Absolute Band Intensity of the Iodine Monochloride Fundamental Mode for Infrared Sensing and Quantitative Analysis

Hughey, Kendall D.; Bradley, Ashley M.; Tonkyn, Russell G.; Felmy, Heather M.; Blake, Thomas A.; Bryan, Samuel A.; Johnson, Timothy J.; Lines, Amanda M.

doi:10.1021/acs.jpca.0c07353

Absolute Band Intensity of the Iodine Monochloride Fundamental Mode for Infrared Sensing and Quantitative Analysis

Journal Article · Thu Nov 05 00:00:00 UTC 2020 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.0c07353· OSTI ID:1725828

Hughey, Kendall D. ^[1]; Bradley, Ashley M. ^[1]; Tonkyn, Russell G. ^[1]; Felmy, Heather M. ^[1]; Blake, Thomas A. ^[1]; ^[1]; ^[1]; Lines, Amanda M. ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Iodine monochloride (ICl) is a gaseous off-product of molten salt reactors; monitoring this heteronuclear diatomic is of great interest for both environmental and safety purposes. In this paper we investigate the possibility of infrared monitoring of ICl by measuring the far-infrared absorption cross section of its fundamental band near 381 cm^-1. We have performed quantitative studies of the neat gas in a 20 cm cell at 25, 35, 50 and 70 oC at multiple pressures up to ~ 9 Torr and investigated the temperature and pressure dependence of the band’s infrared cross section. Quantitative measurements were problematic due to sample adhesion to the cell walls and windows as well as reactions/possible hydrolysis of ICl to form HCl gas. Effects were mitigated by measuring only the neat gas, using short measurement times and subtracting out the partial pressure of the HCl(g). The integrated band strength is shown to be temperature independent and was found to be equal to 9.1 x 10^-19 (cm²/molecule) cm-1. As expected, the temperature dependence of the band profile showed only a small effect over this limited temperature range. Furthermore, we have also investigated using the absorption data along with inverse least squares multivariate methods for the quantitative monitoring of ICl effluent concentrations under different scenarios using infrared (standoff) sensing and compare these results with traditional Beer’s Law (univariate) techniques.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA), Office of Defense Nuclear Nonproliferation; USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1725828

Report Number(s):: PNNL-SA--154340

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 46 Vol. 124; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (33)

