International Journal of Mineral Processing 140 (2015) 5057

Contents lists available at ScienceDirect

International Journal of Mineral Processing

journal homepage: www.elsevier.com/locate/ijminpro

Zeta potential of air bubbles conditioned with typical froth

otation reagents
Arturo Bueno-Tokunaga a, Roberto Prez-Garibay a,, Diego Martnez-Carrillo b
a
b

Cinvestav-IPN, Industria metalrgica No. 1062, Parque industrial Saltillo-Ramos Arizpe, Ramos Arizpe, Coahuila C.P. 25900, Mexico
Escuela Superior de Ingeniera de la Universidad Autnoma de Coahuila, Blvd. Adolfo Lpez Mateos, Nueva Rosita, Coahuila, Mexico

a r t i c l e

i n f o

Article history:
Received 28 April 2014
Received in revised form 7 March 2015
Accepted 29 April 2015
Available online 30 April 2015
Keywords:
Zeta potential
Microbubbles
Flotation reagents

a b s t r a c t
The effect of chemical otation reagents on the zeta potential () of particles is well known, but their effect on
bubbles is practically unknown. This study characterizes the of air bubbles conditioned with typical froth otation reagents and presents a novel experimental setup and method for estimating the electrophoretic velocity. It
was observed that collectors strongly affect in the following order from more to less anionic: xanthate,
dithiophosphinate, deionized water, mercaptobenzothiazole and dodecylamine. By contrast, frothers affect
only slightly. In this study, it was also observed that pH affects the microbubble diameter and that under acidic
or basic conditions, the bubble diameter decreases.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Once the chemical reagents used to condition particle surfaces in
froth otation processes are hydrolyzed, the ions in the aqueous solution distribute themselves between the particles and bubbles according
to the laws of electrostatics and thermodynamics. The ions that carry
the opposite charge to that of the particle or bubble surfaces are preferentially attracted to these surfaces. Consequently, an electric potential
produced by each charged surface arises in the solution and decreases
with increasing distance from the surface because of the screening
of its electric eld by mobile ions. A charged surface and the diffuse
layer of mostly oppositely charged ions that surrounds it comprise an
electrical double layer. Generally, the zeta potential (), also called
the electro-kinetic potential, is dened as the value of the electric potential at the shear plane of the particle (or, in this case, the bubble). At
this point, it is important to discuss briey the state of the art of zeta
potential measurements, which have been analyzed and sometimes
questioned by several authors. Leja (1982) clearly summarizes the difculties in measuring the electrokinetic effects, and therefore estimating
the zeta potential, in a reproducible manner. All of these difculties
mean that, in certain recent cases, the measured electrophoretic mobility is being reported instead of the calculated zeta potential. Regardless
of these critical opinions about the techniques for measuring the zeta
potential, all of the authors accept that the only value that should not
be affected by the evaluation technique is the point of zero charge.
Corresponding author.
E-mail addresses: arturobueno@uadec.edu.mx (A. Bueno-Tokunaga),
roberto.perez@cinvestav.edu.mx (R. Prez-Garibay), diegomartinez@uadec.edu.mx
(D. Martnez-Carrillo).

http://dx.doi.org/10.1016/j.minpro.2015.04.028
0301-7516/ 2015 Elsevier B.V. All rights reserved.

Some of the arguments questioning the zeta potential estimation suggest that the properties of the solids or bubbles comprising one of the
two phases in an electrokinetic system are not taken into account at
all (Leja, 1982). The author mentions that Eqs. (1) and (2) are based
on two broad assumptions (which are sometimes not valid):
1. The electrical double layer (along which separation of charge occurs)
consists of the Helmholtz condenser-like layers of opposite charges.
This assumption would apply only to concentrated electrolyte solutions.
2. When a steady-state condition is reached, the charges carried away
by convection in the owing liquid are supposed to be compensated
by an electronic current (the ow of which has never been dened or
identied). Such compensation is not likely to take place in every
solidelectrolyte system without an extraneous charge buildup on
some solids. According to the same author, a large number of side effects (such as changes in viscosity caused by the applied potential
gradient, surface conductance, electrode effect, etc.) have been
introduced into evaluations of the zeta potential for the purpose of
overcoming the difculties of irreproducible measurements.
According to Leja (1982), other causes of this measurement irreproducibility are the interferences caused by the presence of impurities,
some of which may be very active at interfaces even if they are present
only in trace amounts. Even in some cases when the arguments
questioning the zeta potential measurement are valid, it is noteworthy
that these measurements give practical useful information to evaluate
the charge of the surface. Frequently, these measurements reect not
only the effects due to the but also the superimposed effects due
to the non-applicability of the assumptions used in the derivation of

