Organic radicals and the theory of chemical structure

 Organic radicals and the theory of chemical structure

Both problems were finally resolved through the further development of organic chemistry. The leading organic chemists of the day were the German Justus von Liebig and the Frenchman Jean-Baptiste-André Dumas. In 1830 Liebig invented a device that made organic analysis rapid, convenient, and accurate, and his laboratory institute at the tiny University of Giessen in Hesse became the most famous chemical school in the world. Liebig taught an enormous number of chemists, and his students assisted in his research program. He was the leading figure in the rise of the research university and in the idea of a research group. As a professor at Giessen, and later at the University of Munich, he laid much emphasis on practical applications of chemistry, especially for physiology, agriculture, and consumer products. Dumas exerted a similar influence in France, training students and pursuing research at a private laboratory in Paris.

Both Liebig and Dumas initially accepted the Berzelian scheme and sought to understand organic molecules as composed of identifiable radicals held together electrochemically. The younger French chemists Auguste Laurent and Charles Gerhardt pursued chlorine substitution reactions and cast doubt on this simple model; sometime after 1840 Liebig and Dumas both retreated into positivism. In 1852 Liebig’s English former postdoctoral assistant Edward Frankland noticed a regularity in the combining capacity of the atoms of certain metals and semimetals. At about the same time, two former students of both Liebig and Dumas, Alexander Williamson in London and Charles-Adolphe Wurtz in Paris, were independently approaching the same idea from a different direction. Using a system of atomic weights and formulas developed by Gerhardt and Laurent—a modified version of Berzelius’s system that incorporated Avogadro’s ideas more consistently—they proposed that oxygen atoms could combine with two other simple atoms, such as hydrogen, or with two organic radicals and that nitrogen atoms could combine with three. This was the beginning of the concept of atomic valence.

In 1858 the young German theorist August Kekule then expanded this concept to carbon, not only proposing that carbon atoms were tetravalent but adding the idea that they could bond to each other to form chains, comprising a molecular “skeleton” to which other atoms could cling. Kekule’s theory of chemical structure clarified the compositions of hundreds of organic compounds and served as a guide to the synthesis of thousands more. (The self-chaining of carbon atoms was independently developed by the Scottish chemist Archibald Scott Couper.) This theory experienced dramatic expansion when Kekule successfully applied it to aromatic compounds (after 1865) and after Jacobus Henricus van ’t Hoff of the Netherlands and Joseph LeBel of France independently began to investigate molecular structures in three dimensions—later called stereochemistry.

Atomic and molecular theory

 Atomic and molecular theory

Lavoisier’s set of chemical elements, and the new way of understanding chemical composition, proved to be invaluable for analytic and inorganic chemistry, but in a real sense the chemical revolution had only just begun. Around the turn of the century, the English Quaker schoolteacher John Dalton began to wonder about the invisibly small ultimate particles of which each of these elemental substances might be composed. He thought that if the atoms of each of the elements were distinct, they must be characterized by a distinct weight that is unique to each element. Although these atoms were far too small to weigh individually, he realized that he could deduce their weights relative to each other—the ratio of the weight of an atom of oxygen to one of hydrogen, for instance—by examining reacting weights of macroscopic quantities of these elements. In fact, the laws of stoichiometry (combining weights of elements) were just then being developed, and Dalton used these regularities to justify his inferences. His first discussion of these issues dates to 1803, and he presented his atomic theory in the multivolume New System of Chemical Philosophy (1808–27).

Dalton’s atomic theory was a landmark event in the history of chemistry, but it had a crucial flaw. His procedure required that one know the formulas of the simple compounds resulting from the combination of the elements. For example, analytical data of that day indicated that water resulted from the combination of seven parts by weight of oxygen with one part of hydrogen. If the resulting water molecule was HO (one atom of each element combining to form a molecule of water), then the weight ratio of the atoms of these elements must be the same, seven to one. However, if the formula were H2O, then the weight of an oxygen atom would have to be 14 times the weight of a hydrogen atom. There was simply no way to determine molecular formulas at that time, so Dalton made assumptions based on the simplicity of nature. He chose HO as his water formula and, therefore, seven as the relative atomic weight of oxygen.

In the following years, several leading chemists adopted essential elements of Dalton’s theory, but many objected to the hypothetical elements just described; some also doubted the very possibility of investigating the world of the invisibly small. In 1808 the French chemist Joseph-Louis Gay-Lussac discovered that when gases combine chemically, they do so in small integral multiples by volume. Three years later the Italian physicist Amedeo Avogadro argued that this fact suggested that equal volumes of gases contain equal numbers of constituent particles (Avogadro’s law), physical conditions being the same. This idea provided a physical method of determining certain molecular formulas. For instance, Gay-Lussac had pointed out that exactly two volumes of hydrogen combine with precisely one of oxygen to form water. If Avogadro was right, the formula for water had to be H2O. But this line of reasoning also led to the uncomfortable notion that elementary gases had polyatomic molecules (O2, H2, and so on), and therefore many chemists rejected Avogadro’s hypotheses.

