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- W2054402752 abstract "The accuracy of pulsed high pressure mass spectrometry (PHPMS) thermochemical measurements was assessed using a ladder of charge transfer equilibria involving aromatic molecules. The ladder was constructed using ΔH° values from variable temperature measurements. For the 14 compounds in the ladder, the average agreement of the equilibrium results with spectroscopic ionisation potentials (IPs) is ± 0.6 kcal mol−1. Over the span of the ladder, from 1,2,3,5-tetramethylbenzene to C6F6, the thermochemical ladder yields a ΔIP of 40.7 kcal mol−1, compared with the spectroscopic value of 42.3 kcal mol−1 i.e., the equilibrium values cover the span of 40 kcal mol−1 with an accuracy of ±5%. The sources of error in these studies are evaluated, and some common pitfalls in PHPMS studies are discussed. These include: steady states that appear as equilibria; isomerisation; pyrolysis of ions and neutrals; slow reactions and non-reactive systems; reaction outside the ion source; vapor pressure problems; and mass coincidences. Tests and solutions for these complications are also discussed." @default.
- W2054402752 created "2016-06-24" @default.
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- W2054402752 date "1991-11-01" @default.
- W2054402752 modified "2023-10-10" @default.
- W2054402752 title "Equilibrium studies by pulsed high pressure mass spectrometry: a calibration, and some pitfalls and solutions" @default.
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- W2054402752 doi "https://doi.org/10.1016/0168-1176(91)85104-t" @default.
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