Sensitive Mass Spectrometer for Time-Resolved Gas-Phase Chemistry Studies at High Pressures
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Here, we report the construction of a new experimental apparatus for direct time-resolved probing of high-pressure gas-phase chemical reactions by photoionization mass spectrometry. The apparatus uses a laser photolysis slow-flow reactor, capable of operating at P = 0.3 — 100 bar and T = 300 — 1000 K. In this report, we initiate reactions in homogeneous gas mixtures by the photolysis of appropriate radical precursor using laser pulses at repetition rates of 1 — 10 Hz. The reacting mixture is continuously sampled into a vacuum chamber, ionized by VUV photons from laboratory-based discharge lamps or from a synchrotron beamline, and analyzed by a custom-designed mass spectrometer. Soft near-threshold ionization by tunable synchrotron radiation enables spectroscopic quantification of many key intermediates and products of chemical reactions. A novel ionization scheme in the high-density region of the sample gas jet increases the experimental sensitivity 100-fold, compared with existing instruments, without compromising mass resolution. A 40-kHz pulsed reflectron time-of-flight mass spectrometer in the orthogonal acceleration geometry achieves simultaneous detection of all ionized species with 25-μs time resolution. We show the power of this apparatus by investigating the ethyl radical oxidation reaction using very dilute (<1012 molecules • cm-3) ethyl concentrations at pressures up to 25 bar.
- Research Organization:
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- Grant/Contract Number:
- AC04-94AL85000; NA0003525; AC02-05CH11231
- OSTI ID:
- 1574695
- Report Number(s):
- SAND-2019-10135J; 678901; TRN: US2001320
- Journal Information:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 123, Issue 50; ISSN 1089-5639
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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