Iodine Clock Reaction
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The iodine clock reaction is a classical chemical clock demonstration experiment to display
chemical kinetics Chemical kinetics, also known as reaction kinetics, is the branch of physical chemistry that is concerned with understanding the rates of chemical reactions. It is different from chemical thermodynamics, which deals with the direction in which a ...
in action; it was discovered by
Hans Heinrich Landolt Hans Heinrich Landolt (5 December 1831 – 15 March 1910) was a Swiss chemist who discovered iodine clock reaction. He is also one of the founders of Landolt–Börnstein database. He tested law of mass conservation which was given by Lavoisier. ...
in 1886. The iodine clock reaction exists in several variations, which each involve
iodine Iodine is a chemical element; it has symbol I and atomic number 53. The heaviest of the stable halogens, it exists at standard conditions as a semi-lustrous, non-metallic solid that melts to form a deep violet liquid at , and boils to a vi ...
species (
iodide An iodide ion is I−. Compounds with iodine in formal oxidation state −1 are called iodides. In everyday life, iodide is most commonly encountered as a component of iodized salt, which many governments mandate. Worldwide, iodine deficiency ...
ion, free iodine, or
iodate An iodate is the polyatomic anion with the formula . It is the most common form of iodine in nature, as it comprises the major iodine-containing ores. Iodate salts are often colorless. They are the salts of iodic acid. Structure Iodate is pyra ...
ion) and
redox Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is t ...
reagents in the presence of
starch Starch or amylum is a polymeric carbohydrate consisting of numerous glucose units joined by glycosidic bonds. This polysaccharide is produced by most green plants for energy storage. Worldwide, it is the most common carbohydrate in human diet ...
. 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.


Hydrogen peroxide variation

This method starts with a solution of
hydrogen peroxide Hydrogen peroxide is a chemical compound with the formula . In its pure form, it is a very pale blue liquid that is slightly more viscosity, viscous than Properties of water, water. It is used as an oxidizer, bleaching agent, and antiseptic, usua ...
and
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid (English in the Commonwealth of Nations, Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen, ...
. To this a solution containing
potassium iodide Potassium iodide is a chemical compound, medication, and dietary supplement. It is a medication used for treating hyperthyroidism, in radiation emergencies, and for protecting the thyroid gland when certain types of radiopharmaceuticals are u ...
,
sodium thiosulfate Sodium thiosulfate (sodium thiosulphate) is an inorganic compound with the formula . Typically it is available as the white or colorless pentahydrate (x = 5), which is a white solid that dissolves well in water. The compound is a reducing agent an ...
, and
starch Starch or amylum is a polymeric carbohydrate consisting of numerous glucose units joined by glycosidic bonds. This polysaccharide is produced by most green plants for energy storage. Worldwide, it is the most common carbohydrate in human diet ...
is added. There are two reactions occurring simultaneously in the solution. In the first, slow reaction, iodine is produced: : + 2 + 2 → + 2 In the second, fast reaction, iodine is reconverted to two iodide ions by the thiosulfate: :2 + → + 2 After some time the solution changes color to a very dark blue, almost black. When the solutions are mixed, the second reaction causes the
iodine Iodine is a chemical element; it has symbol I and atomic number 53. The heaviest of the stable halogens, it exists at standard conditions as a semi-lustrous, non-metallic solid that melts to form a deep violet liquid at , and boils to a vi ...
to be consumed much faster than it is generated, and only a small amount of iodine is present in the
dynamic equilibrium In chemistry, a dynamic equilibrium exists once a reversible reaction occurs. Substances initially transition between the reactants and products at different rates until the forward and backward reaction rates eventually equalize, meaning the ...
. Once the thiosulfate ion has been exhausted, this reaction stops and the blue colour caused by the iodine – starch complex appears. Anything that accelerates the first reaction will shorten the time until the solution changes color. Decreasing the pH (increasing concentration), or increasing the concentration of iodide or hydrogen peroxide will shorten the time. Adding more thiosulfate will have the opposite effect; it will take longer for the blue colour to appear. Aside from using sodium thiosulfate as a substrate,
cysteine Cysteine (; symbol Cys or C) is a semiessential proteinogenic amino acid with the chemical formula, formula . The thiol side chain in cysteine enables the formation of Disulfide, disulfide bonds, and often participates in enzymatic reactions as ...
can also be used. Iodide from potassium iodide is converted to iodine in the first reaction: 2 + 2 H+ + H2O2 → I2 + 2 H2O The iodine produced in the first reaction is reduced back to iodide by the
reducing agent In chemistry, a reducing agent (also known as a reductant, reducer, or electron donor) is a chemical species that "donates" an electron to an (called the , , , or ). Examples of substances that are common reducing agents include hydrogen, carbon ...
, cysteine. At the same time, cysteine is oxidized into cystine. 2 C3H7NO2S + I2 → C6H12N2O4S2 + 2 + 2 H+ Similar to the thiosulfate case, when cysteine is exhausted, the blue color appears.


