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Adsorption and surface tension analysis of concentrated alkali halide brine

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Article in Minerals Engineering · February 2009

DOI: 10.1016/j.mineng.2008.08.001

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 Minerals Engineering 22 (2009) 263–271

Contents lists available at ScienceDirect

Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Adsorption and surface tension analysis of concentrated alkali halide brine solutions
Orhan Ozdemir a,*, Stoyan I. Karakashev a, Anh V. Nguyen a, Jan D. Miller b
a
Division of Chemical Engineering, School of Engineering, The University of Queensland, St. Lucia, Brisbane, QLD 4072, Australia
b
Department of Metallurgical Engineering, University of Utah, Salt Lake City, UT 84112, USA

a r t i c l e i n f o a b s t r a c t

Article history: In this study, the equilibrium and dynamic surface tensions of sodium chloride and potassium chloride
Received 28 July 2008 solutions have been measured as a function of concentration up to saturation (5.2 M for NaCl and
Accepted 11 August 2008 4.1 M for KCl) using sessile bubble tensiometry. The experimental results show that the surface tension
Available online 27 September 2008
of these and other salts significantly increases with increasing concentration due to negative adsorption
of ions at the air/brine interface, regardless of their structure maker and breaker nature. Furthermore, the
Keywords: effect of these salts on the surface tension of aqueous solutions of sodium dodecyl sulfate (SDS) and
Sodium chloride and potassium chloride
methyl isobutyl carbinol (MIBC) was also studied. These results show that the salts increased the surface
Surface tension
Water structure maker and breaker
activity of SDS and MIBC. In the case of SDS, KCl increased the surface activity of SDS more significantly
than NaCl did. In the case of MIBC, the effect of NaCl on MIBC surface activity was more significant than
that of KCl.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction electrophoretic technique showed that KCl has a negative surface

Potash ores are a mixture of a sylvite (KCl) and halite (NaCl)
with water-insoluble minerals such as clay and carbonate miner-
als. Potash is widely used as fertilizer in the agriculture industry.
Potash is also used in glass manufacturing, soaps, plastics and
pharmaceuticals (Perucca, 2003). Most of the potash ores in the
world are concentrated by froth flotation. In this method, sylvite
is floated from halite using amine collectors along with frothers
(Miller and Yalamanchili, 1994). Since potash ores contain water-
soluble salts, flotation is carried out in a brine, which is about
7 mol/L of NaCl–KCl solution (Gaska et al., 1965). This high salt
concentration significantly changes the interfacial water structure
which affects collector adsorption at the surface of soluble salt
minerals as well as at the air/brine interface.
There have been many models proposed to explain the flotation
behavior of soluble salts in their saturated solutions such as an ion
exchange model (Fuerstenau and Fuerstenau, 1956), a heat of solu-
tion model (Rogers and Schulman, 1957), and a surface charge-ion
pair model (Schubert, 1988). One of the most accepted theories is
the surface charge model which suggests that the separation of
KCl from NaCl is achieved because the positively charged amine col-
lector colloid adsorbs on negatively charged KCl particles, while
there is no adsorption of the cationic collector at the positively
charged NaCl particles (Yalamanchili et al., 1993). Surface charge
measurements of salt minerals made using a nonequilibrium
* Corresponding author. Tel.: +61 7 3365 3777; fax: +61 7 3365 4199.
E-mail addresses: o.ozdemir@uq.edu.au (O. Ozdemir), Anh.Nguyen@eng.uq.
edu.au (A.V. Nguyen).
charge whereas NaCl has a positive surface charge (Miller et al.,
1992).
Unfortunately the surface charge theory could not answer the
question of why negatively charged KCl particles are also floated
with 12C anionic collectors such as sodium dodecyl sulfate (SDS).
Subsequently research by Hancer showed that consideration of
hydration phenomena at salt crystal surfaces provides a better
explanation for the flotation of alkali halide salts even when the
collector is charged the same as the salt (Hancer et al., 2001).
Our recent studies showed that the flotation of soluble salts de-
pends on their structure breaking and making properties (Du
et al., 2008; Ozdemir et al., 2006, 2007). These studies indicated
that a salt may be either a water structure maker or a water struc-
ture breaker. If the salt serves as a structure maker for water, such
as NaCl, the water molecules will be strongly bonded at the salt
surface and the adsorption of collector at the hydrated surface is
prevented. Therefore, the flotation of structure maker salts with
either cationic or anionic 12C collectors is not possible. Unlike
the structure maker salts, the structure breaker salts such as KCl
have a tendency to disrupt the structure of water at the salt sur-
face; thus a collector may reach the surface, create a hydrophobic
surface state and allow for the flotation of such salts with cationic
collectors such as dodecylamine (DAA) and octadecylamine, or an-
ionic collectors, such as sodium dodecyl sulfate (SDS).
The presence of salt ions in solution not only changes the prop-
erties of solid/water interfaces but also the air/water interfaces,
thus additionally affecting the interaction between particles and
bubbles during flotation. It is important to understand how these
electrolytes behave at the interfaces. In particular, their effect at

