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The effect of increasing hydrogen ion concentrationupon the emulsifying power of sodium oleate
Item Type text; Thesis-Reproduction (electronic)
Authors Potthoff, Herbert Benjamin, 1903-
Publisher The University of Arizona.
Rights Copyright © is held by the author. Digital access to this materialis made possible by the University Libraries, University of Arizona.Further transmission, reproduction or presentation (such aspublic display or performance) of protected items is prohibitedexcept with permission of the author.
Download date 26/06/2018 09:25:18
Link to Item http://hdl.handle.net/10150/621865
THE EFFECT OF INCREASING HYDROGEN ION CONCENTRATION
UPON THE EULSIFYING POWER OF SODIUM OLEATE.
by
Herbert B. Potthoff
Submitted in partial fulfillment of the
requirements for the degree of
Master of Science
in the College of Letters, Arts, and Sciences,
University of Arizona
1 9 3 4
Approved: 644- 23Major professo ate
TABLE OF CONTENTS*
THE- EFFECT OF IIICREASiAG HYDWGEN ION CONC=TRATiON
UPON TilE EL7LSIFYIN G POW Mt OF SODIUU OLEATE.
Page
The Objectives or the Study ..
The Relationship of the flb j e ives to the GeneralField of Colloid Chemistry - ... . 4
The Variation of the Stability _ of the EmulsionsStudied with Decreasing pli Values -
The Variation of the Viscosity and Surface Tension
DecreasingAg..ns tA.r o,
ValuesOleate Solutions with
pH Vii lu .± s - 14
The Variation of the Foaming Capacity of SodiumOleate Solutions with Decreasing pa Values - - 19
The Application of the Mudd Interfacial Techniquein the S tu4y of the Single Emulsion Droplets atDifferen t pa Values - - . -21
The Variation of the Cataphoretic Mobility of theSingle Emulsion Droplets at Different pa Values - 25
The Variation of the Turbidity and Salting OutRelationships of Sodium. Oleate Solutions withDecreasing pa Values - - 23
Summary and Conclusions - kw was -.0r 34
Grateful acknowledgment is
made here to Dr. Robert L. Nugent for
his assistance, advice and suggestions
throughout the course of this invest-
igation.
II#iJ.i f
THE EFFECT OF INCREASING HYDROGEN ION. CO.CNTRkTIO TWON
THE EITIZIFYING POWER OF SODIUM (MUTE.
The Objectives of the .
The chief xiu1iry1ng agent for oil-in-water emulsions
are the proteins, the gums and the alkali soaps. (1) Sodium
oleate is a typical alkali soap (2) which is dispersed by
distilled water to give a solution of pH value close to ten.
As the hydrogen ion concentration is increased from this
value, marked changes occur In the physical properties of the
solution such as its turbidity, viscosity and surface tension
against air, changes which presumably result from two general'
causes, first variation in the colloidal condition or the
sodium oleate itself, and secondly the interaction of the
added acid with the soap.
Recent results obtained by McBain and his associates (3)
indicate that the first results or the interaction or soaps
with mineral acids is the ,ormation or so-called acid soaps
such as (sodium oleate). (oleic acid). Other hypothetical
acid soaps might have such formulae as (sodium oleate)2.
(oleic'acid) and (sodium oleate).(oleic acid The final
result of the interaction is the practically complete
liberation of the oleic acid in the free state with the
formation of an equivalent quantity of sodium chloride:, For
purposes of discussion all solutions or suspensions obtained
by the acidification of olutions of sodium oleate in distilled
water will hereinafter be referred to as sodium oleate solutions
although it is recognized that they are presumably mixtures of
varying proportions of sodium oleate and acid soaps.
The changes in physical properties which occur indicate
that the emulsifying power of sodium oleate should also exhibit
marked variations with increasing hydrogen ion concentration*
Preliminary experiments proved this to be the case, and a
study of these variations was undertaken with three principle
objectives in 'View, the first and most direct of these being
the elucidation of the changes thems lves. The importance
of this objective arises from the fact that, although at
present time there is considerable knowledge of the variation
of the emulsifying powers of the proteins (4) and the gums (r)
with pH, a corresponding knowledge of the behavior shown by
the alkali soaps is lacking. This knowledge might well lead
to important theoretical and practical results* It was felt
that, in the time available, it would be of more value to carry
out an as complete as possible a study of the behavior of one
typical alkali soap rather than less complete studies of several.
Sodium oleate was chosen because of its availability and its
comparative ease of dispersion in water at room temperature.
The first objective as described above deals with the
behavior of a principle class of oil-in-water emulsifying
in contac-Lwith new and improved methods. This entails a
program of adult education conducted by. the University or
some other organization that is qualified to present these
new and improved methods to farmers. The attitude of
farm owners and operators should determine very largely
the advisability of attempting such a program. It is also
necessary to find_ out if there is a sufficient number of
these farmers who would actually enroll for such- a course
were it to be given. This is necessary to make it worth
while to offer the instruction. In order to construct a
course for_adult farmers it is necessary. to find out what
farm operations they would want instruction in and what
plan of meeting would best suit their needs. To know whether
those who are interested an a would attend classes are the
old experienced farmers or whether they are young in
experience in farming would make a difference in construc-
tion of the course-and in method of teaching. It seemed
that material of this nature would aetermine whether or not
the farmers are able to recognize an existing need for
instruction. It would also allow them to express their
wishes and desires concerning the making of a course in
adult education offered in the Salt River Valley.
