Chemical oscillator

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A stirred BZ reaction mixture showing changes in color over time Bzr fotos.jpg
A stirred BZ reaction mixture showing changes in color over time

In chemistry, a chemical oscillator is a complex mixture of reacting chemical compounds in which the concentration of one or more components exhibits periodic changes. They are a class of reactions that serve as an example of non-equilibrium thermodynamics with far-from-equilibrium behavior. The reactions are theoretically important in that they show that chemical reactions do not have to be dominated by equilibrium thermodynamic behavior.

Contents

In cases where one of the reagents has a visible color, periodic color changes can be observed. Examples of oscillating reactions are the Belousov–Zhabotinsky reaction (BZ reaction), the Briggs–Rauscher reaction, and the Bray–Liebhafsky reaction.

History

The earliest scientific evidence that such reactions can oscillate was met with extreme scepticism. In 1828, G.T. Fechner published a report of oscillations in a chemical system. He described an electrochemical cell that produced an oscillating current. In 1899, W. Ostwald observed that the rate of chromium dissolution in acid periodically increased and decreased. Both of these systems were heterogeneous and it was believed then, and through much of the last century, that homogeneous oscillating systems were nonexistent. While theoretical discussions date back to around 1910, the systematic study of oscillating chemical reactions and of the broader field of non-linear chemical dynamics did not become well established until the mid-1970s. [1]

Theory

Chemical systems cannot oscillate about a position of final equilibrium because such an oscillation would violate the second law of thermodynamics. For a thermodynamic system which is not at equilibrium, this law requires that the system approach equilibrium and not recede from it. For a closed system at constant temperature and pressure, the thermodynamic requirement is that the Gibbs free energy must decrease continuously and not oscillate. However it is possible that the concentrations of some reaction intermediates oscillate, and also that the rate of formation of products oscillates. [2]

Theoretical models of oscillating reactions have been studied by chemists, physicists, and mathematicians. In an oscillating system the energy-releasing reaction can follow at least two different pathways, and the reaction periodically switches from one pathway to another. One of these pathways produces a specific intermediate, while another pathway consumes it. The concentration of this intermediate triggers the switching of pathways. When the concentration of the intermediate is low, the reaction follows the producing pathway, leading then to a relatively high concentration of intermediate. When the concentration of the intermediate is high, the reaction switches to the consuming pathway.

Different theoretical models for this type of reaction have been created, including the Lotka-Volterra model, the Brusselator and the Oregonator. The latter was designed to simulate the Belousov-Zhabotinsky reaction. [3]

Types

Belousov–Zhabotinsky (BZ) reaction

A Belousov–Zhabotinsky reaction is one of several oscillating chemical systems, whose common element is the inclusion of bromine and an acid. 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 the Briggs–Rauscher reactions and the BZ using the chemical ruthenium bipyridyl as catalyst can be excited into self-organising activity through the influence of light.

Boris Belousov first noted, sometime in the 1950s, that in a mix of potassium bromate, cerium(IV) sulfate, propanedioic acid (another name for 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 propanedioic acid to cerium(III) ions, which are then oxidized back to cerium(IV) ions by bromate(V) ions.

Briggs–Rauscher reaction

The Briggs–Rauscher 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 color changes: the freshly prepared colorless solution slowly turns an amber color, suddenly changing to a very dark blue. This slowly fades to colorless and the process repeats, about ten times in the most popular formulation.

Bray–Liebhafsky reaction

The Bray–Liebhafsky reaction is a chemical clock first described by W. C. Bray in 1921 with the oxidation of iodine to iodate:

5 H2O2 + I2 → 2 IO
3
+ 2 H+ + 4 H2O

and the reduction of iodate back to iodine:

5 H2O2 + 2 IO
3
+ 2 H+ → I2 + 5 O2 + 6 H2O [4]

See also

Related Research Articles

In a chemical reaction, chemical equilibrium is the state in which both the reactants and products are present in concentrations which have no further tendency to change with time, so that there is no observable change in the properties of the system. This state results when the forward reaction proceeds at the same rate as the reverse reaction. The reaction rates of the forward and backward reactions are generally not zero, but they are equal. Thus, there are no net changes in the concentrations of the reactants and products. Such a state is known as dynamic equilibrium.

<span class="mw-page-title-main">Oscillation</span> Repetitive variation of some measure about a central value

Oscillation is the repetitive or periodic variation, typically in time, of some measure about a central value or between two or more different states. Familiar examples of oscillation include a swinging pendulum and alternating current. Oscillations can be used in physics to approximate complex interactions, such as those between atoms.

In chemical thermodynamics, activity is a measure of the "effective concentration" of a species in a mixture, in the sense that the species' chemical potential depends on the activity of a real solution in the same way that it would depend on concentration for an ideal solution. The term "activity" in this sense was coined by the American chemist Gilbert N. Lewis in 1907.

<span class="mw-page-title-main">Belousov–Zhabotinsky reaction</span> Non-equilibrium thermodynamic reaction

A Belousov–Zhabotinsky 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 oscillators is the inclusion of bromine and an acid. The reactions are important to theoretical chemistry 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; as such, mathematical models and simulations of the BZ reactions themselves are of theoretical interest, showing phenomenon as noise-induced order.

In chemistry, a chemical reaction is said to be autocatalytic if one of the reaction products is also a catalyst for the same reaction. Many forms of autocatalysis are recognized.

<span class="mw-page-title-main">Boris Belousov (chemist)</span> Soviet scientist (1893–1970)

Boris Pavlovich Belousov was a Soviet chemist and biophysicist who discovered the Belousov–Zhabotinsky reaction in the early 1950s. His work initiated the field of modern nonlinear chemical dynamics.

