Chemical clock

Last updated
In an iodine clock reaction, colour changes after a time delay.

A chemical clock (or clock reaction) is a complex mixture of reacting chemical compounds in which the onset of an observable property (discoloration or coloration) occurs after a predictable induction time due to the presence of clock species at a detectable amount. [1] 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.

Contents

Types

Clock reactions may be classified into three or four types: [2]

Substrate-depletive clock reaction

The simplest clock reaction featuring two reactions: [2]

A → C (rate k1)
B + C → products (rate k2, fast)

When substrate (B) is present, the clock species (C) is quickly consumed in the second reaction. Only when substrate B is all used up or depleted, species C can build up in amount causing the color to change. An example for this clock reaction is the sulfite/iodate reaction or iodine clock reaction, also known as Landolt's reaction.

Sometimes, a clock reaction involves the production of intermediate species in three consecutive reactions.

P + Q → R
R + Q → C
P + C → 2R

Given that Q is in excess, when substrate (P) is depleted, C builds up resulting in the change in color.

Autocatalysis-driven clock reaction

The basis of the reaction is similar to substrate-depletive clock reaction, except for the fact that rate k2 is very slow leading to the co-existing of substrates and clock species, so there is no need for substrate to be depleted to observe the change in color. The example for this clock is pentathionate/iodate reaction. [2] [3]

Pseudoclock behavior

The reactions in this category behave like a clock reaction, however they are irreproducible, unpredictable and hard to control. Examples are chlorite/thiosulfate and iodide/chlorite reactions. [2]

Crazy clock reaction

The reaction is irreproducible in each run due to the initial inhomogeneity of the mixture which result from variation in stirring rate, overall volume as well as geometry of the reactors. Repeating the reaction in the statistically meaningful manners leads to the reproducible cumulative probability distribution curve. The example for this clock is iodate/arsenous acid reaction. [4]

One reaction may fall into more than one classification above depending on the circumstance. For example, iodate−arsenous acid reaction can be substrate-depletive clock reaction, autocatalysis-driven clock reaction and crazy clock reaction.

Examples

One class of example is the iodine clock reactions, in which an iodine species is mixed with redox reagents in the presence of starch. After a delay, a dark blue color suddenly appears due to the formation of a triiodide-starch complex.

Additional reagents can be added to some chemical clocks to build a chemical oscillator. For example, the Briggs–Rauscher reaction is derived from an iodine clock reaction by adding perchloric acid, malonic acid and manganese sulfate. [5]

See also

Related Research Articles

<span class="mw-page-title-main">Oxidizing agent</span> Chemical compound used to oxidize another substance in a chemical reaction

An oxidizing agent is a substance in a redox chemical reaction that gains or "accepts"/"receives" an electron from a reducing agent. In other words, an oxidizer is any substance that oxidizes another substance. The oxidation state, which describes the degree of loss of electrons, of the oxidizer decreases while that of the reductant increases; this is expressed by saying that oxidizers "undergo reduction" and "are reduced" while reducers "undergo oxidation" and "are oxidized". Common oxidizing agents are oxygen, hydrogen peroxide, and the halogens.

<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.

<span class="mw-page-title-main">Organolithium reagent</span> Chemical compounds containing C–Li bonds

In organometallic chemistry, organolithium reagents are chemical compounds that contain carbon–lithium (C–Li) bonds. These reagents are important in organic synthesis, and are frequently used to transfer the organic group or the lithium atom to the substrates in synthetic steps, through nucleophilic addition or simple deprotonation. Organolithium reagents are used in industry as an initiator for anionic polymerization, which leads to the production of various elastomers. They have also been applied in asymmetric synthesis in the pharmaceutical industry. Due to the large difference in electronegativity between the carbon atom and the lithium atom, the C−Li bond is highly ionic. Owing to the polar nature of the C−Li bond, organolithium reagents are good nucleophiles and strong bases. For laboratory organic synthesis, many organolithium reagents are commercially available in solution form. These reagents are highly reactive, and are sometimes pyrophoric.

