Abstract

The theoretical or experimental basis of some persistent statements in the literature on the general features of atomic absorption analysis is examined. The reputed advantages of atomic absorption over flame emission analysis, with respect to sensitivity and absence of excitation interference, are critically discussed, as well as the often over-estimated influence of resonance broadening on the shape of the analytical curve. Also, the curvature of the analytical curve with a continuum source is analyzed. The use of an auxiliary flame emitting a strongly self-absorbed metal line, as an effective continuum source, is suggested.

© 1968 Optical Society of America

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References

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  1. R. Mavrodineanu, H. Boiteux, Flame Spectroscopy (John Wiley & Sons, Inc., New York, 1965).
  2. A. C. G. Mitchell, M. W. Zemansky, Resonance Radiation and Excited Atoms (Cambridge University Press, Cambridge, England, 1961).
  3. F. Burriel-Martí, J. Ramírez-Munoz, Flame Photometry, a Manual of Methods and Applications (Elsevier Publishing Company, Inc., Amsterdam, 1960).
  4. J. A. Dean, Flame Photometry (McGraw-Hill Book Company, Inc., New York, 1960).
  5. W. T. Elwell, J. A. F. Gidley, Atomic Absorption Spectrophotometry (Pergamon Press, Inc., New York, 1961).
  6. R. Herrmann, C. Th. J. Alkemade, Chemical Analysis by Flame Photometry (Interscience, New York, 1963).
  7. B. W. Lvov, Atomic Absorption Spectral Analysis (U.S.S.R. Academy of Sciences Press, Moscow, 1966).
  8. N. S. Poluéktov, Techniques in Flame Photometric Analysis (Consultants Bureau, New York1961).
  9. Ref. 1, p. 193.
  10. T. S. West, Analyst 91, 72 (1966).
  11. C. Th. J. Alkemade, J. M. W. Milatz, Appl. Sci. Res. B4, 289, 1955.
  12. R. W. Johnson, W. G. Schrenk, Appl. Spectrosc. 18, 144 (1964).
    [CrossRef]
  13. T. S. West, Symposium on Trace Characterization—Chemical and Physical, Gaithersburg, Maryland (1966).
  14. J. W. Robinson, Atomic Absorption Spectroscopy (M. Dekker, Inc., New York, 1966).
  15. W. Slavin, Atomic Absorption Newsletter No. 24,1964.
  16. C. Th. J. Alkemade, in A Handbook of Flame Emission and Absorption Methods; Practical Techniques and Procedures, J. A. Dean, T. C. Rains, Eds. (M. Dekker, Inc., New York, to be published), Chap. 4.
  17. J. W. Robinson, Anal. Chim. Acta 24, 254 (1961).
    [CrossRef]
  18. C. Th. J. Alkemade, in Analytical Flame Spectroscopy, Selected Topics, R. Mavrodineanu, Ed. (Centrex Publishing Co., Eindhoven, The Netherlands, to be published).
  19. I. Rubeška, V. Svoboda, Anal. Chim. Acta 32, 253 (1965).
    [CrossRef]
  20. W. Behmenburg, H. Kohn, M. Mlailänder, J. Quant. Spectrosc. Radiat. Transfer 4, 149 (1964).
    [CrossRef]
  21. W. Behmenburg, H. Kohn, J. Quant. Spectrosc. Radiat. Transfer 4, 163 (1964).
    [CrossRef]
  22. H. Prugger, Optik 21, 320 (1964).
  23. C. van Trigt, T. Hollander, C. Th. J. Alkemade, J. Quant. Spectrosc. Radiat. Transfer 5, 813 (1965).
    [CrossRef]
  24. M. A. Mazing, N. P. Penkin, Opt. Spectrosc. 21, 408 (1966).
  25. F. W. Hofmann, H. Kohn, J. Opt. Soc. Amer. 51, 512 (1961).
    [CrossRef]
  26. N. P. Penkin, L. N. Shabanova, Fifth International Conference on the Physics of Electronic and Atomic Collisions, Leningrad, 1967 (Abstracts of Papers, p. 519).
  27. W. Behmenburg, J. Quant. Spectrosc. Radiat. Transfer 4, 177 (1964).
    [CrossRef]
  28. M. Shimazu, A. Hashimoto, Science of Light 11, 131 (1962).
  29. K. Yasuda, Anal. Chem. 38, 592 (1966).
    [CrossRef]
  30. V. A. Fassel, V. G. Mossotti, W. E. L. Grossman, R. N. Kniseley, Spectrochim. Acta 22, 347 (1966).
    [CrossRef]
  31. M. Margoshes, in Activities of the NBS Spectrochemnical Analysis Section1965–1966; B. F. Scribner, Ed., NBS Tech. Note 401.
  32. L. de Galan, M. W. McGee, J. D. Winefordner, Anal. Chim. Acta 37, 436 (1967).
    [CrossRef]
  33. C. W. Frank, W. G. Schrenk, C. E. Meloan, Anal. Chem. 39, 534 (1967).
    [CrossRef]
  34. M. W. McGee, J. D. Winefordner, J. Quant. Spectrosc. Radiat. Transfer 7, 261 (1967).
    [CrossRef]
  35. W. Snelleman, Spectrochim. Acta 23B, 403 (1968).
  36. C. S. Rann, Spectrochim. Acta 23B, 245 (1968).