Previous studies in the field. -- So far as coula be
determined there have been no other studies of the same
nature in the field of adillt agricultural education. There
has been a study made in Iowa in which questionnaires were
examination of single emulsion droplets under the various
conditions would serve as an exzellent test of certain of
the important possibilities pointed out by Nugent, as well
as contribute to the knowledge of the specific emulsions
studied.
The Relationship of the Objectives
to the General Field of Colloid Chemistry. w
Before proceeding to a more detailed discussion of the
three objectives and the experimental attack upon each it
is desirable to outline briefly the relationship of these
particular studies to the general field of colloid chemistry,
and to modern opinions as to emulsions and emulsification.
Colloid systems are those which present an interfacial
area which is enormous as compared with the mass of
material involved, and as such must consist of at least
two phases. In the vast majority of such systems one of
these phases, called the dispersed phase, is dispersed in
the second which is called the dispersing phase. An
emulsion is a colloid system in which these two phases are
a pair of immiscible liquids, one being dispersed in the
other in the form of minute droplets. In any emulsion
system, surface tension forces continually tend to cause
coalescence of the minute droplets to form larger droplets,
(7) a process which in the iimit leads to the complete
separation of the two liquids or 'breaking of the
emulsion. In a stable emulsion this tendency has
obviously been overcome,
As a matter of fact, all emulsions of practical
importance involve a third substance which promotes
stability,, and is called the emulsifying agent. (8) It
is true that extremely dilute emulsions of oil droplets
in water have been prepared without the addition of an
agent of this type, (9) but these are of purely theoretical
interest. It is apparent that the action of emulsifying
agents is a special case of - the phenomenon of protective
action, so important in the general field of the stability
of colloidal solutions.
As has been stated, the important emulsifying agents
for oil-in-water emulsions, that is those which promote the
stable dispersion of oil droplets in a continuous aqueous
phase, are the proteins, the gums and the alkali soaps. It
is important to note that these substances are all repre-
sentatives of the general class of hydrophilic colloids,
substances which readily form colloidal dispersions in
aqueous media in which the dispersed particles are associated
with large quantities of water. (i0 ) It is further char-
acteristic of these substances that they markedly increase
the viscosity of water and markedly lower its surface
tension against air. Because of these latter two facts,
certain workers have considered that the emulsifying
power of these substances is specifically associated with
the high viscosity or low surface tension exhibited by their
water solutions.
The,theory of the action: of emulsifying agents which
however is generally accepted at the present time was first
clemly put forward by Bancroft. (11) Briefly, when oil
droplets are scattered through an aqueous dispersion of an
emulsifying agent by some means such as simple mschanical
agitation, films of the emulsifying agent are believed to
form around each droplet. These films then prevent
coalescence, and the emulsion is stabilized*
The formation of films of the emulsifying agent around
the dispersed droplets is an example of the general
phenomenon of adsorption (12) which may be defined as the
accumulation of any substance in an interface by some process
not involving stoichiametric compound formation. Vs
emulsifying agent is thus believed to be adsorbed in the
oil-water interface bounding each droplet with the resulting
formation of a more or less complete protective film. Accord .
ing to Bancroft (13) any substance will act as a satisfactory
emulsifying agent if it is adsorbed at the surface of the
dispersed droplets, and forms there a sufficiently viscous
or plastic film. However, the first stage in the coalescence
of two droplets must be the occurrence of contact between
then. This being the case, it would seem that the most
important action characteristic of an emulsifying agent
11001,71.,
might well not be the viscosity or plasticity of the film
which it forms about the dispersed oil droplets, but rather
its ability to prevent contact or at least permanent
aggregation of single droplets. The theoretical considerations
involved here are essentially those bearing upon the
aggregation of colloidal particles in general, a subject
which has recently been treated at some length by Mudd,
Nugent and Bullock. (14)
In ordinary emulsions the concentration of the dispersed
droplets is such as to afford frequent opportunities for
contact between them. When contact has been made in any case,
surface tension forces tend to cause the droplets to cohere,
that is to remain in contact with one another. Two means
are available, either of which alone is capable of prevent
ing the coherence of particles under these conditions* First
the particles may bear sufficient surface electrical charges
of like sign, in which case electrostatic repulsion prevents
acttra contact of the droplets when mechanical opportunity
is offered therefor. Secondly the interfacial tension
between the droplets and their dispersion medium may be
sufficiently low so that, even after contact has been made,
the forces tending to hold them together are sufficiently
small as to permit their reseparation by very slight
mechanical agitation. If particles dispersed in an aqueous
medium are to have sufficiently low surface tensions against
the medium for this purpose, experience has shown that their
surfaces must be extremely hydrous, that is that these
surfaces must be associated with comparatively large
quantities of titer. The more hydrous the surface the more
nearly it approaches water in nature and the lower its
surface tension against an aqueous phase.
In accord with the foregoing considerations Kruyt (15)
has emphasized the importance of hydration and charge in
promoting the stability of colloidal dispersions0and refers
to them as 'the two stability factors'.
In addition to tending to prevent the aggregation of
droplets as described, surface hydration, in lowering the
droplet-dispersion medium interfacial tension, should
decrease the tendency toward coalescence even when
aggregation occurs.
The foregoing brief discussion of the relationship
of the objectives of the present study to the general field
of colloid chemistry and to present opinions as to emulsions
and emulsification affords a basis for a. more complete out-
line of the objectives which precedes the descriptions of
the various portions of the experimental work. The
objectives were as followsz
(I) To observe the changes in emulsifying power
of certain sodium oleate solutions, which occur with increas
ing hydrogen ion concentration (decreasing pH values).
