Oscillating Reactions

In an oscillating chemical reaction, the concentrations of the reactants and products change
with time in a periodic or quasi-periodic manner (i.e., they do not move directly or evenly
toward their final concentrations). Chemical oscillators exhibit chaotic behavior, in which
concentrations of products and the course of a reaction depend on the initial conditions of the
reaction. Oscillating reactions are thought to play key roles in such diverse processes as
biological morphogenesis and geologic stratigraphy.

Scientists have a long-standing fascination with the complexities of oscillating systems. In the
seventeenth century, the English-Irish chemist Robert Boyle, reported the periodic "flaring up" of
phosphorus in contact with the air. The classic modern example of an oscillating reaction is the
Belousov-Zhabotinsky oscillating reaction that yields a red solution that turns blue at varying
intervals of time. In a stirred vessel, the Belousov-Zhabotinsky reaction mixture will change color
from red to blue dozens or hundreds of times before equilibrium is established. If the mixture is
poured into a shallow vessel, the oscillation will be triggered at randomly spaced points and
give rise to outgoing waves of alternating red and blue color.

Another example of an oscillating reaction is provided by the Bray reaction, the first identified
homogeneous isothermal chemical oscillator, which is a complex reaction of iodate, iodine, and
hydrogen peroxide. As hydrogen peroxide decomposes to oxygen and water, the resulting rate
of the evolution of oxygen and I2 vary periodically.

A distinguishing feature of oscillating reactions is the phenomena of autocatalysis. In

autocatalytic reactions the increasing rate of reaction increases with the concentration of the
reactants. Autocatalytic reactions eventually achieve a steady state (where the net production
of products is zero) that can be determined by setting all the time derivatives equal to zero and
solving the resulting algebraic equations for the concentrations of reactants and products. In
oscillating reactions, small changes may result in a dramatic departure from the steady state.

Many skeptics of oscillating reactions dismisses these classic examples as aberrations due to
contamination. Concerns that oscillating reactions could not exist because of apparent
violations of thermodynamic laws have recently been refuted by careful studies that establish
that oscillating reactions are in accord with thermodynamic laws. Oscillating chemical reactions
are unlike the oscillations of a pendulum. Oscillating chemical reactions do not have to pass
through an equilibrium point during each oscillating cycle. Although this seems counter-intuitive
(outside of experience with the natural world) it is in perfect accord with quantum theory.

Because a closed system must eventually reach equilibrium, closed systems can sustain
oscillating chemical reactions for only a limited time. Sustained oscillating reactions require an
open system with a constant influx of reactants, energy and removal of products.

Oscillating reactions, a common feature of biological systems, are best understood within the
context of nonlinear chemical dynamics and chaos theory based models that are used to
predict the overall behavior of complex systems. A chaotic system is unpredictable, but not
random. A key feature is that such systems are so sensitive to their initial conditions that future
behavior is inherently unpredictable beyond some relatively short period of time. Accordingly,
one of the goals of scientists studying oscillating reactions is to determine mathematical patterns
or repeatable features that establish relationships to observable phenomena related to the
oscillating reaction.
Oscillating systems can interact with interesting results. Much like waves can cancel one another
out, two oscillating systems can interact to produce a steady state of oscillation. On the other
hand, the joining of two systems already at steady state can cause rhythmogenesis in which the
two systems will depart from the steady state.
The exact mechanisms (a series intermediate reactions or steps) of oscillating reactions are
elusive and difficult to obtain for all but the simplest reactions. The chemical equations and
mechanisms commonplace to stoichiometric chemistry describe only the overall reactions, they
do not specify the molecular transformations that place between colliding molecules.

Resources

Periodicals
Kuzovkov, V.N., O. Kortluke, and W. von Niessen. "Comment on Surface Restructuring, Kinetic
Oscillations, and Chaos in Heterogeneous Catalytic Reactions." Phys Rev E Stat Phys Plasmas
Fluids Relat Interdiscip Topics (February 2001.)
Zhuravlev, A.I., and V.M. Trainin. "Chemiluminescent Reactions in the Belousov-Zhabotinskii
Oscillating System." J Biolumin Chemilumin (October 1990): 227-34.

Other
University of Michigan. "Oscillating Reactions Web Module." Chemical rxn Engineering. [cited
November 21, 2002] <http://www.engin.umich.edu/~cre/web_mod/oscil/bz/module.htm>.

K. Lee Lerner

Read more: Oscillating Reactions - Chemical, Systems, Time, and Steady - JRank Articles
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OSCILLATION

Oscillation is the repetitive variation, typically in time, of some measure about a central value (often a
point of equilibrium) or between two or more different states. The term 'vibration' is precisely used to
describe mechanical oscillation but as a synonym of 'oscillation' too. Familiar examples include a
swinging pendulum and alternating current power.

