Proc. Nat. Acad. Sci.

USA

Vol. 71, No. 11, pp. 4477-4481, November 1974

On the Mechanism of Oscillations in the "Beating Mercury Heart"

(electrocapillarity)

SHU-WAI LIN*, JOEL KEIZER*, PETER A. ROCK*, AND HERBERT STENSCHKEt

* Chemistry Department, University of California, Davis, Calif. 95616; and t Institut ffr Theoretische Physik, Freie Universitat Berlin,
1 Berlin 33, W. Germany

Communicated by Terrell L. Hill, August 6, 1974

ABSTRACT
The discovery of a class of electrochemicalmechanical oscillators-similar to the beating mercury
heart -are reported and characterized. Chemical and
physical effects on the voltage-time oscillations in these
systems have been measured and a mechanism consistent
with these effects is given. Interesting cross-catalytic
effects involving the electrocapillarity of mercury are
proposed to be the origin of the oscillations in these
systems.

Interest in oscillating systems has been stimulated in recent

years by discoveries of oscillatory behavior in a number of
physical and biochemical systems (1-3). The classical example
of an electrochemical-mechanical oscillator is the "beating
mercury heart." This system was originally reported by
Lippmann (4, 5) over 100 years ago and is particularly simple
to prepare. Approximately a cubic centimeter of mercury
is placed in a watch glass and covered with a dilute aqueous
solution of a strong acid, e.g., HNO3, H2SO4, or HC1, containing a few crystals of K2Cr2O7, Na2S208, or KMnO4. These
solutions are complex chemically and produce insoluble films
on the mercury surface. If now an iron nail or sewing needle
is brought up to touch the mercury drop from the side, the
drop rhythmically changes its shape with a frequency of two or
three times a second. The oscillations can be easily sustained
for periods greater than an hour.
We have been investigating the mechanism of oscillations
in systems of this sort, which we will describe by the following
type of notation:
[1]
Fe(s) IH+(aq), Cr2O72-(aq) IHg(l),
where the negative electrode is on the left. One of our initial
observations on the mercury heart was that oscillations occur
when Cr(NO3)3 is substituted for K2Cr2O7 and even when no
salt is added to dilute aqueous HNO3, H2SO4, HC1, or HC104.
Although with these solutions the mercury remains shiny and
the oscillations are weaker and may occur less frequently, the
oscillations appear qualitatively the same as when K2Cr2O7
is added to the system. The absence of additional oxidizing
agent in the solution greatly simplifies the chemistry in these
systems, but the mechanism of the oscillations is still clouded
by possible effects arising from the active-passive transition
in iron (6). This led us to look for even simpler oscillators of
this sort. In this note we report the discovery of the following
new electrochemical-mechanical oscillators and propose a
mechanism for the oscillations:

Al(s) OH-(aq), 02(aq)jHg(l)

Al(s) H+(aq), Cr2O72-(aq)lHg(l)

[2]
[3]
4477

MgjH+(aq), 02(aq)jHg(l)
Al(s) ILiCl(CH30H), 02(CH30H) Hg(l)
Fe(s) IH(aq) Hg(l)

[4]
[5]

[6]

EXPERIMENTAL

Reagent-grade chemicals were used without further purification. Carbonate-free NaOH(aq) was prepared by diluting 18
M NaOH(aq). The mercury used was Ballard Bros. C.P.,
triple-distilled grade. Diagrams of the two types of apparatus
used to study the oscillations are shown in Fig. 1. Note especially that the geometry is quite different from the usual
watch-glass arrangement for the beating mercury-heart. This
capillary geometry is not only quantitatively reproducible, but
minimizes, if not eliminates, the purely hydrodynamic motion
of the mercury. The position of the tungsten electrode tip in
relation to the mercury was adjusted by means of two Brinkmann model no. 06-20-04 micromanipulators. The apparatus
was located in a Lucite enclosure, so that the atmosphere over
the solutions and the temperature of the solutions could be
controlled. Voltage-time curves were recorded on a Textronix
type 564B storage oscilloscope (3A9 differential amplifier,
2B67 time base). In order to obtain reproducible voltagetime curves it is necessary to use fresh mercury for each experiment. Because there is an initial transient period, oscilloscope traces were recorded at least 2 min after the oscillations
were induced by touching the tungsten electrode tip to the
mercury surface.
RESULTS
A typical voltage-time oscillation is given in Fig. 2, and can
be characterized by the peak height (in volts) and by the
period, the gap, and the flat-line (all in milliseconds). Note
that the gap time plus the flat-line time is equal to the period.
The factors that affect the parameters of the Al(s)JOH-(aq),
02(aq)JHg(l) voltage-time oscillations can be conveniently
divided into physical and chemical factors.
Physical Factors. The only factor we have discovered that
affects appreciably the period of the oscillations is the diameter of the mercury column in the tube (see Fig. 1). It was
observed that the oscillation period, T. depends linearly on the
diameter, d, of the mercury column according to r(msec) =
4.2d(mm). The standard tube diameter used in all of the
other experiments reported herein is 16.7 mm inner diameter.
It was found that the peak height was affected by a number
of physical factors including: stirring the aqueous solution
above the mercury; increase of the height of the solution

