PRODUCTION
OPERATIONS
Effect of pH on Interfacial Films and Stability of
Crude Oil-Water Emulsions
J. E. STRASSNER
Abstract
Oilfield emulsions are stabilized primarily by film-form-
ing asphaltenes and resins containing organic acids and
bases. Adding inorganic acids and bases radically changes
the physical properties of these films and their emulsion-
stabilizing properties. Interfacial films show one of three
different physical characteristics when retracted in pendent
drop tests. These compressed films have rigid, soap-type
or minimum film properties depending on the quantity of
asphaltenes and resins in the crude oil and on the pH and
composition of the brine.
There exists for each crude oil-brine system an optimum
pH range over which the adsorbed film exhibits minimum
contracted film properties. In this range, interfacial tension
is high - frequently near its maximum value - indicating
the absence of highly surface-active species; crude ai/-
brine emulsions generally show minimum stability; and
surfactant requirements for breaking these emulsions are
significantly reduced - sometimes no surfactant is needed.
Introduction
About two-thirds of the world's crude oil is produced
as emulsions that must be treated (demulsified) to be
marketed.' Approximately three-fourths of all domestic
crude oil produced must be treated. The percentage of crude
requiring treatment increases as fields become older and
more water is produced. Demulsification most frequently
is attained through use of surfactants, heat and electric
treaters. It is estimated that over 75 percent of all oilfield
emulsions are broken by chemicals generally containing
alkylene oxide condensates.' Although acids and bases are
known to affect emulsion stability;-' they rarely are used
in the oil field except in batch treatment of the most
severe emulsions.
Nevertheless, pH adjustment by using acids or bases in
demulsification has some advantages over other methods.
Mainly, it is cheaper. Acids and bases frequently are
cheaper to use than surfactants, or can appreciably reduce
the amount of surfactant required for demulsification.
Secondary advantages are that less oil is lost by emulsi-
fication into the aqueous phase, and that less corrosion is
encountered when the optimum pH is basic. Limitations
to the use of pH include (1) use in brines containing high
concentrations of reactive ions, (2) closer supervision for
Original manuscript received in Society of Petroleum Engineers office
Aug 16 1967 Revised manuscript received Feb. 12, 1968. Paper (SPE
1939') w;"s pre~ented at SPE 42nd Annual Fall Meeting held in Houston,
Tex., Oct. 1-4, 1967. © Copyright 1968 American Institute of Mining,
Metal1urgicaI. and Petroleum Engineers, Inc.
'References given at end of paper.
This paper will be printed in Transactions volume 243, which will
cover 1968.
MARCH, 1968
ESSO PRODUCTION RESEARCH CO.
HOUSTON, TEX.
pH control than is required for surfact~nts and (~) need
for corrosion protection when the optimum pH IS suffi-
ciently acidic.
These factors indicate that the economics of pH con-
trol in demulsification will be maximized when relatively
large treating facilities are needed, when relatively large
surfactant concentrations are required to break an emul-
sion when a relatively low concentration of the aqueous
pha~e is emulsified in the oil and when the e~ulsified
aqueous phase contains relatively low concentratIOns of
reactive ions.
Because there are no broad guide lines for using pH
control in breaking oilfield emulsions (and because the
limited guides availal: 1e ar~ highly specific an? frequen~ly
contradictory), this paper will attempt to clanfy the pnn-
ciples involved in using acids and bases to break emulsions.
These principles also should be useful in refinery separa-
tions and in other oilfield applications where stable or
unstable petroleum emulsions are involved.
Principles of Emulsion Stability
Oilfield emulsions generally occur as water droplets dis-
persed in oil (wi 0) and occasionally as oil droplets in
water (o/w). These emulsion droplets are usually in the
0.1- to lO-micron range. However, more coarsely dispersed
water droplets frequently are present in the emulsion. Pure
hydrocarbons and water will not form stable emulsions
except in extreme dilutions where the large d~stance be-
tween droplets inhibits coalescence. An emulSIOn breaks
because interfacial tension acts to minimize the surface
area of the dispersed drops by coalescence. However.
emulsions can be stablized for long periods of time by
the presence of a third phase that adsorbs at the oil-water
interface and inhibits coalescence of the dispersed phase.""
Emulsions generally are stabilized by (1) repUlsive
charges on the surfaces of the dispersed phase and (2)
adsorbed films that, being preferentially wetted by the con-
tinuous phase, act as a physical barrier to inhibit contact
between the dispersed droplets.
Both these factors generally are important in stabilizing
and in breaking o/w emulsions. However, repUlsive charges
are less effective in stabilizing wi 0 emulsions which gen-
erally are stabilized by adsorbed films.s For this reason
the nature and importance of these films at oil-water in-
terfaces were examined closely; as will be shown, pH
changes were found to affect the films significantly, and
this work led to laboratory tests of pH adjustment in
emulsion breaking.
This paper will present evidence to show that emulsions
are stabilized primarily by films that form around droplets
303
of the dispersed phase. These films contain organic acids
and bases in widely different amounts. Adding inorganic
acids and bases strongly influences ionization of the or-
ganic acids and bases in the interfacial films, and radical
changes in physical properties of the films (rigidity and
mobility) occur with changes of pH in the aqueous phase.
For most crude oil-brine emulsions, there exists an opti-
mum pH range for which the adsorbed film exhibits mini-
mum emulsion-stabilizing properties. Surfactant require-
ments for breaking the emulsion at this minimum film pH
are significantly reduced; sometimes no surfactant is needed
at all. An example of an optimum pH range for a crude
oil-brine emulsion is shown in Fig. 1; in this case, the best
separation occurred in the neutral pH range of 6 to 8.
Appal'atus and Pl'ocedures for
Making Emulsions
Conventional techniques employed in emulsifying medi-
um-gravity crude oils are unsatisfactory for making repro-
ducible emulsions with viscous crude oils. Heating fre-
quently is desired in emulsifying viscous crude oils, and
care must be taken to prevent loss of volatiles and oxida-
tion of crude oil components at elevated temperatures. A
shaking mechanism that could make reproducible emul-
sions with 10- to ISO-ml volumes was designed so that the
emulsions could be made inside a temperature-controlled
uven and maintained in an inert atmosphere to prevent
oxidation and loss of volatiles.
Emulsifying Apparatus
A diagram of the shaking mechanism is shown in Fig. 2.
An electric motor rotates a disk. A sidearm is connected
to the disk and to a universal joint that connects to a rod
passing through the side of the oven. Samples to be emul-
sified are placed in appropriate-sized holders attached to
this rod. They are emulsified by shaking at controlled
speeds up to 1,000 rpm. Stroke lengths can be 2, 4 or 6 in.
In most tests emulsions were made by shaking for 5 min-
utes at 600 rpm on a 4-in. stroke.
Fig, I-Example of optimum pH range of 6 to 8 giving
maximum water breakout for crude oil-brine emulsion,
304
Emulsion-Measuring Tubes
Fig. I is a photograph of a series of pH tests made with
screw-cap tubes of approximately IS-ml capacity. The
tubes are calibrated with O.l-rnl markings and readings
are repeatable to ± 0.05 ml. These tubes fit into a six-tube
holder that attaches to the shaking arm. Six 50-ml tubes
were similarly employed using a large tube holder. Two
200-ml tubes were used to determine the water remaining
emulsified in the oil layer; these large tubes were equipped
with circular stopcocks to allow removal of known quan-
tities of water or emulsion for analyses.
Preparation of Emulsions
Emulsions were made by adding the desired volumes of
oil and brine until approximately two-thirds of the con-
tainer's capacity was filled, the air space was flushed out
with nitrogen and then the mixture was shaken for the
desired length of time at a selected shaking rate. The
emulsifying tubes were calibrated and the percent of water
breakout was determined directly from the calibrated read-
ings. In tests at elevated temperatures, the system was pre-
heated 30 minutes to bring the liquids into temperature
equilibrium before they were emulsified. After it was pre-
pared, the emulsion was aged 30 minutes at the test tem-
perature to allow additional adsorption to occur at the
oil-water interface. Then the demulsifier was added and
the mixture was reshaken using the previous shaking
schedule.
Measuring Emulsion-Stahilizing Films
The ability of crude oils to form films can be measured
easily with a pendent drop apparatus.'o In this method the
tip of a capillary is immersed in water and an oil drop is
formed by forcing oil through the capillary into the
aqueous phase. The oil drop is allowed to age in the water
for a short time and then is retracted into the capillary.
As the surface area of the drop is compressed to smaller
dimensions, the film-forming materials that have adsorbed
at the oil-water interface are compressed until the film
assumes a crinkly or prune-skin appearance (lower part
of oil drop, Fig. 3).
The pendent drop technique can be used to approximate
the quantity of film-forming materials present in a crude-
brine system. In the technique used for this paper, a
freshly formed oil drop is photographed after being aged
for 20 seconds in brine. The oil drop then is contracted
until a sharp change is observed in the geometry of the
drop. This occurs when the materials adsorbed at the oil-
water interface become highly compressed. The drop then
is filled out to the size it attained just before this change
in geometry occurred, and a second photograph is taken
(Fig. 4) . The cross-section areas of these two drops are
measured from these photographs with a planimeter. The
ratio of the cross-section area of the compressed drop to
that of the original drop is the film ratio and is a measure-
ment of the rate of film formation.
SCREW CAP
CALIBRATED
BOTTLES WITH
STOPCOCKS
TEMP CONTROLLED OVEN
Fig. 2-Shaking apparatus for preparing emulsions.
JOURNAL OF PETROLEUM TECHNOLOGY
 The film ratIo is directly proportional to the concentra- was used as a stabilny criterion. Viscosity contributes to
tion of film-forming materials in the interface. This does the stability of emulsions because it increases the floccu-
not imply that the same concentration of surface-active lating time of the dispersed water droplets and because
materials in different crude oil-brine systems would give larger fractions of polar asphalts and resins are present in
identical film ratios. This will be demonstrated later. How- these higher-viscosity, higher-density crude oils." Brines
ever, Harveyll showed that film ratio (film factor) can be
used together with the Gibbs equation and the film gas
law to calculate the concentration of surface-active com-
ponents in a given crude oil-brine system.

