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Henri Moissan Winner of the Nobel Prize for Chemistry 1906.

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DOI: 10.1002/anie.200601600
History of Science
Henri Moissan: Winner of the Nobel Prize for Chemistry
Alain Tressaud*
electrochemistry · fluorine · high-temperature
chemistry · history of science
n December 10, 1906, Henri Moissan (1852–1907) became the first French
chemist to be awarded the Nobel Prize.
At the award ceremony in Stockholm,
the President of the Royal Swedish
Academy of Sciences, P. Klason, described the two essential aspects of this
great scientist.s work in the following
terms, saying the prize had been awarded to Moissan, “for having isolated and
investigated the chemical element fluorine and for having introduced the electric furnace into the service of science—
exploits whereby he has opened up new
fields for scientific research and industrial activity”.[1] Indeed, Moissan had
isolated fluorine twenty years earlier
during a historic experiment; he also
paved the way for high-temperature
“Srie du Cyanogne” (The Cyanogen
Series).[2, 3]
It was only in 1884 that Moissan
began to concentrate solely on isolating
fluorine, a halogen discovered in the
early years of the 19th century thanks to
the work of A. M. AmpAre in France
and H. Davy in England (see inset).[4–7]
Yet the gas had never been isolated
because of its violent reactivity.
1886: A Great Year for Fluorine
Figure 1. Henri Moissan (1852–1907).
The Early Years
Henri Moissan was born in Paris in
1852 but spent much of his teenage years
and his early professional life in Meaux,
where he was an apprentice clockmaker
(Figure 1). In 1870 war against Prussia
obliged his family to return to Paris, and
he joined the army for a year before
enrolling at the Ecole Sup:rieure de
Pharmacie de Paris. Henri Moissan was
divided for many years between his two
loves, pharmacy and experimental
[*] Dr. A. Tressaud
Institut de Chimie de la
Condens/e de Bordeaux (ICMCB-CNRS)
Universit/ Bordeaux 1
87 Avenue Dr. A. Schweitzer
33608 Pessac Cedex (France)
Fax: (+ 33) 5-4000-2761
chemistry, and enrolled first in 1872 at
the Ecole de Chimie Exp:rimentale,
headed by Edmond Fr:my at the Mus:um, before joining P. P. Deh:rain.s
research group, also at the Mus:um,
where he carried out research into
vegetable physiology, the absorption of
oxygen, and the emission of carbon
dioxide in plants kept in obscurity. He
was appointed a senior chemist in 1879.
An account of his research during this
period into the chemistry of pyrophoric
iron and metal oxides of the iron family
can be found in the doctoral thesis he
wrote in 1880. At the same time, he
climbed the hierarchical ladder at the
Ecole Sup:rieure de Pharmacie de Paris. In 1880 he was appointed Ma<tre de
Conf:rences and Chef de Travaux Pratiques, before becoming Professeur
Agr:g: in 1882 with a thesis entitled
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Several generations of chemists had
tried in vain to isolate fluorine, notably
by electrolyzing phosphorus and arsenic
fluorides, but Moissan was determined
to find a way. His genius lay in the idea
of turning the bath into a conductor by
adding a molten potassium fluoride salt,
KHF2. (Pure hydrogen fluoride, HF,
could not suffice as its capacity as an
electric conductor was too weak.) Moissan devised a platinum electrolyzer and
lowered the reaction temperature of the
electrolytic solution of HF + KHF2 to
limit corrosion. The platinum electrolyzer was U-shaped and stopped with
fluorite (CaF2) stoppers (Figure 2). The
cathode and the anode were made of
irridated platinum to provide better
resistance to the fluorine. The traces of
hydrogen fluoride were condensed at
the end of the apparatus in a lowtemperature trap and also by sodium
fluoride. On June 28, 1886, a gaseous
product was identified at the anode of
the electrolyzer: Fluorine (F2) had been
successfully isolated, thus resolving one
of the most difficult challenges in the
realm of inorganic chemistry (Figure 3).[8] The yellow-green gas obtained
was highly toxic and proved to be a
Angew. Chem. Int. Ed. 2006, 45, 6792 – 6796
Figure 2. Moissan’s Nobel Prize diploma and the electrolytic cell used for producing fluorine
(courtesy of the Moissan Museum, Facult/ de Pharmacie, Universit/ Paris 5—Ren/ Descartes;
photograph taken by A. Tressaud).
