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The sensitivity of a chemical ionization mass spectrometer (ionsformed per number density of analytes) is fundamentally limited by thecollision frequency between reagent ions and analytes, known as the collisionlimit, the ion–molecule reaction time, and the transmission efficiency ofproduct ions to the detector. We use the response of a time-of-flightchemical ionization mass spectrometer (ToF-CIMS) to N<sub>2</sub>O<sub>5</sub>, known toreact with iodide at the collision limit, to constrain the combined effectsof ion–molecule reaction time, which is strongly influenced by mixing andion losses in the ion–molecule reaction drift tube. A mass spectrometricvoltage scanning procedure elucidates the relative binding energies of theion adducts, which influence the transmission efficiency of molecular ionsthrough the electric fields within the vacuum chamber. Together, thisinformation provides a critical constraint on the sensitivity of a ToF-CIMStowards a wide suite of routinely detected multifunctional organic moleculesfor which no calibration standards exist. We describe the scanningprocedure and collision limit determination, and we show results from theapplication of these constraints to the measurement of organic aerosolcomposition at two different field locations

atmospheric measurement techniques

Constraining the sensitivity of iodide adduct chemical ionization mass spectrometry to multifunctional organic molecules using the collision limit and thermodynamic stability of iodide ion adducts