Abstract

A photoelectric photometer designed for the measurement of absolute turbidity, dissymmetry, and depolarization of dilute solutions of high molecular weight materials, and hence determination of their molecular weights, is described. The photometer comprises essentially a monochromatic parallel primary beam of radiation, a six-sided scattering cell for measurements at 0°, 45°, 90°, and 135°, a multiplier phototube and galvanometer, a standard opal glass diffusor, and removable polarizer and analyzer. Turbidity is determined in terms of a ratio of deflections for the 90° scattering and for the primary beam reduced in intensity by neutral filters and diffused by an opal glass plate. Working relationships leading to determination of absolute turbidity are developed. These relationships include corrections for refraction and reflection effects, and for imperfect diffusion by the opal glass. The latter is evaluated by comparison of the opal glass with reflecting diffusors corrected for specular component of reflectance. The response of some multiplier photo-tubes is shown to be dependent on the plane of polarization of the incident radiation. Data illustrating the performance of the photometer include comparison of molecular weights of polystyrene fractions, beta-lactoglobulin, bovine serum albumin, lysozyme, sucrose octaacetate, Raleigh’s ratio and depolarization for benzene, turbidity of a “standard” polystyrene, and particle size of a <i>GR-S</i> latex, with data obtained by other methods or other investigators.

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  1. P. Debye, J. App. Phys. 15, 338 (1944).
  2. P. Debye, J. Phys. and Colloid Chem. 51, 18 (1947).
  3. B. H. Zimm, R. S. Stein, and P. Doty, Polymer Bull. 1, 90 (1945); G. Oster, Chem. Rev. 43, 319 (1948); R. H. Ewart, C. P. Roe, P. Debye, and J. R. McCartney, J. Chem. Phys. 14, 686 (1946); P. M. Doty, B. H. Zimm, and H. Mark, J. Chem. Phys. 13, 159 (1946).
  4. F. W. Billmeyer, Jr., Rubber Reserve Company, Technical Report, "The absolute determination of scattered intensity" (January 15, 1945).
  5. F. W. Billmeyer, Jr., Rubber Reserve Company, Technical Report, "The determination of molecular weights and particle sizes by light scattering" (March 1, 1945).
  6. C. I. Carr, dissertation, University of California, "An investigation of the molecular weights of molecules in solution by the light scattering method" (September, 1949). See also P. Outer, C. I. Carr, and B. H. Zimm, J. Chem. Phys. 18, 830 (1950).
  7. R. S. Stein and P. Doty, J. Am. Chem. Soc. 68, 159 (1946).
  8. P. P. Debye, J. App. Phys. 17, 392 (1946).
  9. R. F. Stamm, T. Mariner, and J. K. Dixon, J. Chem. Phys. 16, 423 (1948).
  10. B. H. Zimm, J. Chem. Phys. 16, 1099 (1948).
  11. R. H. Blaker, R. M. Badger, and T. S. Gilman, J. Phys. and Colloid Chem. 53, 794 (1949).
  12. H. J. Hadow, H. Sheffer, and J. C. Hyde, Can. J. Research 27B, 791 (1949).
  13. P. Putzeys and J. Brosteaux, Trans. Faraday Soc. 31, 1314 (1935).
  14. R. Speiser and B. A. Brice, J. Opt. Soc. Am. 36, 364A (1946).
  15. B. T. Barnes and W. E. Forsythe, J. Opt. Soc. Am. 27, 83 (1937).
  16. Radiation terms and symbols are essentially those proposed by the Committee on Colorimetry of the Optical Society of America, J. Opt. Soc. Am. 34, 245 (1944).
  17. See also H.-J. Helwig, Optik 5, 419 (1949).
  18. A. H. Taylor, Bur. Stand. Sci. Pap. No. 391 (July 28, 1920).
  19. V. G. W. Harrison, Proc. Phys. Soc., London 58, 408 (1946).
  20. J. S. Preston, Trans. Opt. Soc., London 31, 15 (1929–30).
  21. I. G. Priest and J. O. Riley, J. Opt. Soc. Am. 20, 156–157A (1930).
  22. R. S. Hunter, Paper Trade J. 126, 47 (1948)
  23. J. W. Ryde, Proc. Roy. Soc., London 131A, 451 (1931); J. W. Ryde and B. S. Cooper, ibid., 464; J. W. Ryde and B. S. Cooper, J. Soc. Glass Tech. 16, 408, 430 (1932).
  24. M. Luckiesh, Elec. World 60, 1040 (1912); 61, 883 (1913).
  25. P. Peyrot, Comptes Rendus 203, 1512 (1936).
  26. T. Alfrey, A. Bartovics, and H. Mark, J. Am. Chem. Soc. 65, 2319 (1943).
  27. B. H. Zimm and I. Myerson, J. Am. Chem. Soc. 68, 911 (1946).
  28. B. A. Brice and R. Speiser, J. Opt. Soc. Am. 36, 363A (1946). Complete details will be published.
  29. M. Halwer, J. Am. Chem. Soc. 70, 3985 (1948). The coefficient of c2 in the equation should be 0.02831