The high-resolution infrared spectrum of iodine monochloride Hedderich, Hartmut G.; Bernath, Peter F.; McRae, Glenn A. Journal of Molecular Spectroscopy, Vol. 155, Issue 2 https://doi.org/10.1016/0022-2852(92)90527-U	journal	October 1992
Multivariate calibration. I. Concepts and distinctions Martens, Harald; Næs, Tormod TrAC Trends in Analytical Chemistry, Vol. 3, Issue 8 https://doi.org/10.1016/0165-9936(84)85008-6	journal	January 1984
Mid-infrared versus far-infrared (THz) relative intensities of room-temperature Bacillus spores Johnson, Timothy J.; Valentine, Nancy B.; Sharpe, Steven W. Chemical Physics Letters, Vol. 403, Issue 1-3 https://doi.org/10.1016/j.cplett.2004.12.095	journal	February 2005
Use of CAP88 PC to infer differences in the chemical form of 129I emitted from a fuel reprocessing facility Fritz, Brad G.; Phillips, Nathan R. J. Journal of Environmental Radioactivity, Vol. 120 https://doi.org/10.1016/j.jenvrad.2013.01.015	journal	June 2013
Materials and processes for the effective capture and immobilization of radioiodine: A review Riley, Brian J.; Vienna, John D.; Strachan, Denis M. Journal of Nuclear Materials, Vol. 470 https://doi.org/10.1016/j.jnucmat.2015.11.038	journal	March 2016
Reference spectroscopic data for hydrogen halides. Part I: Construction and validation of the ro-vibrational dipole moment functions Li, Gang; Gordon, Iouli E.; Le Roy, Robert J. Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 121 https://doi.org/10.1016/j.jqsrt.2013.02.005	journal	May 2013
Quantitative vapor-phase IR intensities and DFT computations to predict absolute IR spectra based on molecular structure: I. Alkanes Williams, Stephen D.; Johnson, Timothy J.; Sharpe, Steven W. Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 129 https://doi.org/10.1016/j.jqsrt.2013.07.005	journal	November 2013
The HITRAN2016 molecular spectroscopic database Gordon, I. E.; Rothman, L. S.; Hill, C. Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 203 https://doi.org/10.1016/j.jqsrt.2017.06.038	journal	December 2017
Infrared absorption cross-sections in HITRAN2016 and beyond: Expansion for climate, environment, and atmospheric applications Kochanov, R. V.; Gordon, I. E.; Rothman, L. S. Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 230 https://doi.org/10.1016/j.jqsrt.2019.04.001	journal	June 2019
Molten salt reactor waste and effluent management strategies: A review Riley, Brian J.; McFarlane, Joanna; DelCul, Guillermo D. Nuclear Engineering and Design, Vol. 345 https://doi.org/10.1016/j.nucengdes.2019.02.002	journal	April 2019
Smoothing and Differentiation of Data by Simplified Least Squares Procedures. Savitzky, Abraham.; Golay, M. J. E. Analytical Chemistry, Vol. 36, Issue 8 https://doi.org/10.1021/ac60214a047	journal	July 1964
Multivariate Analysis for Quantification of Plutonium(IV) in Nitric Acid Based on Absorption Spectra Lines, Amanda M.; Adami, Susan R.; Sinkov, Sergey I. Analytical Chemistry, Vol. 89, Issue 17 https://doi.org/10.1021/acs.analchem.7b02161	journal	August 2017
Multivariate Analysis To Quantify Species in the Presence of Direct Interferents: Micro-Raman Analysis of HNO ₃ in Microfluidic Devices Lines, Amanda M.; Nelson, Gilbert L.; Casella, Amanda J. Analytical Chemistry, Vol. 90, Issue 4 https://doi.org/10.1021/acs.analchem.7b03833	journal	January 2018
Micro-Raman Technology to Interrogate Two-Phase Extraction on a Microfluidic Device Nelson, Gilbert L.; Asmussen, Susan E.; Lines, Amanda M. Analytical Chemistry, Vol. 90, Issue 14 https://doi.org/10.1021/acs.analchem.7b04330	journal	May 2018
Online, Real-Time Analysis of Highly Complex Processing Streams: Quantification of Analytes in Hanford Tank Sample Lines, A. M.; Tse, P.; Felmy, H. M. Industrial & Engineering Chemistry Research, Vol. 58, Issue 47 https://doi.org/10.1021/acs.iecr.9b03636	journal	October 2019
Quantitative Infrared Absorption Spectra and Vibrational Assignments of Crotonaldehyde and Methyl Vinyl Ketone Using Gas-Phase Mid-Infrared, Far-Infrared, and Liquid Raman Spectra: s-cis vs s-trans Composition Confirmed via Temperature Studies and ab Initio Methods Lindenmaier, Rodica; Williams, Stephen D.; Sams, Robert L. The Journal of Physical Chemistry A, Vol. 121, Issue 6 https://doi.org/10.1021/acs.jpca.6b10872	journal	February 2017
Online Monitoring of Solutions Within Microfluidic Chips: Simultaneous Raman and UV–Vis Absorption Spectroscopies Nelson, Gilbert L.; Lines, Amanda M.; Bello, Job M. ACS Sensors, Vol. 4, Issue 9 https://doi.org/10.1021/acssensors.9b00736	journal	August 2019
