Johann Wolfgang Dobereiner

THE DISCOVERY OF CATALYSIS AND THE REFINING

OF RUSSIAN PLATINUM

By Donald McDonald
Johnson Matthey & Co Limited

Many of the most important contributors and, through his Theory of Triads, as a
to the progress of chemistry in the eighteenth pioneer of the Periodic System for classifying
and nineteenth centuries have intervened in the elements.
the story of platinum, fascinated by the Dobereiner was born the son of a Bavarian
extraordinary properties of the metal and the coachman and his education amounted to
difficulties of rendering it malleable and nothing very much. At the age of 14 he
fabricating it. For instance there was Baume, entered a pharmacy as apprentice and, after
who first introduced the idea of forging it like three years of that, practised as assistant at
iron, and Wollaston, who made a scientific several places including Karlsruhe, Bayreuth
business of this proposal. Another and later and Strasbourg. At the last he came into
one was the German chemist, J. W. contact with scientific men like Gmelin and
Dobereiner, best known as a great practical Bockmann, realised his educational short-
teacher, as a founder of the study of catalysis, comings and determined to overcome them.

Johann Wolfgang Dobereiner

1780-1849
Professor of Chemistry at Jena for
thirtynine years, a friend and prot6g.g
of Goethe. and the founder of the study of
catalysis. His discovwy of the power of
finely divided platinum to ignite a stream
of hydrogen caused a considerable stir
in chemical circles, and he was thefirst to
make use of what we now know as a
supported catalyst.
(From a portrait i n the City Museum
at Jena)

Platinum Metals Rev., 1965, 9 , (4),136-139 136

He could not afford a university course, but
assiduously attended lectures on chemistry,
mineralogy, botany and philosophy, while
trying to finance himself by means of three
entries into business, all of which ended
unfortunately. But in the meantime he had
begun to write on scientific subjects and had
attracted the attention of the well-known
editor-publishers Gehlen and Schweigger, so
much so that the former, in 1810, proposed
him for an Extraordinary Professorship of
Chemistry at the University of Jena.

Association with Goethe

Jena is twelve miles south-east of Weimar,
then the capital of the small, and at that time
independent, German state of Saxe-Weimar,
ruled by an hereditary prince with, after 1815,
the title of Grand Duke. From 1775 this
position was held by Karl August, a highly
intelligent patron of art, literature and
The Grand Duchess Maria Pavlovna
The daughter of Czar Paul I and the daughter-in-
science, and a supporter of the new liberal luw of Duke Kurt August won Weimur. Her
ideas that were beginning to creep into interest i n Dobereiner’s work on platinum com-
politics. bined with her connections with the Russian court
led to his being called upon to help in the refining
In order to forward these aims, he had of the platinum deposits that had recently been
appointed as his Minister of State no less a discovered i n the Urals
person than the young Goethe, who helped
him to attract to Weimar and Jena a remark- Alexander I and Nicholas I. The latter, who
able galaxy of intellectual talent. When in reached the Imperial rank at the end of 1825,
1810 Gehlen offered Dobereiner’s name to desired to develop the natural resources of
Karl August it was without much hope, as his Russia, and his principal agent in this
protege was not a graduate and had not even a activity was his very able Minister of Finance,
school certificate. But Karl August was Count Egor Kankrin. Kankrin, in his ex
satisfied with Gehlen’s recommendation and ojjicio capacity of Head of the Mining
saw that the candidate was given a doctorate Department, interested himself very deeply
at half the usual fee, paid, as the minutes in the discoveries of platinum deposits made
record, “in rather worn thalers”. It seems that in the Urals from 1824 onwards. This
Goethe approved of the appointment and material was already in demand in Western
Dobereiner became his chemical assistant. Europe for both decorative and scientific
Now the intellectual fame of Saxe-Weimar purposes but, as the basis for neither of these
had spread rapidly around Europe and attrac- was available in Russia, Kankrin, after con-
ted a flow of visitors, eager to partake in so sulting that great international authority
much that was new and progressive. They Alexander von Humboldt, had decided to
came from all over the continent and among use it for coinage. T o refine the native
them was the Grand Duchess Maria Pavlovna material for this purpose, he had com-
from Russia. She was a daughter of the Czar missioned the well-known Russian chemist
Paul I and was married to Karl August’s son; Sobolevsky to make the necessary arrange-
two of her brothers became the Czars ments and this had been done in the Govern-

