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Jaime Wisniak
Department of Chemical Engineering, Ben-Gurion University of the Negev, Beer-Sheva, Israel 84105
wisniak@exchange.bgu.ac.il
Palabras claves: aceite de tung, eucaliptus, fisiologa vegetal, meteorito de Orgueil, nitrificacin, nuez moscada,
ozono, polen, qumica agrcola, qumica analtica, qumica mineral, respiracin de plantas.
Keywords: agricultural chemistry, analytical chemistry, eucalyptus, mineral chemistry, nitrification, nutmeg, Orgueil
meteor, ozone, plant physiology, plant respiration, pollen, tung oil
RESUMEN. Franois Stanislas Cloez (1803-1881), farmacutico francs pionero en qumica y fisiologa vegetal,
qumica analtica y qumica orgnica, estudi el mecanismo de respiracin de plantas acuticas, la absorcin de
nitrgeno por las plantas, la nitrificacin de los suelos, la fotosntesis en plantas con hojas de color, los venenos de los
batracios y salamandras, descubri las primeras aminas etilnicas. (etilndiamina, dietilndiamina, and
trietilndiamina), separ e identific el eucaliptol, el principal componente del aceite de eucaliptus, sintetiz la
cianamida (junto con Cannizzaro), la tricloracetamida, la primera acetamida clorada, hizo un anlisis detallado del
famoso meteorito de Orgueil, diseo un aparato para el lavado continuo de materiales pulverulentos o gelatinosos,
etc.
ABSTRACT. Franois Stanislas Cloez (1803-1881), French pharmacist, pioneer in the chemistry and physiology of
plants, analytical chemistry, and organic chemistry, studied the respiration mechanism of aquatic plants, the
absorption of nitrogen by plants, soil nitrification, photosynthesis of colored leaves, the poisons of toads and
salamanders, discovered the first ethyleneamines (ethylenediamine, diethylenediamine, and triethylenediamine),
isolated and identified eucalyptol, the main component of eucalyptus oil, synthesized cyanamide (together with
Cannizzaro), trichloracetamide, the first chlorinated acetamide, made a detailed analysis of the famous Orgueil
meteor, designed an apparatus for the continuous washing of pulverulent or gelatinous materials, etc.
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In 1866 Cloez was appointed Chevalier of the Lgion d'Honneur. He was a founding member of the Socit
Chimique of France and its treasurer and president (1868); in 1879 he was elected senior member of the Conseil
d'Hygine de la Seine, and in 1882 president of the same. In 1878 he was candidate to the chemistry section of the
Acadmie, losing to Charles Friedel (1832-1899) and Louis Joseph Troost (1825-1911).1,2
Cloez passed away in Paris on October 12, 1883.
Scientific work
Cloez wrote about 100 papers, booklets and books in the areas of chemistry and physiology of plants, analytical
and organic chemistry, nitrification, animal poisons, metallurgy, etc. He also wrote a short booklet describing his
academic activities and his research and results.7 In addition to the subjects discussed below Cloez studied the
extraction of a new acid from the mother liquor of mercury fulminant; 8 use of KI for the analysis of ozone;9 non-
existence of iodine in the atmosphere;10 use of potassium permanganate as an oxidizing agent in the determination of
sulfur in gunpowder and organic sulfur compounds;11 the states of sulfur;12 apparatus for continuous washing of
precipitates;13 introduction of yellow horn poppy (Glaucium flavum) in non-cultivated terrains near the seashore;14
relative value of oil-producing plants;15 a new method for the combustion or organic substances;16 synthesis of a large
number of cyanic ethers, their composition, and isomerization phenomena; 4 chemical composition of the dye green of
China;17 metallurgy,18 etc.
Vegetable principles
Eucalyptus
Cloez was the first chemist to report on the properties of the leaves and chemicals from eucalyptus. In his first paper
on the subject he wrote that Ramel, the well-known traveller, had introduced in France a species of eucalyptus known
as Eucalyptus globulus, a tree originating from Australia, which grew to very large height and had been discovered by
the botanist Jacques La Billardire (1755-1834).19 The parenchyma of the eucalyptus leaves were covered by a
number of small transparent vesicles containing an essential volatile oil having a very pleasant aromatic odor.20
Cloez subjected the leaves to a series of treatments to determine the physiological effects of the resulting materials. A
steam distillation of the leaves yielded about 2% of the original weight as an essential colorless oil, lighter than water
and having a more concentrated odor of the raw material. The water solution had a fresh, bitter, and agreeable taste
and could be swallowed without consequences. Extraction with hot water produced a slightly colored infusion, bitter,
astringent, and having a strong smell originating from the rupture of the cells by the high temperature. The solution
produced a black precipitate with iron salts and was muddied by gelatin, indicating the presence of tannin. By
evaporation it yielded a brown precipitate that the only effect it had on a small dog was an increase in appetite.
