para quitarle el polvo Educ. quím., 21(1), 60-69, 2010.

© Universidad Nacional Autónoma de México, ISSN 0187-893-X

The History of Catalysis.

From the Beginning to Nobel Prizes
Jaime Wisniak1

Abstract
Although the effects of catalysis are known from very ancient times, the understanding of the
phenomena started only in the 18th century and in due course led to the awarding to two Nobel
prizes at the beginning of the 20th century.

Keywords: Catalysis, mechanism, platinum, platinum group metals, fermentation, sulfuric acid

Resumen (La historia de la catálisis. Desde sus Here we trace the development of the concept and its ex-
principios hasta los premios Nobel) planation, from the dawn of its history until the first Nobel
Aun cuando los efectos de la catálisis son conocidos desde la Prizes were awarded in 1909 and 1912 for significant contri-
antigüedad, la comprensión del fenómeno comenzó sólo en el bution in the field. By the beginning of the 19th century the
siglo XVIII y con el tiempo culminó con la adjudicación de catalytic properties of many metals, notably platinum, had
dos Premios Nobel en el siglo XX. been noticed and extensively investigated, and a crude de-
scription of homogeneous catalysis using an unstable inter-
Introduction mediate was suggested. By the 1830s the pieces of the puzzle
Catalysis is a phenomenon known from very ancient times, were falling in place, the phenomenon was given its present
although not so its theory or characteristics; nowadays it plays name, and physical adsorption proposed as its possible mech-
a fundamental role in the manufacture of the vast majority of anism.
chemicals used by our society. The term catalysis, proposed in
1835 by Jöns Jakob Berzelius (1779-1848), comes from the Development
Greek words kata meaning down and lyein meaning loosen. The art of producing alcohol from sugar by fermentation is
Berzelius wrote that by the term catalysis he meant “the known from the beginning of human history. The first known
property of exerting on other bodies an action which is very use of inorganic catalysts is from 1552 when Valerius Cordus
different from chemical affinity. By means of this action, they (1514-1554) used sulfuric acid to catalyze the conversion of
produce decomposition in bodies, and form new compounds alcohol to ether (Cordus, 1575). In 1781 Antoine Augustin
into the composition of which they do not enter” (Berzelius, Parmentier (1737-1813) observed that potato starch mixed
1835). with distilled water and cream of tartar (potassium hydrogen
According to Kilani and Batis (Kilani, Batis and Chas- tartrate), acquires a sweet taste after several months, which is
trette, 2001), by the end of the 18th and the beginning of the more pronounced if acetic acid has been added (Parmentier,
19th centuries the accumulation of experimental data rela- 1781). This reaction was more thoroughly studied by Johann
tive to the modification of diverse chemical reactions by the Wolfgang Döbereiner (1780-1849) who found that starch
presence of small amounts of foreign substances was enough dissolved in water is fermented into alcohol; he assumed that
to see the beginning of explanation of the phenomena in a the starch was first converted into sugar (Döbereiner, 1816).
frame outside the theory of chemical affinity. Nevertheless, He also discovered the catalytic action of manganese dioxide
for certain reactions like decomposition catalysis was due to on the thermal decomposition of potassium chlorate, the ba-
the activity of solids previously heated and could be attrib- sis for the preparation of oxygen (Kauffman, 1999).
uted to heat. In 1811 Sigismund Konstantin Kirchhoff (1764-1833) dis-
covered that heating an aqueous solution of starch with min-
eral acids changed it into a gum, dextrin and raisin sugar,
without the acids being modified by the reaction and without
release of gas. Treating the resulting solution with alkali re-
1
Department of Chemical Engineering, Ben-Gurion University of covered all the acid employed (Kirchhoff, 1811).
the Negev, Beer-Sheva, Israel 84105 In 1833 Anselme Payen (1795-1871) and Jean-François
Correo electrónico: [email protected] Persoz (1805-1868) (Payen and Persoz, 1833) found that the
Recibido: septiembre 12 de 2009; aceptado: 14 de octubre de transformation of starch discovered by Kirchhoff was attrib-
2009. utable to the action of a special substance, which they called

