Abstract

Simplified equations are developed for computing the emissivity of the carbon dioxide 4.3µ, band. The harmonic oscillator model is assumed in computing band intensities, but anharmonicity is considered in computing the spectral distribution of emitted radiation. Calculated values of <i>S¯</i>/<i>d</i> and 2α<sub>0</sub><sup>½</sup><i>S¯</i><sup>½</sup>/<i>d</i> are presented for temperatures ranging from 300° to 3000°K, from which emissivities may be readily computed for a given pressure and optical path in both the weak-line and strong-line approximations. In the absence of significant Doppler broadening, both approximations provide upper limits to the emissivity. Emissivities are also computed for the case of a pure Doppler line shape for temperatures ranging from 300° to 1500°K. Doppler broadening is shown to be an important factor in setting a lower limit to the possible values of emissivity obtained at low pressures and long path lengths. Comparisons are made with published experimental data using the weak-line approximation; in several cases, the strong-line approximation as well as a mixed strong-line-weak-line approximation is also shown. The results of the present work are shown to be in good agreement with published experimental data and in definite disagreement with other theoretical calculations.

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  1. G. N. Plass, J. Opt. Soc. Am. 49, 821 (1959).
  2. C. C. Ferriso, Astronautics Report AE 61–0910, "High Temperature Infrared Emission and Absorption Studies," September 1961; also published in J. Chem. Phys. 37, 1955 (1962).
  3. R. H. Tourin, J. Opt. Soc. Am. 51, 175 (1961).
  4. D. E. Burch and D. A. Gryvnak, "Infrared Radiation Emitted by Hot Gases and its Transmission Through Synthetic Atmospheres," Aeronutronic Rep. U-1929, October 1962.
  5. M. Steinberg and W. O. Davies, J. Chem. Phys. 34, 1373 (1961).
  6. G. Herzberg, Infrared and Raman Spectra (D. Van Nostrand Inc., Princeton, New Jersey, 1945), p. 380.
  7. W. Malkmus and A. Thomson, Convair Report ZPh-095, "Infrared Emissivity of Diatomic Gases for the Anharmonic Vibrating Rotator Model," May 1961; also published in J. Quant. Spectry. Radiative Transfer 2, 17 (1962).
  8. G. N. Plass, J. Opt. Soc. Am. 48, 690 (1958).
  9. W. Malkmus, "Infrared Emissivity of Diatomic Gases with Doppler Line Shape," Convair Report ZPh-119, September 1961; also to be published in another journal.
  10. Reference 5, p. 211.
  11. Reference 5, p. 215.
  12. This approximation is based on Dennison's values (x13= -21.9, x23= -11.0) as given by Herzberg,13 and used by Plass.8 Courtoy's14 more recent measurements differ somewhat (x13= 19.37, x23= 12.53); however, the exactness of the approximation x13≈2x23 is not critical since x13υ1+x23υ2≡ x¯υ+½(½x13-x23)(2υ12). The second term is dropped in Eq. (6); its coefficient is small compared with x¯ (using either set of data), and the factor |2υ12| ≤υ. The approximation ω1≈2ω2 is very close; however, the same remarks apply to its noncriticality.
  13. Reference 6, p. 276.
  14. C. P. Courtoy, Can. J. Phys. 35, 608 (1957).
  15. Reference 5, p. 503.
  16. S. S. Penner, Quantitative Molecular Spectroscopy and Gas Emissivities (Addison-Wesley Publishing Company, Inc., Reading, Massachusetts, 1959), p. 152.
  17. D. M. Dennison, Rev. Mod. Phys. 3, 280 (1931).
  18. W. S. Benedict and E. K. Plyler, "High-Resolution Spectra of Hydrocarbon Flames," in Energy Transfer in Hot Gases, pp. 57–73, Natl. Bur. Std. Circ. No. 523, 1954.
  19. L. D. Kaplan and D. F. Eggers, J. Chem. Phys. 25, 876 (1956).
  20. R. Herman and R. F. Wallis, J. Chem. Phys. 23, 635 (1955).
  21. R. P. Madden, J. Chem. Phys. 35, 2083 (1961).
  22. D. W. G. Ballentyne and L. E. Q. Walker, A Dictionary of Named Effects and Laws in Chemistry, Physics and Mathematics (The Macmillan Company, New York, 1961), 2nd ed., p. 14; Van Nostrand's Scientific Encyclopedia (D. Van Nostrand Inc., New York, 1958), 3rd ed., p. 181; Encyclopaedic Dictionary of Physics (Pergamon Press, Inc., New York, 1961), p. 388. Also known as Beer-Bouguer or Beer-Lambert Law.
  23. Assume a statistical distribution of lines of intensity S with an arbitrary probability distribution P(S). Then we have8 [equation] where p is the total pressure, c the mole fraction of absorbing gas, and b(p, ω) the normalized line shape factor. If we assume the line shape to be linearly pressure broadened, but otherwise arbitrary we have b(p ω) = p-1[(ω-ω0)/p], where f is an arbitrary function of its argument. If we change the lower limit of the integral over ω from 0 to -∞ for mathematical convenience and make the substitution u= (ω-ω0)/p, we find [equation] Thus In(I0/I) is linear in p, although Beer's law is not satisfied in general, as is seen from the complicated functional dependence on l.
  24. A. Thomson (private communication).
  25. H. J. Babrov, P. M. Henry, and R. H. Tourin, The Warner & Swasey Company Scientific Report No. 2 under Contract AF19(604)-6106, "Methods of Predicting Infrared Radiance of Flames by Extrapolation from Laboratory Measurements," October 1961; also published in J. Chem. Phys. 37, 581 (1962).
  26. U. P. Oppenheim and Y. Ben-Aryeh, J. Opt. Soc. Am. 53, 344 (1963).