Calcination and analysis of the precipitate indicated the presence of potassium and calcium salts. The residue of the
water extraction was treated with alcohol and ether and the extract found to have similar properties than the aqueous
one.20
The leaves were slowly burned in a pipe made of metal sheet and the resulting gas separated by successive washings
in flasks containing distinct solutions. The different volatile components and the tar produced were found to produce
an effect opposite to that of tobacco: more excitant than narcotic. According to Cloez his results indicated the leaves
did not contain materials toxic to animals; they could be burned and aspired through the mouth without mayor
consequences. The essence they contained seemed to have the same composition as turpentine, constituting another
example of isomerism. It had a density of 0.896, boiled at 175 0C, and its elemental composition corresponded to the
formula C20H16, for four volumes of vapor.20
In a following paper Cloez he reported a mode detailed study of the essence extracted from the leaves of eucalyptus. 21
From 10 kg of fresh leaves he obtained 275 g of the essential oil by steam distillation, that is, 2.75 % of the original
weight. Using leaves taken from the trees in another geographic region he was able to obtain 489 g of essence from 8
kg of leaves, that is, near 6% of the original weight. These results showed that the oil enclosed in the vesicles was
released very slowly. Anyhow, the properties of the oil were independent of the source; it was very fluid, almost
colorless, and smelling similar to camphor. It begun boiling at 170C and continued its distillation until above 200 C.
The first fraction collected, boiling between 1700C and 1780C, after purification with KOH and fused calcium
chloride of calcium, was found to boil regularly at 175C. According to Cloez, this material was a pure immediate
principle, different from all other known chemicals, which he named eucalyptol. Eucalyptol had specific gravity
0.905 at 8C; rotatory power +10.42 0 (for a length of 100 mm); did not freeze; at -180C and its vapor, mixed with air,
was fresh, agreeable when inhaled, and could be employed as a therapeutic agent. Eucalyptol was sparingly soluble in
water and very soluble in alcohol; its alcoholic solution, when highly diluted, smelled like rose. An elemental analysis
indicated that its composition corresponded to the formula C20H20O (vapor density 6.22). It was slowly attacked by
nitric acid and produced, among others, a crystallizable acid, which did not contain nitrogen and was probably
analogous to camphoric acid; treated with concentrated sulfuric acid it turned black and deposited a tarry substance,
which by distillation generated a volatile hydrocarbon.21
Eucalyptol was attacked by phosphorus pentoxide producing several derivatives. One of them was a colorless liquid
of density 0.836 at 12 0C and boiling at 165 0C; its composition seemed to be that of eucalyptol, less one equivalent of
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water, that is, C20H18. Cloez named it eucalyptene and assumed it corresponded to cymene. Another product was a
liquid boiling at above 300C and decomposing at higher temperatures, which Cloez named eucalyptolene. Treating
eucalyptol cooled to 0 0C with a stream of dry HCl gas, it absorbed the gas abundantly and solidified to form a wet
crystalline mass, which underwent spontaneous decomposition, into an aqueous solution of HCl and a hydrocarbon,
boiling about 168C, and apparently identical with eucalyptene. 21
A third paper discussed the possible uses of the eucalyptus tree for forestation and construction purposes. 22
Plant physiology
Composition of pollen
As stated by Edmond Frmy (1814-1894) and Cloez, previous researchers had shown pollen to be essentially built
of external membranes enveloping an internal substance, which had been named of fovilla. The composition of fovilla
was very complex; it contained a dense liquid, oily drops, small granular corpuscles, and sometimes starch. Frmy
and Cloez decided to carry on a chemical examination of pollen to determine the composition of the membranes
covering the grain, and the fatty and viscous substances that were enclosed in this membrane, or on its surface. The
latter caused the grains of pollen to adhere one to another.27
For their objectives they chose the pollen of the orange lily (Lilium croceum) known to contain an amount of this
fatty external substance that was extracted easily with ether without altering the grain of pollen. This pollen was of a
deep yellow color, unctuous and sticky, insoluble in water, sparingly soluble in cold and boiling alcohol, easily
dissolved in ether, non crystallizable, neutral to colored reagents, often holding a powerful waxy odor, and
saponifiable with difficult by alkalis. Elemental analysis of the material showed it contained 79.53-79.65 % of carbon,
12.00-12.09 % hydrogen, and 8.26-8.46% oxygen. The yellow substance coloring the external fatty body of pollen
was found to decompose rapidly in contact with the air, under the influence of even diffused light. These results
indicated that the external fatty substance of pollen presented a certain analogy to yellow wax; it was not a pure
