TY - JOUR

T1 - Knudsen Effusion Mass Spectrometry: Current and Future Approaches

AU - Jacobson, Nathan

AU - Colle, Jean-Yves

AU - Столярова, Валентина Леонидовна

AU - Markus, Torsten

AU - Nuta, Ioana

N1 - Jacobson N., Colle J.-Y., Stolyarova V.L., Markus T., Nuta I. Knudsen Effusion Mass Spectrometry: Current and Future Approaches. // Rapid Communications in Mass Spectrometry. 2024. V. 38. P. e9744. doi: 10.1002/rcm.9744

PY - 2024/7/30

Y1 - 2024/7/30

N2 - Rationale: Knudsen effusion mass spectrometry (KEMS) has been a powerful tool in physical chemistry since 1954. There are many excellent reviews of the basic principles of KEMS in the literature. In this review, we focus on the current status and potential growth areas for this instrumental technique. Methods: We discuss (1) instrumentation, (2) measurement techniques, and (3) selected novel applications of the technique. Improved heating methods and temperature measurement allow for better control of the Knudsen cell effusive source. Accurate computer models of the effusive beam and its introduction to the ionizer allow optimization of such parameters as sensitivity and removal of background signals. Computer models of the ionizer allow for optimized sensitivity and resolution. Additionally, data acquisition systems specifically tailored to a KEMS system permit improved quantity and quality of data. Results: KEMS is traditionally utilized for thermodynamic measurements of pure compounds and solutions. These measurements can now be strengthened using first principles and model-based computational thermochemistry. First principles can be used to calculate accurate Gibbs energy functions (gefs) for improving third law calculations. Calculated enthalpies of formation and dissociation energies from ab initio methods can be compared to those measured using KEMS. For model-based thermochemistry, solution parameters can be derived from measured thermochemical data on metallic and nonmetallic solutions. Beyond thermodynamic measurements, KEMS has been used for many specific applications. We select examples for discussion: measurements of phase changes, measurement/control of low-oxygen potential systems, thermochemistry of ultrahigh-temperature ceramics, geological applications, nuclear applications, applications to organic and organometallic compounds, and thermochemistry of functional room temperature materials, such as lithium ion batteries. Conclusions: We present an overview of the current status of KEMS and discuss ideas for improving KEMS instrumentation and measurements. We discuss selected KEMS studies to illustrate future directions of KEMS.

AB - Rationale: Knudsen effusion mass spectrometry (KEMS) has been a powerful tool in physical chemistry since 1954. There are many excellent reviews of the basic principles of KEMS in the literature. In this review, we focus on the current status and potential growth areas for this instrumental technique. Methods: We discuss (1) instrumentation, (2) measurement techniques, and (3) selected novel applications of the technique. Improved heating methods and temperature measurement allow for better control of the Knudsen cell effusive source. Accurate computer models of the effusive beam and its introduction to the ionizer allow optimization of such parameters as sensitivity and removal of background signals. Computer models of the ionizer allow for optimized sensitivity and resolution. Additionally, data acquisition systems specifically tailored to a KEMS system permit improved quantity and quality of data. Results: KEMS is traditionally utilized for thermodynamic measurements of pure compounds and solutions. These measurements can now be strengthened using first principles and model-based computational thermochemistry. First principles can be used to calculate accurate Gibbs energy functions (gefs) for improving third law calculations. Calculated enthalpies of formation and dissociation energies from ab initio methods can be compared to those measured using KEMS. For model-based thermochemistry, solution parameters can be derived from measured thermochemical data on metallic and nonmetallic solutions. Beyond thermodynamic measurements, KEMS has been used for many specific applications. We select examples for discussion: measurements of phase changes, measurement/control of low-oxygen potential systems, thermochemistry of ultrahigh-temperature ceramics, geological applications, nuclear applications, applications to organic and organometallic compounds, and thermochemistry of functional room temperature materials, such as lithium ion batteries. Conclusions: We present an overview of the current status of KEMS and discuss ideas for improving KEMS instrumentation and measurements. We discuss selected KEMS studies to illustrate future directions of KEMS.

UR - https://www.mendeley.com/catalogue/6534b4c1-ef2f-3671-a2a1-0b964debcbe7/

U2 - 10.1002/rcm.9744

DO - 10.1002/rcm.9744

M3 - Article

VL - 38

JO - Rapid Communications in Mass Spectrometry

JF - Rapid Communications in Mass Spectrometry

SN - 0951-4198

IS - 14

M1 - e9744

ER -