(2) To determine the role of such physical
properties of solutions of the emulsifying agent as viscosity
and surface tension against air in emulsification, which
certain authorities have considered to be most important
in themselves* (16)
(3) To determine whether or not evidence appears
pointing toward the existence of films of the emulsifying
agent around the single emulsion droplets.
(4) If evidence is obtained pointing tow4rd the
existence of such films, to attempt to determine the
relative protective action of two properties in addition to
their viscous or plastic nature, namely their surface charge
and their surface hydration*
(5) To test and, if .øasibie,, to extend the
application of the Mudd int..rfacial technique to the study
of single emulsion droplets and the properties at their
protective films*
The investigation of the above question* has been
carried out without immediate consideration of the extent
of the transformation of the solium oleate into acid soaps
in any ease. It is believed that the conclusions reached
are independent of such consideration*
The Variation of the Stability of the Emulsions
studied with Decreasing pli Values.
One per cent solutions of Me1s spdium oleate were
employed throughout the experimental portion of the. work.
Two series of emulsions -ere studied involving respectively
one volume of commercial "Pompeian' olive oil and one
vOlume of Merck's purified benzene emulsified in two
volumes of the sodium oleate solution. The following method
of emulsification was used in all eases. The oil and the
sodium oleate solution. were placed together in sa. stoppered
test tube, 150 mm. long and with an internal diameter of
20 mm. The test tube was then given four vigorous double
shakes with the right hand wial a brief pause between
double shakes. (17 ) The whole operation required
approximately five seconds in all cases This method
was adopted because it was found to be one which allowed
differences In the stability of the resulting emulsions to
become manifest in comparatively short periods of time.
The pH of the standard one per ceni =odium oleate
solution in distilled water was determined by means of an
ordinary hydrogen electrode system. The hydrogen was from
a cylinder obtained from the Vegetable Oil Products Co. of
Wilmington California. This was bubbled through washing
bottles containing alkaline potassium permanganate solution,
alkaline pyrogallol and distillE4 water in that order.
Platinum wire electrodes were used platinized according
the directions of Popoff, Kunz and snow (18) and used with
a Hildebrand electrode vessel, a saturated calomel electrode,
and a Leeds and Northrop self-cantained potentiometric unite
The entire system was checked at intervals against standard
phosphate buffer solutions. (19) Using 'the method of pa
measurement described, the pH of the standard sodium oleate
solution was found to be 0.07.
Olive oil and benzene emulsions were prepared with the
standard sodium oleate solution in the usual manner, and
placed in their stoppered test tubes in a rack in the ice
chest at a temperature of 15 degrees plus or minus two degrees
centigrade, the time of placing them in the ice chest being
noted.
Portions of standard sodium oleate solution were
subsequently titrated with half normal hydrochloric acid to
definite pH values as determined by means of the hydrogen
electrode system, a series of sodium oleate solutions being
thus obtained at gradually decreasing pH values. With the
exception of the solution of lowest value, the pH results
ara based upon readings which remained constant for periods
of at least 1.5 hours. Olive oil and benzene emulsions were
prtpared with each of these sodium oleate solutions, and
placed in the ice chest with this two original emulsiona,
the time of placing each emulsion therein being carefully
no ted.
The method of comparing the emulsifying powers at the
different pli values was that which has been employed by
numerous investigators* (20) Each emulsion was examinid at
regular intervals for signs of breaking. In the present
case an attempt was made to measure the extent of such
breaking, the measure adopted being the volume per cent of
the total oil which had separated at the surface of the
particular emulsion at any time* Using this method, the
general trend of emulsifying power with pH was hardly in
doubt after twenty-four hours standing* However, it is
best shown by the data obtained on observing the emulsions
after one month's standing. These are shown in Table I*
Table 1,
THE EXTENT OF THE BREAKING OF EMULSIONS OF OLIVE OIL
AND OF BENZENE IN ONE PER CENT SOLUTIONS OF SODIUM
OLEATE AFTER STANDING FOR ONE MONTH AT 15 DEGREES PLUS
OR MINUS 2 DEGREES C. AT DIFFERENT pH VALUES.
PH Per eent of total oil separated.
Olive oil emulsion. Benzene emulsion.
9.97 0 89.32 9 116.73 12 157.55 57 257.03 76 366.06 94 404.88 loo 100
The results in the case of both emulsions clearly
indicate decreasing emulsifying powers with decreasing pH
values, with complete loss of emulsifying power in the
neighborhood of pH 4.8. The percentages of separated oil
are plotted against the pH values in Figure 1.
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-14-
The Variation of the Viscosity and Surface
Tension Against Air of Sodium Oleate
Solutions .at Decreasing
pH Values.
The general postulate of the viscosity theory of
the action of emulsifying agents is that the more viscous
the solution of a given emulsifying agent, the greater its
emulsifying power. (21) Since it was shown, as described
in the previous section, that the emulsifying power of one
per cent sodium oleate solutions decreases continually with
pa as this value is lowered from 9,97 to about 4.8, it is
apparent that, if relative viscosity values were available
for the solutions at the corresponding pH values, one would
be able to draw conclusions as to the relationship between
emulsifying power and the viscosity of the solutions
of the emulsifying agent in these cases.
Portions of the sodium oleate solutions at the
different pH values, used in making the series of emulsions,
were used to determine the respective relative viscosities
employing a one cc. Ostwald viscometer (22) with the
temperature controlled at P5 degrees C. in a waterbath
thermostat. The results of this work are shown in TABLE II.
