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Table of contents
- Preparation of Chemical Substances for Analysis
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In the initial years of the Nobel Prize, about invitations to nominate for the Nobel Prize for Chemistry were sent out, but this number has increased over the years and was as high as 2, in The number of nominations received has also increased dramatically from during the first decade to in the s. The number of candidates is usually smaller than the number of nominations, since many candidates receive more than one nomination.
During the first few years only about 10 scientists were nominated, but in recent years this number has been in the range of The invitations to nominate are personal, and it is stressed that nominations should not be discussed with the candidate or with colleagues. This is unfortunately not always respected as is obvious from the fact that many identically worded nominations are some years received from the same university.
For this reason the Committee does not put much weight on the number of nominations a given candidate receives, unless clearly independent nominations come from different universities in different countries. Often the same candidate receives nominations both for chemistry and for physics or for chemistry and for medicine.
This problem was met already in , when Arrhenius had been nominated both for the Prize for Chemistry and that for Physics, and in its deliberations the Committee for Chemistry suggested that he should be awarded half of each Prize, but this idea was rejected by the Committee for Physics. Because of such borderline problems, the Committee for Chemistry nowadays has joint meetings with those for Physics and for Physiology or Medicine.
It was undoubtedly this rule that excluded Stanislao Cannizzaro from receiving one of the first Nobel Prizes, since his work on drawing up a reliable table of atomic weights, helping to establish the periodic system, was done in the middle of the 19th century. A more recent example is Henry Eyring, whose brilliant theory for the rates of chemical reactions, published in , was apparently not understood by members of the Nobel Committee until much later. The Nobel Prize was, however, awarded for his later work on chemical kinetics and equilibria and on the osmotic pressure in solution, published in and , when he held a professorship in Amsterdam.
When he received the prize he had, however, left this for a position at Akademie der Wissenschaften in Berlin in An apparent exception was aqueous solutions of electrolytes acids, bases and their salts , but in the following year Arrhenius showed that this anomaly could be explained, if it is assumed that electrolytes in water dissociate into ions.
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Arrhenius had already presented the rudiments of his dissociation theory in his doctoral thesis, which was defended in Uppsala in and was not entirely well received by the faculty. It was, however, strongly supported by Ostwald in Riga, who, in fact, travelled to Uppsala to initiate a collaboration with Arrhenius.
When Arrhenius was awarded the Nobel Prize for Chemistry in , he was since professor of physics in Stockholm, and he was also nominated for the Prize for Physics see Section 1. The award of the Nobel Prize for Chemistry in to Ostwald was chiefly in recognition of his work on catalysis and the rates of chemical reactions. Ostwald had in his investigations, following up observations in his thesis in , shown that the rate of acid-catalyzed reactions is proportional to the square of the strength of the acid, as measured by titration with base.
Three of the Nobel Prizes for Chemistry during the first decade were awarded for pioneering work in organic chemistry.
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At the award ceremony in the importance of his discoveries for chemical industry was emphasized. Two of the early prizes were given for the discovery of new chemical elements. Sir William Ramsay from London received the Nobel Prize for Chemistry for his discovery of a number of noble gases, a new group of chemically unreactive elements. The following year Ramsay found helium, observed earlier only in the solar spectrum hence its name , in emanations from radium, thus anticipating later prizes for nuclear chemistry see below.
The isolation of another element, fluorine, by Henri Moissan in Paris was honored with the Nobel Prize. Ernest Rutherford [Lord Rutherford since ], professor of physics in Manchester, was awarded the Nobel Prize for Chemistry in for his investigations of the chemistry of radioactive substances. In his studies of uranium disintegration he found two types of radiation, named a — and b -rays, and by their deviation in electric and magnetic fields he could show that a -rays consist of positively charged particles.
