Abstract

The optimum concentration technique for increasing the intensity of the Raman spectrum of a colored substance has been considered in detail. Intensity-concentration data are given for a number of Raman lines. An optimum concentration for a maximum in observed Raman intensity is shown to exist for each of the Raman lines examined. An expression has been derived relating the observed Raman intensity with the molar concentration of a solution of absorbing substance in a transparent solvent by consideration of the absorption of both the exciting radiation and the scattered radiation. The agreement between the theoretical curves and the experimental points is good. More experimental data are necessary to check further the theoretical expression. The best technique for obtaining the Raman spectra of colored substances is to use excitation radiation which will not be absorbed and which will not cause photochemical decomposition. When light sources which emit such radiation are not available, the optimum-concentration technique has been shown to be a possible alternative method for obtaining a Raman spectrum.

© 1959 Optical Society of America

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References

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  1. D. H. Rank and et al., Anal. Chem. 19, 700 (1947).
    [Crossref]
  2. F. T. King and E. R. Lippincott, J. Opt. Soc. Am. 46, 661 (1956).
    [Crossref]
  3. Stammreich, Forneris, and Tavares, J. Chem. Phys. 25, 580 (1956).
    [Crossref]
  4. H. Stammreich, Spectrochim. Acta 8, 41 (1956).
    [Crossref]
  5. H. Stammreich and R. Forneris, Spectrochim. Acta 8, 46 (1956).
    [Crossref]
  6. H. Stammreich and R. Forneris, Spectrochim. Acta 8, 52 (1956).
    [Crossref]
  7. E. R. Lippincott and R. D. Nelson, J. Chem. Phys. 21, 1307 (1953).
    [Crossref]
  8. F. T. King and E. R. Lippincott, J. Am. Chem. Soc. 78, 4192 (1956).
    [Crossref]
  9. Fateley, Curnutte, and Lippincott, J. Chem. Phys. 26, 1471 (1957).
    [Crossref]
  10. R. D. Fisher, Master’s thesis, “Raman spectra of certain colored substances and the existence of an optimum concentration for maximum intensity of scattered radiation,” Kansas State College (1954).
  11. Long, Milner, and Thomas, Proc. Roy. Soc. (London) A237, 186 (1956).
  12. A. Lofthus, Spectrochim. Acta 9, 216 (1953).
    [Crossref]
  13. J. Chien and P. Bender, J. Chem. Phys. 15, 376 (1947).
    [Crossref]
  14. R. A. Bafford, Master’s thesis, “The construction of an automatic recording Raman spectrometer,” University of Maryland (1956).
  15. J. H. Hibben, The Raman Effect and Its Chemical Applications (Reinhold Publishing Corporation, New York, 1939), p. 29.
  16. Prosen, Johnson, and Rossini, J. Am. Chem. Soc. 69, 2068 (1947).
    [Crossref]
  17. A. C. Cope and C. G. Overberger, J. Am. Chem. Soc. 70, 1433 (1948).
    [Crossref] [PubMed]
  18. Eccleston, Coleman, and Adams, J. Am. Chem. Soc. 72, 3866 (1950).
    [Crossref]
  19. Lippincott, Lord, and McDonald, J. Am. Chem. Soc. 73, 3370 (1951).
    [Crossref]
  20. E. Noelting and O. Kohn, Ber. deut. chem. Ges. 17, 371 (1884).
    [Crossref]
  21. E. Noelting and E. Salis, Ber. deut. chem. Ges. 14, 987 (1881).
  22. Braude, Fawcett, and Timmons, J. Chem. Soc. 1019 (1950).
  23. A. E. Gillam and E. S. Stern, An Introduction to Electronic Absorption Spectroscopy in Organic Chemistry (Edward Arnold, London, 1954), p. 8.
  24. Harrison, Lord, and Loofbourow, Practical Spectroscopy (Prentice-Hall, Inc., Englewood Cliffs, New Jersey, 1948), p. 364.
  25. E. C. C. Baly, Spectroscopy (Longmans Green and Company, New York, 1912), p. 492
  26. Ungnade, Kerr, and Youse, Science 113, 60 (1951).
    [Crossref]
  27. Vandenbelt, Henrich, and Bash, Science 114, 576 (1951).
    [Crossref]
  28. I. G. Ross, J. Opt. Soc. Am. 44, 40 (1954).
    [Crossref]
  29. Rosenbaum, Cerato, and Lauer, J. Opt. Soc. Am. 42, 670 (1952).
    [Crossref]
  30. G. H. Dieke and H. M. Crosswhite, J. Opt. Soc. Am. 35, 476 (1945).
    [Crossref]
  31. L. A. Woodward and J. H. B. George, Nature 167, 193 (1951).
    [Crossref]
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    [Crossref]
  33. H. J. Bernstein and G. Allen, J. Opt. Soc. Am. 45, 237 (1955).
    [Crossref]
  34. Long, Milner, and Thomas, Proc. Roy. Soc. (London) A237, 197 (1956).
  35. D. S. McClure, J. Chem. Phys. 19, 670 (1951).
    [Crossref]

