Abstract

The ion formation in both electrohydrodynamic (EH) and electrospray (ES) mass spectrometry (MS) is based on the electrohydrodynamic disintegration of sample solutions which are passed through a capillary biased at high potential. Vacuum is applied in EH and atmospheric pressure in ES MS. For glycerol applied as solvent in EH MS optical studies of its disintegration behavior revealed a change from axial spray modes to a rim emission mode in vacuum and a change from axial spray modes to a droplet ejection mode at atmospheric pressure conditions with increasing potential. EH MS investigations of the ion emission from only one or a few emission sites at the rim of the capillary showed a pulsed ion emission whose frequency increased with applied potential. The pulsed ion emission is attributed to an imbalance between the supply and loss of liquid at an emission site. By lowering the surface tension of glycerol with dodecyl sulfate sodium salt an increase of mass spectral ion intensity by more than one order of magnitude could be observed.

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