Historia Chemii
The history of chemistry
The history of alchemy represents a time span from ancient history to the present. By 1000 BC, civilizations used technologies that would eventually form the basis of the various branches of chemistry. Examples include extracting metals from ores, making pottery and glazes, fermenting beer and wine, extracting chemicals from plants for medicine and perfume, rendering fat into soap, making glass, and making alloys like bronze.
The protoscience of chemistry, alchemy, was unsuccessful in explaining the nature of matter and its transformations. However, by performing experiments and recording the results, alchemists set the stage for modern chemistry. The distinction began to emerge when a clear differentiation was made between chemistry and alchemy by Robert Boyle in his work The Sceptical Chymist (1661). While both alchemy and chemistry are concerned with matter and its transformations, chemists are seen as applying scientific method to their work.
Chemistry is considered to have become an established science with the work of Antoine Lavoisier, who developed a law of conservation of mass that demanded careful measurement and quantitative observations of chemical phenomena. The history of chemistry is intertwined with the history of thermodynamics, especially through the work of Willard Gibbs.
Ancient history
Early metallurgy
History of ferrous metallurgy and History of metallurgy in the Indian subcontinent
The earliest recorded metal employed by humans seems to be gold which can be found free or "native". Small amounts of natural gold have been found in Spanish caves used during the late Paleolithic period, c. 40,000 BC. Silver, copper, tin and meteoric iron can also be found native, allowing a limited amount of metalworking in ancient cultures. Egyptian weapons made from meteoric iron in about 3000 BC were highly prized as "Daggers from Heaven". Arguably the first chemical reaction used in a controlled manner was fire. However, for millennia fire was seen simply as a mystical force that could transform one substance into another (burning wood, or boiling water) while producing heat and light. Fire affected many aspects of early societies. These ranged from the simplest facets of everyday life, such as cooking and habitat lighting, to more advanced technologies, such as pottery, bricks, and melting of metals to make tools.
It was fire that led to the discovery of glass and the purification of metals which in turn gave way to the rise of metallurgy.During the early stages of metallurgy, methods of purification of metals were sought, and gold, known in ancient Egypt as early as 2900 BC, became a precious metal.
Bronze Age
Certain metals can be recovered from their ores by simply heating the rocks in a fire: notably tin, lead and (at a higher temperature) copper, a process known as smelting. The first evidence of this extractive metallurgy dates from the 5th and 6th millennium BC, and was found in the archaeological sites of Majdanpek, Yarmovac and Plocnik, all three in Serbia. To date, the earliest copper smelting is found at the Belovode site, these examples include a copper axe from 5500 BC belonging to the Vinča culture. Other signs of early metals are found from the third millennium BC in places like Palmela (Portugal), Los Millares (Spain), and Stonehenge (United Kingdom). However, as often happens with the study of prehistoric times, the ultimate beginnings cannot be clearly defined and new discoveries are continuous and ongoing.
Mining areas of the ancient Middle East. Boxes colors: arsenic is in brown, copper in red, tin in grey, iron in reddish brown, gold in yellow, silver in white and lead in black. Yellow area stands for arsenic bronze, while grey area stands for tin bronze.
These first metals were single ones or as found. By combining copper and tin, a superior metal could be made, an alloy called bronze, a major technological shift which began the Bronze Age about 3500 BC. The Bronze Age was period in human cultural development when the most advanced metalworking (at least in systematic and widespread use) included techniques for smelting copper and tin from naturally occurring outcroppings of copper ores, and then smelting those ores to cast bronze. These naturally occurring ores typically included arsenic as a common impurity. Copper/tin ores are rare, as reflected in the fact that there were no tin bronzes in western Asia before 3000 BC.
After the Bronze Age, the history of metallurgy was marked by armies seeking better weaponry. Countries in Eurasia prospered when they made the superior alloys, which, in turn, made better armor and better weapons. This often determined the outcomes of battles. Significant progress in metallurgy and alchemy was made in ancient India.
Iron Age
The extraction of iron from its ore into a workable metal is much more difficult than copper or tin. It appears to have been invented by the Hittites in about 1200 BC, beginning the Iron Age. The secret of extracting and working iron was a key factor in the success of the Philistines.
In other words, the Iron Age refers to the advent of ferrous metallurgy. Historical developments in ferrous metallurgy can be found in a wide variety of past cultures and civilizations. This includes the ancient and medieval kingdoms and empires of the Middle East and Near East, ancient Iran, ancient Egypt, ancient Nubia, and Anatolia (Turkey), Ancient Nok, Carthage, the Greeks and Romans of ancient Europe, medieval Europe, ancient and medieval China, ancient and medieval India, ancient and medieval Japan, amongst others. Many applications, practices, and devices associated or involved in metallurgy were established in ancient China, such as the innovation of the blast furnace, cast iron, hydraulic-powered trip hammers, and double acting piston bellows.
