Zeta-Potential Measurements on Microbubbles Generated Using Various Surfactants

R O E - H O A N Y O O N ~ AND J O R G E L. Y O R D A N
Department of Mining and Minerals Engineering, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061

Received July 8, 1985; accepted January 16, 1986 The zeta-potentials of microbubbles in the 40- to 80-~m size range have been determined by means of a simple microelectrophoresistechnique. In general, the sign of the bubble charge is determined by the polar head of the surfactant when an ionic surfactant is used to produce the bubbles. When using hydrolyzable ionic surfactants, however, the bubble charge is significantly affected by the hydrolysis products. In the presence of nonionic surfactants, bubbles can be charged either positivelyor negatively depending on the pH, and the isoelectric points appear to be related to the oxygen-to-carbonratio of the surfactant molecule. With ionic surfactants, an increase in concentration results in an increase in bubble charge,whilewith nonionic surfactantsthe zeta-potentialschangelittle in the concentration range studied. The negative charges observed with air bubbles and oil droplets in the absence of surfactants can be explained by the differences in the hydration energies of H+ and OH- ions. 1986Academic
Press, Inc.

INTRODUCTION In froth flotation, air bubbles collect hydrophobic particles selectively and rise to the surface leaving hydrophilic particles behind in the pulp. There are m a n y factors affecting the efficiency of this separation process, including electrostatic charges of the particles and the bubbles. Since the 1950's, the role of surface charges of minerals in the adsorption of surfactants and in the bubble-particle adhesion process has been studied extensively. One of the significant findings is that the rate of flotation and, hence, the recovery is m a x i m u m when the zeta-potential of the particle to be floated is at a m i n i m u m (1). The explanation is that air bubbles, which are usually negatively charged, can approach mineral particles more readily without experiencing m u c h electrostatic resistance when the particles have no appreciable surface charge. More recently, Derjaguin and Dukhin (2) have suggested that Address all correspondence to: Dr. Roe-Hoan Yoon, Professor, Department of Mining and Minerals Engineering, 213 Holden Hall, VirginiaTech, Blacksburg,Virginia 24061. 0021-9797/86 $3.00
Copyright 1986 by Academic Press, Inc. All rights of reproduction in any form reserved.

when bubbles and particles have opposite charges, flotation is almost instantaneous. It is unfortunate, however, that there is a general lack of information on the bubble charges while there is an abundance of information on the charges of particles. According to McTaggart (3), Quincke was probably the first to carry out systematic studies on the electrification of liquid/gas interfaces. His major findings were that air bubbles acquire different charges depending on the solution composition, and that air bubbles exhibit negative charges in pure water. Essentially the same findings were made later by McTaggart (3), Alty (4), and Gilman and Bach (5). The first systematic study made in recent years was by Dibbs et al. (6) who used a streaming current technique to determine the signs and the changes in magnitude of bubble charges for the quartz-amine flotation system. It was shown that bubbles produced in the presence ofdodecylamine hydrochloride gave a positive current which increased with increasing amine concentration. They also showed that the best flotation results were obtained when the quartz particles had charges

430
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ZETA

POTENTIAL

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431

opposite to those of the bubbles. One important limitation of the streaming current technique was that there was a lack of theoretical analysis to obtain more meaningful information, such as zeta-potential, from the streaming current. The streaming current technique employed by Dibbs et al. (6) was essentially the same as the Dorn potential technique used by Usui and Sasaki (7). These investigators reported their results in terms of zeta-potential, using the equation commonly employed for calculating zeta-potential from sedimentation potential. The results show that in the case of ionic surfactants, the sign of the zeta-potential is determined invariably by the charge of the polar group of the surfactant, i.e., cationic surfactants produce positively charged bubbles and anionic surfactants produce negatively charged bubbles. With nonionic surfactants, the bubbles exhibit negative zeta-potential, the magnitude of which does not change significantly with surfactant concentration. More recent work by Usui et al. (8) shows that the zetapotential of a bubble varies with its size. Collins et al. (9) measured the electrophoretic mobilities of small gas bubbles that were generated by electrolysis at the bottom of a flat cell. The bubble sizes were small enough that their mobilities could be measured while they were rising slowly. However, the experimental data presented by these investigators were not extensive. Fukui and Yuu (10), using the same technique, found that bubbles generated in the presence of cetyltrimethylammonium bromide (CTAB) and ethanol were positive and the zeta-potentials decreased with increasing electrolyte (sodium sulfate) concentration. Kubota et al. (11) also used a fiat cell, but the small bubbles were generated using the dissolved air technique. These investigators showed that when using long chain anionic surfactants the negative zeta-potential increased with increasing concentration until it reached a plateau near the critical micelle concentration (CMC). McShea and Callaghan (12) used a spinning cylinder to measure the mobilities. They showed that bubbles are neg-