immediate principle for it was formed of a yellow coloring matter, a fatty body saponifiable by alkalis, and of another
fatty body, which resisted the action of concentrated KOH.27
Additional experiments done with the pollen of white and yellow lily showed it was not affected by cold water but
boiling water generated a yellow solution charged with a gummy substance, which proved to be dextrin; prolonged
action of heat transformed the dextrin into glucose. These results proved clearly the presence of starch in the interior
of pollen and of a ferment (enzyme), which acted on the starch in the same manner as diastase. A nitrogenous
substance was also found to be present. Extraction of the pollen with ether or alcohol indicated the presence of an oily
substance, easily saponifiable, and containing 75.56 % carbon, 12.90 % hydrogen, and 11.74 % oxygen, a
composition very similar to the fatty oil extracted from oleaginous grains. Treatment with several chemical reagents
showed the external membranes of the pollen were not formed of cellulose; they resisted the action even of
concentrated sulfuric acid, which colored them black but did not dissolve them. Further analysis showed that the
nitrogenous substance contained 50.06 % carbon, 7.28 % hydrogen, 30.20 % oxygen, and 12.46 % nitrogen, a
composition resembling that of albuminous bodies.27
Frmy and Cloez also examined the pollen of two species of pines (pinus mughus and pinus austriaca) and two
species of cattails (typha latifolia and typha angustifolia), and found that although their shape was different from the
pollen of the lilies, they had essentially the same chemical composition.27
Nitrification
It so happened that Cloez was present during the test of Ville's results conducted at the Museum of Natural History,
under the inspection of a committee of the Academy of Sciences. The phenomena observed led him to consider in a
more general way the question of the assimilation of nitrogen by vegetables. He asked himself if plants were able of
directly absorbing the nitrogen in the state of simple gas, as it existed in the atmosphere, or could they assimilate it
only when it was in the form of a binary combination, as ammonia and nitric acid, or were they were able to derive
their nitrogen simultaneously from both these sources. His experiments about the property possessed by plants
exposed to the light of disengaging oxygen by the decomposition of water and CO2 had led him to consider the
possibility that the nitrogen present in plants could originate principally from the nitrates which existed, or could be
formed in the soil in which they grew.36
Cloez understood that the natural conditions favored the formation of nitric acid: nitrogen and oxygen in the
atmosphere, moisture, alkaline substances in the ashes added to the soil, a porous structure, etc. For these reasons he
decide to conduct a series of carefully conducted experiments to test this possibility. In his experiments he passed a
current of air, free of acid and ammonia vapors, through a series of flasks filled with fragments of a porous substance,
impregnated with an alkaline or earthy carbonate. Previous to admission, the air was purified by bubbling
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successively through a series of wash flasks containing an alkaline carbonate to eliminate acid vapors, dilute sulfuric
acid for absorbing ammonia, and concentrated sulfuric acid to retain the humidity. The purified air was passed
through 20 flasks filled with pieces of different porous materials (e.g. new brick previously calcined, pumice, calcined
porous bones, calcareous mark, chalk, kaolin, clay, etc.) mingled with pure or mixed chemicals (e.g. carbonates of
calcium, magnesium, potassium, etc.), dried or in solution. All the porous materials had been properly treated to
eliminate all nitrogenous or ammoniacal substances. For example, pumice was first calcined with sulfuric acid,
afterwards washed with distilled water, and then again heated to redness, without the addition of acid. The experiment
was commenced on September 15, 1854, and concluded towards the end of the following April, at which time saline
efflorescence appeared in some of the flasks.36
Analysis of the contents showed the presence of a considerable amount of nitrates in the flasks containing brick,
calcined pumice and ordinary pumice; a small amount of the same salts in the flasks containing chalk, pure calcareous
marl, the marl containing alkaline carbonate; and none in the pots containing calcined bones, or clay. According to
Cloez, the results of his experiments showed clearly that a current of air freed from acid and ammoniacal vapors, in
passing through porous matters, may give rise, in certain cases, to the formation of nitric acid and nitrates.36
In a class given to the member of the Socit Chimique de France in 1861, Cloez gave an historical review of the
theories regarding nitrification and the role of nitrates on vegetation, and a more detailed explanation of the
experimental equipment and procedure, results, and analysis of the same. 37,38 Two interesting consequences were that
plants did not assimilate nitrogen directly from the atmosphere and that porosity alone was not enough to induce the
synthesis of nitric acid, even in the presence of water an alkalis. He could not explain it but assumed that in the case