4478

Proc. Nat. Acad. Sci. USA 71 (1974)

Chemistry: Lin et al.

A

Al

NaOH
+NaC

FIG. 1. The apparatus in which oscillations are studied. In

this geometry the mercury miniscus is convex and the center of
the miniscus is initially set even with the top of the tube. In A,
the corroding electrode (Al) is in the same vessel as the mercury.
In B, the corroding metal is located in a separate container connected to the solution above the mercury by a 1.0 M NaCl salt
bridge (S.B.). The polarity of the oscilloscope (OSC) is as indicated.

above the mercury; the composition of the conducting tip;

and the sharpness of the conducting tip. In addition, all of the
parameters of the voltage-time curves depend on the exact
placement of the tungsten tip with respect to the mercury
surface. All these parameters have been controlled in the
present work, and the quantitative data on these effects will
be included in a future publication. In the experiments reported here, a sharp tungsten tip was used and the tungsten
was placed above the center of the mercury miniscus. The distance between the tungsten tip and the mercury surface is
adjusted by means of micromanipulators, which permit precise
adjustment of the W-to-Hg separation. The zero point for the
separation distance measurement is determined by the indication (either visual or on the oscilloscope) of a break in metallic conduction as the W tip is slowly cranked upward from
the (nonoscillating) mercury surface. For all experiments in
this work the W-to-Hg separation was set initially at 0.040
mm. The parameters of the voltage-time curve are independent of whether the corroding aluminum is located in the

vessel with the mercury or in a separate vessel connected to

the mercury-containing vessel by means of a salt bridge.
However, the parameters of the voltage-time curve depend
on the amount of aluminum surface that is undergoing reaction, which was fixed at 1.0 cm of a 0.81-mm diameter Al
wire in the results reported here.
Static electromotive force (emf) differences were measured
with the oscilloscope, after the oscillations were stopped,
with a Hg(l)lHgO(s) OH-(aq) reference electrode (7) located
in the vessel with the aluminum electrode; the two vessels
were connected by an agar salt bridge. The solutions in the
two vessels were 0.020 M NaOH(aq) plus 0.98 M NaCl and
1.00 M NaCl(aq), with the latter solution in contact with the
mercury surface. In each case the left electrode is negative
(250C): HgjHgO to Hg (0.046 V); Al(W) to HgIHgO (1.410
V); Al to HgjHgO (1.790 V); AI(W) to Hg (1.270 V); W to
HgjHgO (0.212 V). The Al(W) to Hg emf difference at the
flat portion of the voltage curve is 0.0001 V.
The mercury surface can be set into oscillations with a
sufficiently negative fixed external voltage, which suggests
that the only function of the aluminum is to transfer electrons
to the mercury.

Chemical Factors. The peak height of the voltage-time curve

depends on the relative concentration of NaCl and NaOH at
fixed ionic strength in the solution above the mercury. The
peak height also changes if the ionic strength is changed. Indeed, all the parameters of the voltage-time curve depend on
the nature and composition of the electrolyte solution above
the mercury, but especially on the concentration of electron
acceptors. In fact, without suitable electron acceptors present
in the solution, the Al(s) OH-(aq)jHg(l) system will not
oscillate. In Table 1 we have assembled the results of experiments carried out with aqueous solutions of different compositions in contact with the mercury surface. For the solutions
listed, the surface of the mercury remains shiny, showing no
evidence of gas evolution or film formation.
The results of a study of the effect of oxygen on the nature
of the oscillations have provided a crucial clue to the chemical
part of the mechanism of the oscillations. If oxygen is removed from the aqueous solution over the mercury surface
(e.g., by purging the system with argon), then the system will
no longer oscillate. The peak height of the voltage-time curve
is linearly related to the concentration of dissolved oxygen
(determined with a Beckman Oxygen Analyzer model 1008)
TABLE 1. Effect of solution composition

Period
(msec)