Iodate variation

An alternative protocol uses a solution of
iodate An iodate is the polyatomic anion with the formula . It is the most common form of iodine in nature, as it comprises the major iodine-containing ores. Iodate salts are often colorless. They are the salts of iodic acid. Structure Iodate is pyra ...
ion (for instance potassium iodate) to which an acidified solution (again with
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid (English in the Commonwealth of Nations, Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen, ...
) of
sodium bisulfite Sodium bisulfite (or sodium bisulphite, sodium hydrogen sulfite) is a chemical mixture with the approximate chemical formula NaHSO3. Sodium bisulfite is not a real compound, but a mixture of salts that dissolve in water to give solutions compose ...
is added. In this protocol,
iodide An iodide ion is I−. Compounds with iodine in formal oxidation state −1 are called iodides. In everyday life, iodide is most commonly encountered as a component of iodized salt, which many governments mandate. Worldwide, iodine deficiency ...
ion is generated by the following slow reaction between the iodate and bisulfite: : + 3 → + 3 This first step is the rate determining step. Next, the iodate in excess will oxidize the iodide generated above to form iodine: : + 5 + 6 → 3 + 3 However, the iodine is reduced immediately back to iodide by the bisulfite: : + + → 2 + + 2 When the bisulfite is fully consumed, the iodine will survive (i.e., no reduction by the bisulfite) to form the dark blue complex with starch.


Persulfate variation

This clock reaction uses
sodium Sodium is a chemical element; it has Symbol (chemistry), symbol Na (from Neo-Latin ) and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 element, group 1 of the peri ...
,
potassium Potassium is a chemical element; it has Symbol (chemistry), symbol K (from Neo-Latin ) and atomic number19. It is a silvery white metal that is soft enough to easily cut with a knife. Potassium metal reacts rapidly with atmospheric oxygen to ...
or
ammonium persulfate Ammonium persulfate (APS) is the inorganic compound with the formula (NH4)2S2O8. It is a colourless (white) salt that is highly soluble in water, much more so than the related potassium salt. It is a strong oxidizing agent that is used as a cataly ...
to
oxidize Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...
iodide An iodide ion is I−. Compounds with iodine in formal oxidation state −1 are called iodides. In everyday life, iodide is most commonly encountered as a component of iodized salt, which many governments mandate. Worldwide, iodine deficiency ...
ions to
iodine Iodine is a chemical element; it has symbol I and atomic number 53. The heaviest of the stable halogens, it exists at standard conditions as a semi-lustrous, non-metallic solid that melts to form a deep violet liquid at , and boils to a vi ...
.
Sodium thiosulfate Sodium thiosulfate (sodium thiosulphate) is an inorganic compound with the formula . Typically it is available as the white or colorless pentahydrate (x = 5), which is a white solid that dissolves well in water. The compound is a reducing agent an ...
is used to reduce iodine back to iodide before the iodine can complex with the
starch Starch or amylum is a polymeric carbohydrate consisting of numerous glucose units joined by glycosidic bonds. This polysaccharide is produced by most green plants for energy storage. Worldwide, it is the most common carbohydrate in human diet ...
to form the characteristic blue-black color. Iodine is generated: :2 + → + 2 And is then removed: : + 2 → 2 + Once all the thiosulfate is consumed the iodine may form a complex with the starch. Potassium persulfate is less soluble (cfr. Salters website) while ammonium persulfate has a higher solubility and is used instead in the reaction described in examples from Oxford University.


