The Development of Catalysis
The Development of Catalysis
From 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 (miopio) 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 n