Terminal and Intermediate Combustion Products Observed from 2.0 to 5.0 μ m in Flame/Furnace Infrared Emission Spectrometry

Abstract

A computer-controlled, dispersive, scanning spectrometer with a wavelength range from 1 to 15 μm is described and used to study the flame/furnace infrared emission (FIRE) spectra of combustion products formed in a small analyte/air flame and in an electrically heated furnace (570°C), operated with and without a column of heated hopcalite (370°C). When lead selenide was used as the detector, the emission spectra of the combustion products of pentane, benzene, dichloromethane, and methanol could be measured over the wavelength range from 2 to 5 μm. In addition to discrete emission bands from terminal combustion products such as CO₂, H₂O, and HCl, discrete emission from CO (4.6–4.9 μm) and continuum emission associated with soot formation were also observed under oxygen-limited combustion of benzene, dichloromethane, and possibly pentane. Bands centered at approximately 3.3 μm (3030 cm⁻¹) and 3.5 μm (2857 cm⁻¹) were observed in several spectra and attributed to C-H stretching in intermediate combustion products, with the 3.5-μm band being assigned to the stretching of the carbonyl hydrogen of aldehydes (formaldehyde, in particular). On the basis of these results, the “anomalous emission” observed at 3.8 μm in previous studies employing electrothermal excitation is attributed either to the presence of formaldehyde or to the formation of particulate carbon, which are both associated with conditions favoring the incomplete combustion of hydrocarbons.

Keywords

Infrared emission spectroscopy FIRE spectrometer Hopcalite Oxidative degradation of hydrocarbons Formaldehyde formation during combustion of hydrocarbons Combustion intermediates in FIRE spectrometry

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References

Busch

M. A.

and Busch

K. W

, Spectrochim. Acta Rev. 14, 303 (1991).

Busch

M. A.

and Busch

K. W

, Amer. Lab. 23(11), 18 (1991).

Kubala

S. W.

Tilotta

D. C.

Busch

M. A.

and Busch

K. W

, Anal. Chem. 61, 2785 (1989).

Kubala

S. W.

Tilotta

D. C.

Busch

M. A.

and Busch

K. W

, Anal. Chem. 61, 1841 (1989).

Kubala

S. W.

Tilotta

D. C.

Busch

M. A.

and Busch

K. W

, Talanta 38, 589 (1991).

Tilotta

D. C.

Busch

M. A.

and Busch

K. W

, Appl. Spectrosc. 45, 178 (1991).

Ravishankar

Tilotta

D. C.

Busch

K. W.

and Busch

M. A

, Appl. Spectrosc. 44, 1247 (1990).

Lam

C. K. Y.

Zhang

Busch

M. A.

and Busch

K. W

, Abstracts of Papers, 43rd Pittsburgh Conference on Analytical Chemistry and Applied Spectroscopy, New Orleans (1992), Abstract 275.

Zhang

Busch

M. A.

and Busch

K. W

, Appl. Spectrosc. 46, 631 (1992).

10.

Tilotta

D. C.

Busch

K. W.

and Busch

M. A

, Appl. Spectrosc. 43, 704 (1989).

11.

Ravishankar

Tilotta

D. C.

Busch

K. W.

and Busch

M. A

, Appl. Spectrosc. 45, 1684 (1991).

12.

Kuehn

A. J.

Zhang

Busch

M. A.

and Busch

K. W

, Abstracts of Papers, 43rd Pittsburgh Conference on Analytical Chemistry and Applied Spectroscopy, New Orleans (1992), Abstract 229.

13.

Hopcalite Catalyst: General Information and Applications Bulletin (Callery Chemical Co., Pittsburgh, 1989), p. 9.

14.

Busch

M. A.

and Busch

K. W

, Appl. Spectrosc. 45, 546 (1991).

15.

Wilkinson

G. R.

Ford

M. A.

and Price

W. C

, in Molecular Spectroscopy, Sell

Ed. (Institute of Petroleum, London, 1955), pp. 192–202.

16.

Handbook of Chemistry and Physics, Lide

D. R.

Ed. (CRC Press, Boca Raton, Florida, 1991), 72nd ed.

17.

Donovan

R. E.

, J. Chem. Phys. 27, 324 (1959).

18.

Mavrodineanu

, Flame Spectroscopy (John Wiley and Sons, New York, 1965), Chap. 1, p. 28.

19.

