was extensive.
Therefore, 10 experiments were selectively disregarded and are indicated by stars in Figure 11.
The source of the experimental error has not been fully explained, though it is suspected that the
centrifuging process had an impact.

Fig. 11C14-ester-sulfonate on kaolinite in 6% NaCl at 85F.

A flow test was conducted at 70F with the 3-ft column packed with 10% kaolinite, 5%
silica flour and 85% 100-mesh sand. The column was characterized as having a PV of 340 mL
and contained 195 g of kaolinite. A fluid sequence consisting of 1500 mL of 0.0010 M C14ester-sulfonate, 300 mL of 0.010 M C14-ester-sulfonate, and 3500 mL of 6% NaCl was
scheduled for the test. All fluids were prepared in 6% (1 M) NaCl as the base fluid, and were
pumped at 6 mL/min. A total of 55 samples (10 mL each) were collected across 5300 mL of
effluent.
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Fig. 12C14-ester-sulfonate flow test at 70F.

The results of the TOC data are reported in Figure 12, along with the modeling fit and
relevant isotherm parameters. Initially, the immediate (at 1 PV) appearance of organic material
with a low surface tension was troubling. However, in a duplicate flow test experiment, the
effluent from 200 to 700 mL (except for several 10 mL samples) was collected. The organic
material was subjected to wet-chemical and spectroscopy techniques, thereby identifying it as
purified C14-ester-sulfonate. This finding validated the use of the zero-intercept isotherm. The
zero-intercept modified Langmuir (Figure 11) was used as the starting point for modeling the
effluent surfactant profile, but it did not provide a good fit. An optimized isotherm was found by
adjusting the isotherm parameters, which indicated that the adsorption capacity was about 50%
higher than measured by the depletion method. In addition, the point of essentially zero
adsorption had shifted higher. Figure 13 compares the isotherm determined from the flow
experiment to the data obtained from the depletion experiments. Note that the post-adsorption
CMC was located at less than 60% of the plateau capacity.

Fig. 13Comparison of flow test isotherm and depletion data.

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Figure 14 reports the observed effluent surface-tension data from the flow test. Also
shown is the predicted profile (solid line) using the adsorption/desorption model fit to the
surfactant concentration and the pre-adsorption surface-tension regression lines. The calculated
profile clearly failed to match any of the effluent data. The surface-tension data from the first
2100 mL of the flow experiment were then used to determine the post-adsorption CMC reported
in Figure 10.

Fig. 14Surface-tension profiles from flow test.

It was expected that the regression lines from the fit of the surface-tension data would be
useful for matching the entire effluent surface-tension profile for the flow test. The predicted
profile (dashed line) using the adsorption/desorption model fit and the post-adsorption surfacetension regression lines matched the first 2100 mL of effluent (as expected). However, it failed
to match the surface-tension data during desorption. As such, it can be said that there is much to
learn about the recovery and behavior of surfactants used in formation invasion processes.

Practical Implications
Although the implications from this study may seem fairly obvious, they are often
overlooked. For example, it is fairly clear that commercial surfactants are complex mixtures due
to the natural variations in the hydrophobe sources, the incompleteness of chemical reactions,
and the distributions created by chemical reactions such as alkoxylations. However, it is easy to
overlook the fact that these issues can induce surface-tension profiles and CMCs that are not
invariant, but rather can change dramatically during their application in a matrix. As such, simple
laboratory testing may not provide an accurate indication of downhole performance.
Table 1 summarizes the pre- and post-adsorption CMC data. As an example, one might
expect the surface-tension behavior of alkoxylated terpene to be fairly tolerant of dilution in the
matrix. Alkoxylated terpene seems to have a CMC of approximately 6E-4 M, which would
effectively remove oily residues from the matrix in preparation for a subsequent treatment stage.
A solution of 0.5% product in brine would be about 6E-3 M, which is approximately 10 times
more concentrated than the pre-adsorption CMC. Unfortunately, the adsorption process depletes
surfactant from the leading edge of the injected fluid and causes the post-adsorption CMC to be
nearly 10 times higher, both of which would result in substantially less surface and interfacial
activity than expected. In fact, a solution of 0.5% product would be at the post-adsorption CMC
after only 30% dilution.
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Table 1Pre- and Post-Adsorption CMCs