Classical antiquity and atomism
Democritus, Greek philosopher of atomistic school.
Philosophical attempts to rationalize why different substances have different properties (color, density, smell), exist in different states (gaseous, liquid, and solid), and react in a different manner when exposed to environments, for example to water or fire or temperature changes, led ancient philosophers to postulate the first theories on nature and chemistry. The history of such philosophical theories that relate to chemistry can probably be traced back to every single ancient civilization. The common aspect in all these theories was the attempt to identify a small number of primary classical element that make up all the various substances in nature. Substances like air, water, and soil/earth, energy forms, such as fire and light, and more abstract concepts such as ideas, aether, and heaven, were common in ancient civilizations even in absence of any cross-fertilization; for example in Greek, Indian, Mayan, and ancient Chinese philosophies all considered air, water, earth and fire as primary elements.
Ancient world
Around 420 BC, Empedocles stated that all matter is made up of four elemental substances—earth, fire, air and water. The early theory of atomism can be traced back to ancient Greece and ancient India. Greek atomism dates back to the Greek philosopher Democritus, who declared that matter is composed of indivisible and indestructible atoms around 380 BC. Leucippus also declared that atoms were the most indivisible part of matter. This coincided with a similar declaration by Indian philosopher Kanada in his Vaisheshika sutras around the same time period. In much the same fashion he discussed the existence of gases. What Kanada declared by sutra, Democritus declared by philosophical musing. Both suffered from a lack of empirical data. Without scientific proof, the existence of atoms was easy to deny. Aristotle opposed the existence of atoms in 330 BC. Earlier, in 380 BC, a Greek text attributed to Polybus argues that the human body is composed of four humours. Around 300 BC, Epicurus postulated a universe of indestructible atoms in which man himself is responsible for achieving a balanced life.
With the goal of explaining Epicurean philosophy to a Roman audience, the Roman poet and philosopher Lucretius wrote De Rerum Natura (The Nature of Things) in 50 BC. In the work, Lucretius presents the principles of atomism; the nature of the mind and soul; explanations of sensation and thought; the development of the world and its phenomena; and explains a variety of celestial and terrestrial phenomena.
Much of the early development of purification methods is described by Pliny the Elder in his Naturalis Historia. He made attempts to explain those methods, as well as making acute observations of the state of many minerals.
Medieval alchemy
Seventeenth century alchemical emblem showing the four Classical elements in the corners of the image, alongside the tria prima on the central triangle.
The elemental system used in Medieval alchemy was developed primarily by the Arabian alchemist Jābir ibn Hayyān and rooted in the classical elements of Greek tradition. His system consisted of the four Aristotelian elements of air, earth, fire, and water in addition to two philosophical elements: sulphur, characterizing the principle of combustibility; "the stone which burns", and mercury, characterizing the principle of metallic properties. They were seen by early alchemists as idealized expressions of irreducibile components of the universe] and are of larger consideration within philosophical alchemy.
The three metallic principles: sulphur to flammability or combustion, mercury to volatility and stability, and salt to solidity. became the tria prima of the Swiss alchemist Paracelsus. He reasoned that Aristotle's four-element theory appeared in bodies as three principles. Paracelsus saw these principles as fundamental and justified them by recourse to the description of how wood burns in fire. Mercury included the cohesive principle, so that when it left in smoke the wood fell apart. Smoke described the volatility (the mercurial principle), the heat-giving flames described flammability (sulphur), and the remnant ash described solidity (salt).
Late 19th century
German engineer Carl von Linde's invention of a continuous process of liquefying gases in large quantities formed a basis for the modern technology of refrigeration and provided both impetus and means for conducting scientific research at low temperatures and very high vacuums. He developed a methyl ether refrigerator (1874) and an ammonia refrigerator (1876). Though other refrigeration units had been developed earlier, Linde's were the first to be designed with the aim of precise calculations of efficiency. In 1895 he set up a large-scale plant for the production of liquid air. Six years later he developed a method for separating pure liquid oxygen from liquid air that resulted in widespread industrial conversion to processes utilizing oxygen (e.g., in steel manufacture).