Salts of the 1,1,2,3,3,-pentacyanopropenide anion: crystallographic and spectroscopic studies Johnson, T. J.; Hipps, K. W.; Willett, Roger D. The Journal of Physical Chemistry, Vol. 92, Issue 24 https://doi.org/10.1021/j100335a011	journal	December 1988
Kinetics of hydrolysis of iodine monochloride measured by the pulsed-accelerated-flow method Wang, Yi Lai; Nagy, Julius C.; Margerum, Dale W. Journal of the American Chemical Society, Vol. 111, Issue 20 https://doi.org/10.1021/ja00202a026	journal	September 1989
Iodine Monochloride. IV. The System Potassium Chloride—Iodine Monochloride ¹ Cornog, Jacob; Bauer, Eldon E. Journal of the American Chemical Society, Vol. 64, Issue 11 https://doi.org/10.1021/ja01263a028	journal	November 1942
The Hydrolysis of Iodine Monochloride Philbrick, Frederick Arthur Journal of the American Chemical Society, Vol. 56, Issue 6 https://doi.org/10.1021/ja01321a001	journal	June 1934
Infrared Spectra of Iodine Monochloride Charge-transfer Complexes ¹ Person, Willis B.; Humphrey, Ray E.; Deskin, William A. Journal of the American Chemical Society, Vol. 80, Issue 9 https://doi.org/10.1021/ja01542a006	journal	May 1958
Gas-Phase Hydrolysis of SOCl ₂ at 297 and 309 K: Implications for Its Atmospheric Fate Johnson, Timothy J.; Disselkamp, Robert S.; Su, Yin-Fong The Journal of Physical Chemistry A, Vol. 107, Issue 32 https://doi.org/10.1021/jp022090v	journal	August 2003
Quantitative Infrared Intensity Studies of Vapor-Phase Glyoxal, Methylglyoxal, and 2,3-Butanedione (Diacetyl) with Vibrational Assignments Profeta, Luisa T. M.; Sams, Robert L.; Johnson, Timothy J. The Journal of Physical Chemistry A, Vol. 115, Issue 35 https://doi.org/10.1021/jp204532x	journal	September 2011
Absorption spectroscopy for the quantitative prediction of lanthanide concentrations in the 3LiCl–2CsCl eutectic at 723 K Schroll, Cynthia A.; Lines, Amanda M.; Heineman, William R. Analytical Methods, Vol. 8, Issue 43 https://doi.org/10.1039/C6AY01520D	journal	January 2016
Vibrational Intensities. V. BrCl and ICl Brooks, Wendell V. F.; Crawford, Bryce The Journal of Chemical Physics, Vol. 23, Issue 2 https://doi.org/10.1063/1.1741969	journal	February 1955
Disseminator for rapid, selectable, and quantitative delivery of low and semivolatile liquid species to the vapor phase Johnson, Timothy J.; Sharpe, Steven W.; Covert, Matthew A. Review of Scientific Instruments, Vol. 77, Issue 9 https://doi.org/10.1063/1.2349298	journal	September 2006
Molten Salt Catalysis of Gas Reactions Kenney, C. N. Catalysis Reviews, Vol. 11, Issue 1 https://doi.org/10.1080/01614947508079985	journal	January 1975
Quantum cascade lasers: ultrahigh-speed operation, optical wireless communication, narrow linewidth, and far-infrared emission Capasso, F.; Paiella, R.; Martini, R. IEEE Journal of Quantum Electronics, Vol. 38, Issue 6 https://doi.org/10.1109/JQE.2002.1005403	journal	June 2002
Creation of 0.10-cm ^-1 resolution quantitative infrared spectral libraries for gas samples Sharpe, Steven W.; Sams, Robert L.; Johnson, Timothy J. Environmental and Industrial Sensing, SPIE Proceedings https://doi.org/10.1117/12.455730	conference	February 2002
Gas-Phase Databases for Quantitative Infrared Spectroscopy Sharpe, Steven W.; Johnson, Timothy J.; Sams, Robert L. Applied Spectroscopy, Vol. 58, Issue 12 https://doi.org/10.1366/0003702042641281	journal	December 2004
HWVP Iodine Trap Evaluation Burger, Leland L.; Scheele, Randall D. https://doi.org/10.2172/15009659	report	September 2004
Gas-phase pyrolysis products emitted by prescribed fires in pine forests with a shrub understory in the southeastern United States Scharko, Nicole K.; Oeck, Ashley M.; Myers, Tanya L. Atmospheric Chemistry and Physics, Vol. 19, Issue 15 https://doi.org/10.5194/acp-19-9681-2019	journal	January 2019

Similar Records

Quantitative far-infrared band strengths of iodine monochloride (ICl), a molten salt off-gas product

Conference · Fri Apr 24 04:00:00 UTC 2020 · OSTI ID:1617190

Intraatomic correlation correction in the FORS model

Journal Article · Thu May 23 04:00:00 UTC 1985 · J. Phys. Chem.; (United States) · OSTI ID:5133773

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Iodine
absorption
genetics
hydrolysis
infrared light

Absolute Band Intensity of the Iodine Monochloride Fundamental Mode for Infrared Sensing and Quantitative Analysis

Citation Formats

References (33)

Similar Records

Related Subjects