Figure 3. Moissan’s very first note on the isolation of fluorine.[8a]
powerful oxidizing agent, causing organic materials to burst into flames on
entering into contact with it and combining directly, and often violently, with
almost all other elements.[9–11]
Angew. Chem. Int. Ed. 2006, 45, 6792 – 6796
Henri Moissan: The Great
Several months after having isolated
fluorine, Moissan was appointed Professor of Toxicology at the Ecole Sup:rieure de Pharmacie. Although this dis-
cipline was not his specialty, he taught
toxicology for 13 years. During this
period, he drew up a highly detailed list
of rules to be respected for drafting
expert reports in, for instance, the study
of epidemics. He also carried out studies
into hygiene in the professional environment, the analysis of air in factories,
urban sanitation, diet and food, and so
on. His rethinking of the teaching of
toxicology was rewarded with a seat on
the prestigious Acad:mie de M:decine
in 1888. Yet Moissan.s work as Professor
of Toxicology did not stifle his passion
for inorganic chemistry, and his research
in this field quickly brought him to the
forefront of chemistry in France along
with wide international acclaim. In 1891
he was appointed to the Acad:mie des
Sciences, and in July 1900 he became
Professor of Inorganic Chemistry at the
Facult: des Sciences, Universit: de Paris. Until 1890, his research was devoted
entirely to fluorine and the properties of
its derivatives, in collaboration with his
students, Lebeau, Meslans, and Poulenc,[12–14] or eminent colleagues such as
Becquerel or Berthelot. Moissan was a
first-class teacher and published a multitude of books dealing with the main
aspects of the inorganic chemistry of his
In the latter part of his career,
Moissan had great success in the field
of inorganic synthesis. He obtained a
pure state of boron together with a good
number of borides. From 1890 on, he
worked on an even more challenging
task than that of isolating fluorine—that
of artificially creating diamonds.[16a] In
order to achieve the extremely high
temperatures required to transform carbon into diamond, he designed an
electric furnace based on the principle
of an electric arc between two blocks of
limestone (Figure 4). He described this
furnace in a report dating from 1892,[16b]
and explained how the furnace could
reach temperatures between 3000–
3500 8C, quite exceptional at that time.
He heated a compound of iron and
sugar carbon to a temperature of
3000 8C, and then immersed the carbon
crucible into cold water. High pressure
was thus created inside the solid. Moissan found microscopic crystals of different types of diamond in the residues,
although in quantities of only a few
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The Search for the Missing Halogen through the 19th Century: From A.-M. Amp!re
and H. Davy to E. Fr%my
In 1809, when the discovery of sodium and potassium by English chemist Humphrey
Davy (1778–1829) was announced in France, Andr/-Marie (1775–1836)
grasped the idea that chlorine and fluorine were both chemical elements but did not
publish his hypotheses. He was astonished by the analogies between muriatic acid
(chlorhydric acid) and fluoric acid (fluorhydric acid) and concluded that an element first
called oxy-fluoric and later fluorine (in French) must exist, once he had understood that
fluorhydric acid did not contain any oxygen. Among the letters that he exchanged with
Davy during the war raging between their two nations, he even suggested on
November 1, 1810, the possibility of isolating the element fluorine through the
electrolysis of anhydrous fluorhydric acid.[4] “What remains to be discovered is whether the
electricity will not decompose the hydrofluoric acid into its liquid form, when we have
removed the water to the greatest extent, by bringing the hydrogen to one side and the oxyfluoric to the other.” In his reply in February 1811, Davy does not concede that a single
body be present as asserts, but rather, considers that this body also contains
oxygen. At that time, Davy could not state categorically that fluorine was an element: “In
the views that I have ventured to develop, neither oxygen, chlorine or fluorine are asserted to
be elements”. However, allowed Davy, who was now convinced that the French
scientist’s views were correct after 3 years of corresponding with him, to reap the glory
of announcing in 1813 that a new element had been discovered.[5] An autobiographical
note by, in which he refers to himself in the third person, does however
establish the anteriority of his own discovery, which is also fully recognized by Davy:
“During the period I was engaged in these investigations, I received two letters from M.