In 1883, Svante Arrhenius developed an ion theory to explain conductivity in electrolytes. In 1884, Jacobus Henricus van 't Hoff published Études de Dynamique chimique (Studies in Dynamic Chemistry), a seminal study on chemical kinetics. In this work, van 't Hoff entered for the first time the field of physical chemistry. Of great importance was his development of the general thermodynamic relationship between the heat of conversion and the displacement of the equilibrium as a result of temperature variation. At constant volume, the equilibrium in a system will tend to shift in such a direction as to oppose the temperature change which is imposed upon the system. Thus, lowering the temperature results in heat development while increasing the temperature results in heat absorption. This principle of mobile equilibrium was subsequently (1885) put in a general form by Henry Louis Le Chatelier, who extended the principle to include compensation, by change of volume, for imposed pressure changes. The van 't Hoff-Le Chatelier principle, or simply Le Chatelier's principle, explains the response of dynamic chemical equilibria to external stresses.
In 1884, Hermann Emil Fischer proposed the structure of purine, a key structure in many biomolecules, which he later synthesized in 1898. He also began work on the chemistry of glucose and related sugars. In 1885, Eugene Goldstein named the cathode ray, later discovered to be composed of electrons, and the canal ray, later discovered to be positive hydrogen ions that had been stripped of their electrons in a cathode ray tube; these would later be named protons. The year 1885 also saw the publishing of J. H. van 't Hoff's L'Équilibre chimique dans les Systèmes gazeux ou dissous à I'État dilué (Chemical equilibria in gaseous systems or strongly diluted solutions), which dealt with this theory of dilute solutions. Here he demonstrated that the "osmotic pressure" in solutions which are sufficiently dilute is proportionate to the concentration and the absolute temperature so that this pressure can be represented by a formula which only deviates from the formula for gas pressure by a coefficient i. He also determined the value of i by various methods, for example by means of the vapor pressure and François-Marie Raoult's results on the lowering of the freezing point. Thus van 't Hoff was able to prove that thermodynamic laws are not only valid for gases, but also for dilute solutions. His pressure laws, given general validity by the electrolytic dissociation theory of Arrhenius (1884-1887) - the first foreigner who came to work with him in Amsterdam (1888) - are considered the most comprehensive and important in the realm of natural sciences. In 1893, Alfred Werner discovered the octahedral structure of cobalt complexes, thus establishing the field of coordination chemistry.
Ramsay's discovery of the noble gases
William Ramsay and Noble gas
The most celebrated discoveries of Scottish chemist William Ramsay were made in inorganic chemistry. Ramsay was intrigued by the British physicist John Strutt, 3rd Baron Rayleigh's 1892 discovery that the atomic weight of nitrogen found in chemical compounds was lower than that of nitrogen found in the atmosphere. He ascribed this discrepancy to a light gas included in chemical compounds of nitrogen, while Ramsay suspected a hitherto undiscovered heavy gas in atmospheric nitrogen. Using two different methods to remove all known gases from air, Ramsay and Lord Rayleigh were able to announce in 1894 that they had found a monatomic, chemically inert gaseous element that constituted nearly 1 percent of the atmosphere; they named it argon.
J.J. Thomson
The following year, Ramsay liberated another inert gas from a mineral called cleveite; this proved to be helium, previously known only in the solar spectrum. In his book The Gases of the Atmosphere (1896), Ramsay showed that the positions of helium and argon in the periodic table of elements indicated that at least three more noble gases might exist. In 1898 Ramsay and the British chemist Morris W. Travers isolated these elements—called neon, krypton, and xenon—from air brought to a liquid state at low temperature and high pressure. Sir William Ramsay worked with Frederick Soddy to demonstrate, in 1903, that alpha particles (helium nuclei) were continually produced during the radioactive decay of a sample of radium. Ramsay was awarded the 1904 Nobel Prize for Chemistry in recognition of "services in the discovery of the inert gaseous elements in air, and his determination of their place in the periodic system."
In 1897, J. J. Thomson discovered the electron using the cathode ray tube. In 1898, Wilhelm Wien demonstrated that canal rays (streams of positive ions) can be deflected by magnetic fields, and that the amount of deflection is proportional to the mass-to-charge ratio. This discovery would lead to the analytical technique known as mass spectrometry in 1912.
