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Analytical Pyrolysis. Techniques and Applications by Kent J. Voorhees

By Kent J. Voorhees

1984 (this quantity is the results of lectures awarded on the 5th foreign Symposium on Analytical Pyrolysis, held at Vail, Colorado), hardcover variation, Butterworths, London, U.K. Hardcover identify, 486 pages

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7. 46 Thus enhancement of i n t a c t molecule vaporization over pyrolysis i s achieved by reaching the higher temperatures rapidly. The term "vol a t i 1 i t y enhancement" has been used t o describe the process, where i n t a c t neut r a l molecules are desorbed, and an electron beam o r reagent gas ions a r e required t o carry out the (gas phase) ioni z a t i on. THERMAL DESORPTION OF IONS Ions can be desorbed d i r e c t l y by heating, w i t h o u t the aid of an electron beam, reagent gas, or h i g h f i e l d .

Note that most of the peaks in both the positive and negative spectra correspond to complexes between cobalt, cyanide and iodide. In the positive ion spectrum one can see CoL + (m/z 119), CoLI + (m/z 246), Co2LI + (m/z 306) and Co2l3 + (m/z 619). However, the negative ion spectrum is devoid of any species con­ taining a ligand, and all peaks can be accounted for by combinations of cobalt, cyanide and iodide. Note that peaks up to m/z 1252 have been observed. An attempt was made to decrease peaks resulting from ion molecule reactions by decreasing laser power, however there was not a significant effect on the spectrum.

During the f i r s t 10 to 20 microseconds, Na , K , and (CH3)^N ions (from a tetramethyl ammonium c h l o ­ ride sample) are emitted. The sodium decays quickly as the temperature pulse subsides, followed by K , and then the quaternary i o n , again i n the order o f decreasing bond strengths or l a t t i c e energies. All of these ions are increased i n i n t e n s i t y when the electron beam i s o n , suggesting t h a t neutral salt clusters are also desorbed, which act as precursors f o r molecular cations produced by e l e c t r o n impact, s i m i l a r to the " i n beam" methods.

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