A. Bueno-Tokunaga et al. / International Journal of Mineral Processing 140 (2015) 5057

Eqs. (1) and (2) and to the specic adsorption of impurities. With these
considerations, this paper reports the estimations and the electrophoretic mobility (Appendix A) in order to give all of the necessary information to evaluate the electrical charge, provided by the froth otation
reagents, to the bubble surface.
Returning to the main issue of this paper, there are four basic types
of electrokinetic effects, and each one can be utilized to evaluate the
zeta potential for a given set of conditions: electrophoresis, streaming
potential, electro-osmosis, and sedimentation potential. Of these four
electrokinetic effects, the electrophoretic effect is most frequently
used in studies relating to minerals.
The effect of chemical surfactants on the of particles is well known,
but their effect on bubbles is practically unknown (Paulson and Pugh,
1996). The supercial properties of bubbles are important primarily in
the froth otation of ne particles and in ion otation, in which the
supercial forces of attraction can be more important than the force of
gravity. Although the effect of of the bubbles does not appear to be
very evident in conventional froth otation, it is possible that it has
some impact on bubble coalescence and the entrainment of ne gangue.
In addition to the technical impacts, it is important to advance the understanding of all chemical and physical phenomena related to bubbles
and their chemical conditioning. In particular, this paper characterizes
the of air bubbles conditioned with froth otation reagents and presents a novel experimental setup and method for estimating the electrophoretic velocity without the need for a commercial zeta-potential
meter. The experimental results published in the literature (even for
deionized water, simple salts and other reagents) are very scattered,
but the results reported by the proposed technique here, aided by the
number of measurements, show very low scattering.
Nguyen and Schulze (2004) explain that measuring the of gas bubbles is more difcult than measuring those of solid particles, principally
due to the inherent bubble rise in liquid solutions. They mention that
conventional microelectrophoretic cells are used to measure the potentials of microbubbles (Laskowski et al., 1989; Li and Somasundaran,
1991, 1992, 1993; Yoon and Yordan, 1986). The same reference detailed
that knowledge of how the bubble size affects the bubble is not available yet, most likely because of the available measuring techniques.
In addition, the of microbubbles measured with electrophoretic techniques is assumed to be independent of the bubble size. However, the
experimental data of Usui and Sasaki (1978) shows that the of bubbles
measured using the Dorn effect technique increases with the bubble
size, although hydrodynamic considerations complicate the interpretation of this result. Similar results were also reported by McShea and
Callaghan (1983) who used the spinning cylinder electrophoretic technique to measure the . It is generally observed that the measured by
spinning techniques is different from that measured by microelectrophoretic techniques (using microbubbles).
2. Background
Smoluchowski (1903) considered laminar ow of an incompressible
aqueous electrolyte owing between two nonconducting plates and
derived basic expressions for the zeta potential estimation with the
following methods: (a) streaming potential and (b) electrophoresis
(Leja, 1982).
In streaming potential, different pressures (P) are applied to the
electrolyte, forcing it through a capillary (or a set of pores), and the
corresponding streaming potential (V) is determined.

V
P

where V is the measured potential, P is the pressure applied to the

liquid, and I is the distance between electrodes, is the viscosity, is
the conductivity and is the dielectric constant of the electrolyte bulk

51

solution. In streaming potential the becomes zero when V/P = 0 or

V = 0.
In electrophoresis the of a charged particle or bubble can be estimated when it is electrically displaced by a eld of direct current and
the velocity of displacement is known, using the follow equation
(Eq. (1)).

