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Minerals Engineering 20 (2007) 1296–1302

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Comparing the effect of salts and frother (MIBC) on gas dispersion

and froth properties
J.J. Quinn a, W. Kracht a, C.O. Gomez a, C. Gagnon b, J.A. Finch a,*

a
Department of Mining and Materials Engineering, McGill University, 3610 University Street, Montreal, QC, Canada H3A 2B2
b
COREM, 1180 rue de la Minéralogie, Québec City, Canada G1N 1X7

Received 18 April 2007; accepted 27 July 2007

Available online 11 September 2007

Abstract

The Raglan concentrator (Xstrata Nickel) does not employ frother. It was considered this might be the result of the high salt content
in the process water (ca. 30 000 ppm). Two-phase (solution–air) and three-phase (slurry–air) tests were undertaken in a laboratory col-
umn to quantify the effect of inorganic ions present in the water (a range of polyvalent ions). The measurements focused on gas disper-
sion (bubble size and gas holdup) and froth overflow rate. The results were compared to a typical frother (MIBC) system. The two-phase
tests revealed reduced bubble size, increased gas holdup and limited froth formation in salt solutions. The gas holdup correlated with
ionic strength. At an ionic strength ca. 0.4 (=0.4 M NaCl) the increase in gas holdup was comparable to ca.10 ppm MIBC. In three-phase
tests on a sulphide ore, bubble size and froth overflow rate were again comparable between 0.4 M NaCl and 10 ppm MIBC. The obser-
vations help explain why the Raglan plant can operate without frother addition.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Froth flotation; Flotation frothers; Flotation bubbles; Flotation froths

1. Introduction suggesting that flotation in saline water results in lower

Several flotation plants around the world use process
water with high inorganic salt content. This arises from a
combination of soluble components of the ore, increasing
use of recycle water and the use of sea or well water in some
locations. Extreme examples include the Mt Keith opera-
tion in Western Australia with salt concentrations around
60 000–80 000 ppm (George, 1996) and the processing of
potash in saturated brine (Strathdee, 2000). The example
of interest here is Xstrata Nickel’s (formerly Falconbridge)
Raglan mine in northern Quebec where salt levels range
from ca. 20 000 to 35 000 ppm, winter to summer. An
apparent consequence of the high salt content is that the
flotation circuit is able to operate without addition of
frother. This observation corresponds to previous evidence
*
Corresponding author. Fax: +1 514 398 4492.
E-mail address: jim.finch@mcgill.ca (J.A. Finch).
reagent consumption (Haig-Smillie, 1974; Yoon and Sabey,
1989). Since the role of frother is to decrease bubble size
and increase froth stability, salts must have some similar
capability.
Generally, the action of frothers is believed to result from
retarding coalescence (Harris, 1982). It is well documented
that many salts inhibit bubble coalescence (Marrucci and
Nicodemo, 1967; Lessard and Zieminski, 1971; Craig
et al., 1993; Hofmeier et al., 1995; Laskowski et al., 2003;
Craig, 2004). Inorganic ions appear to slow inter-bubble
film drainage. There are, however, significant differences
between inorganic salts and frothers. High salt concentra-
tions are required for coalescence inhibition (Lessard and
Zieminski, 1971; Craig et al., 1993; Zahradnik et al., 1999)
compared to a few parts per million of frother (Harris,
1982). Inorganic salts generally tend to increase surface ten-
sion while frothers reduce it; and inorganic ions are usually
not able to form froth (foam) in two-phase (water–gas) sys-
tems. Lekki and Laskowski (1975) observed that only in the