1957 (1)

Fateley, Curnutte, and Lippincott, J. Chem. Phys. 26, 1471 (1957).
[Crossref]

1956 (8)

Long, Milner, and Thomas, Proc. Roy. Soc. (London) A237, 186 (1956).

F. T. King and E. R. Lippincott, J. Opt. Soc. Am. 46, 661 (1956).
[Crossref]

Stammreich, Forneris, and Tavares, J. Chem. Phys. 25, 580 (1956).
[Crossref]

H. Stammreich, Spectrochim. Acta 8, 41 (1956).
[Crossref]

H. Stammreich and R. Forneris, Spectrochim. Acta 8, 46 (1956).
[Crossref]

H. Stammreich and R. Forneris, Spectrochim. Acta 8, 52 (1956).
[Crossref]

F. T. King and E. R. Lippincott, J. Am. Chem. Soc. 78, 4192 (1956).
[Crossref]

Long, Milner, and Thomas, Proc. Roy. Soc. (London) A237, 197 (1956).

1955 (1)

1954 (1)

1953 (3)

R. F. Stamm and C. F. Salzman, J. Opt. Soc. Am. 43, 126 (1953).
[Crossref]

E. R. Lippincott and R. D. Nelson, J. Chem. Phys. 21, 1307 (1953).
[Crossref]

A. Lofthus, Spectrochim. Acta 9, 216 (1953).
[Crossref]

1952 (1)

1951 (5)

L. A. Woodward and J. H. B. George, Nature 167, 193 (1951).
[Crossref]

D. S. McClure, J. Chem. Phys. 19, 670 (1951).
[Crossref]

Lippincott, Lord, and McDonald, J. Am. Chem. Soc. 73, 3370 (1951).
[Crossref]

Ungnade, Kerr, and Youse, Science 113, 60 (1951).
[Crossref]

Vandenbelt, Henrich, and Bash, Science 114, 576 (1951).
[Crossref]

1950 (2)

Eccleston, Coleman, and Adams, J. Am. Chem. Soc. 72, 3866 (1950).
[Crossref]

Braude, Fawcett, and Timmons, J. Chem. Soc. 1019 (1950).

1948 (1)

A. C. Cope and C. G. Overberger, J. Am. Chem. Soc. 70, 1433 (1948).
[Crossref] [PubMed]

1947 (3)

D. H. Rank and et al., Anal. Chem. 19, 700 (1947).
[Crossref]

J. Chien and P. Bender, J. Chem. Phys. 15, 376 (1947).
[Crossref]

Prosen, Johnson, and Rossini, J. Am. Chem. Soc. 69, 2068 (1947).
[Crossref]

1945 (1)

G. H. Dieke and H. M. Crosswhite, J. Opt. Soc. Am. 35, 476 (1945).
[Crossref]

1884 (1)

E. Noelting and O. Kohn, Ber. deut. chem. Ges. 17, 371 (1884).
[Crossref]

1881 (1)

E. Noelting and E. Salis, Ber. deut. chem. Ges. 14, 987 (1881).

Adams,

Eccleston, Coleman, and Adams, J. Am. Chem. Soc. 72, 3866 (1950).
[Crossref]

Allen, G.