4 v
;
V=L

where is the zeta potential (volts), is the solution viscosity (poise), v

is the electrophoretic velocity, V is the applied electrical potential
(volts), is the dielectric constant (80.1) and L is the distance between
the electrodes (cm). In electrophoresis the becomes zero for v = 0.
In general, the literature concerning the of bubbles is oriented
toward a) developing an experimental setup for the measurement of
this variable, b) determining the of air bubbles, c) determining the
of bubbles of gases different than air or d) measuring the of air bubbles
immersed in chemical reagents such as surfactants and electrolytes.
a) One of the difculties in measuring the of bubbles is the lack of a
specialized meter intended for the measurement of bubbles.
Some of the pioneers in designing a cell for the measurement of
the electrophoretic velocity of bubbles were McTaggart (1922) and
Alty (1926), who developed a technique for controlling the natural
buoyancy of bubbles using a gyratory electrophoretic cell. They
were the rst to report that the air bubbles in distilled water have
a negative charge. This technique was improved to prevent the
internal electroosmosis from occurring, by Saulnier et al. (1998).
Also, Collins et al. (1978) generated small bubbles by electrolysis
and measured their electrophoretic mobility while the bubbles
were rising slowly through an electrophoretic cell.
b) Graciaa et al. (1995) have reported a of 65 mV for the air bubbles
in deionized water, whereas Takahashi (2005) has reported a of
35 mV for distilled water (pH = 5.8). Even when there is a divergence from these results, the difference in value may be attributed to
the purity of the water. More recently, Kelsall et al. (1996) have attributed the negative value of to the predominance of hydroxyl
ions in the rst molecular layer of the interface. By contrast,
Takahashi (2005) believes that the negative potential is attributable
to the hydrogen bonds in the molecular layer of the interface. According to Nagayama et al. (2006), the presence of these hydrogen
bonds explains the stability of nanobubbles. Ohgaki et al. (2010)
have postulated that this hydrogen bonding has been detected via
infrared spectroscopy.
c) Yang et al. (2001) have pursued an electrophoretic technique using
small bubbles of oxygen and hydrogen gases. Their experimental
setup was instrumented to facilitate vertical translation of the cell.
Thus, when the bubbles ascended, the cell descended, permitting
better focalization with the microscope. The authors noted that
their apparatus could follow the movement of bubbles with diameters greater than 80 m for a duration of 4 to 8 s. In this study, the effects of several metallic ions on the of bubbles were analyzed.
Ushikubo et al. (2010) have studied the effect of the gas composition
on , nding negative values for oxygen bubbles (between 34 and
45 mV) and reporting that this potential uctuated between 17
and 20 mV for air bubbles. These measurements were performed
while varying the pH from 6.2 to 6.4 for oxygen and from 5.7 to 6.2
for air.
d) Related to the characterization of the induced by chemical
reagents, the following reports are particularly notable. Using an
electrophoretic technique, Laskowski et al. (1989) have studied the
electro-kinetic potentials developed by certain otation collectors,
primary amines and fatty acids. It was found that a cationic surfactant applies a positive charge to the surface, whereas an anionic
surfactant imposes a negative charge. Saulnier et al. (1996) have

52

A. Bueno-Tokunaga et al. / International Journal of Mineral Processing 140 (2015) 5057

Table 1
of bubbles in water.a
Isoelectric point (Iep)

pH

(mV)

Experimental conditions

Reference

1.5

1.511.5

N3
33.5
2.5
33.5

311
2.411.5
2.511
212
5.8
6.26.4
5.76.2
212

0 to 58
65
0.27 to 29.7
5.5 to 51.8
0 to 58
8 to 39
35
34 to 45
17 to 20
20 to 80

Bubbling nitrogen with a porous glass sparger in water, 102 M NaCl

Air bubbles in deionized water
Ultrasonic vibration, 102 M KCl
Electrolysis of the water using platinum electrodes, 102 M NaCl
Micropipette, without electrolyte
Ultrasonic vibration
Air bubbles in distilled water
Oxygen bubbles
Air bubbles
Air bubbles in water, 0.01100 mM NaCl or KCl

Li and Somasundaran (1991)

Graciaa et al. (1995)
Kim et al. (2000)
Yang et al. (2001)
Fan et al. (2004)
Cho et al. (2005)
Takahashi (2005)
Ushikubo et al.
Ushikubo et al.
Nguyen and Schulze (2004)

1.52.5
a

Note: in some cases the water quality and the experimental conditions were not specied.

determined that from pH 5 to 8, with anionic or non-ionic surfactants, there is little electrophoretic movement. They concluded
that for non-ionic surfactants, their adsorption on the bubble surface
is poor but sufcient to generate a small . Using microbubbles of air
generated via air nucleation using ultrasonic webs, Elmahdy et al.
(2008) have concluded that the addition of low frother concentrations (b20 ppm) does not contribute signicantly to the of bubbles; the primary effect of the addition of frothers is to decrease
the bubble size. They have also observed that above 100 ppm,
pentanol causes a decrease in , whereas methyl isobutyl carbinol
(MIBC) and heptanol increase the negative charge. Describing the
effect of the inorganic electrolytes, Nguyen and Schulze (2004)
found that in general the gas bubbles are negatively charged in
aqueous solutions with NaCl and KCl at pH N 23 and the isoelectric
point oscillates between pH = l.5 and 2.5. The negative of bubbles
at pH N 3 in water indicates that OH ions preferentially adsorb at
the clean gaswater interface. The same authors suggests that Na+,
K+, and Cl behave as indifferent electrolyte ions, which control
the effective diffuse layer thickness but do not specically adsorb
on the gaswater interface. Table 1 presents a summary of recent research regarding the of bubbles.

