[H+]
and
M,
10-5
M,
M,
A-PX rMl kl
kia [MA]0 [I2]I/(klb+[I2]0)
=
I. Lengyci, Department
sity, Walham,
MA
Chemistry, Kossuth
cen,
Hungary.
Complex
02R5.
650
1.5
0.75
Estimated from
mobility data
1.4
1.5
1.2
0.70
0.75
0.60
(25)
As C102
Estimated from
values for Iand I3- (25)
Estimated from
0.4
0.8
105 x DMA (Cm2 S-')
mobility data
*In the callations D,- was taken as 5 x 10-7cm2 s-' because of the binding ofl2 and I3- to the gel (see text).
SCIENCE, VOL. 251
[I-]
[I2]
conditions,
O1-4
1IUU
but, by removing X, it serves as an inhibitor
for
the
Turing
instability.
Stable steady state
k,'
80
The
necessary
condition,
Eq.
13,
requires
, 25/c,
Domain with
+ Dx (a2x/az2)
(7)
that the diffusion coefficients ofthe reactants
60
be different and that the inhibitor (C102-)
ay/at = k2'x - k3'xy/(u + x2)
40
diffuse more rapidly than the activator (I-).
>
1 *-,
!
+ Dy (a2y/az2)
(8) With plausible values for the other paramep ' 3a5-2/a
20
where z is the spatial variable, and Dx and ters, we find that the ratio Dy/DX must be at
Oscillatory state
DY are the diffusion coefficients of x and y, least 10 for Eq. 13 to hold. In aqueous
Uv
'
respectively. It is useful to define the follow- solution, diffusion coefficients of typical
20
40
60
80
0'
100
a
ing dimensionless constants:
small ions are of the order of -` CM2 S-1,
and the diffusion coefficient of C102 can- Fig. 1. Stability diagram of the two-variable
a = kl[MA]W/(k2ulu2 [CG02]0)
(9a) not be ten times greater than that
and the domain of diffiusion-induced instaof I-. In model
bility with DY/DX = 15 in the (a, 1) plane.
general,
diffusion-induced
with
instability
1 = k3b [I2]Wl(k2uu"2 [C102]o
(9b) nearly equal diffusion coefficients (16) can
When applied to Eqs. 7 through 9, the occur only under very special conditions,
necessary and sufficient conditions (13, 14) which are unlikely to be realized in practice.
4.0O
for diffusion-induced instability in a twoIn the Turing structure experiments, the
variable system can be summarized as fol- gel is not an inert medium like the solvent in
lows, where the aii are the elements of the the corresponding aqueous experiment. The ,hx
2.0
_
Jacobian matrix, and ss signifies steady state starch cannot diffiuse in the gel, nor can the
=
{as with a12 [a(ax/at)/ay]}J:
starch-3- complex; their diffusion coeffi1) The homogeneous system must have a cients are zero (17). More importantly, the
steady state {xs, = u1/2a/5, y,, = (u"1/21) [1 polyacrylamide gel is typically 10 to 30% by
1.0
2.0
3.0
+ (aL5)2]} that is stable to homogeneous weight (2 to 6 mol/dm3) in the acrylamide
Distance (mm)
perturbations. This condition is fiulfilled if monomer, which provides a hospitable environment for both I2 and 13-. Specific Fig. 2. Stationary structures in the five-variable
(10) interactions of I2 and 13- with organic model with parameters given in Table 1. Initial
all + a22 < 0
concentrations in the gel were zero for all compolymers such as polyvinylacetate (18) and ponents. Fixed boundary
and
conditions: all concen(in M) are zero at the gel ends, except
(11) starch (19) are well known. Such interaction trations
alla22- a12a21 > 0
with the -CONH2 side groups of the poly- [MA] = 1.0 x 102 at the left and [I2]=
In our case, inequality 11 always holds, and mer is highly likely and would reduce the 1.0 X 103 [CG02] = 6.0 x 10-4 at the right.