Marie and Pierre Curie
Marie Curie, a pioneer in the field of radioactivity and the first twice-honored Nobel laureate (and still the only one in two different sciences)
Marie Curie, Pierre Curie, and Henri Becquerel
Marie Skłodowska-Curie was a Polish-born French physicist and chemist who is famous for her pioneering research on radioactivity. She and her husband are considered to have laid the cornerstone of the nuclear age with their research on radioactivity. Marie was fascinated with the work of Henri Becquerel, a French physicist who discovered in 1896 that uranium casts off rays similar to the X-rays discovered by Wilhelm Röntgen. Marie Curie began studying uranium in late 1897 and theorized, according to a 1904 article she wrote for Century magazine, "that the emission of rays by the compounds of uranium is a property of the metal itself—that it is an atomic property of the element uranium independent of its chemical or physical state." Curie took Becquerel's work a few steps further, conducting her own experiments on uranium rays. She discovered that the rays remained constant, no matter the condition or form of the uranium. The rays, she theorized, came from the element's atomic structure. This revolutionary idea created the field of atomic physics and the Curies coined the word radioactivity to describe the phenomena.
Pierre Curie, known for his work on radioactivity as well as on ferromagnetism, paramagnetism, and diamagnetism; notably Curie's law and Curie point.
Pierre and Marie further explored radioactivity by working to separate the substances in uranium ores and then using the electrometer to make radiation measurements to ‘trace’ the minute amount of unknown radioactive element among the fractions that resulted. Working with the mineral pitchblende, the pair discovered a new radioactive element in 1898. They named the element polonium, after Marie's native country of Poland. On December 21, 1898, the Curies detected the presence of another radioactive material in the pitchblende. They presented this finding to the French Academy of Sciences on December 26, proposing that the new element be called radium. The Curies then went to work isolating polonium and radium from naturally occurring compounds to prove that they were new elements. In 1902, the Curies announced that they had produced a decigram of pure radium, demonstrating its existence as a unique chemical element. While it took three years for them to isolate radium, they were never able to isolate polonium. Along with the discovery of two new elements and finding techniques for isolating radioactive isotopes, Curie oversaw the world's first studies into the treatment of neoplasms, using radioactive isotopes. With Henri Becquerel and her husband, Pierre Curie, she was awarded the 1903 Nobel Prize for Physics. She was the sole winner of the 1911 Nobel Prize for Chemistry. She was the first woman to win a Nobel Prize, and she is the only woman to win the award in two different fields.
While working with Marie to extract pure substances from ores, an undertaking that really required industrial resources but that they achieved in relatively primitive conditions, Pierre himself concentrated on the physical study (including luminous and chemical effects) of the new radiations. Through the action of magnetic fields on the rays given out by the radium, he proved the existence of particles electrically positive, negative, and neutral; these Ernest Rutherford was afterward to call alpha, beta, and gamma rays. Pierre then studied these radiations by calorimetry and also observed the physiological effects of radium, thus opening the way to radium therapy. Among Pierre Curie's discoveries were that ferromagnetic substances exhibited a critical temperature transition, above which the substances lost their ferromagnetic behavior - this is known as the "Curie point." He was elected to the Academy of Sciences (1905), having in 1903 jointly with Marie received the Royal Society's prestigious Davy Medal and jointly with her and Becquerel the Nobel Prize for Physics. He was run over by a carriage in the rue Dauphine in Paris in 1906 and died instantly. His complete works were published in 1908.
Ernest Rutherford
Ernest Rutherford, discoverer of the nucleus and considered the father of nuclear physics
New Zealand-born chemist and physicist Ernest Rutherford is considered to be "the father of nuclear physics." Rutherford is best known for devising the names alpha, beta, and gamma to classify various forms of radioactive "rays" which were poorly understood at his time (alpha and beta rays are particle beams, while gamma rays are a form of high-energy electromagnetic radiation). Rutherford deflected alpha rays with both electric and magnetic fields in 1903. Working with Frederick Soddy, Rutherford explained that radioactivity is due to the transmutation of elements, now known to involve nuclear reactions.
Top: Predicted results based on the then-accepted plum pudding model of the atom. Bottom: Observed results. Rutherford disproved the plum pudding model and concluded that the positive charge of the atom must be concentrated in a small, central nucleus.
He also observed that the intensity of radioactivity of a radioactive element decreases over a unique and regular amount of time until a point of stability, and he named the halving time the "half-life." In 1901 and 1902 he worked with Frederick Soddy to prove that atoms of one radioactive element would spontaneously turn into another, by expelling a piece of the atom at high velocity. In 1906 at the University of Manchester, Rutherford oversaw an experiment conducted by his students Hans Geiger (known for the Geiger counter) and Ernest Marsden. In the Geiger–Marsden experiment, a beam of alpha particles, generated by the radioactive decay of radon, was directed normally onto a sheet of very thin gold foil in an evacuated chamber. Under the prevailing plum pudding model, the alpha particles should all have passed through the foil and hit the detector screen, or have been deflected by, at most, a few degrees.