Platinum Metals Rev., 1965, 9 , (4), 137

 ment Mining Laboratory at St Petersburg.
But neither Kankrin nor Sobolevsky was
completely satisfied with the chemical
methods with which they had started their
operations and they were continually search-
ing for advice for improvement.
As it happened chemistry was one of the
interests of Maria Pavlovna and, through her
brother the Czar, she was well acquainted
with Kankrin’s work and his problem with
platinum. Similarly at Weimar, through her
father-in-law Karl August, she was aware
that Dobereiner had some experience in this
same field. As early in his career as 1812 he
had interested himself in refining some South
American native platinum in order to provide
himself with his own platinum apparatus and
she had obtained for him some further sup-
plies from Russia to help his work. Also, as
chemical advisor to the Minister of State, he
had to inspect the work of breweries and
distilleries and this led him to a long research
on the oxidation of alcohol and the possibility
of making vinegar from it by direct chemical
means.
One of many types of Dobereiner lamp i n which a
Experiments with Platinum Black jet of hydrogen, generated from zinc und dilute
sulphuric acid, i s ignited by a small amount of
In the course of all this work, he came Jnely divided platinum. ( B y eourtesy qf the Science
upon the experiment of Edmund Davy in Museum)
1820 on the power of chemically-reduced
platinum black to promote the oxidation of wrapped some of this in filter paper and
alcohol. He repeated this in 1821 and found demonstrated its use in gas analysis by ensur-
that not only did it oxidise the alcohol entirely ing the combination of oxygen and hydrogen
to acetic acid alone (without other less desir- in mixtures containing them and so producing
able products), but at the end the platinum easily measurable changes in volume. Finally
black remained unchanged and available on August 3rd, 1823, he showed that if
for more work, It therefore promised well platinum sponge is spread out on a watch-
for the direct production of vinegar from glass and a stream of hydrogen is directed on
alcohol. Before taking this further, however, to it in such a way that it mixes with air
DBbereiner made some further experiments before touching it, the gas bursts into flame
on platinum black, which he thought was a at once.
sub-oxide, and found that it absorbed large This discovery was very quickly developed
quantities of hydrogen and would then into the Dobereiner lamp, an instrument
“imbibe” oxygen until the former was all which, under suitable circumstances, replaced
oxidised to water. Then he turned his the tinder box as a means of lighting domestic
attention to that quite different form of lamps and candles, a function which it
platinum, the so-called sponge obtained by continued until it was replaced by the phos-
calcining ammonium chloroplatinate. He phorus match. It is interesting to note in

Platinum Metals Rev., 1965, 9 , (4), 138

 passing that in 1832 Dobereiner discovered
the power of platinum to oxidise sulphur
dioxide to trioxide, but in this he had been
preceded by Peregrine Phillips in England a
year earlier. Also that he was the first to use
what we call today catalyst carriers. The
filter paper wrapping of 1823 was succeeded
by a dried and ignited mixture of platinum
sponge and potters’ clay; and an improved
version of the Dobereiner lamp had its
platinum sponge applied in an adhesive
coating on a coil of platinum wire. A final
comment on Dobereiner’s work on platinum
is that his process for the direct production
of vinegar was never used, because it was
overtaken by a more convenient indirect one!
But undoubtedly he occasioned a profound
interest in this new phenomenon, to which
Berzelius, the master of chemical nomen-
clature, gave the name “catalysis” in 1835.
So it is evident that Maria Pavlovna must
have found a great deal to interest her in
Dobereiner’s laboratory and no doubt she
reported it to Kankrin on her rcturn to St The title page of DGbereiner’s book on the chemistry
Petersburg, presumably somewhere in the of platinum
1830s. It is evident that he was pleased to be
in touch with the fresh mind of Dobereiner work of the English astronomer and chemist,
and moved at once to take advantage of it. Sir J. F. W. Herschel, in 1830 had clarified
Accommodation was arranged in Professor the subject considerably by showing that the
Osann’s chemical laboratory at the University lime will certainly precipitate the base metals
of Dorpat (now Tartu) and the services of a and the rhodium and iridium, but will leave
Dr Friederich Weiss of that University the platinum in the solution as long as it is
engaged. Dobereiner himself was of course not warmed or exposed to strong light. It
unable to leave Jena for any long period, so was upon this that Weiss and Dobereiner
his son, Franz Dobereiner, was sent to Dorpat based their improved process for the Russian
to work with Weiss and to be the agent for refinery. It was brought into use there after
full communication with Jena. Unlimited Sobolevsky’s death in 1841 and presumably
raw material was of course at their disposal continued until 1846, when the refinery was
and, no doubt, full access to the refining closed on the cessation of coining.
operations at St Petersburg. Their approach As far as is known, J. W. Dobereiner made
to the problem was by way of an attempt to no further contact with platinum after this,
free the solution of the native platinum in but maintained his distinguished teaching
aqua regia from iron and copper by the career until his death on March 24th, 1849.
addition of alkalies. This idea had been tried But among his many publications was a small
by earlier refiners without much success. book of a hundred pages on the history and
Chabaneau had got himself into difficulties properties of platinum, published in Stuttgart
by using milk of lime for the purpose in in 1836, which was remarkably comprehcn-
Madrid in the 1790s. But meanwhile the sive for its time.

Platinum Metals Rev., 1965, 9 , (4), 139