Alfrey, T.

T. Alfrey, A. Bartovics, and H. Mark, J. Am. Chem. Soc. 65, 2319 (1943).

Badger, R. M.

R. H. Blaker, R. M. Badger, and T. S. Gilman, J. Phys. and Colloid Chem. 53, 794 (1949).

Barnes, B. T.

B. T. Barnes and W. E. Forsythe, J. Opt. Soc. Am. 27, 83 (1937).

Bartovics, A.

T. Alfrey, A. Bartovics, and H. Mark, J. Am. Chem. Soc. 65, 2319 (1943).

Billmeyer, Jr., F. W.

F. W. Billmeyer, Jr., Rubber Reserve Company, Technical Report, "The absolute determination of scattered intensity" (January 15, 1945).

F. W. Billmeyer, Jr., Rubber Reserve Company, Technical Report, "The determination of molecular weights and particle sizes by light scattering" (March 1, 1945).

Blaker, R. H.

R. H. Blaker, R. M. Badger, and T. S. Gilman, J. Phys. and Colloid Chem. 53, 794 (1949).

Brice, B. A.

R. Speiser and B. A. Brice, J. Opt. Soc. Am. 36, 364A (1946).

B. A. Brice and R. Speiser, J. Opt. Soc. Am. 36, 363A (1946). Complete details will be published.

Brosteaux, J.

P. Putzeys and J. Brosteaux, Trans. Faraday Soc. 31, 1314 (1935).

Carr, C. I.

C. I. Carr, dissertation, University of California, "An investigation of the molecular weights of molecules in solution by the light scattering method" (September, 1949). See also P. Outer, C. I. Carr, and B. H. Zimm, J. Chem. Phys. 18, 830 (1950).

Debye, P.

P. Debye, J. App. Phys. 15, 338 (1944).

P. Debye, J. Phys. and Colloid Chem. 51, 18 (1947).

Debye, P. P.

P. P. Debye, J. App. Phys. 17, 392 (1946).

Dixon, J. K.

R. F. Stamm, T. Mariner, and J. K. Dixon, J. Chem. Phys. 16, 423 (1948).

Doty, P.

R. S. Stein and P. Doty, J. Am. Chem. Soc. 68, 159 (1946).

B. H. Zimm, R. S. Stein, and P. Doty, Polymer Bull. 1, 90 (1945); G. Oster, Chem. Rev. 43, 319 (1948); R. H. Ewart, C. P. Roe, P. Debye, and J. R. McCartney, J. Chem. Phys. 14, 686 (1946); P. M. Doty, B. H. Zimm, and H. Mark, J. Chem. Phys. 13, 159 (1946).

Forsythe, W. E.