Oscillations occur not only in mechanical systems but also in dynamic systems in virtually every area of
science: for example the beating human heart, business cycles in economics, predator-prey population
cycles in ecology, geothermal geysers in geology, vibrating strings in musical instruments, periodic firing
of nerve cells in the brain, and the periodic swelling of Cepheid variable stars in astronomy.

Chemical
BelousovZhabotinsky reaction
Mercury beating heart
BriggsRauscher reaction
BrayLiebhafsky reaction
BelousovZhabotinsky reaction

Computer simulation of the BelousovZhabotinsky reaction occurring in

a Petri dish

A BelousovZhabotinsky reaction, or BZ reaction, is one of a

class of reactions that serve as a classical example of non-
equilibrium thermodynamics, resulting in the establishment of a
nonlinear chemical oscillator. The only common element in
these oscillating systems is the inclusion of bromine and an acid.
The reactions are theoretically important in that they show that
chemical reactions do not have to be dominated by
equilibrium thermodynamic behavior. These reactions are far
from equilibrium and remain so for a significant length of time
and evolve chaotically. In this sense, they provide an interesting
chemical model of nonequilibrium biological phenomena, and the mathematical models of the
BZ reactions themselves are of theoretical interest and simulations.[1]

Plot of the electrode potential of a BZ reaction, using silver

electrodes against an Ag/AgNO3 half-cell

An essential aspect of the BZ reaction is its so called

"excitability"; under the influence of stimuli, patterns
develop in what would otherwise be a perfectly quiescent
medium. Some clock reactions such as BriggsRauscher
and BZ using the tris(bipyridine)ruthenium(II) chloride as
catalyst can be excited into self-organising activity through
the influence of light.

History
The discovery of the phenomenon is credited to Boris Belousov. He noted, some time in the 1950s
(various sources date ranges from 1951 to 1958), that in a mix of potassium bromate, cerium(IV)
sulfate, malonic acid, and citric acid in dilute sulfuric acid, the ratio of concentration of the
cerium(IV) and cerium(III) ions oscillated, causing the colour of the solution to oscillate between
a yellow solution and a colorless solution. This is due to the cerium(IV) ions being reduced by
malonic acid to cerium(III) ions, which are then oxidized back to cerium(IV) ions by bromate(V)
ions.

Belousov made two attempts to publish his finding, but was rejected on the grounds that he
could not explain his results to the satisfaction of the editors of the journals to which he submitted
his results.[2] Soviet biochemist Simon El'evich Shnoll encouraged Belousov to continue his efforts
to publish his results. His work was finally published in a less respectable, nonreviewed journal.[3]

After Belousov's publication, Schnoll gave the project in 1961 to a graduate student, Anatol
Zhabotinsky, who investigated the reaction sequence in detail;[4] however, the results of these
men's work were still not widely disseminated, and were not known in the West until a
conference in Prague in 1968.

A number of BZ cocktails are available in the chemical literature and on the web. Ferroin, a
complex of phenanthroline and iron, is a common indicator. These reactions, if carried out in
petri dishes, result in the formation first of colored spots. These spots grow into a series of
expanding concentric rings or perhaps expanding spirals similar to the patterns generated by a
cyclic cellular automaton. The colors disappear if the dishes are shaken, and then reappear. The
waves continue until the reagents are consumed. The reaction can also be performed in a
beaker using a magnetic stirrer.

Andrew Adamatzky,[5] a computer scientist in the University of the West of England, reported on
liquid logic gates using the BZ reaction.[6]

Strikingly similar oscillatory spiral patterns appear elsewhere in nature, at very different spatial
and temporal scales, for example the growth pattern of Dictyostelium discoideum, a soil-
dwelling amoeba colony.[7] In the BZ reaction, the size of the interacting elements is molecular
and the time scale of the reaction is minutes. In the case of the soil amoeba, the size of the
elements is typical of single-celled organisms and the times involved are on the order of days to
years.

Investigators are also exploring the creation of a "wet computer", using self-creating "cells" and
other techniques to mimic certain properties of neurons.[8]

Chemical Mechanism
The mechanism for this reaction is very complex and is thought to involve around 18 different
steps which have been the subject of a number of research papers.[9][10]

In a way similar to the BriggsRauscher reaction, two key processes (both of which are auto-
catalytic) occur; process A generates molecular bromine, giving the red colour, and process B
consumes the bromine to give bromide ions.[11]

One of the most common variations on this reaction uses malonic acid (CH2(CO2H)2) as the
acid and potassium bromate (KBrO3) as the source of bromine. The overall equation is:[11]

3CH2(CO2H)2 + 4BrO-3 4Br- + 9CO2 + 6H2O

https://en.wikipedia.org/wiki/Belousov%E2%80%93Zhabotinsky_reaction

Mercury beating heart

The mercury beating heart is an electrochemical redox reaction between the elements
mercury, iron and chromium. The reaction causes a blob of mercury in water to oscillate.

The observeable reaction demonstrates an effect of a non-homogeneous electrical double

layer.[1] It is often used as a classroom demonstration.