Nature and Importance of Films at

Oil-Water Interfaces
Examples of oilfield emulsions and of the emulsion-
stabilizing role played by a film adsorbed at an oil-water
interface are shown by photomicrographs in Figs. 5 and 6.
The distance between two marks on the scale at the bottom
of Fig. 5 is 5 microns, and most of the water droplets in
the system are from 1 to 5 microns in diameter. These
tiny water droplets are surrounded by a film formed by
adsorption of asphaltic and resinous materials from the
crude oil, along with solids that are dispersed in the system.
These films prevent water droplets from coming together
sufficiently to coalesce and separate from the emulsion.
An example of ruptured films that had surrounded water
droplets in an aged crude oil emulsion is shown highly
magnified in Fig. 6.
Correlation of Emulsion Stability with Film
Ratio, Oil Viscosity and Polar Oil Fractions
Film ratio and crude oil viscosity are excellent indexes
of emulsion stability, as shown in Fig. 7, which represents
45 crude oils from 21 reservoirs throughout the world. All
crude oils having film ratios of 20 percent or greater and
viscosities of 6 cp or greater produced stable emulsions;
86 percent of the crude oils tested fit this correlation when
only one of these two indexes (film ratio or viscosity) Fig. 4-Double-exposure method ot measuring film ratio.