However, the actual results surprised Rutherford. Although many of the alpha particles did pass through as expected, many others were deflected at small angles while others were reflected back to the alpha source. They observed that a very small percentage of particles were deflected through angles much larger than 90 degrees. The gold foil experiment showed large deflections for a small fraction of incident particles. Rutherford realized that, because some of the alpha particles were deflected or reflected, the atom had a concentrated centre of positive charge and of relatively large mass - Rutherford later termed this positive center the "atomic nucleus". The alpha particles had either hit the positive centre directly or passed by it close enough to be affected by its positive charge. Since many other particles passed through the gold foil, the positive centre would have to be a relatively small size compared to the rest of the atom - meaning that the atom is mostly open space. From his results, Rutherford developed a model of the atom that was similar to the solar system, known as Rutherford model. Like planets, electrons orbited a central, sun-like nucleus. For his work with radiation and the atomic nucleus, Rutherford received the 1908 Nobel Prize in Chemistry.
20th century
The first Solvay Conference was held in Brussels in 1911 and was considered a turning point in the world of physics and chemistry.
In 1903, Mikhail Tsvet invented chromatography, an important analytic technique. In 1904, Hantaro Nagaoka proposed an early nuclear model of the atom, where electrons orbit a dense massive nucleus. In 1905, Fritz Haber and Carl Bosch developed the Haber process for making ammonia, a milestone in industrial chemistry with deep consequences in agriculture. The Haber process, or Haber-Bosch process, combined nitrogen and hydrogen to form ammonia in industrial quantities for production of fertilizer and munitions. The food production for half the world's current population depends on this method for producing fertilizer. Haber, along with Max Born, proposed the Born–Haber cycle as a method for evaluating the lattice energy of an ionic solid. Haber has also been described as the "father of chemical warfare" for his work developing and deploying chlorine and other poisonous gases during World War I.
Robert A. Millikan, who is best known for measuring the charge on the electron, won the Nobel Prize in Physics in 1923.
In 1905, Albert Einstein explained Brownian motion in a way that definitively proved atomic theory. Leo Baekeland invented bakelite, one of the first commercially successful plastics. In 1909, American physicist Robert Andrews Millikan - who had studied in Europe under Walther Nernst and Max Planck - measured the charge of individual electrons with unprecedented accuracy through the oil drop experiment, in which he measured the electric charges on tiny falling water (and later oil) droplets. His study established that any particular droplet's electrical charge is a multiple of a definite, fundamental value — the electron's charge — and thus a confirmation that all electrons have the same charge and mass. Beginning in 1912, he spent several years investigating and finally proving Albert Einstein's proposed linear relationship between energy and frequency, and providing the first direct photoelectric support for Planck's constant. In 1923 Millikan was awarded the Nobel Prize for Physics.
In 1909, S. P. L. Sørensen invented the pH concept and develops methods for measuring acidity. In 1911, Antonius Van den Broek proposed the idea that the elements on the periodic table are more properly organized by positive nuclear charge rather than atomic weight. In 1911, the first Solvay Conference was held in Brussels, bringing together most of the most prominent scientists of the day. In 1912, William Henry Bragg and William Lawrence Bragg proposed Bragg's law and established the field of X-ray crystallography, an important tool for elucidating the crystal structure of substances. In 1912, Peter Debye develops the concept of molecular dipole to describe asymmetric charge distribution in some molecules.
Niels Bohr
Niels Bohr, the developer of the Bohr model of the atom, and a leading founder of quantum mechanics
Niels Bohr and Bohr model
In 1913, Niels Bohr, a Danish physicist, introduced the concepts of quantum mechanics to atomic structure by proposing what is now known as the Bohr model of the atom, where electrons exist only in strictly defined circular orbits around the nucleus similar to rungs on a ladder. The Bohr Model is a planetary model in which the negatively charged electrons orbit a small, positively charged nucleus similar to the planets orbiting the Sun (except that the orbits are not planar) - the gravitational force of the solar system is mathematically akin to the attractive Coulomb (electrical) force between the positively charged nucleus and the negatively charged electrons.
In the Bohr model, however, electrons orbit the nucleus in orbits that have a set size and energy - the energy levels are said to be quantized, which means that only certain orbits with certain radii are allowed; orbits in between simply don't exist. The energy of the orbit is related to its size - that is, the lowest energy is found in the smallest orbit. Bohr also postulated that electromagnetic radiation is absorbed or emitted when an electron moves from one orbit to another. Because only certain electron orbits are permitted, the emission of light accompanying a jump of an electron from an excited energy state to ground state produces a unique emission spectrum for each element.
