Flame electronically excited atoms

What Really Does Happen to Electronically Excited Atoms in Flames ... 

In recent years numerous experiments have been reported on the fluorescence and energy transfer processes of electronically excited atoms. However, for flame studies the rates of many possible collision processes are not well known, and so the fate of these excited atoms is unclear. An interesting example concerns the ionization of alkali metals in flames. When the measured ionization rates are interpreted using simple kinetic theory, the derived ionization cross sections are orders of magnitude larger than gas kinetic (1,2,3). More detailed analyses (4,5) have yielded much lower ionization cross sections by invoking participation of highly excited electronic states. Evaluation of these models has been hampered by the lack of data on the ionization rate as a function of initial state for the alkali metals. 

Smyth, K. C. et al. What really does happen to electronically excited atoms in flames in Laser Probes for Combustion Chemistry (ed. Crosley, D. R.), ACS Symp. Ser. 134, p. 175, Washington, D.C., Amer. Chem. Soc. 1980... 

Atomic spectroscopy can be divided into several broad classes based on the nature of the means of exciting the sample. One of these classes is generally known as atomic emission spectroscopy, in which excitation is thermally induced by exposing the sample to very high electric fields. Another class is known as flame emission spectroscopy or flame photometry, in which excitation is thermally induced by exposing the sample to a high-temperature flame. These methods differ from atomic absorption spectroscopy, in which the absorption of light from a radiation source by the atom is observed rather than the emission from the electronically excited atom. 

In flame emission spectroscopy, the concentration of electronically excited atoms in the cooler, outer part of the flame is lower than in the warmer, central part of the flame. Emission from the central region is absorbed in the outer region. This selfabsorption increases with increasing concentration of analyte and gives nonlinear calibration curves. In a plasma, the temperature is more uniform, and self-absorption is not nearly so important. Table 20-4 states that plasma emission calibration curves are linear over five orders of magnitude compared with just two orders of magnitude for flames and furnaces. 

The electronically excited atom decays by fluorescence leading to a visible flame, with a color typical of the alkali metal used. 

All the alkali metals have characteristic flame colorations due to the ready excitation of the outermost electron, and this is the basis of their analytical determination by flame photometry or atomic absorption spectroscopy. The colours and principal emission (or absorption) wavelengths, X, are given below but it should be noted that these lines do not all refer to the same transition for example, the Na D-line doublet at 589.0, 589.6 nm arises from the 3s — 3p transition in Na atoms formed by reduction of Na+ in the flame, whereas the red line for lithium is associated with the short-lived species LiOH. 

Flames are also plasmas, characterized by electron densities of about 10 /cm and electron energies of about 0.5 eV. Many excited species are present in the flame, namely free radicals, ions, excited atoms and molecules, and electrons [43]. Excited species that have been observed include O, OH, NH, NO, and CH [44]. 

Emission of electromagnetic radiation in the visible and ultraviolet regions of the spectrum by atoms after electronic excitation in flames. 

Emission spectroscopy utilizes the characteristic line emission from atoms as their electrons drop from the excited to the ground state. The earliest version of emission spectroscopy as applied to chemistry was the flame test, where samples of elements placed in a Bunsen burner will change the flame to different colors (sodium turns the flame yellow calcium turns it red, copper turns it green). The modem version of emission spectroscopy for the chemistry laboratory is ICP-AES. In this technique rocks are dissolved in acid or vaporized with a laser, and the sample liquid or gas is mixed with argon gas and turned into a plasma (ionized gas) by a radio frequency generator. The excited atoms in the plasma emit characteristic energies that are measured either sequentially with a monochromator and photomultiplier tube, or simultaneously with a polychrometer. The technique can analyze 60 elements in minutes. 

This method is based on the emission of light by atoms returning from an electronically excited to the ground state. As in atomic absorption spectrometry, the technique involves introduction of the sample into a hot flame, where at least part of the molecules or atoms are thermally stimulated. The radiation emitted when the excited species returns to the ground state is passed through a monochromator. The emission lines characteristic of the element to be determined can be isolated and their intensities quantitatively correlated with the concentration of the solution. 

Possible applications of laser enhanced ionization in flame diagnostics are 1. simultaneous observation of ionization and fluorescence signals from various levels might provide more information on the sequence of processes leading to and from the ionization continuum 2. the measurement of ion mobilities, relating to cross-sections for elastic collisions between ions and flame particles 3. measurement of ionization rate constants relating to cross-sections for inelastic collisions between excited atoms and other flame particles 4. measurement of recombination rate constants, relating to cross-sections for inelastic collisions between ions, electrons and neutrals. 

In Chapter 1, section 7, it was explained that very precise overlap of atomic absorption and emission profiles is required to obtain sensitive absorbance measurements. Absorption spectra of atoms at flame temperatures are much simpler than the emission spectra emitted by hollow cathode lamps. The possible transitions corresponding to electronic excitation of an atom may be shown as vertical lines on an energy level diagram, in which the vertical displacement... 

Several diatomic species are electronically excited in the reaction of O atoms with C2H2, and their spectra have been observed in flame [169, 170],... 

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