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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
This book gradually brings the reader, through illustrations of the most crucial discoveries, into the modern world of chemical catalysis. Readers and experts will better understand the enormous influence that catalysis has given to the development of modern societies. * Highlights the field's onset up to its modern days, covering the life and achievements of luminaries of the catalytic era * Appeals to general audience in interpretation and analysis, but preserves the precision and clarity of a scientific approach * Fills the gap in publications that cover the history of specific catalytic processes
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Veröffentlichungsjahr: 2017
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Table of Contents
Cover
Title Page
Copyright
Preface
Chapter 1: From the Onset to the First Large-Scale Industrial Processes
1.1 Origin of the Catalytic Era
1.2 Berzelius and the Affinity Theory of Catalysis
1.3 Discovery of the Occurrence of Catalytic Processes in Living Systems in the Nineteenth Century
1.4 Kinetic Interpretation of Catalytic Processes in Solutions: The Birth of Homogeneous Catalysis
1.5 Onset of Heterogeneous Catalysis
1.6 First Large-Scale Industrial Processes Based on Heterogeneous Catalysts
1.7 Fischer–Tropsch Catalytic Process
1.8 Methanol Synthesis
1.9 Acetylene Production and Utilization
1.10 Anthraquinone Process for Hydrogen Peroxide Production
References
Chapter 2: Historical Development of Theories of Catalysis
2.1 Heterogeneous Catalysis
2.2 Chemical Kinetics and the Mechanisms of Catalysis
2.3 Electronic Theory of Catalysis: Active Sites
References
Chapter 3: Catalytic Processes Associated with Hydrocarbons and the Petroleum Industry
3.1 Petroleum and Polymer Eras
3.2 Catalytic Cracking, Isomerization, and Alkylation of Petroleum Fractions
3.3 Reforming Catalysts
3.4 Hydrodesulfurization (HDS) Processes
3.5 Hydrocarbon Hydrogenation Reactions with Heterogeneous Catalysts
3.6 Olefin Polymerization: Ziegler–Natta, Metallocenes, and Phillips Catalysts
3.7 Selective Oxidation Reactions
3.8 Ammoximation and Oxychlorination of Olefins
3.9 Ethylbenzene and Styrene Catalytic Synthesis
3.10 Heterogeneous Metathesis
3.11 Catalytic Synthesis of Carbon Nanotubes and Graphene from Hydrocarbon Feedstocks
References
Chapter 4: Surface Science Methods in the Second Half of the Twentieth Century
4.1 Real Dispersed Catalysts versus Single Crystals: A Decreasing Gap
4.2 Physical Methods for the Study of Dispersed Systems and Real Catalysts
4.3 Surface Science of Single-Crystal Faces and of Well-defined Systems
References
Chapter 5: Development of Homogeneous Catalysis and Organocatalysis
5.1 Introductory Remarks
5.2 Homogeneous Acid and Bases as Catalysts: G. Olah Contribution
5.3 Organometallic Catalysts
5.4 Asymmetric Epoxidation Catalysts
5.5 Olefin Oligomerization Catalysts
5.6 Organometallic Metathesis
5.7 Cross-Coupling Reactions
5.8 Pd(II)-Based Complexes and Oxidation of Methane to Methanol
5.9 Non-transition Metal Catalysis, Organocatalysis, and Organo-Organometallic Catalysis Combination
5.10 Bio-inspired Homogeneous Catalysts
References
Chapter 6: Material Science and Catalysis Design
6.1 Metallic Catalysts
6.2 Oxides and Mixed Oxides
6.3 Design of Catalysts with Shape and Transition-State Selectivity
6.4 Zeolites and Zeolitic Materials: Historical Details
6.5 Zeolites and Zeolitic Materials Structure
6.6 Shape-Selective Reactions Catalyzed by Zeolites and Zeolitic Materials
6.7 Organic–Inorganic Hybrid Zeolitic Materials and Inorganic Microporous Solids
6.8 Microporous Polymers and Metal–Organic Frameworks (MOFs)
References
Chapter 7: Photocatalysis
7.1 Photochemistry and Photocatalysis: Interwoven Branches of Science
7.2 Photochemistry Onset
7.3 Physical Methods in Photochemistry
7.4 Heterogeneous and Homogeneous Photocatalysis
7.5 Natural Photosynthesis as Model of Photocatalysis
7.6 Water Splitting, CO
2
Reduction, and Pollutant Degradation: The Most Investigated Artificial Photocatalytic Processes
References
Chapter 8: Enzymatic Catalysis
8.1 Early History of Enzymes
8.2 Proteins and Their Role in Enzymatic Catalysis
8.3 Enzymes/Coenzymes Structure and Catalytic Activity
8.4 Mechanism of Enzyme Catalysis
8.5 Biocatalysis
References
Chapter 9: Miscellanea
9.1 Heterogeneous and Homogeneous Catalysis in Prebiotic Chemistry
9.2 Opportunities for Catalysis in the Twenty-First Century and the Green Chemistry
References
Index
End User License Agreement
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Guide
Cover
Table of Contents
Preface
Begin Reading
List of Illustrations
Chapter 1: From the Onset to the First Large-Scale Industrial Processes
Figure 1.1 (a) Valerius Cordus, discoverer of ethyl ether formation from ethyl alcohol in the presence of an acid (oil of vitriol). (b) Cover page of
Dispensatorium Pharmacorum
. Images in the public domain.
Figure 1.2 (a) Augustin Parmentier (1737–1813) and (b) Anselme Payen (1795–1871) (images in the public domain). Parmentier discovered the accelerating action of acetic acid in the transformation of potato flour into a sweet substance. Payen attributed the starch transformation induced by few drops of sulfuric acid previously discovered by Constantin Kirchhoff to the concomitant action of a particular biological substance named
diastase
. Thus, we can consider him a true precursor of the modern
enzyme
science (vide infra: Chapter 8).
Figure 1.3 Jöns Jacob Berzelius (1779–1848) (image in the public domain), one of the founders of modern chemistry. He coined the word
catalysis
.
Figure 1.4 From left to right: Cato Maximilian Guldberg (1838–1902) and Peter Waage (1833–1900) (image in the public domain). They jointly formulated the famous law of mass action concerning the variation of equilibrium in chemical reactions that is the milestone of chemical kinetics.
Figure 1.5 (a) Ludwig F. Wilhelmy (1812–1864), (b) George Vernon Harcourt (1834–1919), (c) Marcellin P. Berthelot (1827–1907), and (d) Leopold Pfaundler von Hadermur (1839–1920). They are the main protagonists of the onset of chemical kinetics.
Figure 1.6 (a) Jacobus H. van't Hoff (1852–1911), awarded the 1901 Nobel Prize in Chemistry (image in the public domain: author Nicola Persheid), and (b) Svante Arrhenius (1859–1927), awarded the 1903 Nobel Prize in Chemistry (image in the public domain). They formulated the fundamental laws of chemical kinetics.
