Abstract

Verdet constants over the spectral range 3635 A to 9875 A have now been measured for 11 gases and vapors (also Pyrex glass) in addition to the 22 previously reported. The list includes nitric oxide gas, ammonia, and sulfur dioxide; also the vapors of water, deuterium oxide, ethyl and methyl alcohols, ether, chloroform, carbon tetrachloride, and carbon disulfide. Nitric oxide shows a negative rotation and a larger Verdet constant and Faraday dispersion than any other of the (gaseous) materials tested except carbon disulfide vapor.

For comparison purposes the Verdet constants of the latter eight substances on the list have been measured for the liquid state over the same spectral range. The ratio of Verdet constants for water in the liquid and vapor states is 2 to 5 times larger than for any other material tested. Deuterium oxide in vapor or liquid states shows about the same Verdet ratio to water, viz 0.97, as deuterium and hydrogen gases. Faraday temperature coefficients have also been determined. For constant volume conditions these are very small save for nitric oxide gas. A theoretical explanation of the rotation of nitric oxide is attempted.

© 1958 Optical Society of America

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References

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  1. L. R. Ingersoll and D. H. Liebenberg, J. Opt. Soc. Am. 46, 538 (1956).
    [Crossref]
  2. The terms “gas” and “vapor” are used here in the ordinary sense.
  3. L. R. Ingersoll and D. H. Liebenberg, J. Opt. Soc. Am. 44, 566 (1954).
    [Crossref]
  4. See N. E. Dorsey, Properties of Ordinary Water-Substance (Reinhold Publishing Corporation, New York, 1940), p. 390.
  5. Samuel Steingiser, Magneto-Optic Rotation, Relationship to Chemical Structure (thesis, University of Connecticut, 1949), p. 109.
  6. For gases the only Faraday temperature coefficient directly measurable was under conditions of constant density; for liquids under constant pressure. By “constant density” liquid coefficient is meant merely the constant pressure coefficient corrected for density changes. Actual measurements on liquids under true constant density conditions would be difficult.
  7. A. Okazaki, Proc. Phys.-Chem. Soc. Japan 21, 753 (1939).
  8. For densities of D2O see Heiks, Barnett, Jones, and Orban, J. Phys. Chem. 58, 489 (1954).
    [Crossref]
  9. International Critical Tables,  6, 425 (1929).
  10. Slack, Reeves, and Peoples, Phys. Rev. 46, 726 (1934).
  11. Some years ago I gave Professor de Mallemann some preliminary results on water vapor [see R. de Mallemann, Compt. rend. 235, 1263 (1952)]. Unfortunately, because of our imperfect technique at that time and an inexcusable error on my part, the values were some 20% lower than they should have been. L.R.I.
  12. Such comparisons have been greatly assisted through the kindness of Dr. Jean Grange of the de Mallemann laboratory at the University of Nancy, who furnished a preliminary copy of his doctorate thesis. This gives an excellent survey of the field.
  13. R. de Mallemann and J. Grange, Compt. rend. 241, 5 (1955). We want to express our thanks for a private communication from Professor de Mallemann on several points in connection with this theory.
  14. Robert Serber, Phys. Rev. 41, 489 (1932).
    [Crossref]
  15. G. Herzberg, Spectra of Diatomic Molecules (D. Van Nostrand Company, Inc., Princeton, 1950) p. 558.
  16. Curiously a single term of the diamagnetic form with the ionization frequency (ν1=2.304×1015) chosen as the resonant frequency (see reference 1) fits the data within 4% over the measured spectral range.
  17. J. H. Van Vleck and M. H. Hebb, Phys. Rev. 46, 17 (1934).
    [Crossref]
  18. H. Bizette, Ann. phys. Ser. 12,  1, 232 (1946).
  19. Wiersma, de Haas, and Capel, Leiden Communs. 212b (1930).
  20. J. H. Van Vleck, Phys. Rev. 31, 587 (1928).
    [Crossref]

1956 (1)

1955 (1)

R. de Mallemann and J. Grange, Compt. rend. 241, 5 (1955). We want to express our thanks for a private communication from Professor de Mallemann on several points in connection with this theory.

1954 (2)

L. R. Ingersoll and D. H. Liebenberg, J. Opt. Soc. Am. 44, 566 (1954).
[Crossref]

For densities of D2O see Heiks, Barnett, Jones, and Orban, J. Phys. Chem. 58, 489 (1954).
[Crossref]

1952 (1)

Some years ago I gave Professor de Mallemann some preliminary results on water vapor [see R. de Mallemann, Compt. rend. 235, 1263 (1952)]. Unfortunately, because of our imperfect technique at that time and an inexcusable error on my part, the values were some 20% lower than they should have been. L.R.I.