atively charged both in distilled water and in the presence of 10-4 MKC1 at pH 7. Nonionic surfactants produced negatively charged bubbles, while cationic and anionic surfactants produced positively and negatively charged bubbles, respectively. In the present work, zeta-potentials of bubbles have been determined using a vertical, fiat-type electrophoresis cell. Both ionic and nonionic surfactants were used to generate small bubbles, and the effects ofpH, surfactant concentration and of an indifferent electrolyte have been studied. Knowledge of the effects of different nonionic surfactants on bubble charge may be of particular utility to flotation research since most of the surfactants used to generate bubbles in mineral processing plants are nonionic.
EXPERIMENTAL

Reagents. The surfactants used to generate small bubbles are listed in Table I. These reagents were used as received without further purification. Other reagents such as KC1, HC1, and NaOH were of reagent grade. Double-distilled water, prepared in an all-glass still, was used in all the experiments. Ultrapure nitrogen was used to produce the bubbles. Equipment and procedure. A Rank Brothers particle microelectrophoresis apparatus, Mark II, was used to determine the mobilities ofmicrobubbles of 40-80 ~tm in diameter. These bubbles were generated using a method similar to the one described by Sebba (13). A vertical, fiat-type cell was modified as shown in Fig. 1. The two pieces of glass tubing (1.6 mm i.d.) attached to the cylindrical parts of the cell were to allow continuous passage of the microbubble suspension through the cell while measuring the depth of the cell and focusing the microscope at a stationary level. When the microscope was focused properly, the flow of the microbubble suspension was stopped and the mobilities were measured immediately. A potential field was applied to the solution by means of two platinized-platinum electrodes. Ten readings were taken at each of the two
Journal of Colloid and Interface Science, Vol. 113, No. 2, October 1986

432

YOON AND YORDAN TABLE I Description of Surfactants Used in the Present Work
Surfactants Chemical formula F.W. Status Purity Source

Anionic Sodium dodecyl sulfate Sodium oleate Cationic Dodecylamine hydrochloride Cetylpyridinium chloride Nonionic Polypropylene

C12H25OSO3Na C17H33COONa CH3(CH2)I1NH2HC1 C2zH38C1NH20

288.38 304.0 221.82 358.0

Solid Solid Solid Solid

R.G$ R.G. R.G. R.G.

BHD Chemical, Ltd. Fisher Sci. Co. Eastman Pfaltz and Bauer, Inc.

H[OCH(CHa)CH2],OH CH3(OCH2CH2),OH C12H25(OCH2CH2)23OH (Brij 35) C12H25(OCH2CH2)4OH (Brij 30)

425.0 350.0 1199.6 362.56

Liquid Liquid Solid Liquid

N.S.b N.S. N.S. N.S.

Aldrich Aldrich Aldrich Aldrich

glycol
Polyoxyethylene methyl ether Polyoxyethylene dodecyl ether

Research grade. b Not specified.

stationary levels and averaged in a given experiment. All measurements were carried out at ambient temperature and, after each test, the flat cell was cleaned with chromic acid and double-distilled water prior to the next set of measurements.
RESULTS

Ionic Surfactants
Figure 2 shows the results obtained with sodium dodecyl sulfate (SDS) and dodecylamine

h y d r o c h l o r i d e ( D A H ) as a f u n c t i o n o f conc e n t r a t i o n at p H 10.3 _+ 0.2 a n d p H 7. l + 0.2, respectively. As shown, t h e b u b b l e s g e n e r a t e d using the a n i o n i c surfactant are negatively charged a n d those generated with the cationic surfactant are positively charged. Thus, t h e sign o f a b u b b l e charge is d e t e r m i n e d b y the p o l a r g r o u p o f the surfactant m o l e c u l e t h a t is a d s o r b e d o n its surface, as has b e e n shown b y

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pH=7.10

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io-2

CONCENTRATION ( rnoles/I } FIG. 1. Modified fiat cell. A, inlet; B, outlet; C, platinum electrodes.
Journal of Colloid and Interface Science, Vol. 113, No. 2, October 1986

FIG. 2. Effect of concentration on the zeta-potentials of microbubbles generated using sodium dodecyl sulfate (pH 10.3) and dodecylamine hydrochloride (pH 7.1).