By far the greatest of the early atomists was the Swede Jöns Jacob Berzelius, who accepted parts of Avogadro’s ideas and developed an elaborate version of chemical atomism by 1826. It was Berzelius who in 1813 had proposed the alphabetic system for denoting elements, atoms, and molecular formulas, and the use of formulas as an aid for studying chemical composition and reactions began to blossom about 1830. However, different chemists were still making different assumptions regarding the formulas of simple compounds such as water, and so, for decades, various inconsistent systems of atomic weights and formulas were in use in the various European countries.

Berzelius also developed a theory of chemical combination based on the electrochemical studies that the invention of the battery (1800) had spawned. He became convinced that all molecules were held together by the Coulomb force, the electrostatic attraction between oppositely charged objects. (Berzelius assumed that a molecule’s constituent atoms or groups of atoms were not neutral, and he called these charged components radicals.) This theory of electrochemical dualism worked well with inorganic compounds, but organic substances seemed anomalous. Particularly in the 1830s, when chemists learned how to replace the hydrogen of organic compounds with chlorine atoms, Berzelius’s theory appeared to be threatened—after all, hydrogen and chlorine had opposite electrochemical characteristics, yet the substitution seemed to make little difference in the properties of the compounds. In the 1840s and ’50s, extensive debates over rival systems of chemical atomism and over electrochemical dualism enlivened the journal literature.

The chemical revolution

 The chemical revolution

The new research on “airs” attracted the attention of the young French aristocrat Antoine-Laurent Lavoisier. Lavoisier commanded both the wealth and the scientific brilliance to enable him to construct elaborate apparatuses to carry out his numerous ingenious experiments. In the course of just a few years in the 1770s, Lavoisier developed a radical new system of chemistry, based on Black’s methods and Priestley’s dephlogisticated air.

Lavoisier first determined that certain metals and nonmetals absorb a gaseous substance from the air in undergoing calcination or combustion and, in the process, increase in weight. Initially, he thought that this gas must be Black’s fixed air, for he knew of no other chemical species present in ordinary air; moreover, fixed air was known to be produced in smelting, so it seemed reasonable to think that it was present in the calx that was smelted. At this point (October 1774), Priestley communicated to Lavoisier his discovery of dephlogisticated air. Further experiments led Lavoisier to continuously modify his ideas, until it finally became clear to him that it was this new gas, and not fixed air, that was the active entity in combustion, calcination, and respiration. Moreover, he determined (or so he thought, at least) that this gas was contained in all acids. He renamed it oxygen, Greek for “acid producer.”

Lavoisier’s oxygen was in some respects the inverse of phlogiston. Rather than releasing anything, the combustible or metal absorbed (more precisely, chemically combined with) oxygen in the process that Lavoisier now called oxidation. He showed that atmospheric air was a mixture of two principal components, oxygen and a physiologically inert gas (known to Priestley) that he called azote or nitrogen. He also showed that water is a chemical compound of two substances, oxygen and what Cavendish had called “inflammable air.” The latter gas was now renamed hydrogen (“water producer”). Black’s fixed air proved to be a gaseous form of oxidized carbon, or carbon dioxide. The various parts of Lavoisier’s new system were beginning to fit together beautifully.

The keys to Lavoisier’s success were twofold. First, he carefully accounted for all the substances, including gases, entering into and emerging from the chemical reactions he studied by tracking their weights with the greatest possible precision. He knew to do this partly from Black’s example, but he proceeded with a mastery that the science had never before seen. Second, he established a simple operational definition of a chemical element—namely, a substance that could not be reduced in weight as the result of any chemical reaction that it undergoes. Oxygen, carbon, iron, and sulfur were now regarded as elements, along with close to 30 other substances. Lavoisier wrote a textbook to promote the new oxygenist chemistry, Traité élémentaire de chimie (1789), which appeared in the same year the French Revolution began. He and his associates also developed a new nomenclature—essentially the one used today for inorganic compounds—along with a new journal. As an aristocrat of the ancien régime and an investor in a tax-collection agency, Lavoisier was executed in the Reign of Terror, but by that time (1794) the chemical revolution that he had started had largely succeeded in replacing phlogistonist chemistry.