3. Experimental methodology
An experimental setup was proposed (Fig. 1), designed and constructed to estimate, with the aid of an image-analysis technique, the
electrophoretic mobility of microbubbles subjected to an electrical
eld. The setup contained three major components: the air-saturation
reactor, the electrophoretic cell and the image-acquisition system. The
saturation reactor was constructed out of polyvinyl chloride (PVC, 40;
10 cm internal diameter; 20 cm height).
To reduce the number of bubbles entering the electrophoretic cell,
the volume of the bubbling cell was greater than that of the electrophoretic cell (see Fig. 1). The bubbling cell (30 cm in height, 10 cm in length
and 15 cm in width) was fabricated out of transparent acrylic plaques.
In the central section, the video camera was positioned against the electrophoretic cell, the conguration of which is illustrated in a magnied
diagram in Fig. 2. Although the electrophoretic cell was small, it functioned properly and accurately estimated .
The electrophoretic cell was constructed out of ve acrylic plaques
(0.2 cm in thickness) separated by empty ducts (0.3 cm wide and
0.2 cm deep), which were used to install the platinum electrodes
(wires of 0.75 mm in diameter and 5 cm in length). The fth plaque

Switch
7.03 V
2.02 A

1 2 3
4 5 6
7 8 9 .

Power
source

O
f

PC

Temperature, pH and
Conductivity meter
pH

Output
Electrophoretic
cell

Camera

Input: Air
and solution

Bubbling
cell

Fig. 1. Experimental setup.

Saturator

A. Bueno-Tokunaga et al. / International Journal of Mineral Processing 140 (2015) 5057

Electrodes

liquid recirculation. The two empty lateral channels (at angular positions with respect to the central channel) permitted the installation of
the electrodes and the removal of the O2 and H2 gases generated by
the electrolysis of the water. In addition, the electrodes were coupled
to the direct-current power source and a rocker switch that permitted
the alternation of the polarity of the electrodes (each 40 s) to prevent
polarization.
Another important element of the experimental setup was the
image-acquisition system, which was composed of a digital camera
equipped with a macro lens (Navitar 12). To increase the focusing
precision and the size of the visualization plane, the camera was installed
on a platform with three-dimensional mobility. The video camera
(Toshiba 3-CCD RGB; resolution 1024 768 pixels; 90 frames/s) permitted the user to register the bubble displacement and the time through a
MATHLAB library that linked the video camera to the computer. Each
image was recorded in a le whose name included the time at which
the image was taken. The le names used the following format, in
which the hours, minutes, seconds and milliseconds were recorded:
HH_MM_SS_FFF. Once the voltage had been applied and the displacement distance of the bubble and the time required for the displacement
had been measured, the bubble velocity could be estimated; this was possible once the video le could be replayed ofine.
To obtain reliable images, it was necessary to follow several steps:
(1) visualization of the target zone to capture a reference of a known
size (in this case, a thin Nylon wire of 230 m in diameter), which
was placed close to the front wall of the electrophoretic cell; (2) selection of a single microbubble ascending through free otation; and
(3) quantication of the bubble displacement and the time elapsed at
the completion of the experiment.
The froth otation reagents that were investigated were a) xanthate
ethylic of potassium (C3H5KOS2, 96%; Sigma-Aldrich), b) dodecylamine
(C12H27N, 98%; Sigma-Aldrich), c) mercaptobenzothiazole (C7H5NS2,
97%; Sigma-Aldrich), d) dithiophosphinate of sodium (C8H18O2PS2Na,

3 mm

Fig. 2. Electrophoretic cell. The observation zone is dened by the points H, I, J and K.

was semi-opaque (white) and was glued to the four transparent

plaques, whose function was to enclose the channels and to prevent
the visualization of bubbles passing behind the electrophoretic cell. A
small white-light lamp (7 W) was placed near the semi-opaque plaque
to illuminate the microbubbles. It is noteworthy that the front walls of
the bubbling cell and electrophoretic cells were inclined by 20 with
respect to the vertical plane to permit the visualization of bubbles rising
in a plane closer to the front wall and to increase the image quality. This
orientation also minimized the effects of electro-osmotic ow and

13_04_59_687

53

13_05_00_170

13_05_00_703

13_05_01_264

Fig. 3. Sequence of images depicting the route and horizontal displacement of a bubble.

30

(a)

20
15
10

(b)

Xanthate, 25 ppm.
pH=6.4

10
Standard deviation

Frequency, %

25

12
Xanthate, 25 ppm.
pH=6.4

8
6

4
2

0
<=18.31

(18.32-23.31) (23.32-28.31) (28.32-33.31) (33.32-38.31)

Zeta potential class

10

20

30

40

50

60

Number of measurements

Fig. 4. (a) Typical histogram of measurements and (b) the standard deviation of the arithmetic average as a function of the number of measurements.

54

A. Bueno-Tokunaga et al. / International Journal of Mineral Processing 140 (2015) 5057

30

30

(a)

(b)

Elmahdy et al., 2008.

Bueno-Tokunaga et al. MIBC, 10 ppm.

20

20

Elmahdy et al., 2008. MIBC, 10 ppm.

Bueno-Tokunaga.
10

Azgomi, 2007.