The experiment
In the experiment a droplet of mercury is placed in a watch glass, immersed in an electrolyte
such as sulfuric acid which contains an oxidizing agent such as hydrogen peroxide, potassium
permanganate, or potassium dichromate. The tip of an iron nail is positioned almost touching
the mercury. If the position of the nail tip is just right, the mercury blob begins to oscillate,
changing shape.

The Explanation
In one variation the mechanism is thought to be the following: The dichromate oxidizes the
mercury, forming a layer of mercury oxide. In the process the dichromate is reduced to the
chromium (III) ion. The oxidized layer on the mercury reduces the surface tension of the blob and
the blob flattens out coming in contact with the iron nail. Then the mercury sulfate oxidizes the
iron to the iron (II) ion, and in the process is reduced back to metallic mercury. Once there is no
oxide coating left on the mercury blob, the surface tension increases and the blob rounds up
and loses contact with the nail, to start the process over again.

The net reaction is that the dichromate oxidizes the iron. This favorable reaction drives the
mercury oxidations/reductions and the oscillations in shape. When the dichromate is all
reduced, the reaction stops.

There may be other mechanisms involved, however. Lin et al. appear to report that the
oscillations occur without the presence of the oxidizing agent, though the mercury does not
appear to get an oxidizing layer on it and the oscillations are much weaker.

An electrical double layer forms between the surface of the mercury droplet and the electrolyte
solution. At rest this layer is uniform. When the iron tip is introduced a redox reaction starts in
which iron is oxidized to the ferric ion. At the same time the oxidizing reagent is spent for instance
when hydrogen peroxide together with hydronium ions is reduced to water. Because the
oxidation only takes place in the vicinity of the tip and the reduction process covers the whole
droplet surface the surface tension is no longer homogeneous resulting in oscillations.[2]

Although this reaction is mediated by changes in surface tension, it is very similar in mechanism
to other chemical oscillators such as the BelousovZhabotinsky reaction, which has several
intermediate redox reactions driven by the oxidation of malate by bromine.

The mercury beating heart was first observed by Carl Adolf Paalzow in 1858. Jns Jakob Berzelius
is reported to have used electrodes.

https://en.wikipedia.org/wiki/Mercury_beating_heart

BriggsRauscher reaction

Oscillogram made in July 1972 by Briggs and

Rauscher.

The BriggsRauscher oscillating reaction is one

of a small number of known oscillating chemical
reactions. It is especially well suited for
demonstration purposes because of its visually
striking colour changes: the freshly prepared
colourless solution slowly turns an amber
colour, suddenly changing to a very dark blue.
This slowly fades to colourless and the process
repeats, about ten times in the most popular
formulation, before ending as a dark blue liquid
smelling strongly of iodine.

History
The first known homogeneous oscillating chemical reaction, reported by W. C. Bray in 1921,[1]
was between hydrogen peroxide (H2O2) and iodate (IO3) in acidic solution. Due to
experimental difficulty, it attracted little attention and was unsuitable as a demonstration. In
1958 B. P. Belousov in the Soviet Union discovered the BelousovZhabotinsky reaction (BZ
reaction),[2] which is suitable as a demonstration, but it too met with skepticism (largely because
such oscillatory behaviour was unheard of up to that time) until A. M. Zhabotinsky, also in the
USSR, learned of it and in 1964 published his research.[3] In May 1972 a pair of articles in the
Journal of Chemical Education[4][5] brought it to the attention of two science instructors at
Galileo High School in San Francisco. They discovered the BriggsRauscher oscillating reaction[6]
by replacing bromate (BrO3) in the BZ reaction with iodate and adding hydrogen peroxide.
They produced the striking visual demonstration by adding starch indicator. Since then, many
other investigators have added to the knowledge and uses of this very unusual reaction.

Description
Initial conditions
The initial aqueous solution contains hydrogen peroxide, an iodate, divalent manganese (Mn2+)
as catalyst, a strong chemically unreactive acid (sulphuric acid (H2SO4) or perchloric acid
(HClO4) are good), and an organic compound with an active ("enolic") hydrogen atom
attached to carbon which will slowly reduce free iodine (I2) to iodide (I). (Malonic acid
(CH2(COOH)2) is excellent for that purpose.) Starch is optionally added as an indicator to show
the abrupt increase in iodide ion concentration as a sudden change from amber (free iodine)
to dark blue (the "iodine-starch complex", which requires both iodine and iodide.)[7] Recently it
has been shown, however, that the starch is not only a simple indicator for iodine in the
reaction.[8] In the presence of starch the number of oscillations are higher and the period times
are longer compared to the starch-free mixtures. It was also found that the iodine consumption
segment within one period of oscillation is also significantly longer in the starch containing
mixtures. This suggests that the starch probably acts as a reservoir for the iodine and iodide due
to the starch-triiodide equilibrium, thereby modifying the kinetics of the steps in which iodine and
iodide are involved. In the same study, a method was presented for minimizing the
environmental impact of the reaction mixture before its disposal. The residual mixture contains
iodinated malonic acid, inorganic acid, manganous catalysts, unreacted iodate and hydrogen
peroxide. After the oscillations cease, the iodomalonic acid decomposes and iodine is
produced. The rate of decomposition depends on the conditions. All of the components present
in the residual mixture are of environmental concern: Iodate, iodine and hydrogen peroxide are
strong oxidants, the acid is corrosive and manganese has been suggested to cause
neurological disorders (citation needed). A simple method has been developed employing
thiosulfate and carbonate two inexpensive salts to remove all oxidants, neutralize the acidity
and recover the manganous ion in the form of manganese dioxide. The reaction is "poisoned"
by chloride (Cl) ion, which must therefore be avoided, and will oscillate under a fairly wide
range of initial concentrations. For recipes suitable for demonstration purposes, see
Shakhashiri[9] or Preparations in the external links.