Fig. 3-Emulsion-stabilizing rigid film is visible when Fig. 5-Natural crude oil emulsion (1 scale division
compressed by retraction ot crude oil pendent drop. equals 5 microns).

MAIlCH,1968 305
 TABLE I-EMULSIONS STABILIZED BY POLAR FRACTIONS OF CRUDE OIL
Percent Polar Fraction Interfacial Properties
Asphalt Resin Emulsions Films Glass Wettability

0-0.01 0-0.9 Unstable Mobile if present Water

0.05·0.10 9-10 Moderately stable Mobile Water
0.7-2.4 5·12 Stable Rigid Oil
14 17 Stable Mobile or rigid Usually water,
(depenjing on brine) some oil -wet

varied from 3 to 10 percent in salt content; all contained
salt ratios of 10: 1 NaCljCaCI" and were unbuffered at
pH 7.
Oilfield emulsions are stabilized by polar asphaltene and
resin fractions, as shown in Table 1, which summarizes
data of Table 2. The asphaltene fraction is obtained by
precipitation when the crude oil is diluted 40 times its
original volume with pentane. The resin fraction is ob-
tained by treating the pentane filtrate from the asphaltene
precipitation with fuller's earth and then Soxhlet-extracting
with boiling toluene. Emulsions also can be stabilized by
fine solids such as precipitated waxes, and by formation
solids, scale and corrosion products that become oil-wet
by adsorption of polar asphaltene and resin fractions in
the crude oil.
Many of these emulsifying crude oils showed oil-wetting
characteristics on glass slides (Table 2) but this was not
so reliable an emulsion-stability index as film ratio or
viscosity. Oil-wetting ability on glass slides usually is in-
dicative of nonsterically hindered nitrogen groups, and
occurs only in those crude oils having higher asphaltene
contents. These results extend Bartell's and Neiderhauser's
API Project 27" and support their conclusion that the film-
forming components in crude oil are closely related to
asphaltic substances, and are the chief factors responsible
for petroleum emulsion stability. The contribution of polar
crude oil fractions to emulsion stability is more clearly
illustrated in the following sections.
Film Mobility
Observations of physical characteristics of compressed
films also can be made with the pendent-drop technique.
When a drop of crude oil is aged in brine and retracted
so that the interfacial film is compressed, three types of
film mobility are observed :
I. Solid (or rigid) films that under compression form
relatively insoluble skins as oil is withdrawn into the capil-
lary. (These films are of relatively high interfacial vis-
cosity.)"-"
2. Highly mobile (or liquid) films that pack under com-
pression to give a momentary distortion of the drop, but
rapidly redistribute and return the drop to a symmetrical
shape when contraction is stopped. (These films are simi-
lar to those formed by surfactants and are of relatively
low interfacial viscosity.) 13-14
3. Transition or nonmeasurable films (by the pendent-
drop retraction technique) that show no distortion under
compression of the pendent drop and whose presence is
indicated only by the lowering of interfacial tension.
(These films obviously are of low interfacial viscosity;
the author has not attempted to measure them, however.) "
Effect of Surfactants on Film Properties
Film ratio and film mobility are strongly affected by
commercial surfactants. Relatively low concentrations (a
few ppm) of these surfactants drastically reduce oil-brine
interfacial tension. The surfactants occurring naturally in
crude oil (i.e., asphalts and resins) reduce the interfacial
tension only moderately at intermediate pH values . These
natural materials show strong surfactant properties that
are competitive with commercial surfactants only in highly

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Fig. 7--Correlation of emulsion stability with film ratio