Bueno-Tokunaga et al.. MIBC, 100 ppm.

Deionized water and [NaCl] 10 -2

Z Potential, mV

Z - Potential, mV

10

-10
-20
-30

Elmahdy y col., 2008. MIBC, 100 ppm.

Deionized water, MIBC and [NaCl] 10 -2 M

-10
-20
-30

-40

-40

-50

-50
-60

-60
0

10

12

14

10

12

14

pH

pH

Fig. 5. Comparison of the values for air bubbles reported in the literature and those obtained in this work: (a) for deionized water and (b) for MIBC at 10 and 100 ppm.

Once the image close to the front wall was focused, the imageacquisition system was ready to visualize the bubble dispersion and to
record the bubble trajectory upon application of the electric potential.
When the voltage was applied to the platinum electrodes, the microbubbles were attracted to the electrode of opposed polarity. To acquire
images of sufcient quality for estimation, several images were
collected to permit the selection of at least 40 single bubbles with the
following characteristics: those with small diameters moving near the
front wall and exhibiting free otation. Once the time and the horizontal
displacement were recorded, the electrophoretic velocity and could be
estimated. For each estimation, the electrophoretic velocities of
approximately 40 bubbles were measured. The following sequence of
images illustrates the bubble movement (see Fig. 3a to d).

98%; Cytec S.A de C.V.), e) terpinol (C10H18O, 98%; Sigma-Aldrich) and

f) methyl-isobutyl-carbinol (98%; Sigma-Aldrich).
Prior to each experiment, the electrophoretic cell was prepared
using the following procedure: the cell was soaked for a period of
10 min in a solution of water and detergent. Subsequently, the cell
was rinsed with deionized water and immersed in a solution of chromic
acid for 2 h. Afterward, a second rinse with deionized water was performed, and the cell was then ready for use.
Once the aqueous solution (3.5 l) was prepared, the pH, electrical
conductivity and temperature were recorded. To provide a controlled
electric strength, a sufcient quantity of NaCl was added to the aqueous
solution for it to reach a concentration of 103 M. This aqueous solution
was agitated for 5 min to stabilize the temperature and to homogenize
the solution after reagent addition. A portion of this solution was poured
into the bubbling cell, and the remainder was introduced into the air
saturator. Afterward, the portion that had been introduced into the saturator was manually subjected to high pressure and mixed. To facilitate
air dissolution, the saturator was manually agitated several times until
the saturation point was reached. To initiate bubble dispersion, it was
necessary to open the valve located at the output of the saturator,
which introduced the saturated solution into the bubbling cell, permitting air nucleation.

30

4. Results and discussion

4.1. Evaluation of the standard deviation of estimations
To evaluate how many measurements should be performed to obtain a good estimation, the standard deviation of the arithmetic average
was evaluated as a function of the number of measurements. Fig. 4a
presents a typical frequency histogram of obtained for the xanthate

40

(a)

NaCl 10 -2 M

20

10

10

Potential, mV

Potential, mV

(b)

30

20

-10
-20
-30

-10
-20
-30

Deionized water

NaCl 10 -2 M
Xanthate, 100 ppm.

Dithiophosphinate, 25 ppm.

-40

-40

Xanthate, 25 ppm.

Xanthate, 25 ppm.

-50

Dodecylamine, 25 ppm.

Dodecylamine, 25 ppm.

-50

Dodecylamine, 100 ppm.

2-Mercaptobenzothiazole, 25 ppm.

-60

-60
0

8
pH

10

12

14

10

12

pH

Fig. 6. (a) Effects of typical froth otation collectors (25 ppm) on the of air bubbles. (b) Effects of the addition of the xanthate collector on the z of the air bubbles.

A. Bueno-Tokunaga et al. / International Journal of Mineral Processing 140 (2015) 5057

55

10

10

(b)

-10

-10
Z Potential, mV

Z Potential, mV

(a)

-20

-30

NaCl 10
-40

-2

-20

-30

NaCl 10 -2 M

-40

Deionized water

MIBC, 100 ppm.

Terpinol, 25 ppm.
-50

MIBC, 25 ppm.

-50

MIBC, 25 ppm.

MIBC, 10 ppm.

2 Ethylhexanol, 30 ppm.
-60

-60
0

pH

10

12

14

pH

10

12

14

Fig. 7. Effects of typical froth otation frothers (25 ppm) on the of air bubbles.

collector, and Fig. 4b indicates that after 30 measurements were collected, the standard deviation became relatively constant. It was observed
that for larger numbers of measurements, the standard deviation uctuated between 3 and 6 mV.