1968 (2)

W. Snelleman, Spectrochim. Acta 23B, 403 (1968).

C. S. Rann, Spectrochim. Acta 23B, 245 (1968).

1967 (3)

L. de Galan, M. W. McGee, J. D. Winefordner, Anal. Chim. Acta 37, 436 (1967).
[CrossRef]

C. W. Frank, W. G. Schrenk, C. E. Meloan, Anal. Chem. 39, 534 (1967).
[CrossRef]

M. W. McGee, J. D. Winefordner, J. Quant. Spectrosc. Radiat. Transfer 7, 261 (1967).
[CrossRef]

1966 (4)

K. Yasuda, Anal. Chem. 38, 592 (1966).
[CrossRef]

V. A. Fassel, V. G. Mossotti, W. E. L. Grossman, R. N. Kniseley, Spectrochim. Acta 22, 347 (1966).
[CrossRef]

M. A. Mazing, N. P. Penkin, Opt. Spectrosc. 21, 408 (1966).

T. S. West, Analyst 91, 72 (1966).

1965 (2)

I. Rubeška, V. Svoboda, Anal. Chim. Acta 32, 253 (1965).
[CrossRef]

C. van Trigt, T. Hollander, C. Th. J. Alkemade, J. Quant. Spectrosc. Radiat. Transfer 5, 813 (1965).
[CrossRef]

1964 (6)

W. Behmenburg, H. Kohn, M. Mlailänder, J. Quant. Spectrosc. Radiat. Transfer 4, 149 (1964).
[CrossRef]

W. Behmenburg, H. Kohn, J. Quant. Spectrosc. Radiat. Transfer 4, 163 (1964).
[CrossRef]

H. Prugger, Optik 21, 320 (1964).

R. W. Johnson, W. G. Schrenk, Appl. Spectrosc. 18, 144 (1964).
[CrossRef]

W. Slavin, Atomic Absorption Newsletter No. 24,1964.

W. Behmenburg, J. Quant. Spectrosc. Radiat. Transfer 4, 177 (1964).
[CrossRef]

1962 (1)

M. Shimazu, A. Hashimoto, Science of Light 11, 131 (1962).

1961 (2)

F. W. Hofmann, H. Kohn, J. Opt. Soc. Amer. 51, 512 (1961).
[CrossRef]

J. W. Robinson, Anal. Chim. Acta 24, 254 (1961).
[CrossRef]

1955 (1)

C. Th. J. Alkemade, J. M. W. Milatz, Appl. Sci. Res. B4, 289, 1955.

Alkemade, C. Th. J.