Busch

M. A.

, in Encyclopedia of Physical Science and Technology (Academic Press, New York, 1987), Vol. 6, pp. 409–435.

20.

Ahlstrom

R. C.

Jr. , and Steele

J. M.

, in Kirk–Othmer Encyclopedia of Chemical Technology (John Wiley and Sons, New York, 1979), 3rd ed., Vol. 5, pp. 668–685.

21.

Lewis

and Von Elbe

, Combustion, Flames, and Explosions of Gases (Academic Press, New York, 1951), Chap. 4, pp. 116–188.

22.

Barnard

J. A.

and Bradley

J. N

, Flame and Combustion (Chapman and Hall, London, 1985), 2nd ed., Chap. 6, pp. 132–162.

23.

Hobbs

C. C.

, in Kirk-Othmer Encyclopedia of Chemical Technology (John Wiley and Sons, New York, 1979), 3rd ed., Vol. 12, pp. 826–851.

24.

Nogare

S. D.

Juvet

R. S.

Jr. , Gas-Liquid Chromatography: Theory and Practice (Interscience, New York, 1962), p. 249.

25.

Bartish

C. M.

and Drissel

G. M

, in Kirk-Othmer Encyclopedia of Chemical Technology (John Wiley and Sons, New York, 1978), 3rd ed., Vol. 4, pp. 776–777.

26.

Lamb

A. B.

Bray

W. C.

and Fraser

J. C. W

, Ind. Eng. Chem. 12, 213 (1920).

27.

Lamb

A. B.

Scalione

C. C.

and Edgar

, J. Amer. Chem. Soc. 44, 738 (1922).

28.

Christian

J. G.

and Johnson

J. E

, Int. J. Air Wat. Poll. 9, 1 (1965).

29.

Belcher

Ingram

and Majer

J. R

, Microchem. J. 19, 191 (1974).

30.

Pouchert

C. J.

, The Aldrich Library of Infrared Spectra (Aldrich Chemical Co., Milwaukee, Wisconsin, 1970), pp. 213–214.

31.

The Merck Index, Budavari

Ed. (Merck & Co., Rahway, New Jersey, 1989), 11th ed., p. 4148.

32.

Gerberich

H. R.

Stautzenberger

A. L.

and Hopkins

W. C

, in Kirk-Othmer Encyclopedia of Chemical Technology (John Wiley and Sons, New York, 1980), Vol. 11, pp. 231–250.

33.

The 1990–91 Omega Temperature Handbook (Omega Engineering, Stamford, Connecticut, 1990), p. B-17.

34.

Dannenberg

E. M.

, in Kirk-Othmer Encyclopedia of Chemical Technology (John Wiley and Sons, New York, 1978), 3rd ed., Vol. 4, pp. 631–666.

35.

Mavrodineanu

, Flame Spectroscopy (John Wiley and Sons, New York, 1965), Chap. 1, p. 15.

36.

Gaydon

A. G.

and Wolfhard

H. G

, Flames: Their Structure, Radiation, and Temperature (Chapman and Hall, London, 1960), Chap. 1, pp. 25–29.

37.

Perkin

W. H.

, J. Chem. Soc. 41, 363 (1882).

38.

Beatty

H. A.

and Edgar

, J. Am. Chem. Soc. 56, 112 (1934).

39.

Spence

and Townend

D. T. A

, in Proceedings of the Third Symposium on Combustion, Flame and Explosion Phenomena (Williams and Wilkins, Baltimore, 1949), pp. 404–415.

40.

Emeleus

H. J.

, J. Chem. Soc. 2948 (1926).

41.

Emeleus

H. J.

, J. Chem. Soc. 1733 (1929).

42.

Herzberg

and Franz

, Z. Phys. 76, 720 (1931).

43.

Ubbelohde

A. R.

, Proc. Roy. Soc. 152, 354 (1935).

44.

Pierson

R. H.

Fletcher

A. N.

and Gantz

E. S. C

, Anal. Chem. 28, 1218 (1956).

45.

Brand

J. C. D.

, J. Chem. Soc. 858 (1956).

46.

Nakamoto

, Infrared Spectra of Inorganic and Coordination Compounds (John Wiley and Sons, New York, 1963), p. 95.

47.

Fletcher

C. J.

, Proc. Roy. Soc. (London) 147, 119 (1934).

48.

Pouchert

C. J.

, The Aldrich Library of Infrared Spectra (Aldrich Chemical Co., Milwaukee, Wisconsin, 1970), pp. 485–486.