Bafford, R. A.

R. A. Bafford, Master’s thesis, “The construction of an automatic recording Raman spectrometer,” University of Maryland (1956).

Baly, E. C. C.

E. C. C. Baly, Spectroscopy (Longmans Green and Company, New York, 1912), p. 492

Bash,

Vandenbelt, Henrich, and Bash, Science 114, 576 (1951).
[Crossref]

Bender, P.

J. Chien and P. Bender, J. Chem. Phys. 15, 376 (1947).
[Crossref]

Bernstein, H. J.

Braude,

Braude, Fawcett, and Timmons, J. Chem. Soc. 1019 (1950).

Cerato,

Chien, J.

J. Chien and P. Bender, J. Chem. Phys. 15, 376 (1947).
[Crossref]

Coleman,

Eccleston, Coleman, and Adams, J. Am. Chem. Soc. 72, 3866 (1950).
[Crossref]

Cope, A. C.

A. C. Cope and C. G. Overberger, J. Am. Chem. Soc. 70, 1433 (1948).
[Crossref] [PubMed]

Crosswhite, H. M.

G. H. Dieke and H. M. Crosswhite, J. Opt. Soc. Am. 35, 476 (1945).
[Crossref]

Curnutte,

Fateley, Curnutte, and Lippincott, J. Chem. Phys. 26, 1471 (1957).
[Crossref]

Dieke, G. H.

G. H. Dieke and H. M. Crosswhite, J. Opt. Soc. Am. 35, 476 (1945).
[Crossref]

Eccleston,

Eccleston, Coleman, and Adams, J. Am. Chem. Soc. 72, 3866 (1950).
[Crossref]

Fateley,

Fateley, Curnutte, and Lippincott, J. Chem. Phys. 26, 1471 (1957).
[Crossref]

Fawcett,

Braude, Fawcett, and Timmons, J. Chem. Soc. 1019 (1950).

Fisher, R. D.

R. D. Fisher, Master’s thesis, “Raman spectra of certain colored substances and the existence of an optimum concentration for maximum intensity of scattered radiation,” Kansas State College (1954).

Forneris,

Stammreich, Forneris, and Tavares, J. Chem. Phys. 25, 580 (1956).
[Crossref]

Forneris, R.

H. Stammreich and R. Forneris, Spectrochim. Acta 8, 46 (1956).
[Crossref]

H. Stammreich and R. Forneris, Spectrochim. Acta 8, 52 (1956).
[Crossref]

George, J. H. B.

L. A. Woodward and J. H. B. George, Nature 167, 193 (1951).
[Crossref]

Gillam, A. E.

A. E. Gillam and E. S. Stern, An Introduction to Electronic Absorption Spectroscopy in Organic Chemistry (Edward Arnold, London, 1954), p. 8.

Harrison,

Harrison, Lord, and Loofbourow, Practical Spectroscopy (Prentice-Hall, Inc., Englewood Cliffs, New Jersey, 1948), p. 364.

Henrich,

Vandenbelt, Henrich, and Bash, Science 114, 576 (1951).
[Crossref]

Hibben, J. H.

J. H. Hibben, The Raman Effect and Its Chemical Applications (Reinhold Publishing Corporation, New York, 1939), p. 29.

Johnson,

Prosen, Johnson, and Rossini, J. Am. Chem. Soc. 69, 2068 (1947).
[Crossref]

Kerr,

Ungnade, Kerr, and Youse, Science 113, 60 (1951).
[Crossref]

King, F. T.