C. van Trigt, T. Hollander, C. Th. J. Alkemade, J. Quant. Spectrosc. Radiat. Transfer 5, 813 (1965).
[CrossRef]

C. Th. J. Alkemade, J. M. W. Milatz, Appl. Sci. Res. B4, 289, 1955.

R. Herrmann, C. Th. J. Alkemade, Chemical Analysis by Flame Photometry (Interscience, New York, 1963).

C. Th. J. Alkemade, in A Handbook of Flame Emission and Absorption Methods; Practical Techniques and Procedures, J. A. Dean, T. C. Rains, Eds. (M. Dekker, Inc., New York, to be published), Chap. 4.

C. Th. J. Alkemade, in Analytical Flame Spectroscopy, Selected Topics, R. Mavrodineanu, Ed. (Centrex Publishing Co., Eindhoven, The Netherlands, to be published).

Behmenburg, W.

W. Behmenburg, H. Kohn, M. Mlailänder, J. Quant. Spectrosc. Radiat. Transfer 4, 149 (1964).
[CrossRef]

W. Behmenburg, H. Kohn, J. Quant. Spectrosc. Radiat. Transfer 4, 163 (1964).
[CrossRef]

W. Behmenburg, J. Quant. Spectrosc. Radiat. Transfer 4, 177 (1964).
[CrossRef]

Boiteux, H.

R. Mavrodineanu, H. Boiteux, Flame Spectroscopy (John Wiley & Sons, Inc., New York, 1965).

Burriel-Martí, F.

F. Burriel-Martí, J. Ramírez-Munoz, Flame Photometry, a Manual of Methods and Applications (Elsevier Publishing Company, Inc., Amsterdam, 1960).

de Galan, L.

L. de Galan, M. W. McGee, J. D. Winefordner, Anal. Chim. Acta 37, 436 (1967).
[CrossRef]

Dean, J. A.

J. A. Dean, Flame Photometry (McGraw-Hill Book Company, Inc., New York, 1960).

Elwell, W. T.

W. T. Elwell, J. A. F. Gidley, Atomic Absorption Spectrophotometry (Pergamon Press, Inc., New York, 1961).

Fassel, V. A.

V. A. Fassel, V. G. Mossotti, W. E. L. Grossman, R. N. Kniseley, Spectrochim. Acta 22, 347 (1966).
[CrossRef]

Frank, C. W.

C. W. Frank, W. G. Schrenk, C. E. Meloan, Anal. Chem. 39, 534 (1967).
[CrossRef]

Gidley, J. A. F.

W. T. Elwell, J. A. F. Gidley, Atomic Absorption Spectrophotometry (Pergamon Press, Inc., New York, 1961).

Grossman, W. E. L.

V. A. Fassel, V. G. Mossotti, W. E. L. Grossman, R. N. Kniseley, Spectrochim. Acta 22, 347 (1966).
[CrossRef]

Hashimoto, A.

M. Shimazu, A. Hashimoto, Science of Light 11, 131 (1962).

Herrmann, R.

R. Herrmann, C. Th. J. Alkemade, Chemical Analysis by Flame Photometry (Interscience, New York, 1963).

Hofmann, F. W.

F. W. Hofmann, H. Kohn, J. Opt. Soc. Amer. 51, 512 (1961).
[CrossRef]

Hollander, T.

C. van Trigt, T. Hollander, C. Th. J. Alkemade, J. Quant. Spectrosc. Radiat. Transfer 5, 813 (1965).
[CrossRef]

Johnson, R. W.

Kniseley, R. N.

V. A. Fassel, V. G. Mossotti, W. E. L. Grossman, R. N. Kniseley, Spectrochim. Acta 22, 347 (1966).
[CrossRef]

Kohn, H.

W. Behmenburg, H. Kohn, J. Quant. Spectrosc. Radiat. Transfer 4, 163 (1964).
[CrossRef]

W. Behmenburg, H. Kohn, M. Mlailänder, J. Quant. Spectrosc. Radiat. Transfer 4, 149 (1964).
[CrossRef]

F. W. Hofmann, H. Kohn, J. Opt. Soc. Amer. 51, 512 (1961).
[CrossRef]

Lvov, B. W.