ZETA POTENTIAL OF MICROBUBBLES

433 TABLE II

other investigators (6, 7, 11, 12). It has been shown that the magnitudes of the zeta-potentials increase with increasing surfactant concentration due to increased adsorption of the surfactant at the bubble surface, but tend to taper off near the CMC's. These findings are similar to those obtained by Kubota et aL (11) with SDS. According to the Gibbs equation, the surface excess should not increase above a CMC and, hence, there should be no further increase in the bubble charge. Figure 3 shows the effect of pH on the zetapotentials of the microbubbles stabilized by SDS and sodium oleate. For the case of SDS, the zeta-potential remains constant at a given concentration until the pH reaches approximately 3. The decrease in the negative zetapotential may be attributed to the adsorption of neutral hydrolysis products on the bubble surface. The bubbles generated with sodium oleate behave similarly except that the zetapotential begins to decrease at a much higher pH because of its higher PKa value. To see the effect of indifferent electrolytes, the zeta-potentials ofmicrobubbles were measured at varying concentrations of KC1, while keeping the pH at 10.6 and the SDS concentration at 1 10-5 mole/liter. The results given in Table II show that the zeta-potential decreases with increasing electrolyte concentration. Similar results were obtained by Collins et al. (9) and Fukui and Yuu (10) with different surfactants.

Effect of KC1 Concentration on the Zeta-Potentials of Microbubbles Generated Using 1 10-5 mole/1 Sodium Dodecyl Sulfate Solution at pH 10.6
KCI Concentration (mole/l) Zeta-Potential (mV)

10-4 10-3 10-2

-36.2 -32.3 -25.9

Figure 4 shows the effect of pH on the zetapotentials of microbubbles generated using DAH and cetylpyridinium chloride (CPC) solutions of different concentrations. At a given concentration, the zeta-potentials of bubbles generated with CPC remain substantially constant throughout the pH range studied. However, the positive zeta-potentials of those bubbles generated with DAH begin to decrease at pH values above approximately 8 and eventually become slightly negative above pH 10.5. This behavior seems to be in agreement with the findings of Dibbs et al. (6) obtained using the streaming current technique. These investigators explained this charge reversal in terms of the changing hydrolysis of amminium ions to neutral amine at high pH. Bubbles generated with CPC do not show this behavior since this reagent is not hydrolyzable.

Nonionic Surfactants
Figure 5a gives the results of the zeta-potential measurements conducted on the mi-

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pH FIG. 3. Effect of pH on the zeta-potentials of microbubbles generated using different concentrations of sodium dodecyl sulfate and sodium oleate solutions. FIG. 4. Effect of pH on the zeta-potentials of microbubbles generated using different concentrations of dodecylamine hydrochloride and cetylpyddinium chloride solutions.
Journal of Colloid and Interface Science, Vol. 113, No. 2, October 1986

434

YOON AND YORDAN

4(

(o)

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FIG. 5. (a) Effect of concentration on the zeta-potentials of microbubbles generated using polypropylene glycol solutions of different pH. (b) Effect of pH on the zeta-potentials of microbubbles generated using different concentrations of polypropylene glycol solution.

crobubbles stabilized by polypropylene glycol (PPG) (average mol wt = 425) as functions of concentration and pH. At a given pH, the zetapotential remains nearly constant over the range of concentrations studied. These results, which are contrary to those with the ionic surfactants, suggest either one of the following: (i) the bubbles are completely armored with the surfactant at the concentration range studied; or (ii) increased adsorption does not add to the negative zeta-potential. The same

data that are given in Fig. 5a are replotted in Fig. 5b to show the effect o f p H more clearly; The error bars indicate the spread of the data points due to the change in concentration. As shown, a change in pH has a more profound effect than a change in concentration; the PPG bubbles have an isoelectric point (i.e.p.) at pH about 3.3, being negatively charged above it and positively charged below. Figures 6a and b show a similar set of data obtained with polyoxyethylene methyl ether

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pH

FIG. 6. (a) Effect of concentration on the zeta-potentials of microbubbles generated using polyoxyethylene methyl ether solutions of different pH. (b) Effect of pH on the zeta-potentials of microbubbles generated using different concentrations of polyoxyethylene methyl ether solution.
Journal of Colloid and Interface Science, V o l .
1 1 3 , N o . 2, O c t o b e r 1986