F. T. King and E. R. Lippincott, J. Am. Chem. Soc. 78, 4192 (1956).
[Crossref]

F. T. King and E. R. Lippincott, J. Opt. Soc. Am. 46, 661 (1956).
[Crossref]

Kohn, O.

E. Noelting and O. Kohn, Ber. deut. chem. Ges. 17, 371 (1884).
[Crossref]

Lauer,

Lippincott,

Fateley, Curnutte, and Lippincott, J. Chem. Phys. 26, 1471 (1957).
[Crossref]

Lippincott, Lord, and McDonald, J. Am. Chem. Soc. 73, 3370 (1951).
[Crossref]

Lippincott, E. R.

F. T. King and E. R. Lippincott, J. Am. Chem. Soc. 78, 4192 (1956).
[Crossref]

F. T. King and E. R. Lippincott, J. Opt. Soc. Am. 46, 661 (1956).
[Crossref]

E. R. Lippincott and R. D. Nelson, J. Chem. Phys. 21, 1307 (1953).
[Crossref]

Lofthus, A.

A. Lofthus, Spectrochim. Acta 9, 216 (1953).
[Crossref]

Long,

Long, Milner, and Thomas, Proc. Roy. Soc. (London) A237, 186 (1956).

Long, Milner, and Thomas, Proc. Roy. Soc. (London) A237, 197 (1956).

Loofbourow,

Harrison, Lord, and Loofbourow, Practical Spectroscopy (Prentice-Hall, Inc., Englewood Cliffs, New Jersey, 1948), p. 364.

Lord,

Lippincott, Lord, and McDonald, J. Am. Chem. Soc. 73, 3370 (1951).
[Crossref]

Harrison, Lord, and Loofbourow, Practical Spectroscopy (Prentice-Hall, Inc., Englewood Cliffs, New Jersey, 1948), p. 364.

McClure, D. S.

D. S. McClure, J. Chem. Phys. 19, 670 (1951).
[Crossref]

McDonald,

Lippincott, Lord, and McDonald, J. Am. Chem. Soc. 73, 3370 (1951).
[Crossref]

Milner,

Long, Milner, and Thomas, Proc. Roy. Soc. (London) A237, 186 (1956).

Long, Milner, and Thomas, Proc. Roy. Soc. (London) A237, 197 (1956).

Nelson, R. D.

E. R. Lippincott and R. D. Nelson, J. Chem. Phys. 21, 1307 (1953).
[Crossref]

Noelting, E.

E. Noelting and O. Kohn, Ber. deut. chem. Ges. 17, 371 (1884).
[Crossref]

E. Noelting and E. Salis, Ber. deut. chem. Ges. 14, 987 (1881).

Overberger, C. G.

A. C. Cope and C. G. Overberger, J. Am. Chem. Soc. 70, 1433 (1948).
[Crossref] [PubMed]

Prosen,

Prosen, Johnson, and Rossini, J. Am. Chem. Soc. 69, 2068 (1947).
[Crossref]

Rank, D. H.

D. H. Rank and et al., Anal. Chem. 19, 700 (1947).
[Crossref]

Rosenbaum,

Ross, I. G.

Rossini,

Prosen, Johnson, and Rossini, J. Am. Chem. Soc. 69, 2068 (1947).
[Crossref]

Salis, E.

E. Noelting and E. Salis, Ber. deut. chem. Ges. 14, 987 (1881).

Salzman, C. F.

Stamm, R. F.

Stammreich,

Stammreich, Forneris, and Tavares, J. Chem. Phys. 25, 580 (1956).
[Crossref]

Stammreich, H.

H. Stammreich and R. Forneris, Spectrochim. Acta 8, 52 (1956).
[Crossref]

H. Stammreich, Spectrochim. Acta 8, 41 (1956).
[Crossref]

H. Stammreich and R. Forneris, Spectrochim. Acta 8, 46 (1956).
[Crossref]

Stern, E. S.

