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Review
Abstract
Major recent advances: Recent advances that contribute to our understanding of specific-ion effects in bubble coalescence include new
theoretical and simulation efforts to determine the arrangement of ions at interfaces and a clearer recognition that specific-ion effects in
bubble coalescence are related to many other phenomena that exhibit ion specificity.
D 2004 Elsevier Ltd. All rights reserved.
Keywords: Bubble coalescence; Specific-ion effects; Electrolytes; Thin film stability; Hydrophobic; Hofmeister; Nanobubbles
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . .
2. The importance of ion specificity . . . . . . . . . . . . .
3. Bubble bubble coalescence in the presence of surfactant .
4. Films between two bubbles in the absence of surfactant .
5. Films formed between bubbles and solid surfaces . . . . .
6. Specific-ion effects and bubble stability . . . . . . . . . .
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . .
References. . . . . . . . . . . . . . . . . . . . . . . . . . . .
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178
178
179
180
180
182
183
183
183
1. Introduction
Perhaps, one of the most surprising and easily observed examples of a macroscopic effect of ion specificity
is the influence that dissolved electrolytes have on bubble
coalescence in aqueous solutions. Above a certain concentration, which is dependent on the particular salt
chosen (typically f 0.1 M), many common electrolytes
inhibit the coalescence of bubbles, whereas others have no
influence on bubble coalescence [1,2..]. This simple
observation is not understood. Here, we will attempt to
determine if the ions influence coalescence by action at
the interface or in bulk and investigate their possible
influences on film rupture.
V.S.J. Craig / Current Opinion in Colloid & Interface Science 9 (2004) 178184
179
180
V.S.J. Craig / Current Opinion in Colloid & Interface Science 9 (2004) 178184
Fig. 1. Table depicting the effect of a range of electrolytes on bubble coalescence. A tick indicates that the salt inhibits bubble coalescence. A cross indicates
that no bubble coalescence inhibition has been observed. The properties a and h have been assigned empirically and can be used with the combining rules to
predict the bubble coalescence behavior of an anion cation combination. aa or hh combinations correspond to bubble coalescence inhibition and ah or ha
combinations, no inhibition. No exceptions have been found.
and the rate of film thinning has not been arrested at the
point of rupture. Clearly, the description of film rupture by
capillary waves applied to films formed in the presence of
surfactants cannot be applied here. The lifetimes of these
films is shorter than the characteristic time required for the
Van der Waals forces to rupture the films via capillary waves
[11.]. A description of film rupture in these cases therefore
requires a modification to the capillary wave approach or an
alternative means of film rupture, such as nucleation of
holes.
The absence of surface-active material at the interface
results in an increase in surface mobility. This will lead to a
considerable increase in the drainage rate and film thinning
times comparable with the film lifetimes measured in clean
systems [14.,15.], although the mobility of the interfaces,
important in these calculations, is not truly known. Capillary
waves will also grow more rapidly if the attraction between
the gaseous phases is increased, such as in the presence of a
long-range hydrophobic attraction.
V.S.J. Craig / Current Opinion in Colloid & Interface Science 9 (2004) 178184
181
182
V.S.J. Craig / Current Opinion in Colloid & Interface Science 9 (2004) 178184
4C221
dl2
dM2
1
M1
dc
dc
2
kB TD
V.S.J. Craig / Current Opinion in Colloid & Interface Science 9 (2004) 178184
7. Conclusions
The bubble coalescence process in aqueous electrolyte
solutions remains unresolved. The mechanism of film rupture remains unclear, and the means by which ions influence
coalescence behavior remains elusive. Additionally, the
influence of both ions in combination, as described by the
combining rules, remains a major challenge. However,
recent efforts at understanding the specific-ion interfacial
behavior at high salt concentrations may provide important
clues. A recent suggestion by Marcelja (personal communication and in this issue) focuses on the behavior of ions at
the interface. The recent work by Jungwirth et al. [36.. 38.]
and Ninham et al. [3.,39.,40..], which indicates that some
ions are attracted to the interface despite the image charge
repulsion, has inspired his interpretation. Marcelja proposes
categorizing ions based on their preference for the surface or
the bulk. The beauty of this proposal is that it naturally
incorporates a combining law where the influence of an ion
is dependent upon the nature of the other ions present. Thus,
ions that are both located in the bulk or both at the interface
will have little effect, but ion combinations that are located
in the bulk and at the interface will prevent bubble coalescence. Whilst in its infancy, this is an exciting proposal that
can be tested using mixtures of electrolytes. This permits a
tentative model to be proposed. Ion combinations that are
separated at the interface result in a reduction in the mobility
of the interface. The reduced mobility ensures that thermal
capillary waves grow less quickly, leading to an increase in
the stability of the film. At a sufficient concentration of ions
in bulk, the surface mobility is suppressed to an extent that
bubble coalescence does not take place within the lifetime of
a collision. Another related challenge awaiting experimental
attention is an investigation of electrolyte effects on bubble
coalescence in nonaqueous solvents. I propose that specific-
183
Acknowledgements
Discussions with Barry Ninham, Stjepan Marcelja,
Hakan Wennerstrom and Pavel Jungwirth have been
illuminating. The assistance of Chiara Neto and Mika
Kohonen in the preparation of this manuscript is appreciated. I would like to acknowledge the support of the
Australian Research Council, through the provision of a
research fellowship.
184
V.S.J. Craig / Current Opinion in Colloid & Interface Science 9 (2004) 178184
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