Figure 1.7 (a) Humphry Davy (1778–1829) (image in the public domain), (b) Louis Jacques Thénard (1777–1857) (image in public domain), and (c) Johann Wolfgang Döbereiner (1780–1927) (image in the public domain: authors Carl A. Schwerdgeburth, engraver, and Fritz Ries, painter). Together with Peregrine Phillips, this group of contemporary scientists discovered in the period 1818–1831 the catalytic properties of platinum in gas oxidation (Davy), hydrogen peroxide decomposition (Thénard), hydrogen–oxygen reaction (Döbereiner), and SO
2
to SO
3
oxidation reaction (Phillips).
Figure 1.8 (a) Jean Baptiste Senderens (1856–1937), (b) Paul Sabatier (1854–1941), and (c) Wilhelm Ostwald (1853–1932) (images in the public domain). They are considered as the originators of catalysis science. Paul Sabatier obtained the 1909 Nobel Prize
for his method of hydrogenating organic compounds in the presence of finely disintegrated metals.
Wilhelm Ostwald received the 1912 Nobel Prize
in recognition of his work on catalysis and on the fundamental principles governing chemical equilibria and rates of reactions
.
Figure 1.9 (a) Rudolph Messel (1848–1920) (image by courtesy of the Society of Chemical Industry) and (b) Clemens Winkler (1838–1904) (image in the public domain). They greatly contributed to the catalytic synthesis of sulfuric acid. Messel developed the contact process for producing concentrated sulfuric acid (oleum) with finely divided platinum. Winkler, discoverer of germanium, proposed the use of platinized asbestos in the production process.
Figure 1.10 (a) Henry Le Châtelier (1850–1936), (b) Fritz Haber (1868–1934), (c) Carl Bosch (1874–1940), and (d) Paul Alwin Mittasch (1869–1953) (images in the public domain). They are the protagonists of the ammonia synthesis under high pressure. The first attempt to perform the synthesis under high pressure is attributed to Le Châtelier. Haber (1918 Nobel Prize) was the first to succeed in performing the reaction. Bosch (1931 Nobel Prize) and Mittasch developed the catalysts of the industrial Haber–Bosch process.
Figure 1.11 (a) Luigi Casale (1882–1927), (b) Giacomo Fauser (1892–1971), and (c) Georges Claude (1870–1960) (images in the public domain). They developed the first commercialized ammonia synthesis processes other than the Haber–Bosch process.
Figure 1.12 (a) Franz Fischer (1877–1947) and (b) Hans Tropsch (1879–1935).
Source
: Courtesy of Max Planck Institut für Kohlenforschung. They discovered the process for converting carbon monoxide and hydrogen into liquid hydrocarbons.
Figure 1.13 Wilhelm Manchot. His fundamental contribution on autoxidation reactions was the basis for the anthraquinone process developed by Hans-Joachim Riedl and George Pfleiderer at BASF in 1936.
Chapter 2: Historical Development of Theories of Catalysis
Figure 2.1 Irving Langmuir (1857–1981). Langmuir obtained the Nobel Prize
for his discoveries and investigations in surface chemistry.
Image of Langmuir is in the public domain.
Figure 2.2 (a) Michael Polanyi (1891–1976), (b) Henry Eyring (1901–1981), and (c) John Polanyi (1929–). They can be considered as the main protagonists of the development of twentieth-century chemical kinetics. To Michael Polanyi and Eyring, we owe the formulation of the famous transition-state theory. John Polanyi, son of Michael, received the 1986 Nobel Prize for
contributions concerning the dynamics of chemical elementary processes.
Figure 2.3 Potential energy profile from reactants to products and transition-state energy following the Eyring theory.
Figure 2.4 (a) Eric Rideal (1890–1974) and (b) Cyril Hinshelwood (1897–1967). To them we owe the main theories of surface reaction mechanisms. Rideal is well known for the Eley–Rideal mechanism. Hinshelwood, awarded the 1956 Nobel Prize for his research into the mechanisms of chemical reaction, contributed the Langmuir–Hinshelwood reaction mechanism.
Figure 2.5 The Langmuir–Hinshelwood mechanism. The dashed part is the solid catalyst.
Figure 2.6 (a) Georg-Maria Schwab (1899–1984), (b) Georgy Boreskov (1907–1984), (c) Michel Boudart (1924–2012), and (d) Roald Hoffmann (1937–) They realized that the surface structure of catalysts (surface sites) and the surface orbitals play a fundamental role on the catalytic activity. Schwab directed the attention on surface defects and dislocations, while Boreskov dealt with the industrial consequences of catalyst surface composition. Boudart contributed to the spread of the concept of catalysis science. From his research, he derived the reputation of international ambassador of catalysis. Hoffmann (1981 Nobel Prize in Chemistry) was the first to use approximate quantum methods to study metal complexes and surfaces of potential catalytic interest.
Chapter 3: Catalytic Processes Associated with Hydrocarbons and the Petroleum Industry
Figure 3.1 Title page of
The Houdry Process
commemorative booklet produced by the National Historic Chemical Landmarks program of the American Chemical Society in 1996, with the portrait of Eugene Jules Houdry. The most dramatic benefit of the earliest industrial unit exploiting the Houdry process was the production of 100-octane aviation gasoline, which was of decisive importance in the Battle of Britain in 1940.
Figure 3.2 (a) Vladimir Ipatieff (1867–1952), (b) Herman Pines (1902–1996), and (c) Vladimir Haensel (1914–2002). The highly innovative discoveries in the field of hydrocarbon transformation made by these researchers have been all achieved in industrial laboratories. Ipatieff (who had an adventurous life) and Pines jointly extended the knowledge of acid catalysis mechanisms in the chemistry of petrol. Haensel developed the reforming processes based on Pt particles supported on chlorinated alumina.
Figure 3.3 Electron micrograph of a catalyst constituted by Pt particles (black dots) supported on γ-Al
2
O
3
. This image is similar to that of a reforming catalyst reported in the literature.
Figure 3.4 Schematic representation of the widely accepted hydrogenation mechanism of an olefin molecule on a flat idealized Pt surface. Adsorbed hydrogen atoms, which move freely on the surface, hydrogenate the olefin in the adsorbed state with the formation of an adsorbed alkyl intermediate. The final alkane product goes into the gas phase.
Figure 3.5 The mechanism of semihydrogenation of alkynes on the Lindlar. The surface is poisoned by Pb and by quinoline.
Figure 3.6 (a) Karl Ziegler (1892–1973) and (b) Giulio Natta (1903–1979). They were two of the most significant personalities of the time, who paved the route to new fundamental industrial processes (polymers production) that have completely changed the economy of the world. They were awarded the 1963 Nobel Prize
for their discoveries in the field of the chemistry and technology of high polymers
. Ziegler discovered that TiCl
3
in the presence of aluminum alkyl catalyzes the production of polyethylene at low pressure. Natta succeeded in selectively preparing macromolecules (polypropylene) having a spatially regular structure, an achievement not possible before. Images in the public domain.
