Int. J. Miner. Process.

79 (2006) 18 – 26
www.elsevier.com/locate/ijminpro

Effect of the bubble size on the dynamic adsorption of frothers

and collectors in flotationB
Anh V. Nguyen *, Chi M. Phan, Geoffrey M. Evans
Discipline of Chemical Engineering, School of Engineering, The University of Newcastle, University Drive,
Callaghan, New South Wales 2308, Australia
Received 9 September 2005; received in revised form 22 November 2005; accepted 22 November 2005
Available online 28 December 2005

Abstract

This paper presents an analysis on the dynamic adsorption of frothers and collectors onto air bubbles in flotation. The analysis
was carried out using the theory on the surfactant transfer by diffusion and adsorption. The bubble size was considered when
solving the diffusion equation for the dynamic surface excess. The adsorption kinetics was modelled employing the Langmuir
adsorption isotherm and its extension with the inclusion of the lateral interaction of the adsorbed molecules (the Frumkin
adsorption isotherm). The numerical computation was applied to solve the governing equations. The dynamic adsorption of the
surfactants was measured in terms of the dynamic surface tension for sodium dodecylbenzene sulphonate (SDBS) and Dowfroth
250, using pendant bubble tensiometry. The results show that, for air bubbles with diameter of the order of 1 mm, the bubble size
effect on the dynamic surface tension is small and the solution of the diffusion equation for a planar gas–liquid surface can be used
to describe the dynamic adsorption onto the air bubbles. The experimental data obtained with SDBS were well described by the
Frumkin adsorption isotherm and the molecular diffusion. The model description for the experimental data obtained with Dowfroth
250 required the kinetic equations. The paper is relevant for the analysis of the role of the adsorbed surfactants in the bubble–
particle attachment.
D 2005 Elsevier B.V. All rights reserved.

Keywords: flotation frothers; flotation collectors; flotation bubbles; flotation reagents; froth flotation; dynamic adsorption; dynamic surface tension

