OSA's Digital Library

Applied Optics

Applied Optics


  • Editor: James C. Wyant
  • Vol. 45, Iss. 24 — Aug. 20, 2006
  • pp: 6180–6186

Pulsed laser photofragment emission for detection of mercuric chloride

Alexandra A. Hoops and Thomas A. Reichardt  »View Author Affiliations

Applied Optics, Vol. 45, Issue 24, pp. 6180-6186 (2006)

View Full Text Article

Enhanced HTML    Acrobat PDF (160 KB)

Browse Journals / Lookup Meetings

Browse by Journal and Year


Lookup Conference Papers

Close Browse Journals / Lookup Meetings

Article Tools



The viability of pulsed laser photofragment emission (PFE) is evaluated for the in situ measurement of vapor-phase mercuric chloride ( HgCl 2 ) concentration in combustion flue gas. Dispersed emissions from both the Hg ( 6 P 1 3 ) and HgCl ( B Σ + 2 ) photoproducts are presented, and the dependence of the HgCl 2 PFE signal originating from Hg ( 6 P 1 3 ) on the collisional environment is examined for buffer-gas mixtures of N 2 , O 2 , and CO 2 . Integrated PFE intensity measurements as a function of buffer gas pressure support the assumption that the primary effect of the relevant flue gas constituents is to quench emission from Hg ( 6 P 1 3 ) . The quenching rate constants for PFE from HgCl 2 were measured to be 1.37 ( ± 0.16 ) × 10 5 Torr 1 s 1 for N 2 , 9.35 ( ± 0.25 ) × 10 6 Torr 1 s 1 for O 2 , and 1.49 ( ± 0.29 ) × 10 6 Torr 1 s 1 for CO 2 . These values are in good accord with literature values for the quenching of Hg ( 6 P 1 3 ) . The emission cross section for Hg ( 6 P 1 3 ) generated by photodissociation of HgCl 2 in 760   Torr   N 2 is found to be 1.0 ( ± 0.2 ) × 10 25 m 2 by comparing the PFE signal to N 2 Raman scattering.

© 2006 Optical Society of America

OCIS Codes
(120.0280) Instrumentation, measurement, and metrology : Remote sensing and sensors
(280.1120) Remote sensing and sensors : Air pollution monitoring
(300.2530) Spectroscopy : Fluorescence, laser-induced

Original Manuscript: September 30, 2005
Revised Manuscript: February 24, 2006
Manuscript Accepted: February 27, 2006

Alexandra A. Hoops and Thomas A. Reichardt, "Pulsed laser photofragment emission for detection of mercuric chloride," Appl. Opt. 45, 6180-6186 (2006)

