Ammonium dichromate is an inorganic compound with the formula (NH₄)₂Cr₂O₇. In this compound, as in all chromates and dichromates, chromium is in a +6

oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...

, commonly known as

hexavalent chromium Hexavalent chromium (chromium(VI), Cr(VI), chromium 6) is chromium in any chemical compound that contains the element in the +6 oxidation state (thus hexavalent). Virtually all chromium ore is processed via hexavalent chromium, specifically the ...

. It is a salt consisting of ammonium ions and dichromate ions. Ammonium dichromate is sometimes known as ''Vesuvian Fire'', because of its use in demonstrations of tabletop "volcanoes". However, this demonstration has become unpopular in schools due to the compound's carcinogenic nature. It has also been used in

pyrotechnic Pyrotechnics is the science and craft of creating such things as fireworks, safety matches, oxygen candles, explosive bolts and other fasteners, parts of automotive airbags, as well as gas-pressure blasting in mining, quarrying, and demolition. ...

s and in the early days of

photography Photography is the art, application, and practice of creating durable images by recording light, either electronically by means of an image sensor, or chemically by means of a light-sensitive material such as photographic film. It is employe ...

Properties

At room temperature and pressure, the compound exists as orange, acidic crystals soluble in water and alcohol. It is formed by the action of

chromic acid The term chromic acid is usually used for a mixture made by adding concentrated sulfuric acid to a dichromate, which may contain a variety of compounds, including solid chromium trioxide. This kind of chromic acid may be used as a cleaning mixtu ...

ammonium hydroxide Ammonia solution, also known as ammonia water, ammonium hydroxide, ammoniacal liquor, ammonia liquor, aqua ammonia, aqueous ammonia, or (inaccurately) ammonia, is a solution of ammonia in water. It can be denoted by the symbols NH3(aq). Although ...

with subsequent crystallisation.Richard J. Lewis ''Hawley's Condensed Chemical Dictionary''. Wiley & Sons, Inc: New York, 2007 The (NH₄)₂Cr₂O₇ crystal (C2/c, z=4) contains a single type of ammonium ion, at sites of symmetry C₁(2,3). Each NH₄⁺ centre is surrounded irregularly by eight oxygen atoms at N—O distances ranging from ca. 2.83 to ca. 3.17 Å, typical of hydrogen bonds.

Uses

It has been used in

s and in the early days of photography as well as in

lithography Lithography () is a planographic method of printing originally based on the immiscibility of oil and water. The printing is from a stone (lithographic limestone) or a metal plate with a smooth surface. It was invented in 1796 by the German a ...

, as a source of pure

nitrogen Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...

in the laboratory, and as a

catalyst Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...

. It is also used as a

mordant A mordant or dye fixative is a substance used to set (i.e. bind) dyes on fabrics by forming a coordination complex with the dye, which then attaches to the fabric (or tissue). It may be used for dyeing fabrics or for intensifying stains in ...

for dyeing pigments, in manufacturing of

alizarin Alizarin (also known as 1,2-dihydroxyanthraquinone, Mordant Red 11, C.I. 58000, and Turkey Red) is an organic compound with formula that has been used throughout history as a prominent red dye, principally for dyeing textile fabrics. Historic ...

chrome alum Chrome alum or Chromium(III) potassium sulfate is the potassium double sulfate of chromium. Its chemical formula is KCr(SO4)2 and it is commonly found in its dodecahydrate form as KCr(SO4)2·12(H2O). It is used in leather tanning. Production a ...

, leather tanning and oil purification. Photosensitive films containing PVA, ammonium dichromate, and a phosphor are spin-coated as aqueous slurries in the production of the phosphor raster of television screens and other devices. The ammonium dichromate acts as the photoactive site.

Reactions

Tabletop volcanoes and thermal decomposition

The volcano demonstration involves igniting a pile of the salt, which initiates the following exothermic conversion:- :(''s'') → (''s'') + (''g'') + 4(''g'') (ΔH = −429.1±3 kcal/mol) Like

ammonium nitrate Ammonium nitrate is a chemical compound with the chemical formula . It is a white crystalline salt consisting of ions of ammonium and nitrate. It is highly soluble in water and hygroscopic as a solid, although it does not form hydrates. It is ...

, it is thermodynamically unstable. Its decomposition reaction proceeds to completion once initiated, producing voluminous dark green powdered

chromium(III) oxide Chromium(III) oxide (or chromia) is an inorganic compound with the formula . It is one of the principal oxides of chromium and is used as a pigment. In nature, it occurs as the rare mineral eskolaite. Structure and properties has the corundum ...

. Not all of the ammonium dichromate decomposes in this reaction. When the green powder is brought into water a yellow/orange solution is obtained from left over ammonium dichromate. Observations obtained using relatively high magnification microscopy during a kinetic study of the thermal decomposition of ammonium dichromate provided evidence that salt breakdown proceeds with the intervention of an intermediate liquid phase rather than a solid phase. The characteristic darkening of crystals as a consequence of the onset of decomposition can be ascribed to the dissociative loss of ammonia accompanied by progressive anion condensation to , , etc., ultimately yielding . The has been identified as a possible molten intermediate participating in decomposition.

Oxidation reactions

Ammonium dichromate is a strong

oxidising agent An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or " accepts"/"receives" an electron from a (called the , , or ). In other words, an oxid ...

and reacts, often violently, with any

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 commonly reducing agents include the Earth me ...

. The stronger the reducing agent, the more violent the reaction. It has also been used to promote the oxidation of alcohols and

thiol In organic chemistry, a thiol (; ), or thiol derivative, is any organosulfur compound of the form , where R represents an alkyl or other organic substituent. The functional group itself is referred to as either a thiol group or a sulfhydryl gro ...

s. Ammonium dichromate, in the presence of Mg(HSO₄)₂ and wet SiO₂ can act as a very efficient reagent for the oxidative coupling of thiols under solvent free conditions. The reactions produces reasonably good yields under relatively mild conditions. The compound is also used in the oxidation of

aliphatic In organic chemistry, hydrocarbons ( compounds composed solely of carbon and hydrogen) are divided into two classes: aromatic compounds and aliphatic compounds (; G. ''aleiphar'', fat, oil). Aliphatic compounds can be saturated, like hexane, ...

alcohols to their corresponding

aldehyde In organic chemistry, an aldehyde () is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred to as an aldehyde but can also be classified as a formyl grou ...

s and ketones in ZrCl₄/wet SiO₂ in solvent free conditions, again with relatively high yields.

Safety

Ammonium dichromate, like all chromium (VI) compounds, is highly toxic and a proven carcinogen. It is also a strong irritant.

Incidents

In sealed containers, ammonium dichromate is likely to explode if heated. In 1986, two workers were killed and 14 others injured at Diamond Shamrock Chemicals in

Ashtabula, Ohio Ashtabula ( ) is a city in Ashtabula County, Ohio, United States, and the center of the Ashtabula micropolitan area. It is located at the mouth of the Ashtabula River on Lake Erie, northeast of Cleveland. As of the 2020 census, the city ha ...

, when 2,000 lbs of ammonium dichromate exploded as it was being dried in a heater.

References

External links

{{Chromates and dichromates Ammonium compounds Dichromates Explosive chemicals Light-sensitive chemicals Oxidizing agents