1. Introduction between particles and bubbles in the collection pro-

Numerous inorganic and organic reagents (surface
active agents or surfactants) are employed in flotation
to improve the selectivity and recovery of valuable
minerals. The presence of these surfactants influences
the properties of both the air–water and solid–water
interfaces, and ultimately determines the interaction
B to its adsorption. Frother molecules concentrate at the
Presented at Centenary of Flotation Symposium, Brisbane, Aus-
tralia, 5–9 June 2005.
* Corresponding author. Fax: +61 2 49216920.
E-mail address: Anh.Nguyen@newcastle.edu.au (A.V. Nguyen).
0301-7516/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2005.11.007
cess. For this reason, it is important to understand
how the surfactants adsorb onto the interfaces.
When surfactants react with water, the water
dipoles combine readily with the polar groups and
hydrate them, but there is practically no reaction
with the non-polar hydrocarbon group, the tendency
being to force the latter into the air phase. Thus, the
heteropolar structure of the surfactant molecule leads
surface layer with the non-polar groups oriented to-
wards the air and the polar groups towards the water.
Molecules of ionising collectors strongly adsorb at the
 A.V. Nguyen et al. / Int. J. Miner. Process. 79 (2006) 18–26
water–mineral interface with the non-polar groups
oriented towards the water and polar groups towards
the mineral surface. Therefore, the major role of the
collectors is to make the mineral surface less water
wetted (hydrophobic). Alcohols and related com-
pounds such as the glycol ethers are most widely
used as frothers, largely because of their inability to
adsorb at mineral particles. Ionic collectors are in
many respects chemically similar to frothers and, in-
deed, many of the collectors, such as oleates, sul-
phates and sulphonates, are powerful frothers, being
in fact too powerful to be used as efficient frothers,
since the froths which they produce can be too stable
to allow efficient transport to further processing. The
adsorption of both the frothers and collectors at the
gas–liquid interface leads to:
! Decrease in the bubble size, resulting in the increase
in the specific area of the gas–liquid interface for the
particle attachment. Adsorbed frother molecules pre-
vent bubbles from coalescence.
! Decrease in the bubble rise velocity (decrease the
interface mobility, the bubble size) and the bubble
residence time.
! Increase in the stability of the froth phase for carry-
ing hydrophobic particles to the concentrate.
In addition, the adsorbed frother molecules at the
gas–liquid interface can also increase the efficiency of
the bubble–particle attachment as shown some time
ago by Leja and Schulman (1954) and Leja (1982).
Bubble–particle interactions, gas dispersion into fine
bubbles, and froth stability and drainage involve many
transient processes and, for these reasons, it is instru-
mental to characterize the dynamic adsorption behav-
iour of the frothers and collectors at the gas–liquid
interface. This paper focuses on the modelling of the
dynamic adsorption of the surfactants onto flotation air
bubbles of order of 1 mm in diameter. The dynamic
adsorption is modelled based on both molecular dif-
fusion and adsorption kinetics. The suitability of the
modelling is investigated by measuring the dynamic
surface tension as a function of time and comparing
the results with the model predictions.
2. Theory
The dynamic adsorption of surfactant onto the gas–
liquid interface is determined by two steps, involving
(1) the molecular diffusion of the surfactant molecules
from the bulk solution to the subsurface layer at the
interface and (2) the actual adsorption of the surfactant
19
molecules from the subsurface layer onto the interface.
The modelling will be developed based on these two
characteristic steps.
2.1. Surfactant molecular diffusion
The molecular diffusion of surfactants is well de-
scribed by the diffusion equation (Fick’s law)
Bc
¼ Dj2 c ð1Þ
Bt
where c is the surfactant concentration, D is the mo-
lecular diffusivity, t is the reference time and j2 is the
Laplace operator.
For a planar gas–liquid interface, the partial differ-
ential Eq. (1) reduces to a one-dimensional case, which
can be analytically solved. In terms of the dynamic
surface excess, C(t), of the adsorbed surfactant mole-
cules, the solution of the one-dimensional diffusion
equation can be used to obtain the celebrated Ward
and Tordai (1946) expression, which is widely used
in the modelling of the dynamic surface tension
(Chang and Franses, 1995; Eastoe and Dalton, 2000).
The celebrated Ward and Tordai equation gives
rffiffiffiffi Z t 
D pffi / ðt Þ
Cðt Þ ¼ 2cb t  pffiffiffiffiffiffiffiffiffiffi ds ð2Þ
p 0 ts
where c b is the surfactant concentration in the bulk
solution, /(t) is the surfactant concentration at the
subsurface layer and s is the integration variable.
The use of Eq. (2) for adsorption at planar surfaces
in the modelling of the dynamic adsorption of surfac-
tant molecules onto a flotation air bubble can be ques-
tioned since the gas–liquid interface is strongly curved.
To check the applicability of Eq. (2) for flotation sys-
tems, below we solve Eq. (1) for air bubbles and
establish the asymptotic conditions of the modelling
results.
2.1.1. Surfactant diffusion towards a spherical air bub-
ble surface
The bubble geometry and the boundary conditions
used to solve Eq. (1) are shown in Fig. 1. The spherical
coordinate system with the origin located at the bubble
centre can be conveniently employed to solve Eq. (1)
since the diffusion process is spherically symmetrical.
In the coordinate system, Eq. (1) reduces to
 
Bcðr; t Þ D B 2 Bcðr; t Þ
¼ 2 r ð3Þ
Bt r Br Br
20 A.V. Nguyen et al. / Int. J. Miner. Process. 79 (2006) 18–26

r=

8
c = cb
Applying the boundary conditions given by Eqs. (10)
and (11) yields
r=R
c = φ (t) a¼0 ð14Þ
r
  
c0 pffiffiffi
b ¼ R /˜ ðpÞ  exp R k : ð15Þ
p
The distribution of the surfactant concentration
Bubble around the bubble surface now can be determined by
taking the inverse Laplace transform of Eq. (12). How-
ever, the dynamic surface excess, C(t), of the surfactant
Fig. 1. Bubble geometry and domain for the physical modelling. can be better determined in the following way.