A. E. Gillam and E. S. Stern, An Introduction to Electronic Absorption Spectroscopy in Organic Chemistry (Edward Arnold, London, 1954), p. 8.

Tavares,

Stammreich, Forneris, and Tavares, J. Chem. Phys. 25, 580 (1956).
[Crossref]

Thomas,

Long, Milner, and Thomas, Proc. Roy. Soc. (London) A237, 186 (1956).

Long, Milner, and Thomas, Proc. Roy. Soc. (London) A237, 197 (1956).

Timmons,

Braude, Fawcett, and Timmons, J. Chem. Soc. 1019 (1950).

Ungnade,

Ungnade, Kerr, and Youse, Science 113, 60 (1951).
[Crossref]

Vandenbelt,

Vandenbelt, Henrich, and Bash, Science 114, 576 (1951).
[Crossref]

Woodward, L. A.

L. A. Woodward and J. H. B. George, Nature 167, 193 (1951).
[Crossref]

Youse,

Ungnade, Kerr, and Youse, Science 113, 60 (1951).
[Crossref]

Anal. Chem. (1)

D. H. Rank and et al., Anal. Chem. 19, 700 (1947).
[Crossref]

Ber. deut. chem. Ges. (2)

E. Noelting and O. Kohn, Ber. deut. chem. Ges. 17, 371 (1884).
[Crossref]

E. Noelting and E. Salis, Ber. deut. chem. Ges. 14, 987 (1881).

J. Am. Chem. Soc. (5)

F. T. King and E. R. Lippincott, J. Am. Chem. Soc. 78, 4192 (1956).
[Crossref]

Prosen, Johnson, and Rossini, J. Am. Chem. Soc. 69, 2068 (1947).
[Crossref]

A. C. Cope and C. G. Overberger, J. Am. Chem. Soc. 70, 1433 (1948).
[Crossref] [PubMed]

Eccleston, Coleman, and Adams, J. Am. Chem. Soc. 72, 3866 (1950).
[Crossref]

Lippincott, Lord, and McDonald, J. Am. Chem. Soc. 73, 3370 (1951).
[Crossref]

J. Chem. Phys. (5)

J. Chien and P. Bender, J. Chem. Phys. 15, 376 (1947).
[Crossref]

Fateley, Curnutte, and Lippincott, J. Chem. Phys. 26, 1471 (1957).
[Crossref]

Stammreich, Forneris, and Tavares, J. Chem. Phys. 25, 580 (1956).
[Crossref]

E. R. Lippincott and R. D. Nelson, J. Chem. Phys. 21, 1307 (1953).
[Crossref]

D. S. McClure, J. Chem. Phys. 19, 670 (1951).
[Crossref]

J. Chem. Soc. (1)

Braude, Fawcett, and Timmons, J. Chem. Soc. 1019 (1950).

J. Opt. Soc. Am. (6)

Nature (1)

L. A. Woodward and J. H. B. George, Nature 167, 193 (1951).
[Crossref]

Proc. Roy. Soc. (London) (2)

Long, Milner, and Thomas, Proc. Roy. Soc. (London) A237, 197 (1956).

Long, Milner, and Thomas, Proc. Roy. Soc. (London) A237, 186 (1956).

Science (2)

Ungnade, Kerr, and Youse, Science 113, 60 (1951).
[Crossref]

Vandenbelt, Henrich, and Bash, Science 114, 576 (1951).
[Crossref]

Spectrochim. Acta (4)

A. Lofthus, Spectrochim. Acta 9, 216 (1953).
[Crossref]

H. Stammreich, Spectrochim. Acta 8, 41 (1956).
[Crossref]

H. Stammreich and R. Forneris, Spectrochim. Acta 8, 46 (1956).
[Crossref]

H. Stammreich and R. Forneris, Spectrochim. Acta 8, 52 (1956).
[Crossref]

Other (6)

R. D. Fisher, Master’s thesis, “Raman spectra of certain colored substances and the existence of an optimum concentration for maximum intensity of scattered radiation,” Kansas State College (1954).