ZETA POTENTIAL OF MICROBUBBLES

435

(average mol wt = 350). As has been the case with PPG-425, the zeta-potential does not change significantly with changing surfactant concentration in neutral and acidic solutions. However, at pH 8.2 and 10.2, the negative zeta-potential tends to increase slightly with increasing concentration. As shown in Fig. 6b, the bubbles generated with this surfactant have an i.e.p, at approximately pH 6, which is considerably higher than with PPG. Figure 7 compares the zeta-potentials of microbubbles produced with polyoxyethylene dodecyl ether with those of different ethylene oxide (EO) groups. One has 4 EO groups and the other has 23 EO groups, and both show negative zeta-potentials at 10-5 mole/liter. However, the zeta-potentials become less negative as the pH is reduced. Note also that the bubbles produced with polyethylene dodecyl ether with 23 EO groups tend to be less negative than those produced with 4 EO groups in an acidic pH range, which may suggest that EO groups are basic. Using the same reagents, zeta-potentials were measured as a function of concentration at pH 7.2. As has been the cases with PPG (Fig. 5a) and with polyoxyethylene methyl ether (Fig. 6a), no changes in zeta-potentials were observed in the range 10 -6 to 10-2 mole/liter.
DISCUSSION

The results presented in the foregoing section show that the simple microelectrophoresis
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40
30 20
25

EO o 4EO

Z l.d O~ - 1 0 o. "2O ~ -30

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technique used in the present work offers a convenient method of determining the zetapotentials of air bubbles. It has been shown that different surfactants produce different charges on the bubbles. In general, cationic surfactants produce positively charged bubbles, while anionic surfactants produce negatively charged bubbles. Nonionic surfactants, on the other hand, produce negatively charged bubbles in the alkaline pH range and positively charged bubbles in the acidic pH range. The pH also plays an important role in the charging mechanism of bubbles produced with ionic surfactants. Since the earliest investigations on bubble charge measurements, it has been known that air bubbles produced in pure water are negatively charged (5, 14). The charging mechanism proposed by Currie and Alty (14) presumes an orientation of water dipoles at the interface. The orientation of the dipoles is such that negative ions, i.e., OH-, are attracted to the interface. When a surfactant is present in the system, the nature of the surfactant molecules adsorbed at the air/water interface will determine the bubble charge. Thus, it is not surprising to see that the bubbles are negatively charged when anionic surfactants are used to generate the bubbles, and positively charged when cationic surfactants are used. It appears, however, that some surfactants are undergoing hydrolysis, in which case the hydrolysis products should determine the bubble charge. Since the hydrolysis of surfactants is pH-dependent, the bubble charge must also be pH-dependent. It has been shown in Fig. 3 that bubbles generated using SDS are negatively charged throughout most of the pH range studied. However, the zeta-potential tends to become less negative below approximately pH 3, which may be attributed to acid formation. According to Leja (15), alkylsulfates are hydrolyzed to produce alcohol and bisulfate at pH values below 3. Since alcohol is nonionic, the bubble charge should become less negative below this pH, as has been observed in the present work. It is possible, however, that the adsorption
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YOON

AND

YORDAN

DAH is hydrolyzable at alkaline pH values. Figure 9 shows the distribution of the hydrolysis products as a function o f p H at 1 X 10 -4 mole/liter. The thermodynamic data used for constructing this diagram are from Ananthpadmanabhan et al. (17)~ As shown, the concentrations of charged species such as RNH~, (RNH3)2 and RNH2-RNH~ de:+, crease above pH 10.2, while the neutral species, i.e., RNH2, becomes predominant above this pH. Apparently, the adsorption of neutral molecules at the air/water interface gives rise to a slight negative charge, as will be further discussed below. Before turning the discussion to the effect of nonionic surfactants on the bubble charging " 10-4 mechanism, it may be fruitful to consider the .~e RCOOHI ) ( RCO0charging mechanism of bubbles in pure water 0 10-5 or that of pure hydrocarbons in water. ExperZ m-s (Rcoo~imental data obtained to date all show that C) io.r I-both are negatively charged at neutral pH, fit:: lif which means that OH- ions are in excess of I-Z IO "9 H ions at these interfaces. A thermodynamic tiLl reasoning for this unequal distribution may r.,) fo-IO Z be provided here. According to the "best" 0 0-11 thermodynamic data listed by Conway (18), 5 6 7 9 9 I0 II 12 the euthalpy of hydration (AHg) of H and pH OH- ions are -1104 and -446.8 kJ/mole. Due to this large difference in hydration enerFIG. 8. Species distribution diagram for the sodium oleate-watersystem. gies, H + ions are more likely to stay in the
Journal of Colloid and Interface Science, Vol. 113, No. 2, October 1986