Ferriso, C. C.

C. C. Ferriso, Astronautics Report AE 61–0910, "High Temperature Infrared Emission and Absorption Studies," September 1961; also published in J. Chem. Phys. 37, 1955 (1962).

Penner, S. S.

S. S. Penner, Quantitative Molecular Spectroscopy and Gas Emissivities (Addison-Wesley Publishing Company, Inc., Reading, Massachusetts, 1959), p. 152.

Thomson, A.

A. Thomson (private communication).

Babrov, H. J.

H. J. Babrov, P. M. Henry, and R. H. Tourin, The Warner & Swasey Company Scientific Report No. 2 under Contract AF19(604)-6106, "Methods of Predicting Infrared Radiance of Flames by Extrapolation from Laboratory Measurements," October 1961; also published in J. Chem. Phys. 37, 581 (1962).

Ballentyne, D. W. G.

D. W. G. Ballentyne and L. E. Q. Walker, A Dictionary of Named Effects and Laws in Chemistry, Physics and Mathematics (The Macmillan Company, New York, 1961), 2nd ed., p. 14; Van Nostrand's Scientific Encyclopedia (D. Van Nostrand Inc., New York, 1958), 3rd ed., p. 181; Encyclopaedic Dictionary of Physics (Pergamon Press, Inc., New York, 1961), p. 388. Also known as Beer-Bouguer or Beer-Lambert Law.

Ben-Aryeh, Y.

U. P. Oppenheim and Y. Ben-Aryeh, J. Opt. Soc. Am. 53, 344 (1963).

Benedict, W. S.

W. S. Benedict and E. K. Plyler, "High-Resolution Spectra of Hydrocarbon Flames," in Energy Transfer in Hot Gases, pp. 57–73, Natl. Bur. Std. Circ. No. 523, 1954.

Burch, D. E.

D. E. Burch and D. A. Gryvnak, "Infrared Radiation Emitted by Hot Gases and its Transmission Through Synthetic Atmospheres," Aeronutronic Rep. U-1929, October 1962.

Courtoy, C. P.

C. P. Courtoy, Can. J. Phys. 35, 608 (1957).

Davies, W. O.

M. Steinberg and W. O. Davies, J. Chem. Phys. 34, 1373 (1961).

Dennison, D. M.

D. M. Dennison, Rev. Mod. Phys. 3, 280 (1931).

Eggers, D. F.