0892-6875/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2008.08.001
264 O. Ozdemir et al. / Minerals Engineering 22 (2009) 263–271
the air/brine interface must also be analyzed to determine if they
are a structure maker or breaker with respect to their flotation
behavior. The aim of this study is to investigate the effect of soluble
salts on adsorption and surface tension which might indicate a
possible water structure effect. We measured the surface tension
of these soluble salts up to their saturation points and investigated
their effects on the surface tension of aqueous solutions of sodium
dodecyl sulfate (SDS) and methyl isobutyl carbinol (MIBC) as a col-
lector and frother, respectively. Finally, the Gibbs adsorption iso-
therm was applied for these salts in the absence of chemicals in
order to obtain Gibbs surface excess.
2. Experimental
2.1. Materials
Alkali halide sodium chloride and potassium chloride salts (EMD
Chemicals and Mallinckrodt) used in this study were of reagent
grade. All salts were used without further purification. The anionic
collector, sodium dodecyl sulfate (SDS, C12H25SO4Na) 99% purity,
was purchased from Fluka. Methyl isobutyl carbinol (MIBC, H3C-
CH(CH3)-CH3-CH(OH)-CH3) was obtained from Acros Organics. All
the materials were used as received. De-ionized water (18 MXcm)
obtained with a Milli-Q plus Millipore Ultra Pure Water system
(Millipore Ltd., Molshem, France) was used in all the experiments.
Surface tension of the deionized water was about 72.7 mN/m at
23 °C. All salt solutions were freshly prepared and used.
The needle and syringe used in measuring surface tension were
cleaned using 6% (by volume) Deconex 15E solution (Borer, Swit-
zerland) and rinsed with distilled water several times. Before and
between measurements, the surface tension of the de-ionized
water was measured and compared with the available data to en-
sure that no contamination was present in the system. All glass-
ware and the other components used in the experiments were
soaked for several hours in the Deconex 15E solution, rinsed in
the Milli-Q water, and dried in a cabinet to protect them from dust.
The experiments were carried out at room temperature (23 °C).
2.2. Apparatus
The apparatus and procedures used for the surface tension mea-
surements have been described in a previous paper (Ozdemir et al.,
2006) and were used without modification. Only a brief survey of
the essential information is given here. The measurements were
made using sessile bubble tensiometry with a fully computer-con-
trolled apparatus (System OCA 20, DataPhysics, Germany). The
schematic of the experimental setup is shown in Fig. 1. Since the
container used for the surface tension experiments was enclosed,
the effect of evaporation on surface tension measurements was
minimal.
In this method, first a sessile bubble was generated, then, the
bubble profile was captured, digitized, and finally, the image data
processed. The digitized bubble profiles were fitted numerically
with the solution of the Young–Laplace equation to obtain the sur-
face tension value.
The shape of a bubble is governed by the Young–Laplace equa-
tion, which relates the pressure drop across a curved interface by
 