Fig. 6-Example of ruptured rigid films that once and crude oil viscosity (stable emulsions form when film
stabilized two large water droplets in a crude oil emulsion. ratio is over 20 percent and viscosity is over 6 cp).
306 JOURNAL OF PETROLEUM TECHNOLOGY
acidic or basic solutions. Therefore, commercial surfac- 100r----------------------------,--------,
tants can easily displace natural surfactants from the crude I i
oil-brine interface at the intermediate pH conditions of
u MOBILE FILMS I RI~ID FILMS
most produced emulsions. For economic reasons, how- w I I
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ever, it is desirable to add only the minimum amount of o
surfactant that is required to break the emulsion in the '" I
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time available. Under these conditions, a concentration of g 50 ----.. __L- __
commercial surfactant insufficient to cover all the inter- < I
face present in the emulsion frequently is used. This re- '"
sults in a film of natural and commercial surfactants of a
mixture that determines the stability of the emulsion.
Fig. 8 shows how adsorption of a commercial surfactant
reduces interfacial tension sufficiently to displace the nat-
ural surfactants from the oil-water interface at pH 7.
10 20 40
Addition of 0.01 percent (l00 ppm) surfactant reduced INTERFACIAL TENSION - DYNES/CM
the interfacial tension between a 35° API gravity Vene-
zuelan crude oil and a 3 percent brine from 33 to 23 0.1 .01 o
dynes/ cm. This resulted in a mixed surfactant-crude film % SURFACTANT
having a mobility between that of the rigid crude oil film
Fig. 8-Displacement of a rigid crude oil film by
and the mobile surfactant film. Additional surfactant
caused the interfacial film to assume increased mobile
mobile surfactant film.
surfactant characteristics. Whether this change results in
decreased or increased emulsion stability depends on the oil emulsions. The following section gives some of the
chemical structure of the surfactant, i.e., on its size and results obtained.
ratio of hydrophilic to oleophilic groups. With emulsifying
Polar Fractions Determine Crude
surfactants, displacement of the rigid film did not result in Oil Film Properties
demulsification. When demulsifying surfactants were added, Fig. 9 shows how polar asphaltene and resin fractions
displacement of the rigid film resulted in more rapid de- from a 35° API gravity Venezuelan oil affect film ratio
mulsification. Adding more surfactant increased the mo- and mobility. In this series of tests, the asphaltene fraction
bile surfactant film properties of the interface and resulted was obtained by pentane precipitation, and the 12-percent
in more rapid demulsification until a concentration was resin oil was obtained by evacuating off the excess pentane
reached that retarded demulsification because of the after the asphaltene was removed. Asphaltene then was
strong surfactant film formed. added in increasing amounts, and the film ratio was
These results indicated that film tests should be made measured with the pendent drop apparatus. The 12-per-
of the natural surface-active agents that are present in cent-resin crude oil from which asphaltenes were removed
crude oil (particularly the polar asphaltene and resin frac- produced mobile or liquid films similar to weak surfactant
tions) to help understand their role in stabilizing crude solutions. Addition of asphaltene reduced these mobile

TABLE 2-PROPERTIES OF CRUDE-OIL EMULSIONS

3 to 10 Percent Brine (10:1 NaCI/CaCI,) Unbuffered pH 7
Percent Percent Surface Crude Oil
Gravity Asphaltenes Resins 24-Hour Film Ratio Oil-Wet Viscosity
Crude Oil CAPI) (percent) (percent) Emulsion (Film Rigidity) (percent) (cp)
-------

Wyoming 43.6 0.0 0.9 0 37'" 0 1

(mobile)
Venezuela 41.1 2.2 6.7'~'~ 60 10 30 4
(weak)
Texas Gulf Coast 39.9 0.7 5.2 100 31 70 8
(strong)
Texas Gulf Coast 39.0 1.8 5.0 100 24 80 5
(strong)
France 36.0 2.0 8.5 100 56 75 7
(strong)
Libya 35.0 1.7 100 35 75 13
(strong)
Venezuela 33.8 2.4 12.1 100 40 50 11
(strong)
Texas Gulf Coast 28.0 0.07 9.8 100**'" 3 10 16
(weak)
Venezuela 13.2 14.0 16.8 100 Crude oil >10,000
too viscous
to measure
~'Mobile soap film (all others formed rigid films).
""~Pentane fraction remained dark (may be contaminated).
***Stability is reduced at elevated temperatures more rapidly than that of higher percent asphaltene crudes.