1946 (1)

H. Bizette, Ann. phys. Ser. 12,  1, 232 (1946).

1939 (1)

A. Okazaki, Proc. Phys.-Chem. Soc. Japan 21, 753 (1939).

1934 (2)

Slack, Reeves, and Peoples, Phys. Rev. 46, 726 (1934).

J. H. Van Vleck and M. H. Hebb, Phys. Rev. 46, 17 (1934).
[Crossref]

1932 (1)

Robert Serber, Phys. Rev. 41, 489 (1932).
[Crossref]

1930 (1)

Wiersma, de Haas, and Capel, Leiden Communs. 212b (1930).

1929 (1)

International Critical Tables,  6, 425 (1929).

1928 (1)

J. H. Van Vleck, Phys. Rev. 31, 587 (1928).
[Crossref]

Barnett,

For densities of D2O see Heiks, Barnett, Jones, and Orban, J. Phys. Chem. 58, 489 (1954).
[Crossref]

Bizette, H.

H. Bizette, Ann. phys. Ser. 12,  1, 232 (1946).

Capel,

Wiersma, de Haas, and Capel, Leiden Communs. 212b (1930).

de Haas,

Wiersma, de Haas, and Capel, Leiden Communs. 212b (1930).

de Mallemann, R.

R. de Mallemann and J. Grange, Compt. rend. 241, 5 (1955). We want to express our thanks for a private communication from Professor de Mallemann on several points in connection with this theory.

Some years ago I gave Professor de Mallemann some preliminary results on water vapor [see R. de Mallemann, Compt. rend. 235, 1263 (1952)]. Unfortunately, because of our imperfect technique at that time and an inexcusable error on my part, the values were some 20% lower than they should have been. L.R.I.

Dorsey, N. E.

See N. E. Dorsey, Properties of Ordinary Water-Substance (Reinhold Publishing Corporation, New York, 1940), p. 390.

Grange, J.

R. de Mallemann and J. Grange, Compt. rend. 241, 5 (1955). We want to express our thanks for a private communication from Professor de Mallemann on several points in connection with this theory.

Hebb, M. H.

J. H. Van Vleck and M. H. Hebb, Phys. Rev. 46, 17 (1934).
[Crossref]

Heiks,

For densities of D2O see Heiks, Barnett, Jones, and Orban, J. Phys. Chem. 58, 489 (1954).
[Crossref]

Herzberg, G.

G. Herzberg, Spectra of Diatomic Molecules (D. Van Nostrand Company, Inc., Princeton, 1950) p. 558.

Ingersoll, L. R.

Jones,

For densities of D2O see Heiks, Barnett, Jones, and Orban, J. Phys. Chem. 58, 489 (1954).
[Crossref]

Liebenberg, D. H.

Okazaki, A.

A. Okazaki, Proc. Phys.-Chem. Soc. Japan 21, 753 (1939).

Orban,

For densities of D2O see Heiks, Barnett, Jones, and Orban, J. Phys. Chem. 58, 489 (1954).
[Crossref]

Peoples,

Slack, Reeves, and Peoples, Phys. Rev. 46, 726 (1934).

Reeves,

Slack, Reeves, and Peoples, Phys. Rev. 46, 726 (1934).

Serber, Robert

Robert Serber, Phys. Rev. 41, 489 (1932).
[Crossref]

Slack,

Slack, Reeves, and Peoples, Phys. Rev. 46, 726 (1934).

Steingiser, Samuel

Samuel Steingiser, Magneto-Optic Rotation, Relationship to Chemical Structure (thesis, University of Connecticut, 1949), p. 109.

Van Vleck, J. H.

J. H. Van Vleck and M. H. Hebb, Phys. Rev. 46, 17 (1934).
[Crossref]

J. H. Van Vleck, Phys. Rev. 31, 587 (1928).
[Crossref]

Wiersma,

Wiersma, de Haas, and Capel, Leiden Communs. 212b (1930).

Ann. phys. Ser. 12 (1)

H. Bizette, Ann. phys. Ser. 12,  1, 232 (1946).

Compt. rend. (2)

R. de Mallemann and J. Grange, Compt. rend. 241, 5 (1955). We want to express our thanks for a private communication from Professor de Mallemann on several points in connection with this theory.

Some years ago I gave Professor de Mallemann some preliminary results on water vapor [see R. de Mallemann, Compt. rend. 235, 1263 (1952)]. Unfortunately, because of our imperfect technique at that time and an inexcusable error on my part, the values were some 20% lower than they should have been. L.R.I.