The time of flow in each case is taken as the average of
several readings* The relative viscosity for each of the
solutions measured has been calculated by means of the
formula, ( 23) -Z .
To
where 11 is the relative wi.scositY, ir is the time of flow
in the viscosi.meter, and To is the time of flow for
distilled water. Corrections for the differences between
the densities of distilled water and the various sodium
oleate solutions are not made, because they were found to
be negligible from the point of view of the objectives of
the work.
Table II.
THE $MATIVH VISCOSITIES QF SODIUM °LUT E SOLUTIONS AT
DIFFERENT FII VALUES AND 25 DEGREES C., AS DETEMINED WITH A
ONE CC., OSTWALD VISCOSIMETER OF WATER VALUE 36.9 SECONDS.
pI3 Time of flow in seconds. Relative viscosity.
9.97 40.2 1.099.32 42.6 1,.18
8.73 45.0 1..22
7.55r7.03
42.037.7
4L,141.02
6.06 37f 0 1.003
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K Ec E CO., N. Y.Ai 21802
The relative viscosities are plotted against the pH
values in Figure 2, the curve obtained zhowng a marked
maximum in the region of pH 8.0 8.5. According to the
curve, the viscosity of the solution at pH 7.55 is
approximately equal to that at la, 9.97. This viscosity
curve obviously contrasts markedly with the pH stability
curve shown in Figure 1. The emulsion stability decreases
continuously with pH, the emulsion at pH 7.55 being markedly
less stable than that at pH 97. The viscosity of the
solution of the emulsifying agent shows a sharp maximum at
about pH 8.25, resulting in closely equal viscosities at
pH values 7.55 and 9.97. it is clearly apparent that no
determinative relationship exists between emulsifying power
under a given set of conditions, and the viscosity of the
solution of the emulsifying agent under the same conditions.
Eimilarily, because of the importance someti.es
attributed to the interfacial tension at the interface air
solution of the emulsifying agent, (24) it was decided to
obtain at least roughly comparative data for the surface
tensions of the various sodium oleate solutions. This was
accomplished by means of a 5 cc. Traube stalag 'meter
using the drop number method. (25) The measurements were
made at room temperature which was ascertained to be r7.5
degrees C. The drops were received in an Erlenmeyer
flask bearing a rubber stopper through which pas:,ea the
17-
stalagmometer and an open capillary tube. The uata
obtained are shown in TABLE Iii, the drop numbers in
each case being the mean'of at least two closely
checking determinations. The surface tension valut,,
are calculated using the following formula, (20
y:: 710;
where lr is the surface tension and /'I is the drop number
of a particular sodium oleate solution and and No
are respectively the surface tension and the drop numbers
of distilled water under the conditions of the experiment.
Lensity corrections are omitted here as in the viscosity
experiments. The surface tension of the distilled water is
assumed to be 72 dynes per cm. under these conditions. The
flicieal drop" (27) correction is not employed, because it is
unnecessary from the point of view of the objective of the
experiment.
Table III.
TSE AIR-SOLUTION INTERFACIAL TENSION OF A SERIES OF
SODIUM OLEATE SOLUTIONS AT DECREASING pH VALUES AND
27.5 DEGREES C., USING A TRAUBE STADAGMOMETER GI7ING
A WATER DROP NUMBER OF 35.
p Drop number.. Approximateinterfacial tensionin dynes per cm.
9.97 91 27.79.32 99 25.418.73 98 .12.,5.1 r
7.55 94 26.87.03 85 29:66.04 81 31.1
The surface tension values are plotted against the
pH values in Figure 3, the curve obtained showing a
minimum in the region pS 8.0 through pH 9.0 and, thus,, like
the viscosity curve in contrast to that for emulsion
stability. A similar conclusion can be drawn to that
arrived at in the case of the relative viscosites of the
solutions of the emulsifying agent, namely that no
determinative relationship exists between the emulsifying
powers of sodium oleate solutions at the different phi
values and their surface tensions against air.
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Since viscosity and surface tension against air are
the physical properties of solutions of emulsifying agents
which, in the past, have been suggested as specifically
responsible for variations in the emulsifying power of
such solutions, the general suggested conclusion from the
two sets of experiments is, that it is necessary to look
farther than some one physical property to explain
variations in the emulsifying power of such solutions.
The Variation of the Foam -worming
Capacity of Sodium Oleate
Solutions at Decreasing
pH Values.
Turning now to the modern protective film theory of
the mechanism of the action of emulsifying agents, it may
be helpful to repeat the three possible modes of action of
such films as discussed in the introductory sections of the
paper. The first of these, as emphasized by Bancroft, is
the viscous or plastic nature of the film formed. The
second, as emphasized particularly in the present paper, is
the surface charge which may be present due to the presence
of the protective film, and the third similarly emphasized,
is surface hydration due to the presence of the protective
film.
-20--
Two series of experiments were run in an attempt to
obtain evidence as to whether or not films of emulsifying
agent were present surrounding the single emulsion
droplets, and the variation of the properties of such
films with pH values. The first of these was a simple
foam- fdrming experiment, When stable foam forms on
shaking a liquid, we have visual evidence of the tendency
of the system to form stable interfacial films. (28)
Ten cc. portions of the sodium oleate solutions at
the different pH values were shaken in teat tubes in
exactly the sane manner as employed in the preparation of
the emulsions. After standing for one minute the height of
the foam or lather formed above the surface of the liquid
was measured in miii. , with results as shown in TABLE IV.