MARCH, 1968 307

film ratios to zero at 1.6 percent asphaltene content. Fur-
ther addition of asphaJtene increased the film ratio and
resulted in rigid or solid films. Similar tests with 2.4 per-
cent-asphaltene oil with resins removed formed rigid films
with ratios that decreased slightly in magnitude (film
ratio) as resin content was increased. Thus, the asphaltenes
are responsible for rigid film formation and the resins
form reversible films; their interaction gives the film prop-
erty of the crude oil.
Effect of pH on Film Properties
and Emulsion Stability
Since these polar fractions in crude oil are known to
contain acidic and basic groups," the pH of the water in
an emulsion can be expected to affect both the quantities
and types of materials comprising the interfacial film.
Therefore, an investigation was begun of how pH affects
film properties and emulsion stability.
Effect of pH on Emulsion-Stabilizing
Polar Fractions
It was found that adjusting pH significantly affected the
film-forming, oil-wetting and emulsion-stabilizing proper-
ties of the polar asphaltene and resin fractions. The crude
oil fraction remaining after these polar asphaltenes and
resins were removed consisted primarily of nonpolar waxes
and oils and was not significantly affected by pH. These
results were obtained by making qualitative comparisons
of the properties of polar and nonpolar fractions from
several of the crudes listed in Table 2. Tests with these
crude oil fractions were made in acidic pH 4, neutral pH
7 and basic pH 10 brines containing 3 percent NaCl and
0.3 percent CaCl,. The following observations were made.
1. The rigid interfacial films formed by asphaltenes are
strongest in acid pH, intermediate in strength at neutral
pH and become very weak or are converted to mobile
films in basic pH. (Asphaltenes show both acidic and
basic properties and can be considered as a higher molecu-
lar weight ampholite having more basic amine-type prop-
erties in acid and neutral pH, and more weak-acid proper-
ties in base.)
2. The mobile films produced by resins are strongest in
base and weakest in acid. (Resins show only acidic prop-
erties and can be considered as weak organic acids of
lower molecular weight than the asphaltenes.)
3. The films formed with the remaining wax-oil fraction
are insignificant.
100
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MOBILE FI:MS : RIGID FILMS
0
i=
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OL------L---~-~-----~------~------~
a 2 3 4
% ASPHALTENE
Fig. 9-Asphaltenes give crude oils their rigid
film properties.
308
4. Asphaltenes promote strong oil-wetting of silica sur-
faces. These effects are somewhat stronger in acid than in
base. Resins and wax-oil fractions do not oil-wet silica.
Asphaltenes plus resins promote oil-wetting in acid pH,
but change to water-wetting in basic pH if the salt content
of the brine is kept low. Produced crude oils nearly always
contain some fine solids, and it is well known that when
these solids become partially oil-wet they tend to stabilize
crude oil emulsions.
5. Asphaltenes make more stable emulsions than do
resins. The wax-oil fraction is not emulsifying; its primary
contribution to stabilizing emulsions is in building vis-
cosity. Asphaltenes show slightly greater emulsifying prop-
erties in acid, and resins show slightly greater emulsifying
properties in base. The stability of emulsions containing
both asphaltenes and resins shows varying sensitivities to
pH. This will be discussed in the following section.
Qualitative tests indicated that the stability of most oil-
field emulsions would be sensitive to pH changes. To apply
pH adjustment to breaking oilfield emulsions, a more
quantitative correlation between pH, film properties and
emulsion stability was needed. Therefore, the effect of pH
on the formation of emulsions was examined.
Effect of pH on Emulsion Type
and Stability
The type of emulsion (w/o or o/w) as well as its sta-
bility is affeced by pH, as illustrated in Table 3 for 50:50
emusions of a 13.20 API gravity Venezuelan crude oil and
distilled water. Acid pH produced stable wI 0 emulsions
(corresponding to oil-wetting solid films), whereas basic
pH produced stable olw emulsions (corresponding to
water-wetting mobile soap films). These emulsions were
least stable in the pH 10 to 11 range and showed minimum
stability at pH 10.5. However, increased brine concentra-
tion frequently produced wlo emulsions at higher pH.
Reduction of Emulsion Stability
by Reduction in Film Properties
The relationship between film properties and emulsion
stability is illustrated in Figs. 10 and 11. Film ratio (which
is a direct measurement of the film-forming properties of
the crude oil), interfacial tension (which is a direct
measurement of the ease of distorting the interface) and
percent water breakout (which is a direct measurement of
emulsion instability) are all plotted vs the pH of the
aqueous phase. The oil phase is the same 13.20 API
gravity Venezuelan crude oil used in Table 3. However, it
is diluted 50: 50 with toluene to reduce its viscosity so
that pendent-drop retraction measurements can be made.
The aqueous phase in Fig. 10 is distilled water, and in
Fig. 11 it is brine containing 2,000 ppm of bicarbonate ion
and 4,440 ppm of total salt content.
TABLE 3--EFFECT OF pH ON EMULSION TYPE
AND STABILITY
(13.2° API Gravity Venezuelan Crude Oil + Distilled Water)
Emulsion Emulsion
2.!:!.. Type Stability
wlo High
wlo High
10 wlo Low
5
10.5 none Unstable
11 olw Low
13 olw High
JOURNAT~ OF PETROLEUM TECHNOLOGY
 The film ratio plot in Fig. to shows that solid, prune-
skin-like films are formed in the acid and neutral pH
range. This film ratio becomes very small at pH to. At
still higher pH the film ratio increases and the film changes
to a liquid surfactant type as additional soap formation
occurs. The second plot in Fig. 10 (interfacial tension vs
pH) shows that this liquid film forms simultaneously with
a very rapid decrease in interfacial tension. The interfacial
tension at minimum film ratio is still quite high, indicating
that highly surface-active species are not present. Some
surface-active materials are present, however, or the inter-
facial tension would be in the 40 to 45 dynes/cm range
typical of pure hydrocarbon-water systems. At still more
acid pH than shown in this graph, the interfacial tension
becomes much smaller, similar to the drop in interfacial
tension shown at pH 11 and indicating that strong sur-
factants (probably positively charged nitrogen compounds")
are produced at extremely acid pH. A bell-shaped curve
for pH vs interfacial tension also was observed by Reis-
berg and Doscher." They reported that solid films were
observed in acid and neutral pH, but not in basic pH.
However, no minimum film pH values or liquid-surfactant-
type film properties were reported.
Percent water breakout in 24 hours is plotted against
pH of the distilled water phase in the third curve in Fig.
to. Maximum water breakout occurs at pH to, which is
the pH of minimum interfacial film formation and also a
pH at which the interfacial activity is low (interfacial
tension high). If we go to higher or lower pH, we have
less water breakout. Thus, emulsion instability is related
to minimum adsorption at the interface.
Fig. 11 illustrates these factors for the same crude oil
in 4,440 ppm of brine that contains 2,000 ppm of bicar-
bonate ion. This bicarbonate ion is a strong buffer and
changes the pH required for minimum film properties
from pH to, which was optimum with distilled water, to
a pH of about 6 or 7, as illustrated in the film curve of
Fig. 11. Below pH 5, solid·type interfacial films are
formed. Above pH 7, liquid or surfactant-type films
occur. A transition zone occurs between pH 5 and 7. It
is seen that maximum interfacial tension occurs simul-
taneously with minimum interfacial film formation about
pH 6; the percent water breakout goes through a maxi-
mum in approximately this same pH range. Thus, in two
different aqueous systems, minimum emulsion stabilities
occur at widely different pH values corresponding to mini-
mum adsorption of film-forming components from the
crude oil.
The variation in pH required for breaking emulsions of
the Venezuelan crude oil with distilled water and with
buffering brine may be explained by a difference of pH
in the bulk aqueous phase and at the oil-water interface.'
In buffered systems, these pH values are nearly the same.
In unbuffered systems, their pH values frequently differ
by several pH units. Thus, pH to bulk water and pH 7
bulk buffered-water systems both may have interfacial pH
values near 7 with the Venezuelan crude oil.
The water breakout curve in Fig. 11 is for an emulsion
containing 13 ppm surfactant and a brine-oil ratio of 1: 3.
At the optimum pH of 6.5, 75 percent of the water origi-
nally emulsified broke out in 24 hours. Appreciably less
breakout occurred at higher and lower pH. Similar tests
without surfactant gave a small (6 percent) water break-
out at pH 6 but nothing at the other pH's. A third test
series with 15 ppm of surfactant and an emulsion having
a brine-oil ratio of 1: 2 gave optimum water breakout of
97 percent at pH 7 and 94 percent at pH 6. Appreciably
less breakout occurred at the other pH's.
Generally, emulsions of high water content are easier
to break than emulsions of low water content. Most com-