B. T. Barnes and W. E. Forsythe, J. Opt. Soc. Am. 27, 83 (1937).

Gilman, T. S.

R. H. Blaker, R. M. Badger, and T. S. Gilman, J. Phys. and Colloid Chem. 53, 794 (1949).

Hadow, H. J.

H. J. Hadow, H. Sheffer, and J. C. Hyde, Can. J. Research 27B, 791 (1949).

Halwer, M.

M. Halwer, J. Am. Chem. Soc. 70, 3985 (1948). The coefficient of c2 in the equation should be 0.02831

Harrison, V. G. W.

V. G. W. Harrison, Proc. Phys. Soc., London 58, 408 (1946).

Helwig, H.-J.

See also H.-J. Helwig, Optik 5, 419 (1949).

Hunter, R. S.

R. S. Hunter, Paper Trade J. 126, 47 (1948)

Hyde, J. C.

H. J. Hadow, H. Sheffer, and J. C. Hyde, Can. J. Research 27B, 791 (1949).

Luckiesh, M.

M. Luckiesh, Elec. World 60, 1040 (1912); 61, 883 (1913).

Mariner, T.

R. F. Stamm, T. Mariner, and J. K. Dixon, J. Chem. Phys. 16, 423 (1948).

Mark, H.

T. Alfrey, A. Bartovics, and H. Mark, J. Am. Chem. Soc. 65, 2319 (1943).

Myerson, I.

B. H. Zimm and I. Myerson, J. Am. Chem. Soc. 68, 911 (1946).

Peyrot, P.

P. Peyrot, Comptes Rendus 203, 1512 (1936).

Preston, J. S.

J. S. Preston, Trans. Opt. Soc., London 31, 15 (1929–30).

Priest, I. G.

I. G. Priest and J. O. Riley, J. Opt. Soc. Am. 20, 156–157A (1930).

Putzeys, P.

P. Putzeys and J. Brosteaux, Trans. Faraday Soc. 31, 1314 (1935).

Riley, J. O.

I. G. Priest and J. O. Riley, J. Opt. Soc. Am. 20, 156–157A (1930).

Ryde, J. W.

J. W. Ryde, Proc. Roy. Soc., London 131A, 451 (1931); J. W. Ryde and B. S. Cooper, ibid., 464; J. W. Ryde and B. S. Cooper, J. Soc. Glass Tech. 16, 408, 430 (1932).

Sheffer, H.

H. J. Hadow, H. Sheffer, and J. C. Hyde, Can. J. Research 27B, 791 (1949).

Speiser, R.

R. Speiser and B. A. Brice, J. Opt. Soc. Am. 36, 364A (1946).

B. A. Brice and R. Speiser, J. Opt. Soc. Am. 36, 363A (1946). Complete details will be published.

Stamm, R. F.

R. F. Stamm, T. Mariner, and J. K. Dixon, J. Chem. Phys. 16, 423 (1948).

Stein, R. S.

B. H. Zimm, R. S. Stein, and P. Doty, Polymer Bull. 1, 90 (1945); G. Oster, Chem. Rev. 43, 319 (1948); R. H. Ewart, C. P. Roe, P. Debye, and J. R. McCartney, J. Chem. Phys. 14, 686 (1946); P. M. Doty, B. H. Zimm, and H. Mark, J. Chem. Phys. 13, 159 (1946).

R. S. Stein and P. Doty, J. Am. Chem. Soc. 68, 159 (1946).

Taylor, A. H.

A. H. Taylor, Bur. Stand. Sci. Pap. No. 391 (July 28, 1920).

Zimm, B. H.

B. H. Zimm, J. Chem. Phys. 16, 1099 (1948).

B. H. Zimm, R. S. Stein, and P. Doty, Polymer Bull. 1, 90 (1945); G. Oster, Chem. Rev. 43, 319 (1948); R. H. Ewart, C. P. Roe, P. Debye, and J. R. McCartney, J. Chem. Phys. 14, 686 (1946); P. M. Doty, B. H. Zimm, and H. Mark, J. Chem. Phys. 13, 159 (1946).