The Stille reaction is a chemical reaction widely used in organic synthesis. The reaction involves the coupling of two organic groups, one of which is carried as an organotin compound (also known as organostannanes). A variety of organic electrophiles provide the other coupling partner. The Stille reaction is one of many palladium-catalyzed coupling reactions.

In organic chemistry, an electrophilic aromatic halogenation is a type of electrophilic aromatic substitution. This organic reaction is typical of aromatic compounds and a very useful method for adding substituents to an aromatic system.

<span class="mw-page-title-main">Hydrogen iodide</span> Chemical compound

Hydrogen iodide (HI) is a diatomic molecule and hydrogen halide. Aqueous solutions of HI are known as hydroiodic acid or hydriodic acid, a strong acid. Hydrogen iodide and hydroiodic acid are, however, different in that the former is a gas under standard conditions, whereas the other is an aqueous solution of the gas. They are interconvertible. HI is used in organic and inorganic synthesis as one of the primary sources of iodine and as a reducing agent.

<span class="mw-page-title-main">Iodic acid</span> Chemical compound (HIO3)

Iodic acid is a white water-soluble solid with the chemical formula HIO3. Its robustness contrasts with the instability of chloric acid and bromic acid. Iodic acid features iodine in the oxidation state +5 and is one of the most stable oxo-acids of the halogens. When heated, samples dehydrate to give iodine pentoxide. On further heating, the iodine pentoxide further decomposes, giving a mix of iodine, oxygen and lower oxides of iodine.

<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">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.

<span class="mw-page-title-main">Grignard reagent</span> Organometallic compounds used in organic synthesis

Grignard reagents or Grignard compounds are chemical compounds with the general formula R−Mg−X, where X is a halogen and R is an organic group, normally an alkyl or aryl. Two typical examples are methylmagnesium chloride Cl−Mg−CH3 and phenylmagnesium bromide (C6H5)−Mg−Br. They are a subclass of the organomagnesium compounds.

<span class="mw-page-title-main">Chiral derivatizing agent</span> Reagent for converting a chemical compound to a chiral derivative

In analytical chemistry, a chiral derivatizing agent (CDA), also known as a chiral resolving reagent, is a derivatization reagent that is a chiral auxiliary used to convert a mixture of enantiomers into diastereomers in order to analyze the quantities of each enantiomer present and determine the optical purity of a sample. Analysis can be conducted by spectroscopy or by chromatography. Some analytical techniques such as HPLC and NMR, in their most commons forms, cannot distinguish enantiomers within a sample, but can distinguish diastereomers. Therefore, converting a mixture of enantiomers to a corresponding mixture of diastereomers can allow analysis. The use of chiral derivatizing agents has declined with the popularization of chiral HPLC. Besides analysis, chiral derivatization is also used for chiral resolution, the actual physical separation of the enantiomers.

A cyanogen halide is a molecule consisting of cyanide and a halogen. Cyanogen halides are chemically classified as pseudohalogens.

Unlike its lighter congeners, the halogen iodine forms a number of stable organic compounds, in which iodine exhibits higher formal oxidation states than -1 or coordination number exceeding 1. These are the hypervalent organoiodines, often called iodanes after the IUPAC rule used to name them.

<span class="mw-page-title-main">Chlorine perchlorate</span> Chemical compound

Chlorine perchlorate is a chemical compound with the formula Cl2O4. This chlorine oxide is an asymmetric oxide, with one chlorine atom in +1 oxidation state and the other +7, with proper formula ClOClO3. It is produced by the photodimerization of chlorine dioxide (ClO2) at room temperature by 436 nm ultraviolet light:

<span class="mw-page-title-main">Blue bottle experiment</span> Color-changing redox chemical reaction

The blue bottle experiment is a color-changing redox chemical reaction. An aqueous solution containing glucose, sodium hydroxide, methylene blue is prepared in a closed bottle containing some air. Upon standing, it spontaneously turns from blue to colorless due to reduction of methylene blue by the alkaline glucose solution. However, shaking the bottle oxidizes methylene blue back into its blue form. With further shaking, this color-change cycle can be repeated many times. This experiment is a classic chemistry demonstration that can be used in laboratory courses as a general chemistry experiment to study chemical kinetics and reaction mechanism. The reaction also works with other reducing agents besides glucose and other redox indicator dyes besides methylene blue.