0892-6875/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2007.07.007
 J.J. Quinn et al. / Minerals Engineering 20 (2007) 1296–1302 1297

presence of hydrophobic particles would salt solutions form Camera

a stable froth. They noted that inorganic electrolytes fall
into the category of surface inactive agents while frothers
are surface active. BV v
Light
Researchers have attempted to determine a transition source
concentration at which salts inhibit bubble coalescence
(Lessard and Zieminski, 1971; Craig et al., 1993; Zahradnik
et al., 1999). Zieminski and Whittemore (1971) have shown
that many ions of high valence have a greater effect hinder-
ing bubble coalescence than monovalent ions. This valence
effect will be included here.
The major ions present in Raglan process water are PT
Na+, Cl, SO2 2
4 , and S2 O3 . Tests were designed to exam-
ine the impact of these ions, initially in a two-phase (solu-
tion–gas) system. The salts employed were NaCl, Na2SO4,
CaCl2 and Na2S2O3 to cover the ions present at Raglan
with Al2(SO4)3 included to extend the range of ion charge,
i.e., examples of 1–1, j1–2, 2–1j and 3–2 (cation–anion
charge) salts were tested. As gas dispersion properties,
gas holdup and bubble size distribution were measured. Feed
tank
As a froth property, depth was considered. However, the
salts gave virtually no froth in the absence of solids (cf.
Lekki and Laskowski, 1975). Instead overflow rate was
selected in tests on ore from Brunswick Mine (Xstrata PT
pump
Zinc) conducted at a pilot plant facility (i.e., three-phase
tests). Both two- and three-phase test-work includes com-
parison with a common frother, methyl-isobutyl carbinol
(MIBC). Fig. 1. Schematic of set-up.

2. Methodology
Both the two- and three-phase tests employed a column
with the general features shown in Fig. 1.
2.1. Two-phase tests
The column in this case was 7.6 cm (internal) diameter
and 34 cm high, operated batch. A cylindrical porous spar-
ger was located at the base of the column (vertical orienta-
tion). A Bailey differential pressure transmitter was located
between 162.5 cm and 288 cm to determine gas holdup.
Another pressure transmitter was located at the base of
the column to record the pressure at the sparger. This pres-
sure was used to correct the volumetric airflow rate to the
test conditions. Airflow rate is reported as a superficial
velocity, Jg (cm/s), by dividing the volumetric flowrate

14

12

water
10
Gas Holdup (%)

8 0.05M NaCl

6 0.10M NaCl

4 0.25M NaCl

0
0.0 0.5 1.0 1.5 2.0
Superficial Gas Velocity (cm/s)

Fig. 2. Gas holdup vs. superficial gas velocity as a function of sodium chloride concentration.
1298 J.J. Quinn et al. / Minerals Engineering 20 (2007) 1296–1302

(cm3/s) by the column cross sectional area (cm2). For acid to avoid aluminum hydroxide formation. Prior testing
selected conditions bubble size distribution (BSD) was indicated pH adjustment itself did not influence gas
determined using the McGill Bubble Size Analyzer (or holdup.
Bubble Viewer, BV) (Hernandez et al., 2002; Hernandez- Once pressure signals became constant (i.e., steady state,
Aguilar et al., 2004). Typically over 2000 bubble images taking 5–10 min) readings were recorded. The column was
were processed. The BSD data are presented as number emptied and cleaned between each test.
frequency.
Solutions were prepared using Montréal tap water with
varying concentrations of the following salts: NaCl (Wind- 2.2. Three-phase tests
sor Select Plus), CaCl2, Na2SO4, Na2S2O3 and Al2(SO4)3
(supplied by Fisher and reagent grade unless otherwise These were conducted at the COREM pilot plant facility
noted), and MIBC (methyl-isobutyl carbinol), a common (Québec City). A modular column (10.16 cm by 320 cm)
industrial frother (supplied by Flottec). The tests were con- was assembled on-site and adapted to run continuously.
ducted at natural pH (6–7) except for aluminum sulphate A cylindrical porous sparger was located near the base of
where the solution was adjusted to ca. pH 3 with sulphuric the column (horizontal orientation). Operation was that

30

25
Relative Frequecy (%)

20 Water 0.05M NaCl 0.1M NaCl 0.25M NaCl

15

10

0
0 1 2 3 4 5 6 7 8
Bubble Diameter (mm)

Fig. 3. Bubble size distributions in sodium chloride solutions.