Behavior in Time
The reaction shows recurring periodic changes, both gradual and sudden, which are visible:
slow changes in the intensity of colour, interrupted by abrupt changes in hue. This demonstrates
that a complex combination of slow and fast reactions are taking place simultaneously. For
example, following the iodide ion concentration with a silver/silver iodide electrode[6] (see
Videos) shows sudden dramatic swings of several orders of magnitude separated by slower
variations. This is shown by the oscillogram above. Oscillations persist over a wide range of
temperatures. Higher temperatures make everything happen faster, with some qualitative
change observable (see Effect of temperature). Stirring the solution throughout the reaction is
helpful for sharp colour changes, otherwise spatial variations may develop (see Videos). Bubbles
of free oxygen are evolved throughout, and in most cases, the final state is rich in free iodine.

Variants
Changing the initial concentrations
As noted above, the reaction will oscillate in a fairly wide range of initial concentrations of the
reactants.[10] For oscillometric demonstrations, more cycles are obtained in dilute solutions,
which produce weaker colour changes. See for example the graph, which shows more than 40
cycles in 8 minutes.

Changing the organic substrate

Malonic acid has been replaced by other suitable organic molecules,[11] such as acetone
(CH3COCH3) or 2,4 Pentanedione (CH3COCH2COCH3) ("acetylacetone"). More exotic
substrates have been used.[12][13] The resulting oscillographic records often show distinctive
features, for example as reported by Szalai.[1]

Continuous flow reactors

The reaction may be made to oscillate indefinitely by using a continuous flow stirred tank reactor
(CSTR), in which the starting reagents are continuously introduced and excess fluid is
drawn.[14][15]

Two dimensional phase space plots

By omitting the starch and monitoring the concentration of I2 photometrically, (i.e., measuring
the absorption of a suitable light beam through the solution) while simultaneously monitoring the
concentration of iodide ion with an iodide-selective electrode, a distorted spiral XY-plot will
result. In a continuous-flow reactor, this becomes a closed loop (limit cycle).

Fluorescent demonstration
By replacing the starch with a fluorescent dye, Weinberg and Muyskens (2007) produced a
demonstration visible in darkness under UV illumination.[16]

Use as a Biological Assay

The reaction has been proposed as an assay procedure for antioxidants in foodstuffs.[17] The sample to
be tested is added at the onset of oscillations, stopping the action for a period proportional to its
antioxidant activity. Compared to existing assay methods, this procedure is quick and easy and operates
at the pH of the human stomach.[18] For a detailed description suitable for high school chemistry, see
Preparations. In contrast to the findings referring predominantly to polyphenolic compounds reported in
the above cited literature, it was found that the salicylic acid a simple monophenolic compound did
not stop the oscillations immediately after it was added into the active Briggs-Rauscher mixture.[19] In
the low concentration interval the salicyclic acid only damped the oscillations, while in higher
concentrations the damping effect was much stronger and complete inhibition was also observed.[20] It
is also interesting that the sulfosalicylic acid, a derivative of salicyclic acid practically did not affect the
oscillations.

Chemical Mechanism

The detailed mechanism of this reaction is quite complex.[10][21] Nevertheless, a good general
explanation can be given.
The essential features of the system depend on two key processes (These processes each involve
many reactions working together):
A ("non-radical process"): The slow consumption of free iodine by the malonic acid
substrate in the presence of iodate. This process involves the intermediate production of
iodide ion.
B ("radical process"): A fast auto-catalytic process involving manganese and free radical
intermediates, which converts hydrogen peroxide and iodate to free iodine and oxygen.
This process also can consume iodide up to a limiting rate.
But process B can operate only at low concentrations of iodide, creating a feedback loop as
follows:
Initially, iodide is low and process B generates free iodine, which gradually accumulates.
Meanwhile, process A slowly generates the intermediate iodide ion out of the free iodine at an
increasing rate proportional to its (i.e. I2) concentration. At a certain point, this overwhelms
process B, stopping the production of more free iodine, which is still being consumed by process
A. Thus, eventually the concentration of free iodine (and thus iodide) falls low enough for
process B to start up again and the cycle repeats as long as the original reactants hold out.
The overall result of both processes is (again, approximately):[10]