B. W. Lvov, Atomic Absorption Spectral Analysis (U.S.S.R. Academy of Sciences Press, Moscow, 1966).

Margoshes, M.

M. Margoshes, in Activities of the NBS Spectrochemnical Analysis Section1965–1966; B. F. Scribner, Ed., NBS Tech. Note 401.

Mavrodineanu, R.

R. Mavrodineanu, H. Boiteux, Flame Spectroscopy (John Wiley & Sons, Inc., New York, 1965).

Mazing, M. A.

M. A. Mazing, N. P. Penkin, Opt. Spectrosc. 21, 408 (1966).

McGee, M. W.

L. de Galan, M. W. McGee, J. D. Winefordner, Anal. Chim. Acta 37, 436 (1967).
[CrossRef]

M. W. McGee, J. D. Winefordner, J. Quant. Spectrosc. Radiat. Transfer 7, 261 (1967).
[CrossRef]

Meloan, C. E.

C. W. Frank, W. G. Schrenk, C. E. Meloan, Anal. Chem. 39, 534 (1967).
[CrossRef]

Milatz, J. M. W.

C. Th. J. Alkemade, J. M. W. Milatz, Appl. Sci. Res. B4, 289, 1955.

Mitchell, A. C. G.

A. C. G. Mitchell, M. W. Zemansky, Resonance Radiation and Excited Atoms (Cambridge University Press, Cambridge, England, 1961).

Mlailänder, M.

W. Behmenburg, H. Kohn, M. Mlailänder, J. Quant. Spectrosc. Radiat. Transfer 4, 149 (1964).
[CrossRef]

Mossotti, V. G.

V. A. Fassel, V. G. Mossotti, W. E. L. Grossman, R. N. Kniseley, Spectrochim. Acta 22, 347 (1966).
[CrossRef]

Penkin, N. P.

M. A. Mazing, N. P. Penkin, Opt. Spectrosc. 21, 408 (1966).

N. P. Penkin, L. N. Shabanova, Fifth International Conference on the Physics of Electronic and Atomic Collisions, Leningrad, 1967 (Abstracts of Papers, p. 519).

Poluéktov, N. S.

N. S. Poluéktov, Techniques in Flame Photometric Analysis (Consultants Bureau, New York1961).

Prugger, H.

H. Prugger, Optik 21, 320 (1964).

Ramírez-Munoz, J.

F. Burriel-Martí, J. Ramírez-Munoz, Flame Photometry, a Manual of Methods and Applications (Elsevier Publishing Company, Inc., Amsterdam, 1960).

Rann, C. S.

C. S. Rann, Spectrochim. Acta 23B, 245 (1968).

Robinson, J. W.

J. W. Robinson, Anal. Chim. Acta 24, 254 (1961).
[CrossRef]

J. W. Robinson, Atomic Absorption Spectroscopy (M. Dekker, Inc., New York, 1966).

Rubeška, I.

I. Rubeška, V. Svoboda, Anal. Chim. Acta 32, 253 (1965).
[CrossRef]

Schrenk, W. G.

C. W. Frank, W. G. Schrenk, C. E. Meloan, Anal. Chem. 39, 534 (1967).
[CrossRef]

R. W. Johnson, W. G. Schrenk, Appl. Spectrosc. 18, 144 (1964).
[CrossRef]

Shabanova, L. N.

N. P. Penkin, L. N. Shabanova, Fifth International Conference on the Physics of Electronic and Atomic Collisions, Leningrad, 1967 (Abstracts of Papers, p. 519).

Shimazu, M.

M. Shimazu, A. Hashimoto, Science of Light 11, 131 (1962).

Slavin, W.

W. Slavin, Atomic Absorption Newsletter No. 24,1964.

Snelleman, W.

W. Snelleman, Spectrochim. Acta 23B, 403 (1968).

Svoboda, V.