<span class="mw-page-title-main">Chemical oscillator</span> Reacting chemical mixture in which the concentrations change periodically

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.

The Pinnick oxidation is an organic reaction by which aldehydes can be oxidized into their corresponding carboxylic acids using sodium chlorite (NaClO2) under mild acidic conditions. It was originally developed by Lindgren and Nilsson. The typical reaction conditions used today were developed by G. A. Kraus. H.W. Pinnick later demonstrated that these conditions could be applied to oxidize α,β-unsaturated aldehydes. There exist many different reactions to oxidize aldehydes, but only a few are amenable to a broad range of functional groups. The Pinnick oxidation has proven to be both tolerant of sensitive functionalities and capable of reacting with sterically hindered groups. This reaction is especially useful for oxidizing α,β-unsaturated aldehydes, and another one of its advantages is its relatively low cost.

An insertion reaction is a chemical reaction where one chemical entity interposes itself into an existing bond of typically a second chemical entity e.g.:

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

Protodeboronation, or protodeborylation is a chemical reaction involving the protonolysis of a boronic acid in which a carbon-boron bond is broken and replaced with a carbon-hydrogen bond. Protodeboronation is a well-known undesired side reaction, and frequently associated with metal-catalysed coupling reactions that utilise boronic acids. For a given boronic acid, the propensity to undergo protodeboronation is highly variable and dependent on various factors, such as the reaction conditions employed and the organic substituent of the boronic acid.

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

Trifluoroperacetic acid is an organofluorine compound, the peroxy acid analog of trifluoroacetic acid, with the condensed structural formula CF
3
COOOH
. It is a strong oxidizing agent for organic oxidation reactions, such as in Baeyer–Villiger oxidations of ketones. It is the most reactive of the organic peroxy acids, allowing it to successfully oxidise relatively unreactive alkenes to epoxides where other peroxy acids are ineffective. It can also oxidise the chalcogens in some functional groups, such as by transforming selenoethers to selones. It is a potentially explosive material and is not commercially available, but it can be quickly prepared as needed. Its use as a laboratory reagent was pioneered and developed by William D. Emmons.

References

  1. Wright, Stephen W. (2002-01-01). "Tick Tock, a Vitamin C Clock". Journal of Chemical Education. 79 (1): 40A. doi:10.1021/ed079p40.
  2. 1 2 3 4 Horváth, Attila K.; Nagypál, István (23 February 2015). "Classification of Clock Reactions". ChemPhysChem. 16 (3): 588–594. doi:10.1002/cphc.201402806. PMID   25425415.
  3. Xu, L.; Horváth, A.K. (2014). "A Possible Candidate To Be Classified as an Autocatalysis-Driven Clock Reaction: Kinetics of the Pentathionate-Iodate Reaction". Journal of Physical Chemistry. 118 (32): 6171–6180. Bibcode:2014JPCA..118.6171X. doi:10.1021/jp5057573. PMID   25068832.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  4. Valkai, L.; Csekő, G.; Horváth, A.K. (2015). "Initial inhomogeneity-induced crazy-clock behavior in the iodate-arsenous acid reaction in a buffered medium under stirred batch conditions". Phys Chem Chem Phys. 17 (34): 22187–22194. Bibcode:2015PCCP...1722187V. doi:10.1039/c5cp02572a. PMID   26239390.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  5. Briggs, Thomas S.; Rauscher, Warren C. (1973-07-01). "An oscillating iodine clock". Journal of Chemical Education. 50 (7): 496. Bibcode:1973JChEd..50..496B. doi:10.1021/ed050p496. ISSN   0021-9584.