1 1
r þ ¼ DP
R1 R2
where R1 and R2 are the radii of the two curvatures of the gas/liquid
interface, and DP is the pressure difference across the interface.
Since the sessile bubbles have rotational symmetry, the two radii
of the curvatures can be described in terms of the profile coordi-
nates of bubble images (Hartland and Hartley, 1976).
Lens Cell
Video Camera
Lamp
Syringe
Goniometer
Interface
Air
Salt
Solution
Needle
Fig. 1. A schematic of the sessile bubble tensiometer and the video image
digitization equipment used to determine the dynamic and equilibrium surface
tension of salt solutions (Ozdemir et al., 2006).
3. Results and discussion
3.1. Surface tension of alkali halide salts
The numerical solution and fitting were carried out for each
bubble image and the surface tension corresponding to each bub-
ble image at a given time was found, giving the dependence of sur-
face tension on time (bubble age). With the salts studied, the
surface tension at equilibrium was established very quickly (when
the surface tension versus time reached a constant level). The best
fits with the Young–Laplace equation and the highest accuracy of
the measured surface tension were found with the largest, most
stable bubbles having maximum deviation from the spherical
shape.
The experimental surface tension data obtained with the sessile
bubble method for aqueous NaCl and KCl at room temperature at
different concentrations are depicted in Figs. 2 and 3, respectively.
As can be seen from the figures, the adsorption of the salts onto the
gas/liquid interface is extremely fast (within a second) and the sur-
face tension of the salt solutions does not significantly change with
time.
The surface tensions at equilibrium for NaCl and KCl solutions
were obtained by averaging the data and are tabulated in Tables
1 and 2, respectively. The data shown in the tables were obtained
with five different bubbles for a given concentration of salt. It is
seen that the reproducibility of the measurements is excellent.
The equilibrium surface tensions of NaCl and KCl are presented
in Fig. 4. The surface tensions of the salt solutions increase with
increasing salt concentration up to the saturation concentrations,
which are about 5.2 and 4.1 mol/L for NaCl and KCl, respectively.
The dependence of the equilibrium surface tension on the concen-
tration of NaCl and KCl is strong and linear.
ð1Þ
The increase in surface tension with the addition of electrolytes
has been explained by negative adsorption of ions at the air/water
interface. According to the Gibbs adsorption equation, any solute
that increases the surface tension of water must show a negative
total adsorption at the air/water interface. The Gibbs surface excess
(adsorption), C, can be calculated from the Gibbs adsorption
isotherm:
 O. Ozdemir et al. / Minerals Engineering 22 (2009) 263–271 265

84

NaC l

82 5.35 M
5.2 M
5.0 M

4.5 M

Surface Tension (mN/m)

80
4.0 M

3.5 M

78 3.0 M

2.5 M

2.0 M
76
1.5 M

1.0 M
74 0.5 M

0.25 M

72
0 60 120 180 240 300 360
Bubble Age (sec.)

Fig. 2. Surface tension of NaCl solutions versus time as described by bubble age.

80

KCl
79
4.1 M
78 4.0 M
Surface Tension (mN/m)

3.5 M
77
3.0 M

76 2.5 M

2.0 M
75
1.5 M

1.0 M
74
0.5 M

73 0.25 M

72
0 60 120 180 240 300 360
Bubble Age (sec.)

Fig. 3. Surface tension of KCl solutions versus time as described by bubble age.

  " pffiffi #
1 dr I 2 pffiffi
C¼ ð2Þ ln cM ¼ Z 2M A pffiffi þ lnð1 þ b IÞ
RT d ln a 1þb I b
! !
where r is surface tension (mN/m), a is the electrolyte activity, R is mM C /MX 2 0 Z M C /MX
the universal gas constant, and T is the absolute temperature (K).
þ mX 2BMX þ þ mM mX Z M BMX þ ð3Þ
jZ X =Z M j1=2 jZ M Z X j1=2
The activity used for the brine solutions can be related to con- " pffiffi #
I 2 pffiffi
centration using the Pitzer theory (Pitzer, 1973; Pitzer and Mayor- ln cX ¼ Z 2X A pffiffi þ lnð1 þ b IÞ
ga, 1973, 1974; Pitzer and Kim, 1974), which gives a = cm, where c 1þb I b
is the activity coefficient and m is the molality concentration (mol ! !
mM C /MX 2 0 Z X C /MX
per kg of solvent) of the salt. For the activity coefficient of ions dis- þ mM 2BMX þ þ m m
M X Z B
X MX þ ð4Þ
sociated from single salts described as MX, the Pitzer theory gives: jZ X =Z M j1=2 jZ M Z X j1=2
266 O. Ozdemir et al. / Minerals Engineering 22 (2009) 263–271