Flat line

(V)
0.129

76

35

0.125
0.129
0.071
0.090
0.171

74
77
75
73
76

35
39
35
23
37

0.241

75

35

Peak height

Solution(aq)
FIG. 2. A typical oscilloscope trace of a spontaneous oscillation in set-up B (Fig. 1) for the system Al(W)|NaOH(aq)
The vertical axis is
(0.04 M), NaCl(aq) (0.96 M),
the Hg-to-Al(W) voltage difference, v, which is always positive
(one large division is 50 mV); the horizontal axis is time (one
large division is 20 msec). On the portion of the curve where the
voltage is constant, the "flat line," v = 0.1 mV. The "period" is
the time between two voltage peaks, and the duration of the
rising voltage is the "gap time." The difference between the
highest voltage during a period and the flat line is the "peak
height."

O2(aq)JHg(l).

1.00 M NaCl
1.00 M NaCl +
0.01 M AlCl3

1.00MKI
1.00 M NaF
1.00 M NH4C1
1.00 M (CH3)4NCl
1.00 M NaCl
Saturated with HgO(s)

(msec)

250C; 0.02 M NaOH(aq) + 0.98 M NaCl(aq) in the corrosion

vessel of set-up B (Fig. 1).

"Beating Mercury Heart"

Proc. Nat. Acad. Sci. USA 71 (1974)

4479

E 150
.,

' 100

5.

,0'

/0

C, 50

W0

._c

30
40
20
Time in msec
FIG. 4. The potential difference between the mercury and the
Al(W) electrode for the system in Fig. 2. The circles and dashed
line are the theoretical curve v = 0.045 ln (1 + t/2) with t in
msec; the squares were recorded during spontaneous oscillations;
and the triangles are the 1.0-min interrupter measurement.

04

To

10

tO2]x 104M
as a function of oxygen for the
The
height
FIG. 3.
peak
system described in Fig. 2. The temperature was fixed at 220C
where the ambient 02 concentration in solution is about 2.5 X
10-4 M and the saturation value is 13.1 X 10-4 M. The solution
above the mercury was purged with argon, and two sets of
measurements (0, A) were made by equilibrating the solution
with progressively higher partial pressures of 02-

(Fig. 3). These results are in direct contrast to our results for
the Fe(s) H+(aq), Cr202-7(aq)jHg(l) system-the beating
mercury heart-where the peak height is independent of the
concentration of dissolved oxygen. The effect of purging the
system with N20 is essentially the same as purging with Ar,
which suggests (8) that solvated electrons (e-aq) are not involved in the mechanism of the oscillations.
Because kinetic data on the reduction of 02 in the voltage
range of interest here do not seem to be available, an attempt was made to determine Tafel parameters for the Hg(l)
OH-(aq), 02(aq) electrode by a modification of the Indirect
(interrupter) Method (9). This involved applying periodic
current pulses of 40 msec duration every 0.45 sec to the mercury at a fixed voltage of 1.27 V. The time dependence of the
potential between the Hg and a corroding Al(W) electrode
was recorded when no current was being drawn. After roughly
2 min of pulsing, the shape of the curves changed very little,
although prebubbling the solution above the mercury with
argon or oxygen would, respectively, reduce or increase the
height of these voltage changes. It was concluded that dissolved 02 was being reduced and reaching a steady-state concentration at the mercury surface during the transient period.
As shown in Fig. 4, at an elasped time of 1.0 min the voltage
decay nicely fits the usual "interrupter" equation (9) (e.g.,
see Eq. 10 below) and assuming a Hg surface capacitance of
30 MF cm-2 (10) gives a cathodic current density of 6.75 X
10-4 A cm-2 at 1.27 V and a Tafel "b" value of 0.10 V (11).
When the argon-purged solution of 0.3 M K2S208(aq) was
above the mercury, the Hg surface tarnished and oscillations
could be obtained only when the electrode tip was located on
the side of the miniscus. This latter behavior is also found in
the mercury heart in this geometry, and it is consistent with
the mechanism proposed below which suggests that oscillations can be driven from the side of the mercury when the
electrode reaction on the mercury yields an adsorbed film or
neutral reaction products.