Figure 3.7 Idealized structure of an active center containing a fivefold-coordinated Ti with a growing polymer chain and a coordination vacancy where an olefin molecule can be adsorbed and be inserted into the alkyl chain R.
Figure 3.8 (a) Walter Kaminsky (1941–) and (b) Hans-Herbert Brintzinger (1935–). They discovered metallocene polymerization catalysts. The main contribution of Kaminsky was the discovery that Cp
2
ZrCl
2
activated by partially hydrolyzed Me
3
Al (MAO) is an active olefin polymerization catalyst. Britzinger discovered that chiral-bridged titanocenes and zirconocenes catalyze the formation of partially isotactic polypropylene. The Kaminsky and Britzinger discovery opened the way to an unprecedented selectivity in polymer synthesis through a rational modification of the ligands sphere of the active metallic center.
Figure 3.9 (a) Robert Banks (1921–1989) and (b) J. Paul Hogan (1919–2012). These industrial researchers developed new catalysts for polypropylene and high density polyethylene synthesis (Phillips catalysts for olefin polymerization). This Cr-based catalyst is still responsible for industrial production of a high fraction of polyethylene. The reuse of these images is free because they are of uncertain origin and can be classified as orphan works.
Figure 3.10 Robert Grasselli (1930). Grasselli has greatly contributed to the catalytic oxychlorination and to the pioneering mechanistic analyses and deductions for selective oxidation in terms of the Mars–van Krevelen mechanism.
Figure 3.11 Mechanism of catalytic formation of carbon nanotubes.
Chapter 4: Surface Science Methods in the Second Half of the Twentieth Century
Figure 4.1 (a) Alexander Nikolaevich Terenin (1896–1967), (b) Robert Philip Eischens (1921–2010), and (c) Norman Sheppard (1921–). They pioneered the application of vibrational spectroscopies to adsorbed species. Terenin was the first to use IR spectroscopy for surface studies, using a self-made spectrometer. Eischens was an industrial researcher who applied IR spectroscopy to the study of supported metal catalysts. Norman Sheppard, a recognized expert of vibrational molecular spectroscopy, following Terenin's research line, studied oxidic systems by IR and Raman spectroscopies.
Figure 4.2 The high resolution transmission electron microscopy (HRTEM) image of MgO nanocubes exhibiting nearly perfect low index faces and adsorption properties comparable to those of (001) faces obtained by cleaving MgO single crystals under high vacuum.
Figure 4.3 (a) Gerhard Ertl (1936–), (b) Gabor Somorjai (1935–), and (c) John Meurig Thomas (1932–), ambassadors of the relations between surface science and catalysis. Ertl (2007 Nobel Prize) clarified the mechanism of the ammonia synthesis. Somorjai introduced new technologies such as LEED for the study of surfaces, while Thomas made extensive contributions to relations between structure of surface sites and catalysis.
Chapter 5: Development of Homogeneous Catalysis and Organocatalysis
Figure 5.1 George A. Olah. Olah studied the generation of carbocations
via
interaction of strong Brønsted acids with olefinic hydrocarbons. He was awarded the 1994 Nobel Prize in Chemistry with the motivation
for his contribution to carbocation chemistry
.
Figure 5.2 Structure of the –CF
2
– polymer with pendant branches carrying sulfonic groups at the end, and idealized structure of a membrane tubular channel containing pendant chains and a droplet of water.
Figure 5.3 (a) Otto Roelen (1897–1973) and (b) Walter Julius Reppe (1892–1969), the first protagonists of organometallic catalysis. Roelen discovered the first homogeneous HCo(CO)
4
(hydroformylation) catalyst, while Reppe developed the acetylene chemistry with homogeneous catalysts. The first image refers to the plaque delivered by Gesellschaft Deutscher Chemiker (GDCh) for the discovery of oxo synthesis of Otto Roelen at Ruhrchemie (image in the public domain).
Figure 5.4 Olefin hydrogenation cycle of the Osborn–Wilkinson catalyst.
Figure 5.5 (a) Sir Geoffrey Wilkinson (1921–1996) and (b) John Osborn (1939–2000). Wilkinson in collaboration with Osborn synthesized the homogeneous hydrogenation Rh(I) complex known as Osborn–Wilkinson catalyst.
Figure 5.6 (a) William Knowles (1917–2012), (b) Ryōji Noyori (1938–), and (c) Henry Boris Kagan (1930–). They are the main protagonists of the chiral hydrogenation catalysis. Knowles and Noyori were awarded the 2001 Nobel Prize.
Figure 5.7 (a) Karl Barry Sharpless (1941–), (b) Eric Jacobsen (1960–), and (c) Maurice Brookhart (1943–). They were the protagonists of chiral epoxidation and post-metallocene catalysis.
Figure 5.8 Metathesis general reaction scheme. M stands for the metal carbene.
Figure 5.9 Typical Grubbs carbenoid complexes. The metal center is passing from fivefold to sixfold coordination during the reaction cycle. In the Figure PCy
3
stands for tricyclohexylphosphine.
Figure 5.10 (a) Yves Chauvin (1930–2014), (b) Robert Grubbs (1942–), and (c) Richard Schrock (1945–). Protagonists of metathesis catalysis, they were awarded the 2005 Nobel Prize in Chemistry. Chauvin image by courtesy of CPE Lyon. The Grubbs and Schrock images are in the public domain (authors Saibo and A. mela, respectively).
Figure 5.11 (a) Richard F. Heck (1931–), (b) Ei-ichi Negishi (1935–), and (c) Akira Suzuki (1930–). They were awarded the 2010 Nobel Prize in Chemistry for their discoveries
of palladium-catalyzed cross couplings in organic synthesis.
These reactions are known as Heck, Negishi, and Suzuki reactions. Other cross-coupling reactions discovered in the same period are the Sonogashira, Stille, and Hiyama cross-coupling reactions.
Figure 5.12 Basic structure of (a) metal porphyrin (heme group of hemoglobin) and (b) metal phthalocyanine.
Chapter 6: Material Science and Catalysis Design
Figure 6.1 (a) STM image of gold particles preferentially nucleated at the edges of ceria terraces. (b) TEM image of a Pt nanoparticle interacting with two γ-Al
2
O
3
nanocrystals.
Figure 6.2 (a) Richard Barrer (1910–1996) and (b) Edith Flanigen (1929–) shown with US President Barack Obama in 2014. They can be considered as the main protagonists of zeolite chemistry and synthesis. Barrer, father of zeolite chemistry, discovered the potentialities of zeolites in gas separations. Flanigen synthesized a large variety of zeolites, which have found application in catalysis. For this she can be considered as one of the most inventive chemists of all time.
Figure 6.3 Faujasite structure. Each segment stays for a SiOSi or SiOAl group. The cations counterbalancing the negative charge of the framework (Na
+
, NH
4
+
, and H
+
) are omitted.