60 para quitarle el polvo educación química  •  enero de 2010

diastase (amylase). Payen and Persoz found that the activity monia gas, a crackling noise is produced and becomes red and
of diastase is eliminated by heating to 100°C. Payen estab- scintillates…Oxygen gas does not affect the powder at the
lished the theory of beer fabrication, discovered the process common temperature of the air, but by a moderate heat there
actually used for obtaining dextrin, determined its composi- is a slight combustion, which seems to indicate the presence
tion, and showed it to be an isomer of starch. In 1878 Willy of a little inflammable substance…I have already employed it
Kühne (1837-1900) suggested the name enzyme for biologi- as an easy means of affording heat and light. To produce heat
cal catalysts. it is only necessary to moisten any porous substance, such as
In the late eighteenth century Johann Rudolph Deiman sponge, cork cotton, asbestos, sand, etc., with alcohol or whis-
(1743-1808), Adrien Paets von Trootswijk (1752-1837), An- key, and to let a particle of the powder fall on the substance
thoni Lauwerenburg (1758-1820), Nicolas Bondt (1765- so moistened; it immediately becomes red hot, and remains so
1796), and Pieter Nieuwland (1764-1794), reported that gaz until the spirit is consumed…”
hydrogène carboné huileux (ethylene) could be prepared by Louis-Jacques Thenard (1777-1857) did some research on
treating 25 parts of alcohol with 75 parts of concentrated the subject of alcoholic fermentation and concluded that all
sulfuric acid, without external heating, and also by passing sugary juices, in the process of spontaneous fermentation, de-
alcohol or ether vapors through a glass tube containing silica posited a substance which resembled beer yeast and had the
or alumina, or simply through an empty tube of clay. This power of fermenting pure sugar. He believed that this yeast
work may be considered the first systematic study of catalytic was animal in nature (Thenard, 1803), since it contained ni-
reactions by metals; it was mentioned in a report read by An- trogen and yielded ammonia on distillation (Thenard, P.,
toine Francois de Fourcroy (1755-1809) on December 16, 1950). Thenard asked himself: All of our knowledge about
1796 (Fourcroy, 1797ab). The report was considered so im- fermentation indicates that sugar matter changes into alcohol
portant that it was recommended be published in the Jour- and carbon dioxide by means of an intermediate body. How
nal des Savants Etrangers (Passagez, 1935). does it operate on sugar? In spite of all his efforts, he was un-
In 1817 Humphry Davy (1778-1819) reported that he able to provide a satisfactory answer.
“was making experiments on the increase of the limits of the com- In 1820, when Thenard was studying the effect of finely
bustibility of gaseous mixtures of coal gas and air by increase divided metal on hydrogen peroxide, he compared this phe-
of temperature…when I was accidentally led to the knowl- nomenon to the action of yeast in alcoholic fermentation
edge of the fact, and at the same time, to the discovery of a (Thenard, P., 1950). Louis Pasteur (1822-1895) quoted The-
new and curious series of phenomena…that oxygen and coal nard’s analysis of the fermentation process in his well-known
gas in contact with the hot wire combined without flame, and memory about alcoholic fermentation (Pasteur, 1860).
yet produced enough heat to preserve the wire ignited, and to Thenard’s work on wine fermentation and the decompo-
keep up their own combustion…A temperature much below sition of hydrogen peroxide by metals and certain organic
ignition only was necessary for producing this curious phe- materials may be considered the origin of his interest in ca-
nomenon…The same circumstance occurred with certain in- talysis, although he did not know the meaning of the phe-
flammable vapors…ether, alcohol, oil of turpentine, and nomena. Hearing about Döbereiner’s results he was astound-
naphtha…I have tried…various metals; but succeeded only ed to see that the same material that decomposed water
with platinum and palladium; with copper, silver, iron, gold, peroxide by simple contact was able to induce the reaction
and zinc, the effect is not produced” (Davy, H., 1817). Davy between oxygen and hydrogen. Pierre-Louis Dulong (1785-
suggested that his discovery could be used to build a non- 1838) and Thenard verified and confirmed Döbereiner’s re-
explosive lamp to be employed in mining operations. Hum- sults (Dulong and Thenard, 1823a). They found that a sponge
phrey’s Davy discovery may be considered the first clear evi- of palladium was also able to ignite hydrogen; a sponge of
dence that a chemical reaction between two gaseous reactants iridium heated very strongly also realized this reaction pro-
can occur on a metal surface without the metal being chemi- ducing water. Hydrogen and NO2 or hydrogen and NO in the
cally changed. presence of platinum sponge at room temperature, reacted
In 1820, Edmund Davy (1785-1851) reported that boiling yielding water and ammonia (Dulong and Thenard, 1823ab).
a mixture of platinum sulfate with alcohol or ether precipi- Dulong and Thenard also reported that the platinum sponge
tated a black substance in a finely divided state (Davy, E., became incandescent when it was contacted by hydrogen in-
1820). Heating the powder produced a feeble explosion ac- timately mixed with air. Platinum, reduced to a very fine
companied by a flash of red light and reduction of the plati- powder, or as a wire or sheet, did not act even slowly, at room
num. Davy studied the properties of the powder and indi- temperature. Although these results seemed to suggest that
cated “it is tasteless and does not affect litmus paper…It the porosity of the metal was an essential condition for the
seems to undergo no change by exposure to the air for some phenomenon to take place, it was easy to prove it wrong. Du-
time. When it is heated gently on a slip of platinum or paper, long and Thenard reduced the platinum to a very thin sheet
a hissing noise or a feeble explosion is produced and a flash of and found that in this state the metal also acted at room tem-
red light accompanies this effect and the platinum is re- perature over a mixture of oxygen and hydrogen; the reaction
duced… When the powder is brought into contact with am- became as the sheet was thinned, sheet, even with explosion.

enero de 2010  •  educación química para quitarle el polvo 61

 A very thin platinum sheet rolled up over a glass cylinder or air had condensed with the hydrogen to form water” (Dö-
suspended freely in an explosive mixture did not produce any bereiner, 1828, 1836; Kauffman, 1999).
sensible effect, even after several days, but the same sheet This discovery, producing fire without flint and tinder, cre-
crumpled and burred, detonated the mixture instantly (Du- ated a real sensation and was immediately tested and con-
long and Thenard, 1823a). firmed by numerous chemists and physicists. Berzelius, in his
Davy had considered the phenomenon to be an exclusive Jahres-Bericht (Berzelius, 1823-1825), wrote: “From any point
result of the mutual action between the fluids, without con- of view the most important and, if I may use the expression,
sideration of the nature of the vessels that contained them. the most brilliant discovery of last year is, without doubt, that
According to Dulong and Thenard, the contrary was true; the fine platinum powder has the ability to unit oxygen and hy-
combination took place at a different temperature for each drogen even at low temperatures…made by Döbereiner”
solid substance that came into contact with the combustible (Kauffman, 1999).
substance. All these observations revealed a kind of action In those days, when there was no simple way to produce
that could not be explained by any known theory. Dulong fire, Döbereiner’s discovery led immediately to its applica-
and Thenard tried to discover if electricity played a role tion, the hydroplatinic lamp, also called briquet à hydrogène
in  these phenomena and concluded that so far, and by de- (hydrogen lighter) or Döbereiner Feuerzeug (Döbereiner
fault, they could only explain most of the observed effects by lamp). The Döbereiner Feuerzeug was used for lighting pur-
assuming a pure electrical origin, but without understanding poses for about 100 years until replaced by the phosphorus
how (Dulong and Thenard, 1823b). match.
As told by Prandtl (Prandtl, 1950), Johann Wolfgang Dö- In 1832 Döbereiner discovered that sulfur dioxide can be
bereiner’s (1780-1849) work on heterogeneous catalysis was oxidized to sulfur trioxide by air in the presence of platinum,
an initial outgrowth of his interest in platinum, which he but in the industrial application of this discovery he was an-
needed for manufacturing chemically resistant laboratory ticipated by Peregrine Phillips, a Bristol vinegar merchant,
vessels. In order to obtain a supply of this metal for the man- who in 1831 had already obtained an English patent for the
ufacture of laboratory vessels and also to recover the accom- manufacture of sulfuric acid (Phillips, 1831; McDonald, 1960,
panying metals, Döbereiner began to work up two pounds of 1965; Robertson, 1975; Wisniak, 2005).
American platinum ore in 1812. In 1821 Döbereiner repeat- In 1838 Kuhlmann patented a process for the manufac-
ed the experiments of Humphry and Edmund Davy and ture of sulfuric acid by the oxidation of sulfur over finely di-
found that platinum black, which he name platinschwarz, vided platinum supported on glass or other acid-resistant ma-
caused alcohol to combine, at room temperature, with the terial (Kuhlmann, 1838ab; Gay-Lussac, Thenard and Pelouze,
oxygen of the atmosphere to form a product that he called 1839; Kauffman, 1999).
oxygen ether, and also acetic acid. A most significant fact was William Henry (1774-1836) was the first to study the de-
that platinum not only oxidized alcohol to acetic acid com- activation of platinum-based catalysts. Henry discovered that
pletely but also remained unchanged by the reaction, a find- certain substances (for example, hydrogen sulfide and carbon
ing that suggested its possible use for the direct production of disulfide) inhibited the combustion of hydrogen and that
vinegar from alcohol (Döbereiner, 1823ab, 1828). platinum catalysts were less active for the combustion of
As stated by Kaufmann (Kaufman, 1999) Döbereiner cor- methane and ethylene than for hydrogen and carbon monox-
rectly regarded this important discovery as due to the activity ide. As catalyst he used platinum sponge or balls made of clay
of the platinum rather than to the action of the ethanol on and platinum, as Döbereiner had done previously (Henry,
platinum, as the Davys had mistakenly assumed. In the begin- 1824, 1825).
ning he thought that platinum was a sub-oxide: “The plati- With this new discovery Henry developed procedures for
num sub-oxide, moreover, does not undergo any change dur- separating and analyzing combustible gases based upon their
ing this transformation of the alcohol and can be immediately reactivity in the presence of platinum-based catalysts. To as-
used again to acidify fresh, perhaps limitless, quantities of al- certain this possibility and others, Henry prepared synthetic
cohol…a circumstance that permits its use for the large-scale mixtures of combustible gases in known volumes and sub-
preparation of acetic acid (Döbereiner, 1823b). mitted them, mixed with oxygen. The results allowed Henry
In 1823 Döbereiner prepared platinum sponge by igniting to devise a method for obtaining carburetted hydrogen gas
ammonium hexachloroplatinate (V) and made a remarkable perfectly free from olefiant gas, hydrogen and CO (Henry,
observation. On directing on the sponge a jet of hydrogen is- 1824, 1825).
suing from a gasometer through a capillary held at a distance In his study of the phenomenon of decomposition Henry
of 4 cm, so that it was admixed with air, the metal became Sainte-Claire Deville (1818-1881) did also work in the field
red or white hot almost immediately and the hydrogen caught of catalysis. For example, he found that when heating a mixture
fire. The action took place at room temperature or even at of potassium cyanide in contact with wet air, at 500 to 600°C,
–10°C (Prandtl, 1950). In Döbereiner’s words: “There now under vacuum, the pressure increased to about ½ atmosphere
followed in a few moments that strange reaction; the volume and maintained itself for many hours. But if the potassium
of the gases diminished and after ten minutes all the admitted cyanide was first mixed with sponge platinum large amounts

