Zero kinetic energy electron spectra of aniline are recorded and a number of ion vibrational frequencies accurately measured. The adiabatic ionization potential of aniline is found to be 62 271 ± 2 cm -1. Ab initio calculations provide insights into the bonding changes that take place in aniline upon ionization. Reasonable agreement between calculated and measured frequencies in the ground states of aniline neutral and ion is obtained.

The positive ion electrospray mass spectra of the quaternary ammonium salt herbicides paraquat and diquat are examined by on-line separation with capillary electrophoresis (CE) and by direct infusion of the analytes. The analytes are separated by CE in 7-10 min at pH 3.9 in 50% methanol-water by using several different separation buffer electrolytes. The capillary electrophoresis-electrospray ionization (CE-ES) mass spectra of paraquat and diquat consist primarily of doubly charged molecular ions, singly charged molecular ions, and singly charged deprotonated ions. The direct infusion spectra consist primarily of doubly charged molecular ions and singly charged deprotonated ions. The relative abundances of the doubly charged and deprotonated ions depend strongly on the presence or absence of ammonium ion in the CE separation buffer or the direct infusion solution. A deprotonation mechanism is proposed in which the free base ammonia is the deprotonating agent in the desolvating charged droplets or in the gas phase. The analytical potential of the CE-ES electrospray approach for environmental analyses is evaluated in terms of the precision of replicate injections, linear concentration range, and estimated detection limit.

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The negative ion electrospray mass spectra of six bromo- and chloroacetic acids were measured using two different electrospray interfaces and single quadrupole and bench-top time-of-flight mass spectrometers. With each acid at 50 microg/mL in aqueous methanol at pH 10, the anions observed included deprotonated molecules, adducts, and fragment ions. With each acid at 100 ng/mL in aqueous acetonitrile at pH 10, mainly deprotonated molecules are observed. The exact m/z measuring capability of the time-of-flight mass spectrometer was evaluated to assess the potential for the determination of the individual acids in mixtures without an on-line separation. Mean measurement errors were nearly always less than +/- 9 ppm and the majority were less than +/- 5 ppm. Potential interferences by substances having similar exact masses and the ability to form anions in aqueous solutions were evaluated. The estimated detection limits of the five regulated haloacetic acids in drinking water, without a sample preconcentration step, are in the range of 24-86 ng/mL, which is within about a factor of 10 of the levels required for routine monitoring of the acids. Actual drinking water samples were not analyzed pending the development of slightly more sensitive techniques and quantitative analytical procedures.