Figure 6.4 Silicalite framework. Black sticks stay for oxygen, while gray tetrahedral sticks stay for silicon. When a silicon atom is substituted by Al (ZSM-5), a positive compensating charge (H
+
) is present (right-hand side), which acts as a strong Brønsted acid.
Figure 6.5 Shape selectivity in biphenyl alkylation with propene inside a zeolite cage behaving as a nanoreactor of molecular size.
Figure 6.6 Beckmann rearrangement of cyclohexanone oxime to caprolactam in a silicalite cavity containing hydroxyl nests.
Figure 6.7 (a) Selective partial oxidation reactions catalyzed by TS-1 using H
2
O
2
as oxidant. (b) TS-1 structure. The circles stay for Ti atoms substituting Si in the silicalite structure and acting as single-site catalytic centers. The TS-1 and silicalite frameworks are the same of ZSM-5, where a small fraction of silicon atoms is substituted by Al.
Figure 6.8 Picture from G. Bellussi of the ceremony for the attribution of the 1992 D. Breck Award to the Eni team: (1) A. Esposito, (2) C. Neri, (3) F. Buonomo, (6) G. Bellussi, (7) G. Perego, (8) U. Romano, (9) V. Fattore, (10) M. Clerici, (11) B. Notari. From IZA: (4) H. Karge, (5) P. Jacobs, (12) E.M. Flanigen.
Figure 6.9 Structure of an organic–inorganic hybrid zeolite.
Figure 6.10 Structure of MOF-5
.
The internal cavities are represented by spheres.
Chapter 7: Photocatalysis
Figure 7.1 Generation and migration of photoinduced charges in a spherical semiconductor particle generated by light irradiation. Generated electrons and holes escaping volume and surface recombination are transferred to acceptor and donor species located on the surface.
Figure 7.2 (a) Giacomo Ciamician (1857–1922), (b) Vincenzo Balzani (1936–), and (c) Akira Fujishima (1942–). Ciamician, inspired by photosynthesis, developed solar photochemistry and can be considered as intiator of
green chemistry
. Balzani can be considered as the ideal continuer of the Ciamician tradition at the University of Bologna. Fujishima made the important observation that water splitting could be obtained under illumination using TiO
2
(rutile) with dispersed platinum supported on the surface.
Figure 7.3 (a) Schematic representation of the function of platinum particles (black hemispheres) supported on TiO
2
that catalyze the evolution of hydrogen and oxygen. (b) Transmission electron microscopy image of a Pt/TiO
2
catalyst similar to that used by Akira Fujishima. The black dots are the Pt particles supported on the surfaces of TiO
2
microcrystals.
Figure 7.4
[
Ru(bpy)
3
]
2+
grafted on an idealized TiO
2
particle as co-catalyst.
Figure 7.5 [Ni–Fe] hydrogenase attached to
[
Ru(bpy)
3
]
2+
-sensitized TiO
2
nanoparticle. (1) The hydrogenase enzyme and (2) the light-absorbing Ru photosensitizer attached to the TiO
2
via phosphate groups.
Source
: Adapted from Reisner
et al
., 2009. This complex hydrogen-generating photosystem is representative of a recent direction of the scientific efforts.
Figure 7.6 Z-scheme of a photocatalytic system constituted by two components.
Source
: Adapted from Horiuchi
et al
., 2013.. Phocatalysts A and B have finely tuned band gaps and are connected by IO
3
−
/I
−
shuttle.
Chapter 8: Enzymatic Catalysis
Figure 8.1 (a) Charles Cagniard de la Tour (1777–1859) and (b) Moritz Traube (1826–1894). These scientists actively participated in the debate on the nature of fermentation. Cagniard proved for the first time that the yeast is a living organism and that it is capable of multiplying and belongs to the plant kingdom. Traube concluded that all fermentation process caused by living organisms is due to chemical reactions. Images in the public domain.
Figure 8.2 (a) Theodor Schwann (1810–1882) and (b) Eduard Buchner (1860–1917). While Schwann and Anselme Payen (see Figure 1.2) are precursors of modern enzyme science, Buchner is considered the first modern enzyme scientist. We owe to Schwann the discovery of pepsin and the invention of the term “metabolism.” The discovery of enzyme diastase is instead attributed to Payen. Buchner showed that a cell-free extract of yeast cells is active in fermentation. For this discovery, which put the definite end to vitalism theory, he was awarded the 1907 Nobel Prize. Images in the public domain.
Figure 8.3 Schematic representation of the conversion of a substrate S to a product P in absence and in presence of the catalyst. The equilibrium between substrate and product is unaffected by (enzymatic) catalysis. The lowering of the energy barrier is due to the formation of the enzyme–substrate (
ES
) complex.
Figure 8.4 (a) Otto Funke (1828–1879) and (b) Felix Hoppe-Seyler (1825–1895). In 1851 Funke succeeded in growing hemoglobin crystals. Hoppe-Seyler recognized that hemoglobin contains iron and binds oxygen reversibly to form oxyhemoglobin. The results obtained by Funke and Hoppe-Seyler were of fundamental importance for successive studies on the protein structures. Images in the public domain.
Figure 8.5 (a) Franz Hofmeister (1850–1922) and (b) Emil Fischer (1852–1919). Hofmeister was the first, with Fischer, to propose that polypeptides are amino acids linked by peptide bonds and invented a method of protein purification that is still in use today. Fischer, awarded with the 1902 Nobel Prize for his work on sugar and purine syntheses, performed the synthesis of oligopeptides. Emil Fischer was also interested in enzymes and first proposed
the key and lock model.
Images in the public domain.
Figure 8.6 Structure of the porphyrin ring and of the parent porphyrin ring with an Fe at its center (heme group).
Figure 8.7 Tetrameric structure of oxygenated hemoglobin. In the inset the heme group carries an oxygen molecule and a histidine molecule. The strands are polypeptide chains.
Figure 8.8 (a) John Cowdery Kendrew (1917–1997) and (b) Max Ferdinand Perutz (1914–2002). They are the founders of structural biology and shared the 1962 Nobel Prize. Kendrew determined by X-ray crystallography the structure of myoglobin, which is the first protein to have its three-dimensional structure clarified. Perutz determined the structure of oxy- and deoxyhemoglobin at high resolution. Images in the public domain.
Figure 8.9 Onset and evolution of the structural biology of proteins (including enzymes).
Figure 8.10 (a) James Sumner (1887–1955), (b) John Northrop (1891–1987), and (c) Otto Warburg (1883–1970). Summer and Northrop shared the 1946 Nobel Prize. Sumner demonstrated that enzymes can be crystallized and in 1926 isolated the first crystallized enzyme (urease). In 1929 Northrop isolated and crystallized pepsin. Warburg (1931 Nobel Prize) was a prominent biochemist. Among his numerous contributions, the structure and function of the respiratory enzyme must be mentioned. Images in the public domain.