62 para quitarle el polvo educación química  •  enero de 2010

of hydrogen were generated and a double cyanide of potassi- same manner that ferments present in the organism had aris-
um and platinum formed (Deville and Debray, 1876). en. “All these ferments had the power of transferring to other
In spite of having been determined that many metals were bodies the oxygen taken up in one or the other manner…to
capable of catalytic action, the most interesting one contin- become again reduced…and to be put into the state to take
ued to be platinum and centralized most of the research up new quantities of oxygen, again to transfer it and so on.
work. In his book about catalysis, Paul Sabatier (1854-1941; In this way all ferments may transfer free or bound oxygen
1912 Nobel Prize for Chemistry) summarized the known to  other substances in almost endless amounts… (Traube,
facts about platinum as follows (Sabatier, 1913): “Platinum 1858).
did not behave in this manner only when made as a sponge; In 1896 Henri Moissan (1852-1907; 1906 Nobel Prize for
it did also when finely divided as filings, wire, or turnings, as Chemistry) and Moureu tried the fixation of acetylene by
long as it was first heated slightly. Many experiments led to passing a current of acetylene on slivers of iron, nickel, or
think that this activity increased the more the platinum was cobalt freshly reduced from their oxides by hydrogen, and
divided; it even increased more if before calcination the aque- observed a brilliant incandescence. According to Moissan
ous solution of chloroplatinate was boiled with a little of so- and Moureu “this reaction is due to a physical effect”: reduced
dium carbonate and sugar. The chloroplatinate was complete- iron, nickel, or cobalt being extremely porous, absorbed the
ly decomposed and the metal precipitated as a black powder. acetylene with production of enough heat to cause its spon-
This powder was much more active than the sponge; it ab- taneous destruction (Moissan, 1904-1906).
sorbed hydrogen rapidly and the smallest particle led to the Sabatier and Senderens repeated the experiments but us-
instantaneous ignition of a mixture of hydrogen and air. Th- ing ethylene instead of acetylene, a hydrocarbon less violent
enard then found that black platinum decomposed hydrogen in its reactions. But they also found methane almost pure.
peroxide rapidly and with violence into oxygen and water, Sabatier and Senderens concluded that an unstable combina-
without absorbing the gas releasing or loosing its activity (Th- tion between nickel and ethylene had formed, analogous to
enard, 1818-1819ab)”. By 1900 this property of platinum nickel carbonyl, which doubled itself into carbon, methane
was found also in other metals (such as copper and iron), and nickel, which could then repeat an identical process (Sa-
metallic oxides (such as manganese dioxide), carbon, certain batier, 1897a). It seemed that reduced nickel had the prop-
acids, etc. (Bertrand, 1955). erty of hydrogenating ethylene. This result, they believed
Intensive research in the area of catalysis, particularly by “ought certainly to be attributed to the temporary formation
Sabatier and his students, led to the discovery that many met- of a direct and specific combination of nickel and ethylene”
als, particularly nickel and the platinum group elements, (Sabatier, 1897b).
alone or supported, possessed a unique catalytic activity, es- Sabatier and Mailhe found that some metal oxides were
pecially for hydrogenation reactions, that ultimately would catalysts not for hydrogenation and dehydrogenation, but in-
become the base for the fast development of the petrochem- stead for hydration and dehydration (Sabatier, 1910ab). They
ical industry. The basic work of Sabatier in this fundamental also observed that amorphous oxides were more active cata-
scientific and industrial subject forms the basis of our modern lysts for dehydrogenation or dehydration than the crystalline
theories about catalysis and catalysts, as well as many of the oxides ones (Sabatier, 1911). Calcination reduced the active
processes used today in the petrochemical industry. Sabatier surface by modifying the nature and distribution of the ac-
and Jean-Baptiste Senderens (1856-1937) discovered cata- tive centers. This was the first example of the sintering effects,
lytic hydrogenation, a finding that gave Sabatier the 1912 which were later used to graduate the activity of catalysts
Nobel Prize in Chemistry: the hydrogenation metal catalysts (Wisniak, 2005).
(and particularly nickel) make it possible, by their only pres-
ence, to fix hydrogen on the most various molecules. Explanation of the phenomena
Today, the most important catalysts are of the type Pt-γ- As discussed below, Thenard, for lack of a more plausible rea-
Al2O3. The application of supported noble metal catalysts for son, attributed the action of catalysts to the action of the
the treatment of exhaust gases from automobiles has been “electric fluid”. Döbereiner believed that it was due to an ef-
introduced in recent years in all industrialized countries. fect of the crystalline nature of the agent and Angelo Bellani
Combinations of metals that have a catalytic action of ex- (1776-1852) even in 1824, laid the foundations of the ab-
haust gases include Pt-Rh, Pt-Pd and Pt-Pd-Rh. The demand sorption theory (Bellani, 1824). In any case, abstraction made
for these materials amounts to more than one-third of the of the explanations given Clément and Désormes for the ho-
annual production of platinum and to more than four-fifths mogeneous oxidation of sulfur dioxide by oxides of nitrogen;
of the annual production of rhodium (Robertson, 1975; Wis- the opening hypotheses on the mechanism of catalysis con-
niak, 2005). tain the first ideas of a physical explanation (surface effects).
In 1858 Morris Traube (1826-1894) discussed the phe- These limited the catalytic effect to a physical action on the
nomena of fermentation and decay and concluded that the course of the reaction only and thus, emphasized that any
pertinent agents were definite chemical compounds arising chemical change of the reagents takes place according to the
from the reaction of the protein substances with water, in the laws of stoichiometry.