DISCUSSION

Although we feel that most of the basic features of the mechanism of the oscillations are the same for systems with or
without film formation, the discussion here is limited primarily to those systems 2, 4, 5 and 6 in which no film is
formed.
We believe the important electrochemical steps in these
oscillations to be: (i) The transfer of electrons from the corroding negative electrode to the mercury surface by the anodic half-reaction of the corrosion process, i.e., Al(s) + 40H-(aq) = Al(OH)4-(aq) + 3e- (12). This transfer occurs at
direct metallic contact between the electrode tip and the mercury and is accompanied by a rapid fall in voltage. This rapid
short circuit is followed by the nearly zero voltage difference
(the flat portion of the voltage time curve) while metallic
contact is maintained. (ii) A cathodic half-reaction then
occurs on the mercury surface; the exact nature of this reaction depends on the composition of the solution above the
mercury surface. In the systems for which the peak height is
proportional to the amount of dissolved 02, e.g., systems 2 or 4,
the cathodic reaction is believed to be the reduction of 02,
which is a net process of the form 02 + 2H20 4e- = 40H(13). Besides the important effect of 02 on the oscillations,
this reaction is also consistent with the fact that the mercury
surface remains shiny and shows no evidence of gas evolution
during the oscillations, although H2 gas does evolve from the
W electrode. Furthermore, the pH in an oscillating Al(s)
02(aq) Hg(l) system, which was originally neutral, increases
with time, indicating the release of OH- anion. In the acid
systems that are unaffected by 02, e.g., Fe(s)jH+(aq) Hg(l),
it is our opinion that the cathode process on the mercury is
the reduction of protons (14). The reaction is consistent with
the fact that H2 gas evolves from the mercury in this system.
In systems with film formation, the important cathode process
may be the production of the film. The final important electrochemical process is thought to be: (iii) the desorption of reaction product from the mercury surface.
The mechanism of the oscillations can be analyzed in terms
of three variables that change during the course of the oscillations: s, the mercury-to-conducting-tip separation; c, the
surface concentration of reaction product on the mercury
surface (in units corresponding to coulombs per unit area);
and v, the mercury-to-conducting-tip voltage difference. The
rate equations describing the kinetic coupling of these vari-

4480

Chemistry: Lin et al.

ables are

ds/dt = Lh[e(c,v) - y(s)]

[7]
dc/dt = [ioexp( - v/vo) - io exp(v/vto)] -D(c - c) [8]
C dv/dt = [io exp( - v/vo) - i'o exp(v/v'o0) ]- (S)V
[9]
Eq. 7 expresses the fact that when the equilibrium surface
tension at the actual separation, 'y(s), differs from the surface
tension, 'y(cv), prescribed by the actual voltage and concentration on the mercury surface, there will be a "thermodynamic force" which changes the shape of the surface (15). L is a
phenomenological coefficient. Eq. 8 describes the rate at
which the surface concentration of electrode reaction product
changes with time. The first term is the net rate of the electrode processes and is a Butler-Volmer term (16); io is the
cathodic current density (in amperes per unit area); v0 is
0.434 times the "b" value for the cathodic Tafel equation.
The primed terms are for the anodic reaction. The second term
in Eq. 8 represents the rates of adsorption and desorption of
the reaction product from the adsorbed layer of the mercury
surface (17). D is a first-order rate constant for this process
and co is the concentration of reaction product that would result from equilibration with the bulk electrolyte solution.
For a weakly adsorbed species like OH-, c0 is essentially
zero (18). The voltage Eq. 9 expresses the fact that the charge
density that lies on the mercury side of the surface, q, can
change, i.e., dq = Cdv, where C is the differential capacity
per unit area of the surface. The change in charge density on
the mercury results from the loss of electrons by the electrode
reactions, described by the Butler-Volmer term in Eq. 9,
and from the direct conduction of electrons between the mercury and the conducting tip in the second term; a(S) is the
mercury-to-conducting-tip conductivity and is nonzero only
when the tip directly contacts the mercury surface. Because
of contact resistance, a is not infinite, but only very large,
when direct contact is made.
For the system Al(W)OH-(aq), O2(aq)#Hg(l) the set of
coupled differential equations have been solved numerically,
and for appropriate parameters the solution exhibits limit(a)
+

Cl<C2<C3

Proc. Nat. Acad. Sci. USA 71

(1974)

cycle type oscillations. A discussion of this work will be rea future publication, although in the following we
explain briefly how the oscillations come about. For this system the equations have two natural, limiting steady states.
One corresponds to the positive voltage difference of 1.27 V
that develops when the metallic tip is placed far away from the
mercury; the other is the steady state that occurs when the
tip is placed deep into the mercury with a short-circuited
voltage of v8, = 0.0001 V. If the metallic tip is moved from
the far away position toward the surface, but not deep into
served for