takes place as alkylsulfuric acid unless the surfactant has been aged in an acidic medium for a prolonged period of time. Hydrolysis plays a more important role when sodium oleate is used to produce the bubbles. As shown in Fig. 5, the zeta-potential is negative throughout the pH range investigated, but it becomes less negative as the pH becomes lower than the pKa value of the surfactant. Figure 8 represents the distribution diagram for the species present in the sodium oleate-water system. The thermodynamic data used for the construction of this diagram are from Ralston (16). As shown, the concentrations of the negatively charged species, i.e., RCOO- and (RCOO) 2-, are reduced below pH 7.9, and the neutral species, such as RCOOH(aq) and RCOOH(1), become predominant below this pH. This may provide an explanation for the decrease in the negative zeta-potential. Note, here, that the most stable oleate species in the acidic pH solutions is in liquid form, i.e., the surfactant precipitates out as RCOOH(1). For this reason, the bubbles become unstable in acidic pH, and the measurements of bubble charge become difficult, as reflected in Fig. 5. It has been shown that while the zeta-potentials of bubbles generated with CPC are independent ofpH, those with DAH are not (Fig. 4). The reason for this is that, unlike CPC,

Io-4

Z 0 ~-<~ 1(~6
IZ to tJ Z O IO-e

( ~

t51o

6
pH

I0 12

F/G.9. Speciesdistributiondiagramforthe dodecylamminiumhydrochloride-watersystem.

ZETA POTENTIAL

OF MICROBUBBLES

437

bulk water phase than are the OH- ions. This explanation may be termed "negative adsorption" or "exclusion" of protons at the interface. The proposed mechanism suggests further that the charge arises due to the intrinsic property of water rather than to the nature of the interface as long as the second phase, e.g., hydrocarbon and air, does not have a significant acid-base property. Saturated hydrocarbons are not known to have such a property (19) and, of course, neither does air. Although the proposed mechanism explains why air bubbles and hydrocarbon oils should be negatively charged in pure water, the charge density must vary with pH. At a low pH, some of the H + ions can move back to the interface due to the increased chemical potential, and at a higher pH, more o f the OH- ions will be found at the interface for the same reason. McShea and Callaghan (12) indeed showed this to be the case; using the spinning cylinder technique, they showed that the zeta~potential of air bubbles produced in pure water is -74.2 _ 60.0 mV at pH 7 , - 2 2 . 5 7.7 mV at pH 6, and -0.6 _ 0. I mV at pH 4. Likewise, Wen and Sun (20) reported that the zeta-potentials of the hydrocarbon oil-in-water emulsions are pH-dependent; the i.e.p, values of octane and dodecane are found to be pH 2.5~and that'of hexane is pH 2. Many investigators (4-6, 12) have studied the effects of inorganic electrolytes on the bubble charge, and showed that the bubbles are negatively charged regardless of the types of electrolytes used. The most likely reason for the negative charge is that, in general, cations have significantly larger hydration energies than anions (18, 2L 22). O n t h e other hand, Home and Young (23) suggested that the cation exclusion from an interface is due to the structural differences between the vicinal and the bulk water. It has been shown in the present work that the bubbles generated in the presence of nonionic surfactants are negatively charged in neutral and alkaline pH solutions, and become positively charged at acidic pH values. The charging mechanism may be considered to be

similar to that of the hydrocarbons discussed above. However, the mechanism must also be influenced by the presence of a more polar element, such as oxygen, in the molecular structure. It is conceivable that as the oxygento-carbon ratio is increased, the molecule becomes more basic, and the i.e.p, will shift toward the alkaline pH. The fact that the bubbles generated with polyoxyethylene methyl ether show a higher i.e.p. (pH 6) than those generated with polypropylene glycol (pH 3.5) may be explained by the difference in the oxygento-carbon ratio. The same explanation may be given for the results presented in Fig. 7, which show that the zeta-potential becomes more negative when the number of EO groups is reduced from 23 to 4 in the polyoxyethylene dodecyl ether molecule. The mechanism proposed here may also apply to the charging mechanism of polymers.
SUMMARY AND CONCLUSIONS