Table 1 25 °C. C /MX in these equations is the Pitzer parameter related to

Average equilibrium surface tension of NaCl solutions versus concentration at 23 °C the third virial coefficients. In Eqs. (3) and (4) BMX and B0MX describe
Concentration (M) Surface tension (mN/m) Standard deviation (mN/m) the interaction parameters for the oppositely charged ions which
0.00 72.72 0.03
are defined as explicit functions of the ionic strength by;
0.25 73.03 0.09
0.50 73.46 0.03
BMX ¼ b0 þ b1 f ða1 I1=2 Þ þ b2 f ða2 I1=2 Þ ð5Þ
1=2 1=2
1.00 74.05 0.05 B0MX I 0
¼ b1 f ða1 I 0
Þ þ b2 f ða2 I Þ ð6Þ
1.50 74.75 0.04
2.00 75.54 0.05 where bi for i = 0, 1, and 2 are the Pitzer coefficients determined by
2.50 76.52 0.05
the second virial coefficients, and functions f and f0 are defined as
3.00 77.48 0.05
3.50 78.09 0.04 f ðxÞ ¼ 2½1  ð1 þ xÞ expðxÞ=x2 and f 0 ðxÞ ¼ 2½1  ð1 þ x þ 0:5x2 Þ
4.00 79.31 0.02 expðxÞ=x2 . For univalent electrolytes, only the first two terms of
4.50 80.08 0.05 Eq. (5) and only the first term of Eq. (6) are considered where
5.00 80.80 0.08 a1 = 2. For higher valence type electrolytes, such as 2–2 electrolytes,
5.20 (saturation) 81.75 0.03
the full equations are used and a1 = 1.4 and a2 = 12.
The Pitzer coefficients for NaCl and KCl are described in Table 3.
The conversion of the molar, C, to molality, m, concentrations and
Table 2 vice versa can be carried out using experimental data for solution
Average equilibrium surface tension of KCl solutions versus concentration at 23 °C density.
Concentration (M) Surface tension (mN/m) Standard deviation (mN/m)
Fig. 5 shows the dependence of the activity coefficient on the
salt concentration of NaCl and KCl. The figure indicates that the
0.00 72.72 0.03
activity coefficient of KCl does not change significantly after 1 M
0.25 72.89 0.05
0.50 73.26 0.06 in contrast to NaCl. This contributes to the weaker dependence of
1.00 73.77 0.05 the surface tension on the KCl concentration compared to NaCl. It
1.50 74.29 0.02 is known from the literature that the increase in surface tension
2.00 74.94 0.04
is directly proportional to the enthalpy of hydration, indicating
2.50 75.71 0.02
3.00 76.61 0.06 that ions prefer to be fully hydrated in the bulk solution (Ozdemir
3.50 77.19 0.01 et al., 2006) rather than partially hydrated at the interface. Further,
4.00 78.09 0.05 the more hydrated the ions, the more they are displaced toward
4.10 (saturation) 78.58 0.04 the bulk (Hey et al., 1981).
Fig. 6 shows the adsorption of NaCl and KCl versus the level of
saturation for each of the salts in their aqueous solutions. The fig-
ure shows negative adsorption for both salts. The negative adsorp-
84
tion of NaCl is higher compared to KCl. It is noted that the two salts
have the same value of adsorption at complete saturation.
82 In addition to NaCl and KCl, the surface tension of aqueous solu-
tions of other salts such as KI, KNO3, K2SO4, and NaF have also been
Surface Tension, mN/m

80 measured. Fig. 7 shows the surface tension results for these salts.
As shown in Fig. 7, the surface tension of the aqueous solutions in-
78 creases with increasing salt concentration up to their saturation
points. As mentioned before, an increase in surface tension in the
presence of electrolytes has been explained by negative adsorption
76
of ions at the air/water interface, however, some electrolytes such
as HCl, HNO3, etc., decrease the surface tension of the water which
74 is an indication of a positive value for adsorption (Weissenborn
and Pugh, 1996).
NaCl
72 The surface tensions of these salts are also presented in terms of
KCl saturation (Fig. 8). It is interesting to note that the solubility of
70 these salts plays a significant role on their surface tension values
0 1 2 3 4 5 6
with a more soluble salt giving higher surface tension at a given le-
Salt Concentration, M vel of saturation.
The Pitzer coefficients for the given salts are presented in Table
Fig. 4. Average equilibrium surface tension of NaCl and KCl brine solutions versus
concentration up to the point of saturation (5.2 M and 4.1 M for NaCl and KCl, 4 and the activity coefficient vs concentration data is presented in
respectively). Fig. 9. The adsorption isotherms for these salts are presented in
Fig. 10.
The increase in surface tension of electrolyte solutions was first
where zM and zX are the charges of the cation M and anion X, confirmed theoretically by Wagner (1924), and then Onsager and
respectively, and b = 1.2 is an empirical parameter. The ionic Samaras (1934). According to them, the repulsive electrostatic
strength is defined as I ¼ ðmM z2M þ mX z2X Þ=2, where mM and mX are image forces are responsible for the increase in surface tension in
the molality concentrations of the cations and anions, respectively.
The Debye–Hückel coefficient, A, in Eqs. (3) and (4) is defined as Table 3
A ¼ ð2pN A dw =1000Þ1=2 ð4pew e0 kB T=e2 Þ3=2 =3, where NA is the Avoga- The Pitzer coefficients for NaCl and KCl (Kim and Frederick, 1988)
dro number, e is the charge of a proton, kB is the Boltzmann con-
Salt b0 b1 C /MX
stant, eo is the permittivity of vacuum, and dw and ew are the
density and relative dielectric constant of water, respectively. The NaCl 0.07722 0.25183 0.00106
KCl 0.04661 0.22341 0.00044
value A = 0.392 is usually used in calculating Eqs. (3) and (4) at