His demonstration that these particles are helium nuclei came in the same year as he received the Nobel Prize. The vitalistic outlook had been fiercely defended by Louis Pasteur, who maintained that alcoholic fermentation can only occur in the presence of living yeast cells. Buchner was awarded the Nobel Prize for Chemistry in , when he was professor at the agricultural college in Berlin. A survey of the Nobel Prizes for Chemistry awarded during the 20th century, reveals that the development of this field includes breakthroughs in all of its branches, with a certain dominance for progress in physical chemistry and its subcategories chemical thermodynamics and chemical change , in chemical structure, in several areas of organic chemistry as well as in biochemistry.
Of course, the borders between different areas are diffuse, therefore many Laureates will be mentioned in more than one place. Most atomic weights in Cannizzaros table see Section 1. In Richards had discovered that the atomic weight of natural lead and of that formed in radioactive decay of uranium minerals differ. This pointed to the existence of isotopes, i.
Aston also showed that the atomic weights of pure isotopes are integral numbers, with the exception of hydrogen, the atomic weight of which is 1. For his achievements Aston received the Nobel Prize for Chemistry in One branch of physical chemistry deals with chemical events at the interface of two phases, for example, solid and liquid, and phenomena at such interfaces have important applications all the way from technical to physiological processes.
Detailed studies of adsorption on surfaces, were carried out by Irving Langmuir at the research laboratory of General Electric Company, and when he was awarded the Nobel Prize for Chemistry in , he was the first industrial scientist to receive this distinction. Two of the Prizes for Chemistry in more recent decades have been given for fundamental work in the application of spectroscopic methods to chemical problems. The most used spectroscopic method in chemistry is undoubtedly NMR nuclear magnetic resonance , and Richard R. Section 3. Already in Walther Hermann Nernst of Berlin received this award for work in thermochemistry, despite a year opposition to this recognition from Arrhenius .
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Nernst had shown that it is possible to determine the equilibrium constant for a chemical reaction from thermal data, and in so doing he formulated what he himself called the third law of thermodynamics. This states that the entropy, a thermodynamic quantity, which is a measure of the disorder in the system, approaches zero as the temperature goes towards absolute zero. Willard Gibbs at Yale, who certainly had deserved a Nobel Prize, but his work had been published in an obscure place].
According to the second law, heat of reaction is not an accurate measure of chemical equilibrium, as had been assumed by earlier investigators.
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But Nernst showed in that it is possible with the aid of the third law, to derive the necessary parameters from the temperature dependence of thermochemical quantities. To prove his heat theorem the third law Nernst carried out thermochemical measurements at very low temperatures, and such studies were extended in the s by G. Lewis see Section 1.
With this he managed to reach temperatures a few thousandths of a degree above absolute zero and could thereby provide extremely accurate entropy estimates.
He also showed that it is possible to determine entropies from spectroscopic data. Giauque was awarded the Nobel Prize for Chemistry in for his contributions to chemical thermodynamics. The next Nobel Prize given for work in thermodynamics went to Lars Onsager of Yale University in for contributions to the thermodynamics of irreversible processes. Classical thermodynamics deals with systems at equilibrium, in which the chemical reactions are said to be reversible, but many chemical systems, for example, the most complex of all, living organisms, are far from equilibrium and their reactions are said to be irreversible.
With the aid of statistical mechanics Onsager developed in his so-called reciprocal relations, describing the flow of matter and energy in such systems, but the importance of his work was not recognized until the end of the s. A further step forward in the development of non-equilibrium thermodynamics was taken by Ilya Prigogine in Bruxelles, whose theory of dissipative structures was awarded the Nobel Prize for Chemistry in The chief method to get information about the mechanism of chemical reactions is chemical kinetics, i. Only molecules with sufficient kinetic energy in the collision do, in fact, react, and Arrhenius derived an equation in allowing the calculation of this activation energy from the temperature dependence of the reaction rate.
With the advent of quantum mechanics in the s see Section 3. Strangely, Eyring never received a Nobel Prize see Section 1. A limit in investigating reaction rates is set by the speed with which the reaction can be initiated. If this is done by rapid mixing of the reactants, the time limit is about one thousandth of a second millisecond. The methods involve disturbing an equilibrium by rapid changes in temperature or pressure and then follow the passage to a new equilibrium. Another way to initiate some reactions rapidly is flash photolysis, i.