Alchemy

 Alchemy

Three different sets of ideas and skills fed into the origin of alchemy. First was the empirical sophistication of jewelers, gold- and silversmiths, and other artisans who had learned how to fashion precious and semiprecious materials. Among their skills were smelting, assaying, alloying, gilding, amalgamating, distilling, sublimating, painting, and lacquering. The second component was the early Greek theory of matter, especially Aristotelian philosophy, which suggested the possibility of unlimited transformability of one kind of matter into another. The third of alchemy’s roots consisted of a complex combination of ideas derived from Asian philosophies and religions, Hellenistic mystery religions, and what became known as the Hermetic writings (a body of pseudonymous Greek writings on magic, astrology, and alchemy ascribed to the Egyptian god Thoth or his Greek counterpart Hermes Trismegistos). It is important to note, however, that Hellenistic Egypt is only one of several candidates for the homeland of alchemy; at about the same time, similar ideas were developing in Persia, China, and elsewhere.

In general, alchemists sought to manipulate the properties of matter in order to prepare more valuable substances. Their most familiar quest was to find the philosopher’s stone, a magical substance that would transmute ordinary metals such as copper, tin, iron, or lead into silver or gold. Important materials in this craft included sulfur, mercury, and electrum (a gold-silver alloy). However, many other alchemists spurned alchemical transmutation (aurifaction), devoting their efforts instead to a pharmaceutical preparation known as the “elixir of life” that would cure any disease, including the ultimate disease, death. The philosopher’s stone and the elixir of life could be considered parallel quests, for each would “cure” metallic or human bodies, respectively, yielding immortal perfection. There was a parallel religious dimension to all this as well. Finally, some alchemists spurned material manipulations entirely, devoting themselves to meditation with the goal of achieving spiritual purity and ultimate redemption.

After the rise of Islam, Arabic-speaking scholars of the 9th century translated Greek scientific and philosophical works into their own language. Thereafter, philosophers in the Islamic world pursued chemical and alchemical ideas with enthusiasm and success. The sizable number of modern chemical words derived from Arabic—alcohol, alkali, alchemy, zircon, elixir, natron, and others—suggests the importance of this period for the history of chemistry. One of the leading ideas of medieval Arabic alchemy was the theory that all metals were formed of sulfur and mercury in various proportions and that altering those proportions could transform the metal under study—even to produce silver or gold from lead or iron. Not every alchemist, however, believed in the possibility of such transmutations.

Later, scholars in Christian western Europe learned of ancient Greek and early medieval Arabic philosophy by translating these books into Latin. Thus, the alchemical tradition, along with the rest of the Greco-Arabic philosophical and scientific corpus, passed to the West in the course of the 12th century. Well-known Scholastic philosophers of the 13th century, such as Roger Bacon in England and Albertus Magnus in Germany and France, wrote on alchemy. Alongside this learned literature, the empirical chemical arts continued to flourish and comprised a largely separate realm of expertise among artisans, engineers, and mechanics.

An important Western alchemist of the late 13th century was the pseudonymous Latin writer who called himself Geber in homage to the 8th-century Arab alchemist Jābir ibn Ḥayyān. Geber was the first to record methods for the preparation and use of sulfuric acid, nitric acid, and hydrochloric acid; the earliest clear evidence for widespread familiarity with distilled alcohol also does not much predate his day. These substances could only have been produced by novel stills that were more robust and efficient than their predecessors, and the appearance of these remarkable new materials produced dramatic changes in the repertoire of chemists.

The Renaissance saw even stronger interest in the science. The German-Swiss physician Paracelsus practiced alchemy, Kabbala, astrology, and magic, and in the first half of the 16th century he championed the role of mineral rather than herbal remedies. His emphasis on chemicals in pharmacy and medicine was influential on later figures, and lively controversies over the Paracelsian approach raged around the turn of the 17th century. Gradually the Hermetic influence declined in Europe, however, as certain celebrated feats of putative aurifaction were revealed as frauds.

History of Paint

 

History of Paint

The abundance and widespread use of paint in our daily lives makes it easy to take paint for granted. A look at the chemistry of paint leads to a better appreciation of its complexities.

Paint is a liquid composition that dries to an opaque film. It is composed of four basic types of ingredients: pigments, which are powders that give opacity and color; binders, which act like glue to hold the pigments together and cause the film to adhere to the surface being painted; liquids, which make the paint thin enough to spread on a surface, and additives, which perform special functions such as thickening, reducing mildew, and more.

Paints are generally classified as either solvent-borne or waterborne. Solvent-borne wall paints, such as oil paints, use a petroleum derivative (for example, mineral spirits) as the solvent. Waterborne paints use water.