IO3 + 2H2O2 + CH2(COOH)2 + H+ ICH(COOH)2 + 2O2 + 3H2O

The colour changes seen during the reaction correspond to the actions of the two processes:
the slowly increasing amber colour is due to the production of free iodine by process B. When
process B stops, the resulting increase in iodide ion enables the sudden blue starch colour. But
since process A is still acting, this slowly fades back to clear. The eventual resumption of process
B is invisible, but can be revealed by the use of a suitable electrode.[6]
A negative feedback loop which includes a delay (mediated here by process A) is a general
mechanism for producing oscillations in many physical systems, but is very rare in nonbiological
homogeneous chemical systems. (The BZ oscillating reaction has a somewhat similar feedback
loop.)

https://en.wikipedia.org/wiki/Briggs%E2%80%93Rauscher_reaction

BrayLiebhafsky reaction

The BrayLiebhafsky reaction is a chemical clock first described by William C. Bray in 1921 and
the first oscillating reaction in a stirred homogeneous solution.[1] He investigated the role of the
iodate (IO3), the anion of iodic acid in the catalytic conversion of hydrogen peroxide to oxygen
and water by the iodate. He noticed that the concentration of iodine molecules oscillated and
that oxygen did build up pulsating.

An increase in temperature reduces the cycle in the range of hours. This oscillating reaction
consisting of free radical on non-radical steps was investigated further by his student Herman A.
Liebhafsky,[2] hence the name BrayLiebhafsky reaction. During this period, most chemists
rejected the phenomenon and tried to explain the oscillation by invoking heterogeneous
impurities.

A fundamental property of this system is that hydrogen peroxide has a redox potential which
enables the simultaneous oxidation of iodine to iodate:
5 H2O2 + I2 2 IO3 + 2 H+ + 4 H2O

and the reduction of iodate back to iodine:

5 H2O2 + 2 IO3 + 2 H+ I2 + 5 O2 + 6 H2O

these two reactions the system oscillates causing a concentration jump of the iodide and the
oxygen production. The net reaction is:
H2O2 2 H2O + O2

necessitating a catalyst and IO3.

https://en.wikipedia.org/wiki/Bray%E2%80%93Liebhafsky_reaction
Oscillation - Real-life applications

Springs and Damping

Elastic potential energy relates primarily to springs, but springs are a major part of everyday life.
They can be found in everything from the shock-absorber assembly of a motor vehicle to the
supports of a trampoline fabric, and in both cases, springs blunt the force of impact.

If one were to jump on a piece of trampoline fabric stretched across an ordinary tableone
with no springsthe experience would not be much fun, because there would be little bounce.
On the other hand, the elastic potential energy of the trampoline's springs ensures that anyone
of normal weight who jumps on the trampoline is liable to bounce some distance into the air. As
a person's body comes down onto the trampoline fabric, this stretches the fabric (itself highly
elastic) and, hence, the springs. Pulled from a position of equilibrium, the springs acquire elastic
potential energy, and this energy makes possible the upward bounce.

As a car goes over a bump, the spring in its shock-absorber assembly is compressed, but the
elastic potential energy of the spring immediately forces it back to a position of equilibrium, thus
ensuring that the bump is not felt throughout the entire vehicle. However, springs alone would
make for a bouncy ride; hence, a modern vehicle also has shock absorbers. The shock absorber,
a cylinder in which a piston pushes down on a quantity of oil, acts as a damperthat is, an
inhibitor of the springs' oscillation.

SIMPLE HARMONIC MOTION AND DAMPING.

Simple harmonic motion occurs when a particle or object moves back and forth within a stable
equilibrium position under the influence of a restoring force proportional to its displacement. In
an ideal situation, where friction played no part, an object would continue to oscillate
indefinitely.

Of course, objects in the real world do not experience perpetual oscillation; instead, most
oscillating particles are subject to damping, or the dissipation of energy, primarily as a result of
friction. In the earlier illustration of the spring suspended from a ceiling, if the string is pulled to a
position of maximum displacement and then released, it will, of course, behave dramatically at
first. Over time, however, its movements will become slower and slower, because of the
damping effect of frictional forces.

HOW DAMPING WORKS.

When the spring is first released, most likely it will fly upward with so much kinetic energy that it
will, quite literally, bounce off the ceiling. But with each transit within the position of equilibrium,
the friction produced by contact between the metal spring and the air, and by contact
between molecules within the spring itself, will gradually reduce the energy that gives it
movement. In time, it will come to a stop.

