In the Laboratory

Playing with Liquid Foams: Learning Physical Chemistry

Hernn Ritacco Departamento de Qumica-Fsica I, Facultad de Ciencias Qumicas, Universidad Complutense de Madrid, 28040 Madrid, Spain; ritacco@quim.ucm.es

I savor the flavor of cappuccino coffee in the morning, and after a hard work day, I enjoy drinking a beer with friends and talking to them while looking the popping bubbles at the top of my glass. Foams and froths (1) are ubiquitous in nature and everyday life. Cappuccino and beer as well as meringue, Champagne, and chocolate mousse (mousse is the French word for foam) are a few examples of edible foams (2). Liquid foams are also present in fire-fighting systems, separation techniques (3), shampooing, detergency, and in many other areas of science and technology. In general, we need to increase the foam stability and lifetime, such as in shaving foams. However, in other cases (detergents for front-loading washing machines), we need to avoid foams by controlling and reducing their stability. Successful control of foams requires a good understanding on the physics and physical chemistry of these systems. Foams are an incredibly rich and well-suited subject to explore the physics and chemistry of surfaces (4). The experiment described here, jointly with previous articles on surface tension (5) and wetting dynamics (6), completes a series of laboratory experiments on interfacial phenomena for advanced undergraduate students. These experiments and others (79) can expose the students to surface phenomena in an original fashion that stimulates their interest. Foams Dynamics Liquid foams are out-of-equilibrium systems. Foams have no future; they disappear as the result of three simultaneous processes: drainage, coarsening, and collapse. Drainage is the process that dries the foam. The liquid flows out of the foam by gravity. The liquid content in foams is represented by the liquid fraction, l, defined as,
l

in the boundary conditions, from slip to non-slip, as the surface viscosity is increased (10). Collapse is the rupture of films or bubbles and it is the most difficult area in the study of foams. It is related to many factors that affect the stability of films individually (surface tension, surface elasticity, disjoining pressure) and collectively (cooperatively in the rupture of several bubbles or avalanches of rupturing bubbles and liquid films) (11). The pressure differences between small and large bubbles of disordered foams drive the diffusion of gas through the thin films that separate the bubbles: small bubbles disappear and large bubbles grow. This process is called coarsening. In this article I will focus on the coarsening process because it is the most suited phenomena in the dynamics of foams to be studied at an undergraduate level. Moreover it will also allow us to introduce concepts on physics and physical chemistry. In particular it permits us to illustrate the YoungLaplace law. The starting point of our analysis is the one-dimensional Ficks law, c J D (2) x where J is the diffusion flux, the amount of transferred substance per unit area and time; D is the diffusion coefficient; c concentration; and x distance of diffusion. Here we are dealing with the diffusion of gas molecules trough liquid films separating bubbles. When a gas is in contact with a liquid surface, the quantity of gas dissolved into the liquid is proportional to the partial pressure, Pi, in bubble i of the gas. This simple relation is given by the Henrys law, (3) where H is proportionality constant and ci is the gas concentration in the liquid (Figure 1). Different gases have different solubilities and the proportionality constant in Henrys law must take this into account. If we combine eqs 2 and 3 and express the quantity of gas transferred in terms of the bubble volume ci HPi

V liquid Vfoam

(1)

where V is the volume. Drainage involves liquid flow through the channels between the bubbles (called plateau borders, PBs). The cross section of these channels varies with time and liquid fraction making the resolution of this fluid mechanics problem difficult. Even more, surfactants are needed to stabilize foams, introducing another degree of complexity at the molecular level. Surface viscoelasticity, which depends on the specific surfactant molecule, determines the boundary conditions at the liquid walls of the PBs channels and the form of the velocity profile of the liquid flow (for more details see the online material). To observe the effects of different surfactants on the liquid flow throughout a single PB, surfactant solutions are injected between two narrowly spaced glass plates forming a liquid bridge between them. This liquid bridge has a geometry similar to a PB; therefore, following the changes produced in its geometry as the liquid flow rate is changed allows us to observe the switch

bubble 2
P2 c2 x c1 P1

liquid film between bubbles

bubble 1
Figure 1. A schematic defining ci, Pi, and x for two adjacent bubbles.