where r is the radial coordinate. The initial condition is 2.1.2. Surface excess of adsorbed surfactant molecules
described by at the bubble surface
The dynamic surface excess, C(t), can be determined
cðr; 0Þ ¼ cb ð4Þ from the mass balance at the interface, which is des-
The boundary conditions are described by cribed by
 
cðl; t Þ ¼ cb ð5Þ dC Bc
¼D ð16Þ
dt Br r¼R
cð R; t Þ ¼ /ðt Þ ð6Þ
Since C(0) = 0, taking the Laplace transform of Eq. (16)
where R is the bubble radius. The partial differential yields
Eq. (3) can be analytically solved employing the  
dc̃c ðr; pÞ
Laplace transform given by C ð pÞ ¼ D
pC̃ ð17Þ
Z l dr r¼R
cðr; t Þ ¼ c̃c ðr; pÞexpð  pt Þdp ð7Þ Inserting Eq. (12) into Eq. (17), one obtains
0
" sffiffiffiffi! sffiffiffiffiffi!#
Z l D D ˜ D D
c̃c ðr; pÞ ¼ cðr; t Þexpð  pt Þdt ð8Þ C ð pÞ ¼ 
C̃ þ / ð pÞ þ cb þ
0
Rp p Rp2 p3

Applying the Laplace transform to Eq. (3) gives ð18Þ

 2 
d c̃c 2 dc̃c Taking the inverse Laplace transform of Eq. (18) gives
D þ ¼ pc̃c ðr; pÞ  cb ð9Þ rffiffiffiffi
dr2 r dr Z t 
D pffi /ðsÞ
The Laplace transforms of the boundary conditions Cðt Þ ¼ 2cb t  pffiffiffiffiffiffiffiffiffiffi ds
p 0 ts
given by Eqs. (5) and (6) give  Z t 
Z l D
þ tcb  /ðsÞds : ð19Þ
c̃c ðl; pÞ ¼ ept cðl; t Þdt ¼ cb =p ð10Þ R 0
0
Z l
The first term on the right-hand side of Eq. (19) is
c̃c ð R; pÞ ¼ ept /ðt Þdtu/˜ ðpÞ ð11Þ the same as that of the celebrated Ward and Tordai
0 equation, Eq. (2). The second term of Eq. (19) is a
The general solution of Eq. (9) is as follows function of the bubble radius and describes the correc-
 pffiffiffi  pffiffiffi tion to the Ward and Tordai equation due to the curva-
aexp r k þ bexp  r k cb ture effect of the spherical bubble surface.
c̃c ðr; pÞ ¼ þ ð12Þ
r p
2.2. Adsorption of surfactant molecules from the sub-
where a and b are the integration constants and k is
surface layer
defined by
p The adsorption of surfactant molecules from the
k¼ ð13Þ
D subsurface layer is usually described by the Langmuir
 A.V. Nguyen et al. / Int. J. Miner. Process. 79 (2006) 18–26 21

adsorption isotherm (Adamson and Gast, 1997), i.e. with the subsurface concentration. Therefore, the dy-
namic adsorption is controlled by the surfactant diffu-
Cðt Þ
/ðt ÞK ¼ ð20Þ sion from the bulk solution to the interface and is
C m  C ðt Þ often referred to as the diffusion-controlled dynamic
where K is the (equilibrium) adsorption constant and adsorption.
C m is the maximum of C. The dynamic surface excess In practice, the adsorption from the subsurface layer
can be described in terms of the experimentally mea- need not be instantaneous and may be controlled by the
sured dynamic surface tension by the Gibbs adsorption adsorption kinetics itself. For this case, the local equi-
equation (Adamson and Gast, 1997), which can be librium is no longer applied and the dynamic adsorption
described by is known as kinetics-controlled adsorption. The gener-
alized adsorption kinetics gives (Miller and Kretzsch-
c dr mar, 1980; Borwankar and Wasan, 1983)
C¼  ð21Þ
nRg T dc