of bricks it could be due to the presence of an oxidizable substance, such as iron sulfide. 37,38
Chemistry
Cyanamides
In 1838 Amand Bineau (1812-1861) described the synthesis of a large number of ammonia derivatives, among
them ammonium chlorocyanide. He reported that the gases cyanogen chloride (ClCN) and ammonia reacted almost
immediately to produce white crystals of ammonium chlorocyanide, which he believed was represented by the
formula C4N2Cl2.2N2H6.44 In a paper published in 1851 Cloez and Stanislao Cannizzaro (1826-1910) reported that the
results they had obtained while trying so synthetize the new bases of Charles-Adolph Wrtz (1817-1884) by reacting
cyanogene chloride with ammonia,45 had led them to re-examine the results of Bineau about ammonium
chlorocyanide. They promptly realized that this substance was actually a mixture of ammonium chloride and an
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amide having the formula C2H2N2 (the actual formula is CH2N2, using the modern values of the atomic mass of
carbon and nitrogen), which they named cyanamide.46
They described cyanamide as a white crystalline substance, melting at 400C. At about 1500C the liquid suddenly
solidified with a large release of heat and became a compound having the same composition of cyanamide, but
different properties. Cloez and Cannizzaro believed that the solid had the same properties of melamine and should be
considered the amide of cyanuric acid (cyanuramide). Cyanuramide was stable in contact with dry air and soluble in
water, anhydrous alcohol, and ether. Evaporation of the aqueous solution left a solid residue, almost insoluble in
water, which Cloez and Cannizzaro believed was cyanuramide.46
The experimental results of Cloez and Cannizzaro indicated that the volatile bases discovered by Wrtz, and a large
number of organic bases, behaved in the same manner as ammonia with cyanogen chloride, the resulting product was
the hydrochloride of the base and the corresponding cyanic amide (cyanomethylamide, C 4H4N2, cyanoethylamide,
C6H6N2, and cyanamylamide C12H12N2). Cyanamide was easily prepared by bubbling dry gaseous cyanogen chloride
through an ethereal solution of ammonia. The precipitate of ammonium chloride formed was separated by filtration
and the filtrate distilled to dryness over a water bath.46
August Wilhelm Hofmann (1818-1892), found that the reaction between aniline and cyanogen chloride resulted in
the formation of the hydrochloride of a base containing the double equivalent of aniline where one "molecule" of
hydrogen and been replaced by one "molecule" of cyanogen (melaniline)47:
Cahours and Cloez compared this result with one obtained by Cloez and Cannizzaro, where ammonia and cyanogen
chloride produced a mixture of crystalline ammonium chlorine and cyanamide:
Bubbling pure and dry cyanogen through an ether solution of aniline contained in a vessel surrounded with crushed
ice, formed a crystalline deposit of pure aniline hydrochloride and evaporation of the residual liquid left reddish
translucent mass resembling colophony, which after purification proved to be cyanic anilide:
Heating an equimolar mixture of aniline hydrochloride and cyanic anilide resulted in formation of a solid substance
having all the properties of melaniline. The same results were obtained with toluidine and naphthalidam.
Methylaniline, ethylaniline, amylaniline, methylamine, ethylamine, amylamine, diethylamine, methylethylamine, and
diamylamine, yielded the corresponding cyanic alkylanilide. All these compounds proved to be weak bases, capable
of combining with concentrated acids and forming compounds, which decomposed in the presence of an excess of
water. Cahours and Cloez concluded that all these reactions could be represented by the general formula
At the conclusion of their paper Cahours and Cloez described a very simple process for preparing cyanogen chloride:
100 g of mercuric cyanide and 4 liters of water are introduced into a bottle of capacity 6 liters and then the water
saturated with chlorine at 00C. A considerable amount of HCl is formed and the mercuric cyanide is converted in the
course of 24 hours into mercuric chloride, which precipitates, and cyanogen chloride, which remains dissolved.
Heating the remaining solution releases the cyanogen chloride, which is purified by passing over of turnings of
copper and a calcium chloride.48
Oxidation of benzene
In 1858 Cloez and Charles-Ernest Guignet reported that potassium permanganate was able to convert nitro
derivatives into potassium nitrate. Among the many examples, they mentioned that nitrobenzene was converted into a
salt crystallizing as large rhomboidal blades, which were little soluble in water.49 The details of this particular reaction
were discussed in another paper were they reported that boiling nitrobenzene with potassium permanganate
precipitated manganese oxide and left a solution containing potassium carbonate, potassium nitrate, potassium
oxalate, and a potassium salt containing an acid sparingly soluble in water. This acid precipitated when adding HCl to
the solution separated by filtration. Cloez and Guignet mentioned that the oxidation of nitrobenzene was unruly and
for this reason decided to exchange potassium permanganate by a mixture of nitric acid and potassium dichromate.
