Photofragment fluorescence as an analytical technique:  application to gas-phase alkali chlorides

Oldenborg, Richard C.; Baughcum, Steven L.

doi:10.1021/ac00298a035

Cited by 69 publications

(33 citation statements)

References 31 publications

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“…30,31 Thus, KCl absorption cross sections in this wavelength region are of interest for quantitative analysis of laser induced photofragmentation data.…”

Section: -9mentioning

confidence: 99%

Development of an alkali chloride vapour-generating apparatus for calibration of ultraviolet absorption measurements

Leffler

Brackmann

Berg

et al. 2017

Review of Scientific Instruments

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A novel design of alkali chloride vapour-generating cell has been developed, which can serve as a calibration cell for quantitative ultraviolet absorption concentration measurements and meticulous spectral investigations of alkali compounds. The calibration cell was designed to provide alkali vapour of well-controlled concentrations and temperatures, and consisted of a sealed quartz cell measuring 0.4 m in length with a temperature-controlled reservoir containing solid alkali salt. The cell was placed in a furnace and the alkali vapours generated from the reservoir have direct access to the measuring chamber. Investigations of potassium chloride (KCl) were made on sublimated vapour at temperatures 650, 700, 750, 780, and 800 °C while the reservoir temperature was kept 50 °C lower to avoid condensation. The cell provides stable KCl vapour pressures, and the furnace provides a homogenous temperature profile along the cell. KCl vapour pressures are well characterised and conform the base for determination of the KCl concentration in the cell. The alkali chloride levels matched the concentration range of the absorption setup and indicated a previously employed calibration method to overestimate KCl concentrations. The KCl absorption cross sections for wavelengths λ=197.6 nm and λ=246.2 nm were calculated to be 3.4 × 10−17 and 2.9 × 10−17 cm2/molecule, respectively. The absorption cross section spectra did not show any structural differences with increasing temperature, which could indicate influence of dimers or significant changes of the population in the KCl vibrational states. The KCl absorption cross sections thus did not show any temperature dependence in the temperature region of 700–800 °C. Moreover, the applicability of the calibration cell for measurement of other alkali chlorides and hydroxides is discussed.

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“…30,31 Thus, KCl absorption cross sections in this wavelength region are of interest for quantitative analysis of laser induced photofragmentation data.…”

Section: -9mentioning

confidence: 99%

Development of an alkali chloride vapour-generating apparatus for calibration of ultraviolet absorption measurements

Leffler

Brackmann

Berg

et al. 2017

Review of Scientific Instruments

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“…Several different methods are suggested in the literature: [3][4][5][6][7][8][9][10][11] surface ionization ͑SI͒, 3 molecular beam mass spectroscopy, 4,5 plasma excited alkali resonance line spectroscopy, 6,7 flame emission excimer laser induced fragmentation fluorescence, 8,9 fiber optical alkali monitor, 10 and a sorber bed method. 11 Most methods have been reviewed by Monkhouse.…”

Section: Introductionmentioning

confidence: 99%

Principle, calibration, and application of the in situ alkali chloride monitor

Forsberg

Broström

Backman

et al. 2009

Review of Scientific Instruments

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The extended use of biomass for heat and power production has caused increased operational problems with fouling and high-temperature corrosion in boilers. These problems are mainly related to the presence of alkali chlorides (KCl and NaCl) at high concentrations in the flue gas. The in situ alkali chloride monitor (IACM) was developed by Vattenfall Research and Development AB for measuring the alkali chloride concentration in hot flue gases (less than or approximately 650 degrees C). The measurement technique is based on molecular differential absorption spectroscopy in the UV range. Simultaneous measurement of SO(2) concentration is also possible. The measuring range is 1-50 ppm for the sum of KCl and NaCl concentrations and 4-750 ppm for SO(2). This paper describes the principle of the IACM as well as its calibration. Furthermore, an example of its application in an industrial boiler is given.

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“…The optical measurements of the alkali chlorides are based on their dissociative electronic transition at wavelengths shorter than 300 nm [3]. During the past few decades, two different optical in situ techniques have been proposed for detection of alkali chlorides: excimer laser induced fluorescence (ELIF) [4] and differential optical absorption spectroscopy (DOAS) [5]. In the ELIF technique, alkali chloride molecules are dissociated using 193 nm light to excited alkali atoms and chlorine atoms.…”

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confidence: 99%

Optical detection of potassium chloride vapor using collinear photofragmentation and atomic absorption spectroscopy

2012

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A sensitive and selective optical technique to detect potassium chloride (KCl) vapor is introduced. The technique is based on the photofragmentation of KCl molecules, using a pulsed UV laser, and optical probing of the temporarily increased amount of potassium atoms with a near-infrared laser. The two laser beams are aligned to go through the sample volume along the same optical path. The performance of the technique is demonstrated by detecting KCl concentrations from 25 ppb to 30 ppm in a temperature-controlled cell.

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Photofragment fluorescence as an analytical technique: application to gas-phase alkali chlorides

Cited by 69 publications

References 31 publications

Development of an alkali chloride vapour-generating apparatus for calibration of ultraviolet absorption measurements

Development of an alkali chloride vapour-generating apparatus for calibration of ultraviolet absorption measurements

Principle, calibration, and application of the in situ alkali chloride monitor

Optical detection of potassium chloride vapor using collinear photofragmentation and atomic absorption spectroscopy

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