I. Rubeška, V. Svoboda, Anal. Chim. Acta 32, 253 (1965).
[CrossRef]

van Trigt, C.

C. van Trigt, T. Hollander, C. Th. J. Alkemade, J. Quant. Spectrosc. Radiat. Transfer 5, 813 (1965).
[CrossRef]

West, T. S.

T. S. West, Analyst 91, 72 (1966).

T. S. West, Symposium on Trace Characterization—Chemical and Physical, Gaithersburg, Maryland (1966).

Winefordner, J. D.

L. de Galan, M. W. McGee, J. D. Winefordner, Anal. Chim. Acta 37, 436 (1967).
[CrossRef]

M. W. McGee, J. D. Winefordner, J. Quant. Spectrosc. Radiat. Transfer 7, 261 (1967).
[CrossRef]

Yasuda, K.

K. Yasuda, Anal. Chem. 38, 592 (1966).
[CrossRef]

Zemansky, M. W.

A. C. G. Mitchell, M. W. Zemansky, Resonance Radiation and Excited Atoms (Cambridge University Press, Cambridge, England, 1961).

Anal. Chem. (2)

K. Yasuda, Anal. Chem. 38, 592 (1966).
[CrossRef]

C. W. Frank, W. G. Schrenk, C. E. Meloan, Anal. Chem. 39, 534 (1967).
[CrossRef]

Anal. Chim. Acta (3)

I. Rubeška, V. Svoboda, Anal. Chim. Acta 32, 253 (1965).
[CrossRef]

J. W. Robinson, Anal. Chim. Acta 24, 254 (1961).
[CrossRef]

L. de Galan, M. W. McGee, J. D. Winefordner, Anal. Chim. Acta 37, 436 (1967).
[CrossRef]

Analyst (1)

T. S. West, Analyst 91, 72 (1966).

Appl. Sci. Res. (1)

C. Th. J. Alkemade, J. M. W. Milatz, Appl. Sci. Res. B4, 289, 1955.

Appl. Spectrosc. (1)

Atomic Absorption Newsletter No. 24 (1)

W. Slavin, Atomic Absorption Newsletter No. 24,1964.

J. Opt. Soc. Amer. (1)

F. W. Hofmann, H. Kohn, J. Opt. Soc. Amer. 51, 512 (1961).
[CrossRef]

J. Quant. Spectrosc. Radiat. Transfer (5)

C. van Trigt, T. Hollander, C. Th. J. Alkemade, J. Quant. Spectrosc. Radiat. Transfer 5, 813 (1965).
[CrossRef]

W. Behmenburg, H. Kohn, M. Mlailänder, J. Quant. Spectrosc. Radiat. Transfer 4, 149 (1964).
[CrossRef]

W. Behmenburg, H. Kohn, J. Quant. Spectrosc. Radiat. Transfer 4, 163 (1964).
[CrossRef]

M. W. McGee, J. D. Winefordner, J. Quant. Spectrosc. Radiat. Transfer 7, 261 (1967).
[CrossRef]

W. Behmenburg, J. Quant. Spectrosc. Radiat. Transfer 4, 177 (1964).
[CrossRef]

Opt. Spectrosc. (1)

M. A. Mazing, N. P. Penkin, Opt. Spectrosc. 21, 408 (1966).

Optik (1)

H. Prugger, Optik 21, 320 (1964).

Science of Light (1)

M. Shimazu, A. Hashimoto, Science of Light 11, 131 (1962).

Spectrochim. Acta (3)

V. A. Fassel, V. G. Mossotti, W. E. L. Grossman, R. N. Kniseley, Spectrochim. Acta 22, 347 (1966).
[CrossRef]

W. Snelleman, Spectrochim. Acta 23B, 403 (1968).

C. S. Rann, Spectrochim. Acta 23B, 245 (1968).

Other (15)

M. Margoshes, in Activities of the NBS Spectrochemnical Analysis Section1965–1966; B. F. Scribner, Ed., NBS Tech. Note 401.

