Photochemistry

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Photochemistry, a sub-discipline of chemistry, is the study of the interactions between atoms, small molecules, and light (or electromagnetic radiation).^[1]

Like most scientific disciplines, photochemistry utilizes the SI or metric measurement system. Important units and constants that show up regularly include the meter (and variants such as centimeter, millimeter, micrometer, nanometer, etc.), seconds, hertz, joules, moles, the gas constant R, and the Boltzmann constant. These units and constants are also integral to the field of physical chemistry.

The first law of photochemistry, known as the Grotthuss-Draper law (for chemists Theodor Grotthuss and John W. Draper), states that light must be absorbed by a chemical substance in order for a photochemical reaction to take place.

The second law of photochemistry, the Stark-Einstein law, states that for each photon of light absorbed by a chemical system, only one molecule is activated for a photochemical reaction. This is also known as the photoequivalence law and was derived by Albert Einstein at the time when the quantum (photon) theory of light was being developed.

Photochemistry may also be introduced to laymen as a reaction that proceeds with the absorption of light. Normally a reaction (not just a photochemical reaction) occurs when a molecule gains the necessary activation energy to undergo change. A simple example can be the combustion of gasoline (a hydrocarbon) into carbon dioxide and water. This is a chemical reaction where one or more molecules/chemical species are converted into others. For this reaction to take place activation energy should be supplied. The activation energy is provided in the form of heat or a spark. In case of photochemical reactions light provides the activation energy.

The absorption of a photon of light by a reactant molecule may also permit a reaction to occur not just by bringing the molecule to the necessary activation energy, but also by changing the symmetry of the molecule's electronic configuration, enabling an otherwise inaccessible reaction path, as described by the Woodward-Hoffmann selection rules. A 2+2 cycloaddition reaction is one example of a pericyclic reaction that can be analyzed using these rules or by the related frontier molecular orbital theory.

Main concepts

The pillars of photochemistry are UV/VIS spectroscopy, photochemical reactions in organic chemistry and photosynthesis in biochemistry.

Regions of the electromagnetic spectrum

The electromagnetic spectrum is broad, however, a photochemist will find themselves working with several key regions. Some of the most widely used sections of the electromagnetic spectrum include:

• Visible Light: 400–700 nm wavelengths
• Ultraviolet: 100–400 nm wavelengths
• Near Infrared: 700–1000 nm wavelengths
• Far infrared: 15–1000 µm wavelengths

Applications

There are important processes based in the photochemistry principles. One case is photosynthesis, which some plants use light to create glucose in their chloroplasts to contribute to cell metabolism. The glucose is used by the plant's mitochondria to produce Adenosine Triphosphate. Medicine bottles are made with darkened glass to prevent the medicine itself from reacting chemically with light. In fireflies, an enzyme in the abdomen works to produce bioluminescence. The mercaptans or thiols produced by Chevron Phillips Chemical Company are produced by photochemical addition of hydrogen sulfide (H₂S) to alfa olefins. Among their many uses as a chemical reagent these mercaptans are used to provide a distinctive odor (an odorant) to otherwise odorless natural gas.

See also

• Photoelectrochemical cell
• Photochemical Logic Gates
• Photochemical and Photobiological Sciences

References

1. ↑ International Union of Pure and Applied Chemistry. "photochemistry". Compendium of Chemical Terminology Internet edition.

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