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"'
~ 30 ~RANSITION J
ZONE
o
~
a:
20
I'" ~~ 0
........,
i'... f- ~ J
'~"
"1'\.1
I
10
I l
o
2 4 6
~
8 10 pH
40
0
~ y
0 40
2 4 6 8 10 pH

30
~
"'i\ ...-+--.
20
V r'a 20

Io V \ It>
1\ Io

"'
a:
I
10 0
2 4 6 8 10 pH
o
on
10 0
2 4 6 8
~ 10 pH
o
.,. L~
a:
I
N 75
;1;7 5
~
I-
::>
~ 50
) ~
I-
::>
o / "'"'\
<t
W
a:
ID

~ 25
[..-D'" ~ 50
LoJ
a:
ID
JV " 3 BRINE 'OIL
EMULSION
1\
r\
a:

Vr
w2 5 +
~
I- I-
~ ~ ppm
T'ON'C
0
o 4 6 8 10 12 o
pH OF DISTILLEO WATER PHASE
o 4 6 8 10 12
pH OF BUFFER BRINE PHASE

Fig. 10-Stability of Venezuelan crude oil-distilled water Fig. ll-Stability of Venezuelan crude oil-bicarbonate
emulsion reduced by reducing film properties. hrine emulsion reduced by reducing film properties.
MARCH, 1968
309
 mercial emulsion treaters contain a water layer and a
-sparge to produce additional water-oil contacts that are
helpful in diluting the emulsifying surfactants of the crude
oil, thus aiding in demulsification. Higher concentrations
of treating surfactant, within a limited economic treating
range, generally result in more rapid breakouts but at
proportionally higher treating costs.
Application to Specific Crude Oil-Brine Systems
13.2° API Gravity Venezuelan
Crude Oil Emulsion
A series of tests with undiluted 13.2° API gravity Vene-
zuelan crude oil-brine emulsions at 185F showed that
maximum demulsification occurred in the pH range of 6
to 7 (Fig. 12), the same pH as in the toluene-diluted tests
at 75F in Fig. 11. At a water-oil ratio of 2: 1, 95 percent
water breakout occurred at pH 6 to 7 whether demulsify-
ing surfactant was used or not. However, surfactant did
broaden the pH range over which maximum water break-
out was achieved. At a water-oil ratio of 1: 1, percent
water breakout was slightly lower, even with 50 ppm of
surfactant.
In Fig. 15, water breakout in 24 hours is plotted vs pH
for this same crude oil emulsified with a 2 percent NaCl
non buffering brine. The higher optimum pH of 11 to 11.7
again illustrates that nonbuffering brines have higher opti-
mum treating pH requirements. The actual amount of base
needed, however, is less than that required for the buffer-
ing brine at lower pH. Appreciably higher concentrations
of surfactant would have been needed to attain equivalent
(99 to 100 percent) water breakout at the natural pH of 7.
The water breakout curve for 18 ppm of surfactant
with NaOH added for pH adjustment is particularly sig-
nificant. The amount of NaOH required for pH adjust-
ment was calculated and added to the prepared emulsion.
In the other three tests the pH of the brine had been ad-
justed before emulsification. Similar results were obtained
in both types of pH adjustment. The same optimum pH of
11 was obtained when NaOH was added to the emulsion
as when NaOH was added to the brine before emulsifica-
100
90

.f
u..
37.7° API Gravity Illinois Crude °1/\ 80 I

Oil Emulsions
The beneficial effect of pH adjustment in breaking 37.7° ".... 70
....:J<
API gravity Illinois crude oil emulsions is shown in Fig.
13, which shows percent water breakout as a function of
pH. Optimum pH for demulsification is 10. More rapid
breaking was observed at pH 10 when 30 ppm of demulsi-
0
~
60
30 PPM SAA
J 1_ ~_R_ ' - \
i i
--t
fier was added. The 24-hour tests with 30-ppm surface <
LLI
50 +- NO SAA
c.:: '24 HRS
active agent (SAA) show fairly complete demulsification c:a
for pH 4 to 10. This field concentration is too high for 40 - .J-
c.::
laboratory tests since 100 percent breakout is observed ....
LLI
30
I
over the entire pH range of 4 to 10; these results suggest < I~-
that a combination of pH and demulsifier may be most ~
advantageous for treating emulsions. 20
~
24.8° API Venezuelan Crude Oil Emulsion 10
Fig. 14 shows the effect of pH adjustment on 4,440 ppm
of brine containing 2,000 ppm of bicarbonate emulsified 00
in 24.8° API gravity Venezuelan crude oil. With no de- 4 6 8 10 12 14
mulsifying surfactant added, maximum water breakout pH
occurred at pH 10 but water breakout was only 45 per- Fig. 13--37.7° API gravity lllinois crude oil emulsion
cent. With 30 ppm of surfactant added, maximum water with 10 percent brine (10:1 ratio oj NaCl/CaCI,)
breakout was 98 percent. Still higher concentrations of is least stable near pH 10.
surfactant would have been needed to attain 98 percent
water breakout at the natural pH of 8.3. 100
90