Table IV.
TIiE RELATIVE HEIGHTS OF STABL E FQA2 FORMED ABOVE
SOLÜTIQNS OF SODIUM OLEATE AT DIFFERENT pH VALUES, A
STANDARD SHAKING TRI"ATUE2dT HAVING BEEN APPLIED TO EACH
SOLDTIOD3.
pH Height of foam in mm.
9.97 509.32 278,73 237.53 117.03 74.86 0
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K&ECO.,N.Y.7M 21002
The heights are plotted against the pH values in
Figure 4. It is apparent that the curve obt 'ained closely
parallels that for emulsion stability as opposed to those
for viscosity and surface tension. The indication is
clearly that a determinative relationship may well exist
between emulsifying power and the tendency to fora stable
interfacial films as postulated by the modern protective
film theory.
The Application of the Mudd Interfacial
Technique to Single Emulsion
Droplets at Different
pH Values*
The interfacial technique developed by Mudd and
Mudd (29) and used by them in the study of bacteria, red
blood cells etc., has recently been applied by Nugent (so)
to the examination of single emulsion droplets. The
reader is referred to his paper for the details of this
application which cannot be discussed in full here.
Briefly, in employing this technique, a drop of the
emulsion to be studied and a drop of a suitable oil are
placed close together upon a microscope slide. A coverglass
is then placed over both drops which spread under it with
the formation of an oil -water interface. The oil then tends
to displace the water from contact ith the glass, and,.
as a result, the interface moves slowly in the direction of
the water side.
The moving interface is followed with a microscope,
usually employing dark field illumination, and observation
is made of the behavior of the single emulsion droplets
when the interface makes contact with them. Nugentts
paper describes various types of behavior which have been
observed under different conditions, and suggests an
interpretation for each.
In the present work, ten cc. portions of M/15
phosphate buffer solutions (31) were placed in test tubes,
and five drops of an olive oil or benzene emulsion made with
standard one per cent sodium oleate at pH 9.37 were added.
It was assumed that under these conditions the droplets in
the diluted emulsions would still bear protective films, if
such had originally been present, and that this film would
exhibit properties characteristic of the pH of the particular
buffer solution. The general behavior observed was entirely
similar to that previously reported by ¿ugent in the study
of the fat droplets from cream. In the preparations which
exhibited the least protective power, the droplets
coalesced with the advancing oil phase the moment that
contact was made. In those which exhibited the greatest
protective power, the droplets were picked up by the advanc-
ing interface and carried by it more or less permanently..
Under these conditions, the droplets appeared to be
entirely on the aqueous side, being apparently just
tangent to the interface* As in the case of the cream
fat studies, intermediate protective powers were clearly
distinguishable between these extremes, characterized
by temporary carry followed by coalescence with the oil
phase. In such cases the droplets are picked up by the
interface and carried for varying short periods of time,
when they suddenly disappear due to coalescence with the
oil* The times of carry were observed for a number of
droplets and the average time of carry was taken as a
measure of the resistance to coalescence*
The mechanism whereby temporary carry is possible
is somewhat obscure, but the reproducible nature of the
phenomenon and the parallelism which has been shown to
exist between this behavior and the relative stability
of emulsions, makes it highly probable that its
interpretation as an indication of intermediate
protective action is correct*
TABLE V indicates the results obtained with the
standard olive oil and benzene emulsions diluted with
M/15 phosphate buffer solutions as described, and each
studied with two interfacial oils, Kahlbaums, triolein
and commercial sNujolv,
Table V.
THE BEHAVIOR ON TRE APPLICAT.IßN OF THE MUDD INTERFACIAL
TECHNIQUE TO SINGLE EMULSION DROPLETS AT BIFFERENT
pH VALUES.ESi
Olive oil emulsions.,
p Average time of carry in seconds'
Triolein as interfacial Eujol as interfacialoil. oil.
8.0 . Perm.snent 26.9 , 10 1.5.9 Less than one Less than one-5 . 3 0 o
Benzene emulsions.
8.0 Permanent6.9 105.9 25.3 Less than one ,
10
1Less than one
It is believed that in every case, when coalescence
fails to occur at the moment when contact is made, proof
i$ obtained of the existence of some sort of protective film,
either on the droplets, on the advancing interfacial front,
or on both. If this is true, then the experimental results
obtained in Table V prove the existence of more or less
protective films at all pH values investigated above pH 6.
If time of carry is taken as a measure of the relative
protective power of such films, then a clearcut gradual
decrease in protective power is indicated as the pH value
decreases from pH 8 to pH 5 in all cases. These results
then are in accord with the variation of the emulsifying
power with pH over the range, and constitute perhaps the
most direct proof of the protective action of films of
emulsifying agent yet obtained.
The parallelism demonstrated between these results and
the emulsifying páwers is further in entire accord with the
previous results and predictions of Nugent,, and therefore
serves to confirm the value, and to extend the application
of this new method for emulsion research.
The Variation of the Cataphoretic
Mobility of Single Emulsion
Droplets at Different
pH Values..
It is generally assumed that the direction and speed
of migration of colloidal or microscopic objects under
standard conditions of cataphoresis serve respectively as
an indication of the sign of any surface charge borne by
the particles, and as a measure of the relative extents
of this charge under varying conditions.