Figure 8.11 David Chilton Phillips (1924–1999), the first, in 1965, to determine in atomic detail the structure of an enzyme (lysozyme) by X-ray crystallography. Lysozyme is classified as a hydrolase and is part of the innate immune system. Chilton Phillips image is in the public domain (author: Tomos Antigua Tomos).
Figure 8.12 (a) Arthur Harden (1865–1940), (b) Hans von Euler-Chelpin (1863–1964), and (c) Fritz Lipmann (1899–1986). These scientists were all involved in the understanding of the role of coenzymes. Harden and von Euler-Chelpin obtained the 1929 Nobel Prize for their investigations on the fermentation of sugar and fermentative enzymes. Fritz Lipmann, 1953 Nobel Prize, discovered the coenzyme A.
Figure 8.13 Catalytic center of methane monooxygenase (sMMO) that contains an Fe dimer. The mechanism of methane to methanol reaction is likely involving the coordination of methane to an Fe–O group, followed by C–H bond dissociation and methanol elimination. The missing oxygen is then replaced in a successive oxidation step.
Figure 8.14 Shneior Lifson (1914–2001). Lifson used statistical mechanics to investigate the structural changes of macromolecules in solution. He collaborated to the formulation of the theory of the helix–coil transition in biological macromolecules and of protein folding processes.
Figure 8.15 (a) Martin Karplus (1930–), (b) Michael Levitt (1947–), and (c) Arieh Warshel (1940–). They are known for having developed computer modeling methods of proteins and enzymes. They shared the 2013 Nobel Prize. Karplus developed the CHARMM program for molecular dynamics simulations. Levitt conducted molecular dynamics simulations of DNA and proteins. Warshel developed methods known today as computational enzymology. Images in the public domain.
Chapter 9: Miscellanea
Figure 9.1 (a) Harold Clayton Urey (1893–1981) and (b) Stanley Lloyd Miller (1930–2007) with his apparatus (images of public domain). Urey (1934 Nobel Prize for the discovery of deuterium) was also interested in the chemistry at the birth of planets and Earth and in the chemical aspects of the origin of life. Miller, in collaboration with Urey, designed and realized the experiment that propelled him to instant fame.
Figure 9.2 (a) Joan Orò (1923–2004) and (b) Fred Hoyle (1915–2001). The synthesis of adenine by Orò is, together with the Miller–Urey experiment, one of the fundamental pillars of prebiotic chemistry. Hoyle was an expert in nucleosynthesis and promoted the idea that the first life on Earth came from outer space.
Figure 9.3 Ronald Breslow (1931–). Breslow is known for his contribution on the autocatalytic mechanism of the formose reaction and on the origin of homochirality.
Figure 9.4 Quarz and calcite crystals.
The Development of Catalysis
A History of Key Processes and Personas in Catalytic Science and Technology
Adriano Zecchina
Salvatore Califano
Copyright © 2017 by John Wiley & Sons, Inc. All rights reserved
Published by John Wiley & Sons, Inc., Hoboken, New Jersey
Published simultaneously in Canada
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Library of Congress Cataloging-in-Publication Data:
Names: Zecchina, Adriano, 1936- | Califano, S.
Title: The development of catalysis : a history of key processes and personas in catalytic science and technology / Adriano Zecchina, Salvatore Califano.
Description: Hoboken, New Jersey : John Wiley & Sons, Inc., [2017] | Includes bibliographical references and index.
Identifiers: LCCN 2016039869| ISBN 9781119181262 (cloth) | ISBN 9781119181309 (pdf) | ISBN 9781119181293 (epub)
Subjects: LCSH: Catalysis–History. | Photocatalysis–History. | Biocatalysis–History. | Chemistry, Physical and theoretical–History.
Classification: LCC QD505 .Z43 2017 | DDC 541/.395–dc23 LC record available at https://lccn.loc.gov/2016039869
Preface
Alchemists and chemists have always known how to increase reaction rates by raising the temperature. Only much later, chemists realized that the addition to the reaction of a third chemical substance, the catalyst, could give rise to the same effect. Catalysis, whose discovery date is difficult to establish, goes back to the period of transition from alchemy to chemical science. Actually it is a type of science with a prominent interdisciplinary character. Several branches of scientific disciplines have contributed to its development, including chemical kinetics; inorganic, organic, and protein chemistry; material and surface science; advanced physical methods, and computer modeling. The early development of catalysis science received a great impulse from the contribution of many scientists active in the nineteenth century and in the first decade of twentieth century. To mention only a few, Berzelius coined the word “catalysis,” van't Hoff and Arrhenius are remembered for their discoveries in the field of chemical kinetics, and then Davy, Dobereiner, Thenard, and Philips, for having discovered the catalytic properties of platinum. This group could be considered the fathers of heterogeneous catalysis. They were great scientists in a period of great discoveries and advancements, and their work has formed the basis of catalytic science. However, it is only with Sabatier and Ostwald in the first decade of the twentieth century that catalysis in its heterogeneous version became worthy of Nobel Prize recognition. Homogeneous catalysis came later with the seminal contributions of Roelen (use of cobalt carbonyls as catalysts in hydroformylation reaction) and of Wilkinson and Osborn (hydrogenation reactions using organometallic complexes as catalysts), and they are only a few who can be considered the initiators. The start of enzymatic catalysis could coincide with the isolation and crystallization of the first enzymes by Sumner (urease) and Northrop (pepsin) and the structural determination of lysozyme by Chilton Phillips. However, it is worth recalling that already in eighteenth century, Payen correctly recognized the catalytic action of a particular biological substance, which he termed “diastase,” and then at the end of nineteenth century, Fischer had the remarkable intuition to use the so-called key and lock model to explain the selectivity of enzymes.
After these starts, the number of publications involving explicitly the word “catalysis” in all versions (heterogeneous, homogeneous, photo, and enzymatic) gradually increasing from few tens in the 1920s to several hundred in the 1950s and to more than ten thousands in the 2000s, which is a consistent fraction of all the documents having chemistry as a key word. This exponential growth is continuing today. In a parallel way the number of Nobel laureates directly or indirectly involved in catalysis greatly increased in the twentieth century, approaching the total number of about 40 in 2014. This number is only a small fraction of all valuable researchers who have contributed to the development of catalysis science and technology. In this book we document the importance and richness of many of these contributions. We describe the main branches of catalytic science (heterogeneous, homogeneous, and enzymatic) and how they evolved separately with little reciprocal contamination. Today the need to design selective and super-selective catalysts is being inspired by the research on enzymes and by the environmental issues that are gaining increasing consideration and contributing to fruitful contamination. As the development of catalysis and its industrial applications in the twentieth century are definitely a complex matter, the scope of this small book is more to give a picture of the major trends than a detailed illustration of all discoveries and contributions. We only underline catalysis science and technology are still evolving and can be a source of inspiration for the present and future generation of scientists.