R. A. Bafford, Master’s thesis, “The construction of an automatic recording Raman spectrometer,” University of Maryland (1956).

J. H. Hibben, The Raman Effect and Its Chemical Applications (Reinhold Publishing Corporation, New York, 1939), p. 29.

A. E. Gillam and E. S. Stern, An Introduction to Electronic Absorption Spectroscopy in Organic Chemistry (Edward Arnold, London, 1954), p. 8.

Harrison, Lord, and Loofbourow, Practical Spectroscopy (Prentice-Hall, Inc., Englewood Cliffs, New Jersey, 1948), p. 364.

E. C. C. Baly, Spectroscopy (Longmans Green and Company, New York, 1912), p. 492

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Figures (5)

Fig. 1
Fig. 1

Assumed direction of incident light entering the Raman tube for the calculation of the average intensity over a cross-sectional area of the tube.

Fig. 2
Fig. 2

A comparison of the experimental points and the theoretical curves for the variation of Raman line intensity with concentration for the 1350 cm−1 (○) and the 1610 cm−1 (●) lines of 4,6-dinitro-o-cresol. (Tube radius=0.628 cm, tube length=10.3 cm.)

Fig. 3
Fig. 3

A comparison of the experimental points and the theoretical curves for the variation of Raman line intensity with concentration for the 1350 cm−1 (○) and 1610 cm−1 (●) lines of 4,6-dinitro-o-cresol. (Tube radius=0.299 cm, tube length=13.4 cm.)

Fig. 4
Fig. 4

A comparison of the experimental points and the theoretical curves for the variation of Raman line intensity with concentration for the 3003 cm−1 (○) and 1651 cm−1 (●) lines of cyclooctatetraene. (Tube radius=0.628 cm, tube length=10.2 cm.)

Fig. 5
Fig. 5

A comparison of the experimental points and the theoretical curves for the variation of Raman line intensity with concentration for the 3003 cm−1 (○) and 1651 cm−1 (●) lines of cyclooctatetraene. (Tube radius=0.299 cm, tube length=13.2 cm.)

Tables (4)

Tables Icon

Table I Intensity-concentration data for the 1651 cm−1 line of cyclooctatetraene (a″=2.60, a′=0.394).

Tables Icon

Table II Intensity-concentration data for the 3003 cm−1 line of cyclooctatetraene (a″=2.60, a′=0.0578).

Tables Icon

Table III Intensity-concentration data for the 1350 cm−1 line of 4,6-dinitro-o-cresol (a″=13.9, a′=0.864).

Tables Icon

Table IV Intensity-concentration data for the 1610 cm−1 line of 4,6-dinitro-o-cresol (a″=13.9, a′=0.509).

Equations (10)

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

d I s = ( K A I 0 - I s a ) c d L ,
I = ( K A I 0 / a ) ( 1 - e - a c L ) .
I 0 = - R R 0 y = 2 ( R 2 - x 2 ) 1 2 I 00 e - a c y d y d x ,
I 0 = 2 I 00 a c 0 R { 1 - exp [ - 2 a c ( R 2 - x 2 ) 1 2 ] } d x .
Ī 0 = 2 I 00 a c π R { 1 - 1 R 0 R exp [ - 2 a c ( R 2 - x 2 ) 1 2 ] d x } .
Ī 0 = 0 π R / 2 I 0 d x 0 π R / 2 d x .
I 0 = I 00 e - c a x ,
Ī 0 = 2 I 00 π R c a [ 1 - e ( - π a / 2 ) R c ] .
I = 2 K A I 00 π R c a a [ 1 - e ( - π a / 2 ) R c ] ( 1 - e - a L C ) .
I = 2 K A I 00 π R c a a { 1 - 1 + π a 2 R c - [ ( - π a / 2 ) R c ] 2 2 ! } × { 1 - 1 + a L c - ( a L c ) 2 2 ! } .