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Friedrich
Wöhler (1800-1882)
ON
THE ARTIFICIAL PRODUCTION OF UREA
Annalen der Physik und Chemie, 88, Leipzig, 1828
In a brief earlier communication, printed in Volume III of
these Annals, I stated that by the action of cyanogen on liquid
ammonia, besides several other products, there are formed
oxalic acid and a crystallizable white substance, which is
certainly not ammonium cyanate, but which one always obtains
when one attempts to make ammonium cyanate by combining cyanic
acid with ammonia, e.g., by so-called double decomposition.
The fact that in the union of these substances they appear
to change their nature, and give rise to a new body, drew
my attention anew to this subject, and research gave the unexpected
result that by the combination of cyanic acid with ammonia,
urea is formed, a fact that is noteworthy since it furnishes
an example of the artificial production of an organic, indeed
a so-called animal substance, from inorganic materials.
I have already stated that the above-mentioned white crystal-line
substance is best obtained by breaking down silver cyanate
with ammonium chloride solution, or lead cyanate with liquid
ammonia. In the latter way I prepared for myself the not unimportant
amounts employed in this research. It was precipitated in
colourless, transparent crystals, often more than an inch
long...
With caustic soda or chalk this substance developed no trace
of ammonia; with acids it showed none of the breakdown phenomena
of cyanates which occur so easily, namely, the evolution of
carbon dioxide and cyanic acid; neither could the lead and
silver salts be precipitated from it, as from it, as from
a true cyanate; it could thus contain neither cyanic acid
nor ammonia as such. Since I found that by the last named
method of preparation no other product was formed and the
lead oxide was separated in a pure form, I imagined that an
organic substance might arise by the union of cyanic acid
with ammonia, possibly a substance like a vegetable salifiable
base. I therefore made some experiments from this point of
view on the behaviour of the crystalline substance to acids.
But it was indifferent to them, nitric acid excepted; this,
when added to a concentrated solution of the substance, produced
at once a precipitate of glistening sales. After these had
been purified by several recrystallizations, they showed very
acid characters, and I was already inclined to take the compound
for a real acid, when I found that after neutralization with
bases it gave salts of nitric acid, form which the crystallizable
substance could be extracted again with alcohol, with all
the characters it had before the addition of nitric acid.
This similarity to urea in behaviour induced me to make parallel
experiments with perfectly pure urea separated from urine,
from which I drew the conclusion that without doubt urea and
this crystalline substance, or ammonium cyanate, if one can
so call it, are absolutely identical compounds.
I will describe the behaviour of this artificial urea no
further, since it coincides perfectly with that of urea from
urine, according to the accounts of Proust, Prout and others,
to be found in their writings, and I will mention only the
fact, not specified by them, that both natural an d artificial
urea, on distillation, evolve first large amounts of ammonium
carbonate, and then give off to a remarkable extent the stinging,
acetic-acid-like smell of cyanic acid, exactly as I found
in the distillation of mercuric cyanate or uric acid, and
especially of the mercury salt of uric acid. In the distillation
of urea, another white, apparently distinct substance also
appears, with the examination of which I am still occupied.
But if the combination of cyanic acid and ammonia actually
gives urea, it must have exactly the composition allotted
to ammonium cyanate by calculation from my composition formula
for the cyanates; and this is in fact the case if one atom
of water is added to ammonium cyanate, as all ammonium salts
contain water, and if Prout's analysis of urea is taken as
the most correct. According to him, urea consists of
| Nitrogen
| 46.650
| 4
atoms
|
| Carbon
| 19.975
| 2
atoms
|
| Hydrogen
| 6.670
| 8
atoms
|
| Oxygen
| 26.650
| 2
atoms
|
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| 99.875
|
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But ammonium cyanate would consist of 56.92 cyanic acid,
28.14 ammonia, and 14.75 water, which for the separate elements
gives
| Nitrogen
| 46.78
| 4 atoms
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| Carbon
| 20.19
| 2 atoms
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| Hydrogen
| 6.59
| 8 atoms
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| Oxygen
| 26.24
| 2 atoms
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| 99.80
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One would have been able to reckon beforehand that ammonium
cyanate with 1 atom of water has the same composition as urea,
without having discovered by experiment the formation of urea
from cyanic acid and ammonia. By the combustion of cyanic
acid with copper oxide one obtains 2 volumes of carbon dioxide
and 1 volume of nitrogen, but by the combustion of ammonium
cyanate one must obtain equal volumes of these gases, which
proportion also holds for urea, as Prout found.
I refrain from the considerations which so naturally offer
themselves as a consequence of these facts, e.g., with respect
to the composition proportions of organic substances, and
the similar elementary and quantitative composition of compounds
of very different properties, as for example fulminic acid
and cyanic acid, a liquid hydrocarbon and olefiant gas (ethylene).
From further experiments on these and similar cases,a general
law might be deduced.
______________________
Friedrich
Wöhler (1800-1882) foi um professor na University of Goettingen.
Ele tornou-se famoso pela síntese da uréia e outros
compostos de amônia partindo de reagentes inorgânicos.
Este experimento foi um marco na história da química,
e acabou de vez com a teoria da "força vital",
que ditava que compostos orgânicos somente poderiam ser
obtidos através de organismos vivos. Além disso,
ele foi o primeiro a isolar o alumínio e o berílio.
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