B. H. Zimm and I. Myerson, J. Am. Chem. Soc. 68, 911 (1946).

Other (29)

P. Debye, J. App. Phys. 15, 338 (1944).

P. Debye, J. Phys. and Colloid Chem. 51, 18 (1947).

B. H. Zimm, R. S. Stein, and P. Doty, Polymer Bull. 1, 90 (1945); G. Oster, Chem. Rev. 43, 319 (1948); R. H. Ewart, C. P. Roe, P. Debye, and J. R. McCartney, J. Chem. Phys. 14, 686 (1946); P. M. Doty, B. H. Zimm, and H. Mark, J. Chem. Phys. 13, 159 (1946).

F. W. Billmeyer, Jr., Rubber Reserve Company, Technical Report, "The absolute determination of scattered intensity" (January 15, 1945).

F. W. Billmeyer, Jr., Rubber Reserve Company, Technical Report, "The determination of molecular weights and particle sizes by light scattering" (March 1, 1945).

C. I. Carr, dissertation, University of California, "An investigation of the molecular weights of molecules in solution by the light scattering method" (September, 1949). See also P. Outer, C. I. Carr, and B. H. Zimm, J. Chem. Phys. 18, 830 (1950).

R. S. Stein and P. Doty, J. Am. Chem. Soc. 68, 159 (1946).

P. P. Debye, J. App. Phys. 17, 392 (1946).

R. F. Stamm, T. Mariner, and J. K. Dixon, J. Chem. Phys. 16, 423 (1948).

B. H. Zimm, J. Chem. Phys. 16, 1099 (1948).

R. H. Blaker, R. M. Badger, and T. S. Gilman, J. Phys. and Colloid Chem. 53, 794 (1949).

H. J. Hadow, H. Sheffer, and J. C. Hyde, Can. J. Research 27B, 791 (1949).

P. Putzeys and J. Brosteaux, Trans. Faraday Soc. 31, 1314 (1935).

R. Speiser and B. A. Brice, J. Opt. Soc. Am. 36, 364A (1946).

B. T. Barnes and W. E. Forsythe, J. Opt. Soc. Am. 27, 83 (1937).

Radiation terms and symbols are essentially those proposed by the Committee on Colorimetry of the Optical Society of America, J. Opt. Soc. Am. 34, 245 (1944).

See also H.-J. Helwig, Optik 5, 419 (1949).

A. H. Taylor, Bur. Stand. Sci. Pap. No. 391 (July 28, 1920).

V. G. W. Harrison, Proc. Phys. Soc., London 58, 408 (1946).

J. S. Preston, Trans. Opt. Soc., London 31, 15 (1929–30).

I. G. Priest and J. O. Riley, J. Opt. Soc. Am. 20, 156–157A (1930).

R. S. Hunter, Paper Trade J. 126, 47 (1948)

J. W. Ryde, Proc. Roy. Soc., London 131A, 451 (1931); J. W. Ryde and B. S. Cooper, ibid., 464; J. W. Ryde and B. S. Cooper, J. Soc. Glass Tech. 16, 408, 430 (1932).

M. Luckiesh, Elec. World 60, 1040 (1912); 61, 883 (1913).

P. Peyrot, Comptes Rendus 203, 1512 (1936).

T. Alfrey, A. Bartovics, and H. Mark, J. Am. Chem. Soc. 65, 2319 (1943).

B. H. Zimm and I. Myerson, J. Am. Chem. Soc. 68, 911 (1946).

B. A. Brice and R. Speiser, J. Opt. Soc. Am. 36, 363A (1946). Complete details will be published.

M. Halwer, J. Am. Chem. Soc. 70, 3985 (1948). The coefficient of c2 in the equation should be 0.02831

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