1. A simple modification of a vertical, fiattype electrophoresis cell has made it possible to determine the electrophoretic mobilities of microbubbles from which zeta-potentials can be calculated. 2. In general, bubbles produced using cationic surfactants exhibit positive zeta-potentials, while those produced using anionic surfactants exhibit negative zeta-potentials. It has been found, however, that the magnitudes of the zeta-potentials are reduced when the pH approaches the value of Pga or the pH of precipitation. 3. Bubbles generated using nonionic surfactants exhibit negative zeta-potentials at neutral and alkaline pH values and positive zeta-potentials in acidic solutions. It appears that the higher the oxygen-to-carbon ratio in the surfactant molecule, the higher the i.e.p. value and the more negative the zeta-potential. 4. The zeta-potentials of bubbles produced in the presence of ionic surfactants increase with increasing concentration, while the changes are minimal in the presence of nonionic surfactants.
Journal of Colloid and Interface Science, Vol. 113, No. 2, October 1986

438

YOON AND YORDAN 7. Usui, S., and Sasaki, H., J. Colloid Interface Sci. 65, 36 (1978). 8. Usui, S., Sasaki, H., and Matsukawa, H., J. Colloid Interface Sci. 81, 80 (1981). 9. Collins, G. L., Motarjemi, M., and Jameson, G. L., J. Colloid Interface Sci. 63, 69 (1978). 10. Fukui, Y., and Yuu, S., AICHEJ. 28(5) (1982). 11. Kubota, K., Hayashi, S., and Inoaka, M., J. Colloid Interface Sci. 95, 362 (1983). 12. McShea, J. A., and Callaghan, I. C., ColloidPoly. Sci. 261, 757 (1983). 13. Sebba, F., J. Colloid Interface Sci. 35, 643 (1971). 14. Currie, B. W., and Alty, T. V., Proc. R. Soc. London Ser. A 120, 622 (1930). 15. Leja, J., "Surface Chemistry of Froth Flotation," p. 205. Plenum, New York, 1981. 16. Ralston, A. W., "Fatty Acids and Their Derivatives." Wiley, New York, 1948. 17. Ananthpadmanabhan, K., Somasundaran, P., and Healy, T. W., Trans. A[ME266, 2003 (1980). 18. Conway, B. E., J. Solution Chem. 7(10), 721 (1978). 19. Fowkes, F. M., in "Physicochemical Aspects of Polymer Surfaces" (K. L. Mittal, Ed.), Vol. 2, Plenum, New York, 1983. 20. Wen, W. W., and Sun, S. C., Sep. Sci. Technol. 16(10), 1491 (1981). 21. Noyes, R. M., J. Amer. Chem. Soc. 84(4), 513 (1962). 22. Noyes, R. M., aT.Amer. Chem. Soc. 86(6), 971 (1964). 23. Home, R. A., and Young, R. P., Electrochim. Acta 17, 763 (1972).

5. T h e n e g a t i v e charges o f b u b b l e s a n d hyd r o c a r b o n oil droplets i n p u r e water have b e e n a t t r i b u t e d to the fact that H + i o n s have a higher h y d r a t i o n e n e r g y t h a n O H - ions. ACKNOWLEDGMENTS The authors wish to acknowledge the financial support of the U.S. Department of Energy, Pittsburgh Energy Technology Center, Grant DE-FG22-83PC60806, during the course of this research. They would also like to express their appreciation to the Latin American Scholarship Program of American Universities for supporting J. L. Yordan in his Master's degree work. REFERENCES 1. Derjaguin, B. V., and Dukhin, S. S., Trans. Inst. Min. Eng. 70, 221 (1960). 2. Derjaguin, B. V., and Dukhin, S. S., in "Proc., 13th International Mineral Processing Congress, Warsaw, Poland" (J. Laskowski, Ed.), p. 21. Elsevier, New York, 1981. 3. McTaggart, M. A., Philos. Mag. 44, 386 (1922). 4. Alty, T., Proc. R. Soc. London Ser. A 106, 315 (1924). 5. Gilman, A., and Bach, N., Acta Physicochim. URSS, IX(l) (1938). 6. Dibbs, H. P., Sirois, L. L., and Bredin, R., Canad. Metall. Quart. 13, 395 (1974).

Journal of Colloid and Interface Science, Vol. 113, No. 2, October 1986