Surfactant
Alkoxylated Terpene
C10-EO10
Cocoamine Quat
C12-Ester-Sulfonate
C14-Ester-Sulfonate

Pre-Adsorption Post-Adsorption
CMC (M)
CMC (M)
5.7E-4
3.8E-4
4.4E-5
7.6E-4
1.6E-4

4.2E-3
2.4E-3
1.3E-3
1.6E-3
7.7E-4

Another issue overlooked with pre-adsorption surface-tension data is its inability to

match well returns data. Well returns from aqueous treatments seldom have surface tensions as
low as the injected fluids. It is commonly assumed that adsorption and dilution reduce the
effectiveness of the surfactants. These well returns issues are further complicated by the
difficulty in determining low concentrations of specific surfactant molecules. Nevertheless,
observed low surface tensions are thought to imply a very low residual surfactant concentration.
That assumption works well for cationic surfactants in which desorption occurs very slowly.
However, it might be inadequate for understanding nonionic surfactants such as C10-EO10.
Using the pre-adsorption surface-tension profile of Figure 3, the implied surfactant concentration
of a solution with a surface tension of 45 dynes/cm is 1E-4 M; using the post-adsorption profile,
the implied surface concentration is nearly 10 times higher. In fact, Figure 3 suggests that a
returning concentration of 1E-4 M would have a surface tension of 65 dynes/cm, normally
interpreted as being absent of surfactant.
Another trap could result from using the pre-adsorption CMCs to suggest oil/water
partitioning. At approximately 4E-5 M, the pre-adsorption CMC for the cocoamine quat was
very low. The initial prediction might be that this surfactant would partition much more readily
into oil than the C12-ester-sulfonate with a pre-adsorption CMC of approximately 8E-4 M.
However, the post-adsorption CMCs for both materials were the same at 1.3E-3 M.
Adsorption may also have the effect of increasing the apparent hydrophobic/lipophilic
balance (HLB) of the surfactant mixture. This might potentially alter the emulsification or
demulsification properties of the material in the matrix compared to the original surfactant
behavior out of the bottle.

Conclusions
Based on the results of this study, the following conclusions are made:
Keeping surface-active chemicals at the leading edge of injected fluids during flow through
porous media is extremely difficult because of strong adsorption.
Reducing surface tension in well returns is difficult because of the alteration that occurs in
the surface-tension profiles of surfactants after adsorption onto formation materials.
Surface-tension profiles and CMCs of commercial materials can be determined after
adsorption and should correlate better with well returns observations.

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References
1. Gdanski, R.D. and Funkhouser, G.P.: Adsorption Study of Acid Corrosion Inhibitor
Components, paper No. 4 presented at the NIF 2003 International Oil Field Chemistry
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2. Fowler, R. and Guggenheim, E.A.: Statistical Thermodynamics, Cambridge University
Press, Cambridge (1952) Chapter 10.
3. Gdanski, R.D. and Funkhouser, G.P.: Successful Model of the Kinetic Release of a
Phosphonate Scale Inhibitor, paper presented at the NIF 2001 International Oil Field
Chemistry Symposium, Geilo, Norway, April 1-4.
4. Rouquerol, J. and Partyka, S.: Adsorption of Surfactants on Rocks: Micro-calorimetric
Approach Applied to Tertiary Oil Recovery, J. Chem. Tech. Biotechnol. 1981, 31, 584592.
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Chromatographic Analysis of Alcohol Ethoxylates, Anal. Chem., 1998, 70, 4353-4360.
6. Kibbey, T.C.G. and Hayes, K.F.: A Multicomponent Analysis of the Sorption of
Polydisperse Ethoxylated Nonionic Surfactants to Aquifer Materials: Equilibrium Sorption
Behavior, Environ. Sci. Technol. 1997, 31, 1171-1177.

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