enero de 2010  •  educación química para quitarle el polvo 63

 Désormes and Clément were the first to propose a ratio- Hence, it was clear that nitric oxide was only the instru-
nal theory for the homogeneous catalytic effect of nitrogen ment for the total oxidation of sulfur; it was its base, NO,
oxides in the lead chamber process for the manufacture of that took the oxygen from the atmospheric air and trans-
sulfuric acid. They did so by establishing for the first time a ferred it to SO2, time after time (Désormes and Clément,
quantitative relation between the sulfurous acid, oxygen and 1806). This explanation may be considered the first time
oxides of nitrogen that participates in the process. There were that an intermediate compound is assumed to play a part in
different opinions on the advantages of using potassium ni- a catalytic reaction.
trate in the fabrication of sulfuric acid. Some believed that it In 1818 Thenard concluded his first paper on the decom-
was the high temperature that its deflagration produced, position of water peroxide, as follows: “… the vast majority of
which determined the formation of sulfuric acid; others bodies have upon water peroxide an action that tends to joint
thought that the nitrate contributed the complementary oxygen to water more intimately that to separate it. All acids
amount of oxygen for the combustion started initially by air; belong to the first group, and metals, metal sulfides, metal
while others believed that it could decompose water, etc. Dé- oxides, carbon, etc., to the second; facts which show how
sormes and Clément decided to look only at the first two much the phenomenon is dependent on electricity” (Thenard,
hypotheses, which seemed the most plausible. The first hy- 1818-1819a). In another paper of the same year he offered a
pothesis was discarded immediately because the addition of more definite opinion: “…the cause of these singular results is
potassium nitrate and sulfur was followed by the addition still hidden from us, only we see that it does not reside in af-
of clay and water, which resulted in a diminution of the tem- finity, at least in the manner it is usually conceived, it is prob-
perature, clay by making the combustion slower, and water by ably physical and perhaps linked to electricity” (Thenard,
generating vapor. It was also known that sulfur that burned at 1818-1819b). In 1819 Thenard recognized that widely differ-
least at 1000°C did not generate sulfuric acid at all. The sec- ent catalysts were capable of decomposing water peroxide
ond hypothesis was also unacceptable because it presupposed and admitted that all these effects were due to the same un-
that the oxygen disengaged from potassium nitrate was suffi- identified force (Thenard, 1818-1819ab; Kilani, Batis and
cient for converting all the sulfur dioxide produced into sul- Chastrette, 2001). In 1821 Thenard recognized clearly the
furic acid, but a simple mass balance proved that this was not generality of catalytic phenomena: “Whichever it be the cause
true. Although the precise amounts in which every substance of the phenomena…is it not very probable that it is the same
participated in the reaction were unknown, it was easy to see that produces so many other?” He mentions as examples, the
that the potassium nitrate employed could hardly provide detonation of silver ammonia, of the chloride and iodide of
more than 10% of the oxygen required for converting sulfur nitrogen, fulminating powders, decomposition of ammonia
dioxide into sulfur trioxide. In addition, a visual observation gas by metals, the transformation of starch into sugar by min-
of the burning of a mixture of sulfur, potassium nitrate, and ute amounts of diastase, and the transformation of sugar into
wet clay indicated that the nitric acid did not decompose alcohol and carbon dioxide by a small amount of ferment
completely and that an important part of NO gas went into (Thenard, 1821). In the sixth edition of his Traité de Chimie,
the lead chamber with the sulfur dioxide; its typical color was published in 1834, Thenard repeated, without change, the
clearly visible (Désormes and Clément, 1806). summary of his researches on the decomposition of water
Désormes and Clément believed that the true explana- peroxide, which he had exposed in the 1821 edition. He was
tion of the production of sulfuric acid was the following: very baffled by these facts, as shown by his opinion that “after
The burner generated a mixture of NO and sulfur dioxide having exposed all the phenomena presented by water per­
mixed with water vapor and atmospheric nitrogen. Part of oxide in its contact with most materials, we have failed in
the oxygen did not participate in the burning of the sulfur searching for their reason; unfortunately we can only present
because the gases NO and SO2 could not exist in contact, some conjectures about it…” He then discusses all the possi-
without decomposition of the first and conversion of the sec- ble reasons for the catalytic action and selects again electric-
ond to sulfur trioxide. At the exit of the burner the mixture ity by elimination apparently to the magnetic fluid “We are
encountered a lower temperature that led to a partial con- thus directed to attributing them to the electric fluid” (Kilani,
densation of the steam. The resulting rain entrained with it Batis and Chastrette, 2001).
the sulfur trioxide generated and reduced the pressure of the In his book about the safety lamp (Davy, 1825) Davy re-
remaining substances. After production of the first amount of turned to the catalytic properties of platinum and wrote: “It
sulfur trioxide, the remaining gas mixture contained NO, sul- is probable that the rationale of all these processes is of the
fur dioxide, and residual air containing less oxygen. The NO same kind…It may be supposed that the spongy platinum
would necessarily convert into nitrogen dioxide, which would absorbs hydrogen, or that it contains oxygen, but neither of
then decompose again reacting with a second portion of sul- these hypotheses will apply to the fact that I first observed,
fur dioxide, until all of this oxide or the atmospheric oxygen of the ignition of fine wires in different mixtures of inflam-
became exhausted. After the sulfur dioxide had been con- mable gas and air, at temperatures so far below ignition. A
verted totally into trioxide, the remaining gas was composed probable explanation of the phenomenon may, I think, be
mainly of a large amount of nitrogen and nitrogen oxides. founded upon the electrochemical hypothesis (Davy, 1807)…

