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.
Photochemical reactions involve electronic reorganization initiated by electromagnetic
radiation. The reactions are several orders of magnitude faster than thermal reactions;
reactions as fast as 10-9 seconds and associated processes as fast as 10-15 secs are often
observed.
[edit] Spectral regions
Photochemists typically work in only a few sections of the electromagnetic spectrum. Some
of the most widely used sections, and their wavelengths, are the following:
Ultraviolet: 100–400 nm
Visible Light: 400–700 nm
Near infrared: 700–2500 nm
Mid infrared: 2500 - 25000 nm
Far infrared: 25–1000 µm
[edit] 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. Many
polymerizations are started by photoinitiatiors which decompose upon absorbing light to
produce the necessary free radicals for Radical polymerization Some photochemical
pathways allow synthesis of few classes of chemical compounds, such as cyclobutanes,
stereospecific compounds, which cannot be easily (in some cases almost impossible)
prepared using conventional organic synthesis (aka dark/thermal chemistry).
[edit] See also
Photoelectrochemical cell
Photochemical logic gates
Photochemical and Photobiological Sciences
[edit] References
1. ^ International Union of Pure and Applied Chemistry. "photochemistry".
Compendium of Chemical Terminology Internet edition.
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