the mercury, then an intermediate situation develops which

can correspond to unstable steady states. In this intermediate
regime, oscillations appear as a kind of stabilized back and
forth motion between the two limiting steady states. The
coupling in the kinetic equations that causes the oscillations
is found in Eq. 7. Indeed, the sign of ds/dt is directly proportional to the difference between the "local" surface tensions 'y(c,v) and -y(s); y(c,v) is the concentration and voltagedependent electrocapillary function and is shown schematically for the reaction product OH- in Fig. 5. A study of the
curves of constant surface tension in Fig. 6 shows that at the
short-circuit voltage v8c, y(c,v) increases as the surface concentration of OH- builds up. If this cross-catalytic effect is
large enough so that y(c,v) exceeds oy(s), then ds/dt becomes
positive, causing the separation to increase and possibly leading to a break in metallic contact. Break in metallic contact
is followed by an increase in the voltage, due to the discharge
of the mercury capacitor (Eq. 9), and a decrease in the concentration of OH- at the surface, due to desorption of OH-.
This, again, can cross-catalytically effect the separation between the conducting tip and the mercury. In fact, on this
part of the dashed path indicated in Fig. 6, y(c,v) can decrease and may fall below e(s). This means that ds/dt is less
than zero and so s will decrease. If the separation falls to
zero, then metallic contact and the short circuit will occur.
Because Fig. (6) shows that the short circuit enhances the crosscatalytic decrease of the separation, the cycle can again repeat
itself.
From the proposed mechanism the "short circuit" occurs
when s < 0, i.e., at metallic contact. The steady voltage at
short circuit is determined by Eq. 9 to be v,, = io exp(- v,,/vo)
Um'ax, where the anodic reaction has been neglected and amax
is the conductivity when touching. In theAl(s) OH-(aq), 02(aq)
Hg(l) system, the short-circuiting half-time r is the order of
10q-110- sec and can be used to estimate amax. During the
shorting process the first term in Eq. 9 can be neglected because

(b)

FIG. 5. Schematic representations of the surface concentration, c, and voltage, v, dependence of the surface tension, -y
(the electrocapillary effect) for an adsorbed anionic species like
OH-. The curves in (a) represent the surface tension of mercuryat fixed adsorbed anion concentration-as a function of voltage.
Such curves cannot be measured directly, but their form can be
inferred from the data in ref. 18.

Vg

FIG. 6. Topographic lines of constant surface tension taken

from Fig. 5. The dashed curve is a closed path on which, when
traversed counterclockwise, the surface tension increases between
a minimum value at the open circle to a maximum value at the
closed circle and then decreases on the second half of the path.

Proc. Nat. Acad. Sci. USA 71 (1974)

of the large value of max* Thus, during this process dv/dt = (crmax/C)v, which means that the life-time of this process will
be T = C/amax. Thus, 0nmax = CT-1, and use of a typical value
(10) of C = 30 uF cm-2 gives amasx = 3-30 ohm-'. This can
be used with the values of vo = 0.045 V and io = 6.75 X 10-4
A- cm-2, which the voltage interruption method showed to
be characteristic of the Al(s) OH-(aq), 02(aq)lHg(l) system,
to find that v,, is in the range of 0.02-0.2 mV, which compares favorably with the value of 0.1 mV measured experimentally.
Another simple test of Eq. 9 for the voltage can be made.
The voltage is uncoupled from the other variables in the nontouching region if a constant capacitance is assumed, and
taking v 0 at t = 0, Eq. [9] has the solution
v = voln[(iot/Cvo) + 1]
[10]
The values of io, vo, and C given above yields the dashed line
in Fig. 4. This curve nicely approximates the rising voltage
during spontaneous oscillations in the Al(s)OH-(aq), 02(aq)
Hg(l) system as well as the voltage curve from the periodic
interrupter measurements recorded in this system.
In order for the mechanism to show sustained oscillations,
the electrocapillary function, 'y(cv), and the equilibrium surface tension, e'(s), must have properties like those described
in Fig. 6. For neutral products or films, the electrocapillary
function will not be appreciably skewed to lower voltages,
as are the curves for anionic products in Fig. 6. This effect
can be used to explain why in film systems initiation in the
capillary geometry occurs only from the side and, including
additional inertial effects, explains why the mercury heart
in a watch glass can be triggered only when the nail is at the
side of the mercury.
We acknowledge assistance by Mr. Eric Vorpagel at the inception of this work. Support for research and travel was supplied by N.A.T.O. Research Grant 696, the Committee on
Research at University of California, Davis, and an N.S.F.
Institutional Grant.

"Beating Mercury Heart"

4481

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Chem. Rev. 95, 365-384.
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16. Vetter, K. J. (1967) Electrochemical Kinetics (Academic

Press, New York), p. 115.
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Theory of Electrocapillarity," Chem. Rev. 41, 441-500. See
especially Section V and Figs. 7 and 8.