Electrospray ionization (ESI) has been combined with a time-of-flight
(TOF) mass spectrometer for elemental analysis. With the use of a heat
ed-capillary interface, the instrument is shown to be stable to within
5% relative standard deviation (RSD) over a 60-min period. The ratio
between the isotopes of rubidium is measured with a precision of 0.4%
RSD for a 1-min integration time. With the addition of a supporting el
ectrolyte as a spray stabilizer and internal standard, the dynamic ran
ge is linear over at least three orders of magnitude. The extent of so
lvent-cluster fragmentation is found to be governed primarily by the v
oltage differential between the capillary and skimmer and, to a lesser
extent, by the capillary temperature. The capillary voltage also affe
cts the distribution of species among the parent and its fragment ions
for ferrocene and tetraethyllead. Under ''mild'' interface conditions
, a resolving power of 1400 is achieved for an organolead complex. A s
pectrum for a larger molecule, polypropylene glycol, is presented to s
how the versatility of the ESI-TOF instrument for both atomic and mole
cular analysis.