Sort:  Author  |  Year  |  Journal  |  Reset  


  1. C. L. Senior, J. J. Helble, and A. F. Sarofim, "Emissions of mercury, trace elements, and fine particles from stationary combustion devices," Fuel Process. Technol. 65-66, 263-288 (2000). [CrossRef]
  2. V. M. Fthenakis, F. W. Lipfert, P. D. Moskowitz, and L. Saroff, "An assessment of mercury emissions and health risks from a coal-fired power plant," J. Hazard. Mater. 44, 267-283 (1995). [CrossRef]
  3. G. Offen, N. Shick, R. Chang, P. Chu, C. Dene, and R. Rhudy, "Mercury controls for coal-fired power plants--status and challenges," Modern Power Syst. 25, 24-29 (2005).
  4. P. Monkhouse, "On-line diagnostic methods for metal species in industrial process gas," Prog. Energy Combust. Sci. 28, 331-381 (2002). [CrossRef]
  5. J. B. Simeonsson and R. C. Sausa, "A critical review of laser photofragmentation/fragment detection techniques for gas-phase chemical analysis," Appl. Spectrosc. Rev. 31, 1-72 (1996). [CrossRef]
  6. U. Gottwald and P. Monkhouse, "Single-port optical access for spectroscopic measurements in industrial flue gas ducts," Appl. Phys. B 69, 151-154 (1999). [CrossRef]
  7. P. Templet, J. R. McDonald, S. P. McGlynn, C. H. Kendrow, J. L. Roebber, and K. Weiss, "Ultraviolet absorption spectra of mercuric halides," J. Chem. Phys. 56, 5746 (1972). [CrossRef]
  8. C. Roxlo and A. Mandl, "Vacuum ultraviolet absorption cross sections for halogen containing molecules," J. Appl. Phys. 51, 2969-2972 (1980). [CrossRef]
  9. D. Spence, R.-G. Wang, and M. A. Dillon, "Pseudo-optical absorption spectra in HgCl2 and HgBr2 from 4 to 14 eV," Appl. Phys. Lett. 41, 1021-1023 (1982). [CrossRef]
  10. D. Spence, R.-G. Wang, and M. A. Dillon, "Excitation of Rydberg states of HgCl2 and HgBr2 by electron impact," J. Chem. Phys. 82, 1883-1889 (1985). [CrossRef]
  11. W. R. Wadt, "The electronic structure of HgCl2 and HgBr2 and its relationship to photodissociation," J. Chem. Phys. 72, 2469-2478 (1980). [CrossRef]
  12. W. R. Wadt, "The electronic structure of HgCl and HgBr," Appl. Phys. Lett. 34, 658-660 (1979). [CrossRef]
  13. T. A. Cool, J. A. McGarvey, Jr., and A. C. Erlandson, "Two-photon excitation of mercury atoms by photodissociation of mercury halides," Chem. Phys. Lett. 58, 108-113 (1978). [CrossRef]
  14. C. Whitehurst and T. A. King, "Multiphoton excitation of mercury atoms by photodissociation of HgX2 (X = Cl, Br, I)," J. Phys. B: At. Mol. Phys. 20, 4053-4064 (1987). [CrossRef]
  15. R. B. Barat and A. T. Poulos, "Detection of mercury compounds in the gas phase by laser photofragmentation/emission spectroscopy," Appl. Spectrosc. 52, 1360-1363 (1998).
  16. R. C. Weast, ed., CRC Handbook of Chemistry and Physics, 67th ed. (CRC Press, 1986).
  17. G. Stark, P. L. Smith, J. Rufus, A. P. Thorne, J. C. Pickering, and G. Cox, "High-resolution photoabsorption cross-section measurements of SO2 at 295 K between 198 and 220 nm," J. Geophys. Res. 104, 16585-16590 (1999). [CrossRef]
  18. L. J. Curtis, R. E. Irving, M. Henderson, R. Matulioniene, C. F. Fischer, and E. H. Pinnington, "Measurements and predictions of the 6s6p1,3P1 lifetimes in the Hg isoelectronic sequence," Phys. Rev. A 63, 042502-1-7 (2001). [CrossRef]
  19. A. Sibata, M. Takahasi, H. Mikuni, H. Horiguchi, and S. Tsuchiya, "Chemiionization of excited mercury atom with 253.7 nm irradiation in the presence of N2 and CH4," Bull. Chem. Soc. Jpn. 52, 15-20 (1979). [CrossRef]
  20. J. Pitre, K. Hammond, and L. Krause, "63P1--63P0 excitation transfer in mercury, induced in collisions with N2 molecules," Phys. Rev. A 6, 2101-2106 (1972). [CrossRef]
  21. J. S. Deech, J. Pitre, and L. Krause, "Quenching and depolarization of mercury resonance radiation," Can. J. Phys. 49, 1976-1981 (1971). [CrossRef]
  22. J. Calvert and J. Pitts, Photochemistry (Wiley, 1966), p. 74.
  23. J. V. Michael and G. N. Suess, "Absolute quenching cross sections of Hg (3P1) with various molecules," J. Phys. Chem. 78, 482-487 (1974). [CrossRef]
  24. J. P. Barrat, D. Casalta, J. L. Cojan, and J. Hamel, "Depolarisation et (quenching) du niveau 63P1 du mercure lors de collisions avec des gaz etrangers," J. Phys. (Paris) 27, 608-618 (1966). [CrossRef]
  25. A. J. Yarwood, O. P. Strausz, and H. E. Gunning, "Quenching of 2537-Å resonance radiation of mercury," J. Chem. Phys. 41, 1705-1713 (1964). [CrossRef]
  26. H. Horiguchi and S. Tsuchiya, "Quenching of excited mercury atoms (63P1 and 63P0) in molecular collisions," Bull. Chem. Soc. Jpn. 47, 2768-2774 (1974). [CrossRef]
  27. The N2 Raman cross section was calculated from the information provided by A. C. Eckbreth, Laser Diagnostics for Combustion Temperature and Species, 2nd ed. (Gordon and Breach, 1996), Chap. 5. The N2 depolarization ratio is 0.024.
  28. A. A. Hoops, Sandia National Laboratories, P. O. Box 969, MS 9056, Livermore, California 94551, and T. A. Reichardt are preparing a manuscript to be called "Time-resolved measurement of HgCl2 photofragment emission."
  29. D. A. V. Kliner, F. Di Teodoro, J. P. Koplow, S. W. Moore, and A. V. Smith, "Efficient second, third, fourth, and fifth harmonic generation of a Yb-doped fiber amplifier," Opt. Commun. 210, 393-398 (2002). [CrossRef]

Cited By

Alert me when this paper is cited

OSA is able to provide readers links to articles that cite this paper by participating in CrossRef's Cited-By Linking service. CrossRef includes content from more than 3000 publishers and societies. In addition to listing OSA journal articles that cite this paper, citing articles from other participating publishers will also be listed.


Fig. 1 Fig. 2 Fig. 3
Fig. 4 Fig. 5

« Previous Article  |  Next Article »

OSA is a member of CrossRef.

CrossCheck Deposited