Chemiluminescence

Chemiluminescence

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When two molecules react chemically so that there is a release of energy (an exothermic reaction), that energy sometimes manifests itself not as heat but as light. This occurs because the energy excites the product molecules into which it has been funneled. A molecule in this excited state either relaxes to the ground state, with the direct emission of light, or transfers its energy to a second molecule, which becomes the light emitter. This process is referred to as chemiluminescence. The originally green, now multicolored, commercially made "light sticks" (often in the form of bracelets and necklaces) work in this way, utilizing the (exothermic) reaction of hydrogen peroxide with an oxalate ester . This oxidation reaction produces two molecules of carbon dioxide (CO₂), and the released energy is transferred to a fluorescent dye molecule, usually an anthracene derivative. Light sticks were developed by the U.S. Navy as an inconspicuous and easily shielded illumination tool for special operations forces dropped behind enemy lines. Besides their use as children's toys, they are also used extensively as a navigation aid by divers searching in muddy water.

Chemiluminescence is also found in fireflies. The male firefly uses the reaction of a luciferin substrate and the enzyme luciferase with oxygen, with adenosine triphosphate (ATP) as an energy source, to create the illumination it uses to attract a mate. Because the detection of very minute amounts of light is possible, chemiluminescence and bioluminescence have become the basis of many sensitive analytical and bioanalytical techniques or assays used to quantify particular compounds in samples. Indeed, the use of these techniques is broad enough to justify the existence of a journal devoted to them, the Journal of Bioluminescence and Chemiluminescence.

In 1669 Hennig Brand, a German alchemist, was attempting to recover, by means of intense heat, the gold he hoped was lurking in human urine. The waxy white substance that he did retrieve, which glowed green when exposed to air, was in fact elemental phosphorus.

The emission of light observed by Brand was actually chemiluminescence. The light arises from PO₂ molecules in an excited state. This excited state of PO₂ is brought about by the reaction between PO and ozone, which are both intermediates in the fundamental reaction between oxygen in air and P₄ vapor evaporating from the solid white phosphorus. It is unfortunate that the chemiluminescent glow of phosphorus gave rise to the term

"phosphorescence." Scientifically, phosphorescence is a process whereby absorbed photons are emitted at a later time, as exemplified by the glow of a watch face in the dark after its earlier exposure to light.

Luminol (3-aminophthalhydrazide) is used in a commercially available portable device called the Luminox that measures minute concentrations (parts per billion) of the pollutant nitrogen dioxide in air. Luminol is also used frequently in laboratory demonstrations of the chemiluminescence phenomenon. Luminol-mediated chemiluminescence is the result of an oxidation reaction. The oxidation proceeds in two steps, which ultimately lead to the production of the aminophthalate anion in an excited state and the elimination of water and molecular nitrogen. The formation of the strong triple bond (N≡N) is a major factor in the release of energy in the form of light.

Probably the simplest chemiluminescent reaction (and one that has been studied extensively) is the reaction between nitric oxide , NO, and ozone, O₃. The reaction (with about 10% efficiency) yields nitrogen dioxide in an excited state (NO₂*)

NO + O₃ = NO₂* + O₂

NO₂* = NO₂ + hν

The reaction was developed in the early 1970s as a specific and instantaneous method to detect nitric oxide in the exhaust of automobiles. This use of chemiluminescence rapidly led to application of the same phenomenon to monitor the presence of NO in the atmosphere. Both applications continue in use. Ozone can easily be produced by passing dry air or oxygen through an electric discharge. The ozone-containing stream and the sample to be evaluated are mixed in a dark chamber adjacent to a photomultiplier tube, and the chemiluminescence signal that is produced is amplified. These devices are capable of monitoring NO levels ranging from parts per trillion to thousands of parts per million; an individual instrument can sometimes measure concentrations extending across six orders of magnitude.

The familiar yellow glow from a natural gas or wood-burning flame is not the result of chemiluminescence, but is due to bright, red-hot particles of carbon soot. The blue, green, and other colors produced when metals are put into flame can indeed be ascribed to chemiluminescence; in these instances the luminescence is accompanied by heat production.

According to information provided by the Harbor Branch Oceanographic Institution in Ft. Pierce, Florida, more than 90 percent of organisms living in the oceans at depths from 200 to 1,000 meters (656 to 3,281 feet) use chemiluminescence for activities such as attracting prey and avoiding predators. Light from the sky is quite weak at those depths; a fish that emits a dim glow from its lower parts could become invisible from below, while a fish without this capability would appear as a dark shadow.

see also Bioluminescence; Phosphorus; Radiation.

Donald H. Stedman

Internet Resources

Chemiluminescence Home Page. "Chemiluminescence Movies." Available from <http://www.shsu.edu/~chm_tgc/chemilumdir/chemiluminescence2.html>.

Science Is Fun in the Lab of Shakhashiri. "Home Experiments: Chemiluminescence—Cool Light." Available from <http://scifun.chem.wisc.edu/homeexpts/Chemilum.html>.