64 para quitarle el polvo educación química  •  enero de 2010

and which has seen been adopted and explained, according to of an electric nature…the continuance of the action greatly
their own ideas, by different philosophers”. depended upon the purity of the gases used (poisoning)…
Döbereiner’s numerous experiments on platinum and These experiments led to the expectation that the power of
platinum black led to a slow change in his ideas about the causing oxygen and hydrogen to combine, which could be
way the material acted. He claimed that platinum black “was conferred upon any piece of platina by making it the positive
not a simple but a mechanical combination of this metal with pole of a voltaic pile, was not essentially dependent upon the
compressed oxygen gas…the platinum reduced or isolated by action of the pile, or upon any structure or arrangement of
the wet method has the property of absorbing and then com- parts it may receive whilst in association with it, but belonged
pressing a large amount of oxygen gas and that it becomes to the platina at all times, and was always effective when the
capable of combining chemically with diverse readily oxidis- surface was perfectly clean…These experiments are abundant-
able substances…In the process of oxidation and acidification ly sufficient to show that the mere mechanical cleansing of
of alcohol, platinum plays a role corresponding to the func- the surface of platina is sufficient to enable it to exert its com-
tion of the nitrous gases in the process of sulfuric acid for­ bining power over oxygen and hydrogen at common tem-
mation” (Döbereiner, 1828). He also referred to the effect peratures…There can be no doubt that the property of in-
being caused entirely by an electric action, “whereby hydro- ducing combination, which can be conferred upon masses of
gen forms an electrical chain with the platinum” (Döbereiner, platina and other metals by connecting them with the poles
1823b). In a book on the phenomenon that he published in of a battery, or by cleansing processes either of a mechanical
1823 he considered that it was “probably of a quite special or chemical nature, is the same as that which was discovered
nature, i.e., neither mechanical nor electrical nor magnetic by Döbereiner in 1823, to belong in so eminent a degree to
(Döbereiner, 1823a; Kauffman, 1999). spongy platina…Dulong and Thenard observe that the action
The first attempt to give a detailed theoretical discussion is of a kind that cannot be connected with any known theory,
of heterogeneous catalytic oxidation on platinum was made and though it is very remarkable that the effects are transient,
by Ambrogio Fusinieri (1775-1852) in a paper published in like those of most electrical actions, yet they state that the
1824 (Fusinieri, 1824, 1825). He discussed the effects discov- greater number of the results observed by them are inexpli-
ered by Döbereiner and others and also explained in full his cable, by supposing them to be of a purely electric origin”.
own experimental observations remarking that these would Faraday went on to express his opinion that catalytic ac-
dispel all confusion and doubt (Farinelli, Gale and Robertson, tion was due to physical forces: “All the phenomena connected
1974; Robertson, 1975). Fusinieri contended, in opposition with this subject…are connected upon the natural conditions
to Davy, that combustion of ether on platinum occurred with of gaseous elasticity (pressure) combined with the exertion of
flame, which was either invisible or probably hidden by light that attractive forces…by which they are drawn into associa-
from the platinum. He further argued that during the oxida- tion more or less close, without at the same time undergoing
tion of ether “concrete sheets” of the combustible substance chemical combination…Bodies which become wetted by flu-
could be seen with the naked eye, the sheets running over the ids with which they do not combine chemically, or in which
platinum surface and then disappearing by burning. Fusinieri they do not dissolve, are…well known instances of this kind
thought that the ether forming the sheets was solidified, al- of attraction…. the gases are those which…might show some
though he noted a relation between the appearance and dis- mutual action, whilst jointly under the influence of the plati-
appearance of the sheets and capillary action of liquids, that na or other solid acting substance…it would seem that the
is, in contact with platinum the gases lost their elastic state particles of hydrogen or any other gas or vapor which are
and became solid. The platinum catalyst acted like a candle- next to platina…much be in such contact...as if they were in
wick with the sheets burning like candle wax. He justified the the liquid state….The course of events when platina…com-
formation and burning of the concrete sheets, on the exis- bines oxygen and hydrogen…is as follows: …the deficiency of
tence of native caloric. Michael Faraday (1791-1867) reviewed elastic power and the attraction of the metal for the gases, the
Fusinieri’s views at some length, but confessed that he could latter, when they are in association with the former…
not understand the concept of native caloric, probably because The consequence of their combination is the production
of his imperfect knowledge of Italian (Faraday, 1834; Farinel- of the vapor of water and an elevation of temperature…But
li, Gale and Robertson, 1974; Robertson, 1975). as the attraction of the platina for the water formed is not
In 1834 Faraday published a very thorough analysis of the greater than for the gases, if so great (for the metal is scarcely
phenomena observed with solid platinum and added the re- hygrometric), the vapor is quickly diffused through the re-
sults of extensive experimentation when using platinum in a maining gases. The platina is not considered as causing com-
voltaic cell (Faraday, 1834). Faraday wrote: “These experi- bination of any particles with itself but only associating them
ments reduced the phenomena to the consequence of a pow- closely around it…” (Faraday, 1834).
er possessed by the platina, after it had been the positive pole Faraday went on to describe what today we call catalyst
of a voltaic pile, of causing the combination of oxygen and hy- poisoning: …“some very extraordinary interferences with this
drogen at common…This effect is…altogether new, and was phenomenon, dependent, not upon the nature or condition
immediately followed out to ascertain whether it was really of the metal, or other acting solid, but upon the presence of