4.2. Validation of the experimental methodology

To validate the experimental setup and the methodology, select
chemical reagents were chosen for which has already been reported
in the literature. Fig. 5a compares the results for bubbles immersed
in deionized water reported in this work with those obtained by
Azgomi et al. (2007) and Elmahdy et al. (2008). This gure indicates
strong agreement between our results and those obtained by the
other researchers. These results permit to discuss about the reproducibility of the electrophoretic technique when the buoyancy effect is
present. According to Leja (1982) one of disadvantages of the electrophoretic techniques is the lack of results reproducibility. However, the
agreement of the results reported in the literature, obtained with
commercial instruments (Azgomi et al., 2007; Elmahdy et al., 2008)
(without buoyancy effect), and the results here obtained (with buoyancy effect) is an indirect form to revalorize the electrophoretic technique.
Fig. 5b presents the results obtained for MIBC at 10 ppm and 100 ppm
and the corresponding results obtained by Elmahdy et al. (2008), and
comparison between the two indicates that the results were similar
throughout the investigated range of pH values, although a marked
divergence was observed under acidic conditions. By comparing the
results presented in Fig. 5b, it can be observed that after the frother

concentration was increased from 10 to 100 ppm, slightly decreased.

In addition, because the results obtained in this work were similar to
those obtained by other researchers, the experimental methodology
was validated; it was therefore possible to use the experimental setup
to characterize the of air bubbles in the presence of typical froth otation reagents, which was the primary objective of this study.
4.3. Effect of typical collectors on the of air bubbles
Fig. 6a presents the values measured for air bubbles as a function of
pH in the presence of typical froth otation collectors at 25 ppm. It was
observed that dodecylamine is a stronger cationic collector, whereas
xanthate and dithiophosphinate are stronger anionic collectors. In this
gure, it is also evident that mercaptobenzothiazole causes a slight increase in the of air bubbles in deionized water. Based on this gure,
the collectors can be ranked in the following order from more anionic
to more cationic: xanthate, dithiophosphinate, deionized water,
mercaptobenzothiazole and dodecylamine. Fig. 6b presents the effect
of the addition of xanthate with increasing reagent concentration
from 25 to 100 ppm; little change is apparent. Table A.1 of Appendix A
presents the quantitative results for , the isoelectric point, pH and the
standard deviation for a collector concentration of 25 ppm.
4.4. Effect of typical frothers on the of air bubbles
Fig. 7 compares the effects of typical froth otation frothers (at
25 ppm) on the of air bubbles. Contrary to what was observed for

60

70

(a)
Bubble diameter, m

Bubble diameter, m

(b)

60

50
40
30
20

50
40
30
20

10

MIBC, 10 ppm
[NaCl] = 10 -2 M

Xanthate, 25 ppm
[NaCl] = 10 -2 M

10

0
0

pH

10

12

14

pH

10

12

Fig. 8. Effect of pH on the diameters of the bubbles selected for the estimations: (a) MIBC at 10 ppm and (b) xanthate at 25 ppm.

14

56

A. Bueno-Tokunaga et al. / International Journal of Mineral Processing 140 (2015) 5057

the collectors, the frothers have only a minimal effect on . Lower values
were obtained for MIBC and terpinol, whereas the bubbles that formed
in the presence of ethylhexanol exhibited slightly higher values.

4.5. Effect of the pH on the bubble diameter

One phenomenon that has not been reported in the literature is that
pH affects bubble diameter. It was observed that even when the collector or frother concentration was held constant, any non-neutral pH
(acidic or basic) caused a decrease in bubble diameter, which reached
its maximum at pH = 7. This behavior was observed for all investigated
collectors and frothers. Fig. 8 presents plots of the bubble diameter versus pH for MIBC (10 ppm) and xanthate (25 ppm). It is worth noting
that the bubble diameter presented here is the average of the selection
of smaller microbubbles that was used to estimate , but these gures
nevertheless permit the observation of the effect of the pH on the bubble size.

5. Conclusions
A novel procedure and experimental setup were proposed and validated for the measurement of the electrophoretic velocity and the of
air bubbles. This validation was performed by comparing the results obtained using the proposed approach with those reported in the literature.
The was characterized in the presence of typical froth otation reagents, and it was observed that this potential is strongly affected by
collectors but only slightly modied by frothers.
Even when frother or collector concentration is held constant,
changes in pH affect the diameters of the microbubbles; under acidic
or basic conditions, the bubble diameter decreases.
Acknowledgments
The authors are grateful to CONACYT (Project 2007-01-83186;
Mexico) for scholarships and funding and to Carmelita Yamamoto
Chavarria for the assistance in data collection.

Appendix A

(See Tables A.2 and A.3.)