As has been pointed out,_ one possibility is that
surface films of an emulsifying agent may bear sufficiently
high charges to prevent actual contact of emulsion
droplets when mechanical forces tend to bring such contact
about. Under such conditions the charge due to the films
might well be the factor of outstanding importance in
determining the protective action of the emulsifying agent.
It was believed, that a conclusion as to this matter could
be reached in the present case by a simple comparison of the
cataphoretic mobilities of the emulsion droplets at different
p$ values, and a comparison of these relative mobilities with
the corresponding emulsifying powers*
Accordingly five drops of either a standard olive oil .
or a standard benzene emulsion were added to 10 cc. portions
of various M /15 phosphate buffer solutions, the same
assumptions being made as in the case of the diluted
emulsion's used in the interfacial technique werk. The
buffers ranged from straight dibasic sodium phosphate) whose
pH value was determined to be 3.20 to the mixture of pH 5.2.
The mobility observations were made using a Northrop- Kunits
microcataphoresis cell. (32) with accessory apparatus as
suggested by Mudd. (33) All observations were nade at 0.21
of the depth of the cell from the bottom. At this level the
electrical endosmotic movement of the liquid in the closed
cell is theoretically zero, (34) and therefore the observed
mobilities of the particles approximate the true mobilities.
Dark - field illumination was obtained with a Bausch and
Lomb cardioid condenser. A const ant potential was applied
from three 45 volt radio IRBY batteries.
In the case of each preparation the times were noted,
by means of a stopwatch, which were required for the droplets
to traverse five divisions of-an arbitrary ocular micrometer
scale. This was taken in all cases as the mean of a number
of observations on different droplets with the direction of
the applied potential reversed after each reading by means
of a commutating switch. From these values the mobilities
of the droplets were calculated im scale divisions per
second. The results are shown in TABLE VI.
PH
THE RELATIVE MaBILITIES OF OIL EMULSION
DROPLETS WITH SODIUM OLEATE AS THE
EMULSIFYING AGENT AT DIFFEREN T pH VALUES.
Time required to traversefive scale divisions inseconds.
Mobility inscale divisionsper second.
Olive oilemulsion.
Benzeneemulsion.
Olive oilemulsion.
Benzeneemulsion.
9.20 3.4 3.8 1.47 1.288.04 2.7 2.5 1.85 2.006.98 3.3 3.0 1.51 1.675.91 4.6 4.4 1.09 1.145.29 5.3 6.2 0.94 0..81
The mobilities for both the olive oil and benzene
droplets are plotted against the pH values in Figure 5. The
agreement between the two is strikingly good and affords
excellent evidence for the fact that one is dealing here not
with olive oil and benzene surfaces, but with the same
surface in each case, namely a surface of sodium oleate or
of sodium oleate modified by increasing hydrogen ion
concentration. This conclusion affords excellent support
for the surface film theory of the action of emulsifying
agents, and, together with the foaming tests an.L the
interfacial technique experiments, affords a practically
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1Y 21802
conclusive picture.
From the point of view of surface charge relationships,
the outstanding result is the maximum shown by both curves
in the region p8 8.0 .. 8.5, the identical region in which
a maximum is exhibited by the viscosity curve and a
minimum by the surface tension curve. if surface charge
were the factor of outstanding importance in determining
the stability oi» the emulsions at the different pH
values, the cataphoresis curves would have shown a
continuously decreasing surface charge with decreasing pli
value. The indication however, is that droplets at a p8
value aS low as 6.5 'bear about the ,same surface charge as
those at pH 9.:7 '1n spite of the u rked difference in the
stability of the "emulsions at the two values. The conclusion
is clearly that the surface charge on the droplets due to
the presence of protective films is ty no means the factor
which determines the protective action of the emulsifying
agent.
The Variation of the Turbidity and the
Salting Out Relationships of
Sodium Oleate Solutions
with Decreasing pH.
If surface hydration due to the prefcnce of films of
hydrophilic material is thy; important factor in determining
the protective action of sodium oleate in emulsification,
it would be expected that surface hydration would decrease
with any set of conditions which lead to decreasing emulsify-
ing powers, as for example with decreasing pH values.
Unfortunately the direct investigation oÍ variations in the
state of surface hydration of particles is a difficult
matter. The Mudd interfacial technique described in a
previous section of this paper offers possibilities in
certain cases, but did not prove helpful in this regard in the
present work.
Two lines of indirect investigation were attempted;
first a simple comparison of the turbidities of sodium oleate
solutions with decreasing pH values, and, secondly, the
variation of the amounts of sodium chloride necessary to
salt out the soap under the same conditions.
In general, in any suspension the more hydrous the
particles the less turbid the suspension, because the more
hydrous the particles the more nearly their refractive index
approaches that of an aqueous medium. (35) There is there-
fore good reason to assume that increasing turbidity of a
suspension is an indication of a decrease in the extent of
the hydration or hydrous nature of the dispr,,eu particles.
The turbidities of the sodium olevte solutions at decreasing
pH values were simply compared by noting t aepth of each
solution just sufficient t co.lpletely obecur bi.eck cross
on white paper, placed beneath a flat bott-I-cl g1s tube ilito
which the solutions were gradually delivered by means of a
pipette. The reci.procal of the height in millimeters was
taken as the measure of the turbidity in each case as shown
in TABLv VII.
,
Table VII.
THE VARIATION OF THE TURBIDITY OF SODIUM
OLEATE SOLUTIONS AT DECREASING pH VALUES
pH. Obscuring depth in mm. Turbidity
9..97 137;0 0.0079.32 34.8 0.0298,75 23.5 . 0*0427.55 7.0 0.1427.03 5..7 0..1754.86 4.5
The turbidities are plotted against the pH values in
Figure 8 the curve obtained exhibiting a continuously increasing turbiditT with decreasing pH.