'"ar:::E: ..... 80
.... 0
o:t 80 ::>11)
N 70
z 0"
::'=:t-
560---
«w 60
WATER.i:-Of[ SAA ar:1I)
o::.c: A 1': 1 50 PPM:
caar: SO ~

<I: o 2: 1 0 PPM
ar::I:
w w"l"
ar: • 2 :1 SO PPM -- - t-C'I 40
al <ar:
ar: ~w
w
I- ~
....
..... 30 - -- ~---

<I: 20 «
~ 20 - .

~
10
°4~--~5--~6--~7~~8~--9~~10
pH OF AQUEOUS PHASE 00 2 4 6 8 10 12 14
pH
Fig. 12-132° API gravity Venezuelan crude oil emulsion
with bufJering brine (least stable in pH range Fig. 14-24.8° API gravity Venezuelan crude oil with
of 6 to 8 at 185F). bicarbonate bufJer brine (least stable near pH 10).

310 JOURNAL OF PETROLEUM TECHNOLOGY

 100 . ; ; I
pH for demulsification. This versatility greatly broadens

90
! 18 PPM SAA
(pH BY ADDING
{AI
{I t
the manner in which pH adjustment might be made in the
field.

'-0
U-
80 - _. . -.
NaOH TO EMULSION)
--r-~
I I
j _. -1--- Effect of Brine Composition on Demulsification
=>&n
0'"
::.,,:.-
70 ----1- :- Emulsions prepared with several different· crude oils and
brines were SUbjected to a series of tests by adjusting pH
«
LU 60 and treating them with surfactants. The goal of this work
a!: V)
1lQa!:
was to define the effect of brine composition on optimum
~ pH for demulsification. Optimum pH values for demulsifi-
a!::I: 50 ---

LU~
'-('01
<a!:
~LU
~u-
.-
< from distilled water through dilute brines to 10 percent
11
Fig. 15-24.8° API gravity Venezuelan crude oil with
nonhufJering 2 percent NaCI brine (least stable
near pH 11.0 to 11.7).
tion. Therefore, it seems reasonable that pH adjustment
similarly can be applied to break field emulsions or to
prevent their formation.
Effect of Order of Acid or Base Addition and
Concentration on Emulsion Stability
Although most data given in this report were obtained
by measuring water breakout of systems in which pH was
adjusted before emulsification, three series of tests showed
that successful emulsion breaking could be obtained sim-
ilarly by adding acid or base after emulsification. Acid or
base was used successfully in both concentrated and
diluted forms. If too much acid or base was added, the
system could be "back-titrated" with base or acid; in fact,
accelerated demulsification was observed in one series of
tests in which excess base was added purposely to an
emulsion and then back-titrated with acid to the optimum
cation of four crudes and seven brines are given in Table 4,
which shows a definite correlation between the optimum
pH observed from water breakout data and that predicted
from minimum film pH data. Brine strength was varied
brines that contained single sa Its or combinations of NaC!,
CaCl" MgSO" NaHCO, and Na,HP04 • Each crude oil-
brine system tested showed preferred but frequently dif-
ferent optimum pH ranges for demulsification. In those
12 cases where the optimum pH range was broader than two
pH units, the pH giving most rapid demulsification is
underlined.
Although the optimum pH for demulsification varies
widely when brine-oil compositions vary widely, the pH
range from 5 to 12 appears optimum for treating most
oilfield emulsions. An insufficient number and variety of
crude oil-brine systems were tested to draw final conclu-
sions regarding the effect of brine and oil composition on
the optimum pH for demulsification. Nevertheless, some
qualitative relationships appear warranted and may be
helpful in locating more quickly the optimum treating pH.
In general, basic pH is optimum for most brines that
do not contain appreciable quantities of buffering ions
such as bicarbonates and bisulfides. Crude oils emulsified
with non buffering brines generally have optimum pH
ranges of 8 to 12 for demulsification, and most of these
fall in the pH range of 9 to 11. For crude oils emulsified
with buffering brines, a lower optimum treating pH range
of 6 to 10 frequently is observed. More viscous, lower
API-gravity crude oils generally favor lower portions of
these pH ranges, whereas less viscous, higher API-gravity
crude oils favor higher portions of these pH ranges for

TABLE 4-EFFECT OF BRINE ON OPTIMUM TREATING pH'~

Optimum pH for Demulsification (Crude Oils)"

Venezuela Illinois Venezuela Venezuela
Brine Test Procedure 13.2° API 37.7° API 35.0° API 24.8° API
Distilled water Maximum water breakout 9-11 10-12 10-12
Minimum film ratio 9·10 9·11 9-11
0.44 percent NaCI Maximum water breakout 8·10
Minimum film ratio 6-9
0.44 percent CaCl, Maximum water breakout 4-12
Minimum film ratio 5-12
0.44 percent brine (0.2% HCO;) Maximum water breakout 6-7 6-10 6-8 8-10
Minimum film ratio 6-7 9-10 7-8 7-9
0.44 percent Na,HPO, Maximum water breakout 6-8
Minimum film ratio 6-7
1 percent (10 NaCI/l CaCl,) Maximum water breakout 4(10)12 10-12 10·12
Minimum film ratio --g:} 1 9-12 9-12
2 percent NaCI Maximum water breakout 10-12
10 percent (10 NaCI/l CaCl,) Maximum water breakout 4-10 4(10)12 8-12
Minimum film ratio 5-11 8-12 6-12
'~Most of these optimum pH ranges for maximum water breakout were obtained from emulsions treated with 15 to 50 ppm
of demulsifying surfactants. The minimum film ratio data were obtained from oil·brine systems free of surfactants.

