History of chemistry

The history of chemistry may be said to begin with the distinction of chemistry from alchemy by Robert Boyle in his work The Sceptical Chymist (1661). Both alchemy and chemistry are concerned with the nature of matter and its transformations but, in contrast with alchemists, chemists apply the scientific method. The history of chemistry is intertwined with the history of thermodynamics, especially through the work of Willard Gibbs.

Early developments

Origins

Although the archives of chemical research draw upon work from ancient Babylon, Egypt, and especially Persia after Islam, the birth of chemistry is often dated to Antoine Lavoisier's discovery of the law of conservation of mass, and thereby to his refutation of the phlogiston theory of combustion in 1783. (Phlogiston was supposed to be an imponderable substance liberated by flammable materials in burning.) Mikhail Lomonosov independently established a tradition of chemistry in Russia in the 18th century. Lomonosov also rejected the phlogiston theory, and anticipated the kinetic theory of gases. He regarded heat as a form of motion, and stated the idea of conservation of matter.

The vitalism debate and organic chemistry

After the nature of combustion (see oxygen) was settled, another dispute, about vitalism and the essential distinction between organic and inorganic substances, was revolutionized by Friedrich Wöhler's accidental synthesis of urea from inorganic substances in 1828. Never before had an organic compound been synthesized from inorganic material. This opened a new research field in chemistry, and by the end of the 19th century, scientists were able to synthesize hundreds of organic compounds. The most important among them are mauve, magenta, and other synthetic dyes, as well as the widely used drug aspirin. The discovery also contributed greatly to the theory of isomerism.

The dispute about atomism

Throughout the 19th century, chemistry was divided between those who followed the atomic theory of John Dalton and those who did not, such as Wilhelm Ostwald and Ernst Mach. Although such proponents of the atomic theory as Amedeo Avogadro and Ludwig Boltzmann made great advances in explaining the behavior of gases, this dispute was not finally settled until Jean Perrin's experimental investigation of Einstein's atomic explanation of Brownian motion in the first decade of the 20th century.

Well before the dispute had been settled, many had already applied the concept of atomism to chemistry. A major example was the ion theory of Svante Arrhenius which anticipated ideas about atomic substructure that did not fully develop until the 20th century. Michael Faraday was another early worker, whose major contribution to chemistry was electrochemistry, in which (among other things) a certain quantity of electricity during electrolysis or electrodeposition of metals was shown to be associated with certain quantities of chemical elements, and fixed quanties of the elements therefore with each other, in specific ratios. These findings, like those of Dalton's combining ratios, were early clues to the atomic nature of matter.

The periodic table

For many decades, the list of known chemical elements had been steadily increasing. A great breakthrough in making sense of this long list (as well as, eventually, in understanding the internal structure of atoms as discussed below) was Dmitri Mendeleev and Lothar Meyer's development of the periodic table, and, particularly, Mendeleev's use of it to predict the existence and the properties of germanium, gallium, and scandium, which Mendeleev called ekasilicon, ekaaluminium, and ekaboron respectively. Mendeleev made his prediction in 1870; gallium was discovered in 1875, and was found to have roughly the same properties that Mendeleev predicted for it.

The modern definition of 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 using 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 Kekule 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.

After the discovery by Ernest Rutherford and Niels Bohr of the atomic structure in 1912, and by Marie and Pierre Curie of radioactivity, scientists had to change drastically their viewpoint on the nature of matter. The experience acquired by chemists was no longer pertinent to the study of the whole nature of matter but only to aspects related to the electron cloud surrounding the atomic nuclei and the movement of the latter in the electric field induced by the former (see Born-Oppenheimer approximation). The range of chemistry was thus restricted to the nature of matter around us in conditions which are not too far from standard conditions for temperature and pressure and in cases where the exposure to radiation is not too different from the natural microwave, visible or UV radiations on Earth. Chemistry was therefore re-defined as the science of matter that deals with the composition, structure, and properties of substances and with the transformations that they undergo. However the meaning of matter used here relates explicitly to substances made of atoms and molecules, disregarding the matter within the atomic nuclei and its nuclear reaction or matter within highly ionized plasmas. Nevertheless the field of chemistry is still, on our human scale, very broad and the claim that chemistry is everywhere is accurate.

Quantum chemistry

Some view the birth of quantum chemistry in the discovery of the Schrödinger equation and its application to 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. 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 the 1940s many physicists turned from molecular or atomic physics to nuclear physics (like J. Robert Oppenheimer or Edward Teller). 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.

Molecular biology and biochemistry

By the mid 20th century, in principle, the integration of physics and chemistry was complete, 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.

This heuristic approach triumphed in 1953 when James Watson and 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.

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, which revolutionized the world.

References

Notes

W. Heitler and F. London, Wechselwirkung neutraler Atome und Homöopolare Bindung nach der Quantenmechanik, Z. Physik, 44, 455 (1927)
P.A.M. Dirac, Quantum Mechanics of Many-Electron Systems, Proc. R. Soc. London, A 123, 714 (1929)
C.C.J. Roothaan, A Study of Two-Center Integrals Useful in Calculations on Molecular Structure, J. Chem. Phys., 19, 1445 (1951)