1 ous solutions of inorganic electrolytes (Bostroem et al., 2005; Mar-
0.8
Activity Coefficient
0.6
0.4
0.2
0
0 1 2 3
Concentration, M
Fig. 5. Activity coefficients of NaCl and KCl versus salt concentration.
1×10 -5
Adsorption (-Γ), mol/m2
1×10 -6
1×10 -7
1×10 -8
0 20 40 60
Level of Saturation, %
Fig. 6. Adsorption isotherm of NaCl and KCl versus level of salt saturation in the
aqueous solutions. (Saturation values of the salts were calculated based on their
actual concentrations.)
the presence of salt ions. They solved the Poisson–Boltzmann
equation analytically assuming a low value of the ionic potential
and obtained an equal increment of the surface tension for all
the inorganic electrolytes.
Further efforts have been focused on developing a theory which
accounts for the individual effects of the ions. According to Randles
there is an ‘‘ion free layer” in the subsurface vicinity (Randles,
1957). He assumed that the smaller ions have larger hydration ra-
dii and vice versa. Therefore, they have a larger affinity to water
resulting in stronger repulsion from the air/water interface and
higher increment of the surface tension (Weissenborn et al., 1996).
Mahanty and Ninham introduced the dispersion theory in the
interpretation of negative adsorption (Mahanty and Ninham,
1977). The role of dispersion forces in the ion-interface interactions
has been investigated and recently reviewed by (Bostroem and
Ninham, 2004; Bostroem et al., 2001; 2005; Kunz et al., 2004; Nin-
ham and Yaminsky, 1997). The improved theory for the image
(Kharkats and Ulstrup, 1991) and dispersion (Bostroem et al.,
2005) forces was aimed at predicting the surface tension of aque-
O. Ozdemir et al. / Minerals Engineering 22 (2009) 263–271 267
kin and Volkov, 2002).
Later on, Jungwirth and Tobias conducted MD simulation for al-
kali halide salts (Jungwirth and Tobias, 2001). They showed that
the anions are closer to the interface than the cations. Based on
these theories, most of the salts increase the surface tension of
aqueous solutions which means that salt ions are excluded from
the air/brine interface. Our previous studies showed that NaCl
and NaF are structure makers. On the contrary, KCl, KI, KNO3,
and K2SO4 are structure breaker salts. As seen from the surface ten-
sion results of these salts, they increase the surface tension of
aqueous solutions. It is evident that there is no correlation between
the surface tension of these salts and their structure making and
NaCl
breaking effect on the flotation response.
KCl
3.2. Surface tension of aqueous solutions of ionic and non ionic
4 5 6 surfactants
In flotation, sylvite is floated from halite using amine collectors
along with frothers (Miller et al., 1992). Besides cationic collectors,
KCl particles are also floated with 12C anionic collectors such as so-
dium dodecyl sulfate (SDS). Meanwhile, alcohols are usually used
to promote the froth in the potash flotation. Frothers adsorb at
the air/water interface and reduce the surface tension, thus stabi-
lizing the air bubble. MIBC is widely used in potash flotation. How-
ever, MIBC plays a different role in potash flotation compared to its
role in other flotation cases. The studies with MIBC for potash flo-
tation showed that MIBC in potash flotation behaves as a co-surfac-
tant which enhances dispersion of the collector in the brine and
spreads the collector on the KCl surface.
In this part of the study, we will show the surface tension of
aqueous solutions of SDS and MIBC in the absence and presence
of NaCl and KCl.
3.3. Surface tension in water
NaCl
KCl First, the dynamic surface tension of aqueous solutions of SDS in
the absence of the salts was measured. The results are presented in
80 100 Fig. 11 which shows the dynamic surface tension of SDS at differ-
ent concentrations. As seen from the figure, the surface tension de-
creases with an increase in time, and finally reaches the
equilibrium point. Furthermore, an equilibrium was reached much
faster at higher concentrations.
The initial and equilibrium surface tension values of aqueous
solutions of SDS as a function of concentration at 23 °C are summa-
rized in Table 5 and shown in Fig. 12 where the surface tension for
MIBC solutions is also presented. The Gibbs surface excesses of SDS
(DS + Na+) and MIBC, obtained from the Gibbs adsorption iso-
therm, are presented in Fig. 13 which shows that SDS is a stronger
surfactant.
3.4. Surface tension in brine
The surface tension of SDS in NaCl and KCl saturated solutions
was measured as a function of concentration to explain the flota-
tion of these alkali halide salts. Each point was obtained from the
dynamic surface tension measurements for a given SDS concentra-
tion (at equilibrium). These equilibrium surface tension data are
plotted in Fig. 14. An example of dynamic surface tension at
1  104 M SDS in both saturated solutions is shown in Fig. 15.
As seen from the figure, adsorption of SDS is time-dependent. In
the case of KCl, the surface tension reaches the equilibrium point
much faster than that of NaCl.
It is known from the literature that the surface activity of the
surfactant is increased by adding a salt since the counteracting
electrostatic free energy is being reduced. In addition to this, at
268 O. Ozdemir et al. / Minerals Engineering 22 (2009) 263–271