Table A.1
Zeta potentials of air bubbles in the presence of typical collectors for froth otation. (mV), U (m/s V/cm).
Potassium xanthate, 25 ppm

Potassium xanthate, 100 ppm

Dodecylamine, 25 ppm

pH

pH

pH

2.48
3.81
5.04
6.36
7.50
8.75
10.24
11.55

11.58
19.41
24.44
27.34
32.59
39.88
43.41
43.85

4.1
4.7
4.9
5.2
4.8
4.4
3.8
3.6

0.82
1.37
1.73
1.94
2.31
2.82
3.07
3.1

2.31
4.63
6.13
7.69
9.02
10.14
11.50

13.91
26.78
34.94
42.20
45.57
48.39
50.50

5.0
5.1
5.8
5.8
5.4
5.2
4.8

0.98
1.9
2.47
2.99
3.23
3.43
3.57

2.45
3.50
5.40
7.15
9.83
11.39

Dodecylamine, 100 ppm

pH

2.30
3.30
5.00
7.10
9.50
11.50

Dithiophosphinate, 25 ppm

35.67
29.01
24.33
19.55
15.28
11.82

4.4
4.5
4.8
5.2
4.9
4.8

U
2.53
2.05
1.72
1.38
1.08
0.84

25.90
20.83
19.34
14.17
10.09
8.09

4.2
4.8
5.1
5.3
4.7
4.5

1.83
1.47
1.37
1
0.71
0.57

2-Mercaptobenzothiazole, 25 ppm
IEP = 5.6

pH

pH

2.08
4.00
6.35
8.13
10.00
12.00

12.08
22.86
28.14
29.89
32.78
38.69

4.8
5.0
5.2
5.1
4.8
4.6

0.86
1.62
1.99
2.12
2.32
2.74

2.03
4.00
6.15
8.03
10.16
12.02

8.61
7.01
6.78
12.72
24.18
30.11

4.7
4.8
5.0
4.8
4.2
4.0

0.61
0.5
0.48
0.9
1.71
2.13

Table A.2
Zeta potentials of air bubbles in the presence of typical frothers. (mV), U (m/s V/cm).
Kerosene; 30 ppm

2-Ethylhexanol, 30 ppm

Terpinol, 25 ppm

pH

pH

pH

2.16
3.69
6.62
7.90
9.80
12.00

9.90
16.35
23.98
29.36
35.67
39.96

3.6
3.1
4.9
4.7
5.3
4.5

0.7
1.16
1.7
2.08
2.53
2.83

1.91
3.22
6.60
8.12
9.50
12.06

7.66
15.62
24.83
31.02
32.79
37.97

2.5
3.7
4.9
5.3
4.9
4.5

0.54
1.11
1.76
2.2
2.32
2.69

2.13
4.44
6.65
8.70
10.30
12.03

9.24
22.08
27.14
34.49
42.30
51.33

2.8
4.5
5.2
5.6
5.4
5.4

0.65
1.56
1.92
2.44
2.99
3.63

pH

pH

pH

2.35
4.40
6.47
8.23
10.17
11.23

8.21
16.97
21.04
25.50
38.48
42.12

3.5
4.1
4.8
4.4
4.1
3.6

0.58
1.2
1.49
1.81
2.72
2.98

3.04
5.24
7.27
9.62
11.62

12.31
23.67
37.07
37.62
44.92

3.6
4.1
4.9
4.4
3.7

0.87
1.68
2.62
2.66
3.18

2.28
3.33
4.98
6.90
8.47
10.55
11.75

13.58
17.47
22.23
35.70
42.29
48.35
49.19

3.3
3.8
4.3
5.1
4.7
4.3
3.8

0.96
1.24
1.57
2.53
2.99
3.42
3.48

MIBC, 10 ppm

MIBC, 25 ppm

MIBC, 100 ppm

A. Bueno-Tokunaga et al. / International Journal of Mineral Processing 140 (2015) 5057

Table A.3
Zeta potentials of air bubbles in deionized water. (mV), U (m/s V/cm).
Deionized water IEP = 2.9
pH