If the damping effect is small, the amplitude will gradually decrease, as the object continues to
oscillate, until eventually oscillation ceases. On the other hand, the object may be
"overdamped," such that it completes only a few cycles before ceasing to oscillate altogether.
In the spring illustration, overdamping would occur if one were to grab the spring on a
downward cycle, then slowly let it go, such that it no longer bounced.
There is a type of damping less forceful than overdamping, but not so gradual as the slow
dissipation of energy due to frictional forces alone. This is called critical damping. In a critically
damped oscillator, the oscillating material is made to return to equilibrium as quickly as possible
without oscillating. An example of a critically damped oscillator is the shock-absorber assembly
described earlier.

Even without its shock absorbers, the springs in a car would be subject to some degree of
damping that would eventually bring a halt to their oscillation; but because this damping is of a
very gradual nature, their tendency is to continue oscillating more or less evenly. Over time, of
course, the friction in the springs would wear down their energy and bring an end to their
oscillation, but by then, the car would most likely have hit another bump. Therefore, it makes
sense to apply critical damping to the oscillation of the springs by using shock absorbers.
Bungee Cords and Rubber Bands

Many objects in daily life oscillate in a spring-like way, yet people do not commonly associate
them with springs. For example, a rubber band, which behaves very much like a spring,
possesses high elastic potential energy. It will oscillate when stretched from a position of stable
equilibrium.

Rubber is composed of long, thin molecules called polymers, which are arranged side by side.
The chemical bonds between the atoms in a polymer are flexible and tend to rotate, producing
kinks and loops along the length of the molecule. The super-elastic polymers in rubber are called
elastomers, and when a piece of rubber is pulled, the kinks and loops in the elastomers
straighten.

The structure of rubber gives it a high degree of elastic potential energy, and in order to stretch
rubber to maximum displacement, there is a powerful restoring force that must be overcome.
This can be illustrated if a rubber band is attached to a ceiling, like the spring in the earlier
example, and allowed to hang downward. If it is pulled down and released, it will behave much
as the spring did.

The oscillation of a rubber band will be even more appreciable if a weight is attached to the
"free" endthat is, the end hanging downward. This is equivalent, on a small scale, to a bungee
jumper attached to a cord. The type of cord used for bungee jumping is highly elastic;
otherwise, the sport would be even more dangerous than it already is. Because of the cord's
elasticity, when the bungee jumper "reaches the end of his rope," he bounces back up. At a
certain point, he begins to fall again, then bounces back up, and so on, oscillating until he
reaches the point of stable equilibrium.

The Pendulum

As noted earlier, a pendulum operates in much the same way as a swing; the difference
between them is primarily one of purpose. A swing exists to give pleasure to a child, or a certain
bittersweet pleasure to an adult reliving a childhood experience. A pendulum, on the other
hand, is not for play; it performs the function of providing a reading, or measurement.

One type of pendulum is a metronome, which registers the tempo or speed of music. Housed in
a hollow box shaped like a pyramid, a metronome consists of a pendulum attached to a sliding
weight, with a fixed weight attached to the bottom end of the pendulum. It includes a number
scale indicating the number of oscillations per minute, and by moving the upper weight, one
can change the beat to be indicated.
ZHANG HENG'S SEISMO-SCOPE.

Metronomes were developed in the early nineteenth century, but, by then, the concept of a
pendulum was already old. In the second century A.D. , Chinese mathematician and
astronomer Zhang Heng (78-139) used a pendulum to develop the world's first seismoscope, an
instrument for measuring motion on Earth's surface as a result of earthquakes.

Zhang Heng's seismoscope, which he unveiled in 132 A.D. , consisted of a cylinder surrounded by
bronze dragons with frogs (also made of bronze) beneath. When the earth shook, a ball would
drop from a dragon's mouth into that of a frog, making a noise. The number of balls released,
and the direction in which they fell, indicated the magnitude and location of the seismic
disruption.

CLOCKS, SCIENTIFIC INSTRUMENTS, AND "FAX MACHINE".

In 718 A.D. , during a period of intellectual flowering that attended the early T'ang Dynasty (618-
907), a Buddhist monk named I-hsing and a military engineer named Liang Ling-tsan built an
astronomical clock using a pendulum. Many clocks todayfor example, the stately and
imposing "grandfather clock" found in some homeslike-wise, use a pendulum to mark time.

Physicists of the early modern era used pendula (the plural of pendulum) for a number of
interesting purposes, including calculations regarding gravitational force. Experiments with
pendula by Galileo Galilei (1564-1642) led to the creation of the mechanical pendulum clock
the grandfather clock, that isby distinguished Dutch physicist and astronomer Christiaan
Huygens (1629-1695).

In the nineteenth century, A Scottish inventor named Alexander Bain (1810-1877) even used a
pendulum to create the first "fax machine." Using matching pendulum transmitters and receivers
that sent and received electrical impulses, he created a crude device that, at the time, seemed
to have little practical purpose. In fact, Bain's "fax machine," invented in 1840, was more than a
century ahead of its time.

THE FOUCAULT PENDULUM.