dCðt Þ Cðt Þ
where r is the surface tension, R g is the universal gas ¼ ka /ðt Þ 1 
dt Cm
constant, n = 1 for non-ionic surfactants and n = 2 for

ionic surfactants, and T is the absolute temperature. Cðt Þ Cðt Þ

 kd exp  2b ð25Þ
Applying Eq. (21), with c being the subsurface con- Cm Cm
centration, /(t), and inserting Eq. (20) into Eq. (21) where k a and k d are the adsorption and desorption rate
yields constants, respectively. Note that the equilibrium ad-

sorption constant is equal to K = k a/k d and, if k aYl
C ðt Þ
r0  rðt Þ ¼  nRg T Cm ln 1  ð22Þ (adsorption is instantaneous), the kinetics-controlled
Cm
model reduces to the diffusion-controlled model.
where r 0 is the surface tension of the clean surface
(pure solvent). Eq. (22) can be used, together with 2.3. Numerical computation methodology
Eqs. (20) and (19), to validate the dynamic adsorption
theory. Numerical computation is required to solve the gov-
There exist a number of extensions to the Langmuir erning Eqs. (19), (20), (22)–(25) for the dynamic ad-
adsorption theory. Firstly, the interaction among the sorption process. Firstly, the time domain (0,t) can be
adsorbed molecules can be included, and leads to the partitioned into i small intervals by Dt j = t j  t j1, where
Frumkin adsorption isotherm (Lyklema, 1991), which j = 1, 2, 3. . .i. Eq. (19) is then discretised by applying
is described by the trapezoidal rule approximation to the integral, lead-
  ing to
Cðt Þ Cðt Þ
/ðt ÞK ¼ exp  2b ð23Þ
C m  C ðt Þ Cm gðti Þ ¼ A  /ðti ÞB ð26Þ
where b is a parameter characterizing the lateral inter- where
action among adsorbed surfactant molecules. The gðti Þ ¼ Cðti Þ=Cm ð27Þ
corresponding surface tension isotherm determined pffiffiffiffiffiffiffiffiffi (
from the Gibbs adsorption equation is then D=p pffiffiffi Xi1
   

A¼ 2cb ti þ / tj þ / tj1
Cm
C ðt Þ j¼1
r0  rðt Þ ¼  Rg T Cm ln 1  )
Cm pffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffi

