ABSTRACT
The use of fire, being the first chemical reaction controlled by humans, is an important marker for the beginning of civilization. The thermal and visible radia tion of fire was used to great benefit for warmth, cooking, nighttime visibility, and warding off predators. For millennia, our ancestors must have marveled at the luminescence and other unique properties of fire; indeed the Greeks consid ered fire one of four basic elements comprising all matter. Chemiluminescent emissions from flames served as one of the first analytical tools used for qualita tive identification of specific elements, and flame emission spectrometry is still one of the most sensitive and selective means for quantification of alkali metals and alkaline earths. The discovery of the ability to produce gas-phase chemilumi nescence without the assistance of the thermal energy provided by flames led to many new analytical applications. This chapter focuses primarily on the analytical utility of these so-called “ cold” chemiluminescent reactions, where reactants are formed and molecular excitation is achieved without the assistance of the thermal energy associated with a flame.