Amp re of Paris, containing many ingenious and original arguments in favour of the analogy
between the muriatic and fluoric compounds. M. Amp re communicated his views to me in
the most liberal manner; they were formed in consequence of my ideas on chlorine and
supported by reasonings drawn from the experiments of […] Gay-Lussac and Th)nard”.
The isolation of this new element continued to occupy many researchers for most of the
nineteenth century. A first step was the preparation of pure water-free hydrofluoric acid
by L. J. Th/nard (1777–1857) and L. J. Gay-Lussac (1778–1850). Their product fumed
strongly in air, rapidly dissolved glass, and caused extraordinary burns if it entered into
contact with the skin—a phenomenon the authors described in great detail. Later on,
J. J. Berzelius (1779–1848) characterized ammonium fluoride. Other researchers paid a
high price to the even more toxic effects of this element, without for so much
succeeding in isolating the element: G. and T. Knox were severely intoxicated, and the
Belgian chemist P. Louyet lost his life. Meanwhile, J. C. Marignac (1817–1894)
described in minute detail around 1860, the preparation and crystal morphology of a
good number of anhydrous or hydrated fluorosalts, such as fluorotitanates or
fluorozirconates, and most of his accurate conclusions are still valid today.[6] Many new
inorganic fluorides were also characterized by scientists such as H. Sainte-Claire Deville
(1818–1881) or E. Fr/my (1814–1894). Nevertheless, it seemed almost impossible to
synthesize fluorine, despite numerous attempts carried out during the latter part of the
An important step was made by Fr/my, Moissan’s first mentor, when he succeeded in
preparing pure anhydrous HF as well as KHF2, the so-called Fr/my’s salt expressed as
“KFl·HFl” using the notations of that time.[7] Fr/my had come very close to solving the
puzzle by electrolyzing anhydrous HF, molten calcium fluoride, or potassium fluoride,
but he seemed not to have had the idea of replacing these compounds by KHF2, perhaps
because of the high melting point of the compound (m.p. 293 8C), which would have led
to insurmountable technical difficulties.
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Although Moissan was never able to
totally fulfill his dream in this field and
his research was contested by Le Chatelier and Parsons, his ideas were nonetheless visionary and paved the way for
high-pressure experiments that led to
the industrial synthesis of an artificial
diamond by General Electric fifty years
later. Today, the annual global production of synthetic diamonds is estimated
at around 450–500 million carats.[17]
With the technological breakthrough brought by the electrical furnace, Moissan turned over a new page in
the history of chemistry, that of hightemperature chemistry. The list of his
discoveries is impressively long and
– crystallization of a large number of
oxides that were reputedly infusible,
– obtaining refractory metals by reducing their oxides in the presence of
– discovering a large number of metallic carbides such as calcium carbide,
which then made way for the discovery of acetylene, but also new borides,
nitrides, and silicides,
– development of a method for preparing calcium in a pure state by reducing calcium iodide with excess sodium, and developing metallic hydrides, etc.
We may also conclude that, along
with Collongues, Moissan is the forebear
of high-temperature chemistry.[18]
The Nobel Prize crowned the career
of this great scientist. However, Moissan
also received an impressive number of
other titles and distinctions, including
entry into the scientific academies of
France and various foreign countries,
honorary doctorates, and other prestigious distinctions. The dedication of
Moissan to his work did not mean that
he neglected the other sides of intellectual life. Although he cared little for
music and the theatre, he showed great
admiration for the work of Jean-Baptiste Corot and had several magnificent
canvasses by the painter that he would
sit and contemplate to rest his mind. He
was also a passionate collector of works
by contemporary artists and antique
engravings. He also had a very fine
collection of autographs relating to the
French Revolution.[19]
Angew. Chem. Int. Ed. 2006, 45, 6792 – 6796
Figure 4. Moissan and his electric furnace at the Facult/ des Sciences, Universit/ de Paris.
Moissan died on February 20, 1907,
at the age of 54 from acute appendicitis,
just two months after receiving his
Nobel Prize. Fluorine and its highly
toxic gaseous derivatives, together with
the carbon monoxide that was emitted
from his electric furnace, had no doubt
weakened his health and may well have
been responsible for his low resistance
to the infection.