enero de 2010  •  educación química para quitarle el polvo 65

 certain substances mingled with the gases acted upon.... It is which is quite different from ordinary chemical affinity, in
perfectly clear from these experiments, that olefiant gas, even that they promote the conversion of the component parts of
in small quantities, has a very remarkable influence in pre- the body they influence into other states, without necessarily
venting the combination of oxygen and hydrogen under these participating in the process with their own component parts,
circumstances, and yet without at all injuring or affecting the even if this should occasionally occur…This is a new power
power of the platina” (Faraday, 1834). to produce chemical activity belonging to both inorganic and
In the section of vegetable chemistry of his 1835 Jahres- organic nature…and the nature of which is still concealed
Bericht (Annual Survey) (Berzelius, 1835) Berzelius summa- from us. I…do not…imply that it is a capacity independent of
rized the findings of different scientists on the formation of the electrochemical properties of the substance...I am unable
ether from alcohols; on the enhanced conversion of starch to to suppose that this is anything other than a special kind of
sugar by acids; the hastening of gas combustion by platinum, special manifestation of these, but as long as we are unable to
of the stability of hydrogen peroxide in acid solution but its discover their mutual relationship…it will also make it easier
decomposition in the presence of alkali and such metals as for us to refer to it if it possesses a name of its own. I shall
manganese, silver, platinum, and gold, and the observation therefore…call it the catalytic power of the substances and
that the oxidation of alcohol to acetic acid was accomplished decomposition by means of this power catalysis…Catalytic
in the presence of finely divided platinum. He repeated this power actually means that substances are able to awaken af-
report in French, in a paper published a year later (Berzelius, finities…by their mere presence and not by their own affinity.
1836). He wrote: “Until 1800 no one suspected that any fac- By means of these, the elements in a compound body rear-
tor other than the degree of affinity could be of importance, range themselves in another manner so as to achieve a greater
with the exceptions of heat and light in certain cases. Then degree of electro-chemical neutrality. Thus their over-all ef-
the influence of electricity was discovered…electrical and fect resembles that of heat, and here the question may arise
chemical relationships are the same…preferential affinity is as to whether the different degrees of catalytic power pos-
nothing other than the result of strong opposite electrical sessed by different substances can produce the same dissimi-
forces that are intensified by heat or light…Then Kirchhoff larity in the products of catalysis as is often caused by heat or
discovered that starch, dissolved in dilute acids at a certain different temperatures, and thus whether different catalytic
temperature, first turns into gum and then into grape sugar... substances are able to produce dissimilar products from a
nothing had evaporated into gas, nothing had united with the given compound body…On this occasion it is sufficient that
acid, the bases of which were recovered in the same amount the existence of catalytic power has been demonstrated with
as that in which they had been used, and in the liquid only a sufficient number of examples…Turning with this idea to
sugar was found, weighing slightly more than the starch”. Th- the chemical processes in living nature…we find that the in-
enard then discovered hydrogen peroxide, “the component soluble starch in the tuber is changed to gum and sugar by
parts of which were rather weakly joined to each other. Un- catalytic power…living tissues” (Berzelius, 1835).
der the influence of acids, they remained in unaltered combi- In 1843 Berzelius, explained the catalytic force within the
nation; under the influence of alkalis, they showed a tendency frame of his dualistic theory: “it acts primarily on the polarity
to separate…Not only soluble substances were found to has- of the atoms, increasing or decreasing it. In other words, the
ten this type of decomposition, but also solid inorganic and catalytic force manifests itself by the excitation of the electri-
organic substances, e.g. manganese dioxide, silver, platinum, cal relations that have so far evaded our researches” (Kilani,
gold, and the fibrous element from animal blood. The foreign Batis and Chastrette, 2001).
agent causing the conversion of the substances did not itself
participate in the new compounds formed but remained un- Further developments
changed, thus operating by means of an internal power, the When Sabatier commenced his investigations on catalysis
nature of which is still unknown…Edmund Davy observed there were two theories of heterogeneous catalysis, a physical
that wetting platinum finely divided with alcohol ren- and a chemical one. The physical theory was supported by
dered the platinum incandescent and the alcohol converted the work of Jacques Duclaux (1877-1978) and Moissan
into acetic acid and water. Now came the discovery that on the absorption of gases by finely divided metals (Moissan,
crowned the foregoing, namely Döbereiner’s finding that plat- 1904-1906; Duclaux, 1911). Wilhelm Ostwald (1853-1932;
inum sponge is able to ignite a stream of hydrogen gas as it 1909 Nobel Prize for Chemistry) and others had also as-
escapes into the air…This discovery was soon followed by the sumed that catalyzed gas reactions resulted from the absorp-
mutual investigation of Dulong and Thenard that showed tion of gases in the cavities of the porous metal, where com-
that several single and compound substances have this prop- pression and local temperature elevation led to chemical
erty…Thus this power was extended from an exceptional combination. Ostwald believed that a catalyst did not induce
property to a more general one possessed by substances to a reaction but rather accelerated it without formation of in-
different degrees...Thus it is certain that substances, both termediate compounds. In other words, a catalyst was a body
simple and compound, in solid form as well as in solution, that modified the reaction a reaction without taking part in it,
have the property of exerting an effect on compound bodies a position clearly different from that of Désormes and Clé-

66 para quitarle el polvo educación química  •  enero de 2010

ment. Ostwald chose to state his theory of catalysis in the carbonyl chloride (Sabatier, 1897a, 1913). While finely di-
course of an abstract, which he prepared for an article by vided metals were able to absorb substantial quantities of gas,
Friedrich Karl Adolph Stohmann (1832-1897) on the heats these absorptions were somewhat specific, being “character-
of combustion of foodstuffs (Stohmann, 1894). He disagreed ized by a sort of selective affinity”. Not only that, some cata-
with Stohmann’s definition that “catalysis is a condition of lytic reactions were extremely specific, for example, zinc ox-
movement of the atoms in a molecule of a labile body which ide decomposed formic acid into hydrogen and carbon
follows the entrance of the energy emitted from one body dioxide, but at the same temperature titania gave carbon
into another and leads to the formation of more stable bodies monoxide and water. The physical theory was unable to ex-
with loss of energy” (Ostwald, 1894). Ostwald had several plain the development of high local pressure and tempera-
objections to make to this definition: “First, the assumption of ture in the cases where the catalyst was held in suspension,
a condition of movement of the atoms in a molecule is hypo- and did not account for the specificity of catalysts and the
thetical and therefore not suitable for purposes of definition. remarkable diversity of effects they produced, depending on
Also, that is plainly not a loss of energy. What is more, in de- the particular metal or oxide used (Sabatier, 1897a, 1913).
scribing characteristic conditions of catalysis, a loss of free Sabatier then formulated a chemical theory of catalysis
energy can follow under conditions even of absolute energy involving the formation of unstable chemical compounds as in-
uptake… the abstractor (Ostwald)…would consider the fol- termediate stages, which determined the direction and rate of
lowing expression as probably most suitable: Catalysis is the the reaction. He assumed that in hydrogenation various nick-
acceleration of a chemical reaction, which proceeds slowly, el hydrides were involved, whose composition depended on
by the presence of a foreign substance…There are numerous the activity of the nickel. He also argued that the formation
substances or combinations of substances, which in them are and decomposition of intermediate compounds usually cor-
not stable but undergo slow change and only seem stable to responds to a diminution of the Gibbs energy of the system
us because their changes occur so slowly that...they do not (Sabatier, 1913).
strike us. Such substances or systems often attain an increased Sabatier postulated the formation of different intermediate
reaction rate if certain foreign substances, that is, substances, compounds, each with its own mode of decomposition, and
which are not in themselves necessary for the reaction, are he also clearly established that some organic reactions are revers-
added. This acceleration occurs without alteration of the gen- ible. In cases where the intermediate compounds could not be
eral energy relations…after the end of the reaction the for- isolated, he assumed the formation of surface compounds, a
eign body can again be separated from the field of the reac- phenomenon, which he named fixation, thus linking the phys-
tion, so that the energy used up by the addition can once ical, and the chemical theories of catalysis (Partington, 1954).
more be obtained by the separation, or the reverse. However, The catalysts sensitivity to poisons, discovered by the
these processes, like all natural ones, must always occur in work of Rudolph Knietsh (1854-1906) on catalysts used for
such a direction that the free energy of the entire system is the synthesis of sulfur trioxide, was shown to be a general
decreased. It is therefore misleading to consider catalytic ac- phenomenon, which could be used to control catalytic reac-
tion as a force which produces something which would not tions. Sabatier, when comparing catalysts to ferments, de-
occur without the substance which acts catalytically; still less scribed poisoning in the following words: “In the same way
can it be assumed that the latter performs work…that time is that organized ferments are killed by infinitesimal amounts of
not involved in the idea of chemical energy…it is only the certain toxins, the mineral ferment which is the metal, is
initial and final states, as well as the whole series of intermedi- killed by traces of chlorine, bromine, iodine, sulfur or arsenic
ate given states which must be passed through, which must that are carried by the hydrogen or by the substance to be
occur…Time is here dependent on conditions, which lie out- hydrogenated…nickel, a little poisoned, can only provide a
side the two chief laws of energetics. The only form of energy, first hydride similar to that of copper and capable of acting
which contains time in its definition, is kinetic energy…All over the nitro groups or on the ethylenic double bond, only
cases in which such energies take a fixed part are therefore nickel cannot provide a hydride able to completely hydroge-
completely determined in time if the conditions are given; nate the aromatic ring” (Sabatier, 1913; Wojtkowiak, 1989).
but all cases in which the vibrational energy does not play this Sabatier and Léo Espil made the interesting discovery that
role are independent of time, that is, they can occur without after being used to hydrogenate nitrobenzene, nickel poi-
violating the laws of energy in any given time. Catalytic pro- soned by chlorine recovered its ability to hydrogenate ben-
cesses are empirically found to be of the type in which this zene (Sabatier, 1913, 1914).
last property is observed; the existence of catalytic processes During the First World War Langmuir’s published a rival
is to me therefore a positive proof that chemical process- theory called “theory of chemisorption” according to which a
es cannot have a kinetic nature” (Ostwald, 1894). gas adsorbed over a catalysts was fixed thanks to its unsatu-
Sabatier did not accept the purely physical view of the rated valences yielding a gas-metal compound of the type
function of the catalyst, remarking that if it was true then MxGy (Langmuir, 1916, 1917, 1918). This theory was con-
charcoal should be almost a universal catalyst, whereas it trary to Sabatier’s hypothesis of distinct, individual interme-
proved to be somewhat mediocre except for the formation of diates and allowed more importance to physical conditions