Chlorate variation

An experimental iodine clock sequence has also been established for a system consisting of iodine potassium-iodide,
sodium chlorate Sodium chlorate is an inorganic compound with the chemical formula Na ClO3. It is a white crystalline powder that is readily soluble in water. It is hygroscopic. It decomposes above 300 °C to release oxygen and leaves sodium chloride. Sever ...
and
perchloric acid Perchloric acid is a mineral acid with the formula H Cl O4. It is an oxoacid of chlorine. Usually found as an aqueous solution, this colorless compound is a stronger acid than sulfuric acid, nitric acid and hydrochloric acid. It is a powerful oxid ...
that takes place through the following reactions.
Triiodide In chemistry, triiodide usually refers to the triiodide ion, . This anion, one of the polyhalogen ions, is composed of three iodine atoms. It is formed by combining aqueous solutions of iodide salts and iodine. Some salts of the anion have been ...
is present in equilibrium with
iodide An iodide ion is I−. Compounds with iodine in formal oxidation state −1 are called iodides. In everyday life, iodide is most commonly encountered as a component of iodized salt, which many governments mandate. Worldwide, iodine deficiency ...
anion and molecular
iodine Iodine is a chemical element; it has symbol I and atomic number 53. The heaviest of the stable halogens, it exists at standard conditions as a semi-lustrous, non-metallic solid that melts to form a deep violet liquid at , and boils to a vi ...
: : + Chlorate ion oxidizes iodide ion to
hypoiodous acid Hypoiodous acid is an inorganic compound with the chemical formula . It forms when an aqueous solution of iodine is treated with mercuric or silver salts. It rapidly decomposes by disproportionation: : Hypoiodous acid is a weak acid with a ...
and
chlorous acid Chlorous acid is an inorganic compound with the formula HClO2. It is a weak acid. Chlorine has oxidation state +3 in this acid. The pure substance is unstable, disproportionating to hypochlorous acid (Cl oxidation state +1) and chloric acid (Cl ...
in the slow and
rate-determining step In chemical kinetics, the overall rate of a reaction is often approximately determined by the slowest step, known as the rate-determining step (RDS or RD-step or r/d step) or rate-limiting step. For a given reaction mechanism, the prediction of the ...
: : + + 2 → + Chlorate consumption is accelerated by reaction of hypoiodous acid to iodous acid and more chlorous acid: : + + → + More
autocatalysis 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.Steinfeld J.I., Francisco J.S. and Hase W.L. ''Chemical Kinetics and ...
when newly generated iodous acid also converts chlorate in the fastest reaction step: : + → + In this clock the
induction period An induction period in chemical kinetics is an initial slow stage of a chemical reaction; after the induction period, the reaction accelerates. Ignoring induction periods can lead to runaway reactions. In some catalytic reactions, a pre-catalyst ...
is the time it takes for the autocatalytic process to start after which the concentration of free
iodine Iodine is a chemical element; it has symbol I and atomic number 53. The heaviest of the stable halogens, it exists at standard conditions as a semi-lustrous, non-metallic solid that melts to form a deep violet liquid at , and boils to a vi ...
falls rapidly as observed by UV–visible spectroscopy.


See also

* Clock reaction * Old Nassau reaction *
Chemical oscillator 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 t ...
* Briggs–Rauscher reaction


References


External links


Hydrogen peroxide variation

Sodium bisulfite variation with a high-speed camera
{{DEFAULTSORT:Iodine Clock Reaction Chemical kinetics Chemistry classroom experiments Clock reactions Clock reaction Thiosulfates Articles containing video clips