By J.H.U. Brown, J.F. Dickson
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Extra info for Advances in Biomedical Engineering. Volume 4
M e t a s t a b l e ions, doubly or triply charged ions, and ions formed by addition m a y be present in E I spectra. M e t a s t a b l e ions (designated as m*) have half-lives on t h e order of a microsecond; this is sufficient for their removal from the source, b u t m a n y cleave during travel to the detector. Some cleavage also occurs in t h e source, so t h a t three types of ion products are observed. If t h e initial ion m x cleaves to yield ion m 2 and a neutral fragment, experimental observations will show both ions m x and m 2 in t h e usual way, and in addition a diffuse peak (usually corresponding to a nonintegral mass) will be observed.
T h e y result from w h a t is now generally termed C I reactions involving the neutral molecule M and fragment ions present in relatively high con+ centration in t h e source. Protonation, leading to M H , is not infrequent, + and acetyl ( C H 3 C O ) addition leading to (M + 43) is often observed in E I spectra of acetate esters. All E I spectra of T M S ethers and esters contain ions a t 73 a m u due to t h e T M S ion; this in t u r n m a y add t o + M to form (M -f 7 3 ) . T h i s reaction is of considerable practical interest, since T M S derivatives are widely used in G C - M S studies.
T h e y are found a t t h e expected m/e values, and m a y not be recognized immediately in low-resolution GAS-PHASE ANALYTICAL METHODS 29 spectra. T r i p l y charged organic ions are extremely rare, so t h a t in p r a c tice t h e only t y p e of multiply charged ion likely to be encountered is doubly charged. , ( C 4 H 2 0 2 ) derived from maleic a n h y d r i d e ] . E I spectra frequently contain small peaks a t m/e values greater t h a n M . T h e y result from w h a t is now generally termed C I reactions involving the neutral molecule M and fragment ions present in relatively high con+ centration in t h e source.