On the Existence of Active Oxygen: Thesis Presented for the Attainment of the Degree of Doctor of Philosophy at the Johns Hopkins UniversityKeiser, Edward Harrison
Science
On the Existence of Active Oxygen: Thesis Presented for the Attainment of the Degree of Doctor of Philosophy at the Johns Hopkins University
Keiser, Edward Harrison
Oxygen; Thesis (Ph. D.)
Baumann then describes results obtained by himself which enable us to
clearly distinguish between active oxygen and ozone. Starting from
the observation of Remsen[18] and Southworth that carbon monoxide, at
ordinary temperatures, is not oxidized by ozone, he suspected that
active oxygen would readily effect its oxidation. Palladium hydrogen
was therefore sealed up in a capacious glass tube with a few cubic
centimeters of clear lime water and a mixture of carbon monoxide and
oxygen free from carbon dioxide. At first the lime water remained
clear, but after several hours a cloudiness in the lime water became
visible and after several days a precipitate of calcium carbonate
settled to the bottom of the tube. He then repeated the experiment in a
modified form. From a gasometer, containing a mixture of three volumes
of oxygen and one of carbon monoxide free from carbon dioxide a slow
current of gas was passed, first into a wash bottle containing a clear
solution of baryta water, then into a tube containing palladium
hydrogen. Then the gases were again passed through a wash bottle
containing baryta water. After the current had been passing for four
hours, the first baryta water was still perfectly clear, but the
second showed a distinct cloudiness of barium carbonate, which slowly
increased in the course of twelve hours. The baryta water in the first
wash bottle remained clear even to the end of the experiment.
The different behavior of ozone and active oxygen was then shown by the
following experiment:--“A slow current of air free from carbon dioxide
was passed into a flask containing moist phosphorus, from there into a
second flask where the ozonized air came in contact with a somewhat
slower current, consisting of a mixture of three volumes of oxygen to
one of carbon monoxide, carefully purified from carbon dioxide. From
the second flask the gases were passed through a clear solution of
baryta water.” “After all carbon dioxide had been removed from the
apparatus the baryta water remained perfectly clear (völlig klar) after
the gases had passed through for six hours.” “But, on the other hand,
if the mixture of carbon monoxide and oxygen was passed into the first
flask, containing the moist phosphorus and in which according to our
theory active oxygen must occur, then the result is quite different,
the baryta water becomes cloudy in a short time and in the course
of an hour there is formed an _abundant precipitate_ (‘reichlicher
Niederschlag’) of barium carbonate.”
From these results he concludes that active oxygen may be detected
by its power of oxidizing carbon monoxide, and states that this fact
enables us to decide whether in oxidations effected by ozone there
occur free atoms of oxygen.
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