Chemical Generation and Visualization
of hydrodynamic Instability
An Extremely Simple Demonstration of Self-organization
Peter G. Bowers and Leonard J. Soltzberg
Simmons College, Boston, MA 021 15
BBnard convection is perhaps the most frequently cited
example of self-organization in a far-from-equilibrium sys-
tem and takes the form of parallel convectionrolls or hexag-
onal convection cells in ashallow liquid layer whichis heated
from below (I). If the laver is sandwiched between two con-
fining plates, the fluid motion, called Rayleigh-BBnard con-
vection is due to the coupling of buoyancy, heat diffusion,
and viscous forces, while if the upper liquid surface is free
(BBnard-Maranaoni convection). surface tension chanaes
(rather than density changes) also become important.'~n
each case, the onset of pattern formation occurs at a sharply
defined temperature difference between the upper and low-
er liquid surfaces. The value of this critical temperature
difference deoends on the deoth of the liouid laver and the
geometry of the confining vessel as well as upon those prop-
erties of the liquid mentioned above. Methods used to visu-
alize and study such convection phenomena have included
suspending fine metal particles in the liquid (often a silicone
oil) and employing special point source illumination. Devel-
opment of these patterns is slow, usuallv on the time scale of
hours.
Buoyancy instabilities can also be produced and visual-
ized in a thin liquid layer by initiating a chemical reaction a t
the upper surface. This was first observed relatively recently
bv Mockel (2).who reoorted the aooearance of concentra-
tfon patterns Ghile irradiating aqueous KIfstarch solutions.
Visualization in this case was due to the formation of the
colored starch-iodine complex formed by air photooxidation
of iodide ion. Kagan and Avnir and their co-workers (3-5)
have subsequently shown that patterns can be produced
from a wide variety of chemical processes that can be carried
out at a surface, either photochemically or by surface ab-
sorption of a reactant, and that give a colored product. The
chemically visualized structures are transient and usually
have lifetimes on the scale of minutes. While it is generally
aereed that what is beine observed is indeed convective
i o t i o n , there has been le& consensus on whether such mo-
tion is generated by the chemical reaction itself (which could
cause, for example, changes in density, diffusion rates, or
surface tension), or whether the color changes simply visual-
ize pre-existing convective motions due to evaporative cool-
inp. I t now appears that in individual systems either of these
factors may dominate (6).
Perhaps the simplest of all the chemical convective sys-
tems, the one we describe here and that appears on the cover
of this issue of the Journal, is the pattern formation seen
when an acidic vaoor comes into contact with the surface of
an aqueous solution containing indicator. The general mcth-
od for ~roducinethe effect. which mas he varied within wide
limits,~consistsuofexposing the surface of an aqueous and
'The spontaneous pattern formation also makes a remarkable
overhead projector demonstration. For best results, the projector
should be allowed to heat up somewhat.
210 Jouinal of Chemical Education
slightly hasic layer (10-3-10-4 M in OH- and 5-8 mm deep)
to HCl vapor. The solution'is contained in a deep Petri dish
and contains sufficient indicator (almost any indicator) to
make even the shallow layer significantly colored. The HCI
vapor originates from a filter paper disc soaked in 6 M HCI,
which is of sufficient size to cover the vessel; the paper is
allowed to rest on the top edge of the dish until pattern
formation begins, typically within 20 t o 40 s depending on
the svstem beina emdoved.
specific condrtion; fo; the pattern development shown in
the cover photographs are given in the Appendix below. T o
facilirate photography, our solution was placed on a light
table', and there is little doubt that it developed a thermal
gradient from the light source, perhaps enhanced by surface
evaporation. The thermal effect acts in concert with the
density gradient produced by HCI absorption. In any case, it
is evident that a thin surface layer develops that has a higher
densitv and substantiallv hiaher aciditv than the liouid be-
neath;such a ~ o n f i ~ u r a t i bkni ,t h the denser liquid Ln top, is
not a t eauilihrium. Eventuallv. .. the svstem is driven far
enough &om equilibrium to undergo-the self-orpaniring
transition shown in the photographs. The sequence clearly
shows how a roll develops, and how liquid in adjacent rolls
rotates in opposite directions; the initial descending vertical
sheets of acidic solution (yellow) formed at the start of the
convection are seen in the first two pictures. When a yellow
sheet reaches the bottom of rhe dish, it flows outwards hori-
zontally along the dish bottom (third photograph) and be-
gins to rise again when it collides with the front boundary of
a neighboring sheet, forming a rising vertical wall common
to both rolls (as in the last i)hotomaoh). On the averare. the
distance between rolls is equal to the depth of the layer, as
predicted by convection theory (I).
- BYvarying the starting conditions, it is possible to observe
a great diversity of patterns. For example, if our procedure is
repeated without background heat, the patterns take much
longer to form (up to 10 min) and then appear as circular,
approximately close-packed cells. Again, if thiosulfate is
present (10-3 M NazSzOs), the acidic regions of the pattern
form a temolate for *orecioitation of sulfur and can be seen
without indicator.
Chemically visualized convective self-oreanization is in-
teresting as ; demonstration because it is quick, easy, and
economical. Clearly the chemistry in the system we describe
is trivial, and t h e solution can-be regenerated and used
indefinitely by adding a few drops of base. Discovery of the
phenomenon has other significance as well. Its occurrence
may complicate the interpretation of true chemical spatial
structures unless precautions are taken (7). The compara-
tively straightforward visualization technique may prove of
use in fluid dynamics, where buoyancy instability is an ac-
tive area of research; the basic physics has application to
atmospheric motion at both local and large-scale levels, to
vertical ocean currents, and to motion of Earth's liquid man-
tle. On a smaller scale, convective patterns are important in
paint technology, where the roughness of a freshly painted with a 12-cm filter paper soaked in 6 M HCI, carefully re-
surface is thought to be due to convective cells "frozen" into moved the paper, and took photographs a t 204 intervals.
the laver as the paint dries ( I ) . The blue color of the indicator solution could be regenerated
for further experiments by adding a minimum amount of
Appendix base (1-2 drops of 0.1 M NaOH).
For the cover photographs, we used a 5-mm-deep layer of
solution in an uncovered 100- X 50-mm Petri dish. The
solution was prepared hy diluting 15 mL of saturated aque-
ous bromcresol green indicator t o 40 mL with 5 X loe4 M
t:r ~~~~~~~;~~'~;~$~~ 1980M311'*
K.,~,M:~~,A.;A~~~,D.N~C~~W~~~.I~~~,~,~.
NaOH. The indicator solution was filtered prior to use to 4. Avnu,D.;Kagan,M.Notunuirs. 1983,70,36l;~ofure198~307,717.
5. Avnir, D.; Kagan, M.: Rosa,W . Cham.Phys.L?tI.198%135,177.
eliminate specks of undissolved indicator. After placing the
solution on the light table, we covered the Petri dish for 10 s
, B O ~ C P.: wwaef,
~D ~~W ~~ IG.;
S ~
,,
7. Field, R J.~ m 4 r . 1985,73,142.
D.:K ~ ~ ~ J.~stat.phya.
Y ~ Y .
1987.48, IMI.

Volume 66 Number 3 March 1989 211