In chemistry, the common-ion effect refers to the decrease in solubility of an ionic precipitate by the addition to the solution of a soluble compound with an ion in common with the precipitate. This behaviour is a consequence of Le Chatelier's principle for the equilibrium reaction of the ionic association/dissociation. The effect is commonly seen as an effect on the solubility of salts and other weak electrolytes. Adding an additional amount of one of the ions of the salt generally leads to increased precipitation of the salt, which reduces the concentration of both ions of the salt until the solubility equilibrium is reached. The effect is based on the fact that both the original salt and the other added chemical have one ion in common with each other.

<span class="mw-page-title-main">Bromic acid</span> Chemical compound

Bromic acid, also known as hydrogen bromate, is an oxoacid with the molecular formula HBrO3. It only exists in aqueous solution. It is a colorless solution that turns yellow at room temperature as it decomposes to bromine. Bromic acid and bromates are powerful oxidizing agents and are common ingredients in Belousov–Zhabotinsky reactions. Belousov-Zhabotinsky reactions are a classic example of non-equilibrium thermodynamics.

<span class="mw-page-title-main">Iodine clock reaction</span> Experiment to show chemical kinetics in action

The iodine clock reaction is a classical chemical clock demonstration experiment to display chemical kinetics in action; it was discovered by Hans Heinrich Landolt in 1886. The iodine clock reaction exists in several variations, which each involve iodine species and redox reagents in the presence of starch. Two colourless solutions are mixed and at first there is no visible reaction. After a short time delay, the liquid suddenly turns to a shade of dark blue due to the formation of a triiodide–starch complex. In some variations, the solution will repeatedly cycle from colorless to blue and back to colorless, until the reagents are depleted.

<span class="mw-page-title-main">Chemical clock</span>

A chemical clock is a complex mixture of reacting chemical compounds in which the onset of an observable property occurs after a predictable induction time due to the presence of clock species at a detectable amount. In cases where one of the reagents has a visible color, crossing a concentration threshold can lead to an abrupt color change after a reproducible time lapse.

<span class="mw-page-title-main">Briggs–Rauscher reaction</span> Oscillating chemical reaction

The Briggs–Rauscher 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, then suddenly changes 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.

A chemical computer, also called a reaction-diffusion computer, Belousov–Zhabotinsky (BZ) computer, or gooware computer, is an unconventional computer based on a semi-solid chemical "soup" where data are represented by varying concentrations of chemicals. The computations are performed by naturally occurring chemical reactions.

<span class="mw-page-title-main">Ferroin</span> Complex of Fe2+ by ortho-phenanthroline

Ferroin is the chemical compound with the formula [Fe(o-phen)3]SO4, where o-phen is an abbreviation for 1,10-phenanthroline, a bidentate ligand. The term "ferroin" is used loosely and includes salts of other anions such as chloride.

The Bray–Liebhafsky reaction is a chemical clock first described by William C. Bray in 1921 and the first oscillating reaction in a stirred homogeneous solution. He investigated the role of the iodate, the anion of iodic acid, in the catalytic conversion of hydrogen peroxide to oxygen and water by the iodate. He observed that the concentration of iodine molecules oscillated periodically and that hydrogen peroxide was consumed during the reaction.

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.

<span class="mw-page-title-main">Bromous acid</span> Chemical compound

Bromous acid is the inorganic compound with the formula of HBrO2. It is an unstable compound, although salts of its conjugate base – bromites – have been isolated. In acidic solution, bromites decompose to bromine.

<span class="mw-page-title-main">Brusselator</span> Theoretical model for a type of autocatalytic reaction

The Brusselator is a theoretical model for a type of autocatalytic reaction. The Brusselator model was proposed by Ilya Prigogine and his collaborators at the Université Libre de Bruxelles.

<span class="mw-page-title-main">Richard M. Noyes</span> American physical chemist

Richard Macy Noyes was an American physical chemist.

Chemical reaction network theory is an area of applied mathematics that attempts to model the behaviour of real-world chemical systems. Since its foundation in the 1960s, it has attracted a growing research community, mainly due to its applications in biochemistry and theoretical chemistry. It has also attracted interest from pure mathematicians due to the interesting problems that arise from the mathematical structures involved.

Cerium compounds are compounds containing the element cerium (Ce), a lanthanide. Cerium exists in two main oxidation states, Ce(III) and Ce(IV). This pair of adjacent oxidation states dominates several aspects of the chemistry of this element. Cerium(IV) aqueous solutions may be prepared by reacting cerium(III) solutions with the strong oxidizing agents peroxodisulfate or bismuthate. The value of E(Ce4+/Ce3+) varies widely depending on conditions due to the relative ease of complexation and hydrolysis with various anions, although +1.72 V is representative. Cerium is the only lanthanide which has important aqueous and coordination chemistry in the +4 oxidation state.

References

  1. Epstein, Irving R., and John A. Pojman. An introduction to nonlinear chemical dynamics: oscillations, waves, patterns, and chaos. Oxford University Press, USA, 1998, p. 3.
  2. Espenson, J.H. Chemical Kinetics and Reaction Mechanisms (2nd ed., McGraw-Hill 2002) p.190 ISBN   0-07-288362-6
  3. "IDEA - Internet Differential Equations Activities". Washington State University. Archived from the original on 2017-09-09. Retrieved 2010-05-16.
  4. Bray, William C. (1921). "A periodic reaction in homogeneous solution and its relation to catalysis". Journal of the American Chemical Society. 43 (6): 1262–1267. doi:10.1021/ja01439a007.