inequality 10 becomes
effective diffusion constant of I-. In particular, the relatively low electron density of constants were determined at 25C, but the
(12) the NH2 moiety would facilitate Lewis
p > 3a/5 - 25/a
acid- Turing structures were found at 7C. Ener2) The stability of the homogeneous base interactions with 137. Simple experi- gies of activation (EA) of the component
steady state against inhomogeneous pertur- ments in which C102- and 12 solutions are reaction are available, so rate constants at
bations can be investigated with either Neu- poured through a column of polyacrylamide 7C can be estimated. We were unable to
mann or Dirichlet boundary conditions. gel show that the latter do have significantly find a direct determination of the diffusion
The following inequality is a necessary con- longer retention times.
coefficient of C102-, but from ion mobility
dition for diffusive instability (14):
We may picture the I- ions moving not in data (22) it must be similar to those of
a simple gel but in a medium with many chlorate and perchlorate ions, that is
alIDY + a22Dx >
traps (gel-bound 12, starch) that capture I- =1.5 x 10-5 cm2 s-1 at 25C. With the
for a period of time before relasing it, there- Stokes-Einstein relationship (diffusion coef2[DxDy (a11a22 - a12a21)]"2 > 0 (13) by
causing I- to diffuse much more slowly ficient D = kT/6ir'a, where j is viscosity, a
Comparing inequalities 10 and 13, we ob- than in the absence of the traps. The effec- is the particle radius, and k is the Boltzmann
serve that a,1 and a22 must have opposite tive diffusible concentration and concentra- constant), the temperature (T) dependence
signs. In our case a22 < 0 at any parameter tion gradient of I- are lower than the cor- of the diffusion coefficients can be calculatvalues, whereas a1, > 0 if
responding stoichiometric quantities. Thus ed. The absolute temperature changes only
the
rate of I- diffusion decreases as if its slightly, but the viscosity of water approxia > 5(5/3)1/2
(14) diffusion
coefficient were lower. The re- mately doubles as the temperature drops
In the standard terminology used to dis- quired tenfold difference between the diffu- from 250 to 7TC.
cuss Turing structures (12), the activator has sion coefficients of I- and C102- is easily
The wavelength of the structures can be
a positive sign (a1l > 0) and the inhibitor achieved by this mechanism. In fact, poly- calculated from:
has a negative sign (a22 < 0) in the Jaco- acrylamide gels have been used for the anad = 2r/q
bian; consequently, I- is the activator and lytical separation of halogen-containing spe- where
C102- is the inhibitor. In the chemical cies (20). For reaching a qualitative picture
sense, X (I-) is a self-inhibitor (15) in the (21), we estimated DY/DX= 15. Figure 1
(15)
q = 4(all/Dx + a221DY)112
crucial process (3); that is, the higher the shows the phase diagram in the a-P phase
concentration of I-, the slower the reac- plane obtained from the inequalities 12 Using the parameters in Table 1, we find
tion. However, X indirectly stimulates its through 14. The domain of diffusive insta- that the wavelength is 50.15 mm, which is
own buildup by inhibiting its own destruc- bility broadens as DY/DX is increased.
close to the experimental result (0.2 mm).
tion. Chemically, Y (C102-) acts directly
The parameters used to calculate the Numerical integration of Eqs. 4 through 6
neither as an activator nor as an inhibitor, structures are given in Table 1. The rate confirmed the existence of Turing struc-
tions is
ax/at =
8 FEBRUARY 1991
REPORTS 65 1
experiment.
652
1588 (1989).
17. Nevertheless, there is evidence that similar structures
arise in starch-free experiments: Q. Ouyang, K. Lee,
H. L. Swinney, unpublished results.
18. S. Hayashi, T. Hirai, S. Shimomichi, N. Hojo, J.
Polym. Sci. Part A 20, 839 (1982).
19. A. Cesdro, J. Benegas, D. Ripoli, J. Phys. Chem. 90,
2787 (1986).
20. D. Saunders and R. L. Pecsok, Anal. Chem. 40, 44
(1968).
21. Strictly speaking, the effective reactivity of I- should
also be reduced by this interaction, but we have
neglected this much smaller effect in the present
treatment.
garnet