Effects of salt concentration on analyte response using electrospray ionization mass spectrometry

The effect of salt concentration on analyte response using electrospray ionization mass spectrometry (ESI-MS) was measured and compared to that predicted by Enke's equilibrium partitioning model. The model predicts that analyte response will be proportional to concentration and that the response factor will decrease with increasing electrolyte concentration. The measured analyte response is proportional to concentration over four orders of magnitude when the electrolyte concentration is below 10(-3) M, as the model predicts. The concentration of excess charge ([Q]) generated by the ESI process increases significantly at 10(-3) M ionic concentration, but the response factor decreases at this concentration. Changes in shape of the spray that cause a loss of ion transmission efficiency may be the basis for the decrease in response. An increase in the analyte response factor with increasing electrolyte concentration is observed for electrolyte concentrations below 10(-3) M. An explanation for this based on the electrical double layer is proposed.