MARCH, 1968 311

 optimum demulsification. Higher pH appears to give bet-
_ter demulsification in brines containing higher concentra-
tions of divalent ions.
Conclusions
1. Emulsions commonly encountered in producing crude
oil are stabilized by films that form at the water-oil inter-
faces and interfere with coalescence of dispersed water
droplets. These emulsion-stabilizing films are composed of
interfacially active materials from the asphaItene and resin
fractions of the crude oil combined with ions from the
aqueous phase and insoluble fines in the crude oil-brine
system.
2. Emulsion stability can be decreased by conditions
that reduce the film-forming capacity of the crude oil.
These films can be minimized or their physical properties
altered by treatment with acids and bases alone or in
conjunction with inorganic salts, surfactants, heat or
electricity.
3. An optimum pH, at which value maximum emulsion-
breaking occurs, exists for most crude oil-brine systems.
The optimum pH for maximum emulsion instability de-
pends on both crude oil and brine composition. Brine com-
position is the more important from the standpoint of
economics of pH adjustment.
4. Laboratory results indicate that many crude oil emul-
sions can be demulsified at significantly lower costs if
they are treated at their optimum pH values. It is not
common field practice at this time to adjust emulsion pH.
5. In addition to pH, many other factors such as crude
oil viscosity, water-oil ratio, brine composition, fine solids,
agitation, temperature and aging also affect emulsion sta-
bility. Because of these numerous variables, the final opti-
mum emulsion-treating system must be established by field
tests. Laboratory tests will serve as useful guides to the
field tests.
Acknowledgments
The author wishes to express his appreciation to Esso
Production Research Co. for permission to publish this
paper. The assistance of F. E. Campion, C. D. McAllister,
J. L. Martin and P. D. Cratin in helping obtain much of
the data presented in this paper and in helpful criticism
of the work is gratefully acknowledged.
References
1. Steinhauff, F.: "Modern Oilfield Demulsification. Part I",
Petroleum (1962) Vol. 25, 294.
312
2. Love, F. E.: "Oilfield Emulsions . . . How to Make and
Break Them. Part I", Oil and Gas Internatl. (1962) Vol. 2,
No. 9,56.
3. Shapiro, A: "Demulsification of Petroleum", U. S. Patent
No. 2,217,387 (1940).
4. Catanach, A E. and Gulley, R. P.: "Process of Breaking
Water and Oil Emulsions", U. S. Patent No. 2,566,980
(1951).
5. Sumerford, S. D.: "Resolving Emulsions", U. S. Patent No.
2,662,062 (1953).
6. Harkins, W. D.: The Physical Chemistry of Surface Films,
Reinhold Publishing Corp., New York (1952).
7. Davies, J. T. and Rideal, E. K: Interfacial Phenomena,
Academic Press, New York (1961).
8. Albers, W. and Overbeek, J. Th. G.: "Stability of Emul-
sions of Water in Oil. I. The Correlation Between Electro-
kinetic Potential and Stability", J. Colloid Sci. (1959) Vol.
14, 501-509; "II. Charge as a Factor of Stabilization Against
Flocculation", J. Colloid Sci. (1959) Vol. 14, 510-518.
9. Sachanen, A. N.: The Chemical Constituents of Petroleum,
Reinhold Publishing Corp., New York (1945).
10. API Recommended Practice for Laboratory Testing and
Field Data Analysis of Surface Active Agents for Well
Stimulation, API, 1st Ed. (Nov., 1962).
11. Harvey, R. R.: "Theoretical Approach to the Investigation
of Films Occurring at Crude Oil-Water Interfaces", Trans.,
AIME (1960) Vol. 219, 350-353.
12. Bartell, F. E. and Neiderhauser, D.O.: "Film Forming
Constituents of Crude Petroleum Oils", Fundamental Re-
search on Occurrence and Recovery of Petroleum, 1946-47,
API (1949) 57.
13. Reisberg, J. and Doscher, T. M.: "Interfacial Phenomena
in Crude-Oil-Water Systems", Prod. Monthly (1956) Vol.
21,43.
14. Kimbler, O. K, Reed, R. L. and Silberberg, I. H.: "Physical
Characteristics of Natural Films Formed at Crude Oil-
Water Interfaces", Soc. Pet. Eng. J. (June, 1966) 153-165.
***
J. E. Strassner is a senior research
chemist with Esso Production Research
Co. in Houston working in surface
chemistry applications to petroleum pro-
duction and operations. Strassner
worked 6 years as a reseCNch chemist
and group leader in surface chemistry
applications at Dowell hefore joining
Es.\·o in 1961. He received his PhD de-
gree in chemistry from Louisiana State
U. in 1955.
JOURNAL OF PETROLEUM TECHNOLOGY