15 June 2016
Adriano ZecchinaTorino
Salvatore CalifanoFirenze
Chapter 1From the Onset to the First Large-Scale Industrial Processes
1.1 Origin of the Catalytic Era
Chemists have always known, even before becoming scientists in the modern term (i.e., during the long alchemist era), how to increase reaction rates by raising the temperature. Only much later on, they realized that the addition to the reaction of a third chemical substance, the catalyst, could give rise to the same effect.
Formerly the word “affinity” was used in chemical language to indicate the driving force for a reaction, but this concept had no direct connection with the understanding of reaction rates at a molecular level.
The first known processes involving reactions in solution accelerated by the addition of small amounts of acids are normally defined today as homogeneous catalysis. Experimental evidence for such processes dates back to the sixteenth century, when the German physician and botanist Valerius Cordus published posthumously in 1549 his lecture notes with the title Annotations on Dioscorides.
Valerius Cordus (1515–1544), born in Erfurt, Germany, organized the first official pharmacopoeia (ϕαρμακoπoιΐα) in Germany. He wrote a booklet that described names and properties of medicaments, completing and improving the famous pharmacopoeia written by the Roman natural philosopher Pliny the Elder and listing all known drugs and medicaments. In 1527, he enrolled at the University of Leipzig where he obtained his bachelor's degree in 1531. During these years, he was strongly influenced by his father Euricius, author in 1534 of a systematic treatise on botany (Botanologicon). Valerius Cordus, after completing his training in the pharmacy of his uncle at Leipzig, moved in 1539 to Wittenberg University. As a young man, he also made several trips to Europe, the last one to Italy where he visited several Italian towns, including Venice, Padua, Bologna, and Rome. There he died in 1544 at the age of only 29 and was buried in the church of Santa Maria dell'Anima.
His role in pharmacy was based on the Dispensatorium, a text he prepared in 1546 that, using a limited selection of prescriptions, tried to create order in the unsystematic corpus of medicaments existing at that time. Soon his dispensatory became obligatory for the complete German territory. In 1540 Cordus discovered ether and described the first method of preparing this special solvent in the De artificiosis extractionibus liber. Following a recipe imported to Europe from the Middle East by Portuguese travelers, he discovered how to synthesize ethyl ether by reacting oil of vitriol, “oleum dulci vitrioli” (sweet oil of vitriol), with ethyl alcohol (Califano, 2012, Chapter 2, p. 40). The synthesis was published in 1548 (Cordus, 1548) after his death and again later in the De artificiosis extractionibus liber (Cordus, 1561) (Figure 1.1).
Figure 1.1 (a) Valerius Cordus, discoverer of ethyl ether formation from ethyl alcohol in the presence of an acid (oil of vitriol). (b) Cover page of Dispensatorium Pharmacorum. Images in the public domain.
He, of course, did not grasp the fact that the presence of an acid in the solution had a catalytic effect on the reaction. Only at the end of the eighteenth century did chemists realize that a few drops of acid or even of a base added to a solution could speed up reactions in solutions, giving rise to the era of homogeneous catalysis.
The chemical importance of these processes became evident only several years later, when the French agronomist and nutritionist Antoine-Augustin Parmentier (1737–1813) realized in 1781 that the addition of acetic acid accelerated the transformation of potato flour into a sweet substance. Parmentier was known for his campaign in which he promoted potatoes as an important source of food for humans not only in France but also throughout Europe (Block, 2008) (Figure 1.2).
Figure 1.2 (a) Augustin Parmentier (1737–1813) and (b) Anselme Payen (1795–1871) (images in the public domain). Parmentier discovered the accelerating action of acetic acid in the transformation of potato flour into a sweet substance. Payen attributed the starch transformation induced by few drops of sulfuric acid previously discovered by Constantin Kirchhoff to the concomitant action of a particular biological substance named diastase. Thus, we can consider him a true precursor of the modern enzyme science (vide infra: Chapter 8).
During the Seven Years' War, while performing an inspection at the first front lines, Parmentier, captured by a Prussian patrol, was sent on probation to the shop of a German pharmacist Johann Meyer, a person who became his friend and had a great influence on his scientific formation. After his return to Paris in the year 1763, he pursued his research in nutrition chemistry. His prison experience came back to his mind in 1772 when he proposed, in a contest sponsored by the Academy of Besançon, to use the potato as a convenient food for dysenteric patients, a suggestion that he soon extended to the whole French population. This suggestion, complemented in 1794 by the book La Cuisinière Républicaine written by Madame Mérigot, definitely promoted the use of potatoes as food for the common people first in France and subsequently over the entire continent. In 1772, he won a prize from the Academy of Besançon with memoirs in which he further emphasized the praise of the potato as a source of nutrients (Parmentier, 1773, 1774).
An additional early example of catalytic processes was found by the Russian chemist Gottlieb Sigismund Constantin Kirchhoff (1764–1833) born in Teterow in the district of Rostock, in Mecklenburg-Western Pomerania (Germany), who was working in St. Petersburg as an assistant in a chemist's shop. In 1811, he became the first person who succeeded in converting starch into sugar (corn syrup), discovering that the hydrolysis of starch in glucose was made faster by heating a solution to which he had added only a few drops of sulfuric acid (Kirchhoff, 1811a, b). This gluey juice was a kind of sugar, eventually named glucose. Kirchhoff showed at a meeting of the Imperial Academy of Sciences in St. Petersburg three versions of his experiments. He apparently discussed the problem with Berzelius who then told the Royal Institute in London about Kirchhoff's experiments, remarking upon the treatment with sulfuric acid.
At the suggestion of Sir Humphry Davy, members of the Royal Institution in London repeated his experiment and produced similar results. It was, however, only in 1814 that the Swiss chemist Nicolas-Théodore de Saussure showed that the syrup contained dextrose.
1.2 Berzelius and the Affinity Theory of Catalysis
The first who coined the name catalysis was Berzelius, one of the founders of modern chemistry, in 1836. Born in 1779 at Väversunda in Östergötland, Sweden, although in continual financial difficulties and suffering many privations, he was able to study at the Linköping secondary school and then enroll at Uppsala University to study medicine during the period between 1796 and 1801, thanks to the moral support of Jacob Lindblom, Bishop of Linköping. At Uppsala, he studied medicine and chemistry under the supervision of Anders Gustaf Ekeberg, the discoverer of tantalum and supporter of the interest in the chemical nomenclature of Lavoisier.
He worked then, as a medical doctor near Stockholm, until Wilhelm Hisinger, proprietor of a foundry, discovered his analytical abilities and decided to provide him with a laboratory where he could work on his research on looking for new elements.
In 1807, the Karolinska Institute appointed Berzelius as professor in chemistry and pharmacy. In 1808, he was elected as a member of the Royal Swedish Academy of Sciences and, in 1818, became secretary of the Academy, a position that he held until 1848. During his tenure, he revitalized the Academy, bringing it into a significant golden era (Figure 1.3).
Figure 1.3 Jöns Jacob Berzelius (1779–1848) (image in the public domain), one of the founders of modern chemistry. He coined the word catalysis.