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In the Laboratory

change we obtain, (4) where is the time rate of the gas volume transfer; Af is the liquid film area; is the permeability constant, which depends on H and x (the liquid film thickness); and P is the pressure difference between bubbles. We can now use the YoungLaplace law to put the pressure difference in terms of surface tension and the bubble radius (assuming spherical bubbles), 2 P (5) r where r is the bubble radius and the surface tension. From eqs 4 and 5 and noting that r 3/ t and Af r 2; the bubble size scales as t1/2 (t = time) and as ( )1/2. All the previous analysis supposes to be constant and because depends on the film thickness x, we have assumed that there is no drainage. Finally we can write the bubble size dependence with time, r t t0
1 2

Af P

tially a series of straight-line paths interrupted by bubble film surfaces where reflection takes place with some mean free path, l*. The mean free path can be associated to the mean bubble size (diameter). The intensity of light transmitted, T, should scale as (Figure 2), 1 l* T t2 (7) L where L is the thickness of the sample. From the changes of the intensity of the transmitted light through a foam we could extract the temporal evolution of the characteristic length l*, which will be the mean cell (or bubble) size. The light source is an inexpensive laser pointer that has been modified to connect to a continuous electric source (avoiding the use of batteries). The laser beam is sent to a transparent glass container filled with the foam sample (see the online material for details about the making the foam). The use of more powerful lasers is not recommended if the experiment is performed by students. If the experiment is performed as a demonstration, the quality of the results will be increased by using more powerful lasers and wider foam containers. Any transparent container that accommodates enough bubbles in the light path can be used for the experiment. As foaming solution, the students used a commercial dishwasher but foams can be formulated using other surfactants. The transmitted light is measured with a photo diode connected to a computer (or to a multimeter). Another possibility is to use a CCD camera to record the light intensity spot as a function of time, but it is more expensive if you want one setup per student. To avoid spurious reflection of light from the environment and laser beam, the device is enclosed inside a black box (Figure 2). Hazards

(6)

where t0 is a constant. The proportionality constant in this relation depends on the permeability constant of the liquid films () and the surface tension (). A test of the validity of eq 6, and thus of the simple coarsening mechanism, is the main objective of the experiment described below. Experiment Useful information can be extracted from multiple light scattering (12). The passage of light through the foam is essen-

black box

Lasers used in this work are low power; however, they can be dangerous. Avoid direct exposure of eyes to the laser beam. Some surfactants are irritating to skin.

laser foam

photodiode
12.5 12.0 11.5

Drainage
tdrainage

Coarsening

T 2 / mV2

11.0 10.5 10.0 9.5 drying front

foam sample

position of the laser beam

light source

transmitted light T2
l* L
2

9.0

Time
8.5 0 1000 2000 3000 4000 5000 6000

Time / s
L
Figure 2. Schematic representation of the experiment. Figure 3. Typical student results on coarsening. Insert shows the vertical profile of liquid over time in the sample: darker color shows greater liquid.

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Journal of Chemical Education Vol. 85 No. 12 December 2008 www.JCE.DivCHED.org Division of Chemical Education