This new reaction took place smoothly and was terminated when the orange color of the dichromate changed to the
green of chromium nitrate. Similar results were obtained with a mixture of potassium dichromate and dilute sulfuric
acid. The new potassium salt was soluble in nitrobenzene and precipitated upon cooling. The resulting crystals were
purified by solution in ammonia, precipitated again with HCl, and by water washes. 50
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The purified acid had a piquant acrid taste and could be further purified by sublimation. The resulting crystals were
sparingly soluble in cold water and more soluble in boiling water. They dissolved easily in alcohol, ether,
nitrobenzene, and acetic acid. Elemental analysis indicated that its global formula was C 18H7(NO4)O6, which Cloez
and Guignet believed corresponded to an oxidation product of nitrocinnamic acid. They also mentioned that they had
conducted the reaction with commercial nitrobenzene and thus the acid could have originated from the oxidation of
an impurity.50
BIBLIOGRAPHIC REFERENCES
1. Deherain P P. Stanislas Cloez - Notice Ncrologique. Ann Agron. 1883: 9; 525-549.
2. Grimaux E F S. Cloez - Notice Biographique. Bull Soc Chim. 1884: 41;146-157.
3. Cloez F S. Observations et Expriences sur l'Oxydation des Matires Grasses d'Origine Vgtale [Thse
prsente l'cole Suprieure de Pharmacie de Paris pour obtenir le titre de pharmacien de premire classe],
Thunot, Paris, 1866.
4. Cloez F S. Recherches sur les thers Cyaniques et leurs Isomres, [Thses prsentes la Facult des
Sciences de Paris, pour obtenir le grade de docteur s sciences physiques], Gauthier-Villars, Paris, 1866.
5. Bouquet J. Cloez F S. Sur un Nouveau Genre de Sels Obtenu par l'Action de l'Hydrogne Sulfur sur les
Arsniates, Compt Rendus. 1844: 19;1100-1105.
6. Bouquet J. Cloez F S. Sur un Nouveau Genre de Sels Obtenu par l'Action de l'Hydrogne Sulfur sur les
Arsniates. Ann Chim Phys.1845: [3]13; 44-59.
7. Cloez F S. Notice sur les Travaux Scientifiques, Gauthier-Villars, Paris, 1877.
8. Cloez F S. Note sur un Nouvel Acide Extrait des Eaux Mres du Fulminate de Mercure. Compt Rendus.
1852: 34; 364-366.
9. Cloez F S. Observations et Expriences sur l'Emploi de Iodure de Potassium comme Ractif de l'Ozone. Ann
Chim Phys. 1857: [3]50; 80-96.
10. Cloez F S. Note sur la Non-Existence de l'Iode Libre dans l'Air Atmosphrique, de Pillet, Paris, 1857.
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45. Wrtz A. Note sur la Formation de lUrethane par lAction du Chlorure de Cyanogne. Compt Rendus. 1846:
22; 503-505.
46. Cloez F S. Cannizzaro S. Recherches sur les Amides Cyaniques. Compt Rendus. 1851: 32; 62-64.
47. Hofmann A W. Action du Cyanogne sur l'Aniline et ses Homologues. J Pharm. 1848: [3]14; 305-310.
48. Cahours A. Cloez F S. Recherches Relatives l'Action du Chlorure de Cyanogne sur les Bases
Ammoniacales. Compt Rendus. 1854: 38; 354-358.
49. Cloez F S. Guignet E. Transformation de l'Azote des Matires Azotes en Nitrate de Potassium. Compt
Rendus. 1858: 47: 710-712.
50. Cloez F S. Guignet E. Nouvel Acide Obtenu par l'Oxydation de la Nitrobenzine. Compt Rendus. 1861: 52;
104-106; Bull Soc Chim. 1861; 3-5.
51. Cloez F S. Note sur la Composition Chimique de la Pierre Mtorique d'Orgueil, Compt Rendus. 1864: 58;
986-988.
52. Cloez F S. Analyse Chimique de la Pierre Mtorique d'Orgueil. Compt Rendus. 1864: 59: 37-40.
53. Cloez F S. Dosage de l'Acide Carbonique Contenu dans le Mtorite d'Orgueil. Compt Rendus. 1864: 59;
830-831.
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