16

Salt Jg (cm/s)
14

NaCl 0.7 cm/s

12
Jg = 1.7 cm/s NaCl 1.7 cm/s
Na2SO4 0.7 cm/s
Gas Holdup (%)

10
Na2SO4 1.7 cm/s
CaCl2 0.7 cm/s
8
CaCl2 1.7 cm/s

6 Na2S2O3 0.7 cm/s

Na2S2O3 1.7 cm/s
4 Al2(SO4)3 0.7 cm/s
Jg = 0.7 cm/s
Al2(SO4)3 1.7 cm/s
2

0
0.0 0.1 0.2 0.3 0.4 0. 5
Salt Concentration (M)

Fig. 4. Gas holdup vs. salt concentration (Jg = 0.7, 1.7 cm/s).
 J.J. Quinn et al. / Minerals Engineering 20 (2007) 1296–1302 1299

of a typical laboratory flotation column (Finch and Dobby, (tailings) was discharged via a pump and overflow (concen-
1990), except no wash water was added. trate) flowed by gravity through a flexible pipe that could
The ore, ground to 85%–85 lm, was prepared following be directed for sampling. Superficial slurry velocity, Jsl,
Brunswick Mine protocol for Cu/Pb bulk rougher flota- was maintained at 1 cm/s. Overflow rate (l/min) was deter-
tion. The slurry (water was Québec City tap) was brought mined manually by collecting overflow in a graduated cyl-
to the target solution conditions (salt or frother concentra- inder over given time intervals. Airflow rate was controlled
tion) in the feed tank. The feed (30 wt% solids) was intro- manually using a Matheson rotameter.
duced about 40 cm below the column lip. Froth depth was To complement the overflow data, images of the top of
estimated from the bottom pressure and controlled auto- the froth were recorded and bubble size measured in the
matically (5 ± 2 cm) by manipulating feed rate. Underflow pulp below the froth using the Bubble Viewer. Bubble size

14
NaCl 0.7 cm/s
NaCl 1.0 cm/s
NaCl 1.4 cm/s
12
NaCl 1.7 cm/s
Na2SO4 0.7 cm/s
10 Na2SO4 1.0 cm/s
Na2SO4 1.4 cm/s
Gas Holdup (%)

Na2SO4 1.7 cm/s

8 CaCl2 0.7 cm/s
CaCl2 1.0 cm/s
CaCl2 1.4 cm/s
6 CaCl2 1.7 cm/s
Na2S2O3 0.7 cm/s
Na2S2O3 1.0 cm/s
4 Na2S2O3 1.4 cm/s
Na2S2O3 1.7 cm/s
Al2(SO4)3 0.7 cm/s
2 Al2(SO4)3 1.0 cm/s
Al2(SO4)3 1.4 cm/s
Al2(SO4)3 1.7 cm/s
0
0.0 0.1 0.2 0.3 0.4 0.5
Ionic Strength

Fig. 5. Gas holdup vs. ionic strength for four superficial gas velocities (in order from bottom to top: 0.7, 1.0, 1.4 and 1.7 cm/s) for all salts tested.

[MIBC] (ppm)
0 2 4 6 8 10 12 14 16 18 20
15

14

13

12
Gas Holdup (%)

MIBC
MIBC
11
NaCl
NaCl
10

6
0.0 0.1 0.2 0.3 0.4 0.5
[NaCl] (M)

Fig. 6. Determining equivalent frother (MIBC) concentration (Jg = 0.7 cm/s).