2  ti  tj  ti  tj1  /ðti1 Þ Dti
Cðt Þ
 bRg T Cm : ð24Þ (
Cm D X
i1
   
þ 2ti cb  / tj þ / tj1
2Cm R
Eqs. (24), (23) and (19) can also be used to validate j¼1
)
the dynamic adsorption theory, in relation to non-
ideal behaviour and lateral interaction of the adsorbed  Dtj  /ðti1 ÞDti ð28Þ
molecules.
Both Eqs. (20) and (23) imply that the adsorption pffiffiffiffiffiffiffiffiffi
from the subsurface layer is considered instantaneous D=p pffiffiffiffiffiffi D
B¼ Dti þ Dti ð29Þ
and the surface concentration is always in equilibrium Cm 2Cm R
22 A.V. Nguyen et al. / Int. J. Miner. Process. 79 (2006) 18–26
For diffusion-controlled dynamic adsorption, Eq.
(26) can be used in conjunction with either Eq. (20)
or Eq. (23) to numerically solve for the transient sub-
surface concentration, /(t), and the dynamic adsorption
excess, C(t). The initial conditions are /(0) = 0 and
C(0) = 0.
For kinetics-controlled dynamic adsorption, Eq. (25)
can be further discretised by applying the implicit
scheme to give
gðti Þ  g ðti1 Þ
¼ ka /ðti Þ½1  g ðti Þ
Dti
 kd g ðti Þexp½  2bg ðti Þ:
Eqs. (30) and (26) can be simultaneously solved for
the dynamic adsorption excess, C(t), by applying the
initial conditions described previously.
3. Experimental
3.1. Materials
The surfactants used to study the dynamic adsorp-
tion included sodium dodecylbenzene sulphate (SDBS)
(Aldrich, Germany), which is used as an anionic col-
lector, and Dowfroth 250 (Dow Chemical, USA),
which is a mixture of polyglycols used as a flotation
frother. The surfactants were used without any further
purification.
Camera
Fig. 2. Experimental set-up for the pendant bubble tensiometry measurements.
A Millipore Milli-Q water purification system was
used to rinse all components and to make all solutions.
The Millipore system provides water with a surface
tension of about 72 mN/m. All glassware and compo-
nents used in the experiments were soaked for several
hours in 6% (by volume) solutions of Deconex 15E
(Borer, Switzerland), rinsed in the Milli-Q water and
dried in a cabinet to protect them from dust. The
needles were also cleaned using a dichromate mixture
and then sonicated repeatedly in the Milli-Q water. All
surfactant solutions were freshly prepared and used
immediately.
ð30Þ
3.2. Apparatus
The dynamic adsorption was experimentally inves-
tigated by measuring the dynamic surface tension ver-
sus concentration using the pendant bubble method
(Adamson and Gast, 1997) with a fully computer-con-
trolled apparatus OCA 20 from DataPhysics (Ger-
many). The experimental set-up for the pendant
bubble apparatus is shown in Fig. 2.
A Perspex cell was filled with the surfactant solution
and placed in the path of a collimated light beam. A
bubble was formed on an inverted needle immersed in
the solution. The light beam cast a bubble shape onto a
CCD camera. The image was recorded and stored in a
computer for further image analysis. The bubble was
rapidly formed using a gas-tight microsyringe, which
 A.V. Nguyen et al. / Int. J. Miner. Process. 79 (2006) 18–26 23

75

65

Surface tension (mN/m)

Planar interface

55
R = 100 μm
R = 1 μm R = 10 μm
45

35

25
0.1 1 10 100 1000
Time (ms)

Fig. 3. Theoretical predictions for the influence of the bubble size on the dynamic surface tension (C m = 5  10 6 mol/m2, c b = 5  10 4 mol/L,
K = 7.0 m3/mol, b = 0 and D = 5  10 10 m2/s).

was motorized and fully controlled by a computer.
Typically, a droplet with volume of approximately
11 AL was formed within a time less than 0.5 s. The
camera was set to strobe, thereby obtaining the bubble
shape as a function of time. Images of the bubbles were
taken at the frequency of 50 Hz. The bubble shapes
were digitised and analysed off-line. The digitised bub-
ble profiles were fitted numerically with the Young–
Laplace equation to obtain the surface tension value.
The surface tension corresponding to each bubble
image was found. The system was calibrated using
the outer diameter of the inverted needle. Checks on
the calibration were performed at regular intervals by
measuring the surface tension of purified Milli-Q water.
The time difference between the first recorded image
and the starting time (t = 0) of the bubble (theoretical
moment of the interface formation) was determined by
fitting the model parameters to the data. The difference
was then used to obtain the btime-correctedQ surface
tension values.
4. Results and discussion
4.1. Effect of the bubble size
Typical results for the dependence of dynamic sur-
face tension on the bubble size are shown in Fig. 3. The
results were obtained using Eqs. (23), (24) and (26),

75
Surface tension (mN/m)

Experimental data
65
Diffusion & planar interface
Diffusion & spherical interface
55
Diffusion-kinetics & spherical interface