Our Inheritance from Henri
Moissan is still considered to be a
pioneer in most of the fields in which he
carried out his research, and a long list
of new technological methods and important scientific discoveries are the
direct result of his innovative work. In
1986, the Moissan Prize was created in
recognition of stimulating research in
the field of fluorine chemistry.[20]
The electric furnace paved the way
for breakthroughs in the fields of electrometallurgy, in aluminothermics, and
the acetylene and calcium cyanamide
industries. The production of crystalline
oxides, the industrial production of
ceramics, and refractory techniques also
owe a great deal to his innovative work.
The importance of carbides, as Moissan
foresaw, is illustrated by the important
role played by composites in a wide
range of strategic fields.[21]
Angew. Chem. Int. Ed. 2006, 45, 6792 – 6796
Today, fluorine is still synthesized
electrochemically using the principle
elaborated by Moissan.[22, 23] One of the
main uses of this process today is the
transformation of uranium tetrafluoride
into its hexafluoride, an essential stage
in the production of nuclear energy.[24]
There are over 600 000 compounds that
contain at least one atom of fluorine,
and the chemistry of fluorine and fluorine-based products has allowed huge
breakthroughs to be made in a wide
variety of fields, including organic
chemistry,[25] materials science,[26] polymers,[27] drugs, and medical applications.[28] Some of the great discoveries
that emerged in the 20th century as a
result include:
– the use of organic and/or inorganic
fluorine in a number of energy-conversion processes (e.g. in Li ion
batteries, fuel cells, and nuclear energy);[24, 29]
– the use of fluoride polymers such as
Teflon, which resist corrosion so remarkably, in packaging highly reactive products, nonstick kitchen utensils, materials for cardiovascular implants, and membranes for fuel
– the use of fluorine and fluoride gases
in microelectronics within the production process of silicon components, which means that all impurities
can be eliminated from the surface of
a semiconductor, thus allowing our
computers to function efficiently;
– the use of fluoro-surfactants to protect fabrics, carpets, and leather, and
as a fire-retardant material;
– the surface coating of materials with
fluorinated compounds to make
them graffiti-proof or UV-absorbent,
or to protect our cultural heritage by
injecting fluoride polymers into lithic
objects and coating metallic structures (as an example, coating the
metallic framework of the Louvre
Pyramid or the metallic parts supporting the structure of the Grande
Arche at La D:fense in Paris);
– the use of fluorinated molecules in
cancer-repressant drugs, anti-inflammatories, antibiotics, neuroleptics, or
antihypertensive drugs as a result of
their associated therapeutic properties, and there are possibilities for
using perfluorocarbons in vitreoretinal surgery and as substitutes for
blood in emergency transfusions;[28]
– the use of molecules containing one
or several atoms of fluorine as efficient herbicides, fungicides, or insecticides;
– the use of 18F positron emission tomography or 19F NMR for medical
imaging to detect the early presence
of tumors and for diagnosing some
diseases of the brain, such as Alzheimer.s Disease.
It is clear that some problems caused
to our environment by fluorinated products should not be underestimated.[30] A
great challenge for the groups dealing
with fluorine and fluoride products is to
find solutions to overcome these problems, such as supervising the use of
fluoride molecules in agrochemicals,
developing a definitive substitute for
chlorofluorocarbons (CFCs), which are
partly to blame for destroying the ozone
layer, and the defluoridation of drinking
water in many areas of the world where
there is a risk of people contracting
fluorosis.[31] Although the isolation of
fluorine by Henri Moissan dates back
over a century, the fabulous destiny of
this element seems to be only in its early
years today, as the breakthroughs and
new vistas brought by it to so many
fields of science brim with potential.[32]
Published online: September 7, 2006
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[1] Nobel Lectures, Chemistry 1901–1921,
Elsevier, Amsterdam, 1966.
[2] “Vie et Œuvre de H. Moissan”: C. Viel,
J. Flahaut, J. Fluorine Chem. 1986, 33,
27 – 44, a lecture given during the International Symposium on the Centenary of
the Discovery of Fluorine, Paris, 1986.