1300 J.J. Quinn et al. / Minerals Engineering 20 (2007) 1296–1302

was used as the gas dispersion measure in this case as using decreases. Keitel and Onken (1982) showed a correlation
pressure to estimate gas holdup is no longer accurate unless between Sauter mean bubble diameter, D32, and ionic
slurry density is continuously monitored. strength (they also noted the possibility of using the diam-
eter of hydrated ions to improve the correlation). As far as
3. Results and discussion is known Fig. 5 is the first time a dependence of gas holdup
on ionic strength has been demonstrated.
3.1. Two-phase It is argued that the higher the charge on the ionic spe-
cies the more coalescence is inhibited. Zieminski and Whit-
3.1.1. Gas holdup and bubble size temore (1971) noted that coalescence behavior was a
Gas holdup is an indirect measure of bubble size, increas- function of ion–water interactions. Highly hydrated inor-
ing as bubble size decreases (for a given air flow rate). This ganic ions tend towards the bulk away from the solution/
reflects that smaller bubbles rise at lower velocities and thus air interface (i.e., negatively adsorb) and are termed ‘struc-
gas residence time (holdup) in the column increases. Bubble
size is dictated by sparger characteristics, airflow rate and
the system chemistry. Fig. 2 shows the expected near linear
response in gas holdup with superficial gas velocity
(obtained up to a limiting Jg) (Finch and Dobby, 1990).
Increasing sodium chloride concentration increased gas
holdup indicative of salt’s ability to reduce bubble size.
Bubble size distribution was measured at three sodium
chloride concentrations (0.05, 0.1 and 0.25 M) at a superfi-
cial gas velocity of 0.7 cm/s (Fig. 3). An effect is not notable
until 0.25 M when the initially dominant mode in water
alone at ca. 4–5 mm shifts to ca. 1 mm. This observation
correlates with the increase in gas holdup when salt concen-
tration increases to 0.25 M (Fig. 2). Interestingly, the
water-only case always showed evidence of fine bubbles
(<1 mm) suggesting they either survive the coalescence pro-
cess or perhaps result from coalescence induced bubble
break-up (Tse et al., 2003).
As a result of this demonstrated relationship between
gas holdup and bubble size and the fact that the former
is easier to measure on-line, gas holdup is used in the
remaining two-phase tests.

3.2. Effect of salts

Fig. 4 shows the gas holdup results obtained at two gas

velocities. The salts fall into groups according to their
valence; aluminum sulphate (3–2 salt) showed the strongest
response followed by the 2–1, 1–2 salts with the weakest
response from monovalent NaCl.
The valence effect is incorporated by introducing the
ionic strength (l) defined as:
X
l ¼ 1=2 C i Z 2i ð1Þ

where Ci is the molar concentration of the ith species and

Zi is the charge of the ith species.
The summation is taken over all ionic species in solution.
Fig. 5 shows that there appears to be a unique relationship
between gas holdup and ionic strength independent of salt
type.
Zieminski and Whittemore (1971) demonstrated a corre-
lation between total bubble surface area and ionic strength Fig. 7. Top views of froth and corresponding image of bubbles below the
(for 11 salts). Total bubble surface area, like gas holdup, is froth for flotation of sample of Brunswick Mine ore (water, Québec City
a function of bubble size, both increasing as bubble size tap).
 J.J. Quinn et al. / Minerals Engineering 20 (2007) 1296–1302 1301

25
Water 5.10
Water
0.1M NaCl 3.66
20 0.1M NaCl

Relative Frequency (%)

0.2M NaCl 2.84
0.2M NaCl
15 0.4M NaCl 2.45
0.4M NaCl
10ppm MIBC 1.93
10ppm MIBC
10

0
0 1 2 3 4 5 6 7 8
Bubble Diameter (mm)

Fig. 8. Evolution of bubble size distribution for conditions in Fig. 7 (Jg = 0.9 cm/s).