Niels Bohr also worked on the principle of complementarity, which states that an electron can be interpreted in two mutually exclusive and valid ways. Electrons can be interpreted as wave or particle models. His hypothesis was that an incoming particle would strike the nucleus and create an excited compound nucleus. This formed the basis of his liquid drop model and later provided a theory base for the explanation of nuclear fission.
In 1913, Henry Moseley, working from Van den Broek's earlier idea, introduces concept of atomic number to fix inadequacies of Mendeleev's periodic table, which had been based on atomic weight. The peak of Frederick Soddy's career in radiochemistry was in 1913 with his formulation of the concept of isotopes, which stated that certain elements exist in two or more forms which have different atomic weights but which are indistinguishable chemically. He is remembered for proving the existence of isotopes of certain radioactive elements, and is also credited, along with others, with the discovery of the element protactinium in 1917. In 1913, J. J. Thomson expanded on the work of Wien by showing that charged subatomic particles can be separated by their mass-to-charge ratio, a technique known as mass spectrometry.
Gilbert N. Lewis
American physical chemist Gilbert N. Lewis laid the foundation of valence bond theory; he was instrumental in developing a bonding theory based on the number of electrons in the outermost "valence" shell of the atom. In 1902, while Lewis was trying to explain valence to his students, he depicted atoms as constructed of a concentric series of cubes with electrons at each corner. This "cubic atom" explained the eight groups in the periodic table and represented his idea that chemical bonds are formed by electron transference to give each atom a complete set of eight outer electrons (an "octet").
Lewis's theory of chemical bonding continued to evolve and, in 1916, he published his seminal article "The Atom of the Molecule", which suggested that a chemical bond is a pair of electrons shared by two atoms. Lewis's model equated the classical chemical bond with the sharing of a pair of electrons between the two bonded atoms. Lewis introduced the "electron dot diagrams" in this paper to symbolize the electronic structures of atoms and molecules. Now known as Lewis structures, they are discussed in virtually every introductory chemistry book.
Shortly after publication of his 1916 paper, Lewis became involved with military research. He did not return to the subject of chemical bonding until 1923, when he masterfully summarized his model in a short monograph entitled Valence and the Structure of Atoms and Molecules. His renewal of interest in this subject was largely stimulated by the activities of the American chemist and General Electric researcher Irving Langmuir, who between 1919 and 1921 popularized and elaborated Lewis's model. Langmuir subsequently introduced the term covalent bond. In 1921, Otto Stern and Walther Gerlach establish concept of quantum mechanical spin in subatomic particles.
For cases where no sharing was involved, Lewis in 1923 developed the electron pair theory of acids and base: Lewis redefined an acid as any atom or molecule with an incomplete octet that was thus capable of accepting electrons from another atom; bases were, of course, electron donors. His theory is known as the concept of Lewis acids and bases. In 1923, G. N. Lewis and Merle Randall published Thermodynamics and the Free Energy of Chemical Substances, first modern treatise on chemical thermodynamics.
The 1920s saw a rapid adoption and application of Lewis's model of the electron-pair bond in the fields of organic and coordination chemistry. In organic chemistry, this was primarily due to the efforts of the British chemists Arthur Lapworth, Robert Robinson, Thomas Lowry, and Christopher Ingold; while in coordination chemistry, Lewis's bonding model was promoted through the efforts of the American chemist Maurice Huggins and the British chemist Nevil Sidgwick.
Quantum mechanics
In 1924, French quantum physicist Louis de Broglie published his thesis, in which he introduced a revolutionary theory of electron waves based on wave–particle duality in his thesis. In his time, the wave and particle interpretations of light and matter were seen as being at odds with one another, but de Broglie suggested that these seemingly different characteristics were instead the same behavior observed from different perspectives — that particles can behave like waves, and waves (radiation) can behave like particles. Broglie's proposal offered an explanation of the restriction motion of electrons within the atom. The first publications of Broglie's idea of "matter waves" had drawn little attention from other physicists, but a copy of his doctoral thesis chanced to reach Einstein, whose response was enthusiastic. Einstein stressed the importance of Broglie's work both explicitly and by building further on it.
In 1925, Austrian-born physicist Wolfgang Pauli developed the Pauli exclusion principle, which states that no two electrons around a single nucleus in an atom can occupy the same quantum state simultaneously, as described by four quantum numbers. Pauli made major contributions to quantum mechanics and quantum field theory - he was awarded the 1945 Nobel Prize for Physics for his discovery of the Pauli exclusion principle - as well as solid-state physics, and he successfully hypothesized the existence of the neutrino. In addition to his original work, he wrote masterful syntheses of several areas of physical theory that are considered classics of scientific literature.