[3] “Aspects historiques de l.isolement du
fluor. Travaux d.Henri Moissan et de ses
collaborateurs directs d:but du
XXe siAcle”, C. Viel in the special issue
of Actualit Chimique, Soci:t: FranPaise
de Chimie, 2006.
[4] “Reste 0 savoir si l1lectricit ne dcomposerait pas l1acide hydro-fluorique sous
sa forme liquide, lorsqu1on en aurait
cart l1eau le plus possible, en portant
l1hydrogne d1un c2t et l1oxy-fluorique
de l1autre.” Taken from “Correspondance du Grand Ampre”, GauthiersVillars, Paris, 1936, including correspondence between the two scientists
from 1810 to 1825.
[5] H. Davy, Philos. Trans. R. Soc. London
1812, 102, 352; H. Davy, Philos. Trans. R.
Soc. London 1813, 103, 263; H. Davy,
Philos. Trans. R. Soc. London 1814, 104,
[6] J.-C. Galissard de Marignac, Œuvres
Compltes“, Tomes 1 & 2 (1840–1887),
Soci:t: de Physique de GenAve, Masson, Paris, 1890; A. De Cian, J. Fisher,
Acta Crystallogr. 1967, 22, 338; J. Fisher,
G. Keib, R. Weiss, Acta Crystallogr.
1967, 22, 340; W. Massa, Z. Anorg.
Allgem. Chem. 1977, 436, 29.
[7] E. Fr:my, Ann. Chim. Phys. 1856, 47, 5 –
[8] a) H. Moissan, C. R. Hebd. Seances
Acad. Sci. 1886, 102, 1543 – 1544; b) H.
Moissan, C. R. Hebd. Seances Acad. Sci.
1886, 103, 202 – 205; c) H. Moissan, C. R.
Hebd. Seances Acad. Sci. 1886, 103,
256 – 258.
[9] E. Banks, J. Fluorine Chem. 1986, 33, 3 –
26 and Fluorine Chemistry at the Millennium: Fascinated by Fluorine (Ed.: R. E.
Banks), Elsevier, Dordrecht, 2000 (partly in J. Fluorine Chem. 1999, 100).
[10] H. Moissan, Das Fluor und seine Verbindungen, Krayn, Berlin, 1900.
[11] P. Lebeau, Bull. Soc. Chim. Fr. 1908, 4,
3 – 4; the same text appeared in “Hommage R Henri Moissan”: Chimie et
Industrie, Paris, 1932.
[12] For some representative reports on
fluorine and fluoride compounds, see:
“Recherches sur l.isolement du fluor”,
H. Moissan, Ann. Chim. Phys. 1887, 12,
472; “Nouvelles recherches sur le fluor”,
H. Moissan, Ann. Chim. Phys. 1891, 24,
224; “Fluorure double de chrome et
potassium”, H. Moissan, Ann. Chim.
Phys. 1894, 2, 66; “Le bifluorure de
platine anhydre”, H. Moissan, C. R.
Hebd. Seances Acad. Sci. 1889, 109, 807.
C. Poulenc, Ann. Chim. Phys. 1894, 2, 5.
H. Becquerel, H. Moissan, C. R. Hebd.
Seances Acad. Sci. 1890, 111, 669 – 672.
H. Moissan, Le Fluor et ses Composs,
Steinhel, Paris, 1900; Le four lectrique,
Steinhel, Paris, 1897; Trait de Chimie
Minrale, Masson, Paris, 1904–1906.
a) O. KrStz, Angew. Chem. 2001, 113,
4739 – 4745; Angew. Chem. Int. Ed.
2001, 40, 4604 – 4610; b) H. Moissan, C.
R. Hebd. Seances Acad. Sci. 1892, 115,
1031 – 1033.
The Canadian Encyclopedia, 2006,
com; search “diamonds”.
R. Collongues, F. Galtier, Pour la Science 1996, 230, 46 – 52.
At the auction of his collection of
autographs at Drouot on October 14,
1921, more than 6000 items and manuscripts were sold off.
Following an international symposium
in 1986 commemorating the isolation of
fluorine, the Moissan Prize was established by co-chairmen, P. HagenmTller
and P. Plurien, in recognition of achievements in the various fields of fluorine
chemistry. Since then, the prize has been
awarded at every International Symposium on Fluorine Chemistry: 1988: G.