Waterborne wall coatings prevailed from prehistoric cave paintings up to medieval wall paintings. Natural proteins were used as binders for the pigments. Tempera used egg whites as a binder; distemper, a similar waterborne paint, used animal glues from hides and hoofs. Whitewash used milk casein to bind lime (calcium hydroxide) onto Tom Sawyer's fictional fence. But all these exhibited poor washability and durability.

Linseed-oil-bound pigments — used by the ancient Egyptians, early Romans and Renaissance artists such as da Vinci and Michelangelo — were more durable, but were scarce until the linen industry expanded to provide ample flax seed, from which linseed oil was pressed. Hardening of the soft linseed oil films by rosin and adding volatile turpentine from the naval stores industry enhanced varnishes for Stradivarius violins, fine furniture and wooden floors. Turpentine was the only historic volatile organic solvent to control paint viscosities until the coke and petroleum industries distilled various naphthas.

These separate crafts came together only in the 1930s, when brilliant exterior waterborne paints enhanced and survived the 1933 Century of Progress Exposition in Chicago and the 1939-40 World's Fair in New York City.

World War II Brings Changes to Paint Industry

 

World War II Brings Changes to Paint Industry

During World War II, the paint industry geared up for defense production. Thousands of military items required paints, including camouflage paint for tanks; aircraft, ship, and truck finishes; and coatings for guns and bombs. Every soldier was equipped with many painted items, some of which had their own special finishes. In addition, construction equipment, water supplies, and electrical lighting systems necessary to a military campaign also required paint.

Sherwin-Williams, a leading paint manufacturer based in Cleveland, Ohio, worked to accommodate this defense conversion. Plant engineers converted old equipment to new manufacturing uses. Chemists experimented with old, almost forgotten oils and resins and treated them with modern processing equipment. Purchasing agents combed the country for raw materials so that shortages would not halt production.

Shortages affected every corner of life during the war, from women who gave up stockings because silk was unavailable, to paint manufacturers who were required to ration linseed oil, a common paint binder. These constraints led Sherwin-Williams to accelerate their research into new coatings concepts. Their chemists took casein, a milk protein used by the ancient Egyptians for making paint, and emulsified (or suspended) varnish in it. They then added a number of other ingredients, with water as the largest component, to create a water-based paint.

The result was Kem-Tone^© paint, a fast-drying emulsion that met with instant public acceptance and would ultimately become one of the best-selling paints in the United States. Kem-Tone^© paint became the first widely accepted waterborne interior wall paint with sufficient binding power to allow washability.

Developed by a team of Sherwin-Williams chemists, Kem-Tone^© paint did not depend on organic solvents (based on carbon, such as petroleum derivatives), and it reduced the required amounts of traditional binders, which were in short supply because of the war. Technologically, the chemists at Sherwin-Williams showed that it was chemically and commercially possible for a paint emulsified in water to produce a durable coating.

Kem-Tone^© was registered as a trademark on Sept. 23, 1941. In the next three years, more than 10 million gallons would be sold.

The widespread acceptance of Kem-Tone^© paint was accelerated by the simultaneous introduction of the hand-roller (called Roller-Koater™), which made application by do-it-yourselfers very easy. Here, too, wartime shortages played a significant role. Richard Adams, an engineer for Sherwin-Williams, invented and patented the roller as an alternative to brushes, which were in short supply because the war between China and Japan restricted the availability of hog bristles.

Kem-Tone^© paint and the Roller-Koater™ applicator ushered in a new era in the do-it-yourself paint market, which comprises about 50 percent of the architectural coatings (paints applied to residences) sold today. The innovative chemistry of Kem-Tone^© paint also opened the door to continued developments in waterborne paints, which account for approximately 80 percent of all the architectural coatings sold today.

Chemistry of Flavor

 

Chemistry of Flavor

Flavor is caused by receptors in the mouth and nose detecting chemicals found within food. These receptors respond by producing signals that are interpreted by the brain as sensations of taste and aroma. Certain taste and aroma combinations are characteristic of particular foods.

For example, a green apple tastes the way it does because the unique combination of chemicals found naturally within it are perceived by our mouths, noses and brains as the distinct blend of sweet and sour tastes and volatile aromas characteristic to the fruit. Identifying this chemical profile allows food producers to retain flavor in preserved green apples and, through synthesis of these flavor compounds, makes possible the production of candy, soda and other products using artificial green apple flavor.

The chemicals that produce flavors are notoriously difficult to study because a single natural flavor may contain hundreds or even thousands of component substances, and some of these substances are present in minute quantities. For example, one of the nine key aroma compounds found in pineapple is so potent that human subjects can detect it at only 6 parts per trillion—the equivalent of a few grains of sugar in an Olympic-size swimming pool. Understanding the components of flavor has become more important than ever with the modernization of food systems and the increased reliance on processed foods.