45

35
0 10 20 30 40
Time (s)
Fig. 4. Experimental (points) and predicted (lines) dynamic surface tension for a 5  10 4 mol/L SDBS solution. The bubble radius used in the
experiment and modelling was R = 1.24 mm. The parameters obtained by the best fit are summarised in Table 1.
24 A.V. Nguyen et al. / Int. J. Miner. Process. 79 (2006) 18–26
Table 1
Adsorption model parameters obtained by the best fit for 5  10 4 mol/L SDBS solution
Model K (m3/mol)
Diffusion-controlled/planar interface 7.66
Diffusion-controlled/spherical interface 7.95
Kinetics-controlled/spherical interface 8.81
i.e., diffusion-controlled dynamic adsorption was con-
sidered. The model parameters as given in the text
capture to Fig. 3 are within the range for typical hy-
drocarbon-based surfactants (Chang and Franses,
1995). The numerical value of 5  10 6 mol/m2 for
C m gives the corresponding molecular cross-sectional
area of ~ 33 Å2 at the maximum packing for adsorbed
surfactants. Similar results were obtained with the ki-
netics-controlled dynamic adsorption model using the
same values for model parameters.
Fig. 3 shows clearly that the bubble size significant-
ly influences the dynamic surface tension and the dy-
namic adsorption onto micrometer size bubbles. For
typical flotation operations, where air bubbles have
diameter of the order of 1 mm, the bubble size effect
is not significant. The agreement between the our
model with the inclusion of the bubble radius in Eq.
(19) and the Ward and Tordai expression by Eq. (2) for
a planar surface is within the width of the line shown in
Fig. 3.
4.2. Comparison with experimental data for the dynamic
surface tension
A previous investigation using the pendant drop
method (Phan et al., 2004) showed that the dynamic
adsorption of SDBS onto the pendant drop interface is
75
70
Surface Tension (mN/m)
65
60
55
50
45
0 100
Fig. 5. Experimental (points) and predicted (lines, kinetics-controlled model) dynamic surface tension for a 100 ppm (part-per-million concentra-
tion) Dowfroth 250 solution. The bubble radius used in the experiment and modelling was R = 1.36 mm.
C m (mol/m2) b D (m2/s) R (mm) k d (1/s)
6
4.76  10 0.057 2.37  10 11 – –
4.83  10 6 0.057 1.97  10 11 1.24 –
4.07  10 6 0.057 2.00  10 10 1.24 1.24
governed by the molecular diffusion and SDBS can be
considered as a diffusive surfactant. In this study, the
adsorption dynamics of SDBS at the interface of an air
bubble is investigated using three models: (1) the
diffusion-controlled model for a planar interface, (2)
the diffusion-controlled model for a spherical interface
and (3) the kinetics-controlled (the kinetics-diffusion
mixed) model for a spherical interface. The best fit of
the three model predictions to the experimental results
was carried out in Excel using the built-in function
Solver and the user-defined macro written in the VBA
(Visual Basic for Application) programming language.
It can be seen from Fig. 4 that all of the three model
predictions match the experimental data. For all the
three models, the best-fit values for C m (given in
Table 1) for SDBS are within the normal range for
surfactant which is from 1 to 10  10 6 mol/m2
(Chang and Franses, 1995). However, both the diffu-
sion-controlled models for planar and spherical surfaces
predict smaller diffusion coefficients. The difference in
the surface tension between the two models is small,
which confirms the theoretical results presented in Fig.
3. The diffusion-kinetic-mixed model predicts the ef-
fective diffusion coefficient comparable with the calcu-
lated value for SDBS (Phan et al., 2004). The close
agreement of the model prediction for diffusion coeffi-
cient with the reported results indicates that an adsorp-
Experiment
Planar interface
Spherical interface
200 300 400
Time (s)
 A.V. Nguyen et al. / Int. J. Miner. Process. 79 (2006) 18–26
Table 2
Adsorption model parameters obtained by the best fit for 100 ppm Dowfroth 250 solution
Model K (m3/mol)
Kinetics-controlled/planar interface 16.713
Kinetics-controlled/spherical interface 13.086
tion barrier, even though very weak, still influences the
dynamic adsorption of SDBS. Therefore, SDBS is not a
perfectly diffusive surfactant. It requires the diffusion-
kinetic-mixed model for predicting the dynamic surface
tension.
The effect of the bubble radius on the diffusion-
kinetic-mixed mechanism for dynamic adsorption was
also investigated by matching the models with the