By far the most important experiments with pendula during the nineteenth century, however,
were those of the French physicist Jean Bernard Leon Foucault (1819-1868). Swinging a heavy
iron ball from a wire more than 200 ft (61 m) in length, he was able to demonstrate that Earth
rotates on its axis.

Foucault conducted his famous demonstration in the Panthon, a large domed building in Paris
named after the ancient Pantheon of Rome. He arranged to have sand placed on the floor of
the Panthon, and placed a pin on the bottom of the iron ball, so that it would mark the sand as
the pendulum moved. A pendulum in oscillation maintains its orientation, yet the Foucault
pendulum (as it came to be called) seemed to be shifting continually toward the right, as
indicated by the marks in the sand.

The confusion related to reference point: since Earth's rotation is not something that can be
perceived with the senses, it was natural to assume that the pendulum itself was changing
orientationor rather, that only the pendulum was moving. In fact, the path of Foucault's
pendulum did not vary nearly as much as it seemed. Earth itself was moving beneath the
pendulum, providing an additional force which caused the pendulum's plane of oscillation to
rotate.
WHERE TO LEARN MORE

Brynie, Faith Hickman. Six-Minute Science Experiments. Illustrated by Kim Whittingham. New York:
Sterling Publishing Company, 1996.

Ehrlich, Robert. Turning the World Inside Out, and 174 Other Simple Physics Demonstrations.
Princeton, N.J.: Princeton University Press, 1990.

"Foucault Pendulum" Smithsonian Institution FAQs (Website).

<http://www.si.edu/resource/faq/nmah/pendulum.html> (April 23, 2001).

Kruszelnicki, Karl S. The Foucault Pendulum (Web site).

<http://www.abc.net.au/surf/pendulum/pendulum.html> (April 23, 2001).

Schaefer, Lola M. Back and Forth. Edited by Gail Saunders-Smith; P. W. Hammer, consultant.
Mankato, MN: Pebble Books, 2000.

Shirley, Jean. Galileo. Illustrated by Raymond Renard. St. Louis: McGraw-Hill, 1967.

Suplee, Curt. Everyday Science Explained. Washington, D.C.: National Geographic Society,
1996.

Topp, Patricia. This Strange Quantum World and You. Nevada City, CA: Blue Dolphin, 1999.

Zubrowski, Bernie. Making Waves: Finding Out About Rhythmic Motion. Illustrated by Roy Doty.
New York: Morrow Junior Books, 1994.

Read more: http://www.scienceclarified.com/everyday/Real-Life-Physics-Vol-2/Oscillation-Real-

life-applications.html#ixzz4B8V8zyx9

Using chemical oscillation to better understand patterns in brain and heart systems
March 18, 2016 by Tony Fitzpatrick

Read more at: http://phys.org/news/2016-03-chemical-oscillation-patterns-brain-heart.html#jCp

Fireflies use oscillation to communicate. A Washington University

in St. Louis engineer has found a new way to control chemical
oscillation that could help regulate biorhythms involving the heart
and brain.

An electrical and systems engineer at Washington University

in St. Louis has designed a method that, figuratively, forces a
leopard to change its spots.

Jr-Shin Li, the Das Family Distinguished Career Development Associate Professor in Electrical &
Systems Engineering in the School of Engineering & Applied Science, has devised a unified
mathematical framework to design a single, global input, or waveform that is able to inspire a
population of nonlinear, rhythmic units ubiquitous in nature and manmade systems.
The theory has been shown on a nickel multi-electrode array (the leopard) to form first one
pattern, the letter O, then a short while later switches to another pattern, the letter K, and then
returns to the initial pattern O again. Each pixel in the letter is a chemical reaction.

The significance of the study is the contribution to advance the ensemble control theory with the
development of effective computational algorithms that will enable researchers to better
understand and control oscillation in a variety of important application domains, such as heart
pacemakers, neuronal firings in the brain and circadian timekeeping. Getting the 20 oscillatory
reactions on an array to switch patterns is an example of "entraining" abundant, often similar
dynamical systems simultaneously by a single command, or input.

The phenomenon of oscillation is nicely illustrated with the arrival of fireflies in summer. Fireflies
oscillate in a barely perceptible pattern to most observers until they eventually are all
communicating on the same wavelength, pulsing simultaneously. During the oscillation
phenomenon, after a chemical reaction, the chemical products often oscillate in different
frequencies (faster or slower).

"In many applications, it's beneficial to synchronize these oscillators," Li said. "So we apply the
input to make things synchronized."

Li and his former student, now at Los Alamos National Laboratory, and collaborators from Saint
Louis University published their results online in Nature Communications March 18.

"We've come up with a unified, systematic theory that will work on any nonlinear oscillating
system," Li said. "Mathematically, it works for any number, be it 20 or 2,000 or more."