In 1822, the American Academy of Arts and Sciences nominated him as Foreign Honorary Member, and in 1837, he became a member of the Swedish Academy. Between 1808 and 1836, Berzelius worked with Anna Sundström, who acted as his assistant (Leicester, 1970–1980).
Berzelius developed a modern system of chemical formula notation in which the Latin name of an element was abbreviated to one or two letters and superscripts (in place of the subscripts currently used today) to designate the number of atoms of each element present in the atom or molecule.
Berzelius discovered several new elements, including cerium and thorium. He developed isomerism and catalysis that owe their names to him. He concluded that a new force operates in chemical reactions, the catalytic force (Califano, 2012, Chapter 2, p. 42).
A first attempt to interpret the mechanism of catalysis was made by Berzelius who, in a report to the Swedish Academy of Sciences of 1835 published in 1836 (Berzelius, 1836a), had collected a large number of results on both homogeneous and heterogeneous catalytic reactions that he reviewed, proposing the existence of a “new catalytic force,” acting on the matter. In 1836, he wrote in the Edinburgh New Philosophical Journal (Berzelius, 1836a):
The substances that cause the decomposition of H2O2 do not achieve this goal by being incorporated into the new compounds (H2O and O2); in each case they remain unchanged and hence act by means of an inherent force whose nature is still unknown… So long as the nature of the new force remains hidden, it will help our researches and discussions about it if we have a special name for it. I hence will name it the catalytic force of the substances, and I will name decomposition by this force catalysis. The catalytic force is reflected in the capacity that some substances have, by their mere presence and not by their own reactivity, to awaken activities that are slumbering in molecules at a given temperature.
Berzelius J. J. Quoted by Arno Behr and Peter Neuber, Applied Homogeneous Catalysis, Wiley-VCH Verlag GMbH and &Co KGaA, 2012
He coined also the word catalysis, combining the Greek words κατά (down) and λύσις (solution, loosening). According to Berzelius a catalyst was a substance able to start a reaction without taking part in it and thus without being consumed. In his famous paper of 1836 (Berzelius, 1836b), he wrote:
the catalytic power seems actually to consist in the fact that substances are able to awake affinities, which are asleep at a particular temperature, by their mere presence and not by their own affinity.
Berzelius J. J., the Edinburgh New Philosophical Journal XXI, 223, 1836c
In 1839, Justus von Liebig, one of the most important organic chemists of his time, tried an interpretation of catalysis based on the concept that a third body, the catalyst, added to the reactants, although not taking part in the reaction, was able to speed up the process (Liebig, 1839). After a few years, the German physicist and physician Julius Robert von Mayer, in the framework of his studies of photosynthetic processes, developed in 1845 a different interpretation of the catalytic mechanism. Mayer put forward the idea that the catalyst was able to release large amounts of sleeping energy that could allow the reaction to break out. Christian Friedrich Schönbein (1799–1868), discoverer of ozone, further developed the idea that the catalyst, without interacting with the reagents, could speed up the reaction producing intermediate products able to open new and faster paths to the reacting molecules. He asserted that a reaction is not a single process but occurs as the consequence of a time-ordered series of intermediate events (Schönbein, 1848). After some years, the German Friedrich Karl Adolf Stohmann (1832–1897) proposed the possibility that a catalyst could release energy to facilitate the reaction. He pointed out that catalysis is a process in which the energy released by the catalyst transforms into the motions of the atoms of the reacting molecules. These in turn reorganize themselves, giving rise to a more stable system by emission of energy (Stohmann, 1894).
The research of Ludwig Wilhelmy (1812–1864) complemented Berzelius's idea of the existence of substances activating the ability of chemical compounds to react. He found that the addition of inorganic acids made the inversion process of cane sugar easier. Augustus George Vernon Harcourt, who discovered the importance of acid catalysis in clock reactions (Shorter, 1980), reached the same conclusion (1834–1919). In 1896, the Scottish mathematician William Esson (1838–1916) interpreted Harcourt's data in terms of a differential equation.
1.3 Discovery of the Occurrence of Catalytic Processes in Living Systems in the Nineteenth Century
In the same period, it became evident that catalytic effects also occur in living systems. Actually, the fact that living organisms contain substances able to facilitate or even trigger chemical reactions was known for a long time, but was never considered the consequence of catalytic processes occurring in the body. As documented in the chapter 8 devoted to enzymes, the use of yeasts for the production of wine was, for instance, a very old technique, already known to the Bronze Age Minoan and Mycenaean civilizations. The ability of the acid juice contained in the stomach of animals to digest meat and even bones was demonstrated by the French scientist René Antoine Ferchault de Réaumur (1683–1757), and later by the Italian biologist Lazzaro Spallanzani (1729–1799) and by the Scottish physician Edward Stevens (1755–1834).
The occurrence of different mechanisms involving living substances and contributing to orient the course of a reaction was proved by a series of fundamental research at the beginning of the nineteenth century. In 1833, Anselme Payen (1795–1871) and Jean-François Persoz (1805–1868) attributed the starch transformation, discovered by Kirchhoff, to the action of a particular biological substance. They called it diastase and further proved that at 100°C it loosed its catalytic activity (Payen and Persoz, 1833).
Anselme Payen studied chemistry at the École Polytechnique under the supervision of the chemists Louis Nicolas Vauquelin and Michel Eugène Chevreul. Besides the discovery in 1833 of the first enzyme (diastase), the synthesis of borax from soda and boric acid and a process for refining sugar can be attributed to him. He also isolated and named the carbohydrate cellulose (Payen, 1838). In 1835 Payen became a professor at the École Centrale and later at the Conservatoire National des Arts et Métiers in Paris. His friend Jean-François Persoz was préparateur of Louis Thénard at the Collège de France, before becoming professor of chemistry at the University of Strasbourg. In 1830 he had become director of the École de Farmacie and in 1850 succeeded Jean-Baptiste Dumas at the Sorbonne. Persoz studied the solubility of chemical compounds and their molecular volumes. His collaboration with Payen led to the discovery of diastase and of its presence in human saliva.
In 1835, in collaboration with Jean-Baptiste Biot, he showed how to follow experimentally the inversion of cane sugar, simply observing with a polarimeter the variation of its rotatory power after acidification.
The German Johann Wolfgang Döbereiner (1780–1849), who became famous for his discovery of similar triads of elements that paved the route to Mendeleev's organization of the elements in the famous periodic table, also investigated starch fermentation. In 1822, he was one of the first to observe the fermentative conversion of starch paste into sugar and gave a correct explanation of alcoholic fermentation, finding that starch transforms into alcohol, only after conversion to sugar (Döbereiner, 1822). Döbereiner, son of a coachman, had in his youth a poor education. Despite very poor schooling, he succeeded in attending the University of Jena where he eventually reached the position of professor.
In the field of catalysis, he worked on the use of platinum as catalyst. For his discovery of the action of solid catalysts, he is considered as one of the initiators of heterogeneous catalysis.