ture makers’. It has been shown that both positive and neg-
ative adsorption can cause bubble coalescence inhibition
(Foulk and Miller, 1931; Machon et al., 1997).
3.3. Equivalent frother concentration
As salt type (among those tested) does not appear to be
a factor, NaCl was selected as representative for this part
of the work. Being monovalent, ionic strength is numeri-
cally equal to the concentration in mol/L (M). Fig. 6 com-
pares gas holdup as a function of the concentration of
NaCl (lower axis) and MIBC (upper axis). The trend-lines
are polynomial fits.
While it is evident that MIBC is capable of greater
increases in gas holdup the results for NaCl cover a similar
range. A water sample from Raglan showed an ionic
strength of ca. 0.4 (vertical line on Fig. 6). From this obser-
vation it can be estimated that salts at Raglan have the
same effect, with respect to increased gas holdup, as
roughly 8–10 ppm MIBC. An MIBC concentration at this
level is typical in plant operations (Gélinas et al., 2005) and
helps explain why Raglan is able to operate without froth-
er. The tests were repeated at three other gas velocities (0.4,
the two-phase tests (Fig. 3). Water alone showed a princi-
pal mode at 4–5 mm (and, again, a minor one below 1 mm)
which shifts progressively to finer size and the distribution
narrows with increasing NaCl concentration. The distribu-
tion for 0.2 and 0.4 M NaCl becomes comparable to
MIBC. This reinforces the conclusion from two-phase tests
that gas dispersion properties are similar between salt solu-
tions of ionic strength ca. 0.4 (i.e., 0.4 M NaCl) and ca.
10 ppm MIBC. Comparing Figs. 3 and 8 indicates that
the presence of solids has little impact on the bubble size
produced, which is dictated by the solution ‘chemistry’.
Fig. 9 gives the measured overflow rates for the three-
phase tests. The overflow rate increases with salt concentra-
tion and becomes similar to that achieved by 10 ppm
MIBC between 0.2 and 0.4 M NaCl. Recalling that in the
two-phase tests salts could not sustain froth it is evident
that the hydrophobic particles (i.e., those attached to the
0.8
water
0.1 M NaCl
0.6
0.2 M NaCl
O/F Rate (L/min)

1.0 and 1.7 cm/s) and gave the same equivalent frother 0.4 M NaCl

concentration. 10 ppm MIBC

0.4

3.4. Three-phase

The three-phase tests were conducted to access froth 0.2

properties but they also gave some further insight into
gas dispersion. Fig. 7 shows overhead views of the froth
with typical images of the bubble size in the pulp below. 0
It is evident that with increasing NaCl concentration the 0 0.5 1 1.5 2 2.5
froth texture and bubble size merge with those obtained Gas Velocity (cm/s)
with 10 ppm MIBC. The evolution of the bubble size distri- Fig. 9. Overflow rates as a function of superficial gas velocity and salt
bution is seen in Fig. 8; the features are similar to those in concentration compared to 10 ppm MIBC (corresponding to Fig. 7).
1302 J.J. Quinn et al. / Minerals Engineering 20 (2007) 1296–1302
bubbles) are responsible for froth formation (Fig. 7) and
overflow.1 Water alone (Fig. 9) even showed some over-
flow. Pugh (2006) recently demonstrated that hydrophobic
particles could build froth in the absence of surfactant.
However, without the small bubbles provided by frother
or salts the overflow (particle recovery) rate is limited,
i.e., flotation capacity is limited.
The combination of gas dispersion and froth overflow
results in both the two- and three-phase systems provides
the evidence that salts present in the Raglan water can sub-
stitute for frother. The important similarity between froth-
er and salts is the ability to produce fine bubbles. Any plant
with process water of ionic strength at least 0.4 should con-
sider the probable impact on bubble size.
4. Conclusions
Two-phase results show increasing gas holdup with
increasing concentration of NaCl, CaCl2, Na2SO4, Na2S2O3
and Al2(SO4)3. The effect increased with ion valence and a
correlation between gas holdup and ionic strength was dem-
onstrated. Gas holdup for salt solutions with ionic strength
ca. 0.4, as at the Raglan concentrator, is similar to that of
ca. 10 ppm MIBC, which is a typical dosage for this com-
mon frother. Continuous three-phase tests with a sulphide
ore showed similar froth texture, bubble size distribution
and froth overflow rate for 10 ppm MIBC and 0.4 M NaCl
(i.e., ionic strength 0.4). The results help interpret why the
Raglan plant can operate without frother; in particular,
high concentration of salts can substitute for the bubble size
reduction normally provided by frother.
Acknowledgements
The funding was under a Collaborative Research and
Development grant from Natural Sciences and Engineering
Research Council of Canada (NSERC) with industrial spon-
sorship from (giving the names at the onset of the sponsor-
ship, 2001): Inco, Teck-Cominco, Noranda, Falconbridge,
COREM and SGS-Lakefield (joined 2003). In particular,
the authors would also like to acknowledge COREM under
project R-116 for additional financial support. Constructive
discussions with Colin Hardie and Carmine Ciriello (Raglan
operation) are also gratefully acknowledged.
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