L. D. Kaplan and D. F. Eggers, J. Chem. Phys. 25, 876 (1956).

Gryvnak, D. A.

D. E. Burch and D. A. Gryvnak, "Infrared Radiation Emitted by Hot Gases and its Transmission Through Synthetic Atmospheres," Aeronutronic Rep. U-1929, October 1962.

Henry, P. M.

H. J. Babrov, P. M. Henry, and R. H. Tourin, The Warner & Swasey Company Scientific Report No. 2 under Contract AF19(604)-6106, "Methods of Predicting Infrared Radiance of Flames by Extrapolation from Laboratory Measurements," October 1961; also published in J. Chem. Phys. 37, 581 (1962).

Herman, R.

R. Herman and R. F. Wallis, J. Chem. Phys. 23, 635 (1955).

Herzberg, G.

G. Herzberg, Infrared and Raman Spectra (D. Van Nostrand Inc., Princeton, New Jersey, 1945), p. 380.

Kaplan, L. D.

L. D. Kaplan and D. F. Eggers, J. Chem. Phys. 25, 876 (1956).

Madden, R. P.

R. P. Madden, J. Chem. Phys. 35, 2083 (1961).

Malkmus, W.

W. Malkmus and A. Thomson, Convair Report ZPh-095, "Infrared Emissivity of Diatomic Gases for the Anharmonic Vibrating Rotator Model," May 1961; also published in J. Quant. Spectry. Radiative Transfer 2, 17 (1962).

W. Malkmus, "Infrared Emissivity of Diatomic Gases with Doppler Line Shape," Convair Report ZPh-119, September 1961; also to be published in another journal.

Oppenheim, U. P.

U. P. Oppenheim and Y. Ben-Aryeh, J. Opt. Soc. Am. 53, 344 (1963).

Plass, G. N.

G. N. Plass, J. Opt. Soc. Am. 49, 821 (1959).

G. N. Plass, J. Opt. Soc. Am. 48, 690 (1958).

Plyler, E. K.

W. S. Benedict and E. K. Plyler, "High-Resolution Spectra of Hydrocarbon Flames," in Energy Transfer in Hot Gases, pp. 57–73, Natl. Bur. Std. Circ. No. 523, 1954.

Steinberg, M.

M. Steinberg and W. O. Davies, J. Chem. Phys. 34, 1373 (1961).

Thomson, A.

W. Malkmus and A. Thomson, Convair Report ZPh-095, "Infrared Emissivity of Diatomic Gases for the Anharmonic Vibrating Rotator Model," May 1961; also published in J. Quant. Spectry. Radiative Transfer 2, 17 (1962).

Tourin, R. H.

H. J. Babrov, P. M. Henry, and R. H. Tourin, The Warner & Swasey Company Scientific Report No. 2 under Contract AF19(604)-6106, "Methods of Predicting Infrared Radiance of Flames by Extrapolation from Laboratory Measurements," October 1961; also published in J. Chem. Phys. 37, 581 (1962).

R. H. Tourin, J. Opt. Soc. Am. 51, 175 (1961).

Walker, L. E. Q.

D. W. G. Ballentyne and L. E. Q. Walker, A Dictionary of Named Effects and Laws in Chemistry, Physics and Mathematics (The Macmillan Company, New York, 1961), 2nd ed., p. 14; Van Nostrand's Scientific Encyclopedia (D. Van Nostrand Inc., New York, 1958), 3rd ed., p. 181; Encyclopaedic Dictionary of Physics (Pergamon Press, Inc., New York, 1961), p. 388. Also known as Beer-Bouguer or Beer-Lambert Law.

Wallis, R. F.

R. Herman and R. F. Wallis, J. Chem. Phys. 23, 635 (1955).

Other

G. N. Plass, J. Opt. Soc. Am. 49, 821 (1959).

C. C. Ferriso, Astronautics Report AE 61–0910, "High Temperature Infrared Emission and Absorption Studies," September 1961; also published in J. Chem. Phys. 37, 1955 (1962).