In 1877 the German physiologist Wilhelm Kühne (1837–1900), a pupil of several outstanding chemists and physiologists of the time, including Claude Bernard in Paris, isolated trypsin from gastric juice (Kühne, 1877) and coined the word ένζυμων (enzumon), enzyme, from the Greek, έν in and ζυμων ferment, to describe cellular fermentation.
1.4 Kinetic Interpretation of Catalytic Processes in Solutions: The Birth of Homogeneous Catalysis
The first interpretation of catalytic events at the beginning of the nineteenth century dealt mainly with reactions occurring in solution. At that time the affinity concept dominated the interpretation of chemical processes. This idea, inherited from the alchemist's vision of the interaction between chemical elements or compounds, formally corresponded to the attraction between human beings. This metaphoric explanation of catalysis, however, did not satisfy the members of the new branch of chemical physics, educated by their training in mechanics and thermodynamics to a mechanistic approach toward the interpretation of chemical reactions. The route to this new comprehension of chemical reaction was paved by the pioneering work of Ludwig Ferdinand Wilhelmy (1812–1864), usually credited for publishing the first quantitative study of chemical kinetics.
Wilhelmy, born in 1812 at Stargard in Pomerania, studied pharmacy in Berlin. After a period spent in an apothecary shop, he studied chemistry and physics at Berlin, Giessen, and Heidelberg, where he obtained his PhD in 1846.
In his life Wilhelmy was always an amateur, not bound to the university system. He conducted the largest part of his research in his private house, a villa that he reorganized as his private laboratory. Nevertheless, he was highly respected in the German physical society that he had founded with Heinrich Gustav Magnus (1802–1870). Together with Paul du Bois-Reymond, Rudolf Clausius, Hermann von Helmholtz, and Carl Wilhelm Siemens, he was considered by all his friends as a leader of the young European chemical physics. After traveling chiefly in Italy and Paris, he returned to Heidelberg and became a Privatdozent in 1849. He remained at the university for only five years.
In 1850 Wilhelmy, in the framework of a series of polarimetric research, studied the inversion of cane sugar catalyzed by inorganic acids and proved experimentally that this reaction leads to the conversion of a sucrose solution into a 1:1 mixture of fructose and glucose (Figure 1.5). Under the assumption that the initial velocity of the reaction is proportional to the concentration of both the cane sugar and the acid and counting the time from the moment in which the sugar solution is brought in contact with the acid, Wilhelmy succeeded in describing the time evolution of the process in terms of the differential equation
where Z and S are the amount (concentration) of sugar and acid at time t, respectively, whereas M is a “velocity coefficient,” which is constant over a large time interval (Califano, 2012, Chapter 2).
Wilhelmy wrote in his paper that the
process is certainly only one member of a greater series of phenomena which all follow general laws of nature
and that these laws can be expressed mathematically. The time, however, was not yet mature to appreciate the importance of his work, and it remained practically ignored for a long time, until Wilhelm Ostwald, the true father of modern chemical physics, realized its importance and even developed a quantitative analytical method to measure the strength of the acids from their ability to catalyze the sugar inversion.
The English chemist George Vernon Harcourt (1834–1919) complemented Wilhelmy's research (Figure 1.5). In the early 1860s Harcourt embarked on a research project on the rates of chemical reactions. He settled on two reactions for which, during definite time intervals, the amount of chemical change could be accurately measured. In close partnership with William Esson, mathematical fellow and tutor of Merton College, he studied the acid-catalyzed clock reaction of iodide and hydrogen peroxide (Harcourt and Esson, 1866a) as well as the oxidation of oxalic acid with potassium permanganate (Harcourt and Esson, 1866b), showing that the reaction rate was proportional to the concentration of reactants present. Their work for the first time gave detailed treatments of the kinetics of different types of reactions, anticipating several later formulations of equilibrium reactions. In 1912, when they both were well in their seventies, they again collaborated on the effect of temperature on the rates of chemical reactions (Harcourt and Esson, 1913). An interesting outcome of this work is that they predicted a “kinetic absolute zero” at which all reaction ceases; their value of −272.6°C is in remarkable agreement with the modern value of −273.15°C.
The results obtained by Wilhelmy and Harcourt were later formalized by the chemist Peter Waage and his brother-in-law Cato Maximilian Guldberg as the law of mass action (Figure 1.4).
Figure 1.4 From left to right: Cato Maximilian Guldberg (1838–1902) and Peter Waage (1833–1900) (image in the public domain). They jointly formulated the famous law of mass action concerning the variation of equilibrium in chemical reactions that is the milestone of chemical kinetics.
The Norwegian mathematician and chemist Cato Maximilian Guldberg (1838–1902) entered the University of Christiania in 1854. He worked independently on advanced mathematical problems, and his first published scientific article won the Crown Prince's Gold Medal in 1859. In 1862, he became professor of applied mechanics and professor at the Royal Military College the following year. In 1869, he developed the concept of “corresponding temperatures” and derived an equation of state valid for all liquids of certain types.
His friend Peter Waage (1833–1900) was also born in Norway. He attended the University of Christiania and passed his matriculation examination in 1854, the same year as Guldberg. After graduation in 1859, in 1861 the University of Christiania appointed him as lecturer in chemistry and promoted him professor in 1866. He became Guldberg's brother-in-law, marrying in 1870 one of Guldberg's sisters.
Cato Guldberg and Peter Waage's names normally occur together, not because of their family relations but for their joint discovery in 1864 of the famous law of mass action, concerning the variation of equilibrium in chemical reactions that is the milestone of chemical kinetics.
For a generic reaction
the velocity of the direct reaction is equal to that of the inverse reaction, and both are proportional to the concentrations of the reagents, according to the equations
where square brackets indicate concentrations. By equalizing the two velocities vdir = vinv, they obtained the relationship
well known to all first-year chemistry students (Guldberg and Waage, 1864).
An important step toward the understanding of the external factors influencing the reaction rates was realized by the publication of papers by Marcellin Berthelot and his student Léon Armand Pean Saint-Gilles (Berthelot and Saint-Gilles, 1862) concerning the kinetics of the esterification reactions of the type
for which they demonstrated that the direct reaction rate is proportional to the product of the concentration of the two reactants (Califano, 2012, Chapter 2).
The Parisian chemist, science historian, and politician Pierre Eugène Marcellin Berthelot (1827–1907), author in 1854 of a PhD thesis Sur les combinaisons de la glycérine avec les acides, in 1859 became professor of organic chemistry at the École Supérieure de Pharmacie and in 1865 at the Collège de France (Figure 1.5). He was also involved in social and political activities: he was general inspector of higher education in 1876, life senator in 1881, minister of public instruction in 1886, and minister of foreign affairs in 1895–1896.
Figure 1.5 (a) Ludwig F. Wilhelmy (1812–1864), (b) George Vernon Harcourt (1834–1919), (c) Marcellin P. Berthelot (1827–1907), and (d) Leopold Pfaundler von Hadermur (1839–1920). They are the main protagonists of the onset of chemical kinetics.
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