CHEMICAL

IONIZATION(CIMS)

Chemical ionization
Most modern mass spectrometers are designed so that
electron-impact ionization and chemical ionization can be
carried out interchangeably. Such sources arc called EI-CI
sources. In chemical ionization, gaseous atoms of the sample
(from either a batch inlet or a heated probe) are ionized by
collision with ions produced by electron bombardment of an
excess of a reagent gas. Usually, positive ions are used, but
nagative ion chemical ionization is occasionally used with
analytes that contain very electronegative atoms. Chemical
ionization is probably the second-most common procedure
for producing ions for mass spectrometry.

 chemical ionization experiments, it is

necessary to modify the electron
beam ionization area shown in
Figure by adding vacuum pump
capacity and by reducing the width
of the slit to the mass analyzer.
These measures allow a reagent
pressure of about 1 torr to be
maintained in the ionization area
while maintaining the pressure in the
analyzer below 10-5 torr. With these
changes, a gaseous reagent is
introduced into the ionization region
in an amount such that the
concentration ratio of reagent to
sample is 103 to 104. Because of this
large concentration difference, the
electron beam reacts nearly
exclusively with reagent molecules.

 One of the most common reagents is methane, which

reacts with high-energy electrons to give several ions such
as CH4+, CH3+ and CH2+. The first two predominate and
represent about 90% of the reaction products. These ions
react rapidly with additional methane molecules as follows:
CH4+ + CH4 --> CH5++ CH3
CH3++ CH4 --> C2H5+ + H2
Generally, collisions between the analyte molecule MH and
CH5+; or C2H5+are highly reactive and involve proton or
hydride transfer. For example,
CH5+ + MH --> MH2+ + CH4 proton transfer
C2H5+ + MH --> MH2+ + C2H4 proton transfer
C2H5+ + MH --> M + + C2H6 hydride transfer

 Note that proton-transfer reactions give the (MH + 1) +

ion whereas the hydride transfer produces an ion with a
mass one less than the analyte, or the (MH -1) + ion.
With some compounds, an (MH + 2) + peak is also
produced from transfer of a C 2H 5+ ion to the analyte. A
variety of other reagents including propane, isobutane,
and ammonia, are used for chemical ionization. Each
produces a somewhat different spectrum with a given
analyte.

 Figure 20-2 contrasts the chemical ionization and

electron-impact spectra for I-decanol. The
electronimpact spectrum (Figure 20-2a) shows evidence
for rapid and extensive fragmentation of the molecular
ion. Thus, no detectable peaks are observed ahove
mass 112, which corresponds to the ion C 8H 16+

 The base peak is provided by the ion C 3H 5+ at mass 41.

Other peaks for C 3 species are grouped around the base
peak. A similar series of peaks, found at 14, 28, and 42
mass units greater, correspond to ions with one, two.
and three additional CH2 groups.

 Relative to the electron-impact spectrum. The chemical

ionization spectrum shown in Figure 20-2h is simple indeed.
consisting of the (M - 1) + peak. a hase peak corresponding to a
molecular ion that has lost an OH group. and a series of peaks
differing from one another by 14 mass units. As in the electronimpact spectrum. these peaks arise from ions formed by
cleavage of adjacent carbon-carbon bonds. As we have just
noted. chemical ionization spectra generally contain welldefined (M + 1) + or (M - 1) -peaks resulting from the addition or
abstraction of a proton in the presence of the reagent ion.

 Principles of Instrumental Analysis BY Douglas A.

Skoog,F James Holler,Stanley R. Crouch, P-557-558