Assuming the probable parallelism to obta.in between
turbidity and the hydration of the dispersed materi.al., the
continuous increase in turbidity indicates a continuous de
crease in the hydration of the sodium oleate or modified
sodium oleate with decreasing pH. From this latter indica»
tion it may be argued that a decrease in emulsifying power
with pH 'value is associated with a parallel decrease in the
hydrous nature of the protective films of the emulsifying
agent.
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-32-
An indirect method was employed in the salting out
experiments. Several benzene emulsions were made with the
sodium oleate solutions at each of the decreasing pH values*
Gradually increasing volumes of saturated sodium chloride
solution were added to the series of emulsions at each pH
value, until that volume was found which resulted in a
definite cracking of the emulsion within ten minutes time.
The results are shown in TABLE VIII.
Table VIII.
THE VARIATION Ili THE VOLUME OF SATURATED SODIU2
CHLORIDE SOLUTION JUST LUFFICIENT TO CAUE THE
CRACKING OF A SERIE OF EMULSIONS AT DIFFERENT
pa VALUES.
PII Volume of saturated sodium chloridesolution in cc.
9.97- 0.69.32 0.47.55 0.57.01 0.14.86 0.0
It is generally believed that the salting out of
hydrophilic colloids is due to a dehydrating action exerted
by the added salt. (36) On this basis, it seems probable
that the greater the degree of hydration of the material
-33-
the greater the concentration of a given salt necessary to
complete the process. The data in Table VIII clearly
demonstrate a decreasing concentration of salt .:ith decreas-
ing pH, which may then be assumed to indicate a decreasing
hydration of the dispersed material with pßì and as in the
case of the turbidity results, a decrease in the extent of
the hydration of the films of emulsifying agent with
decrease in emulsifying power.
The general conclusion from the two indirect methods
employed to test the variation of the states of hydration
of the protective films of sodium oleate or modified sodium
oleate with decreasing pH values, is thus, that there is a
continuous decrease in the cxtent of the hydration of the
films under these conditions. This decrease parallels the
continuous decrease in emulsifying power under the same
conditions. &ince it has been pointed out on theoretical
grounds that the protective action of films of emulsifying
agents might sell depend largely upon their hydrous nature,
these experiments may be taken as confirming this theory.
.144.
Summary and Conclusions.
Emulsions of one volume of olive oil or benzene
in two volumes of one per cent sodium oleate solution have
been shown to decrease continuously in stability with
increase in the hydrogen ion concentration of the aqueous
phase from the pH value of about ten, shown by dispersions
of the soap in distilled water,,,, to about pH 4.5 where -no
stability is shown. These changés are due to a decrease
in the emulsifying power of the sodium oleate or modified
sodium oleate under conditions of increasing acidity,, this
emulsifying power becoming zero at the lower pH value
mentioned. Marked emulsifying power is exhibited by sodium
oleate only at pH values greater than seven.
In . contrast with the decrease in emulsifying power,
the curve obtained on plotting the relative viscosity and
surface tension values of sodium oleate solutions against
decreasing pH values show respectively a well defined
maximum and a well defined minimum in the region pH 8.0 --
pH 9.0. The shapes of these curves indicate clearly that
neither of these properties is of primary importance in
determining the emulsifying powers at the different pH values.
On the other hand the foaming tendency of sodium oleate
solutions decreases continuously with pH thus paralleling the
behavior of the emulsifying power. The foaming tendency
la taken as a measure of the tendency of the solutions to
form stable interfacial films. The parallelism between
foaming tendency and emulsifying po er is in accord with
the best accepted theory of the mechanism of the action of
emulsifying agent namely that the fundamental action is
the formation of stable viscous or plastic films in the
interface surrounding each emulsion droplet.
Further evidence to the same effect is afforded by
the application of the Mudd interfacial technique to the
study of the single emulsion droplets at decreasing pH
values. It is believed that the experiments performed
under this heading afford remarkably direct evidence for
the existence and importance of surface films in emulsification.
Having obtained the foregoing evidence for the
existence of protective surface films., it was next of
interest to determine to what extent surface charge due to
the presence of such films might be the factor of prime
importance in promoting stability. Theoretically it might
well play this role. The relative surface charges were
determined at decreasing p$ values by means of microcat-
aphoresis experiments. The curve obtained on plotting
relative mobilities against pH values shows a clearcut
maximum in the region pH 8.0 - pH 8.5, apparently correspond-
ing to the maximum in the viscosity curve and the minimum
An the surface tension curve. The shape of the curve
definitely rules out surface charge as the factor of
primary importance in determining the emulsifying power
of the sodium oleate solutions.
In contrast with the cataphoretic mobility curve,
further experiments demonstrated that sodium oleate
solutions show a continuous increase in turbidity over the
pH range exhibiting the continuous decrease in emulsify.
Ing power. Over the same range, it was also shown that
continuously decreasing quantities of sodium chloride are
required to salt out the soap. Both of these results admit
of but one reasonable interpretation, namely, that there
is a corresponding continuous decrease in the extent of
the hydration of the dispersed material in the sodium
oleate solutions with pH, and a corresponding decrease in
the extent of the hydration of the protective films formed.
