Ammonium dichromate is used in demonstrations of tabletop "volcanoes".[4] However, this demonstration has become unpopular due to concerns about the compound's carcinogenic nature. It has been used in pyrotechnics and in the early days of photography. It is also used in holography.
The (NH4)2Cr2O7 crystal (C2/c, z = 4) contains a single type of ammonium ion, at sites of symmetry C1(2,3). Each NH+4 centre is surrounded irregularly by eight oxygen atoms at N−O distances ranging from ca. 2.83 to 3.17Å, typical of hydrogen bonds.[6]
Uses
Pyrotechnics
It has been used in pyrotechnics as part of a conversion coating method for magnesium powder. It may also be used when a dichromate compatible with ammonium perchlorate (NH4ClO4) is needed; potassium dichromate (K2Cr2O7) is commonly used, but reacts with ammonium perchlorate over time to form potassium perchlorate and ammonium dichromate. This mixture occupies 5% more volume than the original K2Cr2O7 + NH4ClO4 mixture and leads to eventual cracking of stars and consolidated compositions.[7]
It was used in a composition in the early 20th century in a combination firework called a serpent's nest to produce the green grass (or nest) from which a separately made pharaoh's serpent or black snake composition emerged.[8]
Holography
In holography, it has been used since the 1960s to sensitize dichromated gelatins or other materials on which to expose a hologram. This method has the advantage of being low cost, using relatively common materials, and only requiring isopropyl alcohol for development, but the gelatins created with these methods are sensitive to humidty. Potassium dichromate is also used for this purpose.[9][10][11]
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.[13]
Reactions
Thermal decomposition
Ammonium dichromate decompositionA few drops of ethanol are added to a small pile of ammonium dichromate (NH4)2Cr2O7 and ignited. Sparks are emitted and an ash-like product is formed. The phenomenon resembles the eruption of a volcano. The reaction starts at 180°C (356°F), becoming self-sustaining at approximately 225°C (437°F).[citation needed][14]
The thermal decomposition of ammonium dichromate can be demonstrated by igniting a pile of the salt, which initiates the following exothermic conversion:[15]
(NH4)2Cr2O7(s) → Cr2O3(s) + N2(g) + 4 H2O(g)
(ΔH = −429.1±3kcal/mol)
Like ammonium nitrate, it is thermodynamically unstable.[16][17] Its decomposition reaction produces voluminous dark green powdered chromium(III) oxide. Not all of the ammonium dichromate decomposes in this reaction. When the green powder is added to water a yellow/orange solution is obtained from left over ammonium dichromate.[citation needed]
Observations obtained using 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 (NH4)2Cr2O7 crystals as a consequence of the onset of decomposition can be ascribed to the dissociative loss of ammonia accompanied by progressive anion condensation to Cr3O2−10, Cr4O2−13, etc., ultimately yielding CrO3. The CrO3 has been identified as a possible molten intermediate participating in (NH4)2Cr2O7 decomposition.[18]
Oxidation
Ammonium dichromate is a strong oxidising agent and reacts, often violently, with many reducing agents. In general, the stronger the reducing agent, the more violent the reaction.[16]
It has also been used to promote the oxidation of alcohols and thiols. 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 produce reasonably good yields under relatively mild conditions.[19] The compound is also used in the oxidation of aliphatic alcohols to their corresponding aldehydes and ketones in ZrCl4/wet SiO2 in solvent free conditions, again with relatively high yields.[20]
Safety
Ammonium dichromate is highly acutely toxic. It ranges from having a strong irritant effect on skin to causing severe chemical burns and skin corrosion. Inhalation of dust may be fatal. Ingestion results in death from multi-organ failure if not treated quickly.[21][22]Ascorbic acid may be a useful early treatment.[23]
Like many hexavalent chromium compounds it is a proven carcinogen, mutagen, and reproductive toxin.[1]
Incidents
In sealed containers, ammonium dichromate is likely to explode if heated.[16] In 1986, two workers were killed and 14 others injured at Diamond Shamrock Chemicals in Ashtabula, Ohio, when 2,000lb (910kg) of ammonium dichromate exploded as it was being dried in a heater.[24]
12Lewis, Richard J. (2007). Hawley's condensed chemical dictionary (15thed.). Hoboken (N.J.): Wiley-Interscience. ISBN978-0-471-76865-4.
↑Keresztury, G.; Knop, O. (1982). "Infrared spectra of the ammonium ion in crystals. Part XII. Low-temperature transitions in ammonium dichromate, (NH4)2Cr2O7". Can. J. Chem.60 (15): 1972–1976. doi:10.1139/v82-277.
↑Izzo, Attilio (1950). Pirotecnia E Fuochi Artificialli - Manuale pratico e ricettario per chi fabbrica fuochi artificiali e chi vende materie prime per usi pirotecnici[Pyrotechnics and Fireworks - Practical manual and recipe book for fireworks makers and sellers of raw materials for pyrotechnic uses](PDF) (in Italian). Milan, Italy: Ulricho Hoeppi. pp.173–4, 230. Nido di serpenti (serpenti erba). - Sono giuochi fatti come al solito a forma di cono, avente la base di circa cm 4, contenenti una composizione che quando brucia produce come una zona erbosa da cui emergono i serpenti di faraone. Quando il cono è pieno di composizione simulante il verde della campagna, si aggiunge nel centro (alla base) la compo sizione polverizzata di solfocianuro di mercurio.[Snake Nest (grass snakes). - These are toy (fireworks) usually made in the shape of a cone, with a base of about 4 cm, containing a composition that, when burned, creates a grass-like area from which pharaoh snakes emerge. Once the cone is filled with the grass-simulating composition (given on page 230 as 50% ammonium dichromate, 25% potassium nitrate, and 25% dextrin), a powdered composition of mercury thiocyanide is added to the center (at the base).]
↑Olivares-Pérez, A.; Ibarra-Torres, J.C.; Ortiz-Gutiérrez, M.; Pérez-Cortés, M.; Fuentes-Tapia, I. (December 2005). "Rosin (colophony) holograms sensitized with ammonium dichromate". Optical Materials. 27 (12): 1825–1831. doi:10.1016/j.optmat.2004.07.018.
↑Ponce de León, Yenisey; Montaño Flores, Beatriz; Ortiz-Gutiérrez, Mauricio; Ibarra Torres, Juan Carlos; Pérez Cortés, Mario (September 2021). "Real-time characterization of gelatin doped with potassium dichromate as a photosensitive material". Optik. 242 (167310) 167310. Bibcode:2021Optik.24267310P. doi:10.1016/j.ijleo.2021.167310.
↑Patnaik, Pradyot (2003). Handbook of inorganic chemicals. New York: McGraw-Hill. ISBN0-07-049439-8.
↑Havard, J. M.; Shim, S. Y.; Fr; eacute; chet, J. M. (1999). "Design of Photoresists with Reduced Environmental Impact. 1. Water-Soluble Resists Based on Photo-Cross-Linking of Poly(vinyl alcohol)". Chem. Mater.11 (3): 719–725. doi:10.1021/cm980603y.
↑Planned and performed by Marina Stojanovska, Miha Bukleski and Vladimir Petruševski, Department of Chemistry, FNSM, Ss. Cyril and Methodius University, Skopje, Macedonia.