N. P. Penkin, L. N. Shabanova, Fifth International Conference on the Physics of Electronic and Atomic Collisions, Leningrad, 1967 (Abstracts of Papers, p. 519).

C. Th. J. Alkemade, in A Handbook of Flame Emission and Absorption Methods; Practical Techniques and Procedures, J. A. Dean, T. C. Rains, Eds. (M. Dekker, Inc., New York, to be published), Chap. 4.

C. Th. J. Alkemade, in Analytical Flame Spectroscopy, Selected Topics, R. Mavrodineanu, Ed. (Centrex Publishing Co., Eindhoven, The Netherlands, to be published).

T. S. West, Symposium on Trace Characterization—Chemical and Physical, Gaithersburg, Maryland (1966).

J. W. Robinson, Atomic Absorption Spectroscopy (M. Dekker, Inc., New York, 1966).

R. Mavrodineanu, H. Boiteux, Flame Spectroscopy (John Wiley & Sons, Inc., New York, 1965).

A. C. G. Mitchell, M. W. Zemansky, Resonance Radiation and Excited Atoms (Cambridge University Press, Cambridge, England, 1961).

F. Burriel-Martí, J. Ramírez-Munoz, Flame Photometry, a Manual of Methods and Applications (Elsevier Publishing Company, Inc., Amsterdam, 1960).

J. A. Dean, Flame Photometry (McGraw-Hill Book Company, Inc., New York, 1960).

W. T. Elwell, J. A. F. Gidley, Atomic Absorption Spectrophotometry (Pergamon Press, Inc., New York, 1961).

R. Herrmann, C. Th. J. Alkemade, Chemical Analysis by Flame Photometry (Interscience, New York, 1963).

B. W. Lvov, Atomic Absorption Spectral Analysis (U.S.S.R. Academy of Sciences Press, Moscow, 1966).

N. S. Poluéktov, Techniques in Flame Photometric Analysis (Consultants Bureau, New York1961).

Ref. 1, p. 193.

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Figures (2)

Fig. 1
Fig. 1

Simplified spectral profile of the same resonance line seen in (a) emission and in (b) absorption. The spectral profile of the radiation from the background source is shown in (c). The widths of the profiles are indicated.

Fig. 2
Fig. 2

Relative absorption ΔI/I0 measured with a continuum source is plotted double logarithmically as a function of metal solution concentration C (schematic). A typical spectral profile of the absorption factor α (λ) is also shown schematically for the linear (tan β = 1), parabolic (tan β = ½), and horizontal portions of the curve, respectively. The spectral bandwidth of the monochromator used is indicated by ΔλM. The points of intersection of the dotted asymptotes are indicated at the concentration axis (C1 and C2). The broken curve is obtained when ΔλM is increased by a factor of ten.

Equations (13)

Equations on this page are rendered with MathJax. Learn more.

I e m = J P l ( T F ) Δ λ F ,
Δ I = α J S Δ λ F , if Δ λ S Δ λ F ,
Δ I = α J S Δ λ S , if Δ λ S < Δ λ F .
( λ ) = α ( λ ) .
G = Δ I / I e m = J S / J P l ( T F ) , if Δ λ S Δ λ F
G = Δ I / I e m = [ J S / J P l ( T F ) ] ( Δ λ S / Δ λ F ) , if Δ λ S < Δ λ F .
J P l ( T eff ) J S ,
A + B * A * + B .
Δ I = I 0 - I = I 0 Δ λ α ( λ ) d λ / Δ λ M = I 0 A t / Δ λ M
A t = Δ λ α ( λ ) d λ .
Δ I / I 0 = A t / Δ λ M ,             ( with Δ λ M Δ λ ) .
A 0.43 ( Δ I / I 0 ) ( 1 + 1 2 Δ I / I 0 ) ,
I e m = ( λ ) J P l ( d λ ) λ J P l ( λ 0 ) ( λ ) d λ = J P l ( λ 0 ) α ( λ ) d λ = J P l ( λ 0 ) A t .

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