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.)
He proves by direct experiments that no active oxygen is formed
during this process, and points out that the oxidations observed by
Hoppe-Seyler and Baumann must have been brought about by the hydrogen
dioxide. But this would not account for the oxidation of carbon
monoxide, for it has been previously shown by Remsen[21] that hydrogen
dioxide cannot oxidize carbon monoxide, not even when it is heated
to its point of decomposition. Traube[22] therefore repeats Baumann’s
experiment, he finds that palladium hydrogen in the presence of water
and oxygen does oxidize carbon monoxide; but as he had shown that
no active oxygen was formed during the process, and as the hydrogen
dioxide could not cause the oxidation, he concluded that the palladium
itself must play an important role in the reaction. By further
experiments he soon became convinced that there are two stages in the
process. 1st the palladium hydrogen acting on water and oxygen forms
hydrogen dioxide, 2nd the hydrogen dioxide in the presence of palladium
oxidizes the carbon monoxide. Traube[23] introduced into a glass flask
containing carbon monoxide a dilute solution of hydrogen dioxide and
a small piece of palladium foil, previously ignited, the action was
allowed to continue for 22 hours after which the CO was replaced by
air free from carbon dioxide. After leaving the flask the gas passed
through a solution of barium hydroxide; an abundant precipitate was
formed, showing that in this case the quantity of carbon dioxide formed
was greater than in the first experiment, in which he used palladium
hydrogen, water, oxygen and carbon monoxide.
Traube’s conclusion is as follows:--
“The carbon dioxide obtained in Baumann’s experiments is not formed
during the oxidation of the hydrogen of the palladium hydrogen, (there
being formed by this action merely hydrogen dioxide and palladium free
from hydrogen) but by the combined action of these last two substances
on carbon monoxide.” “Therefore, the proof is given that the act of
slow combustion (Autoxidation) has not in itself the power of making
oxygen active.”
The conclusion reached by Traube was tested by Professor Remsen and
myself in the following way: A current of carbon monoxide was passed
through several wash bottles containing solutions of caustic soda,
then through a wash bottle containing clear baryta water, then into a
flask containing a solution of hydrogen dioxide, containing a slight
excess of hydrochloric acid. The flask also contained a small piece
of palladium foil free from hydrogen. After leaving the flask the gas
passed through a solution of baryta water, which was protected from the
air by a U tube containing solid KOH. It was only necessary to pass the
carbon monoxide through for a very short time to obtain an abundant
precipitate of barium carbonate. We also noticed that under these
conditions the palladium foil was dissolved.
Public-domain text, read in full here on John Shaqi.
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