enero de 2010  •  educación química para quitarle el polvo 67

 (Nye, 1977). Although Langmuir’s theory retained the con- und des Metallischen Platin-staubes, Ann. (Gilbert), 74,
cept of fixation of the reagents on the surface of the catalysts, 269-274, 1823b.
it assigned a predominant importance to the physical condi- Döbereiner, J.W., Vermischte Chemische Erfahrungen Über Pla-
tions that Sabatier had purposed ignored. For a time, Lang- tin, Gährungschemie, usw, Z. Chem. Physik., 54, 412-426,
muir’s theory of the fixation of a monomolecular layer on the 1828.
catalyst gave it a certain advantage because it permitted to Döbereiner, J.W., Zur Chemie des Platins in Wissenchaftlicher
address quantitatively the problem of heterogeneous catalysis und Technischer Beziehung. Für Chemiker, Metallurgen, Pla-
and played a considerable role in experimental studies (Wojt- tinarbeiter, Pharmazeuten, Fabrikanten und die Besitzer der
kowiak, 1989). Langmuir’s theory became particularly Döbereinerschen Platinfeuerzeuge, Stuttgart, 1836.
important because it permits a first quantitative analysis of Duclaux, J., Application de la Théorie Cinétique à l’Étude
the possible mechanism of a reaction. des Phénomènes de Catalyse, Compt. Rendus, 152,1176-
1179, 1911.
References Dulong, P.L., Thenard, L., Note sur la Propriété que Possè-
Bellani, A., Conghietture Sulla Proprietà che Possedono Alcu- dent Quelques Métaux de Faciliter la Combinaison des
ne Sostanze e Specialmente il Platino di Facilitare la Com- Fluides Élastiques, Ann. Chim., [2], 23, 440-444, 1823a.
binazione del Gas Idrogeno coll’Ossigene, Giornale Fis, Dulong, P.L., Thenard L., Nouvelles Observations Sur la Pro-
7,138-151, 1824. priété Dont Jouissent Certains Corps de Favoriser la Com-
Bertrand, G., Paul Sabatier and Catalysis, Bull. Soc. Chim., binaison des Fluides Élastiques, Ann. Chim. [2], 24, 380-
473-475, 1955. 387, 1823b.
Berzelius, J.J., Jahres-Bericht, 4, 60, 1823-1825. Faraday, M., Experimental Researches in Electricity – Sixth
Berzelius, J.J., Sur un Force Jusqu’ici Peu Remarquée qui est Series. On the Power of Metals and other Solids to Induce
Probablement Active Dans la Formation des Composés the Combination of Gaseous Bodies, Phil. Trans., 124, 55-
Organiques, Section on Vegetable Chemistry, Jahres-Be- 76, 1834.
richt, 14, 237, 1835. Farinelli, M., Gale, A.L.B., Robertson, A.J.B., Ambrogio Fusin-
Berzelius, J.J., Quelques Idées sur une Nouvelle Force Agis- ieri and the Adsorption Theory of Heterogeneous Cataly-
sant Dans les Combinaisons des Corps Organiques, Ann. sis, Ann. Sci., 31, 19-20, 1974.
Chim., 61, 146-151, 1836. Fourcroy, A.F., Sur Trois Espèces Différentes de Gaz Hydro-
Cordus, V., Le Guidon des Apotiquaires: C’est à dire, la Vraye gène, Retirées de l’Éther et de l’Alcool par Différents Pro-
Forme et Maniere de Composer les Médicamens, L. Cloque- cédés, Envoyés à l’Institut par la Société des Chimistes
min, E. Michel, Lyons, 1575. Hollandais, Ann. Chim., 21, 48-71, 1797a.
Davy, E., On Some Combinations of Platinum, Phil. Trans., Fourcroy, A.F., Sur Trois Espèces Différentes de Gaz Hydro-
110, 108-125, 1820. gène, Retirées de l’Éther et de l’Alcool par Différents Pro-
Davy, H., The Bakerian Lecture on Some Chemical Agencies cédés, Envoyés à l’Institut par la Société des Chimistes
of Electricity (1806), Phil. Trans., 97, 1-56, 1807. Hollandais, Nicholson J., 1, 44-45, 49-55, 1797b.
Davy, H., Some New Experiments and Observations on the Fusinieri, A., Sulla Causa delle Combustione di Sostanze Ga-
Combustion of Gaseous Mixtures, With an Account of a sose per Mezzo delle Superfice di Alcuni Metalli, Giornale
Method of Preserving a Continued Light in Mixtures of Fis., 7, 371-376, 443-449, 1824.
Inflammable Gases and Air Without Flame, Phil. Trans., Fusinieri, A., Sulla Causa delle Combinazioni di Sostanze Ga-
107, 77-85, 1817. sose per Mezzo delle Superfice Continue; e del Genere di
Davy, H., On the Safety Lamp for Preventing Explosives in Azione da cui Questi e Tantri Altri Effetti Dipendono,
Mines, Houses Lighted by Gas, Spirit Warehouses, or Maga- Giornale Fis., 8, 259-269, 1825.
zines in Ships, etc., with Some Researches on Flame, R. Hunt- Gay-Lussac, J.L., Thenard, L., Pelouze, T.J., Rapport sur un
er, London, 1825. Appendix 2, pp. 148-151. Travail de M. Kuhlmann, Relatif aux Propriétés du Platine
Désormes, C.B., Clément, N., Théorie de la Fabrication de Divisé, et aux Phénomènes de l´Ethérification, Compt.
l’Acide Sulfurique, Ann. Chim., 59, 329-339, 1806. Rendus, 9, 496-501, 1839.
Deville, H.S.C., Debray, H., De la Décomposition de l’Eau Henry, W., On the Action of Finely Divided Platinum on Gas-
par le Platine, Compt. Rendus, 82, 241-243, 1876. eous Mixtures and its Application to their Analysis, Phil.
Döbereiner, J.W., Versuche Über di Gährung, Schweiger J., Trans., 114, 266-289, 1824.
20, 213-214, 1816. Henry, W., On the Action of Finely Divided Platinum on Gas-
Döbereiner, J.W., Ueber neu Entdeckte Höchst Merkwürdige Ei- eous Mixtures and its Application to their Analysis, Phil.
genschaften des Platins und die Pneumatisch-Capillare Thä- Mag., 65, 269-283, 1825.
tigkeit Gesprungener Gläser. Ein Beitrag zur Corpuscular Kauffman, G., The Origins of Heterogeneous Catalysis by
Philosophie, Jena, 1823a. Platinum: Johann Wolfgang Döbereiner’s Contribution,
Döbereiner, J.W., Neu Entdeckte Merkwürdige Eigen schaf- Enantiomer, 4, 609-619, 1999.
ten des Platin-suboxyds, des Oxydirten Schwefel-Platins, Kilani, C.B., Batis, H., Chastrette, M., Développement des