The Schrödinger equation
In 1926 at the age of 39, Austrian theoretical physicist Erwin Schrödinger produced the papers that gave the foundations of quantum wave mechanics. In those papers he described his partial differential equation that is the basic equation of quantum mechanics and bears the same relation to the mechanics of the atom as Newton's equations of motion bear to planetary astronomy. Adopting a proposal made by Louis de Broglie in 1924 that particles of matter have a dual nature and in some situations act like waves, Schrödinger introduced a theory describing the behaviour of such a system by a wave equation that is now known as the Schrödinger equation. The solutions to Schrödinger's equation, unlike the solutions to Newton's equations, are wave functions that can only be related to the probable occurrence of physical events. The readily visualized sequence of events of the planetary orbits of Newton is, in quantum mechanics, replaced by the more abstract notion of probability. (This aspect of the quantum theory made Schrödinger and several other physicists profoundly unhappy, and he devoted much of his later life to formulating philosophical objections to the generally accepted interpretation of the theory that he had done so much to create.)
German theoretical physicist Werner Heisenberg was one of the key creators of quantum mechanics. In 1925, Heisenberg discovered a way to formulate quantum mechanics in terms of matrices. For that discovery, he was awarded the Nobel Prize for Physics for 1932. In 1927 he published his uncertainty principle, upon which he built his philosophy and for which he is best known. Heisenberg was able to demonstrate that if you were studying an electron in an atom you could say where it was (the electron's location) or where it was going (the electron's velocity), but it was impossible to express both at the same time. He also made important contributions to the theories of the hydrodynamics of turbulent flows, the atomic nucleus, ferromagnetism, cosmic rays, and subatomic particles, and he was instrumental in planning the first West German nuclear reactor at Karlsruhe, together with a research reactor in Munich, in 1957. Considerable controversy surrounds his work on atomic research during World War II.
Quantum chemistry
Some view the birth of quantum chemistry in the discovery of the Schrödinger equation and its application to the hydrogen atom in 1926. However, the 1927 article of Walter Heitler and Fritz London is often recognised as the first milestone in the history of quantum chemistry. This is the first application of quantum mechanics to the diatomic hydrogen molecule, and thus to the phenomenon of the chemical bond. In the following years much progress was accomplished by Edward Teller, Robert S. Mulliken, Max Born, J. Robert Oppenheimer, Linus Pauling, Erich Hückel, Douglas Hartree, Vladimir Aleksandrovich Fock, to cite a few.
Still, skepticism remained as to the general power of quantum mechanics applied to complex chemical systems. The situation around 1930 is described by Paul Dirac:
The underlying physical laws necessary for the mathematical theory of a large part of physics and the whole of chemistry are thus completely known, and the difficulty is only that the exact application of these laws leads to equations much too complicated to be soluble. It therefore becomes desirable that approximate practical methods of applying quantum mechanics should be developed, which can lead to an explanation of the main features of complex atomic systems without too much computation.
Hence the quantum mechanical methods developed in the 1930s and 1940s are often referred to as theoretical molecular or atomic physics to underline the fact that they were more the application of quantum mechanics to chemistry and spectroscopy than answers to chemically relevant questions. In 1951, a milestone article in quantum chemistry is the seminal paper of Clemens C. J. Roothaan on Roothaan equations. It opened the avenue to the solution of the self-consistent field equations for small molecules like hydrogen or nitrogen. Those computations were performed with the help of tables of integrals which were computed on the most advanced computers of the time.
In the 1940s many physicists turned from molecular or atomic physics to nuclear physics (like J. Robert Oppenheimer or Edward Teller). Glenn T. Seaborg was an American nuclear chemist best known for his work on isolating and identifying transuranium elements (those heavier than uranium). He shared the 1951 Nobel Prize for Chemistry with Edwin Mattison McMillan for their independent discoveries of transuranium elements. Seaborgium was named in his honour, making him the only person, along Albert Einstein, for whom a chemical element was named during his lifetime.
Molecular biology and biochemistry
By the mid 20th century, in principle, the integration of physics and chemistry was extensive, with chemical properties explained as the result of the electronic structure of the atom; Linus Pauling's book on The Nature of the Chemical Bond used the principles of quantum mechanics to deduce bond angles in ever-more complicated molecules. However, though some principles deduced from quantum mechanics were able to predict qualitatively some chemical features for biologically relevant molecules, they were, till the end of the 20th century, more a collection of rules, observations, and recipes than rigorous ab initio quantitative methods.