Li's collaborator at Saint Louis University, Istvan Z. Kiss, the Arts & Sciences Associate Professor of
Chemistry, has said that it is feasible to show any desired phase pattern changes in an ensemble
of up to 120 chemical oscillatory reactions in his laboratory; however, extensions to thousands
or millionsof reactions are theoretically possible. The results published in Nature
Communications are thought to be a breakthrough of a successful pattern switching in
nonlinear oscillators following a global input.

"The paper shows that this is possible both theoretically and experimentally," Li said.

A global control signal is capable of selectively steering the complex

chemical reaction into chosen spatial patterns, in this example,
between shapes of letters 'O' and 'K' (in blue). Credit: Washington
University in St. Louis

While the method works in synchronization, it also works in cases

where de-synchronization is desired. In Parkinson's disease, for
instance, the part of the brain where the disease rears its ugly
head is pathologically synchronized when it's not supposed to
be. In theory, Li's waveform, applied directly to the brain, would
desynchronize a certain population of neurons that work together pathologically to give
Parkinson's disease sufferers their characteristic tremor.

Li is exploring with Erik Herzog, PhD, professor of biology in Arts & Sciences at Washington
University, how his input, or control, can be used to regulate circadian systems, or biological
clocks.
The waveform in circadian systems is the use of light to change the synchronization behavior of
circadian (biological clock) systems. Each circadian cell might have a different clock, and one
of the goals of this research is to entrain all of the circadian clocks to just one clock.

"This has a potential application in mitigating jet lag," Li said.

Li's theory of ensemble control can design a control input, often referred to as a waveform, or
"pulse," something like a conductor leading an orchestra. It has the ability to drive a great
number of nuclear spins with different frequencies in nuclear magnetic resonance (NMR)
spectroscopy, steering the whole diverse ensemble of nuclear spins from any initial state to any
desired target state to enable a clearer magnetic resonance image for medical diagnosis.

In robotics, Li's theory can design single control inputs that simultaneously would make numerous
robots in a system obey the same command. He collaborates with researchers across disciplines
in the areas of quantum mechanics, neuroscience, computer science, biology, biomedical
engineering and robotics.

Li's next step in entrainment of ensemble systems is to implement his method in biological and
neuroscience systems to see whether it can make inroads in deep brain stimulation, the state-of-
the art Parkinson's disease treatment, aimed at controlling the characteristic trembling of
patients. In these areas, "complexity and uncertainty are the challenges," Li said. "They are much
more difficult to control than chemicals, which are physical systems."

Read more at: http://phys.org/news/2016-03-chemical-oscillation-patterns-brain-heart.html#jCp

Chemical oscillations: The Belousov-Zhabotinsky reaction

Posted By Jyllian Kemsley on Sep 26, 2011 in Miscellaneous

Well take a brief break from chemical safety today in order to participate in the favorite
reaction blog carnival.

Mechanism of the BZ reaction, from J. Am. Chem.

Soc., DOI: 10.1021/ja00780a001

I first recall learning about the Belousov

Zhabotinsky reaction several years ago when I
was working on a story about photos of chemical
reactions on display at the University of
Wisconsin, Madison. Its quite possible that Id
learned and forgotten about the BZ reaction
before, but this time it stuck. We tend to think of
reactions as proceeding to completion or
reaching some sort of equilibrium, but they can
also oscillate: In simplest form, the products of
one reaction become the reactants of another
that regenerates the original reactants.

The actual mechanisms of oscillating reactions

can be quite complex, however. The classic BZ
reaction involves potassium bromate, cerium(IV)
sulfate, and propanedioic acid (aka malonic acid) in dilute sulfuric acid. Ten equations (shown)
make up the overall reaction. The color changes are due to the oscillating oxidation state of
ceriumCe(IV) is yellow and Ce(III) is colorless. If ferroin is used in place of cerium, the color
switches between blue and red.

According to a Journal of Chemical Education article by Purdue University chemistry professor

Arthur T. Winfree, Russian chemist Boris P. Belousov (1893-1970) first observed his namesake
reaction when working in the Laboratory of Biophysics at the USSR Ministry of Health, but he
couldnt get it published. Moscow State University graduate student Anatol Zhabotinsky (1938-
2008) followed up on and extended the work. Richard J. Field and Richard M. Noyes of the
University of Oregon, along with Endre Krs of Hungarys L. Etvs University, published the
mechanism in 1972.

Feedback loops along the lines of what happens in BZ or other oscillating reactions are common
in biology. My college p-chem textbook tells me that oscillating reactions are the source of
heartbeat rhythms, for example. Others point to the interplay of predator and prey populations.
Seeing oscillations happen in real time in a dish or beaker is, for me, a lovely example of the
wonder and power of chemistry.

Other well-known oscillating reactions include the Briggs-Rauscher (video) and mercury beating
heart (video). Janet Stemwedel described another today over at Doing Good Science.

http://cenblog.org/the-safety-zone/2011/09/chemical-oscillations-the-belousov-zhabotinsky-
reaction/