The Allison Magneto-Optic Method of Chemical Analysis

      The Allison Magneto-Optic Method of Chemical Analysis provides a unique opportunity for classroom discussion on a number of topics. It did not start off as pathological science, since the effect could have been a real physical phenomenon based on the state of scientific knowledge at the time of the investigation. It degenerated into pathological science because of poor experimental design and experimenter bias. A full understanding of the concepts involved in the experiment on the part of students is quite an accomplishment, since it requires an understanding of polarized radiation, electrical current, magnetic fields, and spectroscopic sources and detectors. This is one of the most useful cases of pathological science for educational purposes.
      During the first 40 years of the 20th century, scientists were eagerly trying to find real evidence for the existence of elements 85 and 87, which had been predicted by Mendeleyev in the late 19th century.  It was during this time that Fred Allison, an American physicist, devised an analytical method that he called the magneto-optic method of chemical analysis.

Figure 1. The Magneto-Optic Effect
(A) Spark waveform (B) Schematic diagram of the apparatus

      The method was based on the comparison of the difference in response of the Faraday effect induced in different liquids (Allison, F. (1927).  The effect of wavelength on the differences in the lags of the faraday effect behind the magnetic field for various liquids.  Physical Review, 30, 66-70).  The Faraday effect involves the rotation of polarized light passing through a liquid, and induced by a magnetic field applied to the liquid.  He constructed an apparatus in which light from a high-voltage spark was directed through crossed polarizers and two tubes containing the liquids to be analyzed, and surrounded by coils of opposite winding.  The time at which the magnetic field was applied to the different liquids could be varied by adjusting the distance the electric current had to travel to reach the cells.  The observer looked for a minimum in the light from the spark, which indicated the delay in the appearance of the Faraday effect (relative to the reference liquid) after the magnetic field had been applied.
      Allison first applied this procedure to simple solutions of carbon bisulfide and hydrochloric acid and later to mixtures.  He became convinced that compounds would retain their individual maxima in a mixture, regardless of the other components.  He claimed a sensitivity down to less than part-per-billion levels, and he began to use his method to search for the elusive elements 85 and 87.  He rapidly found them and published studies on spectra and compounds of virginium and alabamine.  His results were replicated in part by several other laboratories, but detailed examination by others (MacPherson, H. G. (1934).  An investigation of the Magneto-Optic Method of Chemical Analysis.  Physical Review, 47, 310-315) proved conclusively that the maxima observed by Allison and others "had no objective reality" and "were not a function of the chemical solutions used."  The Allison magneto-optic method disappeared from the pages of scientific journals.  In retrospect, the modern analytical spectroscopist can easily find errors in Allison's reasoning.  He never offered a substantial theory to explain his observations, but more importantly, he ignored several experimental factors that limited his approach from the start.  This was a classic example of the investigator finding what he believed in.  But it certainly didn't hurt his career, since his biography lists him as head of the Auburn physics department and dean of the graduate school in 1953, with the physics building at Auburn named in his honor.  Furthermore, he is still listed as the discover of astatine (i.e., element 85, alabamine) in the 1991 Concise Columbia Encyclopedia and the work at Alabama Polytechnic (later Auburn University) is similarly credited in the 1994 and 1996 editions of Microsoft Encarta.
      The so-called Allison Effect was one of the instances of pathological science discussed by Irving Langmuir in his 1953 lecture that was reprinted in PHYSICS TODAY, Oct 1989, P. 36. Why did Allison make the assumptions that led him to the claims that he made?
      Modern-day spectroscopists can perhaps judge Allison far less harshly than Langmuir.  Let's examine his apparatus in detail. Look at the instrument diagram.  This scheme might have worked if the radiation from the spark light source was temporally very short (ns) and very stable, which it was not!  Unfortunately, a single light pulse from a spark (which is repeated rapidly as the capacitor charges and discharges) is on the order of microseconds, but this was not general knowledge at the time.  Anyway, the idea was to take the light pulse from the spark and pass it through a polarizing prism.  The light pulse then passes through two cells that are wrapped with wire.  The wire goes to the spark circuit so (theoretically) when the capacitor discharges across the spark gap, current flows through the coils and a magnetic field is applied to the cells.  With certain liquids in the cell, the plane of polarization of the light passing through them is rotated.  Now the coil around the second cell is wound completely opposite to the first cell.  Therefore, if the same liquid is in each cell, and the magnetic field is applied to each cell at the same time, the second cell will reverse the Faraday effect on the first cell, thus restoring the direction of polarization defined by the first polarizer.  A final polarizer (Nicol prism) is placed after the second cell and oriented 90 degrees out of phase of the first polarizer.  Thus, no light should pass through the system.  Now, say we have two different liquids in the cells and there is a delay between the application of the magnetic field to the cell and the appearance of the Faraday effect, and this delay depends on the identity of the liquid.  This is what Allison was claiming.  If the light pulse passes through the first cell (containing liquid A) and its polarization is changed, it will pass through the second cell (containing liquid B with a longer delay in the Faraday effect) before the Faraday effect in that cell can restore the direction of polarization defined by the first polarizer.  Therefore, light will pass the system.  Now, all we have to do is shorten the length of the wire to the second cell (a distance corresponding to the time delay of the Faraday effect in the second liquid) until we see a minimum in the light throughput of the system (i.e., the Faraday effects of both liquids overlap) and we have defined the time delay, which is characteristic of the liquid B.
    He started this work with J. Beams at the University of Virginia and Beams himself continued his work with this effect and sparks but then went on to other things.  It is not clear whether he ever discovered his mistake, but he certainly never pushed the technique.  On the other hand, Allison began to make grandiose claims that compounds when dissolved gave delay minima corresponding to the compounds (NOT the ions!) and that the effect was the same down to 10-8 M and then disappeared.  By the early 1930's, the ACS eventually refused to accept any more papers on Magneto-optic Spectroscopy, but not before a good deal of debunking took place and Allison claimed to pass *blind* tests of his methodology.
    What is most telling is that the "hero" of the N-Rays affair, Robert Wood, was taken in by the Allison Effect. It is referenced in a very straightforward manner in his book, Physical Optics! Why was Wood fooled?  Perhaps because at the state-of-the-art in knowledge of spark spectroscopy in the 1920s, Allison's technique might have worked.  It was Allison's dogmatic refusal to accept that he made a mistake that made this episode truly pathological.
    And, as mentioned previously, it looks like we are still being fooled by the Allison Effect ... at least Columbia University Press and Funk & Wagnalls are...

[Thanks are due to Walter Rowe, Professor of Forensic Science at George Washington University,  Alex Scheeline, Professor of Chemistry at the University of Illinois-Urbana]

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Page prepared by: Mike Epstein
Last Modified: 30 April 1999