Cady (Seattle, USA) and N. Bartlett
(Berkeley, USA); 1991: H. J. Emel:us
(Cambridge, UK); 1994: R. N. Haszeldine (UMIST-Manchester, UK); 1997: P.
HagenmTller (Bordeaux, France); 2000:
K. O. Christe (USC-Los Angeles, USA);
2003: R. Chambers (Durham, UK);
2006: D. D. DesMarteau (Clemson, SC,
USA). Besides this prize, Moissan grants
are regularly proposed to students by
the Fluorine Division of the American
Chemical Society.
W. Krenkel, R. Naslain, H. Schneider,
High Temperature Ceramic Matrix Composites, Wiley, New York, 2001.
M. Jaccaud, F. Nicolas, Techniques de
l1Ingnieur 1990, J6020–J1453.
D. Pletcher, Industrial Electrochemistry,
Chapman and Hall, London, 1982,
chap. 5.
“SynthAse :lectrochimique du fluor de
1886 R 2006: le fluor, :l:ment clef pour
l.:nergie nucl:aire”, H. Groult, F. Lantelme, C. Belhomme, B. Morel, F. Nicolas, J. P. Caire in the special issue of
Actualit Chimique, Soci:t: FranPaise
de Chimie, 2006.
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[25] K. Uneyama, Organofluorine Chemistry,
Blackwell, Malden, USA, 2006; R.
Chambers, Fluorine in Organic Chemistry, Blackwell, Malden, USA, 2004;
Handbook of Fluorous Chemistry
(Eds.: J. A. Gladysz, D. P. Curran, I. T.
Horvath), Wiley, New York, 2004; P.
Chemistry—Synthesis & Applications,
Wiley-VCH, Weinheim, 2004; R. E.
Banks, B. E. Smart, J. C. Tatlow, Organofluorine Chemistry: Principles &
Commercial Applications, Kluwer/Plenum, New York, 1994; G. A. Olah,
G. K. S. Prakash, R. D. Chambers, Synthetic Fluorine Chemistry, Wiley, New
York, 1992.
[26] Advanced Inorganic Fluorides: Synthesis, Characterization and Applications
(Eds.: T. Nakajima, B. Zemva, A. Tressaud), Elsevier, Dordrecht, 2000; N.
Watanabe, T. Nakajima, H. Touhara,
Graphite Fluorides, Elsevier, Dordrecht,
1988; Inorganic Solid Fluorides:
Chemistry and Physics (Ed.: P. HagenmTller), Academic Press, New York,
[27] B. Ameduri, B. Boutevin, Well-Architectured Fluoropolymers, Elsevier, Dordrecht, 2004.
[28] J. P. B:gu:, D. Bonnet-Delpon, Chimie
Bioorganique et Mdicinale du Fluor,
EDP-Sciences, Paris, 2005; I. Ojima,
J. R. McCarthy, J. T. Welch, Biomedical
Frontiers in Fluorine Chemistry, American Chemical Society, Washington DC,
1996; J. T. Welch, S. Eswarakrishnan,
Fluorine in Bioorganic Chemistry, Wiley,
New York, 1991.
[29] Fluorinated Materials for Energy Storage (Eds.: T. Nakajima, H. Groult),
Elsevier, Dordrecht, 2005.
[30] L. H. Weinstein, A. Davison, Fluorides
in the Environment: Effect on Plants and
Animals, CABI Publishing, Cambridge,
MA, 2004.
[31] Volumes dedicated to “Fluorine and the
Environment” in the book series Advances in Fluorine Science (Ed.: A.
Tressaud), Elsevier, Dordrecht, 2006.
[32] Celebrations in 2006 for the centenary
of Henri Moissan.s Nobel Prize include
a session at the 18th International Symposium on Fluorine Chemistry, Bremen,
August 3, 2006; special issues of “Actualit Chimique” (Soci:t: FranPaise de
Chimie) and J. Fluorine Chem; the
International Colloquium at Maison de
la Chimie, Paris (November 10, 2006);
and celebrations in the city of Meaux,
Angew. Chem. Int. Ed. 2006, 45, 6792 – 6796
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