68 para quitarle el polvo educación química  •  enero de 2010

 Idées sur la Catalyse au Début du XIXe Siècle, Actualité cal Adviser, J. Chem. Educ., 27, 176-181, 1950.
Chimique, 44-50, 2001. Robertson, A.J.B., The Early History of Catalysis, Platinum
Kirchhoff, S. K., Bull. Neusten. Wiss. Naturwiss., 10, 88-92, Metal Rev., 19, 64-69, 1975.
1811. Sabatier, P., Action du Nickel sur l’Éthylène, Compt. Rendus,
Kuhlmann, F., French Patent, No. 11332, 1838a. 124, 616-618, 1897a.
Kuhlmann, F., French Patent, No. 11333, 1838b. Sabatier, P., Action du Nickel sur l’Éthylène. Synthèse du
Langmuir, I., Constitution and Fundamental Properties of l’Éthane, Compt. Rendus, 124, 1358-1361, 1897b.
Solids and Liquids. I. Solids, J. Am. Chem. Soc., 38, 2221- Sabatier, P., Actions des Oxydes Métalliques sur les Alcools
2295, 1916. Primaires, Ann. Chim. Phys., 20, 289-352, 1910a.
Langmuir, I., Constitution and Fundamental Properties of Sabatier, P., Mailhe, A., Sur le Mécanisme de Déshydratation
Solids and Liquids. II. Liquids, J. Am. Chem. Soc. 39, 1848- des Alcools par Catalyse au Moyen de Divers Oxydes,
1906, 1917. Compt. Rendus, 150, 823-826, 1910b.
Langmuir, I., The Adsorption of Gases on Plane Surfaces of Sabatier, P., Maille, A., Sur la Décomposition Catalytique de
Glass, Mica and Platinum, J. Am. Chem. Soc., 40,1361- l’Acide Formique, Compt. Rendus, 152,1212-1215, 1911.
1402, 1918. Sabatier, P., La Catalyse en Chimie Organique, Librairie Poly-
McDonald, D., A History of Platinum, Johnson Mathey, Lon- technique, Paris, 1913.
don, 1960. Sabatier, P., Espil, L., Sur la Réduction du Protoxide de Nickel
McDonald, D., Johann Wolfgang Döbereiner, Platinum Met- et sur l’Existence d’un Sous-Oxyde, Compt. Rendus, 158,
als Rev., 9, 136-139, 1965. 668-675, 1914.
Moissan, H., Traite de Chimie Minerale, Masson, Paris, 1904- Stohmann, F., Über den Wärmewerth der Bestandtheile der
1906; in 5 vols. Nahrungsmittel, Zeit. Biol., 31, 364-391, 1894.
Nye, M. J., Nonconformity and Creativity: A Study of Paul Thenard, L., Sur la Fermentation Vineuse, Ann. Chim., 46,
Sabatier, Chemical Theory and the French Scientific Com- 224-320, 1803.
munity, Isis, 68, 375-91, 1977. Thenard, L., Observations sur l’Influence de l’Eau dans la
Ostwald, W., Referate Zeit. Phys. Chem., 15, 705-706, 1894. Formation des Acides Oxigénés, Ann. Chim., 9, 314-317,
Parmentier, A.A., Expériences et Réflexions Relatives à l’Analyse 1818-1819a.
du Blé et des Farines, Paris, 1781. Thenard, L., Nouvelles Recherches sur l’Eau Oxigénée, Ann.
Partington, J., Paul Sabatier, 1854-1941, Nature, 174, 859- Chim., 9, 441-443, 1818-1819b.
860, 1954. Thenard, L., Traite de Chimie Élémentaire, Théorique et Prati-
Passagez, A., Contribution à l’Histoire de la Catalyse Chimi- que, Chez Crochard, Paris, 1821, 3rd ed., vol. 1, p. 600.
que, Bull. Soc. Chim., 2, 1000-1002, 1935. Thenard, P., Le Chimiste Thenard, Imprimerie Jobard, Dijon,
Pasteur, L., Mémoire sur la Fermentation Alcoolique, Ann. 1950.
Chim. Phys. [3], 58, 323-426, 1860. Traube, M., Zur Theorie der Gährungs- und Verwesungs-Er-
Payen, A., Persoz, J. F., Mémoire sur la Diastase, les Principaux scheinungen wir der Fermentwirkungen Überhaupt, Pog-
Produits de ses Réactions et leurs Applications Aux Arts gend. Annal., 103, 331-344, 1858.
Industrielles, Ann. Chim., 53, 73-92, 1833. Wisniak, J., Platinum – From Exotic to Commodity, Indian J.
Phillips, P., Certain Improvements in Manufacturing of Sul- Chem. Tech., 12, 601-614, 2005.
furic Acid Commonly Called Oil of Vitriol, Brit. Patent Wojtkowiak, B., Paul Sabatier Un Chimiste Independant: 1854-
6096 (1831). 1941: Naissance de l’Hydrogènation Catalytique, Jonas,
Prandtl, W., Johann Wolfgang Döbereiner, Goethe’s Chemi- Paris, 1989.

enero de 2010  •  educación química para quitarle el polvo 69