Diagrammatic representation of some key structural features of DNA
This heuristic approach triumphed in 1953 when James Watson and Francis Crick deduced the double helical structure of DNA by constructing models constrained by and informed by the knowledge of the chemistry of the constituent parts and the X-ray diffraction patterns obtained by Rosalind Franklin. This discovery lead to an explosion of research into the biochemistry of life.
In the same year, the Miller–Urey experiment demonstrated that basic constituents of protein, simple amino acids, could themselves be built up from simpler molecules in a simulation of primordial processes on Earth. Though many questions remain about the true nature of the origin of life, this was the first attempt by chemists to study hypothetical processes in the laboratory under controlled conditions.
In 1983 Kary Mullis devised a method for the in-vitro amplification of DNA, known as the polymerase chain reaction (PCR), which revolutionized the chemical processes used in the laboratory to manipulate it. PCR could be used to synthesize specific pieces of DNA and made possible the sequencing of DNA of organisms, which culminated in the huge human genome project.
An important piece in the double helix puzzle was solved by one of Pauling's students Matthew Meselson and Frank Stahl, the result of their collaboration (Meselson–Stahl experiment) has been called as "the most beautiful experiment in biology".
They used a centrifugation technique that sorted molecules according to differences in weight. Because nitrogen atoms are a component of DNA, they were labelled and therefore tracked in replication in bacteria.
Late 20th century
In 1970, John Pople developed the Gaussian program greatly easing computational chemistry calculations. In 1971, Yves Chauvin offered an explanation of the reaction mechanism of olefin metathesis reactions. In 1975, Karl Barry Sharpless and his group discovered a stereoselective oxidation reactions including Sharpless epoxidation, Sharpless asymmetric dihydroxylation, and Sharpless oxyamination. In 1985, Harold Kroto, Robert Curl and Richard Smalley discovered fullerenes, a class of large carbon molecules superficially resembling the geodesic dome designed by architect R. Buckminster Fuller. In 1991, Sumio Iijima used electron microscopy to discover a type of cylindrical fullerene known as a carbon nanotube, though earlier work had been done in the field as early as 1951. This material is an important component in the field of nanotechnology. In 1994, Robert A. Holton and his group achieved the first total synthesis of Taxol. In 1995, Eric Cornell and Carl Wieman produced the first Bose–Einstein condensate, a substance that displays quantum mechanical properties on the macroscopic scale.
Mathematics and chemistry
Classically, before the 20th century, chemistry was defined as the science of the nature of matter and its transformations. It was therefore clearly distinct from physics which was not concerned with such dramatic transformation of matter. Moreover, in contrast to physics, chemistry was not using much of mathematics. Even some were particularly reluctant to use mathematics within chemistry. For example, Auguste Comte wrote in 1830, Every attempt to employ mathematical methods in the study of chemical questions must be considered profoundly irrational and contrary to the spirit of chemistry.... if mathematical analysis should ever hold a prominent place in chemistry -- an aberration which is happily almost impossible -- it would occasion a rapid and widespread degeneration of that science.
However, in the second part of the 19th century, the situation changed and August Kekulé wrote in 1867, I rather expect that we shall someday find a mathematico-mechanical explanation for what we now call atoms which will render an account of their properties.
Scope of chemistry
As understanding of the nature of matter has evolved, so too has the self-understanding of the science of chemistry by its practitioners. This continuing historical process of evaluation includes the categories, terms, aims and scope of chemistry. Additionally, the development of the social institutions and networks which support chemical enquiry are highly significant factors that enable the production, dissemination and application of chemical knowledge.
Chemical industry
The later part of the nineteenth century saw a huge increase in the exploitation of petroleum extracted from the earth for the production of a host of chemicals and largely replaced the use of whale oil, coal tar and naval stores used previously. Large-scale production and refinement of petroleum provided feedstocks for liquid fuels such as gasoline and diesel, solvents, lubricants, asphalt, waxes, and for the production of many of the common materials of the modern world, such as synthetic fibers, plastics, paints, detergents, pharmaceuticals, adhesives and ammonia as fertilizer and for other uses. Many of these required new catalysts and the utilization of chemical engineering for their cost-effective production.
In the mid-twentieth century, control of the electronic structure of semiconductor materials was made precise by the creation of large ingots of extremely pure single crystals of silicon and germanium. Accurate control of their chemical composition by doping with other elements made the production of the solid state transistor in 1951 and made possible the production of tiny integrated circuits for use in electronic devices, especially computers.
Source : Wikipedia