79 75

Equilibrium Surface Tension, mN/m

Equilibrium Surface Tension, mN/m

78

77
74
76

75

73
74

73
K
KII K NO33
KNO
72 72
0 1 2 3 4 5 6 7 8 0 1 2 3 4
Salt Concentration, M Salt Concentration, M

74 74

Equilibrium Surface Tension, mN/m

Equilibrium Surface Tension, mN/m

73 73

K2SO
S O44 NaF

72 72
0.0 .2
0.2 0.4 .6
0.6 0.
0.8 0.0 0.4 0.8 1.2

Salt Concentration, M Salt Concentration, M

Fig. 7. Surface tension of other salts up to their saturated concentrations at 23 °C.

80 Table 4
KKI
I (6.8 The Pitzer coefficients for KI, KNO3, NaF, and K2SO4 (Kim and Frederick, 1988)
(6.8M)
M)
KKNO
NO33 (3.5 Salt b0 b1 C /MX
(3.5 M)
M)
Surface Tension, mN/m

78
NaF KI 0.07253 0.27710 0.00381
NaF(1
(1M)
M) KKII
KNO3 0.08511 0.10518 0.00773
KK2S O44 (0.6
2SO (0.6 M)
M) NaF 0.03183 0.18697 0.00840
76 K2SO4 0.07548 0.44371 0

KNO33
KNO

74 NaF
NaF 1.0

KI
K2SO
K SO 4
2 4
72 0.8
Activity Coefficient

70 0.6 NaF
0 20 40 60 80 100
Level of Saturation, %
0.4
Fig. 8. Surface tension of inorganic salts versus saturation point.
KNO3 K
K JI
KI
K2SO 4 NaF
high salt concentrations (>0.1 M) it will be a sensible salting-out 0.2
2
KNO
K NO3
NO3
effect (Eriksson et al., 1989). K22S
SO
SOO444
As seen from Fig. 14, the presence of NaCl and KCl decrease the
surface tension of SDS solutions. The effect of KCl on the surface 0.0
0 2 4 6 8
tension is stronger compared to NaCl. The reason for this is that Salt Concentration, M
a K+ ion and DS ion make ion-pairs at the air/water interface more
effectively than a Na+ ion and DS ion (Karakashev et al., 2001). Fig. 9. Activity coefficients for KI, NaF, KNO3, and K2SO4 versus salt concentration.
 O. Ozdemir et al. / Minerals Engineering 22 (2009) 263–271 269

