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Mass spectrometry chemi-ionization

Intermediate-energy ionization reduces number of fragment species and enhances sensitivity. Structural differences between similar samples are readily distinguished using this technique.

Laudenslager, J. B.↗

Variable fragmentation mass spectrometry using chemi-ionization

A description is given of experiments which provide a verification of three features of Penning ionization mass spectrometry. One of these features is related to the ability to simplify a molecular fragmentation pattern and to intensify the molecular ion peak. Another feature is concerned with the ability to identify uniquely geometric isomers which are indistinguishable using high-energy electron impact methods. The third feature involves the ability to identify components in a mixture, which cannot be discerned using electron impact or chemical ionization methods alone. The investigation shows that Penning ionization is an efficient soft ionization technique which can be used to simplify mass spectra of pure compounds as well as mixtures.

Laudenslager, J. B.↗

An ionic mechanism of carbon formation in flames

The formation of incipient carbon in flames can be described by a series of elementary reactions in which the precursor of soot is the ion C3H3+, and the major building block is acetylene, polyacetylenes, or other hydrocarbon fragments which are present in large concentrations. The precursor ion is produced by nonequilibrium chemi-ionization reactions, e.g., CH asterisk plus C2H2 yields C3H3+ plus e or CH asterisk plus O yields CHO+ plus e. The CHO+ rapidly becomes C3H3+ through a series of ion-molecule reactions. The chemi-ion then adds acetylene in a series of very rapid ion-molecule reactions producing larger and larger ions. Ions isomerize very rapidly to produce aromatic structures overcoming one of the major problems with neutral species mechanisms: how to form the first carbon ring. As the ions grow, their recombination rate coefficients with electrons increase so that the larger ions are removed by dissociative recombination. These neutral species now continue to grow by the addition of more acetylene producing even larger neutral species. With increasing size, the rate coefficient of electron attachment also increases causing the reaction to become important, depending upon the temperature. Appreciable concentrations of negative ions shift the ion removal process to dissociative ion-ion recombination, which is orders of magnitude slower than ion-electron recombination. As the neutral species continue to grow by the addition of acetylene, they gradually take on the aspect of particles, i.e., the bulk properties of the substance CxHy dominate over the chemical properties. This change is gradual and there is no distinct size at which a large molecule becomes a particle. Evidence will be presented supporting the above mechanism. All of the ions proposed in the mechanism have been observed by mass spectrometric analysis, their concentrations measured, and their rates of reaction in the flame environment determined to be adequate to account for the observed rate of formation of carbon.

Calcote, H. F.↗