Absorption spectra of hydrogen chloride and carbon monoxide in smoke

Naofumi Shimizua, Ken Matsuyamab, and Iwao Hosakoc

a

NTT Microsystem Integration Labs., Nippon Telegraph and Telephone Corp., Atsugi, Kanagawa, Japan b Center for Fire Science and Technology, Tokyo University of Science, Noda, Chiba, Japan c National Institute of Information and Communications Technology, Koganei, Tokyo, Japan
1.2 1.0 0.8 0.6 0.4 0.2 0.0 200 400 600 800 Frequency (GHz) 1000

Abstract Absorption spectra of smoke produced from polyvinyl chloride (PVC) and molded charcoal at high temperature are investigated between 500 and 950 GHz. Observed peaks at 626 GHz for PVC and at 692 and 921 GHz for molded charcoal are respectively assigned as the spectral signature of hydrogen chloride and carbon monoxide contained in smoke. Smoke from molded charcoal also showed absorption peaks of hydrogen cyanide that are likely produced by the combustion of adhesive matter in it. These results show the potential of sub-terahertz spectroscopic sensing for instantaneous detection and quantification of multiple harmful gaseous substances in smoke.

I. INTRODUCTION AND BACKGROUND

easuring an absorption spectrum of smoke in the terahertz (THz) band is expected to offer new possibilities for quick and direct inspection of harmful gaseous substances in it. This is because of the low propagation loss of THz waves in diffusive media like smoke and because there is no need for a sampling process to collect gas under investigation [1-2]. We studied absorption spectra between 200 and 500 GHz for smoke that was produced from heated nylon fabric and identified hydrogen cyanide (HCN) and acetonitrile in it [3]. In addition, we succeeded in detecting HCN from a distance in a full-scale simulated fire with a remote-gas sensor based on a continuous-wave (cw) sub-THz spectrometer operating in the same frequency range [4]. However, hydrogen chloride (HCl) and carbon monoxide (CO), which are regarded as typical lethal gases produced at a fire, are impossible to detect with the system since they have no or very weak absorption lines in the frequency range. In this work, we extended the measurement frequency range up to 1000 GHz and investigated absorption spectra of smoke that was expected to contain HCl or CO to clarify the capability of sub-THz spectroscopic sensing. II. RESULTS

Fig. 1: Absorption spectra of fuel alcohol vapor measured with a cw sub-THz spectrometer with a UTCPD photomixer and a quasi-optical Schottky diode detector.

Smoke generated from a sample heated in a combustion cell with a supply of dry air feeds into a 1-m long gas cell placed between the THz wave generator and detector. The exhaust of the gas cell is analyzed with a Fourier-transform infrared (FTIR) spectrometer after isolating flowing particles in the smoke with cellulose and ceramic filters. When we heated polyvinyl chloride (PVC) in the combustion cell to 350 degree Celsius, white smoke billowed out. Figures 2(a) and (b) show photographs of the gas cell without and with the smoke, respectively, which were taken from the photodiode module side. Figure 3 shows the absorption spectrum of the smoke. The experimentally observed frequency of the peak 626 GHz coincides well with that of absorption line of HCl. The HCl concentration of 2520 ppm derived from the analysis of the measured spectrum also agrees well with the FTIR measurement of 2480 ppm.

THz waves for spectral measurement were generated from a uni-traveling carrier photodiode (UTCPD) module [5] irradiated by two cw laser lights with a controlled wavelength difference. As a detector, we used a quasi-optical Schottky diode with a lock-in detection scheme. The system can measure absorption spectra between 200 and 1000 GHz. Figure 1 shows the absorption spectrum of fuel alcohol vapor measured with the system.

(a)

(b)

Fig. 2: Photographs of the gas cell (a) without and (b) with smoke generated from heated PVC, taken from the photodiode module side.

978-1-4673-1597-5/12/$31.00 2012 IEEE

1.2 1.0 0.8 0.6 0.4 0.2 0.0 500 550 600 Frequency (GHz) HO
2

HCl 650

Remarkable is that, as shown in Fig. 6, strong peaks are observed at 709, 798, and 887 GHz from the coarse absorption spectrum measurement of smoke emitted from molded charcoal between 650 and 950 GHz. These peaks coincide well with those for HCN and never appeared in the absorption spectrum of the combustion gas from high-grade charcoal produced from solid wood (blue line in the figure). Therefore, we can conclude that they are fingerprint spectra of HCN likely produced by the combustion of adhesive matter in the molded charcoal.
Molded Charcoal

Fig. 3: Absorption spectrum of smoke produced from PVC heated to 350 degree Celsius.

Yellowish smoke was emitted from molded charcoal, which was produced from sawdust, as shown in Fig. 4. The absorption spectra of the smoke measured between 655 and 705 GHz are shown in Fig. 5. Solid and broken lines correspond to the results for 26 and 14 grams of molded charcoal heated in the combustion cell, respectively. One of the absorption lines of CO exists at 692 GHz. A small peak is observed at that frequency in each spectrum and the peak intensity increases as the mass of molded charcoal increases. The CO concentration of 9.7% derived from the analysis of the measured spectrum agrees well with the FTIR measurement of 7.9%. We also observe the absorption peak of CO at 921 GHz from precise measurement around that frequency.

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High-grade Charcoal

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900 950

Fig. 6: Absorption spectra of smoke produced from molded charcoal (black line) and high-grade charcoal (blue line).

III. CONCLUSION We succeeded in observing absorption lines of HCl and CO in smoke with a cw sub-THz spectrometer. The results, taken together with our recent success with HCN, prove the potential of sub-THz spectroscopic sensing for instantaneous detection and quantification of multiple harmful gases in smoke. REFERENCES
[1] [2] [3] R. A. Cheville and D. Grischkowsky, Optics Lett., 20, 1646-1648, (1995). D. Bigourd A. Cuisset, F. Hindle, S. Maton, E. Fertein, R. Bocquet, and G. Mouret, Opt. Lett. Vol. 31, pp. 2356-2358, 2006. N. Shimizu, K. Kikuchi, T. Ikari, K. Mtsuyama, A. Wakatsuki, S. Kohjiro, and R. Fukasawa , Applied Physics Express, Vol. 4, 032401. N. Shimizu, T. Ikari, K. Kikuchi, K. Matsuyama, A. Wakatsuki, S. Kohjiro, and R. Fukasawa, in 2011 IEEE International Microwave Symposium Digest, Baltimore, WE2G-5. A. Wakatsuki, T. Furuta, Y. Muramoto, T. Yoshimatsu, and H. Ito, Proc. 33rd Int. Conf. Infrared, Millimeter, and Terahertz Waves, 2008, M4K2.

Fig. 4: Photograph of the gas cell filled with smoke generated from molded charcoal heated to 400 degree Celsius.

[4]
[5]

26 g 14 g

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CO 720

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Fig. 5: Absorption spectra of smoke produced from molded charcoal. Solid and broken lines are for 26 and 14 grams in weight, respectively.