1×10-5 80

KI 75

Surface Tension, mN/m

70
1×10-6
Adsorption (-Γ), mol/m2

KNO3
65
NaF
60
1×10-7
K2SO4 55

50
1×10-8 KKI
KJI
45
KKNO
KNO3
NO3
NaF MIBC
NaF 40
SDS
KK2S
2SO
SO
O4
44

1×10-9 35
-6 -5 -4 -3 -2 -1
0 20 40 60 80 100 1×10
1.E -06 1×10
1.E -05 1×10
1.E -04 1×10
1.E -03 1×10
1.E -02 1×10
1.E -01
Level of Saturation, % Surfactant Concentration, M

Fig. 10. Adsorption isotherm of KI, KNO3, NaF, and K2SO4 versus level of salt Fig. 12. Equilibrium surface tension of SDS and MIBC solutions at room temper-
saturation in the aqueous solutions. (Saturation values of the salts were calculated ature (23 °C).
based on their actual concentrations.)

8×10-6
70
1 mM
65
6×10 -6
Surface Tension, mN/m

2 mM
2
Adsorption (+Γ), mol/m

60
3 mM
55
4 mM
4×10-6
50 5 mM
6 mM
45
7 mM

40
7.5 mM 2×10-6
8 mM
SDS
35
0 30 60 90 120 150 180 MIBC
Bubble Age, sec. 0
0 2×10-3 4×10-3 6×10-3 8×10-3 1×10-2
Fig. 11. Change in surface tension at different SDS concentrations as a function of Surfactant Concentration, M
time.
Fig. 13. Adsorption of SDS and MIBC versus surfactant concentration.

Table 5
Dynamic surface tension of SDS as a function of concentration at 23 °C 90
SDS in 5.2 M NaCl
SDS concentration Initial surface tension Equilibrium (3 min) surface in NaCl
(mM) (mN/m) tension (mN/m) SDS in 4 M KCl
80
SDS in Water
Surface Tension, mN/m

0 72.60 72.60
1 67.89 64.83
2 61.49 58.16 70
in KCl
3 57.05 55.31
4 51.56 50.55 in Water
5 49.83 48.77 60
6 46.49 45.67
7 42.54 41.90
7.5a 40.60 40.05 50 precipitation
8 40.03 39.91
a
Critical micelle concentration (CMC) for SDS.
40

Since potash flotation takes place in a saturated solution, the 30

1×10-7 1×10-6 1×10-5 1×10-4 1×10-3 1×10-2 1×10-1
behavior of MIBC in the presence of dissolved ions such as Na+
SDS Concentration, M
and K+ is very important in terms of the development of a flotation
strategy for potash ores. In this regard, the surface tension mea- Fig. 14. Equilibrium surface tension of SDS in water and in the saturated solutions
surements of MIBC were carried out in 5 M NaCl and 4 M KCl solu- of NaCl and KCl at room temperature (23 °C).
270 O. Ozdemir et al. / Minerals Engineering 22 (2009) 263–271

90 uration concentration. The results showed that NaCl increases the

surface tension more than KCl due to its bulk (higher activity coef-
ficient) and surface properties (negative adsorption larger in abso-
80
lute value as compared to KCl). The studies with other salts (KI,
KNO3, NaF, and K2SO4) showed that there is no obvious correlation
Surface Tension, mN/m

NaCl
70 between the surface tension of their solutions and their structure
making and breaking effect on their flotation response.
In addition, the surface tension of aqueous solutions of ionic
60
(SDS) and nonionic surfactants (MIBC) in the presence of salt ions
KCl
was investigated. Based on these results, the presence of NaCl and
50 KCl decrease surface tension of aqueous solutions of SDS which
makes SDS a significantly stronger surfactant in brine than in
water. In the case of MIBC, these salts show a similar effect. How-
40
NaCl ever, the effect of NaCl on MIBC is slightly stronger than KCl.
KCl
30 Acknowledgements
0 5 10 15 20 25 30
Bubble Age, min. The Australian Research Council is gratefully acknowledged for
4 financial support (AVN). In addition, this collaborative research
Fig. 15. Dynamic surface tension of SDS (1  10 M) in the saturated solutions of
NaCl and KCl. was supported by NSF under Grant No. INT 0227583 and DOE Basic
Sciences Grant No. DE-FG02-93E14315.

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