2.36
4.40
6.53
6.80
8.50
9.50
10.23

4.90
12.65
19.57
21.82
30.56
32.41
35.76

3.4
3.8
4.7
4.9
4.1
3.8
3.4

0.35
0.9
1.39
1.54
2.16
2.29
2.53

References
Alty, T., 1926. The origin of the electrical charge on small particles in water. Proc. R. Soc.
Lond. Ser. A 122 (760), 235251.
Azgomi, F., Gomez, C.O., Finch, J.A., 2007. Correspondence of gas holdup and bubble size in
presence of different frothers. Int. J. Miner. Process. 83 (12, 4), 111.
Cho, S.H., Kimb, J.Y., Chuna, J.H., Kima, J.D., 2005. Ultrasonic formation of nanobubbles and
their zeta-potentials in aqueous electrolyte and surfactant solutions. Colloids Surf. A
Physicochem. Eng. Asp. 269, 2834.
Collins, G.L., Motarjemi, M., Jameson, G.J., 1978. J. Colloid Interface Sci. 63, 69.
Elmahdy, A.M., Mirnezami, M.J., Finch, A., 2008. Zeta potential of air bubbles in presence
of frothers. International Journal of Mineral Processing vol. 89, Issues 14. Department of Mining and Materials Engineering, McGill University, Montral, Canada,
pp. 4043.
Fan, X., Zhang, Z., Li, G., Rowson, N.A., 2004. Attachment of solid particles to air bubbles in
surfactant-free aqueous solutions. Chem. Eng. Sci. 59, 26392645.
Graciaa, A., Morel, G., Saulner, P., Lachaise, J., Schechter, R.S., 1995. The zeta-potential of
gas bubbles. J. Colloid Interface Sci. 172, 131136.
Kelsall, G.K., Tang, S., Yurdakul, S., Smith, A.L., 1996. Electrophoretic behaviour of bubbles
in aqueous electrolytes. J. Chem. Soc. Faraday Trans. 92, 38873893.
Kim, J.Y., Song, M.G., Kim, J.D., 2000. Zeta potential of nanobubbles generated by
ultrasonication in aqueous alkyl polyglycoside solutions. J. Colloid Interface Sci. 223,
285291.

57

Laskowski, J.S., Yordan, J.L., Yoonf, R.H., 1989. Electrokinetic potential of microbubbles
generated in aqueous solutions of weak electrolyte type surfactants. Langmuir 5,
373376.
Leja, J., 1982. Surface Chemistry of Froth Flotation. University of British Columbia. Vancouver, British Columbia, Canada. 1st ed. Plenum Press, N.Y. and London, p. 758.
Li, C., Somasundaran, P., 1992. J. Colloid Interface Sci. 148, 587.
Li, Ch. Chin, Somasundaran, P., 1991. Reversal of bubble charge in multivalent inorganic
salt solutions effect of magnesium. J. Colloid Interface Sci. 146 (1).
Li, C., Somasundaran, P., 1993. Colloids Surf. A 81, 13.
McShea, J.A., Callaghan, l.C., 1983. Colloid Polym. Sci. 261, 757.
McTaggart, M.A., 1922. Philos. Mag. 44, 386.
Nagayama, G., Tsuruta, T., Cheng, P., 2006. Molecular dynamics simulation on bubble formation in a nanochannel. Int. J. Heat Mass Transf. 49 (2324), 44374443.
Nguyen, A.V., Schulze, H.J., 2004. Colloidal Science of Flotation. Ed. Taylot & Francis Group,
N.Y, p. 850.
Ohgaki, K., Khan, N.Q., Joden, Y., Tsuji, A., Nakagawa, T., 2010. Physicochemical approach
to nanobubbles solution. Chem. Eng. Sci. 65 (3), 12961300.
Paulson, O., Pugh, R.J., 1996. Flotation of inherently hydrophobic particles in aqueous
solutions of inorganic electrolytes. Langmuir 12, 48084813.
Saulnier, P., Lachaise, J., Morel, G., Graciaa, A., 1996. Zeta potential of air bubbles in surfactant solutions. J. Colloid Interface Sci. 182 (2), 395399 (25 September).
Saulnier, P., Bouriat, P., Morel, G., Lachaise, J., Graciaa, A., 1998. J. Colloid Interface Sci. 200,
81.
Smoluchowski, M., 1903. Krak. Anz. 182.
Takahashi, M., 2005. Zeta potential of microbubbles in aqueous solutions: electrical properties of the gaswater interface. J. Phys. Chem. B 190 (46), 2185821864.
Ushikubo, F.Y., Furukawa, T., Nakagawa, R., Enari, M., Makino, Y., Kawagoe, Y., Shiina, T.,
Oshita, S., 2010. Micro- and nano-bubbles (in this study, referred to as MNB)
present characteristics that make them special in relation to the ordinary bubbles
(macro-bubbles) because of their reduced diameter size. Colloids Surf. A Physicochem.
Eng. Asp. 361, 3137.
Ushikubo, F.Y., Furukawa, T., Nakagawa, R., Enari, M., Makino, Y., Kawagoe, Y., Shiina, T.,
Oshita, S., 2010. Evidence of the existence and the stability of nano-bubbles in
water. Colloids Surf. A Physicochem. Eng. Asp. 361, 3137.
Usui, S., Sasaki, H., 1978. J. Colloid Interface Sci. 65, 36.
Yang, C., Dabros, T., Li, D., Czarnecki, J., Masliyah, J.H., 2001. Measurement of the zeta potential of gas bubbles in aqueous solutions by microelectrophoresis method. J. Colloid
Interface Sci. 243, 128135.
Yoon, R.H., Yordan, J.L., 1986. J. Colloid Interface Sci. 113, 430.