Eigen received one-half and Norrish and Porter shared the other half of the Nobel Prize for Chemistry in The milli- to picosecond time scales gave important information on chemical reactions. However, it was not until it was possible to generate femtosecond laser pulses 10 s that it became possible to reveal when chemical bonds are broken and formed. His experiments relate back to when Arrhenius Nobel Prize, made the important prediction that there must exist intermediates transition states in the transformation from reactants to products.
The latest prize for work in chemical kinetics was that to Dudley R. Herschbach at Harvard University, Yuan T.
Lee of Berkeley and John C. Polanyi from Toronto in Herschbach and his student Lee introduced the use of fluxes of molecules with well-defined direction and energy, molecular beams. By crossing two such beams they could study details of the reaction between molecules at extremely short times.
Another important method to investigate such reaction details is infrared chemiluminescence, introduced by Polanyi. The emission of infrared radiation from the reaction products gives information on the energy distribution in the molecules. Quantum mechanics, developed in the s, offered a tool towards a more basic understanding of chemical bonds. In Walter Heitler and Fritz London showed that it is possible to solve exactly the relevant equations for the hydrogen molecule ion, i. Bright Wilson, Jr. A few years later he published an extensive non-mathematical treatment in The Nature of the Chemical Bond , a book which is one of the most read and influential in the entire history of chemistry.
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Pauling was not only a theoretician, but he also carried out extensive investigations of chemical structure by X-ray diffraction see Section 3. On the basis of results with small peptides, which are building blocks of proteins, he suggested the a -helix as an important structural element. Pauling was awarded the Nobel Peace Prize for , and he is the only person to date to have won two unshared Nobel Prizes. Mulliken from Chicago and later developed further by him as well as by many other investigators.
MO theory considers, in quantum-mechanical terms, the interaction between all atomic nuclei and electrons in a molecule. Mulliken also showed that a combination of MO calculations with experimental spectroscopic results provides a powerful tool for describing bonding in large molecules.
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Mulliken received the Nobel Prize for Chemistry in Theoretical chemistry has also contributed significantly to our understanding of chemical reaction mechanisms. Fukui introduced in the frontier-orbital theory, according to which the occupied MO with the highest energy and the unoccupied one with the lowest energy have a dominant influence on the reactivity of a molecule. Hoffmann formulated in , together with Robert B.
Woodward see Section 3. Rudolph A. Marcus published during ten years, starting in , a series of seminal papers on a comprehensive theory for the rates electron-transfer reactions, the experimental study of which had given Taube a Nobel Prize in see Section 3. Marcus was awarded the Nobel Prize for Chemistry in Pople of Northwestern University but a British citizen. The prize to Kohn, a theoretical physicist, was based on his development of density-functional theory, which facilitates detailed calculations both of the geometrical structures of complex molecules and of the energy map of chemical reactions.
In particular, Pople has designed computer programs based on classical quantum theory as well as on density-functional theory. The most commonly used method to determine the structure of molecules in three dimensions is X-ray crystallography. The diffraction of X-rays was discovered by Max von Laue in , and this gave him the Nobel Prize for Physics in Its use for the determination of crystal structure was developed by Sir William Bragg and his son, Sir Lawrence Bragg , and they shared the Nobel Prize for Physics in Debye did not study crystals, however, but gases, which give less distinct diffraction patterns.
He also employed electron diffraction and the measurement of dipole moments to get structural information. Dipole moments are found in molecules, in which the positive and negative charge is unevenly distributed polar molecules. Many Nobel Prizes have been awarded for the determination of the structure of biological macromolecules proteins and nucleic acids. Proteins are long chains of amino-acids, as shown by Emil Fischer see Section 2 , and the first step in the determination of their structure is to determine the order sequence of these building blocks.