dynamic surface tension measured for Dowfroth 250.
The results are shown in Fig. 5. Dowfroth 250 is a
mixture of polyglycols, which have the slow adsorp-
tion characteristics of non-diffusive surfactants. The
diffusion-kinetic-mixed model was applied to the
Dowfroth 250 experimental data in conjunction with
the diffusion equations for the spherical and planar
interfaces. The best-fit predictions are shown in Table
2. The difference in the two best-fit values for the
effective diffusion coefficients indicates a small effect
of the bubble size, which is within the experimental
error. The dynamic adsorption of Dowfroth 250 onto
air bubbles can be described using the Ward and
Tordai solution for surfactant diffusion toward a pla-
nar gas–liquid interface.
4.3. Relevance to the flotation theory
Both the theoretical analysis and the experimental
data presented in this paper show that the dynamic
surface tension and the dynamic adsorption onto
micrometer size bubbles are not significantly influ-
enced by the bubble size. Therefore, the dynamic
adsorption of surfactants in flotation can be effective-
ly analysed using the theories applied to the planar
gas–liquid interface. In particular, the last term on the
right hand side of Eq. (19) can be safely neglected,
giving the simpler expression for predicting the dynam-
ic surface excess, C(t), by Eq. (2) of the Ward and
Tordai theory. At short adsorption time, the dynamic
surface excess can be determined pffiffiffiffiffiffiffiffiffiffiby the Ward and
Tordai theory by Cðt Þ ¼ 2cb Dt=p, which does not
require the numerical computation. The simplified pre-
diction of the dynamic surface excess will allow a
number of important factors affecting the particle col-
lection by air bubbles to be determined. The important
factors include the mobility of the gas–liquid interface
of rising air bubbles, the elasticity of the bubble surface
25
C m (mol/m2) b D (m2/s) R (mm) k d (1/s)
6
3.97  10 0.61 2.25  10 12 – 0.106
4.14  10 6 0.34 6.55  10 11 1.36 0.110
and the surface tension gradient. For example, the
interface mobility is expected to change the liquid
flow at the bubble surface and to influence the capture
efficiency but it still remains to be quantified (Nguyen,
1999). The analysis given in this paper will provide
important inputs for further developments of the flota-
tion theory, specifically the role of the adsorbed surfac-
tants at the gas–liquid interface in the particle collection
phenomena.
5. Conclusions
The dynamic adsorption of collectors and frothers
onto the air bubble surface was theoretically analysed
using the molecular diffusion and the surfactant adsorp-
tion processes. The governing equations were solved for
the dynamic surface excess of surfactants, which was
described in terms of the experimentally measured dy-
namic surface tension. The adsorption kinetics was
modelled using the Langmuir and Frumkin adsorption
isotherms. The dynamic adsorption of the surfactants
was measured for the dynamic surface tension of
sodium dodecylbenzene sulphonate and Dowfroth
250 frother using pendant bubble tensiometry. The
measurements of the dynamic surface tension were
carried out using the pendant bubble method. The
theoretical analysis using the bubble radius, R, be-
tween 1 Am and 10 mm, and the comparison with
the experimental data obtained using R = 1.24 and 1.36
mm showed that the bubble size effect on the dynamic
adsorption is negligibly small for air bubbles with the
diameter of the order of 1 mm, which is the typical
range of the bubble size encountered in flotation.
Therefore, the dynamic adsorption onto the bubble
surface in flotation can be simply described using
the Ward and Tordai equation derived from the diffu-
sion equation for a planar interface. Furthermore, the
experimental data for SDBS were well described by
the diffusion-controlled model with the Frumkin ad-
sorption isotherm. However, the experimental data for
the dynamic surface tension of Dowfroth 250 were
described by the kinetics-controlled model and the
molecular diffusion. The presented results are signifi-
cant for further analysis of the effect of the adsorbed
surfactants at the bubble surface on the bubble–parti-
cle attachment phenomena in flotation.
26 A.V. Nguyen et al. / Int. J. Miner. Process. 79 (2006) 18–26
Acknowledgement
The authors acknowledge the Australia Research
Council for financial support.
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