# Chemical oscillator

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{{short description|Reacting chemical mixture in which the concentrations change periodically}}
thumb|right|A stirred BZ reaction mixture showing changes in color over time

In [chemistry](/source/chemistry), a '''chemical oscillator''' is a complex mixture of [reacting](/source/chemical_reaction) chemical [compounds](/source/compound_(chemistry)) in which the [concentration](/source/concentration) of one or more components exhibits [periodic](/source/Periodic_function) changes. They are a class of reactions that serve as an example of [non-equilibrium thermodynamics](/source/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](/source/equilibrium_thermodynamics) behavior.

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](/source/Belousov%E2%80%93Zhabotinsky_reaction) (BZ reaction), the [Briggs–Rauscher reaction](/source/Briggs%E2%80%93Rauscher_reaction), and the [Bray–Liebhafsky reaction](/source/Bray%E2%80%93Liebhafsky_reaction).

==History==
The earliest scientific evidence that such reactions can oscillate was met with extreme scepticism. In 1828, [G.T. Fechner](/source/Gustav_Fechner) published a report of oscillations in a chemical system. He described an electrochemical cell that produced an oscillating current. In 1899, [W. Ostwald](/source/Wilhelm_Ostwald) observed that the rate of chromium dissolution in acid periodically increased and decreased. Both of these systems were [heterogeneous](/source/Homogeneous_and_heterogeneous_mixtures) 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.<ref>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.</ref>

==Theory==
{{Thermodynamics}}
Chemical systems cannot oscillate about a position of final [equilibrium](/source/chemical_equilibrium) because such an oscillation would violate the [second law of thermodynamics](/source/second_law_of_thermodynamics). For a [thermodynamic system](/source/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](/source/Gibbs_free_energy) must decrease continuously and not oscillate. However it is possible that the concentrations of some [reaction intermediate](/source/reaction_intermediate)s oscillate, and also that the ''rate'' of formation of products oscillates.<ref>Espenson, J.H. ''Chemical Kinetics and Reaction Mechanisms'' (2nd ed., McGraw-Hill 2002) p.190 {{ISBN|0-07-288362-6}}</ref>

Theoretical models of oscillating reactions have been studied by chemists, physicists, and mathematicians. In an [oscillating system](/source/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](/source/Lotka-Volterra_model), the [Brusselator](/source/Brusselator) and the [Oregonator](/source/Oregonator). The latter was designed to simulate the Belousov-Zhabotinsky reaction.<ref>{{cite web
| url = http://www.idea.wsu.edu/OscilChem/
| title = IDEA - Internet Differential Equations Activities
| publisher = [Washington State University](/source/Washington_State_University)
| accessdate = 2010-05-16
| archive-date = 2017-09-09
| archive-url = https://web.archive.org/web/20170909182522/http://www.idea.wsu.edu/OscilChem/
| url-status = dead
}}</ref>

==Types==

===Belousov–Zhabotinsky (BZ) reaction===
A [Belousov–Zhabotinsky reaction](/source/Belousov%E2%80%93Zhabotinsky_reaction) is one of several oscillating chemical systems, whose common element is the inclusion of [bromine](/source/bromine) and an acid. An essential aspect of the BZ reaction is its so-called "excitability"&mdash;under the influence of stimuli, patterns develop in what would otherwise be a perfectly quiescent medium. Some [clock reactions](/source/chemical_clock) such as the [Briggs–Rauscher reaction](/source/Briggs%E2%80%93Rauscher_reaction)s and the BZ using the chemical ruthenium bipyridyl as catalyst can be excited into [self-organising](/source/self_organization) activity through the influence of light.

[Boris Belousov](/source/Boris_Pavlovich_Belousov) first noted, sometime in the 1950s, that in a mix of [potassium bromate](/source/potassium_bromate), [cerium(IV) sulfate](/source/cerium(IV)_sulfate), [propanedioic acid](/source/propanedioic_acid) (another name for malonic acid) and [citric acid](/source/citric_acid) in dilute [sulfuric acid](/source/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](/source/Briggs%E2%80%93Rauscher_reaction) 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](/source/Bray%E2%80%93Liebhafsky_reaction) is a chemical clock first described by W. C. Bray in 1921 with the [oxidation](/source/oxidation) of [iodine](/source/iodine) to [iodate](/source/iodate):

:5 H<sub>2</sub>O<sub>2</sub> + I<sub>2</sub> → 2 {{chem|IO|3|-}} + 2 H<sup>+</sup> + 4 H<sub>2</sub>O

and the [reduction](/source/Redox) of iodate back to iodine:

:5 H<sub>2</sub>O<sub>2</sub> + 2 {{chem|IO|3|-}} + 2 H<sup>+</sup> → I<sub>2</sub> + 5 O<sub>2</sub> + 6 H<sub>2</sub>O<ref>{{cite journal | doi = 10.1021/ja01439a007 | year = 1921 | author = Bray, William C. | journal = Journal of the American Chemical Society | volume = 43 | pages = 1262–1267 | issue = 6 |title = A periodic reaction in homogeneous solution and its relation to catalysis.| bibcode = 1921JAChS..43.1262B | url = https://zenodo.org/record/1428808 }}</ref>

==See also==
* [Catalytic oscillator](/source/Grigoriy_Yablonsky)
* [Mercury beating heart](/source/Mercury_beating_heart)
* [Blue bottle experiment](/source/Blue_bottle_experiment)
* [Clock reactions](/source/Clock_reactions)

==References==
{{reflist}}

==External links==
*[https://www.youtube.com/watch?v=g3JbDybzYqk Video of BZ reaction]
*[http://www.pojman.com/nlcd/intro.html History of oscillating reactions]

Category:Non-equilibrium thermodynamics
Category:Chemistry classroom experiments
Category:Chemical reactions
Category:Clock reactions

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Adapted from the Wikipedia article [Chemical oscillator](https://en.wikipedia.org/wiki/Chemical_oscillator) by Wikipedia contributors ([contributor history](https://en.wikipedia.org/wiki/Chemical_oscillator?action=history)). Available under [Creative Commons Attribution-ShareAlike 4.0 International](https://creativecommons.org/licenses/by-sa/4.0/). Changes may have been made.