International Critical Tables (1)

International Critical Tables,  6, 425 (1929).

J. Opt. Soc. Am. (2)

J. Phys. Chem. (1)

For densities of D2O see Heiks, Barnett, Jones, and Orban, J. Phys. Chem. 58, 489 (1954).
[Crossref]

Leiden Communs. (1)

Wiersma, de Haas, and Capel, Leiden Communs. 212b (1930).

Phys. Rev. (4)

J. H. Van Vleck, Phys. Rev. 31, 587 (1928).
[Crossref]

Robert Serber, Phys. Rev. 41, 489 (1932).
[Crossref]

Slack, Reeves, and Peoples, Phys. Rev. 46, 726 (1934).

J. H. Van Vleck and M. H. Hebb, Phys. Rev. 46, 17 (1934).
[Crossref]

Proc. Phys.-Chem. Soc. Japan (1)

A. Okazaki, Proc. Phys.-Chem. Soc. Japan 21, 753 (1939).

Other (7)

See N. E. Dorsey, Properties of Ordinary Water-Substance (Reinhold Publishing Corporation, New York, 1940), p. 390.

Samuel Steingiser, Magneto-Optic Rotation, Relationship to Chemical Structure (thesis, University of Connecticut, 1949), p. 109.

For gases the only Faraday temperature coefficient directly measurable was under conditions of constant density; for liquids under constant pressure. By “constant density” liquid coefficient is meant merely the constant pressure coefficient corrected for density changes. Actual measurements on liquids under true constant density conditions would be difficult.

Such comparisons have been greatly assisted through the kindness of Dr. Jean Grange of the de Mallemann laboratory at the University of Nancy, who furnished a preliminary copy of his doctorate thesis. This gives an excellent survey of the field.

G. Herzberg, Spectra of Diatomic Molecules (D. Van Nostrand Company, Inc., Princeton, 1950) p. 558.

Curiously a single term of the diamagnetic form with the ionization frequency (ν1=2.304×1015) chosen as the resonant frequency (see reference 1) fits the data within 4% over the measured spectral range.

The terms “gas” and “vapor” are used here in the ordinary sense.

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Tables (6)

Tables Icon

Table I Gases, also Pyrex glass. Verdet constants in microminutes per oersted-cm-atmos (Pyrex in milliminutes per oer-cm) and (lower part of table) Faraday dispersion, with all values reduced to 1.000 at 5780 A. The approximate gas pressure in cm of mercury (reduced to 0°C), for which rotations were measured, is given for each gas.

Tables Icon

Table II Vapors and liquids. Verdet constants for vapors in microminutes per oer-cm-atmos; for liquids in milliminutes per oer-cm. R is the ratio V(liquid)/V(vapor) at 5893 A. C is the temperature coefficient (pressure constant) of the Verdet constant for the liquids. (For further explanation see Table I.)

Tables Icon

Table III Vapors and liquids, continued (for explanation see Tables I and II).

Tables Icon

Table IV Values of 103 Vt for H2O and D2O. Columns A and A′ are measured values of the Verdet constants, under constant pressure conditions, reduced to V20°=0.01309 min per-oer-cm as the accepted value for H2O at 5893 A. Columns B and B′ are Verdet values calculated for constant volume conditions by dividing by density.

Tables Icon

Table V Comparison of the Faraday dispersion for NO gas with Serber’s theory. Values of r=Vobs/Vcalc. The two-term paramagnetic form has chosen resonant frequencies corresponding to the two dissociation energies of the molecule. The single-term paramagnetic form has a resonant frequency chosen to give the best fit. The diamagnetic single term is shown as a curiosity with the resonant frequency chosen to correspond to the ionization energy of the molecule.

Tables Icon

Table VI Temperature considerations, NO gas. Comparison of observed ratio of Verdet constants, V1/V2, with the inverse temperature ratio and with the Bizette equation.

Equations (5)

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i A i ν 2 ( ν i 2 - ν 2 )             ( paramagnetic , temperature independent ) ,
i B i ν 2 T ( ν i 2 - ν 2 )             ( paramagnetic , temperature dependent ) ,
i C i ν 2 ( ν i 2 - ν 2 ) 2             ( diamagnetic ) .
[ V ¯ 1 - K V ¯ 2 - K ] λ const = [ χ 1 χ 2 ] H const .
V ¯ 1 V ¯ 2 = T 2 T 1 exp [ - 174 ( 1 T 1 - 1 T 2 ) ] · { 1 + e - 174 / T 2 1 + e - 174 / T 1 } .