The general conclusions are reached that, first, the
emulsifying power of the sodium oleate or modified sodium
oleate under the conditions of the experiments performed
is dependent upon the formation of stable -Viscous or plastic
films about the dispersed emulsion droplets in accord with
the general criterion of Bancroft, and secondly that the
state of hydration of the films so formed is a factor of
greatest importance in promoting emulsifying power. While
this hydrous nature may be simply a contributory factor to
the formation of stable interfacial films, the theory is
-57-
advanced here that it is in all probability a factor of
primary importance acting .to minimize the aggregation of
emulsion droplets this latter being necessarily the first
step in any coalescing process, and further to minimize
coalescence if aggregation does occur.
Microcataphoresis experiments demonstrate that
surface charge is not a factor of primary importance in
the emulsions studied.
The application of the Mudd interfacial technique
referred to above has confirmed the importance and extended
the application of this new method for emulsion research.
In final conclusion a tentative explanation is offered
for the occurrence of maxima in the pH - viscosity and the
pa cataphoretic mobility curves and a minimum in the
pH - surface tension curves, all in the range pH 8.0 - 9.0.
Preliminary experiments involving the titration of
known quantities of sodium oleate in solution with standard
hydrochloric acid and the plotting of the number of cc. acid
added against the corresponding pH values obtained, indicate
that the region pH 8.0 - 9.0 corresponds to the addition
of an amount of hydrochloric acid equivalent to one third
of the sodium oleate originally present and to the possible
formation of an acid soap of the constitution (sodium oleate)2.
(oleic acid) . A further investigation of titration curves
of this type might well lead to valuable information with
-33-
regard to the general question of the formation of acid
soaps. As pointed out earlier in the paper, the
conclusions reached herein are believed to be independent
of the extent of the formation of compounds of this type.
BIBLIOGRAPHY
1. Bancroft: *Applied Colloid Chemistry,* 3rd ed., McGraw-Rill Book Co*, Inc., New York and London, 1932, ChapterXII.
2. Bancroft: ibid., p. 364.
3. McBain and McClatchiet J. Am. Chem. Soc., 3266 (1932);McBain and Stewart; J. Chem* Soc., 1300 1392 (1927);.Holmes: *Introductory Colloid ChemistrYow John Wiley andBons, Inc., New York, 1934, p. 98.
4. Holmes and Child: J. Am, Chem. Soc., 42, 2049 (1920);Nugent: J. Phys. Chem., Ag., 449 (193217
5. Krantz and Gordon; Colloid Symposium Monograph, 9., 173(1928).
6. Nugent: loc. cit.
7. Mudd, Nugent, and Bullock: J. Phys Chem., §g40 237 (1932).
8. Kruyt (translated by van Klooster); *Colloids,* End, ed.,John Wiley and Eons, Inc., New York, 1930, p. 266.
9. Kruyt (translated by van Klooster): loc* cit., p. 265.
10. Bancroft: loc cit.* p. 367; Gortner: *Outlines of Bio-chemistry,* John Wiley and Vons Inc., New York, 1929, p.34.
11. Bancroft; J. Phys.. Chem., 17, 415 (1913); 19, 275 (1915);Clayton: The Theory of Emulsions and Their TechnicalTreatment** P. Blakistonts Son and Co., Philadelphia, 1928,p. 120.
12. Bancroft: *Applied Colloid Chemistry,* 3rd. ed., McGrawHill Book Co., Inc., New York and London, 1932, p. Z.
13. Bancroft: ibid,, Chapter XII.
14. Mudd, Nugent, and Bullocks loc. cit.
15. Kruyt (translated by an Klooster): loc. cit., p. 192.
16. Holmes and Child: loc. cit.; Clayton: *The Theory ofEmulsions and Their Technical Treatment,* P. Blakiston'sBon and Co*, Philadelphia, 1928.
_40_
17. Briggs: J. Phys. Chem., .2.1,4 120 (1920) .
18. Popoff, Kunz, and Snow: J. Phys.. Chem., 32 1056 (1928) .
19. Clark: "The Determination. of Hydrogen Ions," 2nd. ed.,Williams and Wilkins Co., Baltimore,, 1925, p. 114.
20. Clayton: loc. cit., Chapters IV, VI, and VIII; Holmesand Child: loe. cit; Krantz and Gordon: loe. cit.
21. Holmes and Child: loc. cit.; Clayton: 'The Theory ofEmulsions and Their Technical Treatments P. BlakistontsSon and Co., Philadelphia' 1920.
22. Findlay: "Practical. Physical Chemistry,* 5th ed.,Lontmans, Green and Co., London, New York and Toronto,1931, p. 74.
23. Findlay: ibid., p. 75.
24. Clayton: loe. cit.
25. Findlay: loc. cit., p. 85.
26. Findlay: ibid., p. 85.
27. Findlay: ibid., footnote p. 85.
28. Bancroft: loc. cit., p. 374.
29. Mudd and Mudd: J. Exptl. Med., 1106 633, 647 (1924);43, 127 (1926); 46, 167, 173 (1927); J. Gen. Physiol,14, 733 1930 31T
33. Nugent: loc. cit.
31. Clark: loc. cit.
32. Northrop and Kunitzt J. Gen. Physiol., 7,, 723 (1924 -25) .
33. The cell with accessory apparatus may be purchased fromthe krthur H. Thomas Co., Philadelphia.
34. McCutcheon, Mudd, Strumia, and Lucke: J. Gen. Physiol.,13, 663 (1930) .
35. Bancroft: loc. cit., p. 223.
36. Kruyt (translated by van Klooster): loc. cit., p. 194.