R. H. Tourin, J. Opt. Soc. Am. 51, 175 (1961).

D. E. Burch and D. A. Gryvnak, "Infrared Radiation Emitted by Hot Gases and its Transmission Through Synthetic Atmospheres," Aeronutronic Rep. U-1929, October 1962.

M. Steinberg and W. O. Davies, J. Chem. Phys. 34, 1373 (1961).

G. Herzberg, Infrared and Raman Spectra (D. Van Nostrand Inc., Princeton, New Jersey, 1945), p. 380.

W. Malkmus and A. Thomson, Convair Report ZPh-095, "Infrared Emissivity of Diatomic Gases for the Anharmonic Vibrating Rotator Model," May 1961; also published in J. Quant. Spectry. Radiative Transfer 2, 17 (1962).

G. N. Plass, J. Opt. Soc. Am. 48, 690 (1958).

W. Malkmus, "Infrared Emissivity of Diatomic Gases with Doppler Line Shape," Convair Report ZPh-119, September 1961; also to be published in another journal.

Reference 5, p. 211.

Reference 5, p. 215.

This approximation is based on Dennison's values (x13= -21.9, x23= -11.0) as given by Herzberg,13 and used by Plass.8 Courtoy's14 more recent measurements differ somewhat (x13= 19.37, x23= 12.53); however, the exactness of the approximation x13≈2x23 is not critical since x13υ1+x23υ2≡ x¯υ+½(½x13-x23)(2υ12). The second term is dropped in Eq. (6); its coefficient is small compared with x¯ (using either set of data), and the factor |2υ12| ≤υ. The approximation ω1≈2ω2 is very close; however, the same remarks apply to its noncriticality.

Reference 6, p. 276.

C. P. Courtoy, Can. J. Phys. 35, 608 (1957).

Reference 5, p. 503.

S. S. Penner, Quantitative Molecular Spectroscopy and Gas Emissivities (Addison-Wesley Publishing Company, Inc., Reading, Massachusetts, 1959), p. 152.

D. M. Dennison, Rev. Mod. Phys. 3, 280 (1931).

W. S. Benedict and E. K. Plyler, "High-Resolution Spectra of Hydrocarbon Flames," in Energy Transfer in Hot Gases, pp. 57–73, Natl. Bur. Std. Circ. No. 523, 1954.

L. D. Kaplan and D. F. Eggers, J. Chem. Phys. 25, 876 (1956).

R. Herman and R. F. Wallis, J. Chem. Phys. 23, 635 (1955).

R. P. Madden, J. Chem. Phys. 35, 2083 (1961).

D. W. G. Ballentyne and L. E. Q. Walker, A Dictionary of Named Effects and Laws in Chemistry, Physics and Mathematics (The Macmillan Company, New York, 1961), 2nd ed., p. 14; Van Nostrand's Scientific Encyclopedia (D. Van Nostrand Inc., New York, 1958), 3rd ed., p. 181; Encyclopaedic Dictionary of Physics (Pergamon Press, Inc., New York, 1961), p. 388. Also known as Beer-Bouguer or Beer-Lambert Law.

Assume a statistical distribution of lines of intensity S with an arbitrary probability distribution P(S). Then we have8 [equation] where p is the total pressure, c the mole fraction of absorbing gas, and b(p, ω) the normalized line shape factor. If we assume the line shape to be linearly pressure broadened, but otherwise arbitrary we have b(p ω) = p-1[(ω-ω0)/p], where f is an arbitrary function of its argument. If we change the lower limit of the integral over ω from 0 to -∞ for mathematical convenience and make the substitution u= (ω-ω0)/p, we find [equation] Thus In(I0/I) is linear in p, although Beer's law is not satisfied in general, as is seen from the complicated functional dependence on l.

A. Thomson (private communication).

H. J. Babrov, P. M. Henry, and R. H. Tourin, The Warner & Swasey Company Scientific Report No. 2 under Contract AF19(604)-6106, "Methods of Predicting Infrared Radiance of Flames by Extrapolation from Laboratory Measurements," October 1961; also published in J. Chem. Phys. 37, 581 (1962).

U. P. Oppenheim and Y. Ben-Aryeh, J. Opt. Soc. Am. 53, 344 (1963).

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