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Title: Quantitative isotopic measurements of gas-phase alcohol mixtures using a broadly tunable swept external cavity quantum cascade laser

Abstract

A swept-ECQCL is used for broadband IR spectroscopy of isotopic mixtures of CH3OH, CH3OD, CH3CH2OH, and CH3CH2OD in a static gas cell over a wavelength range of 9.5 to 10.4 µm. A weighted least squares fitting approach with quantitative library spectra illustrates that significant spectral congestion does not negatively impact the ability for in situ quantification of large isotopic species in a mixture. The noise equivalent concentrations for CH3OH, CH3OD, CH3CH2OH, and CH3CH2OD are 19 ppbv x m, 28 ppbv x m, 450 ppbv x m, and 330 ppbv x m respectively for a 50 second integration time. Based on the observed NECs, isotopic precisions of 0.07‰ and 0.79‰ for a 50 s integration time are calculated for measurements of the [MeOD]/[MeOH] and [EtOD]/[EtOH] isotope ratios , respectively, for the species concentrations in the gas cell.

Authors:
ORCiD logo;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1373833
Report Number(s):
PNNL-SA-123788
Journal ID: ISSN 0003-2654; ANALAO; DN2001000
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Analyst
Additional Journal Information:
Journal Volume: 142; Journal Issue: 13; Journal ID: ISSN 0003-2654
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Brumfield, B. E., and Phillips, M. C. Quantitative isotopic measurements of gas-phase alcohol mixtures using a broadly tunable swept external cavity quantum cascade laser. United States: N. p., 2017. Web. doi:10.1039/c7an00223h.
Brumfield, B. E., & Phillips, M. C. Quantitative isotopic measurements of gas-phase alcohol mixtures using a broadly tunable swept external cavity quantum cascade laser. United States. doi:10.1039/c7an00223h.
Brumfield, B. E., and Phillips, M. C. Sun . "Quantitative isotopic measurements of gas-phase alcohol mixtures using a broadly tunable swept external cavity quantum cascade laser". United States. doi:10.1039/c7an00223h.
@article{osti_1373833,
title = {Quantitative isotopic measurements of gas-phase alcohol mixtures using a broadly tunable swept external cavity quantum cascade laser},
author = {Brumfield, B. E. and Phillips, M. C.},
abstractNote = {A swept-ECQCL is used for broadband IR spectroscopy of isotopic mixtures of CH3OH, CH3OD, CH3CH2OH, and CH3CH2OD in a static gas cell over a wavelength range of 9.5 to 10.4 µm. A weighted least squares fitting approach with quantitative library spectra illustrates that significant spectral congestion does not negatively impact the ability for in situ quantification of large isotopic species in a mixture. The noise equivalent concentrations for CH3OH, CH3OD, CH3CH2OH, and CH3CH2OD are 19 ppbv x m, 28 ppbv x m, 450 ppbv x m, and 330 ppbv x m respectively for a 50 second integration time. Based on the observed NECs, isotopic precisions of 0.07‰ and 0.79‰ for a 50 s integration time are calculated for measurements of the [MeOD]/[MeOH] and [EtOD]/[EtOH] isotope ratios , respectively, for the species concentrations in the gas cell.},
doi = {10.1039/c7an00223h},
journal = {Analyst},
issn = {0003-2654},
number = 13,
volume = 142,
place = {United States},
year = {2017},
month = {1}
}

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