In the Laboratory

Typical Results From eqs 6 and 7, transmitted light evolves with time as T2 k t t0 (8)

using foams. In particular I present an experiment on foam coarsening that demonstrates the YoungLaplace law in an novel manner and using elements that are stimulating for the students: foams and lasers. Acknowledgments I thank Dominique Langevin and Arnaud Saint-Jalmes. Most of the things I know about foams I learned from them. This work began in Paris and it was finished in Madrid in the GSC group. I thank Ramon Gonzalez Rubio, Francisco Ortega, and Francisco Monroy-Muoz of the Grupo de Sistemas Complejos for their support. This work was partially supported by MEC under a Juan de la Cierva contract. Literature Cited
1. Weaire, D.; Hutzler, S. The Physics of Foams; Clarendon Press: Oxford, 1999. 2. Bravo-Daz, C.; Gonzalez-Romero, E. J. Chem. Educ. 1997, 74, 11331135. 3. Skomoroski, R. M. J. Chem. Educ. 1963, 40, 470471. 4. Adamson, A. W. Physical Chemistry of Surfaces, 5th ed.; WileyInterscience Publishers: New York, 1990. 5. Castro, M. J. L.; Ritacco, H.; Kovensky, J.; Fernndez-Cirelli, A. J. Chem. Educ. 2001, 78, 347348. 6. Ritacco, H. J. Chem. Educ. 2006, 83, 114116. 7. Spanoghe, P.; Cocquyt, J.; Van der Meeren, P. J. Chem. Educ. 2001, 78, 338342. 8. Munguia, T.; Smith, C. A. J. Chem. Educ. 2001, 78, 343344. 9. Gugliotti, M.; Baptista, M. S.; Politi, M. J. J. Chem. Educ. 2004, 81, 824826. 10. Drenckhan, W.; Ritacco, H.; Saint-Jalmes, A.; Saugey, A.; McGuinness, P.; Van der Net, A.; Langevin, D.; Weaire, D. Phys. Fluids 2007, 19, 102101. 11. Ritacco, H.; Kiefer, F.; Langevin, D. Phys. Rev. Lett. 2007, 98, 244501. 12. Vera, M. U.; Saint-Jalmes, A.; Durian, D. J. Applied Optics 2001, 40 (24), 42104214.

Figure 3 shows a typical result. We see four regions. In the first region, up to 250 seconds, the transmission intensity does not change with time. At this step, the liquid is draining. However, at the position of the laser beam, which is close to the center of the foam container, the liquid content and the film thickness are constant because the foam receives liquid from the top (see inset in Figure 3). At such a short time the coarsening rate is negligible. In the second region, from about 250 to 1000 seconds, the liquid front has passed the laser beam and the zone is drying, the liquid film thickness is reducing continuously and the intensity of transmitted light shows changes in the liquid content (may be coupling with some coarsening). In the third region, from 1000 to 5000 seconds, T 2 responds linearly with time; the rate of draining is almost zero and the liquid film thickness is constant. Here we have only coarsening and eq 5 applies. In the fourth region, above 5000 seconds, the transmission intensity again becomes constant. Here, the bubble size is of the order of the diameter of the foam container (only alike liquid films remain). By changing the foaming systems students can study the influence of different chemicals. For example, by using surfactant solutions with different quantities of glycerol, they can follow the evolution of the draining and coarsening time as a function of the bulk viscosity of the foaming solution. The coarsening rate can be modified by changing the gas contained in the bubbles. For example by using carbon dioxide in place of air, students can accelerate the coarsening rate (i.e., students can use soda water in place of water to prepare the foaming solution). The aqueous film is more permeable to carbon dioxide than to air. Since its solubility in water is larger than those observed for air, the proportionality constant in Henrys law, eq 3, is larger for carbon dioxide than for air. Such an effect can be measured by the students and the different liquidgas systems can be compared. If students prepare their foams using nitrogen, the effect will be the opposite. Nitrogen solubility is about 50 times less than carbon dioxide, its permeability is consequently reduced, and the coarsening rate slows down. This effect is the reason for the long life time of froth in Guinness beer, the famous Irish beer that contains nitrogen. Summary Foams and froths are fun and beautiful and they can be a useful tool for teaching chemistry, physics, and physical chemistry. In this simple experiment many concepts are involved; among these are surface tension, film permeability, liquid flow through mobile and changing channels (plateau borders), and out-of-equilibrium systems. One or all of them can be developed

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