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Title: 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

Abstract

The sensitivity of a chemical ionization mass spectrometer (ions formed per number density of analytes) is fundamentally limited by the collision frequency between reagent ions and analytes, known as the collision limit, the ion–molecule reaction time, and the transmission efficiency of product ions to the detector. We use the response of a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) to N2O5, known to react with iodide at the collision limit, to constrain the combined effects of ion–molecule reaction time, which is strongly influenced by mixing and ion losses in the ion–molecule reaction drift tube. A mass spectrometric voltage scanning procedure elucidates the relative binding energies of the ion adducts, which influence the transmission efficiency of molecular ions through the electric fields within the vacuum chamber. Together, this information provides a critical constraint on the sensitivity of a ToF-CIMS towards a wide suite of routinely detected multifunctional organic molecules for which no calibration standards exist. We describe the scanning procedure and collision limit determination, and we show results from the application of these constraints to the measurement of organic aerosol composition at two different field locations.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1245630
Alternate Identifier(s):
OSTI ID: 1258742; OSTI ID: 1392631
Grant/Contract Number:  
SC0006867; SC0011791
Resource Type:
Published Article
Journal Name:
Atmospheric Measurement Techniques (Online)
Additional Journal Information:
Journal Name: Atmospheric Measurement Techniques (Online); Journal Volume: 9; Journal Issue: 4; Journal ID: ISSN 1867-8548
Publisher:
Copernicus GmbH
Country of Publication:
Germany
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; iodide adduct; chemical ionization; mass spectrometry; organic ion adducts

Citation Formats

Lopez-Hilfiker, Felipe D., Iyer, Siddarth, Mohr, Claudia, Lee, Ben H., D'Ambro, Emma L., Kurtén, Theo, and Thornton, Joel A. 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. Germany: N. p., 2016. Web. doi:10.5194/amt-9-1505-2016.
Lopez-Hilfiker, Felipe D., Iyer, Siddarth, Mohr, Claudia, Lee, Ben H., D'Ambro, Emma L., Kurtén, Theo, & Thornton, Joel A. 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. Germany. doi:10.5194/amt-9-1505-2016.
Lopez-Hilfiker, Felipe D., Iyer, Siddarth, Mohr, Claudia, Lee, Ben H., D'Ambro, Emma L., Kurtén, Theo, and Thornton, Joel A. Wed . "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". Germany. doi:10.5194/amt-9-1505-2016.
@article{osti_1245630,
title = {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},
author = {Lopez-Hilfiker, Felipe D. and Iyer, Siddarth and Mohr, Claudia and Lee, Ben H. and D'Ambro, Emma L. and Kurtén, Theo and Thornton, Joel A.},
abstractNote = {The sensitivity of a chemical ionization mass spectrometer (ions formed per number density of analytes) is fundamentally limited by the collision frequency between reagent ions and analytes, known as the collision limit, the ion–molecule reaction time, and the transmission efficiency of product ions to the detector. We use the response of a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) to N2O5, known to react with iodide at the collision limit, to constrain the combined effects of ion–molecule reaction time, which is strongly influenced by mixing and ion losses in the ion–molecule reaction drift tube. A mass spectrometric voltage scanning procedure elucidates the relative binding energies of the ion adducts, which influence the transmission efficiency of molecular ions through the electric fields within the vacuum chamber. Together, this information provides a critical constraint on the sensitivity of a ToF-CIMS towards a wide suite of routinely detected multifunctional organic molecules for which no calibration standards exist. We describe the scanning procedure and collision limit determination, and we show results from the application of these constraints to the measurement of organic aerosol composition at two different field locations.},
doi = {10.5194/amt-9-1505-2016},
journal = {Atmospheric Measurement Techniques (Online)},
number = 4,
volume = 9,
place = {Germany},
year = {2016},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.5194